# Patent

## Title
Coloring composition, colored cured film, color filter, solid-state image sensor and image display device

## Abstract

Provided is a coloring composition which uses a dye polymer and which can form a pattern properly. The coloring composition includes a (A) dye multimer having a non-nucleophilic counter anion and a (B) polymerizable compound.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Continuation of PCT International Application No. PCT/JP2014/062375 filed on May 8, 2014, which claims priority under 35 U.S.C §119(a) to Japanese Patent Application No. 2013-099838 filed on May 10, 2013 and Japanese Patent Application No. 2014-068593 filed on Mar. 28, 2014. Each of the above application(s) is hereby expressly incorporated by reference, in its entirety, into the present application.


BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a coloring composition and a colored cured film using the same. It further relates to a color filter having a colored cured film, and a solid-state image sensor and an image display device, each of which has the color filter.
2. Description of the Related Art
As one of the methods for producing a color filter which is used for a liquid crystal display device, a solid-state image sensor, or the like, there is a pigment dispersion method. As the pigment dispersion method, there is a method for producing a color filter by a photolithography method by using a colored photosensitive composition which is obtained by dispersing pigments in various photosensitive compositions. That is, a curable composition is applied onto a substrate by using a spin coater, a roll coater, or the like, the substrate is dried to form a coating film, and the coating film is developed by pattern exposure, thereby obtaining colored pixels. This operation is repeated for the number of the desired hues to manufacture a color filter.
The method is stable with respect to light or heat due to a use of pigments, and positional accuracy is sufficiently secured since patterning is performed by a photolithography method. Accordingly, the method has been widely used as a method suitable for producing a color filter for color display or the like.
Meanwhile, in recent years, there has been a demand for a color filter for a solid-state image sensor such as a CCD to have high definition. As the definition of the color filter is heightened, the pattern size tends to be decreased, but it is considered that the pigment dispersion method which has been widely used in the related art has difficulty in further improving resolution while also decreasing the pattern size. One of the reasons therefor is that coarse particles generated due to the aggregation of pigment particles cause color unevenness in a fine pattern. Accordingly, the pigment dispersion method which has been widely used so far has been in a recent situation where it has not necessarily been used for purposes requiring a fine pattern, such as in a solid-state image sensor.
In the related art, a color filter has been produced using a pigment as a coloring agent, but use of a dye instead of a pigment is under examination. In the case where a dye is used, the points shown below particularly become problems.
(1) A dye is generally inferior to a pigment in terms of light fastness and heat resistance. In particular, there is a problem in that optical characteristics are changed due to a high-temperature process performed at the time when a film is formed of indium tin oxide (ITO) which is widely used as an electrode of a liquid crystal display or the like.
(2) Since a dye tends to inhibit a radical polymerization reaction, there is difficulty in designing a colored photosensitive composition in a system using radical polymerization as curing means.
Particularly, in the case where a photolithography method is used for the manufacture of a color filter, the following points become problems.
(3) Since an ordinary dye exhibits low solubility in an aqueous alkaline solution or an organic solvent (hereinafter simply referred to as a solvent), it is difficult to obtain a colored photosensitive composition having a desired spectrum.
(4) A dye interacts with other components in a colored photosensitive composition in many cases, and thus, it is difficult to regulate the solubility (developability) of exposed and unexposed areas.
(5) In the case where the molar absorption coefficient (s) of a dye is low, it is necessary to add the dye in a large amount. As a result, amounts of other components in a colored photosensitive composition, such as a polymerizable compound (monomer), a binder, and a photopolymerization initiator, have to be relatively reduced, and curability of the composition as well as heat resistance, developability, and the like of the cured composition deteriorate.
Due to these problems, it has been difficult so far to form a colored pattern which is constituted with a fine and thin film for a high-definition color filter and has excellent fastness by using a dye. Further, in the case of a color filter for a solid-state image sensor, a colored layer is required to be formed of a thin film of 1 μm or less. Accordingly, in order to obtain desired absorption, a large amount of a dye needs to be added to a curable composition, and as a result, the aforementioned problems arise.
Furthermore, for a colored photosensitive composition containing a dye, it is pointed out that in the case where a heating treatment is carried out after forming a film, a phenomenon of color transfer easily occurs between different hues of colored patterns adjacent to each other or between layers disposed and stacked on each other. In addition to color transfer, there are also problems in that a pattern is easily peeled off in an area with a low exposure dose due to decrease in sensitivity; since the amount of photosensitive components contributing to photolithographic properties is relatively reduced, an intended shape or color density cannot be obtained due to heat sagging or elution caused at the time of development; and the like.
As methods for solving such problems, methods for resolving the problems by polymerizing a dye have been suggested (see, for example, JP2012-32754A, JP2007-138051A, JP2000-162429A, and JP2003-246935A).
SUMMARY OF THE INVENTION
However, it could be seen that if a dye is polymerized, the dye decomposes in an excessive heating process, and further, color transfer to another pattern occurs. Further, it could be seen that in the case of preparing a pattern, there is a problem in pattern formability. The present invention has been made to solve such problems and has an object to provide a coloring composition which uses a dye polymer and which can form a pattern properly.
The present inventors have conducted extensive studies, and as a result, they have found that the aforementioned problems could be solved by using a dye multimer having a specific counter anion.
Specifically, the problems were solved by the following means <1>, and preferably <2> to <16>.
<1> A coloring composition including a (A) dye multimer having a non-nucleophilic counter anion; and a (B) polymerizable compound.
<2> The coloring composition as described in <1>, in which the (A) dye multimer having a non-nucleophilic counter anion has a partial structure derived from a dye selected from a dipyrromethene dye, a triarylmethane dye, a xanthene dye, a cyanine dye, and a squarylium dye.
<3> The coloring composition as described in <1> or <2>, in which the non-nucleophilic counter anion is selected from a sulfonic acid anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, a carboxylic acid anion, a tetraarylborate anion, —BF4−, —PF6−, and —SbF6−.
<4> The coloring composition as described in any one of <1> to <3>, further including a (C) pigment.
<5> The coloring composition as described in any one of <1> to <4>, further including a (D) photopolymerization initiator.
<6> The coloring composition as described in <5>, in which the (D) photopolymerization initiator is an oxime compound.
<7> The coloring composition as described in any one of <1> to <6>, in which the dye multimer having a non-nucleophilic counter anion has a partial structure derived from a xanthene dye.
<8> The coloring composition as described in any one of <1> to <7>, in which the non-nucleophilic counter anion is selected from a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, and a tetraarylborate anion.
<9> The coloring composition as described in any one of <1> to <8>, in which the dye multimer (A) further has a polymerizable group.
<10> The coloring composition as described in any one of <1> to <9>, which is used for forming a colored layer of a color filter.
<11> A colored cured film formed by curing the coloring composition as described in any one of <1> to <10>.
<12> A color filter including the colored cured film as described in <11>.
<13> A method for producing a color filter, including applying the coloring composition as described in any one of <1> to <10> onto a support to form a coloring composition layer; patternwise exposing the coloring composition layer; and developing and removing an unexposed area to form a colored pattern.
<14> A method for producing a color filter, including applying the coloring composition as described in any one of <1> to <10> onto a support to form a coloring composition layer, and curing the coloring composition layer to form a colored layer; forming a photoresist layer on the colored layer; patterning the photoresist layer by exposure and development to obtain a resist pattern; and dry-etching the colored layer using a resist pattern as an etching mask.
<15> A color filter produced by the method for producing a color filter as described in <13> or <14>.
<16> A solid-state image sensor or image display device including the color filter as described in <12> or a color filter produced by the method for producing a color filter as described in <13> or <14>.
According to the present invention, it became possible to provide a coloring composition which uses a dye polymer and which can form a pattern properly.


DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, the coloring composition, the colored cured film, the pattern forming method, the method for producing a color filter, the solid-state image sensor, and the image display device of the present invention will be described in detail.
The explanation of constituents in the present invention described below will be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In citations for a group (atomic group) in the present specification, when the group is denoted without specifying whether it is substituted or unsubstituted, the group includes both a group having no substituent and a group having a substituent. For example, an “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group), but also an alkyl group having a substituent (substituted alkyl group).
Furthermore, “radiation” in the present specification means, for example, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV rays), X-rays, electron beams, or the like. In addition, in the present invention, light means actinic rays or radiation. “Exposure” in the present specification includes, unless otherwise specified, not only exposure by a mercury lamp, far ultraviolet rays represented by an excimer laser, X-rays, EUV rays, or the like, but also writing by particle rays such as electron beams and ion beams.
In the present specification “(a value) to  ̃(a value)” is used to mean a range including the numeral values represented before and after “(a value) to (a value)” as a lower limit value and an upper limit value, respectively.
In the present specification, the total solid content refers to a total mass of the components remaining when a solvent is excluded from the entire composition of a coloring composition.
Furthermore, in the present specification, “(meth)acrylate” represents either or both of an acrylate and a methacrylate, “(meth)acryl” represents either or both of an acryl and a methacryl, and “(meth)acryloyl” represents either or both of an acryloyl and a methacryloyl.
In the present specification, a “monomer material” and a “monomer” have the same definition. The monomer in the present specification refers to a compound which is distinguished from an oligomer or a polymer and has a weight-average molecular weight of 2,000 or less. In the present specification, a polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in a polymerization reaction.
In the present specification, in the formulae, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, a term “step” includes not only an independent step, but also steps which are not clearly distinguished from other steps if an intended action of the steps is obtained.
The present invention has been made in consideration of the aforementioned situation, and has an object to provide a coloring composition having excellent color characteristics.
The coloring composition of the present invention (hereinafter simply referred to as “the composition of the present invention” in some cases) may contain a (A) dye multimer having a non-nucleophilic counter anion and a (B) polymerizable compound. The coloring composition of the present invention preferably further includes a (C) pigment and/or a (D) photopolymerization initiator, or may include other components such as a crosslinking agent, if desired.
By adopting such a constitution, it becomes possible to color transfer to another pattern is inhibited, and further, it becomes possible to form a pattern having excellent pattern formability.
Further, in a coloring composition into which a dye multimer has been blended in the related art, there were cases where when a fine pattern is formed by a photolithography method, pattern deficit occurs or pattern linearity deteriorates. In contrast, in the present invention, it becomes possible to inhibit pattern deficit or inhibit deterioration of pattern linearity.
Furthermore, in a coloring composition into which a dye multimer has been blended, when a pattern is formed by a dry etching method, there are cases where the resistance to a developing liquid or the resistance to a peeling solution of a photoresist is poor. In contrast, in the present invention, it becomes possible to improve the resistance to a developing liquid or the resistance to a peeling solution of a photoresist.
Therefore, according to the present invention, it is possible to provide a colored cured film having excellent color characteristics, and a color filter having the colored cured film. Further, according to the present invention, it is possible to provide a pattern forming method by which a colored pattern having excellent color characteristics can be formed, and a method for producing a color filter. Further, according to the present invention, it is possible to provide a solid-state image sensor and an image display device (a liquid crystal display device, an organic EL display device, or the like), each of which includes a color filter having excellent color characteristics.
The mechanism of action of the composition has not been clarified, but it is presumed one of the reasons is that the attacking by counter anions during heating is inhibited, and thus, the heat resistance is improved, and further, due to incorporation of a specific counter anion structure, the aggregation of a dye multimer is inhibited, and thus, the curing and the invasion of the developing liquid become uniform.
Hereinafter, the components included in the coloring composition of the present invention will be described in detail.
<(A) Dye Multimer Having Non-Nucleophilic Counter Anion>
The coloring composition of the present invention contains at least one kind of dye multimer having a non-nucleophilic counter anion (hereinafter simply referred to as a “dye multimer (A)” in some cases).
The dye multimer (A) is usually a multimer having a partial structure, which has a dye skeleton of which a maximum absorption wavelength is present in a range of 400 nm to 780 nm, in a molecular structure thereof, and includes the structure of a dimer, a trimer, a polymer, or the like. In the coloring composition of the present invention, the dye multimer (A) functions as, for example, a coloring agent.
Examples of the non-nucleophilic counter anion contained in the dye multimer (A) include known non-nucleophilic anions described in paragraph No. “0075” of JP2007-310315A, the contents of which are incorporated herein. Preferable examples thereof include a sulfonic acid anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, a carboxylic acid anion, a tetraarylborate anion, —CON−CO—, —CON−SO2—, BF4−, PFmRp6− (in which RP represents a fluorinated alkyl group having 1 to 10 carbon atoms, and m represents an integer of 1 to 6), Sb−F6−, B(CN)n(ORB)4-n− (in which RB represents an alkyl group or aryl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 4). The non-nucleophilic counter anion is more preferably selected from a sulfonic acid anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, a carboxylic acid anion, a tetraarylborate anion, —CON−SO2—, BF4−, PF6−, B(CN)3(ORB)−, PF3RP3−, and SbF6−, still more preferably selected from a sulfonic acid anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, a carboxylic acid anion, a tetraarylborate anion, BF4−, PF6−, and SbF6−, even still more preferably selected from a sulfonic acid anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, and a tetraarylborate anion, and particularly preferably selected from a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion, and a tetraarylborate anion. Within these ranges, there is a tendency that the effect of the present invention can be more effectively exhibited.
A non-nucleophilic anion represented by one of the following Formulae (AN-1) to (AN-5) is preferable, and Formulae (AN-1), (AN-2), and (AN-5) are more preferable.




(In Formula (AN-1), X1 and X2 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms, having a fluorine atom, or X1 and X2 may be bonded to each other to final a ring.)
X1 and X2 are preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.




(In Formula (AN-2), X3, X4 and X5 each independently represent a fluorine atom, or an alkyl group having a fluorine atom having 1 to 10 carbon atoms.)
X3, X4 and X5 each independently preferably represent a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.




(In Formula (AN-3), X6 represents an alkyl group having 1 to 10 carbon atoms, having a fluorine atom.)
X6 is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.




(In Formula (AN-4), X7 represents an alkylene group having a fluorine atom having 1 to 10 carbon atoms.)
X7 preferably a perfluoroalkylene group having 1 to 10 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 4 carbon atoms.




(In Formula (AN-5), Ar1, Ar2, Ar3, and Ar4 each independently represent an aryl group.)
The aryl group as Ar1, Ar2, Ar3, and Ar4 may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, and a nitro group, among which a halogen atom and an alkyl group are preferable, a fluorine atom and an alkyl group are more preferable, and a perfluoroalkyl group having 1 to 4 carbon atoms is still more preferable.
Ar1, Ar2, Ar3, and Ar4 are each independently a substituted or unsubstituted benzene ring group, more preferably a phenyl group, a pentafluorophenyl group, or a 3,5-trifluorophenyl group, and still more preferably a pentafluorophenyl group.
Specific examples of the non-nucleophilic counter anion used in the present invention are shown below, but the present invention is not limited thereto.







Hereinafter, dye-derived partial structures in the dye multimer (A), preferable structures of the dye multimer (A), functional groups (substituent group A which will be described later) which may be contained in the dye multimer (A), and preferable physical properties of the dye multimer (A) will be described in detail.
The “dye-derived partial structure” as mentioned herein refers to a structure which is formed when hydrogen atoms are removed from a specific dye (hereinafter also referred to as a “dye compound”) which can form a dye structure which will be described later, and can be linked to a dye multimer linking portion (a polymer chain, a core of dendrimer, and the like).
<Dye-Derived Partial Structure>
The dye-derived partial structure (hereinafter also referred to as a “dye structure”) in the dye multimer (A) is not particularly limited as long as it has a cation in a molecule thereof, and various structures having known dye structures can be applied. Specific examples thereof include dye structures derived from a dye selected from a dipyrromethene dye, a carbonium dye (a diphenylmethane dye, a triarylmethane dye, a xanthene dye, an acridine dye, and the like), a polymethine dye (an oxonol dye, a merocyanine dye, an arylidene dye, a styryl dye, a cyanine dye, a squarylium dye, a croconium dye, and the like), a subphthalocyanine dye, and metal complex dyes of these.
Among these dye structures, from the viewpoint of color characteristics, dye structures derived from a dye selected from a dipyrromethene dye, a carbonium dye, and a polymethine dye are preferable; dye structures derived from a dye selected from a triarylmethane dye, a xanthene dye, a cyanine dye, a squarylium dye, a quinophthalone dye, a phthalocyanine dye, and a subphthalocyanine dye are more preferable; dye structures derived from a dye selected from a dipyrromethene dye, a triarylmethane dye, a xanthene dye, a cyanine dye, and a squarylium dye are still more preferable; and dye structures derived from a dye selected from xanthene dyes are particularly preferable.
Specific dye compounds which can form a dye structure are described in “New Edition of Dye Handbook” (edited by The Society of Synthetic Organic Chemistry, Japan; Maruzen Co., Ltd., 1970), “Color index” (edited by The Society of Dyers and colourists), “Dye Handbook” (Gen Ookawa, et al; Kodansha, Ltd., 1986), and the like.
In the dye multimer (A) according to the present invention, a hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A.
<<Substituent Group A>>
Examples of the substituent which may be contained in the dye multimer include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an amino group (including an alkylamino group and an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoyl amino group, an alkylsulfonylamino or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkylsulfinyl or arylsulfinyl group, an alkylsulfonyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. These will be described in detail below.
Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl); a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl and cyclopentyl, or a polycycloalkyl group, for example, a group having a polycyclic structure such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, a bicyclo[1,2,2]heptan-2-yl group, a bicyclo[2,2,2]octan-3-yl group), and a tricycloalkyl group. Among these, a monocyclic cycloalkyl group and a bicycloalkyl group are preferable, and a monocyclic cycloalkyl group is particularly preferable);
a linear or branched alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, which is preferably an alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, and oleyl); a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl or 2-cyclohexen-1-yl, a polycyclo alkenyl group (for example, a bicycloalkenyl group which is preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, for example, bicyclo[2,2,1]hepto-2-en-1-yl and bicyclo[2,2,2]octo-2-en-4-yl), or a tricycloalkenyl group. Among these, a monocyclic cycloalkenyl group is particularly preferable); an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group, and a trimethylsilylethynyl group);
an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoyl aminophenyl); a heterocyclic group (preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, and monocyclic or ring-fused 5- to 7-membered heterocyclic group, more preferably a heterocyclic group of which ring-constituting atoms are selected from a carbon atom, a nitrogen atom, and a sulfur atom, and which has at least any one of hetero atoms including a nitrogen atom, an oxygen atom, and a sulfur atom, and still more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, and 2-benzothiazolyl); a cyano group; a hydroxyl group; a nitro group; a carboxyl group;
an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, and 2-methoxyethoxy); an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, and 2-tetradecanoylaminophenoxy); a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, and tert-butyldimethylsilyloxy); a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms; a heterocycle portion is preferably the heterocycle portion explained for the heterocyclic group described above; the heterocyclic oxy group is, for example, 1-phenyltetrazol-5-oxy and 2-tetrahydropyranyloxy);
an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, and p-methoxyphenylcarbonyloxy); a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy, and N-n-octylcarbamoyloxy); an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, and n-octylcarbonyloxy); an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, and p-n-hexadecyloxyphenoxycarbonyloxy);
an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a heterocyclic amino group having 0 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, and N-1,3,5-triazin-2-ylamino); an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, and 3,4,5-tri-n-octyloxyphenyl carbonylamino); an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, and morpholinocarbonylamino); an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, and N-methyl-methoxycarbonylamino);
an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and m-n-octyloxyphenoxycarbonylamino); a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N,N-dimethylaminosulfonylamino, and N-n-octylaminosulfonylamino); an alkylsulfonylamino or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino), a mercapto group;
an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, and n-hexadecylthio); an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, and m-methoxyphenylthio); a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, in which a heterocycle portion is preferably the heterocycle portion explained for the heterocyclic group described above, for example, 2-benzothiazolylthio and 1-phenyltetrazol-5-ylthio); a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, and N—(N′-phenylcarbamoyl)sulfamoyl); a sulfo group;
an alkylsulfinyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, and p-methylphenylsulfinyl); an alkylsulfonyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, and p-methylphenylsulfonyl); an acyl group (preferably a formyl group, a substituted or unsubstituted alkyl carbonyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, and p-n-octyloxyphenylcarbonyl); an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, and p-tert-butylphenoxycarbonyl);
an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, and n-octadecyloxycarbonyl); a carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl, and N-(methylsulfonyl)carbamoyl); an arylazo or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (in which a heterocycle portion is preferably the heterocycle portion explained for the heterocyclic group described above), for example, phenylazo, p-chlorophenylazo, and 5-ethylthio-1,3,4-thiadiazol-2-ylazo); an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, for example, N-succinimide and N-phthalimide); a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, and methyl phenoxyphosphino); a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl);
a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy); a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino and dimethylaminophosphinylamino); and a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, tert-butyldimethylsilyl, and phenyldimethylsilyl).
Among the above functional groups, in the functional groups having hydrogen atoms, the portion of hydrogen atoms in the functional groups may be substituted with any one of the above groups. Examples of the functional groups which can be introduced as substituents include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group, and specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.
Particularly preferable dyes (dye compounds) which can form the dye-derived partial structure in the dye multimer (A) will be described in detail.
<<Dipyrromethene Dye>>
One of the embodiments of the dye multimer (A) in the present invention is a dye multimer which has a partial structure derived from the dipyrromethene dye shown below as a partial structure of the dye moiety.
As the dipyrromethene dye in the present invention, a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyromethene compound with a metal or a metal compound are preferable.
Incidentally, in the present invention, a compound having a dipyrromethene structure is referred to as a dipyrromethene compound, and a complex in which a metal or a metal compound is coordinated to the compound having a dipyrromethene structure is referred to as a dipyrromethene metal complex compound.
As the dipyrromethene metal complex compound, a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following General Formula (M) with a metal or a metal compound and a tautomer thereof are preferable. Among these, a dipyrromethene metal complex compound represented by the following General Formula (7) and a dipyrromethene metal complex compound represented by the following General Formula (8) are exemplified as preferred embodiments, and the dipyrromethene metal complex compound represented by the following General Formula (8) is more preferable.
<<Dipyrromethene Metal Complex Compound Obtained from Dipyrromethene Compound Represented by General Formula (M) with Metal or a Metal Compound, and Tautomer Thereof>>
One of the preferred embodiments of the dye structure in the dye multimer (A) is a dye structure which contains, as a dye moiety, a complex (hereinafter appropriately referred to as a “specific complex”) in which a compound (dipyrromethene compound) represented by the following General Formula (M) or a tautomer thereof is coordinated to a metal or a metal compound. In the present invention, the following compound forms an anion structure, but for example, a hydrogen atom bonding to a nitrogen atom of General Formula (M) can from an anion.




(In General Formula (M), R4 to R10 each independently represent a hydrogen atom or a monovalent substituent, provided that R4 and R9 are bonded to each other to form a ring.)
When the compound represented by General Formula (M) is introduced into the structural unit represented by General Formulae (A) to (C), which will be described later, or into the multimer represented by General Formula (D), the introduction site is not particularly limited. However, in view of synthesis suitability, the compound is preferably introduced at any one site of R4 to R9, more preferably introduced at any one site of R4, R6, R7, and R9, and still more preferably introduced at any one site of R4 and R9.
In the case where R4 to R9 in General Formula (M) represent a monovalent substituent, examples of the monovalent substituent include the substituents exemplified in the section of the substituent group A.
In the case where the monovalent substituent represented by R4 to R9 in General Formula (M) is a group which can be further substituted, the group may further have the substituents described for R4 to R9, and in the case where the group has two or more substituents, these substituents may be the same as or different from each other.
In General Formula (M), R4 and R5, R5 and R6, R7 and R8, and R8 and R9 may be each independently bonded to each other to form a 5-, 6-, or 7-membered saturated or unsaturated ring, provided that there is no case where R4 and R9 are bonded to each other to form a ring. In the case where the formed 5-, 6-, or 7-membered ring is a group which can be further substituted, the ring may be substituted with the substituents described for R4 to R9, and in the case where the ring is substituted with two or more substituents, these substituents may be the same as or different from each other.
In General Formula (M), in the case where R4 and R5, R5 and R6, R7 and R8, and R8 and R9 are independently bonded to each other to form a 5-, 6-, or 7-membered saturated or unsaturated ring not having a substituent, examples of the 5-, 6-, or 7-membered saturated or unsaturated ring not having a substituent include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring, and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
R10 in General Formula (M) preferably represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. The halogen atom, the alkyl group, the aryl group, and the heterocyclic group have the same definitions as those of the halogen atom, the alkyl group, the aryl group, and the heterocyclic group, respectively, described in the section of the substituent group A, and a preferred range thereof is also the same.
In the case where R10 represents an alkyl group, an aryl group, or a heterocyclic group, if the alkyl group, the aryl group, and the heterocyclic group are groups which can be further substituted, they may be substituted with the substituents described in the section of the substituent group A. If the groups are substituted with two or more substituents, the substituents may be the same as or different from each other.
 ̃Metal or Metal Compound ̃
The specific complex in the present invention is a complex in which the dipyrromethene compound represented by General Formula (M) or a tautomer thereof is coordinated to a metal or a metal compound.
Herein, the metal or metal compound may be any types of metal or metal compound as long as they can form a complex, and examples thereof include a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, and a divalent metal chloride. Examples of the metal or metal compound include metals such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe, metal chlorides such as AlCl, InCl, FeCl, TiCl2, SnCl2, SiCl2, and GeCl2, metal oxides such as TiO and VO, and metal hydroxides such as Si(OH)2.
Among these, in view of the stability, spectral characteristics, heat resistance, light fastness, and production suitability of the complex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO is preferable, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is more preferable, and Zn is particularly preferable.
Next, a more preferred range of the specific complex of the compound represented by General Formula (M) in the present invention will be described.
A preferred range of the specific complex in the present invention is a range in which in General Formula (M), R4 and R9 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an anilino group, a heterocyclic amino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R5 and R8 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R6 and R7 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an anilino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group; R10 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; and the metal or metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or V═O.
A more preferable range of the specific complex in the present invention is a range in which in General Formula (M), R4 and R9 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, a heterocyclic amino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R5 and R8 are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imide group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R6 and R7 are each is independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R10 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; and the metal or metal compound is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or V═O.
A particularly preferred range of the specific complex in the present invention is a range in which in General Formula (M), R4 and R9 are each a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R5 and R8 are each independently an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group; R6 and R7 are each independently a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; R10 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; and the metal or metal compound is Zn, Cu, Co, or V═O.
Moreover, a dipyrromethene metal complex compound represented by General Formula (7) or (8), which will be described later in detail, is also a particularly preferred embodiment of the dipyrromethene dye.
<<<Dipyrromethene Metal Complex Compound Represented by General Formula (7)>>>
One of the suitable embodiments of the dye structure in the dye multimer (A) is a dye structure derived from a dipyrromethene metal complex compound represented by the following General Formula (7).




(In General Formula (7), R4 to R9 each independently represent a hydrogen atom or a monovalent substituent, and R10 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X1 represents a group which can be bonded to Ma, X2 represents a group which neutralizes the charge of Ma, and X1 and X2 may be bonded to each other to form a 5-, 6-, or 7-membered ring together with Ma. Herein, there is no case where R4 and R9 are bonded to each other to form a ring.)
Incidentally, the dipyrromethene metal complex compound represented by General Formula (7) includes a tautomer.
In the case where the dipyrromethene metal complex compound represented by General Formula (7) is introduced into the structural unit represented by General Formulae (A) to (C), which will be described later, or into the multimer represented by General Formula (D), the introduction site is not particularly limited. However, in view of synthesis suitability, the compound is preferably introduced at any one site of R4 to R9, more preferably introduced at any one site of R4, R6, R7, and R9, and still more preferably introduced at any one site of R4 and R9.
In the case where the dye multimer (A) has an alkali-soluble group, as a method for introducing the alkali-soluble group, a method of bonding the alkali-soluble group to one, two, or more substituents out of R4 to R10, X1 and X2 in General Formula (7) can be used. Among these substituents, any one of R4 to R9 and X1 is preferable, any one of R4, R6, R7, and R9 is more preferable, and any one of R4 and R9 is still more preferable.
The dipyrromethene metal complex compound represented by General Formula (7) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not diminished.
R4 to R9 in General Formula (7) have the same definition as R4 to R9 in General Formula (M), and preferred embodiments thereof are also the same.
In General Formula (7), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any type as long as it is a metal atom or a metal compound which can form a complex, and examples thereof include a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride.
Examples of the metal atom or metal compound include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe; metal chlorides such as AlCl, InCl, FeCl, TiCl2, SnCl2, SiCl2, and GeCl2; metal oxides such as TiO and V═O, and metal hydroxides such as Si(OH)2.
Among these, in view of stability, spectral characteristics, heat resistance, light fastness, and production suitability of the complex, as the metal atom or metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, and V═O are preferable, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, and V═O are more preferable, Zn, Co, V═O, and Cu are still more preferable, and Zn is particularly preferable.
In General Formula (7), R10 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and is preferably a hydrogen atom.
In General Formula (7), X1 may be any group as long as the group can be bonded to Ma, and specific examples thereof include water, alcohols (for example, methanol, ethanol, and propanol), and compounds disclosed in “Metal Chelates” ([1] Takeichi Sakaguchi and Kagehira Ueno (1995, Nankodo Co., Ltd.), [2] (1996), [3] (1997), and the like). Among these, in view of production thereof, water, a carboxylic acid compound, and alcohols are preferable, and water and a carboxylic acid compound are more preferable.
In General Formula (7), examples of the “group which neutralizes the charge of Ma” represented by X2 include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and the like. Among these, in view of production thereof, a halogen atom, a hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and a hydroxyl group and a carboxylic acid group are more preferable.
In General Formula (7), X1 and X2 may be bonded to each other to form a 5-, 6-, or 7-membered ring together with Ma. The formed 5-, 6-, or 7-membered ring may be a saturated or unsaturated ring. In addition, the 5-, 6-, or 7-membered ring may be constituted only with carbon atoms or may form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, or/and a sulfur atom.
In a preferred embodiment of the compound represented by General Formula (7), R4 to R9 each independently represent the group described as the preferred embodiment of R4 to R9; R10 represents the group described as the preferred embodiment of R10, Ma is Zn, Cu, Co, or V═O; X1 is water or a carboxylic acid compound; X2 is a hydroxyl group or a carboxylic acid group; and X1 and X2 may be each independently bonded to each other to form a 5- or 6-membered ring.
<<<Dipyrromethene Metal Complex Compound Represented by General Formula (8)>>>
One of the preferred embodiments of the dye structure in the dye multimer (A) is a dye structure derived from a dipyrromethene metal complex compound represented by the following General Formula (8).




(In General Formula (8), R11 and R16 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R12 to R15 each independently represent a hydrogen atom or a substituent. R17 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X2 and X3 each independently represent NR (in which R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom or a sulfur atom. Y1 and Y2 each independently represent NRc (in which Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom or a carbon atom. R11 and Y1 may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R16 and Y2 may be bonded to each other to form a 5-, 6-, or 7-membered ring. X1 represents a group which can be bonded to Ma, and a represents 0, 1, or 2.
Incidentally, the dipyrromethene metal complex compound represented by General Formula (8) includes a tautomer.
The site at which the dipyrromethene metal complex compound represented by General Formula (8) is introduced into the structural unit represented by General Formulae (A) to (C), which will be described later, or into the multimer represented by General Formula (D) is not particularly limited as long as the effects of the present invention are not diminished. However, the site is preferably at least one of R11 to R17, X1, Y1, Y2. Among these, in view of synthesis suitability, it is preferable that the compound is introduced at one of R11 to R16 and X1. In a more preferred embodiment, the compound is introduced at one of R11, R13, R14 and R16. In a still more preferred embodiment, the compound is introduced at one of R11 and R16.
In the case where the dye multimer (A) has an alkali-soluble group, if a dye monomer or a structural unit having the alkali-soluble group is used, as a method for introducing the alkali-soluble group, it is possible to use a method for introducing the alkali-soluble group into one, two, or more substituents out of R11 to R17, X1, Y1 to Y2 in General Formula (8). Among these substituents, one of R11 to R16 and X1 is preferable, one of R11, R13, R14 and R16 is more preferable, and one of R11 and R16 is still more preferable.
The dipyrromethene metal complex compound represented by General Formula (8) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not diminished.
In General Formula (8), R12 to R15 have the same definition as R5 to R8 in General Formula (M), and preferred embodiments thereof are also the same. R17 has the same definition as R10 in General Formula (M), and preferred embodiments thereof are also the same. Ma has the same definition as Ma in General Formula (7), and preferred ranges thereof are also the same.
More specifically, among R12 to R15 in General Formula (8), as R12 and R15, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are preferable, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are more preferable, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are still more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
As R13 and R14, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group are preferable, and a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group are more preferable. Specific examples of the more preferable alkyl group, an aryl group, and heterocyclic group include the same specific examples as listed for R6 and R7 of General Formula (M).
In General Formula (8), R11 and R16 represents an alkyl group (a linear, branched, or cyclic alkyl group preferably having 1 to 36 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a 1-adamantyl group), an alkenyl group (an alkenyl group preferably having 2 to 24 carbon atoms, and more preferably having 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, and a 3-buten-1-yl group), an aryl group (an aryl group preferably having 6 to 36 carbon atoms, and more preferably having 6 to 18 carbon atoms, for example, a phenyl group and a naphthyl group), a heterocyclic group (a heterocyclic group preferably having 1 to 24 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 2-pyridyl group, a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, and a benzotriazol-1-yl group), an alkoxy group (an alkoxy group preferably having 1 to 36 carbon atoms, and more preferably having 1 to 18 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, a dodecyloxy group, and a cyclohexyloxy group), an aryloxy group (an aryloxy group preferably having 6 to 24 carbon atoms, and more preferably having 1 to 18 carbon atoms, for example, a phenoxy group and a naphthyloxy group), an alkylamino group (an alkylamino group preferably having 1 to 36 carbon atoms, and more preferably having 1 to 18 carbon atoms, for example, a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a hexylamino group, a 2-ethylhexylamino group, an isopropylamino group, a tert-butylamino group, a tert-octylamino group, a cyclohexylamino group, an N,N-diethylamino group, an N,N-dipropylamino group, an N,N-dibutylamino group, and an N-methyl-N-ethylamino group), an arylamino group (an arylamino group preferably having 6 to 36 carbon atoms, and more preferably having 6 to 18 carbon atoms, for example, a phenylamino group, a naphthylamino group, an N,N-diphenylamino group, and an N-ethyl-N-phenylamino group), and a heterocyclic amino group (a heterocyclic amino group preferably having 1 to 24 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a 2-aminopyrrole group, 3-aminopyrazole, a 2-aminopyridine group, and a 3-aminopyridine group).
Among the above groups, as R11 and R16, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group, and a heterocyclic amino group are preferable, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group are more preferable, an alkyl group, an alkenyl group, and an aryl group are still more preferable, and an alkyl group is particularly preferable.
In General Formula (8), in the case where the alkyl group, the alkenyl group, the aryl group, the heterocyclic group, the alkoxy group, the aryloxy group, the alkylamino group, the arylamino group, or the heterocyclic amino group represented by R11 and R16 is a group which can be further substituted, the group may be substituted with the substituents described in the section of the substituent group A. In the case where the group is substituted with two or more substituents, these substituents may be the same as or different from each other.
In General Formula (8), X2 and X3 each independently represent NR, a nitrogen atom, an oxygen atom, or a sulfur atom. Herein, R represents a hydrogen atom, an alkyl group (a linear, branched, or cyclic alkyl group preferably having 1 to 36 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a 1-adamantyl group), an alkenyl group (an alkenyl group preferably having 2 to 24 carbon atoms, and more preferably having 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, and a 3-buten-1-yl group), an aryl group (an aryl group preferably having 6 to 36 carbon atoms, and more preferably having 6 to 18 carbon atoms, for example, a phenyl group and a naphthyl group), a heterocyclic group (a heterocyclic group preferably having 1 to 24 carbon atoms, and more preferably having 1 to 12 carbon atoms, for example, a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, and a benzotriazol-1-yl group), an acyl group (an acyl group preferably having 1 to 24 carbon atoms, and more preferably having 2 to 18 carbon atoms, for example, an acetyl group, a pivaloyl group, a 2-ethylhexyl group, a benzoyl group, and a cyclohexanoyl group), an alkylsulfonyl group (an alkylsulfonyl group preferably having 1 to 24 carbon atoms, and more preferably having 1 to 18 carbon atoms, for example, a methylsulfonyl group, an ethylsulfonyl group, an isopropylsulfonyl group, and a cyclohexylsulfonyl group), and an arylsulfonyl group (an arylsulfonyl group preferably having 6 to 24 carbon atoms, and more preferably having 6 to 18 carbon atoms, for example, a phenylsulfonyl group and a naphthylsulfonyl group).
In General Formula (8), Y1 and Y2 each independently represent NRc, a nitrogen atom, or a carbon atom. Rc has the same definition as R of X2 and X3, and the preferred embodiments thereof are also the same.
In General Formula (8), R11 and Y1 may be each independently bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a piperidine ring, a piperazine ring, a morpholine ring, a tetrahydropyran ring, a dioxane ring, a pentamethylene sulfide ring, a dithiane ring, a benzene ring, a pyridazine ring, a quinoline ring, and a quinazoline ring), or a 7-membered ring (for example, a cycloheptane ring and a hexamethylene imine ring) together with a carbon atom.
In General Formula (8), R16 and Y2 may be each independently bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a piperidine ring, a piperazine ring, a morpholine ring, a tetrahydropyran ring, a dioxane ring, a pentamethylene sulfide ring, a dithiane ring, a benzene ring, a pyridazine ring, a quinoline ring, and a quinazoline ring), or a 7-membered ring (for example, a cycloheptane ring or a hexamethylene imine ring) together with a carbon atom.
In General Formula (8), in the case where the 5-, 6-, and 7-membered rings formed by mutual bonding of R11 and Y1 as well as R16 and Y2 are substitutable rings, the rings may be substituted with the substituents described in the section of the substituent group A. In the case where the rings are substituted with two or more substituents, these substituents may be the same as or different from each other.
In General Formula (8), it is preferable that R11 and R16 are each independently a monovalent substituent of which an −Es' value as a steric parameter is 1.5 or more. The −Es' value is more preferably 2.0 or more, still more preferably 3.5 or more, and particularly preferably 5.0 or more.
Herein, the −Es' value as a steric parameter is a parameter which represents steric bulkiness of a substituent. As the value, the −Es' value disclosed in the document (J. A. Macphee, et al, Tetrahedron, Vol. 34, pp 3553-3562, and Chemistry Special Edition 107, Structure-activity Correlation and Drug Design, edited by Toshio Fujita, published on Feb. 20, 1986 (Kagaku-Doujin Publishing Company, Inc.)) is used.
In General Formula (8), X1 represents a group which can be bonded to Ma. Specific examples thereof include the same group as represented by X1 in General Formula (7), and the preferred embodiments are also the same. a represents 0, 1, or 2.
With respect to a preferred embodiment of the compound represented by General Formula (8), R12 to R15 are each independently in a preferred embodiment cited in the description of R5 to R8 in General Formula (M); R17 is in a preferred embodiment cited in the description of R10 in General Formula (M); Ma represents Zn, Cu, Co, or V═O; X2 represents NR (in which R represents a hydrogen atom or an alkyl group), a nitrogen atom, or an oxygen atom; X3 represents NR (in which R represents a hydrogen atom or an alkyl group) or an oxygen atom; Y1 represents NRc (in which Rc represents a hydrogen atom or an alkyl group), a nitrogen atom, or a carbon atom; Y2 represents a nitrogen atom or a carbon atom; R11 and R16 are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group; X1 represents a group bonded via an oxygen atom; and a represents 0 or 1. R11 and Y1 may be bonded to each other to form a 5- or 6-membered ring; or R16 and Y2 may be bonded to each other to form a 5- or 6-membered ring.
With respect to a more preferred embodiment of the compound represented by General Formula (8), R12 to R15 are each independently in a preferred embodiment cited in the description of R5 to R8 in the compound represented by General Formula (M); R17 is in a preferred embodiment cited in the description of R10 in General Formula (M); Ma is Zn; X2 and X3 are oxygen atoms; Y1 is NH; Y2 is a nitrogen atom; R11 and R16 are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group; X1 is a group bonded via an oxygen atom; and a is 0 or 1. R11 and Y1 may be bonded to each other to form a 5- or 6-membered ring; or R16 and Y2 may be bonded to each other to form a 5- or 6-membered ring.
From the viewpoint of coloring ability, the molar absorption coefficient of the dipyrromethene metal complex compound represented by General Formulae (7) and (8) is preferably as high as possible. Further, from the viewpoint of improving color purity, the maximum absorption wavelength λmax is preferably from 520 nm to 580 nm, and more preferably from 530 nm to 570 nm. If the value is within this range, it is possible to manufacture a color filter having excellent color reproducibility by using the coloring composition of the present invention.
Furthermore, an absorbance at the maximum absorption wavelength (λmax) of the dye multimer (A) having a dye structure derived from a dipyrromethene dye is preferably 1,000 times or more, more preferably 10,000 times or more, and still more preferably 100,000 times or more than the absorbance at 450 nm. If the ratio is within this range, particularly when a blue color filter is manufactured using the coloring composition of the present invention, a color filter having a higher transmissivity can be formed. Incidentally, the maximum absorption wavelength and the molar absorption coefficient are measured by a spectrophotometer Cary 5 (manufactured by Varian Medical Systems, Inc.).
From the viewpoint of solubility, it is preferable that the melting points of the dipyrromethene metal complex compounds represented by General Formulae (7) and (8) are not too high.
The dipyrromethene metal complex compound represented by General Formulae (7) and (8) can be synthesized by the method described in U.S. Pat. No. 4,774,339A, U.S. Pat. No. 5,433,896A, JP2001-240761A, JP2002-155052A, JP3614586B, Aust. J. Chem., 1965, 11, 1835-1845, J. H. Boger, et al., Heteroatom Chemistry, Vol. 1, No. 5,389 (1990), and the like. Specifically, the method described in paragraphs “0131” to “0157” of JP2008-292970A can be applied.
Specific examples of the dipyrromethene dye are shown below, but the present invention is not limited thereto.







Among the above specific examples, (PM-8) and (PM-10) are particularly preferable from the viewpoints of color characteristics and heat resistance.
<<Carbonium Dye>>
Among the carbonium dyes, a triarylmethane dye and a xanthene dye are preferable.
<<<Triarylmethane Dye>>>
One of the embodiments of the dye multimer according to the present invention is a dye multimer having a partial structure derived from a triarylmethane dye (triarylmethane compound). The dye multimer (A) includes a dye multimer which has, as a partial structure of a dye moiety, a partial structure derived from a compound (triarylmethane compound) represented by the following General Formula (TP). The triarylmethane compounds in the present invention collectively refer to compounds having a dye moiety containing a triarylmethane skeleton in a molecule thereof.




(In General Formula (TP), Rtp1 to Rtp4 each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rtp5 represents a hydrogen atom, an alkyl group, an aryl group, or NRtp9Rtp10 (in which Rtp9 and Rtp10 represent a hydrogen atom, an alkyl group, or an aryl group). Rtp6, Rtp7, and Rtp8 represent substituents. a, b, and c represent an integer of 0 to 4. In the case where a, b, and c are 2 or more, Rtp6, Rtp7, and Rtp8 may be linked to each other to form a ring. X− represents a non-nucleophilic anion.)
Rtp1 to Rtp6 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. Rtp5 is preferably a hydrogen atom or NRtp9Rtp10, and particularly preferably NRtp9Rtp10. Rtp9 and Rtp10 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. As the substituents represented by Rtp6, Rtp7, and Rtp8, the substituents exemplified in the section of the substituent group A can be used. In particular, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group, or a sulfo group is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a phenyl group, or a carboxyl group is more preferable. In particular, Rtp6 and Rtp8 are preferably an alkyl group having 1 to 5 carbon atoms, and Rtp7 is preferably an alkenyl group (particularly preferably a phenyl group formed by linking two adjacent alkenyl groups to each other), a phenyl group, or a carboxyl group.
a, b, and c each independently represents an integer of 0 to 4. In particular, a and b are preferably 0 to 1, and c is preferably 0 to 2.
Specific examples of the compounds represented by General Formula (TP) are shown below, but the present invention is not limited thereto.













Among the above specific examples, from the viewpoints of color characteristics and heat resistance, (tp-4), (tp-5), (tp-6), and (tp-8) are particularly preferable.
<<<Xanthene Dye>>>
A preferred embodiment of the dye multimer in the present invention is a dye multimer having a partial structure derived from a xanthene dye (xanthene compound). Examples of such a dye multimer (A) include a dye multimer which has, as a partial structure of a dye moiety, a partial structure derived from a xanthene compound represented by the following General Formula (J).




(In General Formula (J), R81, R82, R83, and R84 each independently represent a hydrogen atom or a monovalent substituent. R85's each independently represent a monovalent substituent, and m represents an integer of 0 to 5. X− represents a non-nucleophilic counter anion.)
The substituents which may be contained in R81 to R84 and R85 in General Formula (J) have the same definitions as the substituents exemplified in the section of the substituent group A.
In General Formula (J), R81 and R82, R83 and R84, and R85's in a case where m is 2 or more may be each independently bonded to each other to form a 5-, 6-, or 7-membered saturated ring or a 5-, 6-, or 7-membered unsaturated ring. In the case where the formed 5-, 6-, or 7-membered ring is a group which can be further substituted, the ring may be substituted with the substituents described for R81 to R85. In the case where the ring is substituted with two or more substituents, these substituents may be the same as or different from each other.
In General Formula (J), in the case where R81 and R82, R83 and R84, and R85's in a case where m is 2 or more are bonded to each other to form 5-, 6-, and 7-membered saturated rings not having a substituent or form 5-, 6-, and 7-membered unsaturated rings, examples of the 5-, 6-, and 7-membered saturated rings not having a substituent or the 5-, 6-, and 7-membered unsaturated rings include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring, and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
R82 and R83 are particularly preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R81 and R84 are particularly preferably a substituted or unsubstituted alkyl group or phenyl group. Further, R85 is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group, or an amide group, and more preferably a sulfo group, a sulfonamide group, a carboxyl group, or an amide group. R85 is preferably bonded to an adjacent portion of carbon linked to a xanthene ring. The substituent contained in the phenyl group represented by R81 and R84 is particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.
The compounds having xanthene skeletons represented by General Formula (J) may be synthesized using methods disclosed in the literature. Specifically, the methods disclosed in Tetrahedron Letters, 2003, vol. 44, No. 23, pp. 4355 to 4360; Tetrahedron Letters, 2005, vol. 61, No. 12, pp. 3097 to 3106; and the like can be applied.
Specific examples of the xanthene compounds are shown below, but the present invention is not limited thereto.







TABLE 1













 











No.
R1
R2
R3
R4





 (XT-1)
—Me
—Me
—Me
—Me


 (XT-2)
—Et
—Et
—Et
—Et


 (XT-3)
-n-Pr
-n-Pr
-n-Pr
-n-Pr


 (XT-4)
-i-Pr
-i-Pr
-i-Pr
-i-Pr


 (XT-5)
-n-Bu
-n-Bu
-n-Bu
-n-Bu


 (XT-6)
-sec-Bu
-sec-Bu
-sec-Bu
-sec-Bu


 (XT-7)
-i-Bu
-i-Bu
-i-Bu
-i-Bu


 (XT-8)
-tert-Bu
-tert-Bu
-tert-Bu
-tert-Bu


 (XT-9)
-n-C6H13
-n-C6H13
-n-C6H13
-n-C6H13


(XT-10)
-n-C18H37
-n-C18H37
-n-C18H37
-n-C18H37


(XT-11)
—Me
—Et
—Me
—Et









(XT-12)
—CH2CH2OCH2CH2—
—CH2CH2OCH2CH2—


(XT-13)
—(CH2)5—
—(CH2)5—


(XT-14)
—(CH2)4—
—(CH2)4—


(XT-15)
—(CH2)5—
—(CH2)4—











(XT-16)
—CH2Ph
—CH2Ph
—CH2Ph
—CH2Ph


(XT-17)
—Et
—CH2CH2OMe
—Et
—CH2CH2OMe


(XT-18)
—Me
-cyclo-C6H11
—Me
-cyclo-C6H11


(XT-19)
—CH2C≡CH
—CH2C≡CH
—CH2C≡CH
—CH2C≡CH


(XT-20)
—CH2CH═CH2
—CH2CH═CH2
—CH2CH═CH2
—CH2CH═CH2


(XT-21)
—Me
—H
—Me
—H


(XT-22)
—Et
—H
—Et
—H


(XT-23)
-n-Pr
—H
-n-Pr
—H


(XT-24)
-i-Pr
—H
-i-Pr
—H


(XT-25)
-n-Bu
—H
-n-Bu
—H


(XT-26)
—H
—H
—H
—H


(XT-27)
-i-Bu
—H
-i-Bu
—H


(XT-28)
-tert-Bu
—H
-tert-Bu
—H


(XT-29)
-n-C6H13
—H
-n-C6H13
H


(XT-30)
-n-C18H37
—H
-n-C18H37
—H


(XT-31)
—Ph
—H
—Ph
—H


(XT-32)
—CH2Ph
—H
—CH2Ph
—H


(XT-33)
-cyclo-C6H11
—H
-cyclo-C6H11
—H


(XT-34)
-cyclo-C5H9
—H
-cyclo-C5H9
—H


(XT-35)
—CH2C≡CH
—H
—CH2C≡CH
—H


(XT-36)
—CH2CH═CH2
—H
—CH2CH═CH2
—H


 


(XT-37)




—H




—H


 


(XT-38)




—H




—H
















TABLE 2













 











No.
R1
R2
R3
R4





(XT-39)
—Me
—Me
—Me
—Me


(XT-40)
—Et
—Et
—Et
—Et


(XT-41)
-n-Pr
-n-Pr
-n-Pr
-n-Pr


(XT-42)
-i-Pr
-i-Pr
-i-Pr
-i-Pr


(XT-43)
-n-Bu
-n-Bu
-n-Bu
-n-Bu


(XT-44)
-sec-Bu
-sec-Bu
-sec-Bu
-sec-Bu


(XT-45)
-i-Bu
-i-Bu
-i-Bu
-i-Bu


(XT-46)
-tert-Bu
-tert-Bu
-tert-Bu
-tert-Bu


(XT-47)
-n-C6H13
-n-C6H13
-n-C6H13
-n-C6H13


(XT-48)
-n-C18H37
-n-C18H37
-n-C18H37
-n-C18H37


(XT-49)
—Me
—Et
—Me
—Et









(XT-50)
—CH2CH2OCH2CH2—
—CH2CH2OCH2CH2—


(XT-51)
—(CH2)5—
—(CH2)5—


(XT-52)
—(CH2)4—
—(CH2)4—


(XT-53)
—(CH2)5—
—(CH2)4—











(XT-54)
—CH2Ph
—CH2Ph
—CH2Ph
—CH2Ph


(XT-55)
—Et
—CH2CH2OME
—Et
—CH2CH2OMe


(XT-56)
—Me
-cyclo-C6H11
—Me
-cyclo-C6H11


(XT-57)
—CH2C≡CH
—CH2C≡CH
—CH2C≡CH
—CH2C≡CH


(XT-58)
—CH2CH═CH2
—CH2CH═CH2
—CH2CH═CH2
—CH2CH═CH2


(XT-59)
—Me
—H
—Me
—H


(XT-60)
—Et
—H
—Et
—H


(XT-61)
-n-Pr
—H
-n-Pr
—H


(XT-62)
-i-Pr
—H
-i-Pr
—H


(XT-63)
—H
—H
—H
—H


(XT-64)
-sec-Bu
—H
-sec-Bu
—H


(XT-65)
-i-Bu
—H
-i-Bu
—H


(XT-66)
-tert-Bu
—H
-tert-Bu
—H


(XT-67)
-n-C6H13
—H
-n-C6H13
—H


(XT-68)
-n-C18H37
—H
-n-C18H37
—H


(XT-69)
—Ph
—H
—Ph
—H


(XT-70)
—CH2Ph
—H
—CH2Ph
—H


(XT-71)
-cyclo-C6H11
—H
-cyclo-C6H11
—H


(XT-72)
-cyclo-C5H9
—H
-cyclo-C5H9
—H


(XT-73)
—CH2C≡CH
—H
—CH2C≡CH
—H


(XT-74)
—CH2CH═CH2
—H
—CH2CH═CH2
—H


 


(XT-75)




—H




—H


 


(XT-76)




—H




—H


 








(XT-77)






 


(XT-78)






 


(XT-79)






 


(XT-80)






 


(XT-81)













<<Cyanine Dye>>
One of the embodiments of the dye multimer according to the present invention is a dye multimer having a partial structure derived from a cyanine dye (cyanine compound). Such a dye multimer (A) includes a dye multimer which has, as a partial structure of a dye moiety, a partial structure derived from a compound (cyanine compound) represented by the following General Formula (PM). The cyanine compounds in the present invention collectively refer to compounds having a dye moiety containing a cyanine skeleton in a molecule thereof.




(In General Formula (PM), a ring Z1 and a ring Z2 each independently represent a heterocycle which may have a substituent. 1 represents an integer of 0 to 3, and X− represents an anion.)
Examples of the ring Z1 and the ring Z2 each independently include oxazole, benzoxazole, oxazoline, thiazole, thiazoline, benzothiazole, indolenine, benzoindolenine, and 1,3-thiadiazine.
The substituents which may be contained in the ring Z1 and the ring Z2 are the same substituents exemplified in the section of the substituent group A. X− represents a non-nucleophilic counter anion.
The compound represented by General Formula (PM) is preferably a compound represented by the following General Formula (PM-2).




(In General Formula (PM-2), the ring Z5 and the ring Z6 each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent;
Y− represents Cl−, Br−, I−, ClO4−, OH−, a monovalent organic carboxylic acid anion, a monovalent organic sulfonic acid anion, a monovalent boron anion, or a monovalent organic metal complex anion. Y− may be linked to the dye skeleton, or may be linked to a portion (a polymer chain or the like) of the dye multimer;
n represents an integer of 0 to 3;
A1 and A2 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a carbon atom, or a nitrogen atom;
R1 and R2 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent;
R3 and R4 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or represent a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, which is formed when one R3 and one R4 are combined with each other; and
a and b each independently represent an integer of 0 to 2.)
In General Formula (PM-2), Y− represents a non-nucleophilic counter anion.
Specific examples of the cyanine compounds are shown below, but the present invention is not limited thereto.










Among the specific examples, structures represented by (pm-1) to (pm-6), (pm-9), and (pm-10) are preferable, and among these, dye structures represented by (pm-1), (pm-2), and (pm-10) are particularly preferable from the viewpoint of color characteristics and heat resistance.
<<Subphthalocyanine Dye>>
One of the embodiments of the dye multimer according to the present invention is a dye multimer having a partial structure derived from a subphthalocyanine dye. Such a dye multimer (A) includes a dye multimer which has, as a partial structure of a dye moiety, a partial structure derived from a subphthalocyanine dye represented by the following General Formula (SP). The subphthalocyanine dyes in the present invention collectively refer to compounds having a dye moiety including a subphthalocyanine skeleton in a molecule thereof. In the present invention, the subphthalocyanine dye usually forms an anion in the portion of B.




(In General Formula (SP), Z1 to Z12 each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, or a thioether group. X represents a non-nucleophilic counter anion.)
General Formula (SP) will be described in detail.
The alkyl group which may be contained in Z1 to Z12 in General Formula (SP) represents a linear or branched substituted or unsubstituted alkyl group. In particular, Z1 to Z12 preferably have 1 to 20 carbon atoms, and more preferably have 1 to 10 carbon atoms. Examples of the substituents which may be contained in Z1 to Z12 include the substituents exemplified in the section of the substituent group A, and among those, a fluorine atom, a hydroxyl group, and a mercapto group are particularly preferable.
Specific examples of the subphthalocyanine dye are shown below, but the present invention is not limited thereto.










Among the above specific examples, (SP-2), (SP-3), (SP-4), (SP-5), (SP-6), and (SP-7) are particularly preferable from the viewpoint of color characteristics and heat resistance.
<Structure of Dye Multimer Used in Coloring Composition of the Present Invention>
The dye multimer (A) used in the coloring composition of the present invention is not particularly defined, but it is preferably a dye multimer which contains at least one of the structural units represented by the following General Formulae (A), (B), and (C), or a dye multimer represented by General Formula (D). The structural units represented by General Formulae (A), (B), and (C) may be one kind or two or more kinds thereof. Further, they may be a combination thereof.
Further, the dye multimer (A) may include other structural units as described later.
In the present invention, it is preferable that the dye multimer represented by General Formula (A) is included.
These will be described in order.
<<Structural Unit Represented by General Formula (A)>>




(In General Formula (A), X1 represents a linking group formed by polymerization, and L1 represents a single bond or a divalent linking group. DyeI represents a dye structure.)
Hereinafter, General Formula (A) will be described in detail.
In General Formula (A), X1 represents a linking group formed by polymerization. That is, X1 represents a portion which forms a repeating unit corresponding to a main chain formed by a polymerization reaction. Moreover, the moiety represented by two *'s is a repeating unit. X1 is not particularly limited as long as it is a linking group formed of a known polymerizable monomer. In particular, X1 is preferably a linking group represented by any one of the following (XX-1) to (XX-24), more preferably a (meth)acryl-based linking chain represented by (XX-1) or (XX-2), a styrene-based linking chain represented by any one of (XX-10) to (XX-17), and a vinyl-based linking chain represented by (XX-24), and still more preferably a (meth)acryl-based linking chain represented by (XX-1) and (XX-2), and a styrene-based linking chain represented by (XX-11).
In (XX-1) to (XX-24), * represents a site for linking to L1. Me represents a methyl group. Further, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.










In General Formula (A), L1 represents a single bond or a divalent linking group. In the case where L1 represents a divalent linking group, the divalent linking group represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butylene group), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, a phenylene group and a naphthalene group), a substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S—, —C(═O)—, —NR—, —CONR—, —O2C—, —SO—, —SO2—, and a linking group formed of two or more of these linked to each other. L1 is preferably a single bond or an alkylene group, and more preferably a single bond or —(CH2)n— (in which n is an integer of 1 to 5). Herein, R's each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
In General Formula (A), DyeI represents a dye structure derived from the dye compound as described above.
The dye multimer having the structure unit represented by General Formula (A) can be synthesized by (1) a method for synthesizing the multimer by means of addition polymerization using monomers having a dye residue, or (2) a method for synthesizing the multimer by causing a reaction between a polymer having a highly reactive functional group such as an isocyanate group, an acid anhydride group, and an epoxy group, and a dye having a functional group (a hydroxyl group, a primary or secondary amino group, a carboxyl group, or the like) which can react with the highly reactive group.
For the addition polymerization, known addition polymerization (radical polymerization, anionic polymerization, or cationic polymerization) can be applied. Among these, it is particularly preferable that the dye multimer is synthesized by radical polymerization, since the reaction condition can be set to be mild conditions, and the dye structure is not degraded. For the radical polymerization, known reaction conditions can be applied.
Among these, from the viewpoint of heat resistance, the dye multimer having the structural unit represented by General Formula (A) in the present invention is preferably a radical polymer which is obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond.
Specific examples of the structural units represented by General Formula (A) are shown below, but the present invention is not limited thereto.

























<<Structural Unit Represented by General Formula (B)>>
Next, details of a structural unit represented by General Formula (B) will be described.




(In General Formula (B), X2 has the same definition as X2 in General Formula (A). L2 has the same definition as L1 in General Formula (A). Y2 represents a group which can form an ionic bond or a coordinate bond with DyeII. DyeII represents a dye structure.)
Hereinafter, General Formula (B) will be described in detail.
In General Formula (B), X2 has the same definition as X1 in General Formula (A), and a preferred range thereof is also the same. L2 has the same definition as L1 in General Formula (A), and a preferred range thereof is also the same. Y2 may be a group which can form an ionic bond or a coordinate bond with DyeII, and may be either an anionic group or a cationic group. Examples of the anionic group include —COO−, —PO3H−, —SO3−, —SO3NH−, and —SO3N−CO—, and among these, —COO−, —PO3H−, and —SO3− are preferable.
Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium, and phosphonium), and among these, an ammonium cation is particularly preferable.
Y2 can be bonded to an anion portion (—COO−, —SO3−, —O−, or the like) or a cation portion (the onium cation described above, a metal cation, or the like) contained in DyeII.
The dye multimer having the structural unit represented by General Formula (B) in the present invention can be synthesized in the same manner as the dye multimer having the structural unit represented by General Formula (A).
Among these, the dye multimer having the structural unit represented by General Formula (B) is preferably a radical polymer which is obtained by radical polymerization by using a dye monomer having an ethylenically unsaturated bond, from the viewpoint of heat resistance.
Specific examples of the structural units represented by General Formula (B) are shown below, but the present invention is not limited thereto.




<<Structural Unit Represented by General Formula (C)>>




(In General Formula (C), L3 represents a single bond or a divalent linking group. DyeIII represents a partial structure of a dye, and m represents 0 or 1).
Hereinafter, General Formula (C) will be described in detail.
In General Formula (C), preferred examples of the divalent linking group represented by L3 include a substituted or unsubstituted linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butylene group), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, a phenylene group or a naphthalene group), a substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S—, —NR— (in which R's each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C(═O)—, —SO—, —SO2—, and a linking group which is formed of two or more of these groups linked to each other. m represents 0 or 1, and is preferably 1.
Specific examples which are suitably used as the divalent linking group represented by L3 in General Formula (C) are shown below, but L3 of the present invention is not limited thereto.







The dye multimer having the structural unit represented by General Formula (C) is synthesized by sequential polymerization. Examples of the sequential polymerization include polyaddition (for example, a reaction between an diisocyanate compound and a diol, a reaction between a diepoxy compound and a dicarboxylic acid, and a reaction between a tetracarboxylic dianhydride and a diol) and polycondensation (for example, a reaction between a dicarboxylic acid and a diol, and a reaction between a dicarboxylic acid and a diamine). Among these, it is particularly preferable to use the polyaddition reaction to synthesize the dye multimer since the reaction conditions can be set to be mild, and a dye structure is not degraded by the reaction. For the sequential polymerization, known reaction conditions can be applied.
Specific examples of the structural units represented by General Formula (C) are shown below, but the present invention is not limited thereto.




<<Dye Multimer Represented by General Formula (D)>>
Next, details of a dye multimer represented by General Formula (D) will be described.




In General Formula (D), L4 represents a linking group having a valency of n. n represents an integer of 2 to 20. When n is 2 or more, the structures of DyeIV may be the same as or different from each other. DyeIV represents a dye structure.
In General Formula (D), n is preferably 3 to 15, and particularly preferably 3 to 6.
In General Formula (D), in the case where n is 2, preferred examples of the divalent linking groups represented by L4 include a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butylene group), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, a phenylene group and a naphthalene group), a substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S—, —NR— (in which R's each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C(═O)—, —SO—, —SO2—, and a linking group which is formed of two or more of these groups linked to each other.
When n is 3 or more, examples of the linking group having a valency of n include linking groups which have, as a central core, substituted or unsubstituted arylene group (a 1,3,5-phenylene group, a 1,2,4-phenylene group, a 1,4,5,8-naphthalene group, or the like), a heterocyclic linking group (for example, a 1,3,5-triazine group), an alkylene linking group, or the like, and are formed when the divalent linking group is substituted.
Specific examples of L4 in General Formula (D) are shown below, but the present invention is not limited thereto.







Specific examples of DyeIV in General Formula (D) are shown below, but the present invention is not limited thereto.




Among the dye multimer having the structural unit represented by General Formula (A), General Formula (B), and/or General Formula (C) and the dye multimer represented by General Formula (D), in the dye multimer having the structural unit represented by General Formulae (A) and (C) and the dye multimer represented by General Formula (D), the partial structures derived from a dye are linked to each other through a covalent bond in the molecular structure. Accordingly, the coloring composition containing such a dye multimer has excellent heat resistance. Therefore, in the case where the coloring composition is used for a pattern forming process including a high-temperature process, it is preferable since an effect of inhibiting color transfer to another colored pattern adjacent thereto is obtained. Further, the compound represented by General Formula (A) is particularly preferable since the compound makes it easy to control the molecular weight of the dye multimer.
<Polymerizable Group Contained in Dye Multimer (A)>
It is preferable that the dye multimer (A) in the present invention has a polymerizable group.
As the polymerizable group, known polymerizable groups which can be crosslinked by a radical, an acid, or heat can be used, and examples thereof include a group having an ethylenically unsaturated bond, a cyclic ether group (an epoxy group or a oxetane group), and a methylol groups. In particular, a groups having an ethylenically unsaturated bond is preferable, a (meth)acryloyl group is more preferable, and a (meth)acryloyl group derived from glycidyl (meth)acrylate and 3,4-epoxy-cyclohexyl methyl (meth)acrylate is still more preferable.
As the method for introducing the polymerizable group, there are (1) a method for introducing the polymerizable group by modifying the dye multimer with a polymerizable group-containing compound, and (2) a method for introducing the polymerizable group by copolymerizing the dye multimer with a polymerizable group-containing compound. Hereinafter, the methods will be described in detail.
—(1) Method for Introducing Polymerizable Group by Modifying Dye Multimer with Polymerizable Group-Containing Compound—
As the method for introducing the polymerizable group by modifying the dye multimer with a polymerizable group-containing compound, known methods can be used without particular limitation. For example, from the viewpoint of production, a (a) method for performing a reaction between a carboxylic acid which the dye multimer has and an unsaturated bond-containing epoxy compound, a (b) method for performing a reaction between a hydroxyl group or an amino group contained in the dye multimer and an unsaturated bond-containing isocyanate compound, and a (c) method for performing a reaction between an epoxy compound which the dye multimer has and an unsaturated bond-containing carboxylic acid compound are preferable.
Examples of the unsaturated bond-containing epoxy compound in the (a) method for performing a reaction between a carboxylic acid which the dye multimer has and an unsaturated bond-containing epoxy compound include glycidyl methacrylate, glycidyl acrylate, allylglycidyl ether, 3,4-epoxy-cyclohexylmethyl acrylate, and 3,4-epoxy-cyclohexylmethyl methacrylate. In particular, glycidyl methacrylate, and 3,4-epoxy-cyclohexylmethyl methacrylate are preferable since these compounds have excellent crosslinking properties and storage stability. Known conditions can be used as the reaction conditions.
Examples of the unsaturated bond-containing isocyanate compound in the (b) method for performing a reaction between a hydroxyl group or an amino group contained in the dye multimer and an unsaturated bond-containing isocyanate compound include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl methacrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. Among these, 2-isocyanatoethyl methacrylate is preferable since this compound has excellent crosslinking properties and storage stability. Known conditions can be used as the reaction conditions.
As the unsaturated bond-containing carboxylic acid compound in the (c) method for performing a reaction between an epoxy compound contained in the dye multimer and an unsaturated bond-containing carboxylic acid compound, any carboxylic acid compounds can be used without particular limitation as long as the compound has a known (meth)acryloyloxy group. However, a methacrylic acid and an acrylic acid are preferable, and methacrylic acid is particularly preferable since this acid has excellent crosslinking properties and storage stability. Known conditions can be used as the reaction conditions.
<(2) Method for Introducing Polymerizable Group by Copolymerizing Dye Monomer and Polymerizable Group-Containing Compound>
—(2) Method for Introducing Polymerizable Group by Copolymerizing Dye Monomer and Polymerizable Group-Containing Compound—
As a (2) method for introducing a polymerizable group by copolymerizing a dye monomer and a polymerizable group-containing compound, any known methods can be used without particular limitation. However, a (d) method for copolymerizing a radically polymerizable dye monomer with a polymerizable group-containing compound which can be radically polymerized, and a (e) method for copolymerizing a dye monomer which can be subjected to polyaddition with a polymerizable group-containing compound which can be subjected to polyaddition are preferable.
Examples of the polymerizable group-containing compound which can be radically polymerized in the (d) method for copolymerizing a radically polymerizable dye monomer with a polymerizable group-containing compound which can be radically polymerized particularly include an allyl group-containing compound (for example, allyl (meth)acrylate), an epoxy group-containing compound (for example, glycidyl (meth)acrylate and 3,4-epoxy-cyclohexyl methyl (meth)acrylate), an oxetane group-containing compound (for example, 3-methyl-3-oxetanyl methyl (meth)acrylate), and a methylol group-containing compound (for example, N-(hydroxymethyl)acrylamide). Among these, an epoxy group-containing compound and an oxetane group-containing compound are particularly preferable. Known conditions can be used as the reaction conditions.
Examples of the polymerizable group-containing compound which can be subjected to polyaddition in the (e) method of copolymerizing a dye monomer which can be subjected to polyaddition with a polymerizable group-containing compound which can be subjected to polyaddition include an unsaturated bond-containing diol compound (for example, 2,3-dihydroxypropyl (meth)acrylate). Known conditions can be used as the reaction conditions.
As the method for introducing a polymerizable group, a method for performing a reaction between a carboxylic acid contained in the dye multimer and an unsaturated bond-containing epoxy compound is particularly preferable.
The amount of the polymerizable group contained in the dye multimer (A) is preferably 0.1 mmol to 2.0 mmol, more preferably 0.2 mmol to 1.5 mmol, and particularly preferably 0.3 mmol to 1.0 mmol, with respect to 1 g of the dye multimer (A).
Specific examples of the structural units contained in the polymerizable group are shown below, but the present invention is not limited thereto.













Among the above specific examples, a dye monomer having an ethylenically unsaturated bond is preferable from the viewpoint of substrate adhesiveness and surface roughness. Among these, a methacryloyl group, an acryloyl group, a styryl group, and a vinyloxy group are preferable, a methacryloyl group and an acryloyl group are more preferable, and a methacryloyl group is still more preferable.
<Other Functional Groups Contained in Dye Multimer (A)>
The dye multimer (A) in the present invention may have other functional groups. The dye multimer (A) preferably has alkali-soluble groups such as a carboxylic acid, a sulfonic acid, a phosphoric acid, and a phenolic hydroxyl group as other functional groups. As the alkali-soluble group, a carboxylic acid is more preferable.
Examples of the method for introducing the alkali-soluble group to the dye multimer include a method for introducing the alkali-soluble group to a dye monomer in advance and a method for copolymerizing monomers (a caprolactone modified product of a (meth)acrylic acid or an acrylic acid, a succinic anhydride modified product of 2-hydroxyethyl (meth)acrylate, a phthalic anhydride modified product of 2-hydroxyethyl (meth)acrylate, a 1,2-cyclohexanedicarboxylic anhydride modified product of 2-hydroxyethyl (meth)acrylate, a carboxylic acid-containing monomer such as styrene carboxylic acid, itaconic acid, maleic acid, and norbomene carboxylic acid, a phosphoric acid-containing monomer such as acid phosphoxy ethyl methacrylate and vinyl phosphonate, and a sulfonic acid-containing monomer such as vinylsulfonic acid and 2-acrylamide-2-methylsulfonic acid) other than the dye monomer having the alkali-soluble group, but it is more preferable to use both the methods.
The amount of the alkali-soluble group contained in the dye multimer (A) is preferably 0.3 mmol to 2.0 mmol, more preferably 0.4 mmol to 1.5 mmol, and still more preferably 0.5 mmol to 1.0 mmol, with respect to 1 g of the dye multimer (A). In the present invention, the acid value of the dye multimer can be calculated from, for example, the average content of the acid group contained in the dye multimer. Further, by varying the content of the monomer unit which contains the acid group constituting the dye multimer, a resin having an intended acid value can be obtained.
Examples of other functional groups contained in the dye multimer (A) include a development accelerator such as lactone, acid anhydride, amide, —COCH2CO—, and a cyano group, and a hydrophobicity- or hydrophilicity-regulating group such as a long-chained alkyl group, a cyclic alkyl group, an aralkyl group, an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimide group, and an amino group. These can be appropriately introduced into the dye multimer (A).
Examples of the method for introducing the functional group include a method for introducing the functional group to the dye monomer in advance, and a method for copolymerizing a monomer having the above functional group.
Specific examples of repeating units having other functional groups contained in the dye multimer (A) are shown below, but the present invention is not limited thereto.













The weight-average molecular weight of the dye multimer (A) is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and particularly preferably 4,000 to 10,000.
In the present specification, as the weight-average molecular weight and the number-average molecular weight, values which are measured by GPC and converted in terms of styrene are used.
Moreover, a ratio [(Mw)/(Mn)] between the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of the dye multimer (A) is preferably 1.0 to 3.0, more preferably 1.6 to 2.5, and particularly preferably 1.6 to 2.0.
The glass transition temperature (Tg) of the dye multimer (A) according to the present invention is preferably 50° C. or higher, and more preferably 100° C. or higher. Further, a 5% weight reduction temperature measured by thermogravimetric analysis (TGA measurement) is preferably 120° C. or higher, more preferably 150° C. or higher, and still more preferably 200° C. or higher. If the temperature is within this range, when the coloring composition of the present invention is applied to the manufacture of a color filter or the like, change in the concentration caused by a heating process can be decreased.
In addition, the absorption coefficient (hereinafter described as ∈′. ∈′=∈/average molecular weight, unit: L/g·cm) per unit weight of the dye multimer according to the present invention is preferably 30 or more, more preferably 60 or more, and still more preferably 100 or more. If the absorption coefficient is within this range, in the case where a color filter is manufactured using the coloring composition of the present invention, a color filter having excellent color reproducibility can be manufactured.
It is preferable that the molar absorption coefficient of the dye multimer (A) used in the coloring composition of the present invention is as high as possible, from the viewpoint of coloring ability.
It is preferable that the dye multimer (A) according to the present invention is a compound soluble in the following organic solvents.
Examples of the organic solvents include esters (for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, and methyl 3-methoxypropionate), ethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone), and aromatic hydrocarbons (for example, toluene and xylene). The dye multimer (A) dissolves in the amount of preferably from 1% by mass to 50% by mass, more preferably from 5% by mass to 40% by mass, and still more preferably from 10% by mass to 30% by mass, with respect to these solvents. If the solubility is within this range, when the coloring composition of the present invention is applied to the manufacture of a color filter or the like, preferable coating surface properties can be obtained or reduction in concentration caused by elution after coating of other colors can be decreased.
In the coloring composition of the present invention, the dye multimer (A) may be used alone or in combination of two or more kinds thereof. In the case where a combination of two or more kinds thereof is used, the total amount preferably corresponds to the content which will be described later.
The content of the dye multimer (A) in the coloring composition of the present invention is determined in consideration of its content ratio to a (C) pigment which will be described later.
The mass ratio of the dye multimer to the pigment (dye multimer (A)/pigment) is preferably 0.1 to 5, more preferably 0.2 to 2, and still more preferably 0.3 to 1.
<(B) Polymerizable Compound>
The coloring composition of the present invention contains a polymerizable compound.
Known polymerizable compounds which can be crosslinked by a radical, an acid, or heat can be used, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, a cyclic ether (epoxy or oxetane), methylol, or the like. From the viewpoint of sensitivity, the polymerizable compound is suitably selected from compounds having at least one and preferably two or more terminal ethylenically unsaturated bonds. Among these, polyfunctional polymerizable compounds having 4 or more functional groups are preferable, and polyfunctional polymerizable compounds having 5 or more functional groups are more preferable.
Such compound groups are widely known in the industrial field of the relevant art and can be used in the present invention without particular limitation. These may be in any type of chemical forms such as a monomer, a prepolymer, that is, a dimer, a trimer, an oligomer, a mixture thereof, and a multimer thereof. The polymerizable compound in the present invention may be used alone or in combination of two or more kinds thereof.
More specifically, examples of the monomer and prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and the like) or esters thereof, amides, and multimers of these, and among these, an ester of unsaturated carboxylic acid and an aliphatic polyol compound, amides of unsaturated carboxylic acid and an aliphatic polyamine compound, and multimers of these are preferable. Moreover, products of an addition reaction between unsaturated carboxylic acid esters or amides having nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group and monofunctional or polyfunctional isocyanates or epoxies, products of a dehydration condensation reaction between the unsaturated carboxylic acid esters or amides and a monofunctional or polyfunctional carboxylic acid, and the like are also suitably used. In addition, products of an addition reaction between unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group and monofunctional or polyfunctional alcohols, amines, or thiols, and products of a substitution reaction between unsaturated carboxylic acid esters or amides having an eliminatable substituent such as a halogen group or tosyloxy group and monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As other examples, instead of the above unsaturated carboxylic acid, vinyl benzene derivatives of unsaturated phosphonic acid, styrene, and the like and compound groups substituted with vinyl ether, allyl ether, or the like can also be used.
As these specific compounds, the compounds described in paragraph Nos. “0095” to “0108” of JP2009-288705A can also be suitably used in the present invention.
Moreover, as the polymerizable compound, a compound which has at least one addition-polymerizable ethylene group and has an ethylenically unsaturated group having a boiling point of 100° C. or higher under normal pressure is also preferable. Examples of the compound include a monofunctional acrylate or methacrylate such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate; a compound which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resultant, such as polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl) isocyanurate, glycerin, and trimethylolethane; the urethane (meth)acrylates described in JP1973-41708B (JP-S48-41708B), JP1975-6034B (JP-S50-6034B), and JP1976-37193A (JP-S51-37193A); the polyester acrylates described in JP1973-64183A (JP-S48-64183A), JP1974-43191B (JP-S49-43191B), and JP1977-30490B (JP-S52-30490B); a polyfunctional acrylate or methacrylate such as epoxy acrylate as a product of a reaction between an epoxy resin and a (meth)acrylic acid; and a mixture thereof.
Other examples thereof include a polyfunctional (meth)acrylate which is obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate, and an ethylenically unsaturated group.
Furthermore, as other preferred polymerizable compounds, the compounds having a fluorene ring and an ethylenically unsaturated group having 2 or more functional groups described in JP2010-160418A, JP2010-129825A, and JP4364216B, and a cardo resin can also be used.
Moreover, as the compound which has a boiling point of 100° C. or higher under normal pressure and has at least one addition-polymerizable ethylenically unsaturated group, compounds described in paragraph Nos. “0254” to “0257” of JP2008-292970A are also suitable.
In addition to those above, radically polymerizable monomers represented by the following General Formulae (MO-1) to (MO-5) can also be used. Incidentally, in the formulae, in the case where T is an oxyalkylene group, the terminal at a carbon atom side binds to R.




In the general formulae, n is 0 to 14, and m is 1 to 8. A plurality of R's and T's which are present in the same molecule may be the same as or different from each other.
In each of the polymerizable compounds represented by General Formulae (MO-1) to (MO-5), at least one of the plurality of R's represents a group represented by —OC(═O)CH═CH2 or —OC(═O)C(CH3)═CH2.
As specific examples of the polymerizable compounds represented by General Formulae (MO-1) to (MO-5), the compounds described in paragraph Nos. “0248” to “0251” of JP2007-269779A can also be suitably used in the present invention.
In addition, a compound which is obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol, which is described as General Formulae (1) and (2) in JP1998-62986A (JP-H10-62986A) together with the specific examples thereof, and then (meth)acrylating the resultant can also be used as a polymerizable compound.
Among these, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (KAYARAD D-310 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (KAYARAD DPHA as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), and a structure in which ethylene glycol or a propylene glycol residue is interposed between these (meth)acryloyl groups are preferable. Oligomer types of these can also be used. Preferred embodiments of the polymerizable compound are shown below.
The polymerizable compound is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If an ethylenic compound has an unreacted carboxyl group as in a case where the ethylene compound is a mixture described above, this compound can be used as is, but if desired, a hydroxyl group of the above ethylenic compound may be reacted with a non-aromatic carboxylic anhydride so as to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.
In the present invention, as a monomer having an acid group, preferable is a polyfunctional monomer which is an ester obtained between an aliphatic polyhydroxy compound and an unsaturated carboxylic acid and provides an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. A monomer in which the aliphatic polyhydroxy compound in the ester is pentaerythritol and/or dipentaerythritol is particularly preferable. Examples of commercially available products thereof include M-510 and M-520, which are polybasic modified acryl oligomers manufactured by TOAGOSEI, CO., LTD.
These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds thereof may be used as a mixture. Moreover, if desired, a polyfunctional monomer not having an acid group and a polyfunctional monomer having an acid group may be used in combination therewith as the monomer.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 mg KOH/g to 40 mg KOH/g, and particularly preferably 5 mg KOH/g to 30 mg KOH/g. If the acid value of the polyfunctional monomer is too low, the development solubility characteristics deteriorates. If the acid value is too high, difficulty is caused in the production and handleability, hence a photopolymerization performance deteriorates, which leads to deterioration of curability such as surface smoothness of pixels. Therefore, in the case where a combination of two or more kinds of polyfunctional monomers having different acid groups is used, or when a combination of polyfunctional monomers not having an acid group is used, it is preferable to adjust the acid value such that the acid value of all the polyfunctional monomers falls within the above range.
Moreover, it is also a preferred embodiment that a polyfunctional monomer having a caprolactone structure is included as a polymerizable compound.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in a molecule thereof, and examples thereof include ε-caprolactone-modified polyfunctional (meth)acrylates which are obtained by esterifying polyols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among these, a polyfunctional monomer having a caprolactone structure represented by the following General Formula (Z-1) is preferable.




In General Formula (Z-1), all of six R's are a group represented by the following General Formula (Z-2). Alternatively, one to five out of six R's are a group represented by the following General Formula (Z-2), and the remainder is a group represented by the following General Formula (Z-3).




In General Formula (Z-2), R1 represents a hydrogen atom or a methyl group, m represents a number 1 or 2, and “*” represents a direct bond.




In General Formula (Z-3), R1 represents a hydrogen atom or a methyl group, and “*” represents a direct bond.
The polyfunctional monomer having such a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd., as a KAYARAD DPCA series, and examples thereof include DPCA-20 (a compound in which m=1 in Formulae (1) to (3), the number of the group represented by Formula (2)=2, and all of R1's are hydrogen atoms), DPCA-30 (a compound in which m=1 in Formulae (1) to (3), the number of the group represented by Formula (2)=3, and all of R1's are hydrogen atoms), DPCA-60 (a compound in which m=1 in Formulae (1) to (3), the number of the group represented by Formula (2)=6, and all of R1's are hydrogen atoms), and DPCA-120 (a compound in which m=2 in Formulae (1) to (3), the number of the group represented by Formula (2)=6, and all of R1's are hydrogen atoms).
In the present invention, the polyfunctional monomer having a caprolactone structure can be used alone or as a mixture of two or more kinds thereof.
Moreover, the specific monomer in the present invention is preferably at least one kind selected from a group of compounds represented by the following General Formula (Z-4) or (Z-5).




In General Formulae (Z-4) and (Z-5), E's each independently represent —((CH2)yCH2O)— or —((CH2)yCH(CH3)O)—, y's each independently represent an integer of 0 to 10, and X's each independently represent an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In General Formula (Z-4), the sum of the acryloyl group and the methacryloyl group is 3 or 4, m's each independently represent an integer of 0 to 10, and the sum of the respective m's is an integer of 0 to 40. Herein, in the case where the sum of the respective m's is 0, any one of X's is a carboxyl group.
In General Formula (Z-5), the sum of the acryloyl group and the methacryloyl group is 5 or 6, n's each independently represent an integer of 0 to 10, and the sum of the respective n's is an integer of 0 to 60. Herein, in the case where the sum of the respective n's is 0, one of X's is a carboxyl group.
In General Formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the sum of the respective m's is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In General Formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Furthermore, the sum of the respective n's is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In addition, —((CH2)yCH2O)— or —((CH2)yCH(CH3)O)— in General Formula (Z-4) or (Z-5) is preferably in the form in which the terminal at an oxygen atom side binds to X.
The compound represented by General Formula (Z-4) or (Z-5) may be used alone or in combination of two or more kinds thereof. In particular, a form in which all of six X's in General Formula (Z-5) are an acryloyl group is preferable.
Moreover, the total content of the compound represented by General Formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
The compound represented by General Formula (Z-4) or (Z-5) can be synthesized by steps known in the related art, which includes a step of binding ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol by a ring-opening addition reaction to form a ring-opening skeleton, and a step of reacting, for example, (meth)acryloyl chloride to a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acryloyl group. Since the respective steps are well-known, so a person skilled in the art can easily synthesize the compound represented by General Formula (Z-4) or (Z-5).
Among the compounds represented by General Formula (Z-4) or (Z-5), a pentaerythritol derivative and/or a dipentaerythritol derivative is/are more preferable.
Specific examples of the compounds include compounds represented by the following Formulae (a) to (f) (hereinafter also referred to as “Examples Compounds (a) to (f)”). Among these, the exemplary compounds (a), (b), (e), and (f) are preferable.




Examples of commercially available products of the polymerizable compounds represented by General Formulae (Z-4) and (Z-5) include SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and DPCA-60 which is a hexafunctional acrylate having six pentyleneoxy chains and TPA-330 which is a trifunctional acrylate having three isobutyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd.
Moreover, as the polymerizable compounds, the urethane acrylates described in JP1973-41708B (JP-S48-41708B), JP1976-37193A (JP-S51-37193A), JP1990-32293B (JP-H02-32293B), and JP1990-16765B (JP-H02-16765B) or urethane compounds having an ethylene oxide-based skeleton described in JP1983-49860B (JP-S58-49860B), JP1981-17654B (JP-S56-17654B), JP1987-39417B (JP-S62-39417B), and JP1987-39418B (JP-S62-39418B) are also preferable. Furthermore, if addition-polymerizable compounds, which have an amino structure or a sulfide structure in a molecule and are described in JP1988-277653A (JP-S63-277653A), JP1988-260909A (JP-S63-260909A), and JP1989-105238A (JP-H01-105238A), are used as the polymerizable compounds, a curable composition which is extremely excellent in photosensitization speed can be obtained.
Examples of commercially available products of the polymerizable compounds include urethane oligomers UAS-10 and UAB-140 (manufactured by Sanyo-Kokusaku Pulp, Co., Ltd.), UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by KYOEISHA CHEMICAL CO., LTD.).
As the cyclic ether (epoxy or oxethane), examples of a bisphenol A type epoxy resin, which have an epoxy group, include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, and JER-1010 (all manufactured by Japan Epoxy Resins Co., Ltd.), and EPICLON 860, EPICLON 1050, EPICLON 1051, and EPICLON 1055 (all manufactured by DIC Corporation); examples of a bisphenol F type epoxy resin include JER-806, JER-807, JER-4004, JER-4005, JER-4007, and JER-4010 (all manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON 830 and EPICLON 835 (both manufactured by DIC Corporation), and LCE-21 and RE-602S (all manufactured by Nippon Kayaku Co., Ltd.); examples of a phenol novolac type epoxy resin include JER-152, JER-154, JER-157 S70, and JER-157 S65 (all manufactured by Japan Epoxy Resins Co., Ltd.), and EPICLON N-740, EPICLON N-770, and EPICLON N-775 (all manufactured by DIC Corporation); examples of a cresol novolac type epoxy resin include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (all manufactured by DIC Corporation), and EOCN-1020 (all manufactured by Nippon Kayaku Co., Ltd.); and examples of an aliphatic epoxy resin include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, and ADEKA RESIN EP-4088S (all manufactured by ADEKA CORPORATION), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (all manufactured by Daicel Chemical Industries, Ltd.), DENACOL EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, and ADEKA RESIN EP-4011S (all manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, and EPPN-502 (all manufactured by ADEKA CORPORATION), and JER-1031S (manufactured by Japan Epoxy Resins Co., Ltd.). Such polymerizable compounds are suitable for a case of forming a pattern by a dry etching method.
Details of how to use these polymerizable compounds, such as the structure, whether the polymerizable compounds are used singly or used in combination thereof, and the amount of the polymerizable compounds added, can be arbitrarily set according to the designed final performance of the coloring composition. For example, from the viewpoint of sensitivity, a structure in which the content of an unsaturated group per molecule is large is preferable, and in many cases, it is preferable that the polymerizable compound has 2 or more functional groups. Moreover, from the viewpoint of enhancing the strength of a cured film formed of the coloring composition, it is preferable that the polymerizable compound has 3 or more functional groups. In addition, a method for adjusting both the sensitivity and the strength by using a combination of compounds which differ in the number of functional groups and have different polymerizable groups (for example, an acrylic acid ester, a methacrylic acid ester, a styrene-based compound, and a vinylether-based compound) is also effective. Further, it is preferable to use polymerizable compounds having 3 or more functional groups and differing in the length of an ethylene oxide chain since the developability of the coloring composition can be adjusted, and excellent pattern formability is obtained.
In addition, from the viewpoints of the compatibility with other components (for example, a photopolymerization initiator, a substance to be dispersed, and an alkali-soluble resin) contained in the coloring composition, and the dispersibility, how to select and use the polymerizable compound is an important factor. For example, if a low-purity compound is used or a combination of two or more kinds thereof is used, the compatibility can be improved in some cases. In addition, from the viewpoint of improving the adhesiveness of the composition to a hard surface of a support or the like, specific structures may be selected in some cases.
The content of the polymerizable compound in the coloring composition of the present invention is preferably 0.1% by mass to 90% by mass, more preferably 1.0% by mass to 60% by mass, and particularly preferably 2.0% by mass to 40% by mass, with respect to the total solid contents of the coloring composition.
The composition of the present invention may include one kind or two or more kinds of polymerizable compound. In the case where the composition includes two or more kinds of the polymerizable compound, the total amount thereof is preferably within the range.
<(C) Pigment>
It is preferable that the coloring composition of the present invention further contains a (C) pigment.
As the pigment used in the present invention, various inorganic or organic pigments known in the related art can be used, and it is preferable to use an organic pigment. It is preferable that the pigment has a high transmittance.
Examples of the inorganic pigment include metal compounds represented by a metal oxide, a metal complex salt, or the like, and specific examples thereof include metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the like, and complex oxides of the above metals.
Examples of the organic pigment include:

    
    
        C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
        C. I. Pigment Orange 36, 38, 43, 71;
        C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
        C. I. Pigment Violet 19, 23, 32, 39;
        C. I. Pigment Blue 1, 2, 15, 15:1, 15:3, 15:6, 16, 22, 60, 66;
        C. I. Pigment Green 7, 36, 37, 58;
        C. I. Pigment Brown 25, 28; and
        C. I. Pigment Black 1, 7.
    
    


Examples of the pigment which can be preferably used in the present invention include the following ones, but the present invention is not limited thereto:

    
    
        C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;
        C. I. Pigment Orange 36, 71;
        C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;
        C. I. Pigment Violet 19, 23, 32;
        C. I. Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66;
        C. I. Pigment Green 7, 36, 37, 58;
        C. I. Pigment Black 1, 7.
    
    


These organic pigments can be used alone or in various combinations for spectral adjustment or improvement of color purity. Specific examples of the combination are shown below. For example, as a red pigment, an anthraquinone-based pigment, a perylene-based pigment, or a diketopyrrolopyrrole-based pigment can be used alone or as a mixture of at least one kind of these with a disazo-based yellow pigment, an isoindoline-based yellow pigment, a quinophthalone-based yellow pigment, or a perylene-based red pigment. Examples of the anthraquinone-based pigment include C. I. Pigment Red 177, examples of the perylene-based pigment include C. I. Pigment Red 155, and C. I. Pigment Red 224, and examples of the diketopyrrolopyrrole-based pigment include C. I. Pigment Red 254. In view of chromatic resolving properties, a mixture of the above pigment with C. I. Pigment Yellow 139 is preferable. The mass ratio between the red pigment and the yellow pigment is preferably 100:5 to 100:50. If the mass ratio is 100:4 or less, it is difficult to reduce the light transmittance at 400 nm to 500 nm, and if it is 100:51 or more, a dominant wavelength moves closer to a short wavelength, so a chromatic resolving power cannot be improved in some cases. In particular, the mass ratio is optimally in a range of 100:10 to 100:30. Moreover, in a case of a combination of red pigments, the mass ratio can be adjusted according to the required spectrum.
In addition, as a green pigment, a halogenated phthalocyanine-based pigment can be used alone or as a mixture of this pigment with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, an azomethine-based yellow pigment, or an isoindoline-based yellow pigment. As an example of such pigments, a mixture of C. I. Pigment Green 7, 36, or 37 with C. I. Pigment Yellow 83, C. I. Pigment Yellow 138, C. I. Pigment Yellow 139, C. I. Pigment Yellow 150, C. I. Pigment Yellow 180, or C. I. Pigment Yellow 185 is preferable. The mass ratio between the green pigment and the yellow pigment is preferably from 100:5 to 100:150. The mass ratio is particularly preferably in a range of 100:30 to 100:120.
As a blue pigment, a phthalocyanine-based pigment can be used alone or as a mixture of this pigment with a dioxazine-based violet pigment. For example, a mixture of C. I. Pigment Blue 15:6 with C. I. Pigment Violet 23 is preferable. The mass ratio between the blue pigment and the violet pigment is preferably from 100:0 to 100:100 and more preferably 100:10 or less.
Moreover, as a pigment for a black matrix, carbon, titanium black, iron oxide, or titanium oxide may be used alone or as a mixture, and a combination of carbon with titanium black is preferable. The mass ratio between carbon and titanium black is preferably in a rage of 100:0 to 100:60.
For the coloring composition of the present invention, it is preferable to blend pigments other than black one, which is suitable for a blue pigment.
In the case where the coloring composition is used for a color filter, the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness or contrast. From the viewpoint of dispersion stability, the primary particle size is preferably 5 nm or more. The primary particle size of the pigment is more preferably from 5 nm to 75 nm, still more preferably from 5 nm to 55 nm, and particularly preferably from 5 nm to 35 nm. The specific dispersion resin according to the present invention can exert excellent effects particularly when it is combined with a pigment of which the primary particle size is in a range of 5 nm to 35 nm.
The primary particle size of the pigment can be measured by a known method such as an electron microscope.
The pigment is preferably a pigment selected from an anthraquinone pigment, a diketopyrrolopyrrole pigment, a phthalocyanine pigment, a quinophthalone pigment, an isoindoline pigment, an azomethine pigment, and a dioxazine pigment. In particular, C. I. Pigment Red 177 (anthraquinone pigment), C. I. Pigment Red 254 (diketopyrrolopyrrole pigment), C. I. Pigment Green 7, 36, 58, C. I. Pigment Blue 15:6 (phthalocyanine pigment), C. I. Pigment Yellow 138 (quinophthalone pigment), C. I. Pigment Yellow 139, 185 (isoindoline pigments), C. I. Pigment Yellow 150 (azomethine pigment), and C. I. Pigment Violet 23 (dioxazine pigment) are particularly preferable.
The content of the pigment is preferably from 10% by mass to 70% by mass, more preferably from 20% by mass to 60% by mass, and still more preferably from 25% by mass to 50% by mass, with respect to the total amount of components excluding a solvent, contained in the coloring composition.
The composition of the present invention may include one kind or two or more kinds of pigment. In the case where the composition includes two or more kinds of the pigment, the total amount thereof is preferably within the range.
<(D) Photopolymerization Initiator>
From the viewpoint of further improving sensitivity, the coloring composition of the present invention preferably contains a photopolymeriation initiator.
The photopolymerization initiator is not particularly limited as long as the photopolymerization initiator has a function of initiating polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, photopolymerization initiators sensitive to light rays in a range from ultraviolet region to visible light are preferable. Moreover, the photopolymerization initiator may be either an activator which interacts with a photo-excited sensitizer in any way and generates active radicals or an initiator which initiates cationic polymerization according to the type of monomer.
Furthermore, it is preferable that the photopolymerization initiator contains at least one kind of compound having at least a molar absorption coefficient of about 50 in a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, a derivative having a triazine skeleton, and a derivative having an oxadiazole skeleton), acyl phosphine compounds such as acyl phosphine oxide, oxime compounds such as hexaaryl biimidazole, and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenone, and oxime compounds are preferable.
Furthermore, from the viewpoint of exposure sensitivity, the compound is preferably a compound selected from a group consisting of a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triallyl imidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound.
The compound is more preferably a trihalomethyl triazine compound, an α-aminoketone compound, an acyl phosphine compound, a phosphine oxide compound, an oxime compound, a triallyl imidazole dimer, an onium compound, a benzophenone compound, or an acetophenone compound, and particularly preferably at least one kind of compound selected from a group consisting of a trihalomethyl triazine compound, an α-aminoketone compound, an oxime compound, a triallyl imidazole dimer, and a benzophenone compound.
Particularly, in the case where the coloring composition of the present invention is used for the manufacture of a color filter included in a solid-state image sensor, a fine pattern needs to be formed in a sharp shape. Accordingly, it is important that the composition has curability and is developed without residues in an unexposed area. From this viewpoint, it is particularly preferable to use an oxime compound as a polymerization initiator. In particular, in the case where a fine pattern is formed in the solid-state image sensor, stepper exposure is used for exposure for curing. However, the exposure machine used at this time is damaged by halogen in some cases, so it is necessary to reduce the amount of a polymerization initiator added. In consideration of this point, in order to form a fine pattern as in a solid-state image sensor, it is most preferable to use an oxime compound as the (D) photopolymerization initiator.
Examples of the halogenated hydrocarbon compound having a triazine skeleton include the compound described in Wakabayashi, et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), the compound described in UK1388492B, the compound described in JP1978-133428A (JP-S53-133428A), the compound described in GE3337024B, the compound described in F. C. Schaefer, et al., J. Org. Chem.; 29, 1527 (1964), the compound described in JP1987-58241A (JP-S62-58241A), the compound described in JP1993-281728A (JP-H05-281728A), the compound described in JP1993-34920A (JP-H05-34920A), and the compound described in U.S. Pat. No. 4,212,976A, in particular, the compound described in paragraph No. “0075” of JP2013-077009A.
In addition, as other photopolymerization initiators above, acridine derivatives are exemplified. Specific examples thereof include the compound described in paragraph No. “0076” of JP2013-077009A, the contents of which are incorporated herein.
Examples of the ketone compound include the compound described in paragraph No. “0077” of JP2013-077009A, the contents of which are incorporated herein.
As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in JP1998-291969A (JP-H10-291969A), and the acyl phosphine oxide-based initiator described in JP4225898B can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (product names, all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (product names, all manufactured by BASF) which are commercially available products can be used. In addition, as the aminoacetophenone-based initiator, the compound described in JP2009-191179A, of which an absorption wavelength matches with a light source of a long wavelength of 365 nm, 405 nm, or the like can be used. Moreover, as the acyl phosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (product name, all manufactured by BASF) which are commercially available products can be used.
Examples of the photopolymerization initiator more preferably include oxime compounds. As specific examples of the oxime compounds, the compound described in JP2001-233842A, the compound described in JP2000-80068A, and the compound described in JP2006-342166A can be used.
Examples of the oxime compound such as an oxime derivative, which is preferably used as the photopolymerization initiator in the present invention, include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
Examples of the oxime compound include the compounds described in J. C. S. Perkin II (1979), pp. 1653-1660, J. C. S. Perkin II (1979), pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 202-232, and JP2000-66385A; and the compounds described respectively in JP2000-80068A, JP2004-534797A, and JP2006-342166A.
As the commercially available product, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also suitably used. Further, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation) can also be used.
Further, as oxime compounds other than the above, the compound described in JP2009-519904A in which oxime is linked to an N-position of carbazole, the compound described in U.S. Pat. No. 7,626,957B in which a hetero-substituent is introduced into a benzophenone moiety, the compounds described in JP2010-15025A and US2009/292039A in which a nitro group is introduced into a dye moiety, the ketoxime compound described in WO2009/131189A, the compound described in U.S. Pat. No. 7,556,910B which contains a triazine skeleton and an oxime skeleton in the same molecule, the compound described in JP2009-221114A, which has maximum absorption at 405 nm and has excellent sensitivity to a light source of a g-ray, and the like may be used.
Moreover, the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be preferably used. Among the cyclic oxime compounds, the cyclic oxime compounds ring-fused to a carbazole dye, which are described in JP2010-32985A and JP2010-185072A, are preferable from the viewpoint of high sensitivity since these compounds have high light absorptivity.
Furthermore, the compound described in JP2009-242469A, which is an oxime compound having an unsaturated bond in a specific moiety, can also be preferably used since this compound makes it possible to improve sensitivity by reproducing active radicals from polymerization-inactive radicals.
The most preferred examples of the oxime compounds include the oxime compound having a specific substituent described in JP2007-269779A and the oxime compound having a thioaryl group described in JP2009-191061A.
Specifically, the oxime compound as a photopolymerization initiator is preferably a compound represented by the following General Formula (OX-1). Incidentally, the compound may be an oxime compound in which an N—O bond of oxime forms an (E) isomer, an oxime compound in which the N—O bond forms a (Z) isomer, or a mixture in which the N—O bond forms a mixture of an (E) isomer and a (Z) isomer.




In General Formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In General Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.
Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Further, these groups may have one or more substituents. Moreover, the above substituents may be further substituted with other substituents.
Examples of the substituents include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group, a 2-ethylhexyl group, a phenacyl group, a 1-naphthoylmethyl group, a 2-naphthoylmethyl group, a 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, a 4-dimethylaminophenacyl group, a 4-cyanophenacyl group, a 4-methylphenacyl group, a 2-methylphenacyl group, a 3-fluorophenacyl group, a 3-trifluoromethylphenacyl group, and a 3-nitrophenacyl group.
The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, an quaterphenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, an o-cumenyl group, an m-cumenyl group, a p-cumenyl group, a mesityl group, a pentalenyl group, a binaphthalenyl group, a ternaphthalenyl group, a quaternaphthalenyl group, a heptalenyl group, biphenylenyl group, an indacenyl group, a fluoranthenyl group, an acenaphthylenyl group, an aceanthrylenyl group, a phenalenyl group, a fluorenyl group, an anthryl group, a bianthracenyl group, a teranthracenyl group, a quateranthracenyl group, an anthraquinolyl group, a phenanthryl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a pleiadenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.
The acyl group is preferably an acyl group having 2 to 20 carbon atoms, and specific examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, a 2-naphthoyl group, a 4-methylsulfanylbenzoyl group, a 4-phenylsulfanylbenzoyl group, a 4-dimethylaminobenzoyl group, a 4-diethylaminobenzoyl group, a 2-chlorobenzoyl group, a 2-methylbenzoyl group, a 2-methoxybenzoyl group, a 2-butoxybenzoyl group, a 3-chlorobenzoyl group, a 3-trifluoromethylbenzoyl group, a 3-cyanobenzoyl group, a 3-nitrobenzoyl group, a 4-fluorobenzoyl group, a 4-cyanobenzoyl group, and a 4-methoxybenzoyl group.
The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.
Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, a 4-phenylsulfanylphenyloxycarbonyl group, a 4-dimethylaminophenyloxycarbonyl group, a 4-diethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2-methylphenyloxycarbonyl group, a 2-methoxyphenyloxycarbonyl group, a 2-butoxyphenyloxycarbonyl group, a 3-chlorophenyloxycarbonyl group, a 3-trifluoromethylphenyloxycarbonyl group, a 3-cyanophenyloxycarbonyl group, a 3-nitrophenyloxycarbonyl group, a 4-fluorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group, and a 4-methoxyphenyloxycarbonyl group.
As the heterocyclic group, an aromatic or aliphatic heterocycle having a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom is preferable.
Specific examples of the heterocyclic group include a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group, a thianthrenyl group, a furyl group, a pyranyl group, an isobenzofuranyl group, a chromenyl group, a xanthenyl group, a phenoxathiinyl group, a 2H-pyrrolyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolizinyl group, an isoindolyl group, a 3H-indolyl group, an indolyl group, a 1H-indazolyl group, a purinyl group, a 4H-quinolizinyl group, an isoquinolyl group, a quinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a pteridinyl group, a 4aH-carbazolyl group, a carbazolyl group, a β-carbolinyl group, a phenanthridinyl group, an acridinyl group, a perimidinyl group, a phenanthrolinyl group, a phenazinyl group, a phenarsazinyl group, an isothiazolyl group, a phenothiazinyl group, an isoxazolyl group, a furazanyl group, a phenoxazinyl group, an isochromanyl group, a chromanyl group, a pyrrolidinyl group, a pyrrolinyl group, an imidazolidinyl group, an imidazolinyl group, a pyrazolidinyl group, a pyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinyl group, an isoindolinyl group, a quinuclidinyl group, a morpholinyl group, and a thioxantolyl group.
Specific examples of the alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, and a trifluoromethylthiocarbonyl group.
Specific examples of the arylthiocarbonyl group include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, a 4-phenylsulfanylphenylthiocarbonyl group, a 4-dimethylaminophenylthiocarbonyl group, a 4-diethylaminophenylthiocarbonyl group, a 2-chlorophenylthiocarbonyl group, a 2-methylphenylthiocarbonyl group, a 2-methoxyphenylthiocarbonyl group, a 2-butoxyphenylthiocarbonyl group, a 3-chlorophenylthiocarbonyl group, a 3-trifluoromethylphenylthiocarbonyl group, a 3-cyanophenylthiocarbonyl group, a 3-nitrophenylthiocarbonyl group, a 4-fluorophenylthiocarbonyl group, a 4-cyanophenylthiocarbonyl group, and a 4-methoxyphenylthiocarbonyl group.
In General Formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents, and examples of the substituents include the substituents described above. In addition, the substituents described above may be further substituted with other substituents.
Among these, the following structures are particularly preferable.
In the following structures, Y, X, and n have the same definitions as Y, X, and n, respectively, in General Formula (OX-2) which will be described later, and the preferred examples thereof are also the same.




In General Formula (OX-1), examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group, and these groups may have one or more substituents. Examples of the substituents include the substituents described above. Further, the substituents described above may further substituted with other substituents.
Among these, as A in General Formula (OX-1), from the viewpoints of improving sensitivity and inhibiting coloring caused by elapse of time during heating, an unsubstituted alkylene group, an alkylene group substituted with an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, and a dodecyl group), an alkylene group substituted with an alkenyl group (for example, a vinyl group and an allyl group), and an alkylene group substituted with an aryl group (for example, a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a styryl group) are preferable.
In General Formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the same ones as the substituents introduced into the substituted aryl groups, which are exemplified above as specific examples of the aryl group which may have a substituent.
Among these, from the viewpoints of improving sensitivity and inhibiting coloration caused by elapse of time during heating, a substituted or unsubstituted phenyl group is preferable.
In General Formula (OX-1), a structure “SAr” formed of Ar and S adjacent thereto in Formula (OX-1) is preferably the following structure from the viewpoints of sensitivity. Incidentally, Me represents a methyl group, and Et represents an ethyl group.




The oxime compound is preferably a compound represented by the following General Formula (OX-2).




In General Formula (OX-2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5. R, A, and Ar in General Formula (OX-2) have the same definitions as R, A, and Ar, respectively, in General Formula (OX-1), and the preferred examples thereof are also the same.
Examples of the monovalent substituent represented by X in General Formula (OX-2) include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents, and examples of the substituents include the substituents described above. Moreover, the substituents described above may be further substituted with other substituents.
Among these, from the viewpoints of improving solvent solubility and absorption efficiency in a long-wavelength region, X in General Formula (OX-2) is preferably an alkyl group.
Furthermore, n in Formula (OX-2) represents an integer of 0 to 5 and preferably represents an integer of 0 to 2.
Examples of the divalent organic group represented by Y in General Formula (OX-2) include the following structures. In the following groups, “*” represents a position where Y binds to an carbon atom adjacent thereto in Formula (OX-2).




Among these, from the viewpoints of improving sensitivity, the following structures are preferable.




Moreover, the oxime compound is preferably a compound represented by the following General Formula (OX-3) or (OX-4).




In General Formula (OX-3) or (OX-4), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5.
R, X, A, Ar, and n in General Formula (OX-3) or (OX-4) have the same definitions as R, X, A, Ar, and n, respectively, in General Formula (OX-2), and the preferred examples thereof are also the same.
Specific examples (C-4) to (C-13) of the oxime compound which are preferably used are shown below, but the present invention is not limited thereto.







The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm and preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and an oxime compound showing a high absorbance at 365 nm and 455 nm is particularly preferable.
From the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, and more preferably from 2,000 to 300,000, and particularly preferably from 5,000 to 200,000.
The molar absorption coefficient of the compound can be measured using a known method, but specifically, it is preferable to measure the molar absorption coefficient by means of, for example, a UV-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian) by using an ethyl acetate solvent at a concentration of 0.01 g/L.
The content of the (D) photopolymerization initiator contained in the coloring composition of the present invention is preferably from 0.1% by mass to 50% by mass, more preferably from 0.5% by mass to 30% by mass, and still more preferably from 1% by mass to 20% by mass, with respect to the total solid contents of the coloring composition. If the content of the photopolymerization initiator is within this range, better sensitivity and pattern formability are obtained.
The composition of the present invention may include one kind or two or more kinds of photopolymerization initiator. In the case where the composition includes two or more kinds of the photopolymerization initiator, the total amount thereof is preferably within the range.
<Polyfunctional Thiol Compound>
The coloring composition of the present invention may contain a polyfunctional thiol compounds having two or more mercapto groups in a molecule thereof for the purpose of promoting the reaction of the polymerizable compounds. The polyfunctional thiol compounds are preferably secondary alkanethiols, and particularly preferably compounds having structures represented by the following General Formula (I).
General Formula (I)




(In General Formula (I), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)
In General Formula (I), it is preferable that the linking group L is an aliphatic group having 2 to 12 carbon atoms, and it is particularly preferable that n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound are compounds represented by the following Structural Formulae (II) to (IV), and a compound represented by (II) is particularly preferable. These polyfunctional thiols can be used alone or in combination of multiple kinds.




The amount of the polyfunctional thiol compound blended into the coloring composition of the present invention is preferably from 0.3% by mass to 8.9% by mass, and more preferably from 0.8% by mass to 6.4% by mass, based on the total solid content excluding the solvent.
One kind or two or more kinds of the polyfunctional thiol compounds may be included. In the case where two or more kinds are included, the total amount thereof is preferably within the range.
In addition, the polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability, adhesiveness, and the like.
<Other Pigment Dispersants>
For the coloring composition of the present invention, pigment dispersants other than the specific dispersion resin can be used in combination with other components, as desired.
Examples of other pigment dispersants which can be used in the present invention include polymer dispersants [for example, a polyamide amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high-molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, a modified poly(meth)acrylate, a (meth)acrylic copolymer, and a naphthalene sulfonate formalin condensate], surfactants such as a polyoxyethylene alkyl phosphoric acid ester, a polyoxyethylene alkylamine, and a alkanolamine; and pigment derivatives.
The polymer dispersants can be classified into straight-chain polymers, terminal-modified polymers, graft polymers, and block polymers, according to the structure.
Examples of the terminal-modified polymers which has a moiety anchored to the pigment surface include a polymer having a phosphoric acid group in the terminal as described in JP1991-112992A (JP-1103-112992A), JP2003-533455A, and the like, a polymer having a sulfonic acid group in the terminal as described in JP2002-273191A, a polymer having a partial skeleton or a heterocycle of an organic dye as described in JP1997-77994A (JP-H09-77994), and the like. Moreover, a polymer obtained by introducing two or more moieties (acid groups, basic groups, partial skeletons of an organic dye, or heterocycles) anchored to the pigment surface into a polymer terminal as described in JP2007-277514A is also preferable since this polymer is excellent in dispersion stability.
Examples of the graft polymers having a moiety anchored to the pigment surface include polyester-based dispersant and the like, and specific examples thereof include a product of a reaction between a poly(lower alkyleneimine) and a polyester, which is described in JP1979-37082A (JP-S54-37082A), JP1996-507960A (JP-H08-507960A), JP2009-258668A, and the like, a product of a reaction between a polyallylamine and a polyester, which is described in JP1997-169821A (JP-H09-169821A) and the like, a copolymer of a macromonomer and a nitrogen atom monomer, which is described in JP1998-339949A (JP-H10-339949A), JP2004-37986A, WO2010/110491A, and the like, a graft polymer having a partial skeleton or a heterocycle of an organic dye, which is described in JP2003-238837A, JP2008-9426A, JP2008-81732A, and the like, and a copolymer of a macromonomer and an acid group-containing monomer, which is described in JP2010-106268A, and the like. From the viewpoint of dispersibility of a pigment dispersion, dispersion stability, and developability which a coloring composition using the pigment exhibits, an amphoteric dispersion resin having basic and acid groups, which is described in JP2009-203462A, is particularly preferable.
As the macromonomer used in production of a graft polymer having a moiety anchored to the pigment surface by radical polymerization, known macromonomers can be used. Examples thereof include macromonomers AA-6 (polymethyl methacrylate having a methacryloyl group as a terminal group), AS-6 (polystyrene having a methacryloyl group as a terminal group), AN-6S (a copolymer of styrene and acrylonitrile which has a methacryloyl group as a terminal group), and AB-6 (polybutyl acrylate having a methacryloyl group as a terminal group) manufactured by TOAGOSEI, CO., LTD.; Placcel FM 5 (a product obtained by adding 5 molar equivalents of ε-caprolactone to 2-hydroxyethyl methacrylate) and FA10L (a product obtained by adding 10 molar equivalents of s-caprolactone to 2-hydroxyethyl acrylate) manufactured by DAICEL Corporation; a polyester-based macromonomer described in JP1990-272009A (JP-H02-272009A), and the like. Among these, from the viewpoint of dispersibility of the pigment, dispersion stability, and the developability which the coloring composition using the pigment dispersion exhibits, the polyester-based macromonomer excellent in flexibility and solvent compatibility is particularly preferable. Further, a polyester-based macromonomer represented by the polyester-based macromonomer described in JP1990-272009A (JP-H02-272009A) is particularly preferable.
As the block polymer having a moiety anchored to the pigment surface, block polymers described in JP2003-49110A, JP2009-52010A, and the like are preferable.
The pigment dispersant which can be used in the present invention can be obtained in the form of commercially available products, and specific examples thereof include “DA-7301” manufactured by Kusumoto Chemicals, Ltd., “Disperbyk-101 (polyamidamine phosphoric acid salt), 107 (carboxylic acid ester), 110, 111 (copolymer including an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, and 170 (polymeric copolymer)”, and “BYK-P104 and P105 (high-molecular weight unsaturated polycarboxylic acid)”, manufactured by BYK-Chemie, “EFKA 4047, 4050 to 4010 to 4165 (polyurethane-based dispersant), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high-molecular weight polycarboxylic acid salt), 6220 (aliphatic polyester), 6745 (phthalocyanine derivative), and 6750 (azo pigment derivative)” manufactured by EFKA, “Ajisper PB821, PB822, PB880, and PB881” manufactured by Ajinomoto Fine-Techno Co., Inc., “Flowlen TG-710 (urethane oligomer)” and “Polyflow No. 50E, No. 300 (acrylic copolymer), manufactured by KYOEISHA CHEMICAL CO., LTD., “Disparlon KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, and DA-725”, manufactured by Kusumoto Chemicals, Ltd., “Demol RN, N (naphthalene sulfonate formaldehyde condensate), MS, C, SN-B (aromatic sulfonate formaldehyde condensate)”, “Homogenol L-18 (polymeric polycarboxylic acid), “Emulgen 920, 930, 935, and 985 (polyoxyethylene nonyl phenyl ether)”, and “Acetamine 86 (stearylamine acetate)”, manufactured by Kao Corporation, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, and 27000 (polymers having a functional portion in the terminal portion), and 24000, 28000, 32000, and 38500 (graft polymers)”, manufactured by The Lubrizol Corporation, Japan, “Nikkol T106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylene monostearate)” manufactured by NIKKO CHEMICALS Co., Ltd., “Hinoact T-8000E” and the like manufactured by Kawaken Fine Chemicals Co., Ltd., “organosiloxane polymer KP341” manufactured by Shin-Etsu Chemical Co., Ltd., cationic surfactants such as “WO01” manufactured by Yusho Co., Ltd., nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan aliphatic acid ester, and anionic surfactants such as “WO04, WO05, and WO17”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, and EFKA polymer 450” manufactured by MORISHITA SANGYO Corporation, polymer dispersants such as “Disperse aid 6, Disperse aid 8, Disperse aid 15, and Disperse aid 9100” manufactured by SAN NOPCO Ltd., “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, and P-123” manufactured by ADEKA Corporation, and “Ionet (product name) S-20” manufactured by Sanyo Chemical Industries, Ltd.
These pigment dispersants may be used alone or in combination of two or more kinds thereof. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. Further, the pigment dispersant may be used in combination with an alkali-soluble resin, together with a terminal-modified polymer having a moiety anchored to the pigment surface, a graft polymer, or a block polymer. Examples of the alkali-soluble resin include a (meth)acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and an acidic cellulose derivative having a carboxylic acid in a side chain, and a (meth)acrylic acid copolymer is particularly preferable. In addition, the N-position-substituted maleimide monomers copolymer described in JP1998-300922A (JP-H10-300922A), the ether dimer copolymers described in JP2004-300204A, and the alkali-soluble resins containing a polymerizable group described in JP1995-319161A (JP-H07-319161A) are also preferable.
In the coloring composition, the total content of the specific dispersion resin and other pigment dispersants is preferably 1 part by mass to 80 parts by mass, more preferably 5 parts by mass to 70 parts by mass, and still more preferably 10 parts by mass to 60 parts by mass, with respect to 100 parts by mass of the pigment. The amount of the specific dispersion resin is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more of the dispersant components contained in the coloring composition.
The composition of the present invention may include one kind or two or more kinds of dispersion resin and other pigment dispersants. In the case where the composition includes two or more kinds of the dispersion resin and other pigment dispersants, the total amount thereof is preferably within the range.
Specifically, in the case where a polymer dispersant is used, the amount of the dispersant used is preferably in a range from 5 parts by mass to 100 parts by mass, and more preferably in a range from 10 parts by mass to 80 parts by mass expressed in terms of mass, with respect to 100 parts by mass of the pigment.
Moreover, in the case where a pigment derivative is used in combination with other components, the amount of the pigment derivative used is preferably in a range from 1 part by mass to 30 parts by mass, more preferably in a range from 3 parts by mass to 20 parts by mass, and particularly preferably in a range from 5 parts by mass to 15 parts by mass expressed in terms of mass, with respect to 100 parts by mass of the pigment.
In the coloring composition, from the viewpoint of curing sensitivity and color density, the total content of the components of the coloring agent and the dispersant (including the specific dispersion resin and other pigment dispersants) is preferably from 50% by mass to 90% by mass, more preferably from 55% by mass to 85% by mass, and still more preferably from 60% by mass to 80% by mass, with respect to the total solid contents constituting the coloring composition.
<(F) Alkali-Soluble Resin>
It is preferable that the coloring composition of the present invention further contains an alkali-soluble resin. Incidentally, the alkali-soluble resin mentioned herein does not include the components as the dispersant component such as like the specific dispersion resin, which is contained in the coloring composition of the present invention.
The molecular weight of the alkali-soluble resin is not particularly defined, but Mw is preferably 5000 to 100,000. Further, Mn is preferably 1000 to 20,000.
The alkali-soluble resin can be appropriately selected from alkali-soluble resins which are linear organic high molecular-weight polymers and have at least one group enhancing alkali-solubility in a molecule (preferably, a molecule having an acrylic copolymer or a styrene-based copolymer as a main chain). From the viewpoint of heat resistance, a polyhydroxystyrene-based resin, a polysiloxane-based resin, an acrylic resin, an acrylamide-based resin, and an acryl/acrylamide copolymer resin are preferable. Further, from the viewpoint of controlling developability, an acryl-based resin, an acrylamide-based resin, and an acryl/acrylamide copolymer resin are preferable.
Examples of the group promoting alkali-solubility (hereinafter also referred to as an “acid group”) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like. The group promoting alkali-solubility is preferably a group which is soluble in an organic solvent and can be developed by an aqueous weak alkaline solution, and particularly preferred examples thereof include (meth)acrylic acid. These acid groups may be used alone or in combination of two or more kinds thereof.
Examples of the monomer which can give the acid group after polymerization include monomers having a hydroxyl group, such as 2-hydroxyethyl(meth)acrylate, monomers having an epoxy group, such as glycidyl (meth)acrylate, and monomers having an isocyanate group, such as 2-isocyanate ethyl(meth)acrylate. The monomers for introducing these acid groups may be used alone or in combination of two or more kinds thereof. In order to introduce the acid group into the alkali-soluble resin, for example, the monomer having the acid group and/or the monomer which can give the acid group after polymerization (hereinafter referred to as a “monomer for introducing an acid group” in some cases) may be polymerized as a monomer component.
Incidentally, in the case where a monomer which can give the acid group after polymerization is used as a monomer component to introduce the acid group, a treatment for giving the acid group, which will be described later, needs to be performed after polymerization.
In order to produce the alkali-soluble resin, for example, a method using known radical polymerization can be applied. Various polymerization conditions for producing the alkali-soluble resin by radical polymerization, such as a temperature, a pressure, the type and amount of a radical initiator, and the type of a solvent, can be easily set by those skilled in the art, and the conditions can also be determined experimentally.
As the linear organic high-molecular weight polymer used as the alkali-soluble resin, polymers having a carboxylic acid in a side chain are preferable, and examples thereof include a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, an alkali-soluble phenol resin or the like such as a novolac resin, an acidic cellulose derivative having a carboxylic acid in a side chain, and a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of a (meth)acrylic acid and another monomer copolymerizable with the (meth)acrylic acid is suitable as the alkali-soluble resin. Examples of another monomer copolymerizable with a (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Examples of the alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate, and cyclohexyl (meth)acrylate. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, a polystyrene macromonomer, and a polymethyl methacrylate macromonomer. Examples of the N-position-substituted maleimide monomer disclosed in JP1998-300922A (JP-H10-300922A) include N-phenylmaleimide and N-cyclohexylmaleimide. Other monomers copolymerizable with a (meth)acrylic acid may be used alone or in combination of two or more kinds thereof.
It is also preferable that the coloring composition contains, as the alkali-soluble resin, a polymer (a) obtained by polymerizing monomer components including a compound represented by the following General Formula (ED) (hereinafter also referred to as an “ether dimer” in some cases) as an essential component.




In General Formula (ED), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent.
Thus, the coloring composition of the present invention can form a cured coating film which has extremely excellent heat resistance as well as transparency. In General Formula (ED) which represents the ether dimer, the hydrocarbon group having 1 to 25 carbon atom, represented by R1 and R2, which may have a substituent, is not particularly limited, and examples thereof include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, and 2-ethylhexyl; aryl groups such as phenyl; alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; and alkyl groups substituted with an aryl group such as benzyl. Among these, from the viewpoints of heat resistance, substituents of primary or secondary carbon, which are not easily eliminated by an acid or heat, such as methyl, ethyl, cyclohexyl, and benzyl, are preferable.
Specific examples of the ether dimer include dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2′-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(n-butyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(isobutyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(tert-butyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(tert-amyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(stearyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(lauryl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(1-methoxyethyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(1-ethoxyethyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, dibenzyl-2,2′-[oxybis(methylene)]bis-2-propenoate, diphenyl-2,2′-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl-2,2′-[oxybis(methylene)]bis-2-propenoate, di(tert-butylcyclohexyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(dicyclopentadienyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(tricyclodecanyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(isobornyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, diadamantyl-2,2′-[oxybis(methylene)]bis-2-propenoate, and di(2-methyl-2-adamantyl)-2,2′-[oxybis(methylene)]bis-2-propenoate. Among these, dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2′-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl-2,2′-[oxybis(methylene)]bis-2-propenoate, and dibenzyl-2,2′-[oxybis(methylene)]bis-2-propenoate are particularly preferable. These ether dimers may be used alone or in combination of two or more kinds thereof. The structure derived from the compound represented by General Formula (ED) may be copolymerized with other monomers.
Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resins and the like containing an allyl group, a (meth)acryl group, an allyloxyalkyl group, and the like on a side chain thereof are useful. Examples of the polymer containing the above polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (a polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264 and KS Resist 106 (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), Cyclomer P series and Placcel CF200 series (all manufactured by DAICEL Corporation), and Ebecryl 3800 (manufactured by DAICEL-UCB Co., Ltd.). As the alkali-soluble resin containing a polymerizable group, a polymerizable double bond-containing acryl-based resin modified with urethane, which is a resin obtained by reacting an isocyanate group and an OH group in advance to leave an unreacted isocyanate group and performing a reaction between a compound having a (meth)acryloyl group and an acryl-based resin having a carboxyl group, an unsaturated bond-containing acryl-based resin which is obtained by a reaction between an acryl-based resin having a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in a molecule, a polymerizable double bond-containing acryl-based resin which is obtained by a reaction between an acid pendant type epoxy acrylate resin, an acryl-based resin having an OH group, and a dibasic acid anhydride having a polymerizable double bond, a resin obtained by a reaction between an acryl-based resin having an OH group and a compound having isocyanate and a polymerizable group, a resin which is obtained by treating a resin, which has an ester group having an elimination group such as a halogen atom or a sulfonate group in an α-position or a β-position described in JP2002-229207A and JP2003-335814A on a side chain, with a base, and the like are preferable.
As the alkali-soluble resin, particularly, a benzyl (meth)acrylate/(meth)acrylic acid copolymer or a multicomponent copolymer including benzyl (meth)acrylate/(meth)acrylic acid/other monomers is suitable. Examples thereof also include a benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth)acrylate/a polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer described in JP1995-140654A (JP-H07-140654A), a 2-hydroxy-3-phenoxypropyl acrylate/a polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, a 2-hydroxyethyl methacrylate/a polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, and a 2-hydroxyethyl methacrylate/a polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and particularly preferably a copolymer of benzyl methacrylate/methacrylic acid.
With respect to the alkali-soluble resin, reference can be made to the descriptions in paragraphs “0558” to “0571” of JP2012-208494A (“0685” to “0700” of the corresponding to US2012/0235099A), the contents of which are incorporated herein.
Furthermore, it is preferable to use the copolymers (B) described in paragraph Nos. “0029” to “0063” of JP2012-32767A and the alkali-soluble resins used in Examples of the document; the binder resins described in paragraph Nos. “0088” to “0098” of JP2012-208474A and the binder resins used in Examples of the document; the binder resins described in paragraph Nos. “0022” to “0032” of JP2012-137531A and the binder resins in Examples of the document; the binder resins described in paragraph Nos. “0132” to “0143” of JP2013-024934A and the binder resins used in Examples of the document; the binder resins described in paragraph Nos. “0092” to “0098” of JP2011-242752A and used in Examples; or the binder resins described in paragraph Nos. “0030” to 0072′′ of JP2012-032770A, the contents of which are incorporated herein. More Specifically, the following resins are preferable.













The acid value of the alkali-soluble resin is preferably 30 mgKOH/g to 200 mgKOH/g, more preferably 50 mgKOH/g to 150 mgKOH/g, and particularly preferably 70 mgKOH/g to 120 mgKOH/g.
Furthermore, the weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.
The content of the alkali-soluble resin in the coloring composition is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 12% by mass, and particularly preferably 3% by mass to 10% by mass, with respect to the total solid contents of the coloring composition.
The composition of the present invention may include may include one kind or two or more kinds of alkali-soluble resin. In the case where the composition includes two or more kinds of the alkali-soluble resin, the total amount thereof is preferably within the range.
<Other Components>
The coloring composition of the present invention may further contain other components such as an organic solvent, a crosslinking agent, a polymerization inhibitor, a surfactant, an organic carboxylic acid, and an organic carboxylic anhydride in addition to the respective components described above, within a range which does not diminish the effects of the present invention.
<<Organic Solvent>>
The coloring composition of the present invention may contain an organic solvent.
Basically, the organic solvent is not particularly limited as long as the solvent satisfies the solubility of the respective components or the coatability of the coloring composition. In particular, it is preferable to select the organic solvent in consideration of the solubility, coatability, and safety of an ultraviolet absorber, the alkali-soluble resin, the dispersant, or the like. In addition, when the coloring composition in the present invention is prepared, the composition preferably includes at least two kinds of organic solvents.
Suitable examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (for example, methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate)), alkyl 3-oxypropionate esters (for example, methyl 3-oxypropionate or ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, or ethyl 3-ethoxypropionate)), alkyl 2-oxypropionate esters (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, or propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, or ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methyl propionate and ethyl 2-oxy-2-methyl propionate (for example, methyl 2-methoxy-2-methyl propionate or ethyl 2-ethoxy-2-methyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethy ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-butanone; and aromatic hydrocarbons such as toluene and xylene.
From the viewpoint of the solubility of an ultraviolet absorber and the alkali-soluble resin, and improvement of the shape of the coated surface, it is also preferable to mix two or more kinds of these organic solvents with each other. In this case, a mixed solution consisting of two or more kinds selected from the aforementioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is particularly preferable.
From the viewpoint of coatability, the content of the organic solvent in the coloring composition is set such that the concentration of the total solid contents of the composition becomes preferably 5% by mass to 80% by mass, more preferably 5% by mass to 60% by mass, and particularly preferably 10% by mass to 50% by mass.
The composition of the present invention may include one kind or two or more kinds of organic solvent. In the case where the composition includes two or more kinds of the organic solvent, the total amount thereof is preferably within the range.
<<Crosslinking Agent>>
If a crosslinking agent is complementarily used in the coloring composition of the present invention, the hardness of the colored cured film obtained by curing the coloring composition can be improved.
The crosslinking agent is not particularly limited as long as it makes it possible to cure a film by a crosslinking reaction, and examples thereof include (a) an epoxy resin, (b) a melamine compound, a guanamine compound, a glycoluril compound, or a urea compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, and (c) a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Among these, a polyfunctional epoxy resin is preferable.
With regard to the details of specific examples of the crosslinking agent, reference can be made to the description of paragraphs “0134” to “0147” of JP2004-295116A.
The amount of the crosslinking agent blended into the composition of the present invention is not particularly limited, but is preferably 2% by mass to 30% by mass, and more preferably 3% by mass to 20% by mass, with respect to the total solid contents of the composition.
The composition of the present invention may include one kind or two or more kinds of crosslinking agent. In the case where the composition includes two or more kinds of the crosslinking agent, the total amount thereof is preferably within the range.
<<Polymerization Inhibitor>>
It is preferable to add a small amount of a polymerization inhibitor to the coloring composition of the present invention in order to suppress the occurrence of unnecessary thermal polymerization of the polymerizable compound during production or storage of the coloring composition.
Examples of the polymerization inhibitor which can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), and cerium (III) N-nitrosophenyl hydroxylamine.
The amount of the polymerization inhibitor added is preferably about 0.01% by mass to about 5% by mass, with respect to the total mass of the composition.
The composition of the present invention may include one kind or two or more kinds of polymerization inhibitor. In the case where the composition includes two or more kinds of the polymerization inhibitor, the total amount thereof is preferably within the range.
<<Surfactant>>
From the viewpoint of further improving coatability, various surfactants may be added to the coloring composition of the present invention. As the surfactants, it is possible to use various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and silicone-based surfactant.
Particularly, if the coloring composition of the present invention contains a fluorine-based surfactant, liquid characteristics (particularly, fluidity) are further improved when the composition is prepared as a coating liquid, whereby evenness of the coating thickness or liquid saving properties can be further improved.
That is, in the case where a coating liquid obtained by applying the coloring composition containing a fluorine-based surfactant is used to form a film, the surface tension between a surface to be coated and the coating liquid is reduced to improve wettability with respect to the surface to be coated, and enhance coatability with respect to the surface to be coated. Therefore, even in the case where a thin film of about several μm is formed of a small amount of liquid, the coloring composition containing a fluorine-based surfactant is effective in that a film with a uniform thickness which exhibits a small extent of thickness unevenness can be more suitably formed.
The fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-based surfactant in which the fluorine content is within this range is effective in terms of the thickness of the coating film or liquid saving properties, and solubility of the surfactant in the coloring composition is also good.
Examples of the fluorine-based surfactant include Megaface F171, Megaface F172, Megaface F173, Megaface F176, Megaface F177, Megaface F141, Megaface F142, Megaface F143, Megaface F144, MegafaceR30, Megaface F437, Megaface F475, Megaface F479, Megaface F482, Megaface F554, Megaface F780, and Megaface F781 (all manufactured by DIC Corporation), Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M), and aSurflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon SC-393, and Surflon KH-40 (all manufactured by ASAHI GLASS Co., Ltd.).
Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylate and propoxylate thereof (for example, glycerol propoxylate and glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2, and Tetronic 304, 701, 704, 901, 904, and 150R1 manufactured by BASF), and Solseperse 20000 manufactured by The Lubrizol Corporation, Japan.
Specific examples of the cationic surfactant include phthalocyanine derivatives (product name: EFKA-745 manufactured by MORISHITA SANGYO Corporation), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, and No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.), and W001 (manufactured by Yusho Co., Ltd.).
Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).
Examples of the silicone-based surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Toray Silicone SH21PA”, “Toray Silicone SH28PA”, “Toray Silicone SH29PA”, “Toray Silicone SH30PA”, and “Toray Silicone SH8400”, manufactured by Dow Corning Toray, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, and “TSF-4452”, manufactured by Momentive Performance Materials Inc., “KP341”, “KF6001”, and “KF6002”, manufactured by Shin-Etsu Silicones, and “BYK307”, “BYK323”, and “BYK330”, manufactured by BYK-Chemie.
The amount of the surfactant added is preferably 0.001% by mass to 2.0% by mass and more preferably 0.005% by mass to 1.0% by mass, with respect to the total mass of the coloring composition.
The composition of the present invention may include one kind or two or more kinds of surfactant. In the case where the composition includes two or more kinds of the surfactant, the total amount thereof is preferably within the range.
<<Organic Carboxylic Acid and Organic Carboxylic Anhydride>>
The coloring composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less, and/or an organic carboxylic anhydride.
Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid and an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid, tricarboxylic acids such as tricarballylic acid, and aconitic acid, and the like. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as a benzoic acid and a phthalic acid, and carboxylic acids in which a phenyl group is bonded to a carboxyl group via a carbon bond. Among these, carboxylic acids having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, and specifically, maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.
Examples of the organic carboxylic anhydride include aliphatic carboxylic anhydride and aromatic carboxylic anhydride. Specific examples thereof include aliphatic carboxylic anhydrides such as acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecylsuccinic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of the aromatic carboxylic anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly having a molecular weight of 50 to 500, specifically, for example, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.
The amount of these organic carboxylic acids and/or the organic carboxylic anhydrizdes added is generally in a range of 0.01% by weight to 10% by weight, preferably 0.03% by weight to 5% by weight, and more preferably 0.05% by weight to 3% by weight in the total solid contents.
The composition of the present invention may include one kind or two or more kinds of each of an organic carboxylic acid and/or organic carboxylic anhydride. In the case where the composition includes two or more kinds of the organic carboxylic acid and/or the organic carboxylic anhydride, the total amount thereof is preferably within the range.
By adding these organic carboxylic acids and/or the organic carboxylic anhydrides having a molecular weight of 1000 or less, it is possible to greatly reduce the amount of the residual undissolved substance of the coloring composition while maintaining a high degree of pattern adhesiveness.
If desired, various additives such as a filler, an adhesion promoting agent, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent may be blended into the coloring composition. Examples of these additives include those described in paragraphs “0155” and “0156” of JP2004-295116A, the contents of which are incorporated herein.
The coloring composition of the present invention can contain the sensitizer or the light stabilizer described in paragraph “0078” of JP2004-295116A, and the thermal polymerization inhibitor described in paragraph “0081” of JP2004-295116A.
The composition of the present invention may include one kind or two or more kinds of the respective components. In the case where the composition includes two or more kinds of the components, the total amount thereof is preferably within the range.
<Method for Preparing Coloring Composition>
The coloring composition of the present invention is prepared by mixing the aforementioned components together.
Incidentally, when the coloring composition is prepared, the respective components constituting the coloring composition may be mixed together at the same time or mixed together sequentially after being dissolved and dispersed in a solvent. Further, the order of adding the components and the operation conditions during the mixing are not particularly restricted. For example, all the components may be dissolved and dispersed in a solvent at the same time to prepare the composition. Alternatively, if desired, the respective components may be appropriately prepared as two or more solutions and dispersions and mixed at the time of use (at the time of coating) to prepare the composition.
The coloring composition prepared as above can be provided for use after being filtered using a filter having a pore diameter of preferably about 0.01 μm to 3.0 μm, and more preferably about 0.05 μm to 0.5 μm, or the like.
The coloring composition of the present invention is preferably used for forming a colored layer of a color filter. More specifically, since the coloring composition of the present invention can form a colored cured film having excellent heat resistance and color characteristics, it is suitably used for forming a colored pattern (colored layer) of a color filter. Further, the coloring composition of the present invention can be suitably used for forming a colored pattern of a color filter or the like used in a solid-state image sensor (for example, a CCD and a CMOS) or an image display device such as a liquid crystal display (LCD). Further, the composition can also be suitably used in an application of the manufacture of a print ink, an ink jet ink, a coating material, or the like. Among these, the composition can be suitably used in an application of the manufacture of a color filter for a solid-state image sensor such as a CCD and a CMOS.
<Colored Cured Film, Pattern Forming Method, Color Filter, and Method for Producing Color Filter>
Next, the colored cured film, the pattern forming method, and the color filter according to the present invention will be described in detail by an explanation of production methods thereof.
The colored cured film of the present invention is formed by curing the coloring composition of the present invention. Such a colored cured film is preferably used in a color filter.
The pattern forming method of the present invention may include a step of applying the coloring composition of the present invention onto a support to form a coloring composition layer, a step of patternwise exposing the coloring composition layer, and a step of removing an unexposed area by development to form a colored pattern.
The pattern forming method of the present invention can be suitably applied for forming a colored pattern (pixel) included in a color filter. With the composition of the present invention, a color filter may be produced by forming a pattern using a so-called photolithography method and a pattern may be formed by a dry etching method.
That is, a first method for producing a color filter of the present invention includes a coloring composition layer forming step of applying the coloring composition of the present invention onto a support to form a coloring composition layer, an exposing step of patternwise exposing the coloring composition layer, and a pattern forming step of removing an unexposed area by development to form a colored pattern.
Furthermore, a second method for producing a color filter of the present invention includes a step of applying the coloring composition of the present invention onto a support to form a coloring composition layer, followed by curing, to form a colored layer, a step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of thy-etching the colored layer using the resist pattern as an etching mask.
In the present invention, production using a photolithography method is more preferable.
Hereinafter, details of these will be described.
The respective steps in the pattern forming method of the present invention will be described in detail below with reference to the method for producing a color filter for a solid-state image sensor, but the present invention is not limited to this method. Hereinafter, the color filter for a solid-state image sensor may be simply referred to as a “color filter” in some cases.
<<Coloring Composition Layer Forming Step>>
In the coloring composition layer forming step, the coloring composition of the present invention is provided on a support to form a coloring composition layer forming step.
As the support which can be used in the present step, for example, it is possible to use a substrate for a solid-state image sensor, which is formed by providing an image sensor (light-receiving element) such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS) onto a substrate (for example, a silicon substrate).
The colored pattern of the present invention may be formed on the surface (front surface) on which an image sensor is formed or on the surface (back surface) where an image sensor is not formed, of a substrate for a solid-state image sensor.
A light shielding film may be disposed between the colored pattern in a solid-state image sensor or onto the back surface of the substrate for a solid-state image sensor.
In addition, if desired, an undercoat layer may be disposed onto the support in order to improve adhesiveness between the support and the upper layer, prevent diffusion of substances, or planarize the substrate surface. A solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, or the like can be blended into the undercoat layer, and it is preferable that these respective components are properly selected from the components blended into the aforementioned composition of the present invention.
As the method for applying the coloring composition of the present invention onto the support, various coating methods such as slit coating, ink jet coating, spin coating, cast coating, roll coating, and screen printing can be applied.
Drying (pre-baking) of the coloring composition layer applied onto the support can be carried out using a hot plate, an oven, or the like at a temperature of 50° C. to 140° C. for 10 seconds to 300 seconds.
<Pattern Forming Step by Photolithography Method>
<<Exposing Step>>
In the exposing step, the coloring composition layer formed in the coloring composition layer forming step is patternwise exposed through a mask having a predetermined mask pattern by using, for example, an exposure device such as a stepper. Thus, a colored cured film is obtained.
As radiation (light) usable in exposure, particularly, ultraviolet rays such as a g-ray and an i-ray are preferably used (particularly, an i-ray is preferably used). The irradiation dose (exposure dose) is preferably from 30 mJ/cm2 to 1500 mJ/cm2, more preferably from 50 mJ/cm2 to 1000 mJ/cm2, and particularly preferably from 80 mJ/cm2 to 500 mJ/cm2.
The film thickness of the colored cured film is preferably from 1.0 μm or less, more preferably from 0.1 μm to 0.9 μm, and still more preferably from 0.2 μm to 0.8 pin.
It is preferable to set the film thickness to be 1.0 μm or less since a high degree of resolution and adhesiveness are obtained.
Moreover, in this step, a colored cured film having a small film thickness of 0.7 μm or less can be suitably formed. Further, if the obtained colored cured film is subjected to a development process in a pattern forming step which will be described later, it is possible to obtain a thin film having a colored pattern which exhibits excellent developability and reduced surface roughness and has an excellent pattern shape.
<<Developing Step>>
Thereafter, by performing an alkaline developing treatment, the coloring composition layer in an area not irradiated with light in the exposing step is eluted into an aqueous alkaline solution, and as a result, only a photocured area remains.
As a developing liquid, an organic alkaline developing liquid not damaging an image sensor, a circuit, or the like in an underlayer is preferable. The development temperature is usually from 20° C. to 30° C., and the development time is from 20 seconds to 90 seconds in the related art. In order to further remove residues, development may be carried out for 120 seconds to 180 seconds. Further, in order to improve residue removal properties, a step of sufficiently shaking the developing liquid every 60 seconds and newly supplying a developing liquid is repeated plural times in some cases.
Examples of an alkaline agent used for the developing liquid include organic alkaline compounds such as aqueous ammonia, ethylamine, diethylamine, dimethyl ethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. An aqueous alkaline solution obtained by diluting these alkaline agents with pure water so as to yield a concentration of the alkaline agent of 0.001% by mass to 10% by mass, and preferably 0.01% by mass to 1% by mass is preferably used as the developing liquid.
Incidentally, inorganic alkali may be used for the developing liquid, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, and the like are preferable.
Furthermore, in the case where a developing liquid formed of such an aqueous alkaline solution is used, the pattern is generally cleaned (rinsed) with pure water after development.
Next, it is preferable to carry out a heating treatment (post-baking) after drying. If a multi-colored pattern is formed, the above steps can be sequentially repeated for each color to produce a cured coat. Thus, a color filter is obtained.
The post-baking is a heating treatment performed after development so as to complete curing, and in the post-baking, a thermal curing treatment is carried out generally at 100° C. to 240° C. and preferably at 200° C. to 240° C.
The post-baking treatment can be carried out on the coating film obtained after development in a continuous or batch manner, by using heating means such as a hot plate, a convection oven (a hot-air circulation type drier), and a high-frequency heater under the conditions described above.
<Case of Forming Pattern by Dry Etching Method>
With the colored layer, the dry etching can be carried out with an etching gas, using a patterned photoresist layer as a mask. Specifically, a positive-type or negative-type radiation-sensitive composition is applied onto the colored layer and dried to from a photoresist layer. In the formation of the photoresist layer, it is preferable to further carry out a pre-bake treatment. In particular, as a process for forming a photoresist, a configuration in which a post-exposure heating treatment (PEB) or a post-development heating treatment (postbake treatment) is carried out is preferable.
As the photoresist, for example, a positive-type radiation-sensitive composition is used. As the positive-type radiation-sensitive composition, a positive-type resist composition suitable for a positive-type photoresist, which responds to radiation, for example, an ultraviolet ray (a g-ray, an h-ray, or an i-ray), a far ultraviolet ray including an excimer laser and the like, an electron beam, an ion beam, or an X-ray, is used. Among the radiations, a g-ray, an h-ray, or an i-ray is preferable, among which the i-ray is more preferable for the exposure.
Specifically, as the positive-type radiation-sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. The positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin utilizes that a quinonediazide group is decomposed into a carboxyl group by light irradiation at a wavelength of 500 nm or less and as a result, the quinonediazide compound is shifted from an alkali-insoluble state to an alkali-soluble state. Since this positive-type photoresist is remarkably excellent in the resolving power, it is used for the manufacture of an integrated circuit, for example, IC and LSI. Examples of the quinonediazide compound include a naphthoquinonediazide compound. Examples of commercially available products thereof include “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.).
The thickness of the photoresist layer is preferably from 0.1 μm to 3 μm, more preferably from 0.2 μm to 2.5 and still more preferably from 0.3 μm to 2 μm. Incidentally, coating of the photoresist layer can be suitably carried out using the coating method described with respect to the above-described colored layer.
Next, a resist pattern (patterned photoresist layer) in which a resist through-hole group is disposed is formed by exposing and developing the photoresist layer. The formation of the resist pattern can be carried out by appropriately optimizing heretofore known techniques of photolithography without particular limitation. By providing the resist through-hole group in the photoresist layer by exposure and development, the resist pattern which is used as an etching mask in the subsequent etching is provided on the colored layer.
Exposure of the photoresist layer can be carried out by exposing a positive-type or negative-type radiation-sensitive composition to a g-ray, an h-ray, or an i-ray, and preferably to an i-ray through a predetermined mask pattern. After the exposure, a development treatment is carried out using a developing liquid to remove the photoresist corresponding to the region where a colored pattern is to be formed.
As the developing liquid, any developing liquid which does not affect a colored layer containing a coloring agent and dissolves the exposed area of a positive resist or the uncured area of a negative resist may be used, and for example, a combination of various organic solvents or an aqueous alkaline solution is used. As the aqueous alkaline solution, an aqueous alkaline solution prepared by dissolving an alkaline compound to yield a concentration of 0.001% by mass to 10% by mass, and preferably 0.01% by mass to 5% by mass is suitable. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. Incidentally, in the case where an aqueous alkaline solution is used as the developing liquid, a cleaning treatment with water is generally carried out after development.
Next, the colored layer is patterned by dry etching so as to form a through-hole group in the colored layer using the resist pattern as an etching mask. Thus, a colored pattern is formed. The through-hole group is provided checkerwise in the colored layer. Thus, a first colored pattern having the through-hole group provided in the colored layer has a plurality of first quadrangular colored pixels checkerwise.
Specifically, the dry etching is carried out by dry etching the colored layer using the resist pattern as an etching mask. Representative examples of the dry etching include the methods described in JP1984-126506A (JP-S59-126506A) JP1984-46628A (JP-S59-46628A), JP1983-9108A (JP-S58-9108A), JP1983-2809A (JP-S58-2809A), JP1982-148706A (JP-S57-148706A), JP1986-41102A (JP-S61-41102A) or the like.
It is preferable that the dry etching is carried out in a configuration as described below from the viewpoint of forming a pattern cross-section closer to that of a rectangle or of further reducing damage to a support.
A configuration is preferable, which includes a first-stage etching of etching up to an area (depth) where the support is not revealed by using a mixed gas of a fluorine-based gas and a oxygen gas (O2), a second-stage etching of preferably etching up to the vicinity of an area (depth) where the support is revealed by using a mixed gas of a nitrogen gas (N2) and an oxygen gas (O2) after the first-stage etching, and an over-etching carried out after the support has been revealed. A specific manner of the dry etching as well as the first-stage etching, the second-stage etching, and the over-etching will be described below.
The dry etching is carried out by determining the etching conditions in advance in the following manner.
(1) An etching rate (nm/min) in the first-stage etching and an etching rate (nm/min) in the second-stage etching are calculated, respectively. (2) A time for etching a predetermined thickness in the first-stage etching and a time for etching a predetermined thickness in the second-stage etching are respectively calculated. (3) The first-stage etching is carried out according to the etching time calculated in (2) above. (4) The second-stage etching is carried out according to the etching time calculated in (2) above. Alternatively, an etching time is determined by endpoint detection, and the second-stage etching may be carried out according to the etching time determined. (5) The over-etching time is calculated in response to the total time of (3) and (4) above, and the over-etching is carried out.
The mixed gas used in the first-stage etching step preferably contains a fluorine-based gas and an oxygen gas (O2) from the viewpoint of processing an organic material of the film to be etched into a rectangle shape. The first-stage etching step may avoid damage to the support by adopting the configuration of etching up to an area where the support is not revealed. After the etching is carried out up to an area where the support is not revealed by the mixed gas of a fluorine-based gas and an oxygen gas in the first-stage etching step, etching treatment in the second-stage etching step and etching treatment in the over-etching step are preferably carried out by using the mixed gas of a nitrogen gas and an oxygen gas from the viewpoint of avoiding damage to the support.
It is important that a ratio between the etching amount in the first-stage etching step and the etching amount in the second-stage etching step is determined so as not to deteriorate the rectangularity by the etching treatment in the first-stage etching step. The ratio of the etching amount in the second-stage etching step in the total etching amount (the sum of the etching amount in the first-stage etching step and the etching amount in the second-stage etching step) is preferably in a range of more than 0% and 50% or less, and more preferably from 10% to 20%. The etching amount means an amount determined by a difference between the remaining film thickness of the film etched and the film thickness of the film before the etching.
Furthermore, the etching preferably includes an over-etching treatment. The over-etching treatment is preferably carried out by determining an over-etching rate. The over-etching rate is preferably calculated from an etching treatment time which is carried out at first. Although the over-etching rate may be arbitrarily determined, it is preferably 30% or less, more preferably from 5% to 25%, particularly preferably from 10% to 15%, of the etching processing time in the etching steps from the viewpoint of etching resistance of photoresist and preservation of the rectangularity of the etched pattern.
Next, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes a step of supplying a peeling solution or a solvent on the resist pattern to make the resist pattern be in a removable state, and a step of removing the resist pattern using cleaning water.
The step of supplying a peeling solution or a solvent on the resist pattern to make the resist pattern be in a removable state includes, for example, a step of paddle development by supplying a peeling solution or a solvent at least on the resist pattern and retaining for a predetermined time. The time for retaining the peeling solution or a solvent is not particularly limited, and is preferably from several tens of seconds to several minutes.
Moreover, the step of removing the resist pattern using cleaning water includes, for example, a step of removing the resist pattern by spraying cleaning water from a spray-type or shower-type spray nozzles onto the resist pattern. As the cleaning water, pure water is preferably used. The spray nozzles include a spray nozzles having a spray area which covers the entire support and mobile spray nozzles having a mobile area which covers the entire support. In the case where the spray nozzles are mobile spray nozzles, the resist pattern can be more effectively removed by moving the mobile spray nozzles twice or more from the center of support to the edge of the support to spray cleaning water in the step of removing the resist pattern.
The peeling solution generally contains an organic solvent and may further contain an inorganic solvent. Examples of the organic solvent include 1) a hydrocarbon-based compound, 2) a halogenated hydrocarbon-based compound, 3) an alcohol-based compound, 4) an ether- or acetal-based compound, 5) a ketone- or aldehyde-based compound, 6) an ester-based compound, 7) a polyhydric alcohol-based compound, 8) a carboxylic acid- or its acid anhydride-based compound, 9) a phenol-based compound, 10) a nitrogen-containing compound, 11) a sulfur-containing compound, and 12) a fluorine-containing compound. The peeling solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.
The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples thereof include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine, among which monoethanolamine, diethanolamine, and triethanolamine are preferable, and monoethanolamine (H2NCH2CH2OH) is more preferable. Further, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ∈-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2-pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenyl morpholine, 2,4-lutidine, and 2,6-lutidine, among which N-methyl-2-pyrrolidone and N-ethyl morpholine are preferable, and N-methyl-2-pyrrolidone (NMP) is more preferable.
The peeling solution preferably contains both the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound, more preferably contains at least one selected from monoethanolamine, diethanolamine, and triethanolamine as the acyclic nitrogen-containing compound, and at least one selected from N-methyl-2-pyrrolidone and N-ethyl morpholine as the cyclic nitrogen-containing compound, and still more preferably contains monoethanolamine and N-methyl-2-pyrrolidone.
In the removal with the peeling solution, it is sufficient that the resist pattern formed on the first colored pattern is removed, and in a case where a deposit of an etching product is attached to the side wall of the first colored pattern, it is not always necessary to completely remove the deposit. The deposit means an etching product attached and deposited to the side wall of colored layer.
For the peeling solution, it is preferable that the content of the acyclic nitrogen-containing compound is from 9 parts by mass to 11 parts by mass based on 100 parts by mass of the peeling solution, and the content of the cyclic nitrogen-containing compound is from 65 parts by mass to 70 parts by mass based on 100 parts by mass of the peeling solution. The peeling solution is preferably one prepared by diluting a mixture of the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.
Incidentally, if desired, the production method of the present invention may include, as a step other than the above steps, a step known as a method for producing a color filter for a solid-state image sensor. For example, in the production method, if desired, a curing step of curing the funned colored pattern by heating and/or exposure may be carried out after the coloring composition layer forming step, the exposing step, and the pattern forming step are carried out.
In the case where the coloring composition according to the present invention is used, for example, a nozzle of an ejection portion or a piping portion of a coating device is clogged, or the coloring composition or a pigment adheres to or is precipitated or dried inside the coating machine, and as a result, contamination and the like occur in some cases. Therefore, in order to efficiently clean off the contamination caused by the coloring composition of the present invention, it is preferable to use the aforementioned solvent relating to the present composition as a cleaning liquid. In addition, the cleaning liquids described in JP1995-128867A (JP-H07-128867A), JP1995-146562A (JP-H07-146562A), JP1996-278637A (JP-H08-278637A), JP2000-273370A, JP2006-85140A, JP2006-291191A, JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can also be suitably used to clean and remove the coloring composition according to the present invention.
Among the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferable.
These solvents may be used alone or as a mixture of two or more kinds thereof. In the case where two or more kinds thereof are mixed, it is preferable to mix a solvent having a hydroxyl group with a solvent not having a hydroxyl group. The mass ratio between the solvent having a hydroxyl group and the solvent not having a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and still more preferably 20/80 to 80/20. A mixed solvent in which propylene glycol monomethyl ether acetate (PGMEA) is mixed with propylene glycol monomethyl ether (PGME) at a ratio of 60/40 is particularly preferable. Incidentally, in order to improve the permeability of the cleaning liquid with respect to the contaminant, it is preferable to add the aforementioned surfactants relating to the present composition to the cleaning liquid.
Since the color filter of the present invention uses the coloring composition of the present invention, exposure having an excellent exposure margin can be carried out, and the formed colored pattern (colored pixel) has an excellent pattern shape. Further, since the surface roughness of the pattern and the amount of residues in a developed area are inhibited, excellent color characteristics are exhibited.
The color filter of the present invention can be suitably used for a solid-state image sensor such as a CCD and a CMOS, and is particularly preferable for a CCD, a CMOS, and the like with a high resolution, having more than 1,000,000 pixels. The color filter for a solid-state image sensor of the present invention can be used as, for example, a color filter disposed between a light-receiving portion of each pixel constituting a CCD or a CMOS and a microlens for condensing light.
Incidentally, the film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less.
Moreover, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.
<Solid-State Image Sensor>
The solid-state image sensor of the present invention includes the above-described color filter of the present invention. The constitution of the solid-state image sensor of the present invention is not particularly limited as long as the solid-state image sensor is constituted to include the color filter in the present invention and functions as a solid-state image sensor. However, for example, the solid-state image sensor can be constituted as below.
That is a constitution in which transfer electrodes consisting of a plurality of photodiodes and transfer electrodes formed of polysilicon or the like constituting a light-receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) are arranged onto a support; a light shielding film which is opened only to the light-receiving portion of the photodiode and is formed of tungsten or the like is disposed onto the photodiodes and the transfer electrodes; a device protecting film which is formed for covering the entire surface of the light shielding film and the light receiving portion of the photodiodes and is formed of silicon nitride or the like is disposed onto the light shielding film; and the color filter for a solid-state image sensor of the present invention is disposed onto the device protecting film.
In addition, the solid-state image sensor may have a constitution in which light-condensing means (for example, a microlens or the like, which shall apply hereinafter) is disposed to a portion positioned on the device protecting portion and under the color filter (side close to the support), a constitution in which light-condensing means is disposed on the color filter, and the like.
<Image Display Device>
The color filter of the present invention can be used not only for the solid-state image sensor, but also for an image display device such as a liquid crystal display device or an organic EL display device. In particular, the color filter is suitable for the applications of a liquid crystal display device. The liquid crystal display device having the color filter of the present invention can display a high-quality image showing good color shade and having excellent display characteristics.
The definition of display devices or details of the respective display devices are described in, for example, “Electronic Display Device (Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., 1990)”, “Display Device (Toshiyuki Ibuki, Sangyo Publishing Co., Ltd., published in 1989), and the like. In addition, the liquid crystal display device is described in, for example, “Liquid Crystal Display Technology for Next Generation (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, the present invention can be applied to liquid crystal display devices employing various systems described in the “Liquid Crystal Display Technology for Next Generation”.
The color filter of the present invention may be used for a liquid crystal display device using a color TFT system. The liquid crystal display device using a color TFT system is described in, for example, “Color TFT Liquid Crystal Display (KYORITSU SHUPPAN Co., Ltd., published in 1996)”. Further, the present invention can be applied to a liquid crystal display device having an enlarged view angle, which uses an in-plane switching driving system such as in-plane switching (IPS) and a pixel division system such as MVA, or to STN, TN, VA, OCS, FFS, R-OCB, and the like.
In addition, the color filter in the present invention can be provided to a Color-filter On Array (COA) system which is a bright and high-definition system. In the liquid crystal display device of the COA system, the characteristics required for a color filter layer need to include characteristics required for an interlayer insulating film, that is, a low dielectric constant and resistance to a peeling solution in some cases, in addition to the generally required characteristics as described above. In the color filter of the present invention, a dye multimer having an excellent hue is used. Accordingly, the color purity, light-transmitting properties, and the like are excellent, and the color shade of the colored pattern (pixel) is excellent. Consequently, a liquid crystal display device of a COA system which has a high resolution and is excellent in long-term durability can be provided. Incidentally, in order to satisfy the characteristics required for a low dielectric constant, a resin coat may be provided on the color filter layer.
These image display systems are described in, for example, p. 43 of “EL, PDP, and LCD Display Technologies and Recent Trend in Market (TORAY RESEARCH CENTER, Research Department, published in 2001)”, and the like.
The liquid crystal display device including the color filter in the present invention is constituted with various members such as an electrode substrate, a polarizing film, a phase difference film, a backlight, a spacer, and a view angle compensation film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted with these known members. These members are described in, for example, “'94 Market of Peripheral Materials And Chemicals of Liquid Crystal Display (Kentaro Shima, CMC Publishing Co., Ltd., published in 1994)” and “2003 Current Situation of Market Relating to Liquid Crystal and Prospects (Vol. 2) (Yoshikichi Hyo, Fuji Chimera Research Institute, Inc., published in 2003)”.
The backlight is described in SID Meeting Digest 1380 (2005) (A. Konno, et al.), December Issue of Monthly “Display”, 2005, pp. 18-24 (Yasuhiro Shima) and pp. 25-30 (Takaaki Hagi) of the literature, and the like.
If the color filter in the present invention is used in a liquid crystal display device, high contrast can be realized when the color filter is combined with a three-wavelength tube of a cold cathode tube known in the related art. Further, if a light source of LED in red, green, and blue (RGB-LED) is used as a backlight, a liquid crystal display device having high luminance, high color purity, and good color reproducibility can be provided.
EXAMPLES
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to Examples as long as the object of the present invention is not impaired. Incidentally, “%” and “part(s)” are based on mass unless otherwise specified.
Synthesis Example 1
Synthesis of Dye Multimer (S-1)




20.0 g (41.8 mmol) of rhodamine B was dissolved in 125 g of chloroform, and then 9.6 g (62.6 mmol) of phosphorus oxychloride was added dropwise thereto while cooling in an ice bath. Then, the mixture was heated at an external temperature of 65° C. for 3 hours. After cooling to 20° C., 9.8 g (75.2 mmol) of 2-hydroxyethyl methacrylate was added to the mixture while cooling in an ice bath, and 30.8 g (304 mmol) of triethylamine was added thereto. After stirring for 3 hours at an internal temperature set to 20° C., 100 g of chloroform was added thereto, the mixture was subjected to liquid separation with water, and then the chloroform layer was concentrated. The obtained concentrate was added to 100 mL of methanol, and 16.4 g (41.8 mmol) of a tetrabutyl ammonium trifluoromethyl sulfonate salt was added thereto. The mixture was subjected to liquid separation with 200 mL of ethyl acetate and 100 mL of water, and the ethyl acetate layer was concentrated to obtain 18.2 g of a monomer X.
The monomer X (8.2 g), methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g), and propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as “PGMEA”) (23.3 g) were put into a three-neck flask, and the solution was heated at 80° C. in a nitrogen atmosphere. To this solution, a mixed solution of a monomer 1 (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), dimethyl 2,2′-azobis(isobutyrate) [product name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g), and PGMEA (23.3 g) was added dropwise for 2 hours. Thereafter, the mixture was stirred for 3 hours, then warmed to 90° C., heated and stirred for 2 hours, and then left to be cooled to obtain a PGMEA solution of an intermediate (MD-1). After cooling, the solution was added dropwise to a mixed solvent of methanol/ion exchange water=100 mL/10 mL to perform reprecipitation. The solution was dried at 40° C. by air-blowing for 2 days to obtain 7.6 g of a dye multimer (S-1).
The weight-average molecular weight (Mw) of the dye multimer (S-1) confirmed by GPC measurement was 7,000. Further, the acid value as measured by titration using a 0.1 N aqueous sodium hydroxide solution was 35 mgKOH/g.
Synthesis Examples 2 to 32
Synthesis of Dye Multimers (S-2) to (S-31), and (S-H1)
Dye multimers (S-2) to (S-31), and (S-H1) were obtained by performing the same operation as in Synthesis Example 1, except that the monomers and the introduction amounts of the monomer X and the methacrylic acid were changed to those corresponding to the repeating unit 1 and the repeating unit 2 described in the following table in Synthesis Example 1, respectively.
Synthesis Example 33
Synthesis of Dye Multimer (S-32)




The monomer X (7.4 g), methacrylic acid (1.4 g), dodecyl mercaptan (0.255 g), and propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as “PGMEA”) (17.6 g) were put into a three-neck flask, and the solution was heated at 80° C. in a nitrogen atmosphere. To this solution, a mixed solution of a monomer X (7.4 g), methacrylic acid (1.4 g), dodecyl mercaptan (0.255 g), dimethyl 2,2′-azobis(isobutyrate) [product name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g), and PGMEA (17.6 g) was added dropwise for 2 hours. Then, the mixture was stirred for 3 hours, then warmed to 90° C., and then heated and stirred for 2 hours. Thereafter, 2.3 g of glycidyl methacrylate and 0.020 g of tetrabutylammonium bromide were added thereto, and the mixture was heated at 105° C. for 15 hours. After cooling, the mixture was added dropwise to a mixed solvent of methanol/ion exchange water=100 mL/10 mL to perform reprecipitation. The solution was dried at 40° C. by air-blowing for 2 days to obtain 17.5 g of a dye multimer (S-32).
The weight-average molecular weight (Mw) of the dye multimer (S-32) confirmed by GPC measurement was 7,200. Further, the acid value as measured by titration using a 0.1 N aqueous sodium hydroxide solution was 50 mgKOH/g.
Synthesis Example 34
Synthesis of Dye Multimer (S-33)




The monomer X (6.9 g), methacrylic acid (0.8 g), 2-hydroxyethyl methacrylate (1.0 g), dodecyl mercaptan (0.255 g), and propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as “PGMEA”) (17.6 g) were put into a three-neck flask, and the solution was heated at 80° C. in a nitrogen atmosphere. To this solution, a mixed solution of a monomer X (6.9 g), methacrylic acid (0.8 g), 2-hydroxyethyl methacrylate (1.0 g), dodecyl mercaptan (0.255 g), dimethyl 2,2′-azobis(isobutyrate) [product name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g), and PGMEA (17.6 g) was added dropwise for 2 hours. Then, after stirring for 3 hours, the mixture was warmed to 90° C., and heated and stirred for 2 hours. Next, 2.5 g of 2-isocyanatoethyl methacrylate and 0.020 g of monobutyl tin dioxide were added thereto, and the mixture was heated at 80° C. for 5 hours. After cooling, the mixture was added dropwise to a mixed solvent of methanol/ion exchange water=100 mL/10 mL to perform reprecipitation. The solution was dried at 40° C. by air-blowing for 2 days to obtain 17.2 g of a dye multimer (S-33).
The weight-average molecular weight (Mw) of the dye multimer (S-33) confirmed by GPC measurement was 8,200. Further, the acid value as measured by titration using a 0.1 N aqueous sodium hydroxide solution was 53 mgKOH/g.












TABLE 3








Repeating unit 1
Repeating unit 2


Acid
















Dye partial
Counter
Introduction

Introduction
Repeating

value



structure
anion
amount (g)
Monomer
amount (g)
unit 3
Mw
mgKOH/g


















(S-1)
(a-xt-7)
(a-1) 
8.2
Methacrylic acid
0.46
—
7000
35


(S-2)
(a-xt-7)
(a-2) 
8.2
Methacrylic acid
0.59
—
7200
44


(S-3)
(a-xt-7)
(a-3) 
8.2
Methacrylic acid
0.48
—
6500
36


(S-4)
(a-xt-7)
(a-4) 
8.2
Methacrylic acid
0.65
—
6000
48


(S-5)
(a-xt-7)
(a-5) 
8.2
Methacrylic acid
0.71
—
5500
52


(S-6)
(a-xt-7)
(a-6) 
8.2
Methacrylic acid
0.49
—
6800
37


(S-7)
(a-xt-7)
(a-7) 
8.2
Methacrylic acid
0.55
—
6500
41


(S-8)
(a-xt-7)
(a-8) 
8.2
Methacrylic acid
0.52
—
5400
39


(S-9)
(a-xt-7)
(a-9) 
8.2
Methacrylic acid
0.76
—
5800
55


(S-10)
(a-xt-7)
(a-10)
8.2
Methacrylic acid
0.68
—
6000
50


(S-11)
(a-xt-7)
(a-11)
8.2
Methacrylic acid
0.61
—
7200
45


(S-12)
(a-xt-7)
(a-12)
8.2
Methacrylic acid
0.71
—
6400
52


(S-13)
(a-xt-7)
(a-13)
8.2
Methacrylic acid
0.70
—
6800
51


(S-14)
(a-xt-7)
(a-14)
8.2
Methacrylic acid
0.74
—
7000
54


(S-15)
(a-xt-7)
(a-15)
8.2
Methacrylic acid
0.73
—
8000
53


(S-16)
(a-xt-7)
(a-16)
8.2
Methacrylic acid
0.56
—
6700
42


(S-17)
(a-xt-7)
(a-17)
8.2
Methacrylic acid
0.58
—
6600
43


(S-18)
(a-xt-7)
(a-18)
8.2
Methacrylic acid
0.61
—
5500
45


(S-19)
(a-xt-7)
(a-19)
8.2
Methacrylic acid
0.59
—
6800
44


(S-20)
(a-xt-7)
BF4−
8.2
Methacrylic acid
0.61
—
6200
45


(S-21)
(a-xt-7)
PF6−
8.2
Methacrylic acid
0.77
—
6100
56


(S-22)
(A-pm-1)
(a-11)
8.2
Methacrylic acid
0.64
—
6800
47


(S-23)
(A-tp-1)
(a-11)
8.2
Methacrylic acid
0.52
—
7100
39


(S-24)
(A-SP-1)
(a-11)
8.2
Methacrylic acid
0.51
—
5900
38


(S-25)
(A-pm-1)
(a-11)
8.2
Methacrylic acid
0.71
—
5800
52


(S-26)
(a-xt-1)
(a-11)
8.2
Methacrylic acid
0.76
—
6500
55


(S-27)
(a-xt-5)
(a-11)
8.2
Methacrylic acid
0.77
—
6800
56


(S-28)
(a-xt-9)
(a-11)
8.2
Methacrylic acid
0.86
—
6200
62


(S-29)
 (a-xt-11) 
(a-11)
8.2
Methacrylic acid
0.77
—
5800
56


(S-30)
(a-xt-5)
(a-11)
8.2
Acrylic acid
0.66
—
6800
58


(S-31)
(a-xt-5)
(a-11)
8.2
Styrene
1.48
—
6500
58






carboxylic acid






(S-32)
(a-xt-7)
(a-1) 
7.4
Methacrylic acid
1.40
Repeating
7200
50








unit (a)




(S-33)
(a-xt-7)
(a-1) 
6.9
Methacrylic acid
0.80
Repeating
8200
53








unit (b)




(S-H1)
(a-xt-5)
Cl−
8.2
Methacrylic acid
0.80
—
6500
58









The dye partial structures shown in the above table are expressed by the numbers of the specific examples of the aforementioned dye multimers. The counter anions are also expressed by the numbers of the specific examples of the aforementioned counter anions except for —BF4−, —PF6−, and —Cl−. In the above table above, Mw represents the weight-average molecular weights of the dye multimers.
Furthermore, in the above table, the repeating unit (a) and the repeating unit (b) represent the following structures, respectively.




1. Preparation of Resist Solution
A resist solution for an undercoat layer was prepared by mixing and dissolving components having the following composition.
<Composition of Resist Solution for Undercoat Layer>













Solvent: propylene glycol monomethyl ether acetate
19.20 parts


(PGMEA)



Solvent: ethyl lactate
36.67 parts


Alkali-soluble resin: 40% PGMEA solution of benzyl
30.51 parts


methacrylate/methacrylic acid/2-hydroxyethyl



methacrylate copolymer (molar ratio = 60/22/18,



weight-average molecular weight of 15,000,



number-average molecular weight of 9,000)



Ethylenically unsaturated double bond-containing
12.20 parts


compound: dipentaerythritol hexaacrylate



Polymerization inhibitor: p-methoxyphenol
 0.0061 parts


Fluorine-based surfactant: F-475, manufactured by
 0.83 parts


DIC Corporation



Photopolymerization initiator: trihalomethyl
 0.586 parts


triazine-based photopolymerization initiator



(TAZ-107, manufactured by Midori Kagaku Co., Ltd.)









2. Manufacture of Undercoat Layer-Attached Silicon Wafer Substrate
A 6-inch silicon wafer was heated in an oven at 200° C. for 30 minutes. Next, the resist solution was applied onto this silicon wafer such that the dry film thickness became 1.5 μm. Further, the resultant was further heated and dried in an oven at 220° C. for 1 hour to form an undercoat layer, thereby obtaining an undercoat layer-attached silicon wafer substrate.
3. Preparation of Coloring Composition
3-1. Preparation of Blue Pigment Dispersion
A blue pigment dispersion 1 was prepared in the following manner.
A mixed solution consisting of 13.0 parts of C. I. Pigment Blue 15:6 (blue pigment, average particle size of 55 nm), 5.0 parts of Disperbyk111 as a pigment dispersant, and 82.0 parts of PGMEA was mixed and dispersed for 3 hours by a beads mill (zirconia beads having a diameter of 0.3 mm) to prepare a pigment dispersion. Thereafter, the pigment dispersion was further subjected to a dispersion treatment under a pressure of 2000 kg/cm3 and at a flow rate of 500 g/min, by using a high-pressure dispersing machine equipped with a depressurizing mechanism, NANO-3000-10 (manufactured by Nihon B.E.E Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion 1 (a dispersion of C. I. Pigment Blue 15:6, pigment concentration of 13%) used in the coloring compositions of Examples or Comparative Examples.
For the obtained blue pigment dispersion, the particle size of the pigment was measured using a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), and as a result, was found to be 24 nm.
A red pigment dispersion was prepared in the same manner as for Preparation of Blue Pigment Dispersion 1 above, except that a combination of the pigment shown in the following table and Disperbyk111 was used instead of the combination of C. I. Pigment Blue 15:6 used as the blue pigment and Disperbyk111 as the pigment dispersant in the blue pigment dispersion 1 in “3-1. Preparation of Blue Pigment Dispersion”.
Incidentally, details of the pigment (PR254) shown in the table are as follows.
 ̃Red Pigment ̃

    
    
        C. I. Pigment Red 254 (PR254) (particle size of 26 nm)
    
    


3-2. Preparation of Coloring Composition
(1) Coloring Compositions of Examples 1 to 42 and Comparative Examples 1 and 2
The following respective components were mixed and dissolved to obtain the respective coloring compositions of Examples 1 to 42 and Comparative Examples 1 and 2.













Cyclohexanone
1.133 parts


Alkali-soluble resin (J1 or J2 shown below: the compound shown in the following
0.030 parts


table)



Solsperse 20000 (1% cyclohexane solution, manufactured by The Lubrizol
0.125 parts


Corporation)



Photopolymerization initiator ((I-1) to (I-8) shown below: the compound described
0.012 parts


in the following table)



Dye multimer (the compound described in the following table) (provided that in
0.040 parts in terms of 


Comparative Example 2, the monomer X was used)
a solid content


Pigment dispersion including the pigment described in the following table (pigment
0.615 parts


concentration of 13.0%)



Dipentaerythritol hexaacrylate
0.070 parts


Glycerol propoxylate (1% cyclohexane solution)
0.048 parts







































4. Manufacture of Color Filter Formed of Coloring Composition
<Pattern Formation>
Each of the coloring compositions of Examples and Comparative Examples prepared as above was applied onto the undercoat layer of the undercoat layer-attached silicon wafer substrate obtained in the above section 2, thereby forming a coloring composition layer (coating film). Then, a heating treatment (pre-baking) was carried out for 120 seconds by using a hot plate at 100° C. such that the dry film thickness of the coating film became 0.6 μm.
Next, by using an i-ray stepper exposure device FPA-3000i5+ (manufactured by CANON Inc.), the wafer was exposed at a wavelength of 365 nm through an island pattern mask having a 1.0 μm×1.0 μm pattern, by varying the exposure dose in a range from 50 mJ/cm2 to 1200 mJ/cm2.
Subsequently, the silicon wafer substrate, which had been irradiated with light and had a coating film formed thereon, was loaded onto a horizontal spin table of a spin shower developing machine (Model DW-30, manufactured by Chemitronics Co., Ltd.), and subjected to paddle development for 60 seconds at 23° C. by using CD-2000 (manufactured by FUJIFILM Electronic Materials CO., LTD.), thereby forming a colored pattern on the silicon wafer substrate.
The silicon wafer on which the colored pattern had been formed was fixed onto the horizontal spin table by a vacuum chuck method, and the silicon wafer substrate was rotated at a rotation frequency of 50 r.p.m. by using a rotation device. In this state, from the position above the rotation center, pure water was supplied onto the wafer from a spray nozzle in the form of shower so as to perform rinsing treatment, and then the wafer was spray-dried.
In the manner described above, monochromatic color filters having the colored pattern formed of the coloring compositions of Examples or Comparative Examples were manufactured.
Thereafter, by using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation), the size of the colored pattern was measured. An exposure dose at which the pattern size became 1.0 μm was determined as an optimal exposure dose.
5. Performance Evaluation
5-1. Pattern Deficit
100 colored patterns were observed, and the number of patterns with deficit was counted. The larger the number is, the worse the pattern deficit is. The results are shown in the following table.
5-2. Pattern Linearity
100 pattern were observed with a length measuring SEM to evaluate the pattern linearity.
A: It has a rectangular shape and the side of the pattern is linear.
B: It has a rectangular shape and the side of the pattern is slightly distorted linear, but it was at a level such that there was no problem in practical use.
C: It is rounded and the side of the pattern is not smooth, but it was at a level such that there was a problem in practical use.
5-3. Heat Resistance
The glass substrate on which the coloring composition obtained above had been applied was loaded onto a hot plate at 200° C. such that it came into contact with the substrate surface and was heated for 1 hour. Then, the color difference (ΔE*ab value) before and after the heating was measured using a colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.), and used as an index for evaluating the fastness against heat, and the index was evaluated in accordance with the following evaluation criteria. A smaller ΔE*ab value indicates better heat resistance. Incidentally, the ΔE*ab value is a value determined from the following color-difference formula according to CIE 1976 (L*, a*, b*) color space (New Edition of Color Science Handbook (1985) p. 266, edited by The Color Science Association of Japan).

ΔE*ab={(ΔL*)2+(Δa*)2+(Δb*)2}1/2

5-4. Evaluation of Color Transfer
The absorbance of the colored pattern in each of the color filters was measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance A).
A CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd., a transparent undercoating agent) was applied onto the surface, on which the colored pattern of the color filter had been formed, such that the dried film thickness became 1 μm, and dried to form a transparent film, and the film was subjected to a heating treatment at 280° C. for 5 minutes.
After the completion of heating, the absorbance of the transparent film adjacent to the colored pattern was measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance B).
The ratio [%] of the absorbance A value of the colored pattern which had been measured before heating to the absorbance B value of the obtained transparent film was calculated [the following (Equation A)]. The ratio was used as an index for evaluating the color transfer to adjacent pixels.

Color transfer (%)=Absorbance B/Absorbance A×100  (Equation A)
















TABLE 4








Photopolymerization
Alkali-soluble
Pattern
Pattern
Heat
Color


Example
Resin
Pigment
initiator
resin
deficit
linearity
resistance
transfer























1
(S-1) 
PB 15:6
(I-1)
J1
5
B
4.3
6


2
(S-2) 
PB 15:6
(I-1)
J1
4
B
4.6
5


3
(S-3) 
PB 15:6
(I-1)
J1
5
B
4.5
6


4
(S-4) 
PB 15:6
(I-1)
J1
6
B
4.4
5


5
(S-5) 
PB 15:6
(I-1)
J1
5
B
4.2
5


6
(S-6) 
PB 15:6
(I-1)
J1
4
B
4.3
7


7
(S-7) 
PB 15:6
(I-1)
J1
5
B
4.4
6


8
(S-8) 
PB 15:6
(I-1)
J1
4
B
4.3
5


9
(S-9) 
PB 15:6
(I-1)
J1
4
B
4.1
6


10
(S-10)
PB 15:6
(I-1)
J1
0
A
1.2
0


11
(S-11)
PB 15:6
(I-1)
J1
0
A
1.3
0


12
(S-12)
PB 15:6
(I-1)
J1
0
A
1.1
0


13
(S-13)
PB 15:6
(I-1)
J1
0
A
1.3
0


14
(S-14)
PB 15:6
(I-1)
J1
0
A
1.2
0


15
(S-15)
PB 15:6
(I-1)
J1
0
A
1.3
0


16
(S-16)
PB 15:6
(I-1)
J1
6
B
4.5
7


17
(S-17)
PB 15:6
(I-1)
J1
5
B
4.4
6


18
(S-18)
PB 15:6
(I-1)
J1
6
B
4.3
7


19
(S-19)
PB 15:6
(I-1)
J1
5
B
4.3
6


20
(S-20)
PB 15:6
(I-1)
J1
5
B
4.5
6


21
(S-21)
PB 15:6
(I-1)
J1
4
B
4.3
7


22
(S-22)
PB 15:6
(I-1)
J1
4
B
4.6
8


23
(S-23)
PB 15:6
(I-1)
J1
6
B
4.2
7


24
(S-24)
PB 15:6
(I-1)
J1
4
B
4.7
8


25
(S-25)
PB 15:6
(I-1)
J1
5
B
4.2
7


26
(S-26)
PB 15:6
(I-1)
J1
0
A
1.3
0


27
(S-27)
PB 15:6
(I-1)
J1
0
A
1.2
0


28
(S-28)
PB 15:6
(I-1)
J1
7
A
4.6
6


29
(S-29)
PB 15:6
(I-1)
J1
8
A
4.7
6


30
(S-30)
PB 15:6
(I-1)
J1
0
A
1.3
0


31
(S-31)
PB 15:6
(I-1)
J1
3
A
3.3
2


32
(S-32)
PB 15:6
(I-1)
J1
0
A
0.4
0


33
(S-33)
PB 15:6
(I-1)
J1
0
A
0.3
0


34
(S-11)
PB 15:6
(I-2)
J1
0
A
3.6
0


35
(S-11)
PB 15:6
(I-3)
J1
5
A
4.2
2


36
(S-11)
PB 15:6
(I-4)
J1
6
A
4.5
3


37
(S-11)
PB 15:6
(I-5)
J1
0
A
0.3
0


38
(S-11)
PB 15:6
(I-6)
J1
4
A
3.3
2


39
(S-11)
PB 15:6
(I-7)
J1
0
A
0.2
0


40
(S-11)
PB 15:6
(I-8)
J1
5
A
4.1
6


41
(S-11)
PB 15:6
(I-1)
J2
5
A
4.2
7


42
(S-11)
PR254
(I-1)
J1
2
A
1.2
0


Comparative
(S-H1)
PB 15:6
(I-1)
J1
13
C
7.1
2


Example 1










Comparative
monomer
PB 15:6
(I-1)
J1
16
C
3.2
32


Example 2
X
















As apparent from the above table, it could be seen that in the case where a color filter was prepared with a photoresist using the composition of the present invention, the pattern deficit was small, the pattern linearity was excellent, the heat resistance was high, and the color transfer was small. In contrast, in the case where a dye multimer or a monomer-type dye, not having a non-nucleophilic counter anion, is used, any one or more effects as described above cannot be accomplished.
6-0. Pattern Forming to which Dry Etching Method is Applied
Preparation of Coloring Composition
The following components were mixed and dissolved to obtain the respective coloring compositions of Examples 43 to 75, and Comparative Examples 3 and 4.













Cyclohexanone
1.133 parts


Dye multimer (the compound described in the follow-
0.040 parts in terms


ing table) (provided that the monomer X was used in
of a solid content


Comparative Example 4)



Blue pigment dispersion above (pigment concen-
0.615 parts


tration of 13.0%)



Polymerizable compound (EHPE-3150 (1,2-epoxy-
0.070 parts


4-(2-oxiranyl)cyclohexane adduct of 2,2-



bis(hydroxymethyl)-1-butanol, manufactured by



Daicel Chemical Industries, Ltd.))



Glycerol propoxylate (1% cyclohexane solution)
0.048 parts









6. Performance Evaluation
6-1. Resistance to Alkaline Developing Liquid (Resistance to Developing Liquid)
The coloring composition was applied onto a glass substrate by using a spin coater such that the film thickness became 0.6 μm, and subjected to a heating treatment (pre-baking) using a hot plate at 100° C. for 120 seconds. Subsequently, a heating treatment (post-baking) was carried out with a hot plate at 220° C. for 300 seconds to prepare a cured film.
The transmittance of the color filter thus obtained was measured at a wavelength region of 300 nm to 800 nm by a (reference: glass substrate), which is a UV-VIS-NIR spectrophotometer, UV3600 (manufactured by SHIMADZU Corporation). In addition, differential interference images were observed through reflective observation (50× magnifications) by using an optical microscope, BX60, manufactured by OLYMPUS Corporation.
Subsequently, the color filter was immersed in an alkaline developing liquid FHD-5 (manufactured by FUJIFILM Electronic Materials CO., LTD.) for 5 minutes, dried, and then subjected to spectrometry again. Thus, the variance (a value represented by an equation |T0−T1|, in the case where the transmittance before peeling is defined as T0 and the transmittance after solvent immersion is defined as T1) in the transmittance before and after solvent immersion was evaluated.
6-2. Resistance to Peeling Solution
Then, a positive-type photoresist “FHi622BC” (manufactured by FUJIFILM Electronic Materials CO., LTD.) was applied onto the colored film manufactured in the section 6-1, and subjected to pre-baking to form a photoresist layer having a film thickness of 0.8 μm. Then, the photoresist layer was subjected to pattern exposure using an i-ray stepper (manufactured by CANON Inc.) in an exposure dose of 350 mJ/cm2 and then to a heating treatment for 1 minute at temperature at which the temperature of the photoresist layer or ambient temperature reached 90° C. Thereafter, a peeling treatment was carried out using a photoresist peeling solution “MS230C” (manufactured by FUJIFILM Electronic Materials CO., LTD.) for 120 seconds to remove the resist pattern, and then cleaning with pure water and spin drying were carried out. Thereafter, dehydration and baking treatments at 100° C. for 2 minutes were carried out.
The obtained colored film was subjected to spectrometry and the variance (a value represented by an equation |T0−T2|, in the case where the transmittance before peeling is defined as T0 and the transmittance after solvent immersion is defined as T2) in the transmittance before and after peeling was evaluated.











TABLE 5








Resistance
Resistance





to developing
to peeling


Example
Resin
Pigment
liquid
solution



















43
(S-1)
PB 15:6
10
12


44
(S-2)
PB 15:6
10
11


45
(S-3)
PB 15:6
11
10


46
(S-4)
PB 15:6
12
12


47
(S-5)
PB 15:6
13
11


48
(S-6)
PB 15:6
15
10


49
(S-7)
PB 15:6
14
9


50
(S-8)
PB 15:6
12
8


51
(S-9)
PB 15:6
12
10


52
(S-10)
PB 15:6
0
0


53
(S-11)
PB 15:6
0
0


54
(S-12)
PB 15:6
0
0


55
(S-13)
PB 15:6
0
0


56
(S-14)
PB 15:6
0
0


57
(S-15)
PB 15:6
0
0


58
(S-16)
PB 15:6
10
9


59
(S-17)
PB 15:6
10
8


60
(S-18)
PB 15:6
11
10


61
(S-19)
PB 15:6
10
9


62
(S-20)
PB 15:6
13
11


63
(S-21)
PB 15:6
14
12


64
(S-22)
PB 15:6
12
14


65
(S-23)
PB 15:6
11
10


66
(S-24)
PB 15:6
10
12


67
(S-25)
PB 15:6
10
11


68
(S-26)
PB 15:6
0
0


69
(S-27)
PB 15:6
0
0


70
(S-28)
PB 15:6
11
11


71
(S-29)
PB 15:6
9
12


72
(S-30)
PB 15:6
0
0


73
(S-31)
PB 15:6
3
3


74
(S-32)
PB 15:6
0
0


75
(S-33)
PB 15:6
0
0


Comparative
(S-H1)
PB 15:6
33
35


Example 3






Comparative
Monomer X
PB 15:6
26
28


Example 4









As apparent from the above table, it could be seen that in the case where a color filter is prepared by an etching resist using the composition of the present invention, a color filter having excellent resistance to a developing liquid and resistance to a peeling solution is obtained. In contrast, it could be seen that in the case where a dye multimer or a monomer-type dye, not having a non-nucleophilic counter anion, is used, any one or more effects as described above cannot be accomplished.
In addition, by using a combination of the dye multimer (S-1) and C. I. Pigment Yellow 139, a coloring composition which can be preferably used for a red color filter could be obtained.

## Claims

1. A coloring composition comprising:
a (A) dye multimer having a non-nucleophilic counter anion; and
a (B) polymerizable compound,
wherein the dye multimer having a non-nucleophilic counter anion has a partial structure derived from a xanthene dye and the non-nucleophilic counter anion is anion represented by the following formula (AN-1):




wherein X1 and X2 each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, or X1 and X2 may be bonded to each other to form a ring, and
wherein the coloring composition achieves a combination of high heat resistance and reduced color migration.

2. The coloring composition according to claim 1, further comprising
a (C) pigment.

3. The coloring composition according to claim 1, further comprising
a (D) photopolymerization initiator.

4. The coloring composition according to claim 3, wherein the (D) photopolymerization initiator is an oxime compound.

5. The coloring composition according to claim 1, wherein the dye multimer (A) further has a polymerizable group.

6. The coloring composition according to claim 1, which is used for forming a colored layer of a color filter.

7. A colored cured film formed by curing the coloring composition according to claim 1.

8. A color filter comprising the colored cured film according to claim 7.

9. A solid-state image sensor comprising the color filter according to claim 8.

10. An image display device comprising the color filter according to claim 8.

11. A method for producing a color filter, comprising:
applying the coloring composition according to claim 1 onto a support to form a coloring composition layer;
patternwise exposing the coloring composition layer; and
developing and removing an unexposed area to form a colored pattern.

12. A color filter produced by the method for producing a color filter according to claim 11.

13. A method for producing a color filter, comprising:
applying the coloring composition according to claim 1 onto a support to form a coloring composition layer, and curing the coloring composition layer to form a colored layer;
forming a photoresist layer on the colored layer;
patterning the photoresist layer by exposure and development to obtain a resist pattern; and
dry-etching the colored layer using a resist pattern as an etching mask.

14. The coloring composition according to claim 1, wherein the (A) dye multimer includes a structural unit represented by General Formula (A):



wherein X1 represents a linking group formed by polymerization; L1 represents a single bond or a divalent linking group; and DyeI represents a dye structure.

15. The coloring composition according to claim 1, wherein the (A) dye multimer includes a partial structure derived from a xanthene dye represented by the following General Formula (J):



wherein R81, R82, R83 and R84 each independently represents a hydrogen atom or a monovalent substituent; R85's each independently represent a monovalent substituent; m represents an integer of 0 to 5; and X− represents a non-nucleophilic counter anion.

16. The coloring composition according to claim 1, wherein the non-nucleophilic counter anion is selected from the group consisting of the following anions (a-9) to (a-14):