# Patent

## Title
Coloring composition, thermal transfer recording ink sheet, thermal transfer recording method, color toner, inkjet ink, color filter, and arylidene-pyrazolone dye

## Abstract

An arylidene-pyrazolone dye of the following formula (1):




wherein R1, R2, R3, R4 and R5 each independently represent a monovalent substituent; n indicates an integer of from 0 to 4; when n is 2 or more, plural R3's may be the same or different; and R1 and R2 may bond to each other to form a cyclic structure.

## Background
TECHNICAL FIELD
The present invention relates to a specific novel arylidene-pyrazolone dye, and a coloring composition, a thermal transfer recording ink sheet, a thermal transfer recording method, a color toner, an inkjet ink and a color filter containing the specific arylidene-pyrazolone dye.
BACKGROUND ART
These days, in particular, a color image-forming material is the mainstream of an image-recording material; and concretely, inkjet-type recording materials, thermal transfer-type recording materials, electrophotographic recording materials, transfer-type silver halide photosensitive materials, printing inks and recording pens are much used. In an image sensor such as CCD as photography machinery and in LCD or PDP as displays, a color filter is used for recording and reproducing color images.
In a color image-recording material and a color filter, used are colorants (dyes, pigments) of three primary colors for an additive mixture process or a subtractive mixture process. At present, however, no one could find a fast colorant that has absorption characteristics capable of realizing a favorable color reproduction range and is durable to various conditions in practical use, and it is strongly desired to improve colorants.
Thermal transfer recording includes a recording system where a thermal transfer material having a thermofusible ink layer formed on a support (base film) is heated with a thermal head to thereby melt the ink for recording on an image-recording material, and a recording system where a thermal transfer material having a transferable dye-containing dye-donating layer formed on a support is heated with a thermal head to thereby thermally diffuse and transfer the dye onto an image-receiving material. In the latter thermal transfer system, the dye transfer rate may be varied by changing the energy to be applied to the thermal head, therefore facilitating gradation recording, and the system is especially advantageous for high-quality full-color recording. However, the transferable dye for use in this system has various limitations, and only an extremely few dyes are known capable of satisfying all the necessary performance requirements.
The performance requirements include, for example, spectral characteristics favorable for color reproduction, easy transferability, fastness to light and heat, fastness to various chemicals, easy producibility, and easy workability to construct thermal transfer recording materials. However, conventional specific dyes that have been proposed as those having spectral characteristics favorable for color reproduction and having fastness to light and heat (for example see Patent JP-A 1-225592 and JP-A 63-189289) could not be on a satisfactory level, and further improvements are strongly desired.
In color copiers and color laser printers to be driven by electrophotography, in general, a toner is widely used that comprises a colorant dispersed in resin particles. The performance requirements for the color toner include absorption characteristics capable of realizing a preferred color reproduction range, especially high transmittance (transparency) required in use in overheat projectors (hereinafter referred to as OHP), and various fastness requirements under environmental conditions in practical use. A toner comprising a pigment colorant dispersed in particles has been proposed (for example, see JP-A 62-157051, JP-A 62-255956 and JP-A 6-118715). The toner of the type may have excellent light fastness, but may readily aggregate as being insoluble and is problematic in point of the transparency reduction and the transmitted color shift. On the other hand, a toner comprising a specific dye as a colorant has also been proposed (for example, see JP-A 3-276161, JP-A 2-207274 and JP-A 2-207273), and the toner of the type has high transparency and is free from the problem of color shift contrary to the above, but is problematic in point of the light fastness.
An inkjet recording method has been rapidly popularized and is being developed further more, since its material cost is low, it enables high-speed recording, it is noiseless in recording operation, and it facilitates color recording.
The inkjet recording method includes a continuous system of continuously jetting out ink droplets and an on-demand system of jetting out ink droplets in accordance with image information signals; and the jetting system includes a system of jetting out ink droplets under pressure given thereto by a piezo device, a system of jetting out ink droplets by generating bubbles in ink by heat, a system of using ultrasonic waves, and a system of electrostatically sucking and jetting out ink droplets. As the inkjet recording ink, usable is water-base ink, oily ink, or solid (fusible) ink.
The requirements for the colorant to be used in the inkjet recording ink are that it well dissolves or disperses in solvent, it enables high-density recording, its color is good, it is fast to light, heat, active gases in the environment (e.g., oxidizing gas such as NOx, SOx, ozone), it is fast to water and chemicals, it may well fix in image-receiving material and hardly blurs it, it is well storable as ink, it is nontoxic, its purity is high, and it is inexpensive and easily available. However, it is extremely difficult to obtain a colorant that satisfies all these requirements at a high level. In particular, it is strongly desired to obtain a colorant that has a good magenta color tone, has high solubility, and is fast to light, humidity and heat, especially highly fast to light.
A color filter is required to have high transparency, for which, therefore, employed is a dyeing method of coloration with a dye. For example, a method that comprises patterning exposure and development of a dyeable photoresist to form a pattern, and then dyeing it with a filter color dye is successively repeated for all filter colors to produce a color filter. Apart form the dyeing method, a method of using a positive resist may also be employed for producing a color filter. The color filters produced according to these methods may have high transparency and excellent optical properties as using dyes, but their light fastness and heat fastness are limited. Accordingly, a colorant having excellent fastness and having high transparency is desired. On the other hand, a method of using an organic pigment having excellent light fastness and heat fastness in place of dye is widely known, but pigment-containing color filters could hardly have good optical properties like those of dye-containing color filters.
Common to those for use in the above-mentioned applications, the dyes are desired to have the following properties. Specifically, they have a color favorable for color reproduction, they have an optimum spectral absorption, their fastness such as light fastness, moisture fastness, chemical fastness is good, their solubility is high.
For use in thermal transfer recording, dyes having a specific arylidene-pyrazolone skeleton have been proposed (for example, see JP-A 2-3450). However, the dyes could not always satisfy the above-mentioned requirements for their properties on a satisfactory level, and further investigations are desired.
SUMMARY OF THE INVENTION
An object of the invention is to provide an arylidene-pyrazolone dye having excellent spectral characteristics with sharp absorption and having high fastness and high solubility to an ink, and to provide a coloring composition having the arylidene-pyrazolone dye, a thermal transfer recording ink sheet having the arylidene-pyrazolone dye, and a thermal transfer recording method. Another object of the invention is to provide a thermal transfer recording ink sheet and a thermal transfer recording method having excellent color reproducibility, image storability and transfer sensitivity in print samples. Still another object of the invention is to provide a color toner, an inkjet ink and a color filter comprising the arylidene-pyrazolone dye.
The present inventors have assiduously studied and, as a result, have found that the above-mentioned objects can be attained by the following constitution:
[1] An arylidene-pyrazolone dye of the following formula (1):




wherein R1, R2, R3, R4 and R5 each independently represent a monovalent substituent; n indicates an integer of from 0 to 4; when n is 2 or more, plural R3's may be the same or different; and R1 and R2 may bond to each other to form a cyclic structure.

[2] A coloring composition containing the arylidene-pyrazolone dye of the above [1].
[3] A thermal transfer recording ink sheet containing the arylidene-pyrazolone dye of the above [1].
[4] A thermal transfer recording method comprising forming an image by use of the thermal transfer recording ink sheet of the above [3] on an image-receiving material comprising a polymer-containing ink-receiving layer on a support.
[5] A color toner containing the arylidene-pyrazolone dye of the above [1].
[6] An inkjet ink containing the arylidene-pyrazolone dye of the above [1].
[7] A color filter containing the arylidene-pyrazolone dye of the above [1].
According to the invention, there are provided a novel arylidene-pyrazolone dye satisfying all the requirements of excellent solubility in various organic solvents, excellent spectral characteristics with sharp absorption, extremely high fastness and excellent transfer sensitivity, a color composition containing the arylidene-pyrazolone dye, a thermal transfer ink sheet containing the arylidene-pyrazolone dye and a thermal transfer recording method. Unexpectedly, the novel arylidene-pyrazolone dye has extremely high light fastness and wet heat fastness, as compared with conventional known arylidene-pyrazolone dyes, and therefore can provide a thermal transfer ink sheet and a thermal transfer recording method capable of satisfying excellent color reproducibility in printed samples. Further, the invention provides a color toner, an inkjet ink and a color filter comprising the arylidene-pyrazolone dye.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a transmission spectrum of the color filter produced in the example 601.



MODES FOR CARRYING OUT THE INVENTION
The thermal transfer recording ink sheet, the color toner, the inkjet ink and the color filter and also the arylidene-pyrazolone dye for use in these of the invention are described in detail hereinunder.
The description of the constitutive elements of the invention given hereinunder is for some typical embodiments of the invention, to which, however, the invention should not be limited. In this description, the numerical range expressed by the wording “a number to another number” means the range that falls between the former number indicating the lowermost limit of the range and the latter number indicating the uppermost limit thereof.
[Arylidene-pyrazolone Dye of Formula (1)]
First described is the arylidene-pyrazolone dye of formula (1) of the invention.
The arylidene-pyrazolone dye of formula (1) is a dye compound characterized by having an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group introduced thereinto as the 2-position substituent of the 3-pyrazolone skeleton of the compound. The arylidene-pyrazolone dye having such a characteristic structure is heretofore not known at all. As compared with other dye compounds where the 2-position substituent of the 3-pyrazolone skeleton is an alkyl group or an aryl group, the arylidene-pyrazolone dye of formula (1) is overwhelmingly excellent in light fastness and in wet heat fastness and is excellent in solubility.
As excellent in solubility, light fastness and wet heat fastness, the arylidene-pyrazolone dye of formula (1) is favorable for use in thermal transfer recording ink sheets and, in addition, it may also be favorably used in other applications (for example, in ink liquids and others).
In formula (1), R3 represents a monovalent substituent. The substituent for R3 is not specifically defined. Its typical examples include a halogen atom, an aliphatic group [a saturated aliphatic group (this means an alkyl group, or a cyclic saturated aliphatic group including a cycloalkyl group, a bicycloalkyl group, a crosslinked cyclic saturated hydrocarbon group, a spiro-saturated hydrocarbon group), an unsaturated aliphatic group (this means a linear unsaturated aliphatic group having a double bond or a triple bond, such as an alkenyl group, an alkynyl group; or a cyclic unsaturated aliphatic group including a cycloalkenyl group, a bicycloalkenyl group, a crosslinked cyclic unsaturated hydrocarbon group, a spiro-unsaturated hydrocarbon group)], an aryl group (preferably a phenyl group optionally having a substituent), a heterocyclic group (preferably a 5- to 8-membered, alicyclic, aromatic or heterocyclic ring having an oxygen atom, a sulfur atom or a nitrogen atom as the ring-constitutive atom, and it may be a condensed ring), a cyano group, an aliphatic oxy group (typically an alkoxy group), an aryloxy group, an acyloxy group, a carbamoyloxy group, an aliphatic oxycarbonyloxy group (typically an alkoxycarbonyloxy group, an aryloxycarbonyloxy group), an amino group [including an aliphatic amino group (typically an alkylamino group), an anilino group, a heterocyclic amino group], an acylamino group, an aminocarbonylamino group, an aliphatic oxycarbonylamino group (typically an alkoxycarbonylamino group), an aryloxycarbonylamino group, a sulfamoylamino group, an aliphatic (typically an alkyl) or arylsulfonylamino group, an aliphatic thio group (typically an alkylthio group), an arylthio group, a sulfamoyl group, an aliphatic (typically an alkyl) or arylsulfinyl group, an aliphatic (typically an alkyl) or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an aliphatic oxycarbonyl group (typically an alkoxycarbonyl group), a carbamoyl group, an aryl or heterocyclic azo group, an aliphatic oxysulfonyl group (typically an alkoxysulfonyl group), an aryloxysulfonyl group, a hydroxyl group, a nitro group, a carboxyl group, a sulfo group. These groups may be further substituted (for example, with the substituent mentioned in the above for R3).
The substituent of R3 and the substituents which these groups may optionally have are described in more detail hereinunder.
The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Above all, preferred are a chlorine atom and a bromine atom; and more preferred is a chlorine atom.
The aliphatic group is a linear, branched or cyclic aliphatic group; and as so mentioned in the above, the saturated aliphatic group includes an alkyl group, a cycloalkyl group, a bicycloalkyl group; and these may be further substituted. Preferably, the number of the carbon atoms constituting the group is from 1 to 30. Its examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an n-octyl group, an eicosyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a benzyl group, a 2-ethylhexyl group. The cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. For the substituted or unsubstituted cycloalkyl group, the cycloalkyl group preferably has from 3 to 30 carbon atoms. Its examples include a cyclohexyl group, a cyclopentyl group, a 4-n-dodecylcyclohexyl group. The bicycloalkyl group is a substituted or unsubstituted bicycloalkyl group having from 5 to 30 carbon atoms, or that is, a monovalent group derived from a bicycloalkane having from 5 to 30 carbon atoms by removing one hydrogen atom therefrom. Its examples include a bicyclo[1.2.2]heptan-2-yl group, a bicyclo[2.2.2]octan-3-yl group. It further includes a tricyclo structure and more multi-cyclo structures.
The unsaturated aliphatic group is a linear, branched or cyclic unsaturated aliphatic group, including an alkenyl group, an cycloalkenyl group, a bicycloalkenyl group, an alkynyl group. The alkenyl group is a linear, branched or cyclic, substituted or unsubstituted alkenyl group. Preferably, the alkenyl group is an unsubstituted or substituted alkenyl group having from 2 to 30 carbon atoms. Its examples include a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group. The cycloalkenyl group is preferably a substituted or unsubstituted cycloalkenyl group having from 3 to 30 carbon atoms, or that is, a monovalent group derived from a cycloalkene having from 3 to 30 carbon atoms by removing one hydrogen atom therefrom. Its examples include a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group. The bicycloalkenyl group includes a substituted or unsubstituted bicycloalkenyl group. The bicycloalkenyl group is preferably a substituted or unsubstituted bicycloalkenyl group having from 5 to 30 carbon atoms, or that is, a monovalent group derived from a bicycloalkene having one double bond by removing one hydrogen atom therefrom. Its examples include a bicyclo[2.2.1]hept-2-en-1-yl group, a bicyclo[2.2.2]oct-2-en-4-yl group. The alkynyl group is preferably a substituted or unsubstituted alkynyl group having from 2 to 30 carbon atoms, including, for example, an ethynyl group, a propargyl group.
The aryl group is preferably a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms, including, for example, a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, an o-hexadecanoylaminophenyl group. Preferred is a phenyl group optionally having a substituent.
The heterocyclic group is a monovalent group derived from a substituted or unsubstituted, aromatic or non-aromatic heterocyclic compound by removing one hydrogen atom therefrom, and it may form a condensed ring. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group, and the ring-constituting hetero atom is preferably an oxygen atom, a sulfur atom, a nitrogen atom. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having from 3 to 30 carbon atoms. The hetero ring of the heterocyclic group includes a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a quinoxaline ring, a pyrrole ring, an indole ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring, an oxazole ring, a benzoxazole ring, a triazole ring, a benzothiazole ring, an isothiazole ring, a benzisothiazole ring, a thiadiazole ring, an isoxazole ring, a benzisoxazole ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, an imidazolidine ring, a thiazoline ring.
The aliphatic oxy group (typically alkoxy group) includes a substituted or unsubstituted aliphatic oxy group (typically alkoxy group), and preferably has from 1 to 30 carbon atoms. For example, it includes a methoxy group, an ethoxy group, an isopropoxy group, an n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy group, a 3-carboxypropoxy group.
The aryloxy group is preferably a substituted or unsubstituted aryloxy group having from 6 to 30 carbon atoms. Examples of the aryloxy group include a phenoxy group, a 2-methylphenoxy group, a 4-tert-butylphenoxy group, a 3-nitrophenoxy group, a 2-tetradecanoylaminophenoxy group. Preferred is a phenyloxy group optionally having a substituent.
The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having from 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having from 6 to 30 carbon atoms. Examples of the acyloxy group include a formyloxy group, an acetyloxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, a p-methoxyphenylcarbonyloxy group.
The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having from 1 to 30 carbon atoms. Examples of the carbamoyloxy group include an N,N-dimethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, a morpholinocarbonyloxy group, an N,N-di-n-octylaminocarbonyloxy group, an N-n-octylcarbamoyloxy group.
The aliphatic oxycarbonyloxy group (typically alkoxycarbonyloxy group) preferably has from 2 to 30 carbon atoms, and it may have a substituent. For example, it includes a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, an n-octylcarbonyloxy group.
The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having from 7 to 30 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a p-n-hexadecyloxyphenoxycarbonyloxy group. Preferred is a phenoxycarbonyloxy group optionally having a substituent.
The amino group includes an amino group, an aliphatic amino group (typically an alkylamino group), an arylamino group and a heterocyclic amino group. The amino group is preferably a substituted or unsubstituted aliphatic amino group (typically an alkylamino group) having from 1 to 30 carbon atoms, or a substituted or unsubstituted arylamino group having from 6 to 30 carbon atoms. Examples of the amino group include an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, a hydroxyethylamino group, a carboxyethylamino group, a sulfoethylamino group, a 3,5-dicarboxyanilino group, a 4-quinolylamino group.
The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having from 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino having from 6 to 30 carbon atoms. Examples of the acylamino group include a formylamino group, an acetylamino group, a pivaloylamino group, a lauroylamino group, a benzoylamino group, a 3,4,5-tri-n-octyloxyphenylcarbonylamino group.
The aminocarbonylamino group is preferably a substitute or unsubstituted aminocarbonylamino group having from 1 to 30 carbon atoms. Examples of the aminocarbonylamino group include a carbamoylamino group, an N,N-dimethylaminocarbonylamino group, an N,N-diethylaminocarbonylamino group, a morpholinocarbonylamino group. The term “amino” in this group has the same meaning as that of the “amino” in the above-mentioned amino group.
The aliphatic oxycarbonylamino group (typically alkoxycarbonylamino group) preferably has from 2 to 30 carbon atoms, and may have a substituent. For example, it includes a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino group.
The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having from 7 to 30 carbon atoms. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, a m-n-octyloxyphenoxycarbonylamino group. Preferred is a phenyloxycarbonylamino group optionally having a substituent.
The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having from 0 to 30 carbon atoms. Examples of the sulfamoylamino group include a sulfamoylamino group, an N,N-dimethylaminosulfonylamino group, an N-n-octylaminosulfonylamino group.
The aliphatic (typically alkyl) or arylsulfonylamino group is preferably a substituted or unsubstituted aliphatic sulfonylamino group (typically an alkylsulfonylamino group) having from 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having from 6 to 30 carbon atoms (preferably a phenylsulfonylamino group optionally having a substituent). For example, it includes a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group.
The aliphatic thio group (typically alkylthio group) is preferably a substituted or unsubstituted alkylthio group having from 1 to 30 carbon atoms. Examples of the alkylthio group include a methylthio group, an ethylthio group, an n-hexadecylthio group.
The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having from 0 to 30 carbon atoms. Examples of the sulfamoyl group include an N-ethylsulfamoyl group, an N-(3-dodecyloxypropyl)sulfamoyl group, an N,N-dimethylsulfamoyl group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, an N-(N′-phenylcarbamoyl)sulfamoyl group.
The aryl thio group is preferably a substituted or unsubstituted aryl thio group having from 1 to 30 carbon atoms. Examples of the aryl thio group include a phenylthio group, a 1-naphthylthio group, 2-naphthylthio group.
The aliphatic (typically alkyl) or arylsulfinyl group is preferably a substituted or unsubstituted aliphatic sulfinyl group (typically an alkylsulfinyl group) having from 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having from 6 to 30 carbon atoms (preferably a phenylsulfinyl group optionally having a substituent). For example, it includes a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group.
The aliphatic (typically alkyl) or arylsulfonyl group is preferably a substituted or unsubstituted aliphatic sulfonyl group (typically an alkylsulfonyl group) having from 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having from 6 to 30 carbon atoms (preferably a phenylsulfonyl group optionally having a substituent). For example, it includes a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, a p-toluenesulfonyl group.
The acyl group is preferably a formyl group, a substituted or unsubstituted aliphatic carbonyl group (typically an alkylcarbonyl group) having from 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having from 7 to 30 carbon atoms (preferably a phenylcarbonyl group optionally having a substituent), a substituted or unsubstituted heterocyclic carbonyl group having from 4 to 30 carbon atoms in which the ring bonds to the carbonyl group via its carbon atoms. For example, it includes an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a p-n-octyloxyphenylcarbonyl group, a 2-pyridylcarbonyl group, a 2-furylcarbonyl group.
The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having from 7 to 30 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, a p-tert-butylphenoxycarbonyl group. Preferred is a phenyloxycarbonyl group optionally having a substituent.
The aliphatic oxycarbonyl group (typically alkoxycarbonyl group) preferably has from 2 to 30 carbon atoms, and may have a substituent. For example, it includes a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group.
The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having from 1 to 30 carbon atoms. Examples of the carbamoyl group include a carbamoyl group, an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, an N,N-di-n-octylcarbamoyl group, an N-(methylsulfonyl)carbamoyl group.
The aryl or heterocyclic azo group includes, for example, a phenylazo group, a 4-methoxyphenylazo group, a 4-pivaloylaminophenylazo group, a 2-hydroxy-4-propanoylphenylazo group.
The imido group includes, for example, an N-succinimide group, an N-phthalimide group.
The aliphatic oxysulfonyl group (typically an alkoxysulfonyl group) preferably has from 1 to 30 carbon atoms, and may have a substituent. For example, it includes a methoxysulfonyl group, an ethoxysulfonyl group, an n-butoxysulfonyl group, etc.
The aryloxysulfonyl group preferably has from 6 to 12 carbon atoms, and may have a substituent. For example, it includes a phenoxysulfonyl group, a 1-naphthoxyphenyl group, etc.
In addition to these, further mentioned are a hydroxyl group, a cyano group, a nitro group, a sulfo group, a carboxyl group.
These groups may be further substituted, and the substituents for them may be the above-mentioned substituents.
R3 is preferably a substituted or unsubstituted aliphatic group having from 1 to 10 carbon atoms (preferably an alkyl group, an alkenyl group, a cycloalkyl group, more preferably an alkyl group), a substituted or unsubstituted aryl group (preferably a phenyl group optionally having a substituent), a substituted or unsubstituted aliphatic oxy group having from 1 to 10 carbon atoms (preferably an alkoxy group, an alkenoxy group, a cycloalkoxy group, more preferably an alkoxy group), or a halogen atom, more preferably a substituted or unsubstituted alkyl group having from 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having from 1 to 5 carbon atoms, a chlorine atom, most preferably an unsubstituted alkoxy group having from 1 to 3 carbon atoms.
In formula (1), R1 and R2 each independently represent a monovalent substituent.
The substituent is not specifically defined. Its typical examples include an aliphatic group (e.g., alkyl group, alkenyl group, alkynyl group), an aryl group. These groups may be further substituted (for example, with the substituent mentioned in the above for R3).
R1 and R2 may bond to each other to form a cyclic structure. The cyclic structure is preferably a 5- to 7-membered cyclic structure, more preferably a 5- or 6-membered cyclic structure. Examples of the cyclic structure to be formed by R1, R2 and the nitrogen atom to which they bond include a pyrrolidine ring, a piperidine ring, a morpholine ring, preferably a piperidine ring, a morpholine ring.
Preferably, R1 and R2 each independently represent a substituted or unsubstituted aliphatic group having from 1 to 20 carbon atoms (typically an alkyl group, an alkenyl group, a cycloalkyl group, more preferably an alkyl group), a substituted or unsubstituted aryl group (preferably a phenyl group optionally having a substituent), a substituted or unsubstituted heterocyclic group, more preferably a substituted or unsubstituted aliphatic group having from 1 to 10 carbon atoms (preferably an alkyl group, an alkenyl group, a cycloalkenyl group, more preferably an alkyl group), a substituted or unsubstituted aryl group, most preferably an unsubstituted alkyl group having from 1 to 4 carbon atoms.
In formula (1), R4 represents a monovalent substituent. The substituent is not specifically defined. Its typical examples are a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted carbamoyl group, and a cyano group.
R4 is preferably a substituted or unsubstituted amino group, or a substituted or unsubstituted alkoxy group, more preferably a dialkylamino group having from 2 to 8 carbon atoms, an unsubstituted amino group, or an unsubstituted alkoxy group having from 1 to 6 carbon atoms, most preferably a dialkylamino group having from 2 to 4 carbon atoms or an unsubstituted alkoxy group having from 1 to 4 carbon atoms.
In formula (1), R5 represents a monovalent substituent. The substituent is not specifically defined. Its typical examples are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted heterocyclic group.
R5 is preferably a substituted or unsubstituted aliphatic group having from 1 to 10 carbon atoms (preferably an alkyl group, an alkenyl group or a cycloalkyl group, more preferably an alkyl group), a substituted or unsubstituted aryl group (preferably a phenyl group optionally having a substituent), a substituted or unsubstituted amino group, or a substituted or unsubstituted heterocyclic group, more preferably an alkyl group having from 1 to 6 carbon atoms, or a dialkylamino group having from 2 to 8 carbon atoms, most preferably an alkyl group having from 1 to 4 carbon atoms.
In formula (1), n indicates an integer of from 0 to 4. When n is 2 or more, then plural R3's may be the same or different.
n is preferably from 0 to 2, more preferably 0 or 1, even more preferably 0.
Regarding the preferred combination of the substituents (combination of R1 to R5 and n) in the dye of formula (1) of the invention, it is desirable that at least one of these substituent is the above-mentioned preferable group, more preferably more various substituents are the above-mentioned preferred groups, most preferably all the substituents are the above-mentioned preferred groups.
Preferred combinations are as follows: R1 is a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, R2 is a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, R4 is a substituted or unsubstituted alkoxy group having from 1 to 4 carbon atoms, or a substituted or unsubstituted amino group, R5 is a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted amino group, and n=0.
More preferred combinations are as follows: R1 is a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, R2 is a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, R4 is a substituted or unsubstituted alkoxy group having from 1 to 3 carbon atoms, or a dialkylamino group having from 2 to 8 carbon atoms, R5 is a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, or a substituted or unsubstituted amino group, and n=0.
Most preferred combinations are as follows: R1 is a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, R2 is a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, R4 is a substituted or unsubstituted alkoxy group having 1 or 2 carbon atoms, or a dialkylamino group having from 2 to 4 carbon atoms, R5 is a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, and n=0.
The molecular weight of the arylidene-pyrazolone dye of formula (1) is preferably at most 550, more preferably at most 500 from the viewpoint of the thermal diffusibility thereof.
Specific examples Y-1 to Y-23 of the arylidene-pyrazolone dye of formula (1) of the invention are shown below; however, the arylidene-pyrazolone dye of formula (1) for use in the invention should not be limitatively interpreted by the following examples.







TABLE 1







Arylidene-pyrazolone Dyes of Formula (1)













Compound
R1
R2
R3
R4
R5
n





Y-1
ethyl
ethyl
—
ethoxy
methyl
0


Y-2
ethyl
ethyl
—
ethoxy
ethyl
0


Y-3
ethyl
ethyl
—
ethoxy
n-propyl
0


Y-4
ethyl
ethyl
—
ethoxy
isopropyl
0


Y-5
ethyl
ethyl
—
ethoxy
n-butyl
0


Y-6
ethyl
ethyl
—
ethoxy
phenyl
0


Y-7
ethyl
ethyl
—
ethoxy
p-tolyl
0


Y-8
ethyl
ethyl
—
ethoxy
dimethylamino
0


Y-9
ethyl
ethyl
—
ethoxy
diethylamino
0


Y-10
ethyl
ethyl
—
ethoxy
morpholino
0


Y-11
ethyl
ethyl
—
dimethylamino
methyl
0


Y-12
ethyl
ethyl
—
dimethylamino
ethyl
0


Y-13
ethyl
ethyl
—
dimethylamino
n-butyl
0


Y-14
ethyl
ethyl
—
dimethylamino
dimethylamino
0


Y-15
propyl
propyl
—
ethoxy
methyl
0


Y-16
n-butyl
n-butyl
—
ethoxy
methyl
0


Y-17
allyl
allyl
—
ethoxy
methyl
0


Y-18
ethyl
ethyl
—
methyl
methyl
0


Y-19
ethyl
ethyl
—
cyano
methyl
0


Y-20
ethyl
ethyl
—
ethoxycarbonyl
methyl
0


Y-21
ethyl
ethyl
chlorine*
ethoxy
methyl
1


Y-22
ethyl
ethyl
methyl*
ethoxy
methyl
1


Y-23
ethyl
ethyl
methoxy*
ethoxy
methyl
1





*The substituent position is the ortho-position relative to methine.






These arylidene-pyrazolone dyes can be produced according to the following scheme [1] or scheme [2]. In the scheme [1], concretely, the dye can be readily produced by reacting under heat a 3-pyrazolone derivative of the following formula (2) and a benzaldehyde derivative of the following formula (3). In the scheme [2], the dye can be produced by reacting an arylidene-pyrazolone dye of the following formula (4) and a sulfonyl chloride of the following formula (5). Concretely, these are exemplified in Examples to be given hereinunder.








In formulae (2) to (5), R1 to R5 and n have the same meanings as those of R1 to R5 and n in formula (1) described hereinabove.
The compounds of formula (2) can be produced, for example, according to the method described in Chemical Abstracts, Vol. 64, p. 9854 (1966). Many of the compounds of formula (3) are easily available as commercial products (for example, Tokyo Chemical's Catalogue No. D0463, etc.). The compounds of formula (4) can be produced according to the method described in Bioorganic & Medicinal Chemistry, Vol. 10, No. 5, p. 1555 (2002). Many of the compounds of formula (5) are easily available as commercial products (for example, Tokyo Chemical's Catalogue No. M0094, etc.).
The arylidene-pyrazolone dye of the invention is preferably used as a yellow color of three primary colors.
The maximum absorption wavelength of the arylidene-pyrazolone dye of the invention preferably falls within a range of from 400 to 500 nm, more preferably from 420 to 470 nm.
[Coloring Composition]
The coloring composition of the invention is characterized by containing the arylidene-pyrazolone dye of formula (1) of the invention. The coloring composition in this description is directed to thermal transfer recording ink sheets, inkjet inks, color toners, color filters, writing pens, color plastics, and other ink liquids.
The coloring composition of the invention is especially effectively used for thermal transfer recording ink sheets, inkjet inks, color toners, and color filters.
[Thermal Transfer Recording Ink Sheet]
The thermal transfer recording ink sheet of the invention is characterized by containing the arylidene-pyrazolone dye of formula (1). The thermal transfer recording ink sheet generally has a structure with a dye-donating layer formed on a support, in which the dye-donating layer contains a dye of formula (1). The thermal transfer recording ink sheet of the invention may be produced as follows: An arylidene-pyrazolone dye of formula (1) is dissolved in a solvent along with a binder therein or dispersed as particles in a solvent, thereby preparing an ink liquid, then the ink liquid is applied onto a support and suitably dried to form a dye-donating layer thereon. In addition to the arylidene-pyrazolone dye, the other dye may be used.
In case where the invention is applied to thermal transfer recording material that enables full-color image recording, it is desirable that a cyan ink sheet containing a thermal diffusible cyan dye capable of forming cyan images, a magenta ink sheet containing a thermal diffusible magenta dye capable of forming magenta images, and a yellow ink sheet containing a thermal diffusible yellow dye capable of forming yellow images are formed successively on a support. If desired, an ink sheet containing a black image-forming substance may be further formed.
As the thermal diffusible cyan dye-containing cyan ink sheet for forming cyan images, for example, preferably used are those described in JP-A 3-103477, 3-150194. As the thermal diffusible magenta dye-containing magenta ink sheet for forming magenta images, for example, preferably used are those described in JP-A 4-357088. As the thermal diffusible yellow dye-containing yellow ink sheet for forming yellow images, for example, preferably used are those described in JP-A 1-225592.
(Support)
As the support of the thermal transfer recording ink sheet of the invention, any ordinary one heretofore used as a support for ink sheets may be suitably selected and used. For example, the material described in JP-A 7-137466, paragraph [0050] may be favorably used. The thickness of the support is preferably from 2 to 30 μm.
(Dye-Donating Layer)
Not specifically defined, the binder resin usable in the dye-donating layer of the thermal transfer recording ink sheet of the invention may be any one having high heat resistance and not interfering with the transference of the arylidene-pyrazolone dye or the other dye into an image-receiving material when heated. For example, its preferred examples are described in JP-A 7-137466, paragraph [0049]. The solvent for dye-donating layer formation may also be any conventional known one; and those described in JP-A 7-137466, Examples are favorably used also herein.
The content of the arylidene-pyrazolone dye of formula (1) in the dye-donating layer is preferably from 0.03 to 1.0 g/m2, more preferably from 0.1 to 0.6 g/m2. The thickness of the dye-donating layer is preferably from 0.2 to 5 μm, more preferably from 0.4 to 2 μm.
(Functional Layer)
The thermal transfer recording ink sheet of the invention may have any other layer than the dye-donating layer within a range not too much detracting from the effect of the invention. For example, an interlayer may be provided between the support and the dye-donating layer; or a back layer may be provided on the surface of the support opposite to the side of the dye-donating layer (this is hereinafter referred to as “back surface”). The interlayer includes, for example, an undercoating layer, and a diffusion-preventing layer for preventing the arylidene-pyrazolone dye or the other dye from diffusing toward the support (hydrophilic barrier layer). The back layer is, for example, a heat-resistant slip layer, which is for preventing a thermal head from sticking to the ink sheet.
[Thermal Transfer Recording]
In thermal transfer recording by the use of the thermal transfer recording ink sheet of the invention, a heating unit such as a thermal head and an image-receiving material are used as combined. Specifically, heat energy is applied to the ink sheet from a thermal head according to an image recording signal, and the arylidene-pyrazolone dye or the other dye dye in the part having received the heat energy is transferred to and fixed in an image-receiving material to attain image recording. The image-receiving material generally has a constitution with a polymer-containing ink-receiving layer formed on a support. As the constitution and the constitutive components of the image-receiving material, for example, preferably used are those described in JP-A 7-137466, paragraphs [0056] to [0074].
[Color Toner]
The color toner of the invention is characterized by containing the arylidene-pyrazolone dye of formula (1). As the binder resin for color toner into which the arylidene-pyrazolone dye of formula (1) of the invention is introduced, usable is any and every binder for general use in toner. For example, it includes styrene resin, acrylic resin, styrene/acrylic resin, polyester resin. For the purpose of improving the flowability of the toner and for static control thereof, an inorganic fine powder or organic fine particles may be added to the toner as external additives. Preferably used are silica particles and titania particles of which the surfaces are processed with an alkyl group-containing coupling agent or the like. Preferably, the particles have a number-average primary particle size of from 10 to 500 nm; and also preferably, the particles are added to the toner in an amount of from 0.1 to 20% by mass.
As the lubricant, any and every lubricant heretofore used in toner may be used herein. Concretely, it includes olefins such as low-molecular-weight polypropylene, low-molecular-weight polyethylene, ethylene-propylene copolymer; and microcrystalline wax, carnauba wax, Sasol wax, paraffin wax. Preferably, the lubricant is added to the toner in an amount of from 1 to 5% by mass.
If desired, a charge-controlling agent may be added to the toner, and it is preferably colorless from the viewpoint of the colorability of the toner. For example, herein usable are those having a quaternary ammonium salt structure or a calixarene structure.
The carrier may be any of a non-coated carrier formed of magnetic material particles alone of iron, ferrite or the like; or a resin-coated carrier prepared by coating the surfaces of magnetic material particles with resin or the like. Regarding the mean particle size thereof, the carrier preferably has a volume-average particle size of from 30 to 150 μm.
The image-forming method to which the toner of the invention is applicable is not specifically defined. For example, the toner is applicable to an image-forming method that comprises repeatedly forming a color image on a photoreceptor followed by transferring it; and a color image-forming method that comprises transferring an image formed on a photoreceptor successively onto an intermediate transfer medium thereby forming a color image on the intermediate transfer medium, followed by transferring the image onto an image-forming member such as paper.
[Inkjet Ink]
The inkjet ink of the invention is characterized by containing the arylidene-pyrazolone dye of formula (1). The ink of the invention may be produced by dissolving and/or dispersing the arylidene-pyrazolone dye of formula (1) in an oleophilic medium or an aqueous medium, and preferably an aqueous medium is used. The ink of the invention contains the dye having excellent spectral characteristics, fastness and further having excellent solubility as so mentioned in the above, and is therefore favorably used as an inkjet recording ink. If desired, other additives may be added to the ink within a range not detracting from the effect of the invention. The additives may be known additives, including, for example, a drying inhibitor (wetting agent), an antifading agent, a emulsion stabilizer, a penetration promoter, a UV absorbent, a preservative, an antifungal agent, a pH controlling agent, a surface tension controlling agent, a defoaming agent, a viscosity controlling agent, a dispersant, a dispersion stabilizer, a rust inhibitor, a chelating agent. In general, these various additives are added to the dye dispersion after its preparation, but as the case may be, they may be added to an oily phase or an aqueous phase in preparing the dye dispersion.
The drying inhibitor is favorably used for the purpose of preventing the inkjet ink from drying at the ink-jetting orifice of the nozzle used in an inkjet recording system.
The drying inhibitor is preferably a water-soluble organic solvent having a vapor pressure lower than water. Its concrete examples include polyalcohols such as typically ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, glycerin, trimethylolpropane; polyalcohol lower alkyl ethers such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether; heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, 3-sulfolene; polyfunctional compounds such as diacetone alcohol, diethanolamine; and urea derivatives. Of those, more preferred are polyalcohols such as glycerin, diethylene glycol. One or more of the above drying inhibitors may be used either singly or as combined. The drying inhibitor may be in the ink preferably in an amount of from 10 to 50% by mass.
The penetration promoter is favorably used for the purpose of more rapidly penetrating the inkjet ink into paper. As the penetration promoter, usable are alcohols such as ethanol, isopropanol, butanol, di(tri)ethylene glycol monobutyl ether, 1,2-hexanediol; sodium laurylsulfate, sodium oleate, nonionic surfactant. When the agent is in the ink in an amount of from 5 to 30% by mass, then it is generally sufficiently effective. Preferably, the agent is used in an amount not causing print blur and print through.
The UV absorbent is used for the purpose of improving the image storability. The UV absorbent includes benzotriazole compounds as in JP-A 58-185677, 61-190537, 2-782, 5-197075, 9-34057; benzophenone compounds as in JP-A 46-2784, 5-194483, U.S. Pat. No. 3,214,463; cinnamic acid compounds as in JP-B 48-30492, 56-21141, JP-A 10-88106; triazine compounds as in JP-A 4-298503, 8-53427, 8-239368, 10-182621, JP-T 8-501291; and also the compounds described in Research Disclosure No. 24239, and compounds capable of absorbing UV rays to emit fluorescent light, or that is, fluorescent brighteners such as typically stilbene compounds and benzoxazole compounds.
The antifading agent is used for the purpose of improving the image storability. As the antifading agent, usable are various organic or metal complex-type antifading agents. The organic antifading agent includes hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic compounds; and the metal complex includes nickel complexes and zinc complexes. More concretely, herein usable are the compounds described in the patent references cited in Research Disclosure No. 17643, Items VII-I to J, ibid., No. 15162, ibid., No. 18716, page 650, left column, ibid., No. 36544, page 527, ibid., No. 307105, page 872, ibid., No. 15162; and the compounds falling within the scope of the typical compounds of the formula and the examples of the compounds described in JP-A 62-215272, pp. 127 to 137.
The rust inhibitor includes sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and its salts. Preferably, this is in the ink in an amount of from 0.02 to 1.00% by mass.
As the pH controlling agent, usable are neutralizing agents (organic base, inorganic alkali). For the purpose of improving the storage stability of the inkjet ink, the pH controlling agent is preferably added to the inkjet ink so that the ink could have a pH of from 6 to 10, more preferably from 7 to 10.
The surface tension controlling agent may be a nonionic, cationic or anionic surfactant. Preferably, the surface tension of the inkjet ink containing the coloring composition of the invention is from 20 to 60 mN/m, more preferably from 25 to 45 mN/m. The viscosity of the inkjet ink of the invention is preferably at most 30 mPa·s, more preferably so controlled as to be at most 20 mPa·s.
Preferred examples of the surfactant include anionic surfactants such as fatty acid salts, alkylsulfate ester salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic salts, dialkylsulfosuccinic acid salts, alkylphosphate ester salts, naphthalenesulfonic acid/formalin condensates, polyoxyethylene alkylsulfate ester salts; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethylene-oxypropylene block copolymers. Also preferred are SURFYNOLS (trade name by Air Products & Chemicals) that are acetylene-type polyoxyethylene oxide surfactants. Also preferred are amine oxide-type ampholytic surfactants such as N,N-dimethyl-N-alkylamine oxide. Further usable herein are the surfactants described in JP-A 59-157636, pp. 37-38, and Research Disclosure No. 308119 (1989).
As the defoaming agent, optionally used herein are fluorine compounds, silicone compounds, and chelating agents such as EDTA.
In case where the arylidene-pyrazolone dye of formula (1) is dispersed in an aqueous medium, it is desirable that coloring particles containing the compound and an oil-soluble polymer are dispersed in an aqueous medium as in JP-A 11-286637, 2001-240763, 2001-262039, 2001-247788, or the arylidene-pyrazolone dye of formula (1) dissolved in a high-boiling-point organic solvent is dispersed in an aqueous medium as in JP-A 2001-262018, 2001-240763, 2001-335734, 2002-80772. Regarding the concrete method of dispersing the arylidene-pyrazolone dye of formula (1) in an aqueous medium, as well as the oil-soluble polymer, the high-boiling-point organic solvent and the additives to be used, and their amount, those described in the above-mentioned patent references are employable herein. As the case may be, the bisazo compound may be dispersed as fine particles directly as it is solid. In dispersing them, a dispersant and a surfactant may be used.
As the dispersing device, usable are simple stirrers, and also impellers, in-line stirrer mills (e.g., colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill), ultrasonic stirrers, high-pressure emulsification dispersers (high-pressure homogenizers; as commercial devices, available are Gaulin homogenizer, Microfluidizer, DeBEE 2000 (by BEE International)). Regarding the method of preparing the above-mentioned inkjet recording ink, its details are described also in JP-A 5-148436, 5-295312, 7-97541, 7-82515, 7-118584, 11-286637, 2001-271003, in addition to the above-mentioned patent references; and these descriptions are applicable to the preparation of the inkjet recording ink of the invention.
As the aqueous medium, usable is a mixture comprising water as the main ingredient and optionally containing a water-miscible organic solvent added thereto. Examples of the water-miscible organic solvent include alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyalcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine), and other polar solvents (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). Two or more of the above-mentioned water-miscible organic solvents may be combined for use herein.
[Color Filter]
The color filter of the invention is characterized by containing the arylidene-pyrazolone dye of formula (1). For producing the color filter, employable is a method of first forming a pattern with a photoresist and then dying it; or a method of forming a pattern with a photoresist to which a colorant is added, as in JP-A 4-163552, 4-128703, 4-175753. As the method of introducing the arylidene-pyrazolone dye of formula (1) into the color filter of the invention, any of the above methods is employable, but preferred is the method described in JP-A 4-175753, 6-35182. The method comprises applying a positive photoresist composition containing a thermosetting resin, a quinonediazide compound, a crosslinking agent, a colorant and a solvent, onto a support, then exposing it through a mask, developing the exposed area to form a positive resist pattern, then exposing the entire surface of the positive resist pattern to light, and thereafter curing the thus-exposed positive resist pattern to produce a color filter. Also employable is a method of forming a black matrix in an ordinary manner thereby obtaining an RGB primary color filter or an Y.M.C complementary color filter.
For the thermosetting resin, the quinonediazide compound, the crosslinking agent and the solvent to be used in the above and their amount, preferred are those described in the above-mentioned patent references.
EXAMPLES
The characteristics of the invention are described more concretely with reference to Production Examples and Examples given below.
In the following Examples, the material used, its amount and the ratio, the details of the treatment and the treatment process may be suitably modified or changed not overstepping the scope of the invention. Accordingly, the invention should not be limitatively interpreted by the Examples mentioned below.
Example 101
Production of Compound (Y-1)




5-Ethoxy-4-(4-diethylaminophenylmethylene)-2,4-dihydropyrazol-3-one (5.75 g, 0.02 mol) was dissolved in N-methylpyrrolidone (30 mL), and with cooling, triethylamine (7.08 g, 0.07 mol) was dropwise added thereto. Further with cooling at an inner temperature of not higher than 10° C., methanesulfonyl chloride (4.65 mL, 0.06 mol) was dropwise added and stirred at 5 to 10° C. for 30 minutes and then at room temperature for 1 hour. The reaction liquid was added to saturated saline water (200 mL), and extracted with ethyl acetate (300 mL), and the extract was washed with saturated saline water (200 mL). The extract was concentrated with a rotary evaporator, and the residue was purified through silica gel column chromatography (developing solvent: methylene chloride/ethyl acetate=10/1 (v/v)) to give Compound (Y-1) (1.13 g, yield 15.5%).
1H NMR (DMSO-d6) δ (ppm): 1.1 (t, 6H), 1.3-1.5 (m, 3H), 3.4-3.6 (m, 4H), 4.2-4.5 (m, 2H), 6.8 (d, 2H), 7.4 (s×2, 1H), 8.1-8.5 (m, 2H).
λmax of Compound (Y-1) in ethyl acetate solution was 468 nm.
Example 102 to 104
Production of Compounds (Y-2), (Y-3) and (Y-7)
Compounds (Y-2), (Y-3) and (Y-7) were produced according to the method of the above Production Example. Other compounds than the compounds may also be produced according to the method of the above-mentioned Production Example from the chemical viewpoint.
Example 105
Production of Compound (Y-8)




2-Dimethylsulfamoyl-5-ethoxy-3-pyrazolone (1.18 g, 5 mmol), 4-diethylaminobenzaldehyde (1.06 g, 6 mmol) and ammonium acetate (0.04 g, 0.5 mmol) were heated under reflux for 1 hour in 2-propanol (6.5 mL) in a nitrogen atmosphere. After the reaction, the reaction liquid was cooled to room temperature, and water (20 mL) was added thereto. This was extracted with methylene chloride (30 mL), and purified through silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=1/1 (v/v)) to give an orange solid of Compound (Y-8) (1.87 g, yield 94.9%).
1H NMR (DMSO-d6) δ (ppm): 1.1 (t, 6H), 1.3-1.5 (m, 3H), 2.9 (s, 6H), 3.5 (m, 4H), 4.2-4.4 (m, 2H), 6.8 (d, 2H), 7.4-7.55 (m, 1H), 8.1-8.6 (2H).
λmax of Compound (Y-8) in ethyl acetate solution was 462 nm.
<Evaluation of Maximum Absorption Wavelength>
The thus-obtained arylidene-pyrazolone dyes of Examples 101 to 105 were analyzed absorption spectrometry in an ethyl acetate solution (concentration: 1×10−6 mol/L, optical path length: 10 mm). The data of the maximum absorption wavelength of the compounds are shown in the following Table 2.










TABLE 2








Maximum Absorption



Dye
Wavelength (nm)




















Example 101
(Y-1)
468



Example 102
(Y-2)
468



Example 103
(Y-3)
469



Example 104
(Y-7)
470



Example 105
(Y-8)
462










Example 201
Construction of Thermal Transfer Recording Ink Sheet
A polyester film (Lumirror, trade name by Toray) having a thickness of 6.0 μm and processed for heat-resistant lubrication with a thermosetting acrylic resin (thickness 1 ρm) on its back was used as a support. Using a wire bar coater, a dye-donating layer-forming coating composition comprising the arylidene-pyrazolone dye of the invention produced in Examples 101 (Compound (Y-1)) mentioned above was applied onto the surface of the film to form thereon a layer having a dry thickness of 1 μm, thereby constructing a thermal transfer recording ink sheet of Example 201.
(Dye-Donating Layer-Forming Coating Composition)













Compound (Y-1)
5.5 mas. pts.


Polyvinylbutyral Resin (Eslec BX-1, trade name by Sekisui
4.5 mas. pts.


Chemical Industry)


Methyl ethyl ketone/toluene (1/1)
 90 mas. pts.









Example 202 to 204, Comparative Example 201 to 203
Construction of Thermal Transfer Recording Ink Sheet
Next, thermal transfer recording ink sheets Example 202 to 204 of the invention and comparative thermal transfer recording ink sheets Comparative Example 201 to 203 were constructed in the same manner as that for the Example 201, for which, however, the compound (Y-1) was changed to the dye shown in Table 3 below. The chemical structures of Comparative dyes 1 to 3 used in Comparative Examples 1 to 3 are as follows:
Comparative Dye 1 (C.I.Disperse Yellow 201)




Comparative Dye 2 (Similar to the Compound 12 Described in JP-A 2-3450)





Comparative Dye 3 (Similar to the Compound 16 Described in JP-A 2-3450)





(Solubility)

The dye solubility of each compound in the solvent of methyl ethyl ketone/toluene (1/1, w/w) was ranked in three, A (easily soluble), B (soluble), C (difficult to dissolve, but soluble). The results are shown in Table 3.
Example 301
Evaluation of Thermal Transfer Recording Ink Sheet and Formation of Thermal Transfer Recording Image by the Thermal Transfer Recording Method
(Construction of Image-Receiving Material)
Synthetic paper (Yupo FPG200, trade name by Yupo Corporation, thickness: 200 μm) was used as a support. A white interlayer-forming coating composition and a receiving layer-forming coating composition mentioned below were applied in that order onto one surface of the support, using a bar coater. Their amount was so controlled that the white interlayer could have a dry thickness of 1.0 g/m2 and the receiving layer could have a dry thickness of 4.0 g/m2. The layers were dried at 110° C. for 30 seconds each.
(White Interlayer-Forming Coating Composition)













Polyester resin (Vylon 200, trade name by TOYOBO)
10 mas. pts.


Fluorescent brightener (Uvitex OB, trade name by
1 mas. pt.


Ciba-Geigy)


Titanium oxide
30 mas. pts.


Methyl ethyl ketone/toluene (1/1)
90 mas. pts.









(Receiving Layer-Forming Coating Composition)














Vinyl chloride-vinyl acetate resin (Solbine A, trade
100 mas. pts. 


name by Nisshin Chemical Industry)


Amino-modified silicone (X22-3050C, trade name by
5 mas. pts.


Shin-etsu Chemical Industry)


Epoxy-modified silicone (X22-300E, trade name by
5 mas. pts.


Shin-etsu Chemical Industry)


Methyl ethyl ketone/toluene (= 1/1)
400 mas. pts. 


Benzotriazole-type UV absorbent (Tinuvin 900, trade
5 mas. pts.


name by Ciba Speciality Chemicals)









The thermal transfer recording ink sheet produced in Example 201 and the image-receiving material constructed as above were combined in such a manner that the dye-donating layer could face the image-receiving layer, and this was printed using a thermal head applied to the back of the dye-donating material. The output power of the thermal head was 0.25 W/dot, pulse width was from 0.15 to 15 msec, the dot density was 6 dots/mm. In that manner, the magenta dye was imagewise fixed on the image-receiving layer of the image-receiving material, and as a result, a sharp image print with no transfer unevenness was obtained.
The thermal transfer recording ink sheets produced in Example 202 to 204 and produced in Comparative Example 201 to 203 were used in place of the thermal transfer recording ink sheet produced in Example 201, tested for image recording.
(Light Fastness)
Next, the thermal transfer image-receiving material that had been recorded by the thermal transfer were exposed to a Xe light (17000 lux) for 7 days, and tested for the light stability (light fastness) of the recorded images. After the exposure, the status A reflection density of the part of each sample having an original status A reflection density of 1.0 before the exposure was measured, and the retention (by percentage) to the reflection density of 1.0 after exposure to that before exposure indicates the image stability. With the retention percentage, the samples were ranked in three, A (from 90% to less than 100%), B (from 80% to less than 90%), C (less than 80%). The results are shown in Table 3 below.
(Wet Heat Fastness)
Further, the thermal transfer image-receiving material that had been recorded by the thermal transfer in the same manner as above were stored under the condition of 80° C. and 70% RH in a dark place for 7 days, and checked for the wet heat stability (wet heat fastness) of the image. After exposure to light, the Status A reflection density of the area having an initial Status A reflection density of 1.0 was measured; and the density retentiveness (percentage) relative to the original reflection density 1.0 before exposure to light was computed. Based on the computed data, the samples were evaluated with regard to the stability into three ranks, A (from 90% to less than 100%), B (from 80% to less than 90%), and C (less than 80%). The results are shown in Table 3 below.











TABLE 3





Thermal






Transfer Ink


Light
Wet Heat


Sheet
Dye
Solubility
Fastness
Fastness







Example 201
(Y-1)
A
A
A


Example 202
(Y-2)
A
A
A


Example 203
(Y-3)
A
A
A


Example 204
(Y-8)
A
A
A


Comparative
Comparative
A
A
C


Example 201
Dye 1


Comparative
Comparative
B
A
C


Example 202
Dye 2


Comparative
Comparative
A
B
C


Example 203
Dye 3









As a result of the above thermal transfer image recording test, it was found that the images transferred onto the image-receiving layer from the ink sheets having the dye of formula (1) of the invention has a sharp color, and as compared with those from the comparative dyes, the images have more improved stability to light and wet heat condition and have excellent image storability.
Unexpectedly, in addition, it was found that, as compared with the comparative dyes, the arylidene-pyrazolone dyes of formula (1) of the invention have more excellent solubility, and therefore can greatly reduce the load in dissolution in ink sheet construction.
Example 401
Formation of Color Toner
3 parts by mass of an arylidene-pyrazolone dye of the invention produced in Example 101 (compound (Y-1)) and 100 parts by mass of a toner resin [styrene-acrylate copolymer, Himer TB-1000F (trade name by Sanyo Chemical)] were mixed and ground in a ball mill, then melted and kneaded under heat at 150° C., and after cooled, this was roughly ground with a hammer mill, and then finely ground with an air jet-type grinder. Further classified, particles of from 1 to 20 μm in size were selected to be a color toner of Example 401.
10 parts by mass of the color toner was uniformly mixed with 900 parts by mass of a carrier iron powder (EFV250/400, trade name by Nippon Iron Powder) to prepare a developer. The developer was tested for copying with a dry-type plain paper electrophotographic copier (NP-5000, trade name by Canon). As a result, the developer had excellent spectral characteristics and had excellent properties as color toner.
Example 501
Formation and Evaluation of Inkjet Ink
<Formation of Inkjet Ink>
An arylidene-pyrazolone dye of the invention produced in Example 101 (compound (Y-1)) (5.63 g) and sodium dioctylsulfosuccinate (7.04 g) were dissolved in a high-boiling-point organic solvent mentioned below (S-2) (4.22 g), a high-boiling-point organic solvent mentioned below (S-11) (5.63 g) and ethyl acetate (50 ml) at 70° C. With stirring with a magnetic stirrer, deionized water (500 ml) was added to the solution to produce an oil-in-water crude particle dispersion.
Next, the crude particle dispersion was led to pass through a microfluidizer (by MICROFLUIDEX INC) five times under a pressure of 60 MPa to be fine particles, and the thus-prepared emulsion was evaporated for solvent removal with a rotary evaporator until it gave no ethyl acetate odor.
Diethylene glycol (140 g), glycerin (50 g), SURFYNOL 465 (trade name by Air Products & Chemicals) (7 g) and deionized water (900 ml) were added to the fine emulsion of the hydrophobic dye thus obtained as above, thereby producing an inkjet ink of Example 501.




<Evaluation>

The thus-obtained ink of Example 501 was filled in a cartridge of an inkjet printer (PM-G800, trade name by Seiko Epson), and tested in the printer for image recording on inkjet paper, Kassai Photofinish Pro (trade name by FUJIFILM). It is known that the obtained image has excellent spectral characteristics and the ink has excellent properties as inkjet ink.
Example 601
Construction and Evaluation of Color Filter
<Construction of Color Filter>
(Preparation of Positive Resist Composition)
3.4 parts by mass of cresol/novolak resin obtained from a mixture of m-cresol/p-cresol/formaldehyde (reaction molar ratio=5/5/7.5) (polystyrene-based mass-average molecular weight, 4300), 1.8 parts by mass of o-naphthoquinonediazido-5-sulfonate ester produced by the use of a phenol compound having a formula mentioned below (in which 2 hydroxyl groups were esterified on average), 0.8 parts by mass of hexamethoxymethylolated melamine, 20 parts by mass of ethyl lactate, and 1 part by mass of the compound (Y-6) were mixed to produce a positive resist composition. Compound (Y-6) was produced according to the above-mentioned method for producing compound (Y-1) in Example 101.
Phenolic Compound:




(Construction of Color Filter)

The obtained positive resist composition was applied onto a silicon wafer in a mode of spin coating, and the solvent was evaporated away. Next, the silicon wafer was exposed to light through a mask to decompose the quinonediazide compound. Next, this was heated at 100° C. and then the exposed area was removed by alkali development to obtain a positive color pattern having a resolution of 0.8 μm. This was exposed on the entire surface, and then heated at 150° C. for 15 minutes to produce a yellow-complementary color filter of Example 601. For the exposure, used was an i-ray exposure stepper HITACHI LD-5010-i (trade name by Hitachi, NA=0.40). As the developer, used was SOPD or SOPD-B (trade name by Sumitomo Chemical Industry).
The transmission spectrum of the obtained color filter is shown in FIG. 1. As is obvious from the data in FIG. 1, the obtained color filter of Example 601 has excellent spectral characteristics and light transmittance, and has excellent properties as color filter.
According to the invention, there are provided a novel arylidene-pyrazolone dye having excellent spectral characteristics with sharp absorption, high fastness and excellent solubility, and a coloring composition containing the azo dye. According to the invention, there are also provided a thermal transfer recording ink sheet and a thermal transfer recording method capable of satisfying all the requirements of excellent color reproducibility, image storability and transfer sensitivity in print samples. Further, the invention provides a color toner, an inkjet ink and a color filter comprising the arylidene-pyrazolone dye. Accordingly, the invention is expected to be effectively used in high-quality full color recording, and its industrial applicability is great.
The present disclosure relates to the subject matter contained in Japanese Patent Application No. 049978/2008 filed on Feb. 29, 2008, which is expressly incorporated herein by reference in its entirety. All the publications referred to in the present specification are also expressly incorporated herein by reference in their entirety.
The foregoing description of preferred embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or to limit the invention to the precise form disclosed. The description was selected to best explain the principles of the invention and their practical application to enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention not be limited by the specification, but be defined claims set forth below.

## Claims

1. An arylidene-pyrazolone dye of the following formula (1):



wherein R1, R2, R3, R4 and R5 each independently represent a monovalent substituent; n indicates an integer of from 0 to 4; when n is 2 or more, plural R3's may be the same or different; and R1 and R2 may bond to each other to form a cyclic structure.

2. The arylidene-pyrazolone dye according to claim 1 wherein R1 and R2 each independently represent a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aryl group.

3. The arylidene-pyrazolone dye according to claim 1 wherein R4 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted carbamoyl group, or a cyano group.

4. The arylidene-pyrazolone dye according to claim 1 wherein R5 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted heterocyclic group.

5. A coloring composition containing the arylidene-pyrazolone dye of claim 1.

6. A thermal transfer recording ink sheet containing the arylidene-pyrazolone dye of claim 1.

7. A thermal transfer recording method comprising forming an image by use of the thermal transfer recording ink sheet of claim 6 on an image-receiving material comprising a polymer-containing ink-receiving layer on a support.

8. A color toner containing the arylidene-pyrazolone dye of claim 1.

9. An inkjet ink containing the arylidene-pyrazolone dye of claim 1.

10. A color filter containing the arylidene-pyrazolone dye of claim 1.