# Patent

## Title
Color filter ink, color filter, image display device, and electronic device

## Abstract

A color filter ink according to the first aspect is adapted to be used to manufacture a color filter by an inkjet method, the color filter ink comprising. The color filter ink includes a pigment, a solvent, a dispersing agent and a curable resin material. The dispersing agent includes an acid-value dispersing agent with a predetermined acid value and an amine-value dispersing agent with a predetermined amine value. The curable resin material includes a first polymer and a second polymer. The first polymer includes at least a first epoxy-containing vinyl monomer as a monomer component. The second polymer includes at least an alkoxysilyl-containing vinyl monomer represented by a prescribed chemical formula as a monomer component.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to Japanese Patent Application No. 2007-306950 filed on Nov. 28, 2007. The entire disclosure of Japanese Patent Application No. 2007-306950 is hereby incorporated herein by reference.
BACKGROUND
1. Technical Field
The present invention relates to a color filter ink, a color filter, an image display device, and an electronic device.
2. Related Art
Color filters are generally used in liquid crystal display devices (LCD) and the like that display color.
Color filters have conventionally been manufactured using a so-called photolithography method in which a coating film composed of a material (color layer formation composition) that includes a colorant, a photosensitive resin, a functional monomer, a polymerization initiator, and other components is formed on a substrate, and then photosensitive processing for radiating light via a photomask, development processing, and the like are performed. In such a method, the color filters are usually manufactured by repeating a process in which a coating film corresponding to each color is formed on substantially the entire surface of the substrate, only a portion of the coating film is cured, and most of the film other than the cured portion is removed, so that there is no color overlap. Therefore, only a portion of the coating film formed in color filter manufacturing remains as a color layer in the finished color filter, and most of the coating film is removed in the manufacturing process. Therefore, not only does the manufacturing cost of the color filter increase, but the process is also undesirable from the perspective of resource saving.
Methods have recently been proposed for forming the color layer of a color filter through the use of an inkjet head (droplet discharge head) (see Japanese Laid-Open Patent Application No. 2002-372613, for example). In such a method, because the discharge position and the like of droplets of the material (color layer formation composition) used to form the color layer are easily controlled, and waste of the color layer formation composition can be reduced, the environmental impact can be reduced, and manufacturing cost can also be minimized. However, in a method for manufacturing a color filter using an inkjet head, when droplets are discharged for long periods of time, and droplets are discharged continuously, the trajectory of the discharged droplets changes (so-called flight deflection occurs), it becomes impossible to land the droplets in the desired region, the droplet discharge quantity becomes unstable, and other problems occur. When such problems occur, on the substrate or the like onto which the droplets are to be discharged, the plurality of types of ink used to form different colored portions mixes together (colors mix), and the color saturation fluctuates between the plurality of colored portions that are originally supposed to have the same color saturation, and as a result, uneven color between regions of the same color filter, uneven saturation, and the like occur, fluctuation occurs in the characteristics (particularly contrast ratio, color reproduction range, and other color characteristics) between numerous color filters, and the reliability of the color filters is reduced. Since the droplet discharge device (industrial) used for color filter manufacturing is entirely different from what is used for a printer (consumer-level), and the droplet discharge device is used for mass production and droplet discharge onto large-scale workpieces (substrates), for example, there is a need to discharge large quantities of droplets for long periods of time. Because the droplet discharge device is used under such harsh conditions, the droplet discharge quantity easily fluctuates in comparison to a consumer droplet discharge device, but when the discharge quantity varies in this manner, fluctuation of the characteristics between numerous manufactured color filters, or fluctuation in the color saturation in different areas of a color filter occurs, and the reliability of the color filter as a product is markedly reduced.
Pigments generally have superior light fastness and other characteristics in comparison to dyes, and pigments are therefore widely used as colorants in color filter ink. However, when a pigment is used as the colorant, problems such as described above that accompany discharging the color filter ink from an inkjet head occur with greater severity. When a pigment is used as the colorant, severe drawbacks occur in that it is difficult to obtain adequately excellent contrast in the image displayed using the manufactured color filter, and when numerous color filters are manufactured by the inkjet method, the contrast characteristics of the manufactured color filters are severely compromised.
SUMMARY
An object of the present invention is to provide an inkjet-type color filter ink that has excellent discharge stability and excellent long-term dispersion stability (dispersion stability) of the pigment, and that can be suitably used to manufacture a color filter having excellent durability and uniformity of characteristics between units, in which unevenness of color and saturation among regions is suppressed, and that enables image display having excellent contrast; to provide a color filter having excellent durability and uniformity of characteristics between units, in which unevenness of color and saturation among regions is suppressed, and that enables image display having excellent contrast; and to provide an image display device and electronic device provided with the color filter.
Such objects are achieved by the present invention described hereinafter.
A color filter ink according to the first aspect is adapted to be used to manufacture a color filter by an inkjet method, the color filter ink comprising. The color filter ink includes a pigment, a solvent, a dispersing agent and a curable resin material. The dispersing agent includes an acid-value dispersing agent with a predetermined acid value and an amine-value dispersing agent with a predetermined amine value. The curable resin material includes a first polymer and a second polymer. The first polymer includes at least a first epoxy-containing vinyl monomer as a monomer component. The second polymer includes at least an alkoxysilyl-containing vinyl monomer represented by a chemical formula (1) below as a monomer component.




In Formula (1), R1 is a hydrogen atom or a C1-7 alkyl group; E is a single bond hydrocarbon group or a bivalent hydrocarbon group; R2 is a C1-6 alkyl group or a C1-6 alkoxyl group; R3 is a C1-6 alkyl group or a C1-6 alkoxyl group; R4 is a C1-6 alkyl group; a value x is 0 or 1; and a value y is an integer from 1 to 10.
It is thereby possible to provide an inkjet-type color filter ink that has excellent discharge stability and excellent long-term dispersion stability (dispersion stability) of the pigment, and that can be suitably used to manufacture a color filter having excellent durability and uniformity of characteristics between units, in which unevenness of color and saturation among regions is suppressed, and that enables image display having excellent contrast.
In the color filter ink as described above, the first polymer is preferably a copolymer having the first epoxy-containing vinyl monomer and a second vinyl monomer as monomer components, the second vinyl monomer having an isocyanate group or a block isocyanate group in which an isocyanate group is protected by a protective group.
It is thereby possible to effectively prevent the color of the color filter (colored portion) manufactured using the color filter ink from changing over time, and to endow the color filter with particularly excellent durability.
In the color filter ink as described above, the first polymer is preferably a copolymer having the first epoxy-containing vinyl monomer and a second vinyl monomer as monomer components, the second vinyl monomer having an isocyanate group or a block isocyanate group in which an isocyanate group is protected by a protective group.
The adhesion to the color filter substrate of the colored portion of the color filter formed using the color filter ink can thereby be reliably maintained over a longer period of time, and the durability of the color filter can be made particularly excellent.
In the color filter ink as described above, a ratio of a content of the first polymer to a content of the second polymer is preferably 25:75 to 75:25 in terms of weight.
The discharge stability of the color filter ink and the durability of the color filter manufactured using the color filter ink can thereby be made particularly excellent.
In the color filter ink as described above, the second polymer is preferably a homopolymer of the alkoxysilyl-containing vinyl monomer represented by the chemical formula (1).
The discharge stability of the color filter ink and the durability of the color filter manufactured using the color filter ink can thereby be made particularly excellent.
In the color filter ink as described above, the predetermined acid value of the acid-value dispersing agent is preferably 5 to 370 KOH mg/g.
The long-term dispersion stability of the pigment particles in the color filter ink can thereby be made particularly excellent, and the color filter ink can be endowed with particularly excellent discharge stability. Particularly excellent contrast can also be obtained in the image displayed using the manufactured color filter.
In the color filter ink as described above, the predetermined amine value of the amine-value dispersing agent is preferably 5 to 200 KOH mg/g.
The long-term dispersion stability of the pigment particles in the color filter ink can thereby be made particularly excellent, and the color filter ink can be endowed with particularly excellent discharge stability. Particularly excellent contrast can also be obtained in the image displayed using the manufactured color filter.
In the color filter ink as described above, content ratios of the acid-value dispersing agent and the amine-value dispersing agent in the color filter ink are preferably arranged to satisfy 0.1≦XA/XB≦1, wherein a value XA (wt %) is the content ratio of the acid-value dispersing agent and a value XB (wt %) is the content ratio of the amine-value dispersing agent.
The long-term dispersion stability of the pigment particles in the color filter ink can thereby be made particularly excellent, and the color filter ink can be endowed with particularly excellent discharge stability. Particularly excellent contrast can also be obtained in the image displayed using the manufactured color filter.
In the color filter ink as described above, the acid-value dispersing agent and the amine-value dispersing agent in the color filter ink are preferably arranged to satisfy 0.01≦(AV×XA)/(BV×XB)≦1.9, wherein a value AV (KOH mg/g) is the predetermined acid value of the acid-value dispersing agent, a value BV (KOH mg/g) is the predetermined amine value of the amine-value dispersing agent, a value XA (wt %) is a content ratio of the acid-value dispersing agent in the color filter ink, and a value XB (wt %) is a content ratio of the amine-value dispersing agent in the color filter ink.
The long-term dispersion stability of the pigment particles in the color filter ink can thereby be made particularly excellent, and the color filter ink can be endowed with particularly excellent discharge stability. Particularly excellent contrast can also be obtained in the image displayed using the manufactured color filter.
In the color filter ink as described above, the solvent preferably includes one or more compounds selected from the group consisting of 1,3-butylene glycol diacetate, bis(2-butoxyethyl)ether, and diethylene glycol monobutyl ether acetate.
The long-term dispersion stability of the pigment particles in the color filter ink can thereby be made particularly excellent, and the color filter ink can be endowed with particularly excellent discharge stability. Particularly excellent contrast can also be obtained in the image displayed using the manufactured color filter.
A color filter according to the second aspect is manufactured using the color filter ink as described above.
It is thereby possible to provide a color filter having excellent durability and uniformity of characteristics between units, in which unevenness of color and saturation among regions is suppressed, and that enables image display having excellent brightness and contrast.
An image display device according to the third aspect includes the color filter according as described above.
It is thereby possible to provide an image display device having excellent durability and uniformity of characteristics between units, in which unevenness of color and saturation among regions is suppressed, and that enables image display having excellent contrast.
The image display device as described above is preferably a liquid crystal panel.
It is thereby possible to provide an image display device having excellent durability and uniformity of characteristics between units, in which unevenness of color and saturation among regions is suppressed, and that enables image display having excellent contrast.
An electronic device according to the fourth aspect includes the image display device as described above.
It is thereby possible to provide an electronic device having excellent durability and uniformity of characteristics between units, in which unevenness of color and saturation among regions is suppressed, and that enables image display having excellent contrast.



BRIEF DESCRIPTION OF THE DRAWINGS
Referring now to the attached drawings which form a part of this original disclosure:
FIG. 1 is a cross-sectional view showing a preferred embodiment of a color filter according to the present invention.
FIG. 2 includes a series of cross-sectional views (1a) to (1e) showing a method for manufacturing a color filter.
FIG. 3 is perspective view showing a droplet discharge device using in the manufacture of the color filter.
FIG. 4 is a view of the droplet discharge means of the droplet discharge device shown in FIG. 3 as seen from the stage.
FIG. 5 is a view showing the bottom surface of the droplet discharge head of the droplet discharge device shown in FIG. 3.
FIG. 6 includes a pair of diagrams (a) and (b) showing a droplet discharge head of the droplet discharge device shown in FIG. 3, wherein FIG. 6(a) is a cross-sectional perspective view and FIG. 6(b) is a cross-sectional view.
FIG. 7 is a cross-sectional view showing an embodiment of a liquid crystal display device.
FIG. 8 is a perspective view showing a mobile (or notebook) personal computer exemplifying an electronic device in accordance with the present invention.
FIG. 9 is a perspective view showing a portable telephone (including PHS) exemplifying an electronic device in accordance with the present invention.
FIG. 10 is a perspective view showing a digital still camera exemplifying an electronic device in accordance with the present invention.



DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
Preferred embodiments of the present invention will be described in detail hereinafter.
Color Filter Ink
The color filter ink of the present invention is an ink used to manufacture (form the colored portion of a color filter) a color filter, and is used particularly in the manufacture of a color filter by an inkjet method.
The color filter ink includes a pigment, a solvent, a dispersing agent, and a curable resin material.
Pigment
Various organic pigments and various inorganic pigments may be used as the pigment, but an organic pigment is preferred. Through the use of an organic pigment the colored portion formed using the color filter ink can be endowed with particularly excellent coloration properties. Examples of organic pigments include compounds classified as pigments in the Color Index (C. I.; issued by The Society of Dyers and Colorists), e.g., compounds such as those below numbered according to the Color Index (C. I.). More specifically, examples of organic pigments include C. I. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 34, 35, 35:1, 37, 37:1, 42, 43, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 157, 166, 168, 175, 180, 184, and 185; C. I. pigment orange 1, 5, 13, 14, 16, 17, 20, 20:1, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, and 104; C. I. pigment violet 1, 3, 14, 16, 19, 23, 29, 32, 36, 38, and 50; C. I. pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 108:1, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, and 265; C. I. pigment blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 17:1, 18, 60, 27, 28, 29, 35, 36, 60, and 80; C. I. pigment green 7, 36, 15, 17, 18, 19, 26, 50, and 58; C. I. pigment brown 7, 11, 23, 25, and 33; C. I. pigment black 1 and 7; and derivatives of these pigments and the like, and one or more types of pigments selected from the above examples may be combined and used.
Particularly when the color filter ink includes C. I. pigment red 177 and a derivative thereof, and/or C. I. pigment red 254 and a derivative thereof as the pigment (red pigment), the color filter ink (red color filter ink) can be endowed with particularly excellent coloration properties. The effects of jointly using a curable resin material and dispersing agent such as described in detail hereinafter can also be more significantly demonstrated, and it is possible to obtain particularly excellent discharge stability of the color filter ink and long-term dispersion stability of the pigment particles in the color filter ink.
Such effects as those described above are even more significantly demonstrated when a compound (derivative) indicated by Formula (2) or Formula (3) below is included as the derivative of C. I. pigment red 177 and the derivative of C. I. pigment red 254.




In Formula (2), n is an integer from 1 to 4.




In Formula (3), n is an integer from 1 to 4.
The coloration properties of the color filter ink (green color filter ink) can be made particularly excellent particularly when the color filter ink includes C. I. pigment green 58 (brominated zinc phthalocyanine pigment) as a pigment (green pigment). Although C. I. pigment green 58 has the characteristic of excellent brightness, the material is conventionally extremely difficult to stably disperse, but in the present invention, the long-term dispersion stability in the color filter ink can be made particularly excellent even when C. I. pigment green 58 is included, which is conventionally extremely difficult to stably disperse. When the color filter ink includes C. I. pigment green 58, the color filter ink preferably also includes a sulfonated pigment derivative as a secondary pigment. Even more excellent coloration properties of the color filter ink can thereby be obtained, and the color filter ink can be endowed with particularly excellent discharge stability.
When C. I. pigment green 58 and a sulfonated pigment derivative are included as pigments, the color filter ink preferably contains a compound (derivative) indicated by Formula (4) below as the sulfonated pigment derivative. The effects of the present invention can thereby be more significantly demonstrated, particularly excellent droplet discharge stability and long-term dispersion stability of pigment particles in the color filter ink can be obtained, and an image having more excellent contrast can be displayed in the manufactured color filter. In a method such as described hereinafter, the fine-dispersion step can be performed with particularly excellent efficiency, and the color filter ink can be manufactured in a short time using a relatively small amount of energy. The color filter ink can therefore be endowed with particularly excellent production properties, which can contribute to reduced production cost.




In Formula (4), n is an integer from 1 to 5.
The inventors discovered as a result of concentrated investigation that such excellent effects as described above are obtained through the use of a pigment derivative (secondary pigment) having a specific chemical structure together with C. I. pigment green 58 (primary pigment), although the mechanism of these effects is not known in detail, the effects are considered to be obtained for such reasons as those described below.
A highly conjugated system is formed by the molecule as a whole in the brominated phthalocyanine that constitutes C. I. pigment green 58, and a planar structure is energetically stable. Planar molecules of the brominated phthalocyanine are in a layered (parallel to each other) arrangement, whereby a stable state occurs in which π electrons of conjugated systems between molecules are overlapped. The C. I. pigment green 58 is therefore easily aggregated, and difficult to stably disperse in a solvent.
In a pigment derivative such as described above, the hydrogen atom bonded to a nitrogen atom in Formula (4) forms a hydrogen bond between the oxygen atoms that form a phthalimide structure. For this reason, the hydrogen atom bonded to a nitrogen atom in Formula (4) substantially forms a strong bond with the nitrogen atom forming the quinoline structure, as well as the oxygen atom forming the phthalimide structure, and in a pigment derivative (sulfonated pigment derivative) such as described above, a stable ring structure (seven-member ring structure) is formed by the seven atoms that are labeled 1 through 7 in Formula (4). A non-parallel state with respect to the plane of the quinoline structure and the plane of the phthalimide structure occurs through the formation of such a seven-member ring structure.
The plane of the quinoline structure, and the plane of the phthalimide structure are thus non-parallel, whereby a pigment derivative (sulfonated pigment derivative) having the appropriate degree of affinity to C. I. pigment green 58 (a brominated phthalocyanine) is introduced between molecules of C. I. pigment green 58, and the C. I. pigment green 58, which is originally easily aggregated as described above, can be made less prone to aggregate. Furthermore, since a pigment derivative (sulfonated pigment derivative) such as described above has a sulfo group in the molecule thereof, the pigment derivative has excellent dispersion properties in the solvent described hereinafter. Such factors as those described above are considered to operate synergistically to produce such excellent effects as described above.
When C. I. pigment green 58 and a pigment derivative (sulfonated pigment derivative) such as described above are included, the content ratio of the pigment derivative (sulfonated pigment derivative) in the color filter ink is not particularly limited, but is preferably 2 to 32 parts by weight, and more preferably 7 to 28 parts by weight with respect to 100 parts by weight of C. I. pigment green 58 (primary pigment). Particularly excellent discharge stability of droplets and long-term dispersion stability of the pigment particles in the color filter ink can thereby be obtained, and the colored portion formed using the color filter ink can be endowed with particularly excellent brightness and contrast.
Particularly excellent coloration properties of the color filter ink (blue color filter ink) can be obtained particularly when the color filter ink includes a derivative of C. I. pigment blue 15:6 or C. I. pigment blue 15 as a pigment (blue pigment). Particularly excellent long-term dispersion stability of pigment particles in the color filter ink, and discharge stability of the color filter ink can also be obtained.
The content ratio of the pigments in the color filter ink is preferably 3 to 25 wt % or higher, more preferably 3.5 to 20 wt %, and more preferably 4.0 to 9.4 wt %. When the content ratio of the pigments is within the aforementioned range, higher color saturation can be maintained in the color filter that is manufactured using the color filter ink, and the color filter can be used for clearer image display. The amount of the color filter ink that is needed to form a colored portion having a predetermined color saturation can also be reduced, which is advantageous from the perspective of resource saving. Since the amount of evaporation of the solvent can be suppressed during formation of the colored portion of the color filter, the environmental impact can be reduced. In the conventional technique, when the pigment is included in such a relatively high concentration, the discharge stability is particularly low, and flight deflection, instability of the droplet discharge quantity, and other problems occur particularly easily when droplets of the color filter ink are discharged. Also in the conventional technique, such problems as a severe occurrence of defects due to fluctuation of the discharge quantity among different locations on the surface, and marked reduction of production properties of the color filter occurs particularly when droplets are discharged onto a large substrate (e.g., G5 or larger) to form colored portions. In the present invention, however, even when the pigment is included at a relatively high concentration, such problems as those described above can be reliably prevented from occurring, unevenness of color, saturation, and the like in different locations of the manufactured color filter, or fluctuation of characteristics between individual units can be reliably prevented, and a color filter can be manufactured with excellent productivity, as described in detail hereinafter. Specifically, the effects of the present invention are more significantly demonstrated when the color filter ink includes a relatively high concentration of the pigment, as described above. The durability of the manufactured color filter can also be made particularly excellent.
The average grain size of the pigment particles in the color filter ink is not particularly limited, but is preferably 10 to 200 nm, and more preferably 20 to 180 nm. The dispersion stability of the pigment in the color filter ink, and the contrast other characteristics in the color filter can thereby be made particularly excellent while making the light fastness of the color filter manufactured using the color filter ink adequately superior.
Solvent
The solvent functions as a dispersion medium for dispersing the pigment in the color filter ink. In a color filter ink manufacturing method such as the one described hereinafter, the solvent usually functions as a medium for dissolving a thermoplastic resin in a liquid dispersion of the dispersion medium. Most of the solvent (dispersion medium) constituting the color filter ink is usually removed in the process of manufacturing the color filter.
Ester compounds, ether compounds, hydroxyketones, carbonic diesters, cyclic amide compounds, and the like, for example, may be used as the solvent, preferred among which are (1) ethers (polyalcohol ethers) as condensates of polyalcohols (e.g., ethylene glycol, propylene glycol, butylene glycol, glycerin, and the like); alkyl ethers (e.g., methyl ether, ethyl ether, butyl ether, hexyl ether, and the like) of polyalcohols or polyalcohol ethers; and esters (e.g., formate, acetate, propionate, and the like); (2) esters (e.g., methyl esters and the like) of polycarboxylic acids (e.g., succinic acid, glutamic acid, and the like); (3) ethers, esters, and the like of compounds (hydroxy acids) having at least one hydroxyl group and at least one carboxyl group in the molecule thereof; and (4) carbonic diesters having a chemical structure such as that obtained by reaction of a polyalcohol and a phosgene. Examples of compounds that can be used as the solvent include 2-(2-methoxy-1-methylethoxy)-1-methyl ethyl acetate, triethylene glycol dimethyl ether, triethylene glycol diacetate, diethylene glycol monoethyl ether acetate, 4-methyl-1,3-dioxolan−2-one, bis(2-butoxyethyl)ether, dimethyl glutarate, ethylene glycol di-n-butyrate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, tetraethylene glycol dimethyl ether, 1,6-diacetoxyhexane, tripropylene glycol monomethyl ether, butoxypropanol, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl butyl ether, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethyl 3-ethoxy propionate, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, diethylene glycol diethyl ether, ethyl octanoate, ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether, cyclohexyl acetate, diethyl succinate, ethylene glycol diacetate, propylene glycol diacetate, 4-hydroxy-4-methyl-2-pentanone, dimethyl succinate, 1-butoxy-2-propanol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-n-butyl acetate, diacetin, dipropylene glycol mono n-propyl ether, polyethylene glycol monomethyl ether, butyl glycolate, ethylene glycol monohexyl ether, dipropylene glycol mono n-butyl ether, N-methyl-2-pyrrolidone, triethylene glycol butyl methyl ether, bis(2-propoxyethyl)ether, diethylene glycol diacetate, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol butyl propyl ether, diethylene glycol ethyl propyl ether, diethylene glycol methyl propyl ether, diethylene glycol propyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol butyl ether acetate, triethylene glycol butyl ethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol ethyl propyl ether, triethylene glycol methyl propyl ether, dipropylene glycol methyl ether acetate, n-nonyl alcohol, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, ethylene glycol 2-ethylhexyl ether, triethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monobutyl ether, diethylene glycol mono-2-ethylhexyl ether, tripropylene glycol mono n-butyl ether, butyl cellosolve acetate, and the like, and one or more types of compounds selected from the above examples may be combined and used. Among these examples, the solvent preferably includes one or more types of compounds selected from the group that includes 1,3-butylene glycol diacetate, bis(2-butoxyethyl)ether, and diethylene glycol monobutyl ether acetate. Particularly excellent long-term dispersion stability of pigment particles in the color filter ink can thereby be obtained. The long-term dispersion stability of the pigment can be made adequately excellent even when the content ratio of the pigment in the color filter ink is high. The color filter ink can also be endowed with particularly excellent discharge stability of droplets; unevenness of color, saturation, and the like in regions of the manufactured color filter can be more effectively suppressed, and the color filter can be endowed with particularly excellent uniformity of characteristics between individual units. When the solvent (for functioning as a dispersion medium in the color filter ink) is composed of a compound such as described above, because of the chemical structural interaction between the compounds, the aforementioned pigments, and a curable resin material such as described in detail hereinafter, the curable resin material can be unevenly distributed on the surfaces of the pigment particles in the color filter ink, particularly excellent discharge stability of droplets can be obtained, the dispersion stability of the pigment particles in the color filter ink can be made particularly excellent, and the color filter ink can be endowed with particularly excellent long-term storage properties while the dissolving properties of the curable resin material are made adequately excellent. When the solvent (for functioning as a dispersion medium in the color filter ink) is composed of such compounds as described above, the color filter ink can be reliably made to spread into the entire cell in the method for manufacturing a color filter such as described hereinafter, and a flattened colored portion can easily be formed even when the conditions for removing the liquid medium are not strictly prescribed. In other words, the internal shape of the pixels is easily controlled during baking.
The boiling point of the solvent at atmospheric pressure (1 atm) is preferably 160 to 300° C., more preferably 180 to 290° C., and even more preferably 200 to 280° C. When the boiling point of the solvent at atmospheric pressure is within this range, blockage and the like in the droplet discharge head for discharging the color filter ink can be more effectively prevented, and the color filter can be manufactured with particularly excellent productivity.
The vapor pressure of the solvent at 25° C. is preferably 0.7 mmHg or lower, and more preferably 0.1 mmHg or lower. When the vapor pressure of the solvent is within this range, blockage and the like in the droplet discharge head for discharging the color filter ink can be more effectively prevented, and the color filter can be manufactured with particularly excellent productivity.
The content ratio of the solvent in the color filter ink is preferably 50 to 98 wt %, more preferably 70 to 95 wt %, and even more preferably 80 to 93 wt %. When the content ratio of the solvent is within this range, the manufactured color filter can be endowed with excellent durability while the discharge properties of the color filter ink from the droplet discharge head are made particularly excellent. Adequate color saturation can also be maintained in the manufactured color filter.
Dispersing Agent
The dispersing agent is a component that contributes to enhancing the dispersion properties of the pigment particles in the color filter ink.
In the present invention, the color filter ink includes as dispersing agents an acid-value dispersing agent having a predetermined acid value, and an amine-value dispersing agent having a predetermined amine value. The effects of an acid-value dispersing agent for demonstrating viscosity-reducing effects whereby the viscosity of the color filter ink is reduced, and the effects of an amine-value dispersing agent whereby the viscosity of the color filter ink is stabilized can thereby be obtained at the same time, particularly excellent dispersion stability of the pigment in the color filter ink can be obtained, and particularly excellent discharge stability of droplets of the color filter ink can be obtained. Particularly excellent contrast and other characteristics can also be obtained in the color filter. Such effects as those described below are also obtained through the use of an acid-value dispersing agent and an amine-value dispersing agent. Specifically, when the color filter ink is manufactured by a method such as described hereinafter, the dispersing agent is efficiently caused to adhere to (adsorb on) the surfaces of the pigment particles (pigment particles having a relatively large grain size that are not fine-dispersed) added to the dispersing-agent-dispersed liquid in the fine-dispersion step, and excellent dispersion properties of the pigment particles (pigment particles having a relatively large grain size that are not fine-dispersed) in the dispersing-agent-dispersed liquid can be obtained. The fine-dispersion process in the fine-dispersion step can thereby be efficiently performed, the production properties of the color filter ink can be made particularly excellent, particularly excellent long-term dispersion stability of the pigment particles (fine-dispersed pigment microparticles) can be obtained in the color filter ultimately obtained, and particularly excellent discharge stability of droplets of the color filter ink can be obtained. A method such as the one described hereinafter has a pre-dispersion step for obtaining a dispersing-agent-dispersed liquid in which the dispersing agent is dispersed in a solvent by stirring a mixture of the dispersing agent, a thermoplastic resin, and the solvent prior to performing the pigment fine-dispersion process, but in such a method, the joint use of an acid-value dispersing agent and an amine-value dispersing agent makes it possible to reliably prevent association of the dispersing agents (association of the acid-value dispersing agent and the amine-value dispersing agent), and to obtain particularly excellent dispersion stability of the pigment.
Acid-Value Dispersing Agent
As described above, the acid-value dispersing agent has a predetermined acid value (not zero)
The acid value (acid value on a solid basis) of the acid-value dispersing agent is not particularly limited, but is preferably 5 to 370 KOH mg/g, more preferably 20 to 270 KOH mg/g, and more preferably 30 to 135 KOH mg/g. When the acid value of the acid-value dispersing agent is within the aforementioned range, the synergistic effects of joint use with an amine-value dispersing agent are more significantly demonstrated, and particularly excellent pigment dispersion stability, droplet discharge stability, and other characteristics can be obtained. The acid value of the dispersing agent can be calculated by a method based on DIN EN ISO 2114, for example.
The acid-value dispersing agent is one having a predetermined amine value, i.e., an amine value of zero.
Specific examples of acid-value dispersing agents include Disperbyk P104, Disperbyk P104S, Disperbyk 220S, Disperbyk 110, Disperbyk 111, Disperbyk 170, Disperbyk 171, Disperbyk 174, and Disperbyk 2095 (all manufactured by Byk Chemie Japan); EFKA 5010, EFKA 5065, EFKA 5066, EFKA 5070, EFKA 7500, and EFKA 7554 (all manufactured by Ciba Specialty Chemicals); Solsperse 3000, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse 36000, Solsperse 36600, and Solsperse 41000 (all manufactured by Nippon Lubrizol); and the like. The acid-value dispersing agent applied in the present invention is, of course, not limited by the examples given above.
Amine-Value Dispersing Agent
As described above, the amine-value dispersing agent has a predetermined amine value (not zero).
The amine value (amine value on a solid basis) of the amine-value dispersing agent is not particularly limited, but is preferably 5 to 200 KOH mg/g, more preferably 30 to 170 KOH mg/g, and more preferably 40 to 130 KOH mg/g. When the amine value of the amine-value dispersing agent is within the aforementioned range, the synergistic effects of joint use with an acid-value dispersing agent are more significantly demonstrated, and particularly excellent pigment dispersion stability, droplet discharge stability, and other characteristics can be obtained. The amine value of the dispersing agent can be calculated by a method based on DIN 16945, for example.
The amine-value dispersing agent is one having a predetermined acid value, i.e., an acid value of zero.
Specific examples of amine-value dispersing agents include Disperbyk 102, Disperbyk 160, Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 167, Disperbyk 168, Disperbyk 2150, Disperbyk LPN6919, Disperbyk 9075, and Disperbyk 9077 (all manufactured by Byk Chemie Japan); EFKA 4015, EFKA 4020, EFKA 4046, EFKA 4047, EFKA 4050, EFKA 4055, EFKA 4060, EFKA 4080, EFKA 4300, EFKA 4330, EFKA 4340, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4403, and EFKA 4800 (all manufactured by Ciba Specialty Chemicals); Ajisper PB711 (manufactured by Ajinomoto Fine Techno); Anti-Terra-205 (manufactured by Byk Chemie Japan); and the like. The amine-value dispersing agent applied in the present invention is, of course, not limited by the examples given above.
The relation 0.1≦XA/XB≦1 is preferably satisfied, and the relation 0.15≦XA/XB≦0.5 is more preferably satisfied, wherein XA (wt %) is the content ratio of the acid-value dispersing agent in the color filter ink, and XB (wt %) is the content ratio of the amine-value dispersing agent in the color filter ink. Satisfying such a relation makes it possible to more significantly demonstrate the synergistic effects of jointly using the acid-value dispersing agent and the amine-value dispersing agent, and to obtain particularly excellent dispersion stability of the pigment, discharge stability of droplets, and other effects.
The relation 0.01≦(AV×XA)/(BV×XB)≦1.9 is preferably satisfied, and the relation 0.10≦(AV×XA)/(BV×XB)≦0.95 is more preferably satisfied, wherein AV (KOH mg/g) is the acid value of the acid-value dispersing agent, BV (KOH mg/g) is the amine value of the amine-value dispersing agent, XA (wt %) is the content ratio of the acid-value dispersing agent, and XB (wt %) is the content ratio of the amine-value dispersing agent. Satisfying such a relation makes it possible to more significantly demonstrate the synergistic effects of jointly using the acid-value dispersing agent and the amine-value dispersing agent, and to obtain particularly excellent dispersion stability of the pigment, discharge stability of droplets, and other effects.
Other Dispersing Agents
In the present invention, the color filter ink may also include a dispersing agent other than the acid-value dispersing agent and the amine-value dispersing agent. In other words, the color filter ink may include a dispersing agent for which the acid value and the amine value are both zero.
Specific examples of such a dispersing agent include Disperbyk 101, Disperbyk 103, Disperbyk 106, Disperbyk 108, Disperbyk 109, Disperbyk 112, Disperbyk 116, Disperbyk 140, Disperbyk 142, Disperbyk 180, Disperbyk 182, Disperbyk 183, Disperbyk 184, Disperbyk 185, Disperbyk 2000, Disperbyk 2001, Disperbyk 2050, and Disperbyk 2070 (all manufactured by Byk Chemie Japan); EFKA 4008, EFKA 4009, EFKA 4010, EFKA 4406, EFKA 4408, and EFKA 4015 (all manufactured by Ciba Specialty Chemicals); Solsperse 9000, Solsperse 13000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 32500, Solsperse 32550, Solsperse 33500, Solsperse 35100, Solsperse 35200, Solsperse 38500, Solsperse 41090, and Solsperse 20000 (all manufactured by Nippon Lubrizol); Ajisper PA111, Ajisper PB821, Ajisper PB822, and Ajisper PB824 (all manufactured by Ajinomoto Fine-Techno); Disparlon 1850, Disparlon 1860, Disparlon 2150, Disparlon 7004, Disparlon DA-100, Disparlon DA-234, Disparlon DA-325, Disparlon DA-375, Disparlon DA-705, Disparlon DA-725, and Disparlon PW-36 (all manufactured by Kusumoto Chemicals); and Floren DOPA-14, Floren DOPA-15B, Floren DOPA-17, Floren DOPA-22, Floren DOPA-44, Floren TG-710, and Floren D-90 (all manufactured by Kyoei Kagaku); and the like, and one or more types of compounds selected from the above examples may be combined and used. However, when such a dispersing agent (other dispersing agent) is included, the content ratio thereof (the sum of the content ratios when a plurality of types of “other dispersing agents” is included) is preferably less than the content ratio of the acid-value dispersing agent and the content ratio of the amine-value dispersing agent. The effects of jointly using the acid-value dispersing agent and amine-value dispersing agent are thereby more reliably demonstrated.
The content ratio of the dispersing agent in the color filter ink is not particularly limited, but is preferably 2.5 to 10.2 wt %, and more preferably 3.2 to 9.2 wt %.
Curable Resin Material
The color filter ink generally includes a resin material (binder resin) for such purposes as enhancing adhesion of the formed colored portion to the substrate. Solvent resistance is needed in the resin material in order to prevent adverse effects due to chemical application or washing in steps subsequent to the ink application step in an inkjet method. In the conventional color filter ink, however, it is difficult to endow the color filter (colored portion) with adequately excellent durability. In the case of the conventional color filter ink, when droplets are discharged for long periods of time, and droplets are discharged continuously by the inkjet method, the trajectory of the discharged droplets changes (so-called flight deflection occurs), it becomes impossible to land the droplets in the desired region, the droplet discharge quantity becomes unstable, and other problems occur. When such problems occur, on the substrate or the like onto which the droplets are to be discharged, the plurality of types of ink used to form different colored portions mixes together (colors mix), and the color saturation fluctuates between the plurality of colored portions that are originally supposed to have the same color saturation, and as a result, uneven color between regions of the same color filter, uneven saturation, and the like occur, fluctuation occurs in the characteristics (particularly contrast ratio, color reproduction range, and other color characteristics) between numerous color filters, and the reliability of the color filters is reduced. Such problems are particularly severe when droplets are discharged on a large substrate (e.g., G5 or larger) to form colored portions, and these problems cause severe reduction of the color filter production properties (process yield).
The inventors conducted a concentrated investigation aimed at overcoming such problems as those described above. As a result, the inventors discovered that the problems described above can be overcome by including a curable resin material (binder resin) such as the one described in detail hereinafter together with the dispersing agents (acid-value dispersing agent and amine-value dispersing agent) described above in the color filter ink. Such excellent effects are obtained through the joint presence of the abovementioned dispersing agents (acid-value dispersing agent and amine-value dispersing agent) and the curable resin material (binder resin) such as described in detail hereinafter in the color filter ink, and are not obtained when only one of the dispersing agents or the curable resin material is present.
The curable resin material (curable resin composition) constituting the color filter ink of the present invention will be described in detail hereinafter.
The curable resin material in the color filter ink of the present invention includes a polymer A (first polymer) containing at least an epoxy-containing vinyl monomer a1 as a monomer component, and a polymer B (second polymer) containing an alkoxysilyl-containing vinyl monomer b1 as a monomer component.
Polymer A
The polymer A contains at least the epoxy-containing vinyl monomer a1 (first epoxy-containing vinyl monomer) as a monomer component. The polymer A may be composed of essentially a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer A is a mixture of a plurality of types of compounds, each of the compounds contains at least the epoxy-containing vinyl monomer a1 as a monomer component.
Epoxy-Containing Vinyl Monomer a1
The polymer A contains at least the epoxy-containing vinyl monomer a1 as a monomer component. Including such an epoxy-containing vinyl monomer a1 as a monomer component makes it possible to easily and reliably introduce an epoxy group into the polymer A. By including the epoxy-containing vinyl monomer a1 as a monomer component, excellent dispersion stability of the pigment such as described above in the color filter ink can be obtained, and the color filter ink can be endowed with excellent long-term storage properties and excellent discharge stability. Including the epoxy-containing vinyl monomer a1 as a monomer component also enables the colored portion formed using the color filter ink to have excellent solvent resistance. Including the epoxy-containing vinyl monomer a1 as a monomer component is also useful because the curable resin material (binder resin) can be cured under relatively mild conditions when a colored portion is formed using the color filter ink, and the formed colored portion is endowed with excellent hardness and other characteristics. When the polymer A includes a vinyl monomer a2 (second vinyl monomer), a vinyl monomer a3 (third vinyl monomer), and other components such as described hereinafter, the polymer can be suitably synthesized, and a polymer A having the desired characteristics can be easily and reliably obtained.
The epoxy-containing vinyl monomer a1 used may have the structure indicated by Formula (5) below, for example. When the epoxy-containing vinyl monomer a1 has such a structure, the dispersion stability of the pigment such as described above in the color filter ink can be made particularly excellent, and the color filter ink can be endowed with excellent long-term storage properties and excellent discharge stability. When the epoxy-containing vinyl monomer a1 has the structure indicated by Formula (5) below, the colored portion formed using the color filter ink can be endowed with even more superior solvent resistance. When the epoxy-containing vinyl monomer a1 has the structure indicated by Formula (5) below, the curable resin material (binder resin) can be cured under relatively mild conditions when a colored portion is formed using the color filter ink, and the formed colored portion is endowed with excellent hardness and other characteristics. When the epoxy-containing vinyl monomer a1 has such a structure, the polymer A can be endowed with particularly excellent compatibility with the polymer B described hereinafter, and the colored portion formed using the color filter ink can be endowed with particularly high transparency.




In Formula (5), R6 is a hydrogen atom or a C1-7 alkyl group; G is a single bond hydrocarbon group or a hydrocarbon group which may contain a bivalent hetero atom; J is an epoxy group or an alicyclic epoxy group which may have a ring-structured C3-10 substituted group; and m is 0 or 1.
In Formula (5), examples of the C1-7 alkyl group indicated by R6 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, and other alkyl groups, but a hydrogen atom or a C1-2 alkyl group is preferred, and a hydrogen atom or a methyl group is more preferred. The dispersion stability of the pigment such as described above in the color filter ink can be made particularly excellent, and the color filter ink can be endowed with excellent long-term storage properties and excellent discharge stability. The contrast of the displayed image can also be made particularly excellent in the manufactured color filter. The colored portion formed using the color filter ink can also be endowed with excellent hardness and other characteristics. The polymer A can also be endowed with particularly excellent compatibility with the polymer B described hereinafter, and the colored portion formed using the color filter ink can be endowed with extremely high transparency.
Typical examples of the hydrocarbon group indicated by G in Formula (5) that may contain a bivalent hetero atom include straight-chain or branched alkylene groups, or more specifically, methylenes, ethylenes, propylenes, tetramethylenes, ethyl ethylenes, pentamethylenes, hexamethylenes, oxymethylenes, oxyethylenes, oxypropylenes, and the like.
Specific examples of the epoxy-containing vinyl monomer a1 include glycidyl(meth)acrylate, methylglycidyl(meth)acrylate, ethylglycidyl(meth)acrylate, glycidyl vinylbenzyl ether (product name: VBGE; manufactured by Seimi Chemical), the alicyclic epoxy-containing unsaturated compounds indicated by Formulas (5-1) through (5-31) below, and the like; and one or more types of these compounds may be selected and used, but (3,4-epoxycyclohexyl)methyl (meth)acrylate is particularly preferred as the epoxy-containing vinyl monomer a1. The dispersion stability of the pigment such as described above in the color filter ink can thereby be made particularly excellent, and the color filter ink can be endowed with excellent long-term storage properties and excellent discharge stability. The colored portion formed using the color filter ink can also be endowed with particularly excellent hardness, solvent resistance, and other characteristics. The polymer A can be endowed with particularly excellent compatibility with the polymer B described hereinafter, and the colored portion formed using the color filter ink can be endowed with extremely high transparency.
Formulas (5-1) through (5-31)







In Formulas (5-1) through (5-31), R7 is a hydrogen atom or a methyl group; R8 is a C1-8 bivalent hydrocarbon group; and R9 is a C1-20 bivalent hydrocarbon group. R7, R8, and R9 may be mutually the same or different, and w is 0 to 10.
The content ratio (which is a value obtained by substitution with the weight of the monomer used to synthesize the polymer) of the epoxy-containing vinyl monomer a1 in the polymer A is preferably 50 to 99 wt %, and more preferably 70 to 94 wt %. When the content ratio of the epoxy-containing vinyl monomer a1 in the polymer A is within the aforementioned range, the dispersion stability of the pigment such as described above in the color filter ink can be made particularly excellent, and the color filter ink can be endowed with excellent long-term storage properties and excellent discharge stability. When the content ratio of the epoxy-containing vinyl monomer a1 in the polymer A is within the aforementioned range, the curable resin material (binder resin) can be cured under relatively mild conditions when a colored portion is formed using the color filter ink, and the formed colored portion is endowed with particularly excellent hardness, solvent resistance, and other characteristics. When the polymer A is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on weight ratio) of the mixed compounds may be used as the content ratio of the epoxy-containing vinyl monomer a1. When the polymer A is a mixture of a plurality of types of compounds, the compounds all preferably contain the epoxy-containing vinyl monomer a1 in such a content ratio as described above.
Vinyl Monomer a2
The polymer A may contain at least the epoxy-containing vinyl monomer a1 as a monomer component, but the polymer A is preferably one (a copolymer) containing the epoxy-containing vinyl monomer a1, as well as a vinyl monomer a2 as a monomer group provided with an isocyanate group or a blocked isocyanate group in which the isocyanate group is protected by a protective group. The content ratio of gas (dissolved gas, bubbles present as microbubbles, or the like) in the color filter ink can thereby be reduced more effectively, and particularly excellent stability of droplet discharge by the inkjet method can be obtained. As a result, it is possible to more effectively prevent the occurrence of uneven color, uneven saturation, and the like between different regions of the manufactured color filter, and fluctuation of characteristics between individual units.
Examples of polymerizable vinyl monomers a2 include 2-acryloyloxyethyl isocyanate (product name: Karenz MOI; manufactured by Showa Denko), 2-methacryloyloxyethyl isocyanate, and other (meth)acryloyl isocyanates and the like in which (meth)acryloyl is bonded with an isocyanate group via a C2-6 alkylene group.
The isocyanate group of the abovementioned (meth)acryloyl isocyanate is preferably a blocked isocyanate group. The term “blocked isocyanate group” refers to an isocyanate group in which the terminal ends are masked by a blocking agent. Examples of monomers having a blocked isocyanate group include ethyl 2-(0-[1′-methylpropylideneamino]carboxyamino)methacrylate and the like, and are commercially available under the trade name Karenz MOI-BM, manufactured by Showa Denko. A combination of one or more types of these polymerizable vinyl monomers may be used.
The content ratio (which is a value obtained by substitution with the weight of the monomer used to synthesize the polymer) of the vinyl monomer a2 in the polymer A is preferably 2 to 20 parts by weight, and more preferably 3 to 15 parts by weight, with respect to 100 parts by weight of the epoxy-containing vinyl monomer a1. When the content ratio of the vinyl monomer a2 in the polymer A is within the aforementioned range, the content ratio of gas (dissolved gas, bubbles present as microbubbles, or the like) in the color filter ink can be reduced more effectively, and particularly excellent stability of droplet discharge by the inkjet method can be obtained while the color filter ink is endowed with adequately excellent long-term storage properties and other characteristics. The colored portion formed using the color filter ink can also be endowed with adequately high transparency. In contrast, when the content ratio of the vinyl monomer a2 in the polymer A is less than the lower limit of the aforementioned range, the effects of including a vinyl monomer a2 such as those described above may not be adequately demonstrated. When the content ratio of the vinyl monomer a2 in the polymer A exceeds the upper limit of the aforementioned range, the compatibility of the polymer A with the polymer B described hereinafter decreases, and the colored portion formed using the color filter ink may be difficult to endow with adequate transparency. When the polymer A is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on weight ratio) of the mixed compounds may be used as the content ratio of the vinyl monomer a2. When the polymer A is a mixture of a plurality of types of compounds, the compounds all preferably contain the vinyl monomer a2 in such a content ratio as described above.
Vinyl Monomer a3
The polymer A may contain at least the epoxy-containing vinyl monomer a1 as a monomer component, but the polymer A is preferably one (a copolymer) containing the epoxy-containing vinyl monomer a1, as well as a vinyl monomer a3 provided with a hydroxyl group. The colored portion formed using the color filter ink can thereby be endowed with particularly excellent adhesion to the substrate, particularly adhesion under repeated exposure to sudden temperature changes that accompany image display. As a result, the occurrence of light leakage (white spots, bright points) and other problems can be reliably prevented even when the color filter is used for a long time, for example. Specifically, the color filter can be endowed with particularly excellent durability. When the polymer A contains the vinyl monomer a3 as a monomer component, the polymer A can be endowed with particularly excellent compatibility with the polymer B described hereinafter, and the colored portion formed using the color filter ink can be endowed with extremely high transparency.
Examples of the vinyl monomer a3 include monoester compounds of a acrylic acid or methacrylic acid with 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, 2,3-dihydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 8-hydroxyoctyl(meth)acrylate, 4-hydroxymethyl cyclohexyl(meth)acrylate, polyalkylene glycol mono(meth)acrylate, and other polyalcohols; compounds in which ε-caprolactone is ring-open polymerized with the abovementioned monoester compounds of a polyalcohol and acrylic acid or methacrylic acid (PLACCEL FA series, PLACCEL FM series, and the like manufactured by Daicel Chemical Industries); compounds in which ethylene oxide and propylene oxide is ring-open polymerized; and the like, and one or more types of compounds selected from the above examples may be used.
The content ratio (which is a value obtained by substitution with the weight of the monomer used to synthesize the polymer) of the vinyl monomer a3 in the polymer A is preferably 2 to 20 parts by weight, and more preferably 3 to 15 parts by weight, with respect to 100 parts by weight of the epoxy-containing vinyl monomer a1. When the content ratio of the vinyl monomer a3 in the polymer A is within the aforementioned range, the color filter manufactured using the color filter ink can be endowed with particularly excellent durability while the color filter ink is endowed with adequately excellent long-term storage properties and other characteristics. The colored portion formed using the color filter ink can also be endowed with high transparency. In contrast, when the content ratio of the vinyl monomer a3 in the polymer A is less than the lower limit of the aforementioned range, the effects of including a vinyl monomer a3 such as those described above may not be adequately demonstrated. When the content ratio of the vinyl monomer a3 in the polymer A exceeds the upper limit of the aforementioned range, it may be difficult to make the content ratio of gas in the color filter ink adequately low. When the polymer A is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on weight ratio) of the mixed compounds may be used as the content ratio of the vinyl monomer a3. When the polymer A is a mixture of a plurality of types of compounds, the compounds all preferably contain the vinyl monomer a3 in such a content ratio as described above.
Other Polymerizable Vinyl Monomer a4
The polymer A may contain as a monomer component a polymerizable vinyl monomer a4 other than the epoxy-containing vinyl monomer a1, the vinyl monomer a2, and the vinyl monomer a3 described above. A vinyl monomer that can be copolymerized with the epoxy-containing vinyl monomer a1 may be used as the polymerizable vinyl monomer a4, and specific examples thereof include methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, phenyl(meth)acrylate, cyclohexyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentanyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, benzyl(meth)acrylate, phenyl ethyl(meth)acrylate, and other C1-12 alkyl and aralkyl(meth)acrylates; styrene, α-methylstyrene, and other vinyl aromatic compounds; CF3(CF2)3CH2CH═CH2, CF3(CF2)3CH═CH2, CF3(CF2)5CH2CH═CH2, CF3(CF2)5CH═CH2, CF3(CF2)7CH═CH2, CF3(CF2)9CH2CH═CH2, CF3(CF2)9CH═CH2, (CF3)2CF(CF2)2CH2CH═CH2, (CF3)2CF(CF2)2CH═CH2, (CF3)2CF(CF2)4CH2CH═CH2, (CF3)2CF(CF2)4CH═CH2, (CF3)2CF(CH2)6CH2CH═CH2, (CF3)2CF(CF2)6CH═CH2, F5C6CH═CH2, CF3(CF2)5CH2CH2OCH2CH═CH2, CF3(CF2)5CH2CH2CH2OCH2CH═CH2, CF3(CF2)7CH2CH2OCH2CH═CH2, CF3(CF2)7CH2CH2CH2OCH2CH═CH2, CF3(CF2)9CH2CH2OCH2CH═CH2, CF3(CF2)9CH2CH2CH2OCH2CH═CH2, H(CF2)6CH2OCH2CH═CH2, H(CF2)8CH2OCH2CH═CH2, (CF3)2CF(CF2)2CH2CH2OCOCH═CH2, (CF3)2CF(CF2)2CH2CH2OCOC(CH3)═CH2, (CF3)2CF(CF2)4CH2CH2OCOCH═CH2, (CF3)2CF(CF2)4CH2CH2OCOC(CH3)═CH2, (CF3)2CF(CF2)6CH2CH2OCOCH═CH2, (CF3)2CF(CF2)6CH2CH2OCOC(CH3)═CH2, CF3(CF2)5CH2CH2OCOCH═CH2, CF3(CF2)5CH2CH2OCOC(CH3)═CH2, CF3(CF2)7CH2CH2OCOCH═CH2, CF3(CF2)7CH2CH2OCOC(CH3)═CH2, CF3(CF2)9CH2OCOCH═CH2, CF3(CF2)9CH2CH2OCOC(CH3)═CH2, H(CF2)6CH2CH2OCOCH═CH2, H(CF2)8CH2CH2OCOC(CH3)═CH2, F(CF2)8CH2CH2OCOCH═CH2, F(CF2)8CH2CH2OCOC(CH3)═CH2, H(CF2)4CH2OCOC(CH3)═CH2, H(CF2)4CH2OCOCH═CH2, and other fluoroalkyl- or fluoroaryl-containing vinyl compounds and the like, and one or more types of compounds selected from the above examples may be combined and used. However, the polymer A does not contain as a monomer component an alkoxysilyl-containing vinyl monomer b1 such as described hereinafter.
The content ratio (which is a value obtained by substitution with the weight of the monomer used to synthesize the polymer) of the polymerizable vinyl monomer a4 in the polymer A is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the epoxy-containing vinyl monomer a1. When the polymer A is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on weight ratio) of the mixed compounds may be used as the content ratio of the polymerizable vinyl monomer a4. When the polymer A is a mixture of a plurality of types of compounds, the content ratio of the polymerizable vinyl monomer a4 with respect to the mixture of compounds preferably satisfies such conditions as those described above.
As described above, the polymer A may contain at least the epoxy-containing vinyl monomer a1 as a monomer component, but preferably contains the epoxy-containing vinyl monomer a1 as well as the vinyl monomer a2 and the vinyl monomer a3. The effects of including a vinyl monomer a2 such as the ones described above, and the effects of including a vinyl monomer a3 such as the ones described above can be obtained at the same time.
The ratio (content ratio) accounted for by the polymer A in the curable resin material (binder resin) is not particularly limited, but is preferably 25 to 80 wt %, and more preferably 33 to 70 wt %. When the polymer A is a mixture of a plurality of types of compounds, the sum of the content ratios of the mixed compounds may be used as the content ratio of the polymer A.
Polymer B
In the color filter ink of the present invention, the curable resin material (binder resin) includes a polymer A such as described above, as well as a polymer B that contains at least the alkoxysilyl-containing vinyl monomer b1 indicated by Formula (1) below as a monomer component.




In Formula (1), R1 is a hydrogen atom or a C1-7 alkyl group; E is a single bond hydrocarbon group or a bivalent hydrocarbon group; R2 and R3 are the same or different C1-6 alkyl groups or C1-6 alkoxyl groups; R4 is a C1-6 alkyl group; x is 0 or 1; and y is an integer from 1 to 10.
In the conventional color filter ink, it is usually the case that relatively large amounts of gas are easily incorporated during preparation of the ink, and even when de-aeration or the like is performed, the gas content is difficult to reduce. Even once the gas content in the conventional color filter ink is reduced to a relatively low level by de-aeration or the like, gas from the atmosphere is incorporated over the course of prolonged storage, and when discharge, fluid depletion, and the like of ink from the discharge holes during droplet discharge are repeated, gas from the atmosphere is incorporated, thereby resulting in a strong tendency for the content ratio of gas (dissolved gas, bubbles present as microbubbles, or the like) in the color filter ink to increase. When the gas content ratio in the color filter ink increases in this manner, the discharge of droplets by the inkjet method becomes unstable, and unevenness of color and saturation between regions, and fluctuation of characteristics between individual units easily occur.
In the present invention, however, the curable resin material (binder resin) includes the polymer A as well as the polymer B (and the abovementioned dispersing agents are also used together with the curable resin material), whereby the content ratio of gas in the color filter ink can be reduced, the color filter ink can be endowed with excellent discharge stability, the color filter manufactured using the color filter ink can be endowed with excellent uniformity of characteristics between individual units, and unevenness of color saturation between different regions can be suppressed. By including the polymer A as well as the polymer B in the curable resin material (binder resin), the color filter manufactured using the color filter ink can be endowed with excellent durability. By including the polymer A as well as the polymer B in the curable resin material (binder resin) in the present invention (and also using the abovementioned dispersing agents together with the curable resin material), excellent mixing stability of the curable resin material with the colorant (pigment) can be obtained over a long period of time, and a color filter having excellent contrast can be manufactured stably over a long period of time. Since the color filter ink, once prepared, can be suitably used for a long time, the frequency of replacing the color filter ink and replacing the color filter ink in the droplet discharge device can be reduced. The color filter can therefore be manufactured with particularly excellent productivity, and the consistency of quality of the manufactured color filter is enhanced. Such excellent effects (synergistic effects) are not obtained with only one of the polymer A or polymer B is used.
The polymer B may be composed of essentially a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer B is a mixture of a plurality of types of compounds, each of the compounds contains at least the alkoxysilyl-containing vinyl monomer b1 as a monomer component.
Alkoxysilyl-Containing Vinyl Monomer b1
The polymer B contains at least the alkoxysilyl-containing vinyl monomer b1 indicated by Formula (1) as a monomer component. Including such an alkoxysilyl-containing vinyl monomer b1 as a monomer component makes it possible to easily and reliably introduce an alkoxysilyl group into the polymer B. By including the alkoxysilyl-containing vinyl monomer b1 as a monomer component, curing of the polymer A can be supplemented when the curable resin material (curable resin composition) is cured to form the colored portion, the colored portion can be formed under relatively mild conditions, and the formed colored portion can be endowed with adequately excellent hardness, adhesion to the substrate, light fastness, thermal resistance, and other characteristics. When the polymer B includes a vinyl monomer b2 or the like such as described hereinafter, the polymer can be suitably synthesized, and a polymer B having the desired characteristics can be easily and reliably obtained.
In Formula (1), examples of the C1-7 alkyl group indicated by R1 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, and other alkyl groups, but a hydrogen atom or a C1-2 alkyl group is preferred, and a hydrogen atom or a methyl group is more preferred. The color filter ink can thereby be endowed with particularly excellent dispersion stability of the pigment in the color filter ink, and discharge stability of the color filter ink, and the formed colored portion can be endowed with particularly excellent hardness, adhesion to the substrate, light fastness, thermal resistance, and other characteristics. The polymer A can also be endowed with particularly excellent compatibility with the polymer B, and the colored portion formed using the color filter ink can be endowed with particularly high transparency.
Typical examples of the bivalent hydrocarbon group indicated by E in Formula (1) include straight-chain or branched alkylene groups, or more specifically, methylenes, ethylenes, propylenes, tetramethylenes, ethyl ethylenes, pentamethylenes, hexamethylenes, and the like. Among these examples, a C1-3 straight-chain alkylene group (e.g., methylene, ethylene, propylene) is particularly preferred.
Examples of the C1-6 alkyl groups indicated by R2, R3, and R4 in Formula (1) include straight-chain or branched alkyl groups, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, and the like. Examples of the C1-6 alkoxyl groups indicated by R2 and R3 include straight-chain or branched alkoxyl groups, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, pentoxy, hexyloxy, and the like.
Specific examples of monomers indicated by Formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, γ-(meth)acryloyloxypropylmethyldiethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, β-(meth)acryloyloxyethyltrimethoxysilane, γ-(meth)acryloyloxybutylphenyldimethoxysilane, and other alkoxysilyl-containing polymerizable unsaturated compounds and the like, and one or more types of compounds selected from the above examples may be combined and used.
The content ratio (which is a value obtained by substitution with the weight of the monomer used to synthesize the polymer) of the alkoxysilyl-containing vinyl monomer b1 in the polymer B is preferably 70 to 100 wt %, and more preferably 80 to 100 wt %. When the content ratio of the alkoxysilyl-containing vinyl monomer b1 in the polymer B is within the aforementioned range, the color filter ink can be endowed with particularly excellent dispersion stability of the pigment in the color filter ink, and discharge stability of the color filter ink. Curing of the polymer A can be supplemented when the curable resin material (curable resin composition) is cured to form the colored portion, and the colored portion can be formed under relatively mild conditions. The formed colored portion can also be endowed with particularly excellent hardness, adhesion to the substrate, light fastness, thermal resistance, and other characteristics. When the polymer B is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on weight ratio) of the mixed compounds may be used as the content ratio of the alkoxysilyl-containing vinyl monomer b1. When the polymer B is a mixture of a plurality of types of compounds, the compounds all preferably contain the alkoxysilyl-containing vinyl monomer b1 in such a content ratio as described above.
Other Polymerizable Vinyl Monomer b2
The polymer B may contain at least the alkoxysilyl-containing vinyl monomer b1 as a monomer component, but may also contain as a monomer component a polymerizable vinyl monomer b2 other than the alkoxysilyl-containing vinyl monomer b1, in addition to the alkoxysilyl-containing vinyl monomer b1. A vinyl monomer that can be copolymerized with the alkoxysilyl-containing vinyl monomer b1 may be used as the polymerizable vinyl monomer b2, and specific examples thereof include 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, 2,3-dihydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 8-hydroxyoctyl(meth)acrylate, 4-hydroxymethyl cyclohexyl(meth)acrylate, polyalkylene glycol mono(meth)acrylate, and other monoester compounds of a polyalcohol and acrylic acid or methacrylic acid; compounds in which ε-caprolactone is ring-open polymerized with the abovementioned monoester compounds of a polyalcohol and acrylic acid or methacrylic acid (PLACCEL FA series, PLACCEL FM series, and the like manufactured by Daicel Chemical Industries); compounds in which ethylene oxide and propylene oxide is ring-open polymerized, and other polymerizable vinyl monomers provided with a hydroxyl group; methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, phenyl(meth)acrylate, cyclohexyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentanyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, benzyl(meth)acrylate, phenyl ethyl(meth)acrylate, and other C1-12 alkyl and aralkyl(meth)acrylates; styrene, α-methylstyrene, and other vinyl aromatic compounds; CF3(CF2)3CH2CH═CH2, CF3(CF2)3CH═CH2, CF3(CF2)5CH2CH═CH2, CF3(CF2)5CH═CH2, CF3(CF2)7CH═CH2, CF3(CF2)9CH2CH═CH2, CF3(CF2)9CH═CH2, (CF3)2CF(CF2)2CH2CH═CH2, (CF3)2CF(CF2)2CH═CH2, (CF3)2CF(CF2)4CH2CH═CH2, (CF3)2CF(CF2)4CH═CH2, (CF3)2CF(CF2)6CH2CH═CH2, (CF3)2CF(CF2)6CH═CH2, F5C6CH═CH2, CF3(CF2)5CH2CH2OCH2CH═CH2, CF3(CF2)5CH2CH2CH2OCH2CH═CH2, CF3(CF2)7CH2CH2OCH2CH═CH2, CF3(CF2)7CH2CH2CH2OCH2CH═CH2, CF3(CF2)9CH2CH2OCH2CH═CH2, CF3(CF2)9CH2CH2CH2OCH2CH═CH2, H(CF2)6CH2OCH2CH═CH2, H(CF2)8CH2OCH2CH═CH2, (CF3)2CF(CF2)2CH2CH2OCOCH═CH2, (CF3)2CF(CF2)2CH2CH2OCOC(CH3)═CH2, (CF3)2CF(CF2)4CH2CH2OCOCH═CH2, (CF3)2CF(CF2)4CH2CH2OCOC(CH3)═CH2, (CF3)2CF(CF2)6CH2CH2OCOCH═CH2, (CF3)2CF(CF2)6CH2CH2OCOC(CH3)═CH2, CF3(CF2)5CH2CH2OCOCH═CH2, CF3(CF2)5CH2CH2OCOC(CH3)═CH2, CF3(CF2)7CH2CH2OCOCH═CH2, CF3(CF2)7CH2CH2OCOC(CH3)═CH2, CF3(CF2)9CH2CH2OCOCH═CH2, CF3(CF2)9CH2CH2OCOC(CH3)═CH2, H(CF2)6CH2CH2OCOCH═CH2, H(CF2)8CH2CH2OCOC(CH3)═CH2, F(CF2)8CH2CH2OCOCH═CH2, F(CF2)8CH2CH2OCOC(CH3)═CH2, H(CF2)4CH2OCOC(CH3)═CH2, H(CF2)4CH2OCOCH═CH2, and other fluoroalkyl- or fluoroaryl-containing vinyl monomers and the like, and one or more types of compounds selected from the above examples may be combined and used. However, the polymer B does not contain as a monomer component an epoxy-containing vinyl monomer a1 such as previously described. The polymer B also preferably does not contain a fluoroalkyl- or fluoroaryl-containing vinyl monomer such as described above as a monomer component.
The content ratio (which is a value obtained by substitution with the weight of the monomer used to synthesize the polymer) of the polymerizable vinyl monomer b2 in the polymer B is preferably 30 wt % or less, and more preferably 20 wt % or less. When the polymer B is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on weight ratio) of the mixed compounds may be used as the content ratio of the polymerizable vinyl monomer b2. When the polymer B is a mixture of a plurality of types of compounds, the content ratio of the polymerizable vinyl monomer b2 with respect to the mixture of compounds preferably satisfies such conditions as those described above.
As described above, the polymer B may contain at least the alkoxysilyl-containing vinyl monomer b1 as a monomer component, and may contain a monomer component other than the alkoxysilyl-containing vinyl monomer b1, but is preferably a homopolymer of the alkoxysilyl-containing vinyl monomer b1. Specifically, the polymer B preferably does not contain components other than the alkoxysilyl-containing vinyl monomer b1 as monomer components. The dispersion stability of the pigment in the color filter ink, the discharge stability of the color filter ink, and the durability of the color filter manufactured using the color filter ink can thereby be made particularly excellent.
The ratio (content ratio) accounted for by the polymer B in the curable resin material (binder resin) is not particularly limited, but is preferably 20 to 60 wt %, and more preferably 25 to 55 wt %. When the polymer B is a mixture of a plurality of types of compounds, the sum of the content ratios of the mixed compounds may be used as the content ratio of the polymer B.
The ratio of the polymer A content and the polymer B content in terms of weight is preferably 25:75 to 75:25, and more preferably 45:55 to 55:45. Satisfying such conditions enables the color filter ink to be endowed with particularly excellent dispersion stability of the pigment in the color filter ink, and discharge stability of the color filter ink. The color filter manufactured using the color filter ink can be endowed with excellent uniformity of characteristics between individual units, and unevenness of color and saturation between different regions can be more reliably prevented. The color filter can also be endowed with excellent durability.
Polymer C
The curable resin material (curable resin composition) includes the polymer A and polymer B such as described above, but also may include a polymer C that contains as a monomer component the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 indicated by Formula (6) below.




In Formula (6), R5 is a hydrogen atom or a C1-7 alkyl group; D is a single bond hydrocarbon group or a hydrocarbon group which may contain a bivalent hetero atom; Rf is a C1-20 fluoroalkyl group or fluoroaryl group; and z is 0 or 1.
Including such a polymer C enables the color filter ink to be endowed with particularly excellent discharge stability. In particular, fluid depletion from the nozzles of the droplet discharge head can be improved, and such problems as solid components of the color filter ink adhering to the nozzles can be more effectively prevented. The colored portion formed using the color filter ink can also be endowed with particularly excellent thermal resistance.
The polymer C may be composed of essentially a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer C is a mixture of a plurality of types of compounds, each of the compounds contains at least the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 as a monomer component.
Fluoroalkyl-or Fluoroaryl-Containing Vinyl Monomer c1
The polymer C contains at least the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 indicated by Formula (6) as a monomer component. Including such a fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 as a monomer component makes it possible to easily and reliably introduce a fluoroalkyl group or a fluoroaryl group into the polymer C. Including the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 as a monomer component enables the color filter ink to be endowed with particularly excellent discharge stability. The colored portion formed using the color filter ink can also be endowed with particularly excellent thermal resistance. When the polymer C includes a vinyl monomer c2 or the like such as described hereinafter, the polymer can be suitably synthesized, and a polymer C having the desired characteristics can be easily and reliably obtained.
Examples of the C1-7 alkyl group indicated by R5 in Formula (6) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, and other alkyl groups, but a hydrogen atom or a C1-2 alkyl group is preferred, and a hydrogen atom or a methyl group is more preferred. The discharge stability of the color filter ink and the thermal resistance of the colored portion formed using the color filter ink can thereby be made particularly excellent.
Typical examples of the bivalent hydrocarbon group (hydrocarbon group which may contain a hetero atom) indicated by D in Formula (6) include straight-chain or branched alkylene groups, or more specifically, methylenes, ethylenes, propylenes, tetramethylenes, ethyl ethylenes, pentamethylenes, hexamethylenes, oxymethylenes, oxyethylenes, oxypropylenes, and the like.
Specific examples of monomers indicated by Formula (6) include CF3(CF2)3CH2CH═CH2, CF3(CF2)3CH═CH2, CF3(CF2)5CH2CH═CH2, CF3(CF2)5CH═CH2, CF3(CF2)7CH═CH2, CF3(CF2)9CH2CH═CH2, CF3(CF2)9CH═CH1, (CF3)2CF(CF2)2CH2CH═CH2, (CF3)2CF(CF2)2CH═CH2, (CF3)2CF(CF2)4CH2CH═CH2, (CF3)2CF(CF2)4CH═CH2, (CF3)2CF(CF2)6CH2CH═CH2, (CF3)2CF(CF2)6CH═CH2, F5C6CH═CH2, CF3(CF2)5CH2OCH2 CH═CH2, CF3(CF2)5CH2CH2CH2OCH2CH═CH2, CF3(CF2)7CH2CH2OCH2CH═CH2, CF3(CF2)7CH2CH2CH2OCH2CH═CH2, CF3(CF2)9CH2CH2OCH2CH═CH2, CF3(CF2)9CH2CH2CH2OCH2CH═CH2, H(CF2)6CH2OCH2CH═CH2, H(CF2)8CH2OCH2CH═CH2, (CF3)2CF(CF2)2CH2CH2OCOCH═CH2, (CF3)2CF(CF2)2CH2CH2OCOC(CH3)═CH2, (CF3)2CF(CF2)4CH2CH2OCOCH═CH2, (CF3)2CF(CF2)4CH2CH2OCOC(CH3)═CH2, (CF3)2CF(CF2)6CH2CH2OCOCH═CH2, (CF3)2CF(CF2)6CH2CH2OCOC(CH3)═CH2, CF3(CF2)5CH2CH2OCOCH═CH2, CF3(CF2)5CH2CH2OCOC(CH3)═CH2, CF3(CF2)7CH2CH2OCOCH═CH2, CF3(CF2)7CH2CH2OCOC(CH3)═CH2, CF3(CF2)9CH2CH2OCOCH═CH2, CF3(CF2)9CH2CH2OCOC(CH3)═CH2, H(CF2)6CH2CH2OCOCH═CH2, H(CF2)8CH2CH2OCOC(CH3)═CH2, F(CF2)8CH2CH2OCOCH═CH2, F(CF2)8CH2CH2OCOC(CH3)═CH2, H(CF2)4CH2OCOC(CH3)═CH2, H(CF2)4CH2OCOCH═CH2, and the like, and one or more types of compounds selected from the above examples may be combined and used.
The content ratio (which is a value obtained by substitution with the weight of the monomer used to synthesize the polymer) of the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 in the polymer C is preferably 15 to 100 wt %, and more preferably 18 to 100 wt %. When the content ratio of the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 in the polymer C is within the aforementioned range, the dispersion stability of the pigment in the color filter ink, the discharge stability of the color filter ink, and the thermal resistance of the colored portion formed using the color filter ink can be made particularly excellent. The polymer C can also be endowed with particularly excellent compatibility with the polymer A or the polymer B, and the colored portion formed using the color filter ink can be endowed with particularly high transparency. In contrast, when the content ratio of the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 in the polymer C is less than the lower limit of the aforementioned range, the effects of including a fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 such as those described above may not be adequately demonstrated. When the polymer C is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on weight ratio) of the mixed compounds may be used as the content ratio of the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1. When the polymer C is a mixture of a plurality of types of compounds, the compounds all preferably contain the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 in such a content ratio as described above.
Other Polymerizable Vinyl Monomer c2
The polymer C may contain as a monomer component a polymerizable vinyl monomer c2 other than the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 such as described above. A vinyl monomer that can be copolymerized with the fluoroalkyl- or fluoroaryl-containing vinyl monomer c1 may be used as the polymerizable vinyl monomer c2, and specific examples thereof include 2-acryloyloxyethyl isocyanate (product name: Karenz MOI; manufactured by Showa Denko), 2-methacryloyloxyethyl isocyanate, and other (meth)acryloyl isocyanates and the like in which (meth)acryloyl is bonded with an isocyanate group via a C2-6 alkylene group; ethyl 2-(0-[1′-methylpropylideneamino]carboxyamino)methacrylate (product name: Karenz MOI-BM; manufactured by Showa Denko) and other polymerizable vinyl monomers provided with an isocyanate group or a blocked isocyanate group in which the isocyanate group is protected by a protective group; 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, 2,3-dihydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 8-hydroxyoctyl(meth)acrylate, 4-hydroxymethyl cyclohexyl(meth)acrylate, polyalkylene glycol mono(meth)acrylate, and other monoester compounds of a polyalcohol and acrylic acid or methacrylic acid; compounds in which ε-caprolactone is ring-open polymerized with the abovementioned monoester compounds of a polyalcohol and acrylic acid or methacrylic acid (PLACCEL FA series, PLACCEL FM series, and the like manufactured by Daicel Chemical Industries); compounds in which ethylene oxide and propylene oxide is ring-open polymerized, and other polymerizable vinyl monomers provided with a hydroxyl group; methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, phenyl(meth)acrylate, cyclohexyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentanyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, benzyl(meth)acrylate, phenyl ethyl(meth)acrylate, and other C1-12 alkyl and aralkyl(meth)acrylates; styrene, α-methylstyrene, and other vinyl aromatic compounds; and one or more types of compounds selected from the above examples may be combined and used. However, the polymer C does not contain as a monomer component the epoxy-containing vinyl monomer a1 and the alkoxysilyl-containing vinyl monomer b1 such as previously described.
The content ratio (which is a value obtained by substitution with the weight of the monomer used to synthesize the polymer) of the polymerizable vinyl monomer c2 in the polymer C is preferably 85 wt % or less, and more preferably 82 wt % or less. When the polymer C is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on weight ratio) of the mixed compounds may be used as the content ratio of the polymerizable vinyl monomer c2. When the polymer C is a mixture of a plurality of types of compounds, the content ratio of the polymerizable vinyl monomer c2 with respect to the mixture of compounds preferably satisfies such conditions as those described above.
When the curable resin material (binder resin) includes the polymer C, the ratio (content ratio) accounted for by the polymer C in the curable resin material (binder resin) is not particularly limited, but is preferably 1 to 20 wt %, and more preferably 2 to 15 wt %. When the polymer C is a mixture of a plurality of types of compounds, the sum of the content ratios of the mixed compounds may be used as the content ratio of the polymer C.
When the curable resin material (binder resin) includes the polymer C, the ratio of the polymer A content and the polymer C content in terms of weight is preferably 50:50 to 99:1, and more preferably 60:40 to 98:2. Satisfying such conditions enables the color filter ink to be endowed with particularly excellent dispersion stability of the pigment in the color filter ink, and discharge stability of the color filter ink. The color filter manufactured using the color filter ink can be endowed with particularly excellent uniformity of characteristics between individual units, and unevenness of color and saturation between different regions can be more effectively prevented. The color filter can also be endowed with particularly excellent durability.
The weight-average molecular weight of each polymer (polymer A, polymer B, polymer C) such as described above is preferably 1000 to 50000, more preferably 1200 to 10000, and even more preferably 1500 to 5000. The degree of dispersion (weight-average molecular weight Mw/number-average molecular weight Mn) of each polymer (polymer A, polymer B, polymer C) such as described above is about 1 to 3.
The content ratio of the curable resin material in the color filter ink is preferably 0.5 to 10 wt %, and more preferably 1 to 5 wt %. When the content ratio of the curable resin material is within this range, the manufactured color filter can be endowed with particularly excellent durability while providing particularly excellent pigment dispersion stability in the color filter ink and particularly excellent discharge properties of the color filter ink from the droplet discharge head. Adequate color saturation can also be maintained in the manufactured color filter.
The content ratio of the curable resin material with respect to 100 parts by weight of the pigment is preferably 15 to 50 parts by weight, and more preferably 19 to 42 parts by weight. Satisfying such conditions enables the color filter ink to be endowed with particularly excellent dispersion stability of the pigment in the color filter ink, and discharge stability of the color filter ink, and enables the color filter manufactured using the color filter ink to be endowed with particularly excellent contrast and coloration properties of the colored portion. Particularly excellent adhesion of the colored portion to the substrate can also be obtained.
The curable resin material (binder resin) constituting the color filter ink may also include a polymer other than the polymer A, polymer B, and polymer C described above.
Thermoplastic Resin
The color filter ink may include a thermoplastic resin. Particularly excellent dispersion properties of the pigment particles in the color filter ink can thereby be obtained. In a manufacturing method such as described hereinafter, the dispersion stability of the pigment particles in the color filter ink can be made extremely excellent by using a thermoplastic resin in the pre-dispersion process.
Examples of thermoplastic resins include alginic acid, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, styrene-acrylic acid resin, styrene-acrylic acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-maleic acid semi-ester resin, methacrylic acid-methacrylic acid ester resin, acrylic acid-acrylic acid ester resin, isobutylene-maleic acid resin, rosin-modified maleic acid resin, polyvinyl pyrrolidone, gum arabic starch, polyallyl amine, polyvinyl amine, polyethylene imine, and the like, and one or more types of compounds selected from the above examples may be combined and used.
The content ratio of the thermoplastic resin in the color filter ink is not particularly limited, but is preferably 1.5 to 7.7 wt %, and more preferably 2.1 to 7.2 wt %.
Other Components
The color filter ink of the present invention may include components other than those described above. Examples of such components include various dyes; various cross-linking agents; thermoacid generators such as diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, selenium salt, oxonium salt, ammonium salt, benzothiazolium salt, and other onium salts; diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, selenium salt, oxonium salt, ammonium salt, and other photoacid generators; various polymerization initiators; acid crosslinking agents; intensifiers; photostabilizers; adhesive improvers; various polymerization accelerants; various photostabilizers; glass, alumina, and other fillers; vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methoxy ethoxy)silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl methyl dimethoxysilane, 2-(3,4-epoxy cyclohexyl) ethyl trimethoxysilane, 3-chloro propyl methyl dimethoxysilane, 3-chloro propyl trimethoxysilane, 3-methacryloxy propyl trimethoxysilane, 3-mercapto propyl trimethoxysilane, and other adhesion accelerants; 2,2-thiobis(4-methyl-6-t-butyl phenol), 2,6-di-t-butyl phenol, and other antioxidants; 2-(3-t-butyl-5-methyl-2-hydroxy phenyl)-5-chloro benzotriazole, alkoxy benzophenone, and other UV absorbers; sodium polyacrylate, and other anti-coagulants; and the like.
Examples of dyes include azo dyes, anthraquinone dyes, condensed multi-ring aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methines, polymethine dyes, and the like. Specific examples of dyes include C. I. direct red 2, 4, 9, 23, 26, 28, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, and 247; C. I. acid red 35, 42, 51, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 145, 151, 154, 157, 158, 211, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 319, 336, 337, 361, 396, and 397; C. I. reactive red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, and 55; C. I. basic red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, and 46; C. I. direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, and 101; C. I. acid violet 5, 9, 11, 34, 43, 47, 48, 51, 75, 90, 103, and 126; C. I. reactive violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, and 34; C. I. basic violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, and 48; C. I. direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, and 163; C. I. acid yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, and 227; C. I. reactive yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, and 42; C. I. basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, and 40; C. I. acid green 16; C. I. acid blue 9, 45, 80, 83, 90 and 185; C. I. basic orange 21 and 23; and the like.
Examples of cross-linking agents that may be used include polycarboxylic acid anhydrides, polycarboxylic acids, polyfunctional epoxy monomers, polyfunctional acrylic monomers, polyfunctional vinyl ether monomers, and polyfunctional oxetane monomers. Specific examples of polycarboxylic acid anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyl tetrahydrophthalic anhydride, himic anhydride, nadic anhydride, and other aliphatic or alicyclic dicarboxylic anhydrides; 1,2,3,4-butane tetracarboxylic acid dianhydride and cyclopentane tetracarboxylic acid dianhydride; benzophenone tetracarboxylic anhydride and other aromatic polycarboxylic acid anhydrides; ethylene glycol bis trimellitate, glycerin tris trimellitate, and other ester-containing organic anhydrides, among which an aromatic polycarboxylic acid anhydride is preferred. An epoxy resin curing agent composed of a commercially available carboxylic acid anhydride can also be suitably used. Specific examples of polycarboxylic acids include succinic acid, glutaric acid, adipic acid, butane tetracarboxylic acid, maleic acid, itaconic acid, and other aliphatic polycarboxylic acids; hexahydrophthalic acid, 1,2-cyclohexane dicarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, cyclopentane tetracarboxylic acid, and other aliphatic polycarboxylic acids; and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalene tetracarboxylic acid, benzophenone tetracarboxylic acid, and other aromatic polycarboxylic acid, but among these, aromatic polycarboxylic acid is preferred. Specific examples of a polyfunctional epoxy monomer include the product name Celloxide 2021 manufactured by Daicel Chemical Industries, the product name Epolead GT401 manufactured by Daicel Chemical Industries, the product name Epolead PB3600 manufactured by Daicel Chemical Industries, bisphenol A, hydrogenated bisphenol A, and triglycidyl isocyanurate. Specific example of a polyfunctional acrylic monomer include pentaerythritolethoxy tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritolethoxy tetraacrylate, ditrimethylolpropane tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxy triacrylate, dipentaerythritol hexaacrylate trimethallyl isocyanurate, and triallyl isocyanurate. Examples of a polyfunctional vinyl ether monomer include 1,4-butanediol vinyl ether, 1,6-hexanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, and pentaerythritol tetravinyl ether. Examples of polyfunctional oxetane monomers include xylylene dioxetane, biphenyl-type oxetane, and novolac-type oxetane.
The thermoacid generator is a component for generating acid by applying heat, and particularly preferred among those described above are sulfonium salt and benzothiazolium. More specific examples of thermoacid generators in terms of product names include Sunaid SI-45, Sunaid SI-47, Sunaid SI-60, Sunaid SI-60L, Sunaid SI-80, Sunaid SI-80L, Sunaid SI-100, Sunaid SI-100L, Sunaid SI-145, Sunaid SI-150, Sunaid SI-160, Sunaid SI-110L, Sunaid SI-180L (all product names, manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (all product names, manufactured by Nippon Soda Co., Ltd.), CP-66, CP-77 (product names, manufactured by Adeka Corporation), and FC-520 (product name, manufactured by 3M Company).
The photoacid generator is a component for generating acid by using light, and more specific examples include the product names Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (all product names, manufactured by US Union Carbide), Irgacure 261 (product name, Ciba Specialty Chemicals), SP-150, SP-151, SP-170, Optomer SP-171 (all product names, manufactured by Adeka Corporation), CG-24-61 (product name, manufactured by Ciba Specialty Chemicals), Daicat II (product name, manufactured by Daicel Chemical Industries, Ltd.), UVAC 1591 (product name, manufactured by Daicel UCB Co., Ltd.), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758 (product name, manufactured by Nippon Soda Co., Ltd.), PI-2074 (product name, manufactured by Rhone Poulenc, pentafluorophenyl borate tolyl cumyl iodonium), FFC509 (product name, manufactured by 3M Company), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (product name, manufactured by Midori Kagaku Co., Ltd.), and CD-1012 (product name, manufactured by Sartomer Co., Inc.).
The color filter ink of the present invention has excellent dispersion stability (long-term dispersion stability) of the pigment particles over long periods of time and excellent droplet discharge stability, and the pigment particles are evenly fine-dispersed. Changes in the characteristics of the color filter ink over time can therefore be effectively prevented, and over long periods of time, for example, the color filter ink can be suitably applied to the shape or the like of a colored portion (color filter) having a uniform color saturation, and the occurrence of uneven color, saturation, and other characteristics in the formed color filter can be effectively prevented. Since the pigment particles are fine-dispersed, the color filter ink has excellent pigment coloration properties. For example, the color filter ink can be suitably used to form a color filter having high contrast and brightness.
The viscosity (viscosity (kinetic viscosity) measured using an E-type viscometer) of the color filter ink at 25° C. is preferably 13 mPa·s or lower, more preferably 12 mPa·s or lower, and more preferably 5 to 11 mPa·s. When the viscosity (kinetic viscosity) of the color filter ink is thus adequately low, the production efficiency (efficiency of forming the colored portion) of the color filter can be made particularly excellent, for example, and unwanted fluctuation of the thickness and other characteristics of the colored portion can be effectively prevented. The viscosity (kinetic viscosity) of the color filter ink can be measured using an E-type viscometer (e.g., RE-01 manufactured by Toki Sangyo), for example, and can particularly be performed in accordance with JIS Z8809.
The amount of change in the viscosity at 25° C. of the color filter ink after the color filter ink is left for 7 days at 65° C. is preferably 0.5 mPa·s or less, more preferably 0.3 mPa·s or less, and more preferably 0.2 mPa·s or less. The color filter ink can thereby be endowed with particularly excellent discharge stability, and the color filter ink can be suitably used for a longer period of time to manufacture a color filter in which the occurrence of uneven color, saturation, and the like is reliably prevented.
Color Filter Ink Manufacturing Method
Preferred embodiments of the method for manufacturing a color filter ink such as described above will next be described.
The manufacturing method of the present embodiment has a pre-dispersion step of obtaining a dispersing-agent-dispersed liquid in which a dispersing agent is dispersed in a solvent, by stirring a mixture of a dispersing agent, a thermoplastic resin, and a solvent; a fine-dispersion step of adding a pigment to the dispersing-agent-dispersed liquid, adding inorganic beads in multi-stage fashion and performing a fine-dispersion process, and obtaining a pigment dispersion; and a curable resin mixing step of mixing the pigment dispersion and the curable resin material.
Pre-Dispersion Step
In the pre-dispersion step, a dispersing-agent-dispersed liquid in which a dispersing agent is dispersed in a solvent is prepared by stirring a mixture that includes a dispersing agent, a thermoplastic resin, and a solvent. The associated state of the dispersing agent can thereby be released (undone). The acid-value dispersing agent and amine-value dispersing agent used in the present invention have the characteristic of being readily attracted to each other electrically, but by performing the pre-dispersion step prior to fine-dispersing the pigments (fine-dispersion step) according to the present embodiment, the acid-value dispersing agent and amine-value dispersing agent can be uniformly and stably adhered to the surfaces of the pigment particles in a state in which association is adequately released; aggregation of the dispersing agents with each other, aggregation of pigment particles with each other, and other effects can be reliably prevented; and particularly excellent pigment dispersion stability and droplet discharge stability can be obtained.
In this step, the thermoplastic resin, the dispersing agent, and the solvent are mixed together in advance, whereby the dispersing agent and the thermoplastic resin are adhered to the surfaces of the pigment particles (pigment particles having a relatively large grain size that are not fine-dispersed) added to the dispersing-agent-dispersed liquid in the fine-dispersion step described hereinafter, and excellent dispersion properties of the pigment particles (pigment particles having a relatively large grain size that are not fine-dispersed) in the dispersing-agent-dispersed liquid can be obtained. The fine-dispersion process in the fine-dispersion step can thereby be efficiently performed, the production properties of the color filter ink can be made particularly excellent, and particularly excellent long-term dispersion stability of the pigment particles (fine-dispersed pigment microparticles) and discharge stability of droplets can be obtained in the color filter ink ultimately obtained.
The content ratio (sum of the content ratios of the plurality of types of dispersing agents) of the dispersing agent in the dispersing-agent-dispersed liquid prepared in the present step is not particularly limited, but is preferably 10 to 40 wt %, and more preferably 12 to 32 wt %. When the content ratio of the dispersing agent is within this range, such effects as previously described are demonstrated more significantly.
The content ratio of the thermoplastic resin in the dispersing-agent-dispersed liquid prepared in the present step is not particularly limited, but is preferably 6 to 30 wt %, and more preferably 8 to 26 wt %. When the content ratio of the thermoplastic resin is within this range, such effects as previously described are demonstrated more significantly.
The content ratio of the solvent in the dispersing-agent-dispersed liquid prepared in the present step is not particularly limited, but is preferably 40 to 80 wt %, and more preferably 53 to 75 wt %. When the content ratio of the solvent is within this range, such effects as previously described are demonstrated more significantly.
In the present step, a dispersing-agent-dispersed liquid is obtained by stirring a mixture of the abovementioned components using various types of agitators.
Examples of agitators that can be used in the present step include a Dispermill or other single-shaft or twin-shaft mixer or the like.
The stirring time for which the agitator is used is not particularly limited, but is preferably 1 to 30 minutes, and more preferably 3 to 20 minutes. The associated state of the dispersing agent can thereby be more effectively released while adequately excellent production properties of the color filter ink are obtained, and particularly excellent dispersion stability of pigment particles in the color filter ink ultimately obtained, particularly excellent discharge stability of the color filter ink can be obtained.
The speed of the stirring vanes of the agitator in the present step is not particularly limited, but is preferably 500 to 4000 rpm, and more preferably 800 to 3000 rpm. The associated state of the dispersing agent can thereby be more effectively released while adequately excellent production properties of the color filter ink are obtained, and it is possible to obtain particularly excellent dispersion stability of pigment particles in the color filter ink ultimately obtained. Degradation, denaturation, and the like of the thermoplastic resin and other components due to heat and the like can also be reliably prevented.
Fine-Dispersion Step
A pigment such as described above is then added to the dispersing-agent-dispersed liquid obtained in the step described above, inorganic beads are added in multiple stages, and a fine-dispersion process is performed (fine-dispersion step).
Prior to adding the pigment, a pre-dispersion step such as the one described above is thus provided in the present embodiment, and inorganic beads are added in multiple stages in the step (fine-dispersion step) of fine-dispersing the pigment. In the fine-dispersion step, adding the inorganic beads in multi-stage fashion makes it possible to form microparticles of the pigment with superior efficiency, and to make the pigment particles adequately small in the color filter ink ultimately obtained. In particular, the effects of jointly using an acid-value dispersing agent and an amine-value dispersing agent such as described above, and the effects of using a method having a pre-dispersion step and a multi-stage fine-dispersion step act synergistically, the color filter ink ultimately obtained can be endowed with extremely excellent dispersion stability of pigment and discharge stability of droplets, and the color filter ink can be used to manufacture a color filter having extremely excellent brightness and contrast.
In contrast, when the fine-dispersion step is not performed in multiple stages, it is difficult to make the pigment particles adequately small in the color filter ink ultimately obtained, and the production properties of the color filter ink can be severely reduced. Even when the fine-dispersion step is performed in multiple stages, such problems as the following can occur when the pre-dispersion step such as described above is omitted. Specifically, when the pre-dispersion step is omitted, since the associated state of the dispersing agent is not adequately released (not undone) when the pigment is added, it is difficult to uniformly adhere the dispersing agent and the thermoplastic resin to the surfaces of the pigment particles in the fine-dispersion step. It is also difficult obtain adequately excellent dispersion properties of the pigment particles (pigment particles having relatively large grain size that are not fine-dispersed) in the solvent in the fine-dispersion step.
It is sufficient for the present step to be performed by adding the inorganic beads in multiple stages, and the inorganic beads may be added in three or more stages, but the inorganic beads are preferably added in two stages. The production properties of the color filter ink can thereby be made particularly excellent while the color filter ink ultimately obtained is endowed with adequately excellent long-term dispersion stability of the pigment particles.
A method for adding the inorganic beads in two stages will be described below. Specifically, a typical example of a method will be described for performing a first treatment using first organic beads, and a second treatment using second organic beads in the fine-dispersion step.
The inorganic beads (first inorganic beads and second inorganic beads) used in the present step may be composed of any material insofar as the material is an inorganic material, but preferred examples of the inorganic beads include zirconia beads (e.g., Toray Ceram milling balls (trade name); manufactured by Toray) and the like.
First Treatment
In the present step, the pigments are first added to the dispersing-agent-dispersed liquid prepared in the pre-dispersion step described above, and a first treatment is performed for primary fine-dispersion using first inorganic beads having a predetermined grain size.
The first inorganic beads used in the first treatment preferably have a larger grain size than the second inorganic beads used in the second treatment. The efficiency of microparticle formation (fine-dispersion) of the pigments in the overall fine-dispersion step can thereby be made particularly excellent.
The average grain size of the first inorganic beads is not particularly limited, but is preferably 0.5 to 3.0 mm, more preferably 0.5 to 2.0 mm, and more preferably 0.5 to 1.2 mm. When the average grain size of the first inorganic beads is within the aforementioned range, the efficiency of microparticle formation (fine-dispersion) of the pigments in the overall fine-dispersion step can be made particularly excellent. In contrast, when the average grain size of the first inorganic beads is less than the lower limit of the aforementioned range, severe reduction of the efficiency of microparticle formation (grain size reduction) of the pigment particles by the first treatment tends to occur according to the type and other characteristics of the pigments. When the average grain size of the first inorganic beads exceeds the upper limit of the aforementioned range, although the efficiency of microparticle formation (grain size reduction) of the pigment particles by the first treatment can be made relatively excellent, the efficiency of microparticle formation (grain size reduction) of the pigment particles by the second treatment is reduced, and the efficiency of microparticle formation (fine-dispersion) of the pigments is reduced in the fine-dispersion step as a whole.
The amount of the first inorganic beads used is not particularly limited, but is preferably 100 to 600 parts by weight, and more preferably 200 to 500 parts by weight with respect to 100 parts by weight of the dispersing-agent-dispersed liquid.
The amount of the pigments added to the dispersing-agent-dispersed liquid is not particularly limited, but is preferably 12 parts by weight or more, and more preferably 18 to 35 parts by weight with respect to 100 parts by weight of the dispersing-agent-dispersed liquid.
The first treatment may be performed by stirring using various types of agitators in a state in which the pigments and the first inorganic beads are added to the dispersing-agent-dispersed liquid.
Examples of agitators that can be used in the first treatment include a ball mill or other media-type dispersing device, a Dispermill or other single-shaft or twin-shaft mixer, or the like.
The stirring time (processing time of the first treatment) for which the agitator is used is not particularly limited, but is preferably 10 to 120 minutes, and more preferably 15 to 40 minutes. Microparticle formation (fine-dispersion) of the pigments can thereby be efficiently advanced without reducing the production properties of the color filter ink.
The speed of the stirring vanes of the agitator in the first treatment is not particularly limited, but is preferably 1000 to 5000 rpm, and more preferably 1200 to 3800 rpm. Microparticle formation (fine-dispersion) of the pigments can thereby be efficiently advanced without reducing the production properties of the color filter ink. Degradation, denaturation, and the like of the thermoplastic resin and other components due to heat and the like can also be reliably prevented.
Second Treatment
A second treatment using second inorganic beads is performed after the first treatment. A pigment dispersion is thereby obtained in which the pigment particles are adequately fine-dispersed.
The second treatment may be performed in a state in which the first inorganic beads are included, but the first inorganic beads are preferably removed prior to the second treatment. Microparticle formation (fine-dispersion) of the pigments in the second treatment can thereby be performed with particularly excellent efficiency. The first inorganic beads can be easily and reliably removed by filtration or the like, for example.
The second inorganic beads used in the second treatment preferably have a smaller grain size than the first inorganic beads used in the first treatment. The pigments can thereby be adequately formed into microparticles (fine-dispersed) in the color filter ink ultimately obtained, particularly excellent dispersion stability (long-term dispersion stability) of the pigment particles in the color filter ink over a long period of time can be obtained, and particularly excellent discharge stability of droplets can be obtained.
The average grain size of the second inorganic beads is not particularly limited, but is preferably 0.03 to 0.3 mm, and more preferably 0.05 to 0.2 mm. When the average grain size of the second inorganic beads is within the aforementioned range, the pigments can be formed into microparticles (fine-dispersed) with particularly excellent efficiency in the fine-dispersion step as a whole. In contrast, when the average grain size of the second inorganic beads is less than the lower limit of the aforementioned range, severe reduction of the efficiency of microparticle formation (grain size reduction) of the pigment particles by the second treatment tends to occur according to the type and other characteristics of the pigments. When the average grain size of the second inorganic beads exceeds the upper limit of the aforementioned range, microparticle formation (fine-dispersion) of the pigment particles can be difficult to adequately advance.
The amount of the second inorganic beads used is not particularly limited, but is preferably 100 to 600 parts by weight, and more preferably 200 to 500 parts by weight with respect to 100 parts by weight of the dispersing-agent-dispersed liquid.
The second treatment can be performed using various types of agitators.
Examples of agitators that can be used in the second treatment include a ball mill or other media-type dispersing device, a Dispermill or other single-shaft or twin-shaft mixer, or the like.
The stirring time (processing time of the second treatment) for which the agitator is used is not particularly limited, but is preferably 10 to 120 minutes, and more preferably 15 to 40 minutes. Microparticle formation (fine-dispersion) of the pigments can thereby be adequately advanced without reducing the production properties of the color filter ink.
The speed of the stirring vanes of the agitator in the second treatment is not particularly limited, but is preferably 1000 to 5000 rpm, and more preferably 1200 to 3800 rpm. Microparticle formation (fine-dispersion) of the pigments can thereby be efficiently advanced without reducing the production properties of the color filter ink. Degradation, denaturation, and the like of the thermoplastic resin and other components due to heat and the like can also be reliably prevented.
A case was described above in which the fine-dispersion process was performed in two stages, but three or more stages of processing may also be performed. In such a case, the inorganic beads used in the later stages preferably have a smaller diameter than the inorganic beads used in the first stages. In other words, the average grain size of the inorganic beads (nth inorganic beads) used in the nth process is preferably smaller than the average grain size of the inorganic beads ((n−1)th inorganic beads) used in the (n−1)th process. By satisfying such a relationship, the pigment particles can be formed into microparticles (fine-dispersed) with particularly excellent efficiency, and the diameter of the pigment particles can be reduced in the color filter ink ultimately obtained.
In the fine-dispersion step (e.g., the first treatment and the second treatment), the solvent may be used for dilution or the like, for example, as needed.
Curable Resin Mixing Step
The pigment dispersion obtained in the fine-dispersion step such as described above is mixed with the curable resin material (curable resin mixing step). The color filter ink is thereby obtained.
The present step is preferably performed in a state in which the second inorganic beads used in the second treatment have been removed. The second inorganic beads can be easily and reliably removed by filtration, for example.
The present step can be performed using various types of agitators.
Examples of agitators that can be used in the present step include a Dispermill or other single-shaft or twin-shaft mixer, or the like.
The stirring time (processing time of the present step) for which the agitator is used is not particularly limited, but is preferably 1 to 60 minutes, and more preferably 15 to 40 minutes.
The speed of the stirring vanes of the agitator in the present step is not particularly limited, but is preferably 1000 to 5000 rpm, and more preferably 1200 to 3800 rpm.
In the present step, a liquid having a different composition than the solvent used in the aforementioned step may be added. A color filter ink having the desired characteristics can thereby be reliably obtained while dispersion of the dispersing agent in the aforementioned pre-dispersion step, and fine-dispersion of the pigment particles in the fine-dispersion step are appropriately performed.
In the present step, at least a portion of the solvent used in the aforementioned step may be removed prior to mixing of the pigment dispersion and the curable resin material, and after mixing of the pigment dispersion and the curable resin material. The composition of the solvent in the pre-dispersion step and the fine-dispersion step, and the composition of the dispersion medium in the color filter ink ultimately obtained can thereby be made to differ from each other. As a result, a color filter ink having the desired characteristics can be reliably obtained while dispersion of the dispersing agent in the aforementioned pre-dispersion step, and fine-dispersion of the pigment particles in the fine-dispersion step are appropriately performed. The solvent can be removed by placing the liquid to be removed in a reduced-pressure atmosphere, heating, or another method, for example.
Ink Set
The color filter ink such as that described above is used in the manufacture of a color filter using an inkjet method. A color filter ordinarily has colored portions having a plurality of colors (ordinarily, RGB corresponding to the three primary colors of light) in correlation with a full color display. A plurality of types of color filter ink that correspond to the plurality of colors of colored portions is used in the formation of the colored portions. In other words, an ink set provided with a plurality of colors of color filter ink is used in the manufacture of a color filter. In the present invention, it is sufficient insofar as a color filter ink such as described above is used to form at least one type of colored portion in the manufacturing of a color filter, but the color filter ink is preferably used to form all of the colors of colored portions.
Color Filter
Following is a description of an example of a color filter manufactured using the color filter ink (ink set) described above.
FIG. 1 is a sectional view showing a preferred embodiment of the color filter of the present invention.
A color filter 1 is provided with a substrate 11 and colored portions 12 formed using the color filter ink described above, as shown in FIG. 1. The colored portions 12 are provided with a first colored portion 12A, a second colored portion 12B, and a third colored portion 12C, having mutually different colors. A partition wall 13 is disposed between adjacent colored portions 12.
Substrate
The substrate 11 is a plate-shaped member having optical transparency, and has a function for holding the colored portions 12 and the partition wall 13.
It is preferred that the substrate 11 be essentially composed of a transparent material. A clearer image can thereby be formed by light transmitted through the color filter 1.
The substrate 11 is preferably one having excellent heat resistance and mechanical strength. Deformations or the like caused by, e.g., heat applied during the manufacture of the color filter 1 can thereby be reliably prevented. Examples of a constituent material of the substrate 11 that satisfies such conditions include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide, norbornene-based ring-opening polymers, and hydrogenated substances.
Colored Portions
The colored portions 12 are formed using a color filter ink such as that described above.
The colored portions 12 are formed using a color filter ink such as that described above, and therefore have little variation in characteristics between pixels, and unintentional color mixing (mixing of a plurality of color filter inks) and the like is reliably prevented. For this reason, the color filter 1 is highly reliable in that the occurrence of unevenness of color and saturation, and the like is reduced. The color filter 1 also has excellent contrast and excellent coloration properties of the colored portions 12.
Each colored portion 12 is disposed inside a cell 14, which is an area enclosed by a later-described partition wall 13.
The first colored portion 12A, the second colored portion 12B, and the third colored portion 12C have mutually different colors. For example, the first colored portion 12A can be a red filter area (R), second colored portion 12B can be a green filter area (G), and the third colored portion 12C can be a blue filter area (B). The colored portions 12A, 12B, 12C as a single set of different colors constitute a single pixel. A prescribed number of the colored portions 12 are disposed in the lateral and longitudinal directions in the color filter 1. For example, when the color filter 1 is a color filter for high definition, 1366×768 pixels are disposed; when the color filter is a color filter for full high definition, 1920×1080 pixels are disposed; and when the color filter is a color filter for super high definition, 7680×4320 pixels are disposed. The color filter 1 may be provided with, e.g., spare pixels outside of the effective area.
Partition Wall
A partition wall (bank) 13 is disposed between adjacent colored portions 12. Adjacent colored portions 12 can thereby be reliably prevented from color mixing, and as a result, a sharp image can be reliably displayed.
The partition wall 13 may be composed of a transparent material, but is preferably composed of material having light-blocking properties. An image with excellent contrast can thereby be displayed. The color of the partition wall (light-blocking portion) 13 is not particularly limited, but black is preferred. Accordingly, the contrast of a displayed image is particularly good.
The height of the partition wall 13 is not particularly limited, but is preferably greater than the thickness of the colored portions 12. Color mixing between adjacent colored portions 12 can thereby be reliably prevented. The specific thickness of the partition wall 13 is preferably 0.1 to 10 μm, and more preferably 0.5 to 3.5 μm. Color mixing between adjacent colored portions 12 can thereby be reliably prevented, and image display devices and electronic devices provided with the color filter 1 can be endowed with excellent visual angle characteristics.
The partition wall 13 may be composed of any material, but is preferably composed principally of a resin material, for example. Accordingly, a partition wall 13 having a desired shape can be easily formed using a method described hereinafter. In the case that the partition wall 13 functions as a light-blocking portion, carbon black or another light-absorbing material may be included as a constituent element of the partition wall.
Method for Manufacturing Color Filter
Next, an example of the method for manufacturing the color filter 1 will be described.
FIG. 2 is a cross-sectional view showing a method for manufacturing a color filter; FIG. 3 is a perspective view showing the droplet discharge device used in the manufacture of the color filter; FIG. 4 is a view of droplet discharge means in the droplet discharge device shown in FIG. 3, as seen from the stage side; FIG. 5 is a view showing the bottom surface of the droplet discharge head in the droplet discharge device shown in FIG. 3; and FIG. 6 is a view showing the droplet discharge head in the droplet discharge device shown in FIG. 3, wherein FIG. 6(a) is a cross-sectional perspective view and FIG. 6(b) is a cross-sectional view.
The present embodiment has a substrate preparation step (1a) for preparing a substrate 11, a partition wall formation step (1b, 1c) for forming a partition wall 13 on the substrate 11, an ink application step (1d) for applying color filter ink 2 into an area surrounded by the partition wall 13 by using an inkjet method, and a colored portion formation step (1e) for forming solid colored portions 12 by removing liquid medium from the color filter ink 2 and curing the curable resin material, as shown in FIG. 2.
Substrate Preparation Step
First, a substrate 11 is prepared (1a). It is preferred that the substrate 11 to be prepared in the present step undergo a washing treatment. The substrate 11 to be prepared in the present step may be washed by chemical treatment using a silane-coupling agent or the like, a plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, or another suitable washing treatment.
Partition Wall Formation Step
Next, a radiation-sensitive composition is applied to substantially the entire surface of one of the surfaces of the substrate 11 to form (1b) a coated film 3. A prebaking treatment may be performed as required after the radiation-sensitive composition has been applied to the substrate 11. The prebaking treatment may be carried out under the conditions of, e.g., a heating temperature of 50 to 150° C. and a heating time of 30 to 600 seconds.
Next, a partition wall 13 is formed (1c) by irradiating the surface via a photomask, performing a post exposure bake (PEB), and carrying out a development treatment using an alkali development fluid. PEB can be carried out under the following example conditions: a heating temperature of 50 to 150° C., a heating time of 30 to 600 seconds, and a radiation intensity of 1 to 500 mJ/cm2. The development treatment can be performed using, e.g., fluid overflow, dipping, vibration soaking, or another method, and the development treatment time can be set to 10 to 300 seconds, for example. After the development treatment, a post baking treatment may be performed as required. The post baking treatment can be carried out under the following example conditions: a heating temperature of 150 to 280° C. and a heating time of 3 to 120 minutes.
Ink Application Step
Next, the color filter ink 2 is applied (1d) to the cells 14 surrounded by the partition wall 13 using the inkjet method.
The present step is carried out using a plurality of types of color filter inks 2 that correspond to the plurality of colors of the colored portions 12 to be formed. In this case, a partition wall 13 is provided, and mixing of two or more color filter inks 2 can therefore be reliably prevented.
The color filter ink 2 is discharged using a droplet discharge device such as that shown in FIGS. 3 to 6.
The droplet discharge device 100 used in the present step is provided with a tank 101 for holding the color filter ink 2, a tube 110, and a discharge scan unit 102 to which the color filter ink 2 is fed from the tank 101 via the tube 110, as shown in FIG. 3. The discharge scan unit 102 is provided with droplet discharge means 103 in which a plurality of droplet discharge heads (inkjet heads) 114 is mounted on a carriage 105, a first position controller 104 (movement means) for controlling the position of the droplet discharge means 103, a stage 106 for holding the substrate 11 (hereinafter simply referred to as “substrate 11”) on which the partition wall 13 is formed in an aforementioned step, a second position controller 108 (movement means) for controlling the position of the stage 106, and control means 112. The tank 101 and the plurality of droplet discharge heads 114 in the droplet discharge means 103 are connected by the tube 110, and the color filter ink 2 is fed by compressed air from the tank 101 to each of the plurality of droplet discharge heads 114.
The first position controller 104 moves the droplet discharge means 103 along the X-axis direction and Z-axis direction orthogonal to the X-axis direction, in accordance with a signal from the control means 112. The first position controller 104 also has a function for rotating the droplet discharge means 103 about the axis parallel to the Z-axis. In the present embodiment, the Z-axis direction is the direction parallel to the perpendicular direction (i.e., the direction of gravitational acceleration). The second position controller 108 moves the stage 106 along the Y-axis direction, which is orthogonal to both the X-axis direction and the Z-axis direction, in accordance with a signal from the control means 112. The second position controller 108 also has a function for rotating the stage 106 about the axis parallel to the Z-axis.
The stage 106 has a surface parallel to both the X-axis direction and the Y-axis direction. The stage 106 is configured so as to be capable of securing or holding the substrate 11 on the planar surface thereof, the substrate having the cells 14 in which the color filter ink 2 is to be applied.
As described above, the droplet discharge means 103 is moved in the X-axis direction by the first position controller 104. On the other hand, the stage 106 is moved in the Y-axis direction by the second position controller 108. In other words, the relative position of the droplet discharge heads 114 in relation to the stage 106 is changed by the first position controller 104 and the second position controller 108 (the substrate 11 held on the stage 106 and the droplet discharge means 103 move in a relative fashion).
The control means 112 is configured so as to receive from an external information processor discharge data that express the relative position in which the color filter ink 2 is to be discharged.
The droplet discharge means 103 has a plurality of droplet discharge heads 114, which have substantially the same structure as each other, and a carriage 105 for holding the droplet discharge heads 114, as shown in FIG. 4. In the present embodiment, the number of droplet discharge heads 114 held in the droplet discharge means 103 is eight. Each of the droplet discharge heads 114 has a bottom surface on which a plurality of later-described nozzles 118 is disposed. The shape of the bottom surface of each of the droplet discharge heads 114 is a polygon having two short sides and two long sides. The bottom surface of the droplet discharge heads 114 held in the droplet discharge means 103 faces the stage 106 side, and the long-side direction and the short-side direction of the droplet discharge heads 114 are parallel to the X-axis direction and the Y-axis direction, respectively.
The droplet discharge heads 114 have a plurality of nozzles 118 aligned in the X-axis direction, as shown in FIG. 5. The plurality of nozzles 118 is disposed so that a nozzle pitch HXP in the X-axis direction in the droplet discharge heads 114 has a prescribed value. The specific value of the nozzle pitch HXP is not particularly limited, but may be 50 to 90 μm, for example. In this case, “the nozzle pitch HXP in the X-axis direction in the droplet discharge heads 114” corresponds to the pitch between a plurality of nozzle images obtained by projecting all of the nozzles 118 in the droplet discharge heads 114 on the X axis along the Y-axis direction.
In the present embodiment, the plurality of nozzles 118 in the droplet discharge heads 114 forms a nozzle row 116A and a nozzle row 116B, both of which extend in the X-axis direction. The nozzle row 116A and the nozzle row 116B are disposed in parallel across an interval. In the present embodiment, 90 nozzles 118 are aligned in a row in the X-axis direction with a fixed interval LNP in each nozzle row 116A and nozzle row 116B. The specific value of LNP is not particularly limited, but may be 100 to 180 μm, for example.
The position of the nozzle row 116B is offset in the positive direction of the X-axis direction by half the length of the nozzle pitch LNP in relation to the position of the nozzle row 116A. For this reason, the nozzle pitch HXP in the X-axis direction of the droplet discharge heads 114 is half the length of the nozzle pitch LNP of the nozzle row 116A (or the nozzle row 116B).
Therefore, the nozzle line density in the X-axis direction of the droplet discharge heads 114 is twice the nozzle line density of the nozzle row 116A (or the nozzle row 116B). In the present specification, “the nozzle line density in the X-axis direction” corresponds to the number per unit length of the plurality of nozzle images obtained by projecting a plurality of nozzles on the X-axis along the Y-axis direction. Naturally, the number of nozzle rows included in the droplet discharge heads 114 is not limited to two rows. The droplet discharge heads 114 may include M number of nozzle rows. In this case, M is a natural number of 1 or higher. In this case, the plurality of nozzles 118 in each of the M number of nozzle rows is aligned at a pitch having a length that is M times that of the nozzle pitch HXP. In the case that M is a natural number of 2 or higher, another (M-1) number of nozzle rows are offset in the X-axis direction without overlapping, by a length i times that of the nozzle pitch HXP, in relation to a single nozzle row among the M number of nozzle rows. Here, i is a natural number from 1 to (M-1).
In the present embodiment, since the nozzle row 116A and the nozzle row 116B are each composed of 90 nozzles 118, a single droplet discharge head 114 has 180 nozzles 118. However, five nozzles at each end of the nozzle row 116A are set as “reserve nozzles.” Similarly, five nozzles at each end of the nozzle row 116B are set as “reserve nozzles.” The color filter ink 2 is not discharged from these 20 “reserve nozzles.” For this reason, 160 nozzles 118 among the 180 nozzles 118 in the droplet discharge heads 114 function as nozzles for discharging the color filter ink 2.
In the droplet discharge means 103, the plurality of droplet discharge heads 114 is disposed in two rows along the X-axis direction, as shown in FIG. 4. One of the rows of droplet discharge heads 114 and the other row of droplet discharge heads 114 are disposed so that a portion of the droplet discharge heads overlap as viewed from the Y-axis direction, with consideration given to the reserve nozzles. The nozzles 118 for discharging the color filter ink 2 are thereby configured so as to be continuous in the X-axis direction at the nozzle pitch HXP across the length of the dimension in the X-axis direction of the substrate 11 in the droplet discharge means 103.
In the droplet discharge means 103 of the present embodiment, the droplet discharge heads 114 are disposed so as to cover the entire length of the dimension in the X-axis direction of the substrate 11. However, the droplet discharge means in the present invention may cover a portion of the length of the dimension in the X-axis direction of the substrate 11.
Each of the droplet discharge heads 114 is an inkjet head, as shown in the diagram. More specifically, each of the droplet discharge heads 114 is provided with a vibration plate 126 and a nozzle plate 128. A fluid reservoir 129 in which the color filter ink 2 fed from the tank 101 via a hole 131 is constantly filled is positioned between the vibration plate 126 and the nozzle plate 128.
A plurality of partition walls 122 is disposed between the vibration plate 126 and the nozzle plate 128. The portions enclosed by the vibration plate 126, the nozzle plate 128, and a pair of partition walls 122 are cavities 120. Since the cavities 120 are disposed in correspondence with the nozzles 118, the number of cavities 120 and the number of nozzles 118 is the same. The color filter ink 2 is fed to the cavities 120 from the fluid reservoir 129 via supply ports 130 positioned between pairs of partition walls 122.
An oscillator 124 is positioned on the vibration plate 126 in correspondence with each of the cavities 120. The oscillator 124 includes a piezoelement 124C, and a pair of electrodes 124A, 124B that sandwich the piezoelement 124C. The color filter ink 2 is discharged from the corresponding nozzle 118 by applying a drive voltage between the pair of electrodes 124A, 124B. The shape of the nozzles 118 is adjusted so that the color filter ink 2 is discharged in the Z-axis direction from the nozzles 118.
The control means 112 (see FIG. 3) may be configured so as to independently apply signals to each of the plurality of oscillators 124. In other words, the volume of the color filter ink 2 discharged from the nozzles 118 can be controlled for each nozzle 118 in accordance with a signal from the control means 112. The control means 112 can also set the nozzles 118 that will perform a discharge operation during a coating scan, as well as the nozzles 118 that will not perform a discharge operation.
In the present specification, the portion that includes a single nozzle 118, a cavity 120 that corresponds to the nozzle 118, and the oscillator 124 that corresponds to the cavity 120 will be referred to as a “discharge portion 127”. In accordance with this designation, a single droplet discharge head 114 has the same number of discharge portions 127 as the number of nozzles 118.
The color filter ink 2 corresponding to the plurality of colored portions 12 of the color filter 1 is applied to the cells 14 using such a droplet discharge device 100. The color filter ink 2 can be selectively applied with good efficiency in the cells 14 by using such a device. As described above, the color filter ink 2 has excellent stable discharge properties, and flight deflection, loss of stability in the droplet discharge quantity, and other problems are much less likely to occur, even when droplet discharge is carried out over a long period of time. Therefore, it is possible to reliably prevent problems such as the mixing (color mixing) of a plurality of types of ink used in the formation of colored portions having different colors, and variability in the color saturation between the plurality of colored portions in which the same color saturation is normally required. In the configuration of the diagrams, the droplet discharge device 100 has a tank 101 for holding the color filter ink 2, a tube 110, and other components for only one color, but these members may have a plurality of colors the correspond to the plurality of colored portions 12 of the color filter 1. Also, in the manufacture of the color filter 1, a plurality of droplet discharge devices 100 corresponding to a plurality of color filter inks 2 may be used.
In the present invention, the droplet discharge heads 114 may use an electrostatic actuator in place of the piezoelement as the drive element. The droplet discharge heads 114 may have a configuration in which an electrothermal converter is used and color filter ink is discharged using the thermal expansion of material produced by an electrothermal converter.
Colored Portion Formation Step (Curing Step)
Next, the liquid medium is removed from the color filter ink 2 in the cells 14, and solid colored portions 12 are formed by curing the curable resin material (1e). The color filter 1 is obtained in this manner.
The present step, heating is ordinarily carried out, but in the present step, for example, treatments involving irradiation of active energy rays, treatments in which the substrate 11 to which the color filter ink 2 has been applied is placed under a reduced-pressure environment, and other treatments may also be performed. The curing reaction of the curable resin material can be made to proceed with good efficiency by irradiating active energy rays; the curing reaction of the curable resin material can be reliably promoted even when the heating temperature is relatively low; the occurrence of adverse effects on the substrate 11 and other components can reliably prevented; and other effects can be obtained. Examples of the active energy rays that may be used include light rays of various wavelengths, e.g., UV rays, X-rays, g-rays, i-rays, and excimer lasers. The substrate 11 on which the color filter ink 2 has been applied can be placed under a reduced-pressure environment, whereby the liquid medium can be removed with good efficiency, the shape of the colored portions in the pixels (cells) can be reliably made into good preferred shapes, the liquid medium can be reliably removed even when the heating temperature is relatively low, the occurrence of adverse effects on the substrate 11 and the like can be reliably prevented, and other effects can be obtained.
The heating temperature in the present step is not particularly limited, but 50 to 260° C. is preferred, and 80 to 240° C. is even more preferred.
Image Display Device
Preferred embodiments of the liquid crystal display device, which is an image display device (electrooptic device) having the color filter 1, will next be described.
FIG. 7 is a cross-sectional view showing a preferred embodiment of the liquid crystal display device. As shown in the diagram, the liquid crystal display device 60 has a color filter 1, a substrate (opposing substrate) 66 arranged on the surface on which the colored portions 12 of the color filter 1 are disposed, a liquid crystal layer 62 composed of a liquid crystal sealed in the gaps between the color filter 1 and the substrate 66, a polarizing plate 67 disposed on the surface (lower side in FIG. 7) opposite from the surface that faces the liquid crystal layer 62 of the substrate 11 of the color filter 1, and a polarizing plate 68 disposed on the side (upper side in FIG. 7) opposite from the surface that faces liquid crystal layer 62 of the substrate 66. A shared electrode 61 is disposed on the surface (the surface opposite from the surface facing the substrate 11 of the colored portions 12 and the partition wall 13) on which the colored portions 12 and the partition wall 13 of the color filter 1 are disposed. Pixel electrodes 65 are disposed in the form of a matrix in positions that correspond to the colored portions 12 of the color filter 1 on the substrate (opposing substrate) 66, facing the liquid crystal layer 62 and color filter 1. An alignment film 64 is disposed between the shared electrode 61 and the liquid crystal layer 62, and an alignment film 63 is disposed between the substrate 66 (pixel electrodes 65) and the liquid crystal layer 62.
The substrate 66 is a substrate having optical transparency with respect to visible light, and is a glass substrate, for example.
The shared electrode 61 and the pixel electrodes 65 are composed of a material having optical transparency with respect to visible light, and are ITO or the like, for example.
Although not depicted in the diagram, a plurality of switching elements (e.g., TFT: thin film transistors) is disposed so as to correspond to the pixel electrodes 65. The pixel electrodes 65 corresponding to the colored portions 12 can be used to control the transmission properties of light in areas that correspond to the colored portions 12 (pixel electrodes 65) by controlling the state of the voltage applied between the shared electrode 61 and the pixel electrodes.
In the liquid crystal display device 60, light emitted from the backlight, which is not depicted, is incident from the polarizing plate 68 side (the upper side in FIG. 7). The light that passes through the liquid crystal layer 62 and enters the colored portions 12 (12A, 12B, 12C) of the color filter 1 is emitted from the polarizing plate 67 (lower side of FIG. 7) as light having a color that corresponds to the colored portions 12 (12A, 12B, 12C).
As described above, the colored portions 12 are formed using the color filter ink 2 (ink set) of the present invention and therefore have reduced variability in the characteristics between pixels. As a result, an image having reduced unevenness of color and saturation, and the like can be stably displayed in the liquid crystal display device 60. Since the colored portions 12 are formed using the color filter ink of the present invention, excellent contrast is also obtained.
Electronic Device
A liquid crystal display device or another image display device (electrooptic device) 1000 having a color filter 1 such as that described above can be used in a display unit of a variety of electronic equipment.
FIG. 8 is a perspective view showing the configuration of a mobile (or notebook) personal computer to which the electronic equipment of the present invention has been applied.
In the diagram, a personal computer 1100 is composed of a main unit 1104 provided with a keyboard 1102, and a display unit 1106. The display unit 1106 is rotatably supported by the main unit 1104 via a hinge structure.
In the personal computer 1100, the display unit 1106 is provided with an image display device 1000.
FIG. 9 is a perspective view showing the configuration of a portable telephone (including PHS) to which the electronic device of the present invention has been applied.
In the diagram, the portable telephone 1200 has a plurality of operating buttons 1202, an earpiece 1204, and a mouthpiece 1206, as well as an image display device 1000 provided to the display unit.
FIG. 10 is a perspective view showing the configuration of a digital still camera in which the electronic device of the present invention has been applied. In the diagram, connection to external apparatuses is displayed in a simplified manner.
In this case, an ordinary camera exposes a silver-salt photography film to the optical image of a photographed object, but in contrast, a digital still camera 1300 photoelectrically converts the optical image of a photographed image and generates an imaging signal (image signal) with the aid of a CCD (Charge Coupled Device) or another imaging element.
An image display device 1000 is disposed in the display portion on the back surface of a case (body) 1302 in the digital still camera 1300, is configured to perform display operation on the basis of a pickup signal from the CCD, and functions as a finder for displaying the photographed object as an electronic image.
A circuit board 1308 is disposed inside the case. The circuit board 1308 has a memory that can store (record) the imaging signal.
A photo-detection unit 1304 that includes an optical lens (imaging optical system), a CCD, and the like is disposed on the front surface side (back surface side in the configuration of the diagram) of the case 1302.
A photographer confirms the image of the object to be photographed displayed on the display unit, and the imaging signal of the CCD when a shutter button 1306 is pressed is transferred and stored in the memory of the circuit board 1308.
In the digital still camera 1300, a video signal output terminal 1312 and a data communication I/O terminal 1314 are disposed on the side surface of the case 1302. A television monitor 1430 is connected to the video signal output terminal 1312 as required, and a personal computer 1440 is connected to the data communication I/O terminal 1314 as required, as shown in the diagram. An imaging signal stored in the memory of the circuit board 1308 is configured to be outputted by a prescribed operation to the television monitor 1430 and the personal computer 1440.
The electronic device of the present invention may be applied to the above-described personal computer (mobile personal computer), portable telephone, and digital still camera, and other examples include televisions (e.g., liquid crystal display devices), video cameras, view finder-type and direct-view monitor-type video tape recorders, laptop personal computers, car navigation devices, pagers, electronic assistants (including those with a communication function), electronic dictionaries, calculators, electronic game devices, word processors, work stations, videophones, security television monitors, electronic binoculars, POS terminals, apparatuses having a touch panel (e.g., cash dispensers for financial institutions, and automatic ticketing machines), medical equipment (e.g., electronic thermometers, sphygmomanometers, blood glucose sensors, electrocardiograph display devices, ultrasound diagnostic devices, and endoscopic display devices), fish finders, various measuring apparatuses, instruments (e.g., instruments in vehicles, aircraft, and ships), flight simulators, and various other monitors, and projectors, and other projection display devices. Among these, televisions have display units that are tending to become markedly larger in recent years, but in electronic devices having such a large display unit (e.g., a display unit having a diagonal length of 80 cm or more), unevenness of color and saturation, and other problems particularly readily occur when a color filter manufactured using a conventional color filter ink is used. However, in accordance with the present invention, the occurrence of such problems can be reliably prevented. In other words, the effect of the present invention is more markedly demonstrated when application is made to an electronic device having a large display unit such as that described above.
The present invention above was described based on preferred embodiments, but the present invention is not limited to these embodiments.
For example, in the embodiments described above, color filter ink corresponding to the colored portions of various colors was applied inside the cells, the solvent (dispersion medium) was thereafter removed in a single process from the color filter ink of each color in the cells, and the resin material was cured. In other words, a process was described in which the colored portion formation step (curing step) was carried out a single time, but the ink application step and the colored portion formation step may be repeated for each color.
It is also possible to substitute or to add as another configuration the parts constituting a color filter, image display device, and electronic device with any part that demonstrates the same function. For example, in the color filter of the present invention, a protective film for covering the colored portions may be provided to the surface opposite from the surface facing the substrate of the colored portions. Damage, degradation, and the like of the colored portions can thereby be more effectively prevented.
The color filter ink of the present invention may be manufactured by any method, and is not limited to being manufacture using a method such as described above. For example, the manufacturing method was described in the embodiment as having a pre-dispersion step and a multi-stage fine-dispersion step, but the color filter ink of the present invention may be manufactured by a method that does not have a pre-dispersion step, or a method that has a fine-dispersion step that is not multi-stage. A thermoplastic resin was also described as being used in the pre-dispersion step in the embodiment, but a curable resin material, e.g., the aforementioned polymer A and polymer B, may also be used in the pre-dispersion step. The curable resin mixing step can thereby be omitted, for example.
In the embodiments described above, the case in which an ink set for a color filter is provided with three types (three colors) of color filter inks corresponding to the three primary colors of light was mainly described, but the number and type (color) of color filter inks constituting the ink set for a color filter is not limited to the arrangement described above. For example, in the present invention, the ink set for a color filter may be one provided with four or more types of color filter inks.
EXAMPLES
Next, specific examples of the present invention will be described.
1. Synthesis of Polymer (Preparation of Polymer Solution)
Synthesis Example 1
As the medium (solvent), 37.6 parts by weight of 1,3-butylene glycol diacetate was placed in a 1-L reaction container provided with an agitator, a reflux condenser, a dropping funnel, a nitrogen introduction tube, and a temperature gauge, and heated to 90° C. Next, 2 parts by weight of 2,2′-azobis(isobutyronitrile) (AIBN) and 3 parts by weight 1,3-butylene glycol diacetate (solvent) were added, and a solution in which 27 parts by weight of (3,4-epoxy cyclohexyl)methyl methacrylate (product name: Cyclomer M100, manufactured by Daicel Chemical Industries), 1.5 parts by weight of 2-(0-[1′-methylpropylideneamino]carboxyamino)methacrylate (product name: MOI-BM, manufactured by Showa Denko), and 1.5 parts by weight of 2-hydroxyethyl methacrylate (HEMA) were admixed was dropped over about 4 hours using a dropping pump. Also, a solution (polymerization initiator solution) in which 5 parts by weight of dimethyl 2,2′-azobis(isobutyrate) (product name V-601, manufactured by Wako Pure Chemical Industries) as the polymerization initiator were dissolved in 20 parts by weight of 1,3-butylene glycol diacetate (medium) was dropped over about 4 hours using a separate dropping pump. After the dropping of the polymerization initiator solution was completed, 0.2 part by weight of AIBN and 1 part by weight of 1,3-butylene glycol diacetate (medium) was added and held for about 2 hours at about the same temperature, after which 0.2 part by weight of AIBN and 1 part by weight of 1,3-butylene glycol diacetate (medium) was added and held for about 2 hours at about the same temperature, and then cooled to room temperature to obtain a polymer solution A1 containing a polymer A and having a solid content of 30 wt %.
Synthesis Examples 2 to 10
The same operation as synthesis example 1 described above was carried out, except that the type of monomer components, usage amount, and type of medium (solvent) used in the synthesis of the polymer (preparation of the polymer solution) were varied in the manner shown in Table 1. As a result, nine polymer solutions (polymer solutions A2 to A10) containing a polymer A and having a solid content of 30 wt % were obtained.
Synthesis Example 11
The same operation as synthesis example 1 described above was carried out, except that 30 parts by weight of γ-methacryloxypropyl trimethoxysilane (product name: SZ6030, manufactured by Dow Corning Toray) was used in place of (3,4-epoxy cyclohexyl)methyl methacrylate (product name: Cyclomer M100, manufactured by Daicel Chemical Industries),
2-(0-[1′-methylpropylideneamino]carboxyamino)methacrylate (product name: MOI-BM, manufactured by Showa Denko), and 2-hydroxyethyl methacrylate (HEMA). As a result, a polymer solution (polymer solution B1) containing a polymer B and having a solid content of 30 wt % was obtained.
Synthesis Examples 12 to 16
The same operation as synthesis example 11 described above was carried out, except that the type of monomer components, usage amount, and type of medium (solvent) used in the synthesis of the polymer (preparation of the polymer solution) were varied in the manner shown in Table 1. As a result, five polymer solutions (polymer solutions B2 to B6) containing a polymer B and having a solid content of 30 wt % were obtained.
Synthesis Example 17
The same operation as synthesis example 1 described above was carried out, except that 30 parts by weight of 1H,1H,5H-octafluoropentyl methacrylate (product name: Biscoat 8FM, manufactured by Osaka Organic Chemical Industry) was used in place of (3,4-epoxy cyclohexyl)methyl methacrylate (product name: Cyclomer M100, manufactured by Daicel Chemical Industries),
2-(0-[1′-methylpropylideneamino]carboxyamino)methacrylate (product name: MOI-BM, manufactured by Showa Denko), and 2-hydroxyethyl methacrylate (HEMA). As a result, a polymer solution C1 (homopolymer solution) containing a polymer C and having a solid content of 30 wt % was obtained.
Synthesis Examples 18 and 19
The same operation as synthesis example 17 described above was carried out, except that the type of monomer components, usage amount, and type of medium (solvent) used in the synthesis of the polymer (preparation of the polymer solution) were varied in the manner shown in Table 1. As a result, two polymer solutions (polymer solutions C2 and C3) containing a polymer C and having a solid content of 30 wt % were obtained.
Synthesis Example 20
The same operation as synthesis example 1 described above was carried out, except that 13.5 parts by weight of (3,4-epoxy cyclohexyl) methyl methacrylate (product name: Cyclomer M100, manufactured by Daicel Chemical Industries), 0.75 part by weight of 2-(0-[1′-methylpropylideneamino]carboxyamino)methacrylate (product name: MOI-BM, manufactured by Showa Denko), 0.75 part by weight of 2-hydroxyethyl methacrylate (HEMA), and 15 parts by weight of γ-methacryloxypropyl trimethoxysilane (product name: SZ6030, manufactured by Dow Corning Toray) were used. As a result, a polymer solution X1 containing a polymer X and having a solid content of 30 wt % was obtained.
The type of material and usage amount (composition of the polymer synthesized in synthesis examples 1 to 20) used in the synthesis of the polymers (preparation of the polymer solutions) in the synthesis example 1 to 20 are summarized in Table 1. In the table, “S” refers to a medium (solvent), and more particularly “S1” refers 1,3-butylene glycol diacetate, “S2” refers to bis(2-butoxyethyl)ether, “S3” refers to diethylene glycol monobutyl ether acetate, and “S4” refers to tripropylene glycol monomethyl ether. Also, “V-601” refers to dimethyl 2,2′-azobis(isobutyrate), “AIBN” refers to 2,2′-azobis(isobutyronitrile), “a1-1” refers to (3,4-epoxy cyclohexyl)methyl methacrylate (Cyclomer M100), “a1-2” refers to (3,4-epoxycyclohexyl)methyl acrylate, “a2-1” refers to 2-(0-[ 1′-methylpropylideneamino]carboxyamino)ethyl methacrylate (MOI-BM), “a2-2” refers to 2-acryloyloxyethyl isocyanate (product name: “Karenz MOI”, manufactured by Showa Denko), “a3-1” refers to 2-hydroxyethyl methacrylate (HEMA), “a3-2” refers to 4-hydroxybutyl acrylate, “a4-1” refers to 1H, 1H,5H-octafluoropentyl methacrylate (Biscoat 8FM), “a4-2” refers to 2-ethylhexyl methacrylate, “b1-1” refers to γ-methacryloxypropyl trimethoxysilane (SZ6030), “b1-2” refers to γ-methacryloxypropyl triethoxysilane, “b2-1” refers to ethyl methacrylate, “c1-1” refers to 1H,1H,5H-octafluoropentyl methacrylate (Biscoat 8FM), “c1-2” refers to 1,2,3,4,5-pentafluorostyrene, “c2-1” refers to 2,3-dihydroxybutyl methacrylate, and “c2-2” refers to cyclohexyl methacrylate. Also shown in the table are the weight-average molecular weights Mw of the polymers that constitute the polymer solutions.








TABLE 1








COMPONENTS (PARTS BY WEIGHT)



MONOMER COMPONENT




















a1-1
a1-2
a2-1
a2-2
a3-1
a3-2
a4-1
a4-2
b1-1
b1-2
b2-1
c1-1





POLYMER SOLUTION A1
27
—
  1.5
—
1.5
—
—
—
—
—
—
—


POLYMER SOLUTION A2
27
—
3
—
—
—
—
—
—
—
—
—


POLYMER SOLUTION A3
27
—
—
—
3  
—
—
—
—
—
—
—


POLYMER SOLUTION A4
24
—
—
—
—
—
6
—
—
—
—
—


POLYMER SOLUTION A5
19
—
5
—
4.5
—
  1.5
—
—
—
—
—


POLYMER SOLUTION A6
  20.5
—
3
—
5.5
—
1
—
—
—
—
—


POLYMER SOLUTION A7
25
—
1
—
2  
—
2
—
—
—
—
—


POLYMER SOLUTION A8
—
27.5
—
1.5
—
1  
—
—
—
—
—
—


POLYMER SOLUTION A9
26
—
—
1  
—
1.5
—
1.5
—
—
—
—


POLYMER SOLUTION A10
  26.5
—
2
—
1.5
—
—
—
—
—
—
—


POLYMER SOLUTION B1
—
—
—
—
—
—
—
—
30
—
—
—


POLYMER SOLUTION B2
—
—
—
—
—
—
—
—
26
—
4
—


POLYMER SOLUTION B3
—
—
—
—
—
—
—
—
23
—
7
—


POLYMER SOLUTION B4
—
—
—
—
—
—
—
—
—
30
—
—


POLYMER SOLUTION B5
—
—
—
—
—
—
—
—
—
28
2
—


POLYMER SOLUTION B6
—
—
—
—
—
—
—
—
30
—
—
—


POLYMER SOLUTION C1
—
—
—
—
—
—
—
—
—
—
—
30


POLYMER SOLUTION C2
—
—
—
—
—
—
—
—
—
—
—
 4


POLYMER SOLUTION C3
—
—
—
—
—
—
—
—
—
—
—
—


POLYMER SOLUTION X1
  13.5
—
  0.75
—
 0.75
—
—
—
15
—
—
—













COMPONENTS (PARTS BY WEIGHT)













MONOMER






COMPONENT

SOLVENT (S)
POLYMER


















c1-2
c2-1
c2-2
S
V-601
AIBN
COMPOSITION
Mw






POLYMER SOLUTION A1
—
—
—
62.6
5
2.4
S1
2700



POLYMER SOLUTION A2
—
—
—
62.6
5
2.4
S1
2800



POLYMER SOLUTION A3
—
—
—
62.6
5
2.4
S3
2800



POLYMER SOLUTION A4
—
—
—
62.6
5
2.4
S1
2800



POLYMER SOLUTION A5
—
—
—
62.6
5
2.4
S2
2700



POLYMER SOLUTION A6
—
—
—
62.6
5
2.4
S3
2700



POLYMER SOLUTION A7
—
—
—
62.6
5
2.4
S2
2800



POLYMER SOLUTION A8
—
—
—
62.6
5
2.4
S4
2800



POLYMER SOLUTION A9
—
—
—
62.6
5
2.4
S2
2800



POLYMER SOLUTION A10
—
—
—
62.6
5
2.4
S4
2800



POLYMER SOLUTION B1
—
—
—
62.6
5
2.4
S1
2800



POLYMER SOLUTION B2
—
—
—
62.6
5
2.4
S3
2700



POLYMER SOLUTION B3
—
—
—
62.6
5
2.4
S4
2700



POLYMER SOLUTION B4
—
—
—
62.6
5
2.4
S1
2800



POLYMER SOLUTION B5
—
—
—
62.6
5
2.4
S3
2800



POLYMER SOLUTION B6
—
—
—
62.6
5
2.4
S2
2800



POLYMER SOLUTION C1
—
—
—
62.6
5
2.4
S1
2800



POLYMER SOLUTION C2
—
26
—
62.6
5
2.4
S3
2800



POLYMER SOLUTION C3
28
—
2
62.6
5
2.4
S2
2800



POLYMER SOLUTION X1
—
—
—
62.6
5
2.4
S1
2700









2. Preparation of Color Filter Ink (Ink Set)
Example 1
Added to an agitator (single-shaft mixer) having a capacity of 400 cc were 5.04 g (14 parts by weight) of Disperbyk 111 as an acid-value dispersing agent, 28.07 g (78 parts by weight) of Disperbyk 166 as an amine-value dispersing agent, 19.53 g (54 parts by weight) of SPCN-17X (manufactured by Showa Highpolymer) as a thermoplastic resin, and 91.14 g (253 parts by weight) of 1,3-butylene glycol diacetate as a solvent, and a dispersing-agent-dispersed liquid was obtained by stirring the mixture for 10 minutes in a Dispermill and performing pre-dispersion (pre-dispersion step). The speed of the stirring vanes of the agitator at this time was set to 2000 rpm.
Pigments were then added as described below to the dispersing-agent-dispersed liquid obtained by the pre-dispersion step, inorganic beads were added in multiple stages, and the fine-dispersion step of performing the fine-dispersion process was performed.
First, 35.99 g (100 parts by weight) of pigments were added to the obtained dispersing-agent-dispersed liquid, and the mixture was stirred for 10 minutes. At this time, the speed of the stirring vanes of the agitator was set to 2000 rpm. The mixture used as the pigments included 17.99 g of a mixture of C. I. pigment red 177 and a pigment derivative indicated by Formula (2) below, and 18.00 g of a mixture of C. I. pigment red 254 and a pigment derivative indicated by Formula (3) below. At this time, the mixture of the pigments and the dispersing-agent-dispersed liquid was diluted by 1,3-butylene glycol diacetate as a solvent to give a pigment content ratio of 16 wt %.




In Formula (2), n is an integer from 1 to 4.




In Formula (3), n is an integer from 1 to 4.
Inorganic beads (first inorganic beads: zirconia beads; “Toray Ceram milling balls” (trade name); manufactured by Toray) in the amount of 720 g having an average grain size of 0.8 mm were then added, the mixture was stirred for 30 minutes at room temperature, and the first stage of dispersion processing (first treatment) was performed. At this time, the speed of the stirring vanes of the agitator was set to 2000 rpm.
The inorganic beads (first inorganic beads) were then removed by filtration using a filter (“PALL HDCII Membrane Filter”; manufactured by PALL), after which 720 g of inorganic beads (second inorganic beads: zirconia beads; “Toray Ceram milling balls” (trade name); manufactured by Toray) having an average grain size of 0.1 mm were added, the mixture was further stirred for 30 minutes, and the second stage of dispersion processing (second treatment) was performed. At this time, the speed of the stirring vanes of the agitator was set to 2000 rpm. The mixture was also diluted at this time by 1,3-butylene glycol diacetate as a solvent to give a pigment content ratio of 13 wt % in the obtained pigment dispersion.
The inorganic beads (second inorganic beads) were then removed by filtration using a filter (“PALL HDCII Membrane Filter”; manufactured by PALL), and a pigment dispersion was obtained.
The pigment dispersion obtained as described above, a polymer solution A1, a polymer solution B1, and a polymer solution C1 were then mixed. The present step was performed by placing the abovementioned pigment dispersion, polymer solution A1, polymer solution B1, and polymer solution C1 in a 400 cc agitator (single-shaft mixer) and stirring the mixture for 10 minutes in a Dispermill. At this time, the speed of the stirring vanes of the agitator was set to 2000 rpm. The desired red color filter ink (R ink) was thereby obtained.
A green color filter ink (G ink) and a blue color filter ink (B ink) were prepared in the same manner as the green color filter ink described above, except that the type of pigment, the usage amount of each component, and the stirring conditions were varied. An ink set composed of the three colors R, G, B was thereby obtained. The average grain size of the pigment constituting the R ink, the average grain size of the pigment constituting the G ink, and the average grain size of the pigment constituting the B ink were 70 nm, 70 nm, and 70 nm, respectively.
Examples 2 through 7
Color filter inks (ink set) were prepared in the same manner as Example 1, except that the types and usage amounts of materials used to prepare the color filter inks, and the processing conditions of the fine-dispersion step (first treatment, second treatment) and the curable resin mixing step were varied as shown in Tables 2 and 4.
Comparative Example 1
Color filter inks (ink set) were prepared in the same manner as Example 1 except that an amine-value dispersing agent was not used, and only Disperbyk 111 was used as the acid-value dispersing agent.
Comparative Example 2
Color filter inks (ink set) were prepared in the same manner as Example 1 except that an acid-value dispersing agent was not used, and only Disperbyk 166 was used as the amine-value dispersing agent.
Comparative Example 3
Color filter inks (ink set) were prepared in the same manner as Example 1 except that an acid-value dispersing agent and amine-value dispersing agent were not used, and Disperbyk 2001 (a dispersing agent that is neither an acid-value dispersing agent nor an amine-value dispersing agent) was used as the dispersing agent.
Comparative Examples 4 through 6
Color filter inks (ink set) were prepared in the same manner as Example 1 except that the types and usage amounts of the polymer solutions, as well as the type and content ratio of the curable resin material included in the color filter ink were set as shown in the tables. Comparative Example 4 is a comparative example of including only the polymer A as the curable resin material; Comparative Example 5 is a comparative example of including only the polymer B as the curable resin material; and Comparative Example 6 is a comparative example of including a polymer X that includes an epoxy-containing vinyl monomer and an alkoxysilyl-containing vinyl monomer as monomer component in the same molecule instead of the polymer A and the polymer B as the curable resin material.
In the abovementioned examples and comparative examples, the solvents (dilution media) added in each step have the same composition as the media (solvents) constituting the corresponding polymer solutions (polymer solution used in the preparation of the color filter ink).
Tables 2 and 3 show the composition of the dispersing-agent-dispersed liquid, the type and usage amount of the pigments added to the dispersing-agent-dispersed liquid in the fine-dispersion step, and the type and solid-based usage amount of the curable resin material used in the curable resin mixing step in the abovementioned examples and comparative examples. In the tables, C. I. pigment red 177 is referred to as “PR177,” C. I. pigment red 254 is referred to as “PR254,” C. I. pigment green 36 is referred to as “PG36,” C. I. pigment green 58 is referred to as “PG58,” C. I. pigment blue 15:6 is referred to as “PB15:6,” the mixture of C. I. pigment red 177 and the pigment derivative indicated by Formula (2) is referred to as “PR177D,” the mixture of C. I. pigment red 254 and the pigment derivative indicated by Formula (3) is indicated by “PR254D,” the powder composed of the pigment derivative (having one sulfo group in the molecule) indicated by Formula (4) below is referred to as “PYD,” 1,3-butylene glycol diacetate is referred to as “S1,” bis(2-butoxyethyl)ether is referred to as “S2,” diethylene glycol monobutyl ether acetate is referred to as “S3,” tripropylene glycol monomethyl ether is referred to as “S4,” Disperbyk 111 is referred to as “DA2,” Disperbyk 2095 is referred to as “DA3,” Disperbyk P104 is referred to as “DA4,” Disperbyk 166 is referred to as “DA6,” Disperbyk 9075 is referred to as “DA7,” Disperbyk 2001 is referred to as “DA8,” and SPCN-17X is referred to as “DR1.” The content ratios of the pigment derivative indicated by the Formula (2) in the mixtures of C. I. pigment red 177 and the pigment derivative indicated by Formula (2) used in the examples and comparative examples were all 0.1 to 10 wt %. The content ratios of the pigment derivative indicated by the Formula (3) in the mixtures of C. I. pigment red 254 and the pigment derivative indicated by Formula (3) used in the examples and comparative examples were all 0.1 to 10 wt %. In Tables 2 and 3, the acid values and amine values of the dispersing agents (acid values and amine values when calculated based on solid content) are shown together with the viscosity of the color filter ink. The acid value column shows values calculated by a method in accordance with DIN EN ISO 2114, and the amine value column shows values calculated by a method in accordance with DIN 16945. In the curable resin material column in Tables 2 and 3, the polymer included in the polymer solution A1 is indicated as A1. In the same manner, the polymers included in the polymer solutions A2 to A9, B1 to B5, C1 to C3, and X are referred to as A2 to A9, B1 to B5, C1 to C3, and X1, respectively. Tables 4 and 5 show the conditions used to manufacture the color filter inks of the examples and comparative examples. Tables 4 and 5 also show the content ratios of the pigments at the end of the first treatment, the end of the second treatment, and the end of the curable resin mixing step (final color filter ink). The viscosity was measured in a 25° C. environment using an E-type viscometer (RE-01, manufactured by Toki Sangyo) in accordance with JIS Z8809.




In Formula (4), n is an integer from 1 to 5.








TABLE 2








COMPOSITION OF DISPERSING-AGENT-DISPERSED LIQUID










DISPERSING AGENT













AMINE-VALUE
ACID-VALUE





DISPERSING
DISPERSING
OTHER
THERMO-



AGENT
AGENT
DISPERSING
PLASTIC














ACID

AMINE

AGENT
RESIN





















VALUE
AMT.

VALUE
AMT.

AMT.

AMT.





(KOH
(PTS BY

(KOH
(PTS BY

(PTS BY

(PTS BY




TYPE
mg/g)
wt.)
TYPE
mg/g)
wt.)
TYPE
wt.)
TYPE
wt.)





EXAMPLE 1
R INK
DA2
50
14
DA6
115
78
—
—
DR1
54



G INK
DA2
50
12
DA6
115
36
—
—
DR1
79



B INK
DA2
50
14
DA6
115
42
—
—
DR1
88


EXAMPLE 2
R INK
DA2
50
22
DA6
115
50
—
—
DR1
40



G INK
DA2
50
28
DA6
115
62
—
—
DR1
30



B INK
DA2
50
17
DA6
115
39
—
—
DR1
88


EXAMPLE 3
R INK
DA3
13
25
DA7
12
74
—
—
DR1
28



G INK
DA3
13
13
DA7
12
37
—
—
DR1
21



B INK
DA3
13
32
DA7
12
95
—
—
DR1
32


EXAMPLE 4
R INK
DA2
50
10
DA6
115
30
—
—
DR1
82



G INK
DA2
50
7
DA6
115
20
—
—
DR1
41



B INK
DA2
50
13
DA6
115
37
—
—
DR1
92


EXAMPLE 5
R INK
DA4
360
20
DA6
115
40
—
—
DR1
112



G INK
DA4
360
14
DA6
115
28
—
—
DR1
84



B INK
DA4
360
21
DA6
115
42
—
—
DR1
123


EXAMPLE 6
R INK
DA2
50
69
DA6
115
23
—
—
DR1
54



G INK
DA2
50
36
DA6
115
12
—
—
DR1
79



B INK
DA2
50
42
DA6
115
14
—
—
DR1
88


EXAMPLE 7
R INK
DA2
50
69
DA6
115
23
—
—
DR1
54



G INK
DA2
50
36
DA6
115
12
—
—
DR1
79



B INK
DA2
50
42
DA6
115
14
—
—
DR1
88

















COMPONENT





COMPONENT
ADDED IN




COMPOSITION
ADDED IN
CURABLE RESIN




OF DISPERSING-
FINE-DISPERSION
MIXING STEP




AGENT-DISPERSED
STEP
CURABLE RESIN




LIQUID
PIGMENT
MATERIAL















SOLVENT

AMT.

AMT.
INK




















AMT.

(PTS BY

(PTS BY
VISCOSITY





TYPE
(PTS BY wt.)
TYPE
wt.)
TYPE
wt.)
(mPa-S)






EXAMPLE 1
R INK
S1
253
PR177D/PR254D
50/50
A1/B1/C1
13/11/6
10.1




G INK
S1
172
PG58/PYD
90/10
A1/B1/C1
9/7/4
8.3




B INK
S1
312
PB15:6
100
A1/B1/C1
18/16/8
8.4



EXAMPLE 2
R INK
S2
287
PR177D
100
A7/B6/C3
23/11/4
10




G INK
S2
179
PG58/PYD
85/15
A7/B6/C3
22/11/4
8.9




B INK
S2
312
PB15:6
100
A7/B6/C3
22/11/3
9.0



EXAMPLE 3
R INK
S3
272
PR177D
100
A6/B2/C2
34/16/5
10.2




G INK
S3
228
PG58/PYD
77/23
A6/B2/C2
33/15/4
8.0




B INK
S3
297
PB15:6
100
A6/B2/C2
31/15/5
7.6



EXAMPLE 4
R INK
S4
277
PR177
100
A8/A10/B3
10/10/13
10.1




G INK
S4
231
PG58
100
A8/A10/B3
11/11/13
8.1




B INK
S4
314
PB15:6
100
A8/A10/B3
10/10/11
8.0



EXAMPLE 5
R INK
S1
227
PR254
100
A2/B4/C1
7/3/4
9.9




G INK
S1
173
PG36
100
A2/B4/C1
7/3/4
7.2




B INK
S1
270
PB15:6
100
A2/B4/C1
7/3/4
8.4



EXAMPLE 6
R INK
S3
253
PR254
100
A3/B5/C2
12/10/10
10




G INK
S3
172
PG36
100
A3/B5/C2
9/6/6
8.9




B INK
S3
312
PB15:6
100
A3/B5/C2
17/12/12
9.1



EXAMPLE 7
R INK
S1
253
PR177/PR254
70/30
A4/B1
6/26
10.1




G INK
S2
172
PG58/PYD
77/23
A5/B6
4/17
9.0




B INK
S2
312
PB15:6
100
A9/B6
8/33
9.1

















TABLE 3








COMPOSITION OF DISPERSING-AGENT-DISPERSED LIQUID



DISPERSING AGENT











AMINE-VALUE
ACID-VALUE
OTHER



DISPERSING
DISPERSING
DISPERSING



AGENT
AGENT
AGENT



















ACID


AMINE


AMT.





VALUE
AMT.

VALUE
AMT.

(PTS BY




TYPE
(KOH mg/g)
(PTS BY wt.)
TYPE
(KOH mg/g)
(PTS BY wt.)
TYPE
wt.)





COMPARATIVE
R INK
DA2
50
92
—
—
—
—
—


EXAMPLE 1
G INK
DA2
50
48
—
—
—
—
—



B INK
DA2
50
56
—
—
—
—
—


COMPARATIVE
R INK
—
—
—
DA6
115
92
—
—


EXAMPLE 2
G INK
—
—
—
DA6
115
48
—
—



B INK
—
—
—
DA6
115
56
—
—


COMPARATIVE
R INK
—
—
—
—
—
—
DA8
92


EXAMPLE 3
G INK
—
—
—
—
—
—
DA8
48



B INK
—
—
—
—
—
—
DA8
56


COMPARATIVE
R INK
DA2
50
14
DA6
115
78
—
—


EXAMPLE 4
G INK
DA2
50
12
DA6
115
36
—
—



B INK
DA2
50
14
DA6
115
42
—
—


COMPARATIVE
R INK
DA2
50
14
DA6
115
78
—
—


EXAMPLE 5
G INK
DA2
50
12
DA6
115
36
—
—



B INK
DA2
50
14
DA6
115
42
—
—


COMPARATIVE
R INK
DA2
50
14
DA6
115
78
—
—


EXAMPLE 6
G INK
DA2
50
12
DA6
115
36
—
—



B INK
DA2
50
14
DA6
115
42
—
—















COMPOSITION OF

COMPONENT




DISPERSING-AGENT-
COMPONENT
ADDED IN




DISPERSED LIQUID
ADDED IN
CURABLE RESIN














THERMO-

FINE-DISPERSION
MIXING STEP
VIS-



PLASTIC

STEP
CURABLE RESIN
COS-



RESIN
SOLVENT
PIGMENT
MATERIAL
ITY




















AMT.

AMT.

AMT.

AMT.
INK





(PTS BY

(PTS BY

(PTS

(PTS
(mPa ·




TYPE
wt.)
TYPE
wt.)
TYPE
BY wt.)
TYPE
BY wt.)
S)





COMPARATIVE
R INK
DR1
54
S1
253
PR177D/PR254D
50/50
A1/B1/C1
13/11/6
11.7


EXAMPLE 1
G INK
DR1
79
S1
172
PG58/PYD
90/10
A1/B1/C1
9/7/4
10.1



B INK
DR1
88
S1
312
PB15:6
100
A1/B1/C1
18/16/8
10.2


COMPARATIVE
R INK
DR1
54
S1
253
PR177D/PR254D
50/50
A1/B1/C1
13/11/6
11.2


EXAMPLE 2
G INK
DR1
79
S1
172
PG58/PYD
90/10
A1/B1/C1
9/7/4
9.7



B INK
DR1
88
S1
312
PB15:6
100
A1/B1/C1
18/16/8
9.8


COMPARATIVE
R INK
DR1
54
S1
253
PR177D/PR254D
50/50
A1/B1/C1
13/11/6
12.1


EXAMPLE 3
G INK
DR1
79
S1
172
PG58/PYD
90/10
A1/B1/C1
9/7/4
11.4



B INK
DR1
88
S1
312
PB15:6
100
A1/B1/C1
18/16/8
10.5


COMPARATIVE
R INK
DR1
54
S1
253
PR177D/PR254D
50/50
A1
30
11.0


EXAMPLE 4
G INK
DR1
79
S1
172
PG58/PYD
90/10
A1
20
9.6



B INK
DR1
88
S1
312
PB15:6
100
A1
42
9.7


COMPARATIVE
R INK
DR1
54
S1
253
PR177D/PR254D
50/50
B1
30
11.1


EXAMPLE 5
G INK
DR1
79
S1
172
PG58/PYD
90/10
B1
20
9.7



B INK
DR1
88
S1
312
PB15:6
100
B1
42
9.9


COMPARATIVE
R INK
DR1
54
S1
253
PR177D/PR254D
50/50
X1
30
11.8


EXAMPLE 6
G INK
DR1
79
S1
172
PG58/PYD
90/10
X1
20
10.3



B INK
DR1
88
S1
312
PB15:6
100
X1
42
10.4

















TABLE 4








FINE-DISPERSION STEP



FIRST TREATMENT










FIRST INORGANIC




BEADS

















AMOUNT








USED PER








100 PARTS








BY WT. OF








DISPERSING-






PRE-DISPERSION STEP
AVERAGE
AGENT-


PIGMENT

















TREATMENT
ROTATIONAL
PARTICLE
DISPERSED
TREATMENT
ROTATIONAL
CONTENT




TIME (min)
SPEED (rpm)
DIAMETER (mm)
LIQUID
TIME (min)
SPEED (rpm)
(wt %)





EXAMPLE 1
R INK
10
2000
0.8
500
30
2000
16



G INK
3
2500
1.0
350
35
1700
17



B INK
7
1800
0.8
500
30
2000
12


EXAMPLE 2
R INK
15
1200
0.6
300
20
2500
17



G INK
5
2000
0.7
450
25
1900
17



B INK
6
1900
0.8
550
25
2300
14


EXAMPLE 3
R INK
2
4200
1.3
550
60
4000
16



G INK
2
4100
1.4
500
70
4200
15



B INK
2
4000
1.3
550
70
4000
10


EXAMPLE 4
R INK
25
2200
0.7
500
10
2000
16



G INK
30
2400
1.1
350
12
1700
13



B INK
25
2000
0.6
500
10
2000
15


EXAMPLE 5
R INK
8
2000
0.4
500
40
2000
17



G INK
10
2500
0.4
350
40
1700
15



B INK
7
1800
0.4
500
40
2000
10


EXAMPLE 6
R INK
15
1000
0.4
200
60
1000
16



G INK
20
1200
0.4
250
70
1100
15



B INK
15
1000
0.4
300
70
1000
10


EXAMPLE 7
R INK
18
1400
0.5
250
50
1800
15



G INK
20
1200
0.4
250
70
1100
17



B INK
15
1300
0.5
250
50
1600
13













FINE-DISPERSION STEP




SECOND TREATMENT











SECOND INORGANIC




BEADS












AMOUNT





USED PER





100 PARTS

CURABLE RESIN



BY WT. OF

MIXING STEP


















AVERAGE
DISPERSING




ROTA-





PARTICLE
AGENT-


PIGMENT

TIONAL
PIGMENT




DIAMETER
DISPERSED
TREATMENT
ROTATIONAL
CONTENT
TREATMENT
SPEED
CONTENT




(mm)
LIQUID
TIME (min)
SPEED (rpm)
(wt %)
TIME (min)
(rpm)
(wt %)





EXAMPLE 1
R INK
0.1
500
30
2000
13
10
2000
7.3



G INK
0.1
450
20
2500
14
25
2000
10.1



B INK
0.1
500
30
2000
8
30
1800
4.9


EXAMPLE 2
R INK
0.07
350
20
3000
13
40
3000
7.1



G INK
0.2
500
25
2200
13
45
3500
9.8



B INK
0.1
550
30
1900
12
35
2800
4.8


EXAMPLE 3
R INK
0.1
180
50
4000
14
15
1400
7.3



G INK
0.1
170
45
4000
13
20
2100
10.1



B INK
0.1
180
50
4000
8
25
2000
4.9


EXAMPLE 4
R INK
0.1
500
35
2300
14
20
1600
7.3



G INK
0.1
450
40
2700
12
25
1800
10.1



B INK
0.1
500
30
2200
10
30
1600
4.9


EXAMPLE 5
R INK
0.07
500
35
2000
15
20
2700
7.3



G INK
0.05
450
30
2500
14
25
3000
10.1



B INK
0.1
500
40
2000
9
30
2500
4.9


EXAMPLE 6
R INK
0.1
600
50
2200
14
15
1600
7.3



G INK
0.1
600
45
2500
13
20
2300
10.1



B INK
0.1
550
50
2300
8
25
2100
4.9


EXAMPLE 7
R INK
0.1
550
35
2700
13
20
2000
7.3



G INK
0.1
600
45
2500
15
20
2300
10.1



B INK
0.1
550
40
2800
10
25
2000
4.9

















TABLE 5








FINE-DISPERSION STEP



FIRST TREATMENT










FIRST INORGANIC
















AMOUNT







USED PER







100 PARTS







BY WT.





PRE-DISPERSION
AVERAGE
OF DISPERSING-





STEP
PARTICLE
AGENT-

PIGMENT

















TREATMENT
ROTATIONAL
DIAMETER
DISPERSED
TREATMENT
ROTATIONAL
CONTENT




TIME (min)
SPEED (rpm)
(mm)
LIQUID
TIME (min)
SPEED (rpm)
(wt %)





COMPARATIVE
R INK
10
2000
0.8
500
30
2000
16


EXAMPLE 1
G INK
3
2500
1.0
350
35
1700
17



B INK
7
1800
0.8
500
30
2000
12


COMPARATIVE
R INK
10
2000
0.8
500
30
2000
16


EXAMPLE 2
G INK
3
2500
1.0
350
35
1700
17



B INK
7
1800
0.8
500
30
2000
12


COMPARATIVE
R INK
10
2000
0.8
500
30
2000
16


EXAMPLE 3
G INK
3
2500
1.0
350
35
1700
17



B INK
7
1800
0.8
500
30
2000
12


COMPARATIVE
R INK
10
2000
0.8
500
30
2000
16


EXAMPLE 4
G INK
3
2500
1.0
350
35
1700
17



B INK
7
1800
0.8
500
30
2000
12


COMPARATIVE
R INK
10
2000
0.8
500
30
2000
16


EXAMPLE 5
G INK
3
2500
1.0
350
35
1700
17



B INK
7
1800
0.8
500
30
2000
12


COMPARATIVE
R INK
10
2000
0.8
500
30
2000
16


EXAMPLE 6
G INK
3
2500
1.0
350
35
1700
17



B INK
7
1800
0.8
500
30
2000
12













FINE-DISPERSION STEP




SECOND TREATMENT











SECOND INORGANIC














AMOUNT






USED PER






100 PARTS

CURABLE RESIN




BY WT. OF

MIXING STEP


















AVERAGE
DISPERSING




ROTA-





PARTICLE
AGENT-


PIGMENT
TREAT-
TIONAL
PIGMENT




DIAMETER
DISPERSED
TREATMENT
ROTATIONAL
CONTENT
MENT
SPEED
CONTENT




(mm)
LIQUID
TIME (min)
SPEED (rpm)
(wt %)
TIME (min)
(rpm)
(wt %)





COMPARATIVE
R INK
0.1
500
30
2000
13
10
2000
7.3


EXAMPLE 1
G INK
0.1
450
20
2500
14
25
2000
10.1



B INK
0.1
500
30
2000
8
30
1800
4.9


COMPARATIVE
R INK
0.1
500
30
2000
13
10
2000
7.3


EXAMPLE 2
G INK
0.1
450
20
2500
14
25
2000
10.1



B INK
0.1
500
30
2000
8
30
1800
4.9


COMPARATIVE
R INK
0.1
500
30
2000
13
10
2000
7.3


EXAMPLE 3
G INK
0.1
450
20
2500
14
25
2000
10.1



B INK
0.1
500
30
2000
8
30
1800
4.9


COMPARATIVE
R INK
0.1
500
30
2000
13
10
2000
7.3


EXAMPLE 4
G INK
0.1
450
20
2500
14
25
2000
10.1



B INK
0.1
500
30
2000
8
30
1800
4.9


COMPARATIVE
R INK
0.1
500
30
2000
13
10
2000
7.3


EXAMPLE 5
G INK
0.1
450
20
2500
14
25
2000
10.1



B INK
0.1
500
30
2000
8
30
1800
4.9


COMPARATIVE
R INK
0.1
500
30
2000
13
10
2000
7.3


EXAMPLE 6
G INK
0.1
450
20
2500
14
25
2000
10.1



B INK
0.1
500
30
2000
8
30
1800
4.9









3. Evaluation of Stability of Color Filter Ink (Durability Evaluation)
3-1. Change in Appearance After Heating
The color filter ink of the examples and comparative examples was left for 7 days in a 65° C. environment, after which the ink was visually observed and evaluated according to the four criteria shown below.
A: No change from the state prior to heating was observed.
B: Slight aggregation/precipitation of pigment particles was observed.
C: Aggregation/precipitation of pigment particles was plainly observed.
D: Severe aggregation/precipitation of pigment particles was observed.
3-2. Change in Viscosity
The viscosity (kinetic viscosity) of the color filter ink of the examples and comparative examples was measured after the ink was left for 7 days in a 65° C. environment, and the difference in viscosity was calculated with respect to the viscosity immediately after manufacture. Specifically, the difference indicated by v1−v0 was calculated, wherein v0 (mPa·s) is the viscosity immediately after manufacturing, and v1 (mPa·s) is the viscosity after the ink was left for 7 days in a 65° C. environment. The values calculated in this manner were evaluated according to the five criteria shown below.
A: The value of v1−v0 is less than 0.3 mPa·s.
B: The value of v1−v0 is 0.3 mPa·s or higher and less than 0.5 mPa·s.
C: The value of v1−v0 is 0.5 mPa·s or higher and less than 0.7 mPa·s.
D: The value of v1−v0 is 0.7 mPa·s or higher and less than 0.9 mPa·s.
E: The value of v1−v0 is 0.9 mPa·s or higher.
4. Evaluation of Stability of Droplet Discharge
(Evaluation of Stable Discharge Properties)
Evaluation by testing as described below was performed using the color filter ink (color filter ink immediately after manufacturing) obtained in the examples and comparative examples, and the color filter ink that was left for 7 days in a 65° C. environment (color filter ink left in a heated environment).
4-1. Evaluation of Landing Position Accuracy
A droplet discharge device such as that shown in FIGS. 3 to 6 disposed in a chamber (thermal chamber) and the ink sets for a color filter of the examples and comparative examples were prepared, and 90,000 droplets (90,000 drops) of the inks were continuously discharged from the nozzles of a droplet discharge head in a state in which the drive waveform of the piezoelement had been optimized. The average value of the offset distance d from the center aim position of the center position of the landed droplets was calculated for the 90,000 droplets discharged from specified nozzles in the vicinity of the center of the droplet discharge head, and an evaluation was made based on the four ranges described below. It is apparent that the smaller this value is the more effectively prevented the occurrence of flight deflection is.
A: The average value of the offset distance d is less than 0.02 μm
B: The average value of the offset distance d is 0.02 μm or more and less than 0.07 μm
C: The average value of the offset distance d is 0.07 μm or more and less than 0.11 μm
D: The average value of the offset distance d is 0.11 or more
4-2. Evaluation of Stability of Droplet Discharge Quantity
A droplet discharge device such as that shown in FIGS. 3 to 6 disposed in a chamber (thermal chamber), and the ink sets for a color filter of the examples and comparative examples were prepared, and 90,000 droplets (90,000 drops) of the inks were continuously discharged from the nozzles of a droplet discharge head in a state in which the drive waveform of the piezoelement had been optimized. The total weight of the discharged droplets was calculated for two specific nozzles at the left and right ends of the droplet discharge head, and the absolute value ΔW (ng) of the difference between the average discharge quantities of the droplets discharged from the two nozzles was calculated. The ratio (ΔW/WT) of the ΔW in relation to the target discharge quantity WT (ng) of the droplets was calculated, and an evaluation was made based on the four ranges described below. It is apparent that the smaller the value of ΔW/WT is, the greater the stability of the droplet discharge quantity.
A: The value of ΔW/WT is less than 0.018
B: The value of ΔW/WT is 0.018 or higher and less than 0.400
C: The value of ΔW/WT is 0.400 or higher and less than 0.700
D: The value of ΔW/WT is 0.700 or higher
4-3. Evaluation of Intermittent Printing Performance
A droplet discharge device such as that shown in FIGS. 3 to 6 disposed in a chamber (thermal chamber), and the ink sets for a color filter of the examples and comparative examples were prepared, and 9000 droplets (9000 drops) of the inks were continuously discharged from the nozzles of a droplet discharge head in a state in which the drive waveform of the piezoelement had been optimized, after which droplet discharge was stopped for 30 seconds (first sequence). Thereafter, droplets were continuously discharged in the same manner and the operation of stopping the discharge of droplets was repeated. The average weight W1 (ng) of the droplets discharged in the first sequence and the average weight W20 (ng) of the droplets discharged in the 20th sequence were calculated for the specified nozzles in the vicinity of the center of the droplet discharge head. The ratio (|W1-W20|/WT) of the absolute value of the difference between W1 and W20 in relation to the target discharge quantity WT (ng) of the droplets was calculated, and an evaluation was made based on the three ranges described below. It is apparent that the smaller the value of |W1-W20|/WT is, the greater the intermittent printing performance (stability of the droplet discharge quantity).
A: The value of |W1-W20|/WT is less than 0.023
B: The value of |W1-W20|/WT is 0.023 or higher and less than 0.600
C: The value of |W1-W20|/WT is 0.600 or higher
4-4. Continuous Discharge Test
The inks constituting the ink set for a color filter were discharged by continuously operating the droplet discharge device for 72 hours in an environment of 40% RH using a droplet discharge device such as that shown in FIGS. 3 to 6 disposed in a chamber (thermal chamber) and the ink sets for a color filter of the examples and comparative examples.
The rate ([(number of clogged nozzles)/(total number of nozzles)]×100) at which clogging of the nozzles constituting the droplet discharge head occurs after continuous operation was calculated, and it was investigated whether clogging can be eliminated using a cleaning member composed of a plastic material. The results were evaluated based on the four ranges described below.
A: Nozzle clogging does not occur.
B: The occurrence rate of nozzle clogging is less than 0.4% (not including 0), and clogging can be eliminated by cleaning.
C: The occurrence rate of nozzle clogging is 0.4% or higher and less than 0.8%, and clogging can be eliminated by cleaning.
D: The occurrence rate of nozzle clogging is 0.8% or higher, and clogging cannot be eliminated by cleaning.
The evaluation described above was carried out in the same conditions for the examples and the comparative examples.
5. Manufacture of Color Filters
A color filter was manufactured in the following manner using the color filter ink (color filter ink immediately after manufacturing) obtained in the examples and comparative examples, and the color filter ink that was left for 7 days in a 65° C. environment (color filter ink left in a heated environment).
First, a substrate (G5 size: 100×1300 mm) composed of soda glass on which a silica (SiO2) film for preventing elution of the sodium ions was formed on the two sides was prepared and washed.
Next, a radiation-sensitive composition for forming a partition wall containing carbon black was applied to the entire surface of one of the surfaces of the washed substrate to form a coated film.
Next, a prebaking treatment was performed at a heating temperature of 110° C. and a heating time of 120 seconds.
The substrate was thereafter irradiated via a photomask, subjected to post exposure baking (PEB), subsequently developed using an alkali development fluid, and then subjected to a post baking treatment to thereby form a partition wall. PEB was carried out at a heating temperature of 120° C., a heating time of 120 seconds, and an irradiation intensity of 150 mJ/cm2. The development treatment time was set to 60 seconds. The post baking treatment was carried out at a heating temperature of 160° C. for a heating time of 5 minutes. The thickness of the partition wall thus formed was 2.1 μm.
Next, the color filter ink was discharged into the cells as areas surrounded by the partition wall by using a droplet discharge device such as that shown in FIGS. 3 to 6. In this case, three color filter inks were used, and care was taken that the color filter ink of each color was not mixed. A droplet discharge head was used in which the nozzle plate had been joined using an epoxy adhesive (AE-40, manufactured by Ajinomoto Fine-Techno).
Thereafter, heat treatment is carried out for 10 minutes at 120° C. on a hot plate, and heat treatment was then carried out for one hour in an oven at 200° C., whereby three colored portions were formed. A color filter such as that shown in FIG. 1 was thereby obtained.
The color filter inks (ink sets) of the examples and the comparative examples were used to manufacture 8000 color filters of each ink set using the method described above.
6. Evaluation of Color Filters
The color filters obtained in the manner described above were evaluated in the manner described below
6-1. Unevenness of Color and Saturation
Among the color filters manufactured using the color filter inks (ink sets) of the examples and the comparative examples, a liquid crystal display device such as that shown in FIG. 7 was manufactured under the same conditions using the 8000th color filter manufactured of each example and comparative example.
Red monochromatic display, green monochromatic display, blue monochromatic display, and white monochromatic display were visually observed in a dark room using these liquid crystal display devices, and the occurrence of uneven color and uneven saturation between different regions was evaluated based on the five levels described below.
A: Uneven color and uneven saturation were not observed.
B: Uneven color and uneven saturation were substantially not observed.
C: Some uneven color and uneven saturation was observed.
D: Uneven color and uneven saturation were plainly observed.
E: Uneven color and uneven saturation were markedly observed.
6-2. Difference in Characteristics Between Units
Of the color filters manufactured using the color filter inks (ink sets) of the examples and the comparative examples, the first to the 10th and the 7990th to the 7999th color filters manufactured of each example and the comparative example were prepared, and 100 pixels were extracted at random from each color filter. Red monochromatic display, green monochromatic display, blue monochromatic display, and white monochromatic display were carried out in a dark room for the extracted 100 pixels, and the colors were measured using a spectrophotometer (MCPD 3000, manufactured by Otsuka Electronics). The average value of the hue calculated for the abovementioned 100 pixels was used as the color filter hue for each color filter. The maximum color differences (color difference ΔE in the Lab display system) in the first to the 10th and the 7990th to the 7999th color filters manufactured for each of the examples and comparative examples were calculated from the results and evaluated based on the five ranges described below.
A: Color difference (ΔE) is less than 0.5.
B: Color difference (ΔE) is 0.5 or more and less than 1.0.
C: Color difference (ΔE) is 1.0 or more and less than 1.5.
D: Color difference (ΔE) is 1.5 or more and less than 2.0.
E: Color difference (ΔE) is 2.0 or more.
6-3. Durability
Among the color filters manufactured using the color filter inks (ink sets) of the examples and the comparative examples, a liquid crystal display device such as that shown in FIG. 7 was manufactured under the same conditions using the 3001th to 3010th color filters manufactured of each example and the comparative example.
Red monochromatic display, green monochromatic display, and blue monochromatic display were visually observed in a dark room using these liquid crystal display devices, and the occurrence of light leakage (white spots, luminescent spots) was checked.
Next, the color filters were removed from the liquid crystal display devices.
The color filters thus removed were left sitting for 1.5 hours at 20° C., then 2 hours at 50° C., subsequently 1.5 hours at 20° C., and then 3 hours at −15° C. Thereafter, the environment temperature was again restored to 20° C. to complete a single cycle (8 hours), and this cycle was repeated for a total of 30 times (total of 240 hours).
Thereafter, liquid crystal display devices such as the one shown in FIG. 7 were again assembled using these color filters.
Red monochromatic display, green monochromatic display and blue monochromatic display were visually observed in a dark room using these liquid crystal display devices, and the occurrence of light leakage (white spots, luminescent spots) was evaluated based on the following five levels.
A: There was no color filter in which light leakage (white spots, luminescent spots) occurred.
B: Light leakage (white spots, luminescent spots) was observed in 1 to 2 color filters.
C: Light leakage (white spots, luminescent spots) was observed in 3 to 5 color filters.
D: Light leakage (white spots, luminescent spots) was observed in 6 to 9 color filters.
E: Light leakage (white spots, luminescent spots) was observed in 10 color filters.
7. Evaluation of Contrast
Evaluation by testing as described below was performed using the color filter ink (color filter ink immediately after manufacturing) obtained in the examples and comparative examples, and the color filter ink that was left for 7 days in a 65° C. environment (color filter ink left in a heated environment).
Red colored films were each formed by an inkjet method on a different glass plate (diameter: 10 cm) using the R inks constituting the ink sets of the examples and comparative examples.
The colored films were formed by discharging droplets onto the glass plates, and thereafter carrying out a heat treatment for 8 minutes at 110° C. on a hot plate, and then carrying out a heat treatment for 45 minutes in an oven at 220° C. The discharge quantity of the color filter ink was adjusted so that the thickness of the formed colored film was 1.5 μm.
The contrast (CR) was obtained for the glass substrates on which a colored film was formed in this manner using a contrast tester (CT-1, manufactured by Tsubosaka Electric), and evaluated based on the three ranges described below.
A: CR was 3300 or higher.
B: CR was 2200 or higher and less than 3300.
C: CR was less than 2200.
Colored films were also formed by an inkjet method on glass substrates (diameter: 10 cm) in the same manner as described above using the G ink and B ink constituting the ink sets of the examples and comparative examples, and the contrast was calculated for the glass substrates on which the colored films were formed.
The glass substrate on which the green colored film was formed was evaluated based on the three ranges described below.
A: CR was 12000 or higher.
B: CR was 5800 or higher and less than 12000.
C: CR was less than 5800.
The glass substrate on which the blue colored film was formed was evaluated based on the three ranges described below.
A: CR was 3000 or higher.
B: CR was 2500 or higher and less than 3000.
C: CR was less than 2500.
In the evaluations described above, the color filters and glass substrates were observed and measured under the same conditions.
These results are shown in Tables 6 and 7. In the tables, the color filter ink immediately after manufacturing is indicated as “before heating,” and the color filter ink left for 7 days in a 65° C. environment (color filter ink left in a heated environment) is indicated as “after heating.”








TABLE 6








STABLE DISCHARGE EVALUATION

















STABILITY OF







LANDING
DROPLET
INTERMITTENT






POSITION
DISCHARGE
PRINTING
CONTINUOUS



APPEARANCE

ACCURACY
AMOUNT
PERFORMANCE
DISCHARGE TEST




















CHANGE

BEFORE
AFTER
BEFORE
AFTER
BEFORE
AFTER
BEFORE





AFTER
VISCOSITY
HEAT-
HEAT-
HEAT-
HEAT-
HEAT-
HEAT-
HEAT-
AFTER




HEATING
CHANGE
ING
ING
ING
ING
ING
ING
ING
HEATING





EXAMPLE 1
R INK
A
A
A
A
A
A
A
A
A
A



G INK
A
A
A
A
A
A
A
A
A
A



B INK
A
A
A
A
A
A
A
A
A
A


EXAMPLE 2
R INK
A
A
A
A
A
A
A
A
A
A



G INK
A
A
A
A
A
A
A
A
A
A



B INK
A
A
A
A
A
A
A
A
A
A


EXAMPLE 3
R INK
A
A
A
A
A
A
A
B
A
A



G INK
A
A
A
A
A
A
A
B
A
A



B INK
A
A
A
A
A
A
A
A
A
A


EXAMPLE 4
R INK
A
A
A
A
A
B
A
B
A
A



G INK
A
A
A
A
A
B
A
B
A
A



B INK
A
A
A
A
A
A
A
B
A
A


EXAMPLE 5
R INK
A
B
B
B
A
A
A
A
B
C



G INK
A
B
B
B
A
A
A
A
B
C



B INK
A
B
A
B
A
A
A
A
A
B


EXAMPLE 6
R INK
A
A
A
A
A
B
A
A
A
A



G INK
A
A
A
A
A
B
A
A
A
A



B INK
A
A
A
A
A
B
A
A
A
A


EXAMPLE 7
R INK
A
B
A
B
A
A
A
B
A
A



G INK
A
B
A
B
A
A
A
B
A
A



B INK
A
B
A
B
A
A
A
A
A
A
















VARIATION OF





UNEVENNESS OF
CHARACTERISTICS





COLOR, SATURATION
BETWEEN UNITS
DURABILITY
CONTRAST




















BEFORE
AFTER
BEFORE
AFTER
BEFORE
AFTER
BEFORE
AFTER





HEATING
HEATING
HEATING
HEATING
HEATING
HEATING
HEATING
HEATING






EXAMPLE 1
R INK
A
A
A
A
A
A
A
A




G INK






A
A




B INK






A
A



EXAMPLE 2
R INK
A
A
A
A
A
A
A
A




G INK






A
A




B INK






A
A



EXAMPLE 3
R INK
A
A
A
A
A
A
A
A




G INK






A
A




B INK






A
A



EXAMPLE 4
R INK
A
B
A
A
A
A
A
A




G INK






A
A




B INK






A
A



EXAMPLE 5
R INK
A
B
A
A
A
A
B
B




G INK






B
C




B INK






A
B



EXAMPLE 6
R INK
A
B
A
A
A
A
A
B




G INK






B
B




B INK






A
A



EXAMPLE 7
R INK
A
B
A
A
A
A
A
A




G INK






A
A




B INK






A
A

















TABLE 7








STABLE DISCHARGE EVALUATION

















STABILITY OF







LANDING
DROPLET







POSITION
DISCHARGE
INTERMITTENT
CONTINUOUS



APPEARANCE

ACCURACY
AMOUNT
PRINTING
DISCHARGE TEST




















CHANGE
VIS-
BEFORE
AFTER
BEFORE
AFTER
BEFORE
AFTER
BEFORE





AFTER
COSITY
HEAT-
HEAT-
HEAT-
HEAT-
HEAT-
HEAT-
HEAT-
AFTER




HEATING
CHANGE
ING
ING
ING
ING
ING
ING
ING
HEATING





COMPARATIVE
R INK
D
E
D
D
D
D
B
C
D
D


EXAMPLE 1
G INK
D
E
C
D
C
D
B
C
D
D



B INK
D
E
C
D
B
C
B
C
D
D


COMPARATIVE
R INK
D
E
D
D
D
D
C
C
D
D


EXAMPLE 2
G INK
D
E
C
D
D
D
C
C
D
D



B INK
D
E
C
D
D
D
C
C
D
D


COMPARATIVE
R INK
D
E
D
D
D
D
C
C
D
D


EXAMPLE 3
G INK
D
E
C
D
C
D
C
C
D
D



B INK
D
E
C
D
C
D
C
C
D
D


COMPARATIVE
R INK
D
D
C
D
C
D
C
C
D
D


EXAMPLE 4
G INK
D
D
C
D
C
D
C
C
D
D



B INK
C
D
B
C
B
C
B
C
C
D


COMPARATIVE
R INK
D
D
C
D
C
D
C
C
C
D


EXAMPLE 5
G INK
D
D
C
D
C
D
C
C
C
D



B INK
C
D
B
C
B
C
B
C
C
D


COMPARATIVE
R INK
D
D
C
D
C
D
C
C
D
D


EXAMPLE 6
G INK
D
D
C
D
C
D
C
C
D
D



B INK
C
D
B
C
B
C
B
C
C
D
















VARIATION OF





UNEVENNESS OF
CHARACTERISTICS





COLOR, SATURATION
BETWEEN UNITS
DURABILITY
CONTRAST




















BEFORE
AFTER
BEFORE
AFTER
BEFORE
AFTER
BEFORE
AFTER





HEATING
HEATING
HEATING
HEATING
HEATING
HEATING
HEATING
HEATING






COMPARATIVE
R INK
E
E
E
E
C
D
C
C



EXAMPLE 1
G INK






C
C




B INK






C
C



COMPARATIVE
R INK
E
E
E
E
A
A
C
C



EXAMPLE 2
G INK






C
C




B INK






C
C



COMPARATIVE
R INK
E
E
E
E
B
B
C
C



EXAMPLE 3
G INK






C
C




B INK






C
C



COMPARATIVE
R INK
C
D
D
E
E
E
C
C



EXAMPLE 4
G INK






C
C




B INK






C
C



COMPARATIVE
R INK
D
E
E
E
D
E
C
C



EXAMPLE 5
G INK






C
C




B INK






C
C



COMPARATIVE
R INK
C
D
E
E
D
E
C
C



EXAMPLE 6
G INK






C
C




B INK






C
C









As is clear from Tables 6 and 7, the stability of droplet discharge was excellent in the present invention, the occurrence of light leakage and unevenness of color and saturation was suppressed in the manufactured color filters, and there was minimal variation of characteristics between units. The color filters also had excellent durability in the present invention. Contrast was also excellent in the present invention. In the present invention, the color filter ink had excellent stability over time, droplet discharge could be suitably performed even after the color filter ink was left in heated conditions, and color filters having excellent quality could be stably manufactured. In contrast, satisfactory results were not obtained in the comparative examples.
The same results as described above were also obtained when a commercially available liquid crystal television was disassembled, the liquid crystal display device unit was replaced by a unit manufactured as described above, and the same evaluations as described above were performed.
General Interpretation of Terms
In understanding the scope of the present invention, the term “comprising” and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and/or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and/or steps. The foregoing also applies to words having similar meanings such as the terms, “including”, “having” and their derivatives. Also, the terms “part,” “section,” “portion,” “member” or “element” when used in the singular can have the dual meaning of a single part or a plurality of parts. Finally, terms of degree such as “substantially”, “about” and “approximately” as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. For example, these terms can be construed as including a deviation of at least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies.
While only selected embodiments have been chosen to illustrate the present invention, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made herein without departing from the scope of the invention as defined in the appended claims. Furthermore, the foregoing descriptions of the embodiments according to the present invention are provided for illustration only, and not for the purpose of limiting the invention as defined by the appended claims and their equivalents.

## Claims

1. A color filter ink adapted to be used to manufacture a color filter by an inkjet method, the color filter ink comprising:
a pigment;
a solvent;
a dispersing agent including an acid-value dispersing agent with a predetermined acid value and an amine-value dispersing agent with a predetermined amine value; and
a curable resin material including a first polymer and a second polymer with
the first polymer including at least a first epoxy-containing vinyl monomer as a monomer component, and
the second polymer including at least an alkoxysilyl-containing vinyl monomer represented by a chemical formula (I) below as a monomer component,






wherein, in Formula (I), R1 is a hydrogen atom or a C1-7 alkyl group; E is a single bond hydrocarbon group or a bivalent hydrocarbon group; R2 is a C1-6 alkyl group or a C1-6 alkoxyl group; R3 is a C1-6 alkyl group or a C1-6 alkoxyl group; R4 is a C1-6 alkyl group; a value x is 0 or 1; and a value y is an integer from 1 to 10.

2. The color filter ink according to claim 1, wherein
the first polymer is a copolymer having the first epoxy-containing vinyl monomer and a second vinyl monomer as monomer components, the second vinyl monomer having an isocyanate group or a block isocyanate group in which an isocyanate group is protected by a protective group.

3. The color filter ink according to claim 1, wherein
the first polymer is a copolymer having the first epoxy-containing vinyl monomer and a third vinyl monomer as monomer components, the third vinyl monomer having a hydroxyl group.

4. The color filter ink according to claim 1, wherein
a ratio of a content of the first polymer to a content of the second polymer is 25:75 to 75:25 in terms of weight.

5. The color filter ink according to claim 1, wherein
the second polymer is a homopolymer of the alkoxysilyl-containing vinyl monomer represented by the chemical formula (I).

6. The color filter ink according to claim 1, wherein
the predetermined acid value of the acid-value dispersing agent is 5 to 370 KOH mg/g.

7. The color filter ink according to claim 1, wherein
the predetermined amine value of the amine-value dispersing agent is 5 to 200 KOH mg/g.

8. The color filter ink according to claim 1, wherein
content ratios of the acid-value dispersing agent and the amine-value dispersing agent in the color filter ink are arranged to satisfy 0.1≦XA/XB≦1, wherein a value XA (wt %) is the content ratio of the acid-value dispersing agent and a value XB (wt %) is the content ratio of the amine-value dispersing agent.

9. The color filter ink according to claim 1, wherein
the acid-value dispersing agent and the amine-value dispersing agent in the color filter ink are arranged to satisfy 0.01≦(AV×XA)/(BV×XB)≦1.9, wherein a value AV (KOH mg/g) is the predetermined acid value of the acid-value dispersing agent, a value BV (KOH mg/g) is the predetermined amine value of the amine-value dispersing agent, a value XA (wt %) is a content ratio of the acid-value dispersing agent in the color filter ink, and a value XB (wt %) is a content ratio of the amine-value dispersing agent in the color filter ink.

10. The color filter ink according to claim 1, wherein
the solvent includes one or more compounds selected from the group consisting of 1, 3-butylene glycol diacetate, bis(2-butoxyethyl)ether, and diethylene glycol monobutyl ether acetate.

11. A color filter manufactured using the color filter ink according to claim 1.

12. An image display device having the color filter according to claim 11.

13. The image display device according to claim 12, wherein
the image display device is a liquid crystal panel.

14. An electronic device having the image display device according to claim 12.