JP2012168364A - Ink for color filter, color filter, image display device, and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ink for a color filter employing an ink-jet system suitably used for manufacturing a color filter, having excellent discharge stability, suppressed color unevenness and density unevenness at respective portions, excellent characteristic uniformity between substances, and excellent durability.SOLUTION: Ink for a color filter of the present invention is used for manufacturing a color filter employing an ink-jet system. The ink for a color filter contains colorant, a resin material, and liquid medium to which the colorant is dissolved and/or dispersed. The resin material contained in the ink for a color filter is a predetermined graft copolymer.

Description

  The present invention relates to a color filter ink, a color filter, an image display device, and an electronic apparatus.

  A color filter is generally used for a liquid crystal display (LCD) or the like that performs color display.

  A color filter has conventionally formed a coating film composed of a material (colored layer forming composition) containing a colorant, a photosensitive resin, a functional monomer, a polymerization initiator, etc. on a substrate, and then a photomask. It has been manufactured by using a so-called photolithography method in which a photosensitive process, a developing process, and the like are performed. In such a method, the colors are usually overlapped by repeating the operation of forming a coating film corresponding to each color on almost the entire surface of the substrate, curing only a part thereof, and removing most of the other part. Manufacture color filters so that they do not match. For this reason, only a part of the coating film formed in the process of manufacturing the color filter remains as a colored layer in the finally obtained color filter, and the most part is removed in the manufacturing process. It will be. For this reason, not only the manufacturing cost of a color filter rises but it is not preferable also from a viewpoint of resource saving.

  On the other hand, in recent years, a method of forming a colored layer of a color filter using an ink jet head (droplet discharge head) has been proposed (see, for example, Patent Document 1). In such a method, waste of the material for forming the colored layer (colored layer forming composition) can be reduced, so that the burden on the environment can be reduced and the manufacturing cost can be suppressed. it can. However, in the method of manufacturing a color filter using an inkjet head, when droplets are ejected for a long period or when droplets are continuously ejected, the trajectory of the ejected droplets changes (so-called flight curve). In some cases, the liquid droplets cannot be landed on the site for the purpose, or the discharge amount of the liquid droplets becomes unstable. When such a problem occurs, a plurality of types of inks used to form colored portions of different colors may be mixed (mixed) on the substrate on which the droplets are to be landed, or may be the same in nature. Variations in color density between multiple colored parts that are required to have a color density occur, resulting in color unevenness, density unevenness, etc. in each part of the color filter, Variations in characteristics (particularly, color characteristics such as contrast ratio and color reproduction range) among a large number of color filters result in low reliability of the color filters. In addition, the droplet discharge device (industrial use) used for manufacturing the color filter is completely different from that applied to the printer (consumer use). For example, mass production or large work (substrate) is performed. Therefore, it is required to eject a large amount of droplets for a long time. Since it is used under such harsh conditions, it tends to cause fluctuations in the discharge amount of liquid droplets compared to those for consumer use. Variations in characteristics between filters and variations in color density in each part of the color filter occur, and the reliability of the color filter as a product is significantly reduced.

Further, in order to ensure a wider color gamut in the color filter, in recent years, there is a tendency to use a high colorant content as the color filter ink, but the higher the colorant content, The above problem becomes more prominent.
In recent years, liquid crystal display devices (LCDs) that perform color display have a tendency to increase the luminance of display images with the aim of further improving image quality. With such high brightness, color filters are required to have improved durability.

JP 2002-372613 A

  The object of the present invention is excellent in ejection stability, suppressed color unevenness and density unevenness in each part, excellent in uniformity of characteristics among individuals, and suitable for manufacturing a color filter excellent in durability. Providing ink for an ink-jet color filter that can be used for the above, color unevenness and density unevenness in each part are suppressed, excellent uniformity of characteristics among individuals, and excellent durability The object is to provide a color filter, and to provide an image display device and an electronic apparatus provided with the color filter.

（式中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は炭素数１〜８の２価の脂肪族飽和炭化水素基を示す。Ｒ^３はイソシアネート基のブロック剤Ｒ^３Ｈの残基を示す）

（式（２）中、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は置換基を有していてもよいフェニル基又はシアノ基を示す。式（３）中、Ｒ^６は水素原子又はメチル基を示し、Ｒ^７は炭化水素基置換オキシ基を有していてもよい炭素数１〜２５の炭化水素基を示す）
これにより、吐出安定性に優れ、各部位での色むら、濃度むらが抑制され、個体間での特性の均一性に優れ、かつ、耐久性にも優れたカラーフィルターの製造に好適に用いることができる、インクジェット方式のカラーフィルター用インクを提供することができる。 Such an object is achieved by the present invention described below.
The color filter ink of the present invention is a color filter ink used for producing a color filter by an inkjet method,
A colorant, a resin material, and a liquid medium in which the colorant is dissolved and / or dispersed,
The resin material corresponds to the monomer unit corresponding to the vinyl monomer A having a blocked isocyanate group represented by the following formula (1) and the vinyl monomer B having a carboxyl group or an acid anhydride group. A monomer unit, a monomer unit corresponding to the vinyl monomer C having a 3- to 5-membered cyclic ether group, and a repeating unit represented by the following formula (2) or the following formula (3) as a main structural unit A monomer unit corresponding to a macromonomer D having a polymer chain and having a (meth) acryloyloxy group at the terminal of the polymer chain and having a weight average molecular weight of 500 to 30,000, and is derived from the macromonomer D The polymer chain part includes a graft copolymer constituting a branch part.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. R ³ is a residue of an isocyanate group blocking agent R ³ H. Indicate)

(In formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a phenyl group or a cyano group which may have a substituent. In formula (3), R ⁶ represents a hydrogen atom or Represents a methyl group, and R ⁷ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrocarbon group-substituted oxy group)
As a result, it is excellent in ejection stability, color unevenness and density unevenness in each part are suppressed, suitable for manufacturing a color filter excellent in uniformity of characteristics among individuals and excellent in durability. Ink jet color filter ink can be provided.

（式中、Ｒ^８は水素原子又はメチル基を示し、Ｒ^９は炭化水素基置換オキシ基を有していてもよい炭素数１〜２５の炭化水素基を示す）
これにより、カラーフィルター用インクの低粘度化により吐出安定性をさらに優れたものとしつつ、形成される着色部の耐溶剤性のさらなる向上、形成される着色部の表面の平坦性の向上による表示画像の輝度、コントラストのさらなる向上を図ることができる。 In the color filter ink of the present invention, the graft copolymer includes a monomer unit corresponding to the vinyl monomer A, a monomer unit corresponding to the vinyl monomer B, a monomer unit corresponding to the vinyl monomer C, and In addition to the monomer unit corresponding to the macromonomer D, at least one selected from the group consisting of a (meth) acrylic acid ester represented by the following formula (4), an aromatic vinyl compound, and a hydroxyl group-containing monomer It is preferable to have a monomer unit corresponding to the monomer.

(Wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrocarbon-substituted oxy group)
As a result, the display stability is improved by further improving the solvent resistance of the formed colored part and improving the flatness of the surface of the formed colored part, while further improving the ejection stability by lowering the viscosity of the color filter ink. The brightness and contrast of the image can be further improved.

In the color filter ink of the present invention, it is preferable that a halogenated phthalocyanine zinc complex is included as the colorant.
The inventor of the present invention uses a halogenated phthalocyanine zinc complex in a color filter ink to obtain C.I. I. It has been found that a green colored portion having excellent brightness and contrast can be formed as compared with the case of using Pigment Green 36. However, the halogenated phthalocyanine zinc complex is inferior in dispersion stability in the ink, and color unevenness occurs when a colored portion is formed using a color filter ink containing a halogenated phthalocyanine zinc complex. It has been difficult to stably prevent the occurrence of density unevenness over a long period of time. In addition, when a color filter ink containing a halogenated phthalocyanine zinc complex is used, it has been difficult to sufficiently improve the ejection stability of the droplets. Therefore, as a result of earnest research, by using the graft copolymer together with the halogenated phthalocyanine zinc complex, the above-mentioned excellent effects can be achieved while sufficiently preventing the occurrence of the above-mentioned problems. It was found that can be obtained. That is, by using a halogenated phthalocyanine zinc complex together with the graft copolymer, the occurrence of adverse effects due to a decrease in pigment dispersion stability is surely prevented, and the brightness and contrast of the colored portions to be formed are particularly improved. It can be excellent.

In the color filter ink of the present invention, 1,3-butylene glycol diacetate, bis (2-butoxyethyl) ether, 2- (2-methoxy-1-methylethoxy) -1-methylethyl is used as the liquid medium. It is preferable to include one or more selected from the group consisting of acetate and diethylene glycol monobutyl ether acetate.
As a result, the state of dissolution of the graft copolymer in the color filter ink can be made more uniform, and the discharge stability of the color filter ink becomes particularly excellent, and the manufactured color filter is used. The contrast ratio and brightness of the displayed image can be made particularly excellent. Further, when the color filter ink contains a pigment as a colorant, the dispersion stability of the pigment particles in the color filter ink can be made particularly excellent.

これにより、カラーフィルター用インクを用いて製造されるカラーフィルターの各部位での色むら、濃度むらの発生やコントラストの低下等をより確実に防止することができ、カラーフィルターの耐久性、信頼性を特に優れたものとすることができる。 In the color filter ink of the present invention, in addition to the polymer M, the resin material includes a monomer component x1 represented by the following formula (11) and a monomer component x3 represented by the following formula (13). And a polymer X containing a monomer component x4 represented by the following formula (14).

As a result, it is possible to more reliably prevent the occurrence of color unevenness, density unevenness, contrast reduction, etc. at each part of the color filter manufactured using the color filter ink, and the durability and reliability of the color filter. Can be made particularly excellent.

これにより、カラーフィルター用インクの吐出安定性等を優れたものとしつつ、製造されるカラーフィルターの耐久性、信頼性を特に優れたものとすることができる。 In the color filter ink of the present invention, the resin material preferably contains, in addition to the polymer M, a polymer Y containing a monomer component y1 represented by the following formula (15).

Thereby, it is possible to make the manufactured color filter particularly excellent in durability and reliability while improving the discharge stability of the color filter ink.

The color filter of the present invention is manufactured using the color filter ink of the present invention.
Thereby, an image excellent in contrast ratio and brightness can be displayed, and a color filter excellent in durability can be provided.
An image display device according to the present invention includes the color filter according to the present invention.
As a result, an image display device that can display an image with excellent contrast ratio and brightness and also has excellent durability can be provided.
The image display device of the present invention is preferably a liquid crystal panel.
As a result, an image display device that can display an image with excellent contrast ratio and brightness and also has excellent durability can be provided.
An electronic apparatus according to the present invention includes the image display device according to the present invention.
As a result, it is possible to provide an electronic device that can display an image with excellent contrast ratio and brightness and is also excellent in durability.

It is sectional drawing which shows suitable embodiment of the color filter of this invention. It is sectional drawing which shows the manufacturing method of a color filter. It is a perspective view which shows the droplet discharge apparatus used for manufacture of a color filter. It is sectional drawing which shows embodiment of a liquid crystal display device. 1 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which an electronic apparatus of the present invention is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device of this invention is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of this invention is applied.

Hereinafter, preferred embodiments of the present invention will be described.
《Color filter ink》
The color filter ink of the present invention is an ink used for the production of a color filter (formation of a colored portion of a color filter), and is particularly used for the production of a color filter by an ink jet method.
The color filter ink includes a colorant, a resin material, a liquid medium in which the colorant is dissolved and / or dispersed, and the like.

<Colorant>
The color filter usually has a plurality of different colored portions (generally, three colored portions corresponding to RGB). The colorant is usually selected according to the color tone of the colored portion to be formed. As a colorant constituting the color filter ink, for example, various pigments and various dyes can be used.

  Examples of the pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 21, 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, 193 194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265; C. I. Pigment Green 7, 36, 15, 17, 18, 19, 26, 50; C.I. I. Pigment blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6, 17: 1,18,60,27,28,29,35,36,60,80; 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, 185; I. Pigment violet 1, 3, 14, 16, 19, 23, 29, 32, 36, 38, 50; 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, 104; C. I. Pigment brown 7, 11, 23, 25, 33; I. Pigment black 1 and 7, halogenated phthalocyanine zinc complex, and derivatives thereof.

  When the color filter ink contains a pigment as a colorant, it is advantageous in improving the light resistance and heat resistance of the formed color filter (colored portion). In addition, when the color filter ink contains a pigment as a colorant, conventionally, as described in detail later, the problem that the ejection stability of the droplets is likely to deteriorate, but in the present invention, Even when a pigment is included as a colorant, the occurrence of such a problem can be reliably prevented. That is, when the color filter ink contains a pigment as a colorant, the effects of the present invention are more remarkably exhibited.

  In addition, in a conventional color filter ink, when a pigment is included as a colorant, it is difficult to make the dispersion state of the colorant excellent over a long period of time. However, in the present invention, since a resin material as will be described in detail later is used in the present invention, the mixing stability of the resin material and the colorant (pigment) is improved over a long period of time. A color filter excellent in contrast and the like can be manufactured stably over a long period of time. In addition, since the color filter ink once prepared can be suitably used for a long period of time, it is possible to reduce the frequency of replacement of the color filter ink and replacement of the color filter ink in the droplet discharge device. Further, the productivity of the color filter can be made particularly excellent, and the stability of the quality of the produced color filter is also improved.

  Among the above colorants, the color filter ink is C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment blue 15: 6, C.I. I. Pigment violet 23, C.I. I. It is preferable to include one or more selected from the group consisting of CI Pigment Yellow 150, a halogenated phthalocyanine zinc complex, and derivatives thereof. Thereby, the effect by using the graft copolymer explained in full detail later is exhibited more notably. Moreover, the color reproduction range and light resistance of the produced color filter can be made particularly excellent.

In particular, the color filter ink is used as a pigment (red pigment) as C.I. I. Pigment red 177 and its derivatives, and / or C.I. I. When the pigment red 254 and derivatives thereof are included, the color developability of the color filter ink (red color filter ink) can be made particularly excellent. Moreover, the effect by using together with the resin material is more remarkably exhibited, and the dispersion stability of the pigment particles in the color filter ink can be made excellent. As a result, an increase in thixotropic property of the color filter ink at the time of forming the colored portion can be suppressed, and the discharge stability of the color filter ink is particularly excellent when the ink is applied to the cells. be able to.
C. I. Pigment Red 177 derivatives, C.I. I. When the compound of pigment red 254 contains a compound (derivative) represented by the following formula (6) or the following formula (7), the effects as described above are more remarkably exhibited.

  In particular, when the color filter ink contains a halogenated phthalocyanine zinc complex as a pigment (green pigment), the color filter ink (green color filter ink) has particularly excellent color developability. can do. In addition, although the halogenated phthalocyanine zinc complex has a feature of excellent lightness, it has heretofore been a material that is extremely difficult to stably disperse.

  However, the present inventor has excellent dispersion stability in color filter inks by using a resin material (graft copolymer), which will be described in detail later, even when a zinc complex of a halogenated phthalocyanine is included. I found out that it can be. As a result, the color developing property of the color filter ink can be further improved, and the increase in thixotropic property of the color filter ink due to the high concentration of the pigment at the time of forming the colored portion can be suppressed. Can do. Further, the long-term dispersion stability of the pigment in the color filter ink (storability of the color filter ink) and the discharge stability of the color filter ink can be made particularly excellent.

Hereinafter, the zinc complex of halogenated phthalocyanine will be described.
A zinc complex of halogenated phthalocyanine includes zinc as a central metal and halogenated phthalocyanine as a ligand. The halogenated phthalocyanine is obtained by substituting at least a part of the hydrogen atoms of the benzene ring constituting the phthalocyanine with a halogen atom. The halogenated phthalocyanine may be any as long as it satisfies such conditions, but preferably has a chemical structure represented by the following formula (8). The zinc complex of a halogenated phthalocyanine having such a structure is excellent in lightness and color developability.

  Further, the present inventor, in a color filter ink containing a graft copolymer described in detail later, contains a sulfonated pigment derivative as a sub-pigment together with a halogenated phthalocyanine zinc complex. It has been found that the dispersion stability in can be further improved. As a result, the color development of the color filter ink can be further improved, and at the time of forming the colored portion, the increase in the thixotropic property of the color filter ink due to the high concentration of the pigment is more effective. Can be suppressed. Further, the long-term dispersion stability of the pigment in the color filter ink (storability of the color filter ink) and the discharge stability of the color filter ink can be further improved.

  When the pigment includes a halogenated phthalocyanine zinc complex and a sulfonated pigment derivative, the sulfonated pigment derivative preferably contains a compound (derivative) represented by the following formula (9). Thereby, the dispersion stability of the pigment particles in the color filter ink can be made particularly excellent, and an image with a better contrast can be displayed on the manufactured color filter.

  When the halogenated phthalocyanine zinc complex and the above pigment derivative (sulfonated pigment derivative) are included, the content of the pigment derivative (sulfonated pigment derivative) in the color filter ink is not particularly limited. Phthalocyanine zinc complex (main pigment): preferably 2 to 32 parts by weight, more preferably 7 to 28 parts by weight, based on 100 parts by weight. Thereby, the dispersion stability of the pigment particles in the color filter ink can be made excellent. Further, the contrast ratio and brightness of the manufactured color filter can be made particularly excellent.

  In particular, the color filter ink is used as a pigment (blue pigment). I. Pigment blue 15: 6 and C.I. I. When the pigment violet 23 is contained, the color developability of the color filter ink (blue color filter ink) can be made particularly excellent. In addition, the dispersion stability of the pigment particles in the color filter ink can be made particularly excellent.

  When the color filter ink is a pigment containing a pigment as a colorant (pigment ink), the average particle size of the pigment is preferably 10 nm or more and 200 nm or less, and more preferably 20 nm or more and 180 nm or less. As a result, the durability (light resistance) of the color filter manufactured using the color filter ink while sufficiently improving the dispersion stability of the pigment in the color filter ink and the discharge stability of the color filter ink. Etc.) can be made sufficiently excellent, and the color developability, contrast, etc. in the color filter can be made particularly excellent.

  Examples of the dye include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine, and polymethine dyes. Specific examples of the dye include C.I. 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, 247, C.I. 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, 397, C.I. I. Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, C.I. I. Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, C.I. I. Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, C.I. I. Acid Violet 5, 9, 11, 34, 43, 47, 48, 51, 75, 90, 103, 126, C.I. I. Reactive violet 1,3,4,5,6,7,8,9,16,17,22,23,24,26,27,33,34, C.I. I. Basic violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, C.I. 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, 163, C.I. 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, 227, C.I. I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40, C.I. I. Acid Green 16, C.I. I. Acid Blue 9, 45, 80, 83, 90, 185, C.I. I. Basic oranges 21, 23, and the like.

  The content of the colorant in the color filter ink is preferably 2% by weight or more and 25% by weight or less, and more preferably 3% by weight or more and 20% by weight or less. When the colorant content is within the above range, a higher color density can be secured in a color filter manufactured using the color filter ink, and the color filter can be used for clearer image display. . Conventionally, when a colorant (especially a pigment) is contained at a relatively high concentration in this way, the ejection stability is particularly low, and the flight when ejecting ink droplets for color filters is performed. Problems such as bending and instability of droplet discharge amount were particularly likely to occur. Also, in the past, particularly when a colored portion is formed by discharging droplets on a large substrate (for example, G5 or more), the occurrence of defective products due to variations in the discharge amount at each site in the surface becomes significant. There is a problem that the productivity of the color filter is remarkably lowered. On the other hand, in the present invention, even when a colorant is contained at a relatively high concentration, as described in detail later, the occurrence of the above problems can be surely prevented, and the produced color It is possible to reliably prevent color unevenness, density unevenness, and the like from occurring in each part of the filter, and variations in characteristics among individuals, and a color filter can be manufactured with excellent productivity. That is, when the color filter ink contains a relatively high concentration of the colorant as described above, the effects of the present invention are more remarkably exhibited. In addition, the durability of the manufactured color filter can be made particularly excellent.

<Resin material>
In general, the color filter ink contains a resin material (binder resin) for the purpose of improving the adhesion of the formed colored portion to the substrate. In general, a color filter manufactured using an ink jet method is subjected to a heat treatment and a cleaning treatment with a solvent or the like in the manufacturing process. For this reason, color filters manufactured using the inkjet method are required to have durability such as heat resistance and solvent resistance, but it has been difficult to obtain satisfactory durability with conventional color filters. .

  In addition, in the production of a color filter by the ink jet method, generally, after performing droplet discharge into a cell provided on a substrate, the liquid medium is removed and the color filter ink is solidified. The thixotropic property and viscosity of the color filter ink increase as the solid content concentration increases due to the removal of the liquid medium, causing unintentional irregularities on the surface of the formed colored part. The contrast ratio and brightness of the displayed image cannot be made sufficiently high, resulting in color unevenness and density unevenness. Such a tendency is more prominent when a pigment is included as a colorant and the content of the pigment is higher than that of the resin material. This is considered to be due to aggregation of pigment particles contained in the ink as the solid content concentration increases.

In addition, in conventional color filter inks, when a droplet is ejected over a long period of time by an inkjet method, the droplet ejection amount becomes unstable or the trajectory of the ejected droplet changes (so-called flight). In some cases, bending occurs, and it becomes impossible to land droplets on the target site. When such a problem occurs, a variation in the color density between a plurality of colored portions that are originally required to have the same color density occurs, on a substrate on which a droplet is to be landed, etc. Multiple types of ink used to form colored parts of different colors are mixed (mixed), resulting in color unevenness, density unevenness, etc. in each part of the color filter. Variations in characteristics (particularly, color characteristics such as contrast ratio and color reproduction range) among a large number of color filters result in low reliability of the color filters. In particular, such a problem arises when an ink containing a pigment that needs to be kept in a dispersed state in the ink and has a large influence on the discharge property of the droplets when the dispersion state is changed. It occurred remarkably.
In order to solve the above problems, the present inventor has conducted intensive research. As a result, it has been found that the above-described problems can be solved by including a resin material as described in detail below in the color filter ink.

Hereinafter, the resin material (curable resin material) constituting the color filter ink of the present invention will be described in detail.
[Graft Copolymer G]
The ink for a color filter of the present invention corresponds to a vinyl monomer A having a blocked isocyanate group represented by the following formula (1) (hereinafter sometimes referred to as “block isocyanate group”) as a resin material. Monomer unit (repeating unit), a monomer unit corresponding to a vinyl monomer B having a carboxyl group or an acid anhydride group, and a monomer unit corresponding to a vinyl monomer C having a 3- to 5-membered cyclic ether group (Repeating unit) and a polymer chain containing the repeating unit represented by the following formula (2) or the following formula (3) as a main structural unit, and a (meth) acryloyloxy group at the terminal of the polymer chain Having a monomer unit (repeating unit) corresponding to the macromonomer D having a weight average molecular weight of 500 to 30,000, and derived from the macromonomer D The polymer chain portion is a graft copolymer constituting the branches (hereinafter referred to as "graft copolymer G") is intended to include.

（式中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は炭素数１〜８の２価の脂肪族飽和炭化水素基を示す。Ｒ^３はイソシアネート基のブロック剤Ｒ^３Ｈの残基を示す）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. R ³ is a residue of an isocyanate group blocking agent R ³ H. Indicate)

（式（２）中、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は置換基を有していてもよいフェニル基又はシアノ基を示す。式（３）中、Ｒ^６は水素原子又はメチル基を示し、Ｒ^７は炭化水素基置換オキシ基を有していてもよい炭素数１〜２５の炭化水素基を示す）

(In formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a phenyl group or a cyano group which may have a substituent. In formula (3), R ⁶ represents a hydrogen atom or Represents a methyl group, and R ⁷ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrocarbon group-substituted oxy group)

  The trunk of this graft copolymer is copolymerized at the vinyl site (carbon-carbon double bond site) of each vinyl monomer and the carbon-carbon double bond site of the (meth) acryloyloxy group of macromonomer D. The polymer chain part (polymer chain part) is formed. When the resin material (curable resin material) constituting the color filter ink of the present invention is cured by heat or active energy rays, the isocyanate group, carboxyl group or acid anhydride group, and 3- to 5-membered cyclic ether group Contributes to curing, and can form a colored portion that is remarkably excellent in various physical properties, in particular, adhesion to the substrate, durability (solvent resistance, etc.) and flatness. In addition, the ejection stability and storage stability of the color filter ink can be improved.

(Monomer unit corresponding to vinyl monomer A)
In monomer A represented by formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. R ³ represents a residue of an isocyanate group blocking agent R ³ H.
Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ² include linear chains such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene groups. Or a branched divalent saturated aliphatic hydrocarbon group (alkylene group). Among these, C2-C4 bivalent saturated aliphatic hydrocarbon groups, such as ethylene, trimethylene, and a propylene group, are preferable.

As the isocyanate group blocking agent R ³ H, a known isocyanate group blocking agent can be used. Oxime-based blocking agents such as diacetyl monooxime and benzophenone oxime; pyrazole-based blocking agents such as 3,5-dimethylpyrazole; alcohol-based blocking agents such as methanol and ethanol; phenol-based blocking agents such as phenol and cresol; butyl mercaptan and the like Mercaptan-based blocking agents; acid amide-based blocking agents such as acetanilide, ε-caprolactam, γ-butyrolactam; active methyls such as dimethyl malonate and methyl acetoacetate Imide block agents such as succinimide and maleic imide; urea block agents; carbamic acid block agents such as phenyl N-phenylcarbamate; amine block agents such as diphenylamine and aniline; ethyleneimine And imine-based blocking agents such as polyethyleneimine.

The isocyanate group blocking agent is preferably a highly stable blocking agent that does not cause gelation in the color filter ink production line. The deblocking temperature of the blocking agent is, for example, in the range of 100 ° C. to 300 ° C., preferably 150 ° C. to 250 ° C. Of the above blocking agents, oxime blocking agents and pyrazole blocking agents are preferred.
Particularly preferred blocking agents include oxime blocking agents represented by the following formula (5).

（式中、Ｒ^１０、Ｒ^１１は、同一又は異なって、炭素数１〜８のアルキル基を示す。Ｒ^１０及びＲ^１１は、互いに結合して、隣接する炭素原子とともに環を形成してもよい）

^(Wherein, R ^{10, R 11} are the same or different, ^{.R 10} and ^{R 11} represents an alkyl group having 1 to 8 carbon atoms, bonded to each other to form a ring together with the adjacent carbon atoms Good)

Examples of the alkyl group having 1 to 8 carbon atoms in R ¹⁰ and R ¹¹ include straight chain such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl and octyl groups. Or a branched alkyl group is mentioned. Among these, a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, and propyl groups is preferable. Examples of the ring in which R ¹⁰ and R ¹¹ are bonded to each other together with the adjacent carbon atom include, for example, about 3 to 12-membered (preferably 5 or 6-membered) cycloalkane such as cyclobutane ring, cyclopentane ring, and cyclohexane ring. A ring etc. are mentioned.

  As a typical example of the vinyl monomer A represented by the formula (1), 2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl methacrylate (= 2- (1-methylpropylidene) Aminooxycarbonylaminoethyl) methacrylate) [trade name “Karenz MOI-BM”, manufactured by Showa Denko KK, the following formula (1a)], 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl methacrylate [Product name “Karenz MOI-BP”, manufactured by Showa Denko KK, the following formula (1b)] and the like. As for the deblocking temperature of the trade name “Karenz MOI-BM”, the 50% deblocking temperature is 130 ° C., and the 90% deblocking temperature is 150 ° C. Further, the deblocking temperature of the trade name “Karenz MOI-BP” is 50 ° C. deblocking temperature of 100 ° C. and 90% deblocking temperature of 120 ° C.

The monomer unit corresponding to the vinyl monomer A represented by the formula (1) is represented by the following formula (I). In the formula, R ¹ , R ² and R ³ are the same as described above.

  Deblocking of the monomer unit corresponding to the vinyl monomer A represented by the formula (1) proceeds as follows. The isocyanate group generated by this deblocking acts as a curable group. The isocyanate group contributes to the improvement of the adhesion of the colored portion formed mainly using the color filter ink to the substrate.

(Monomer unit corresponding to vinyl monomer B)
As vinyl monomer B which has a carboxyl group or an acid anhydride group, unsaturated carboxylic acid or its acid anhydride is mentioned. Examples of unsaturated carboxylic acids and acid anhydrides include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid, and acid anhydrides thereof (maleic anhydride). , Itaconic anhydride, etc.). Among these, acrylic acid and methacrylic acid are particularly preferable.
A carboxyl group and an acid anhydride group have a function of improving heat resistance while contributing to improvement of adhesion of a colored portion formed using a color filter ink to a substrate or the like. Moreover, a carboxyl group and an acid anhydride group can function as a curable group.

(Monomer unit corresponding to vinyl monomer C)
The vinyl monomer C having a 3- to 5-membered cyclic ether group includes an oxirane ring (epoxy group) -containing polymerizable unsaturated compound, an oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound, and an oxolane ring (oxolanyl group). Contains polymerizable unsaturated compounds.
Examples of the oxirane ring (epoxy group) -containing polymerizable unsaturated compound include oxiranyl (meth) acrylate, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, and 2-oxy Polymerizable unsaturated compounds containing an oxirane ring (monocyclic) such as ranylethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl (meth) acrylate, etc. ((Meth) acrylic acid ester derivatives, etc.); 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate Epoxy group-containing fats such as 3,4-epoxycyclohexane rings such as 2- (3,4-epoxycyclohexylmethyloxy) ethyl (meth) acrylate and 3- (3,4-epoxycyclohexylmethyloxy) propyl (meth) acrylate Polymerizable unsaturated compounds containing a cyclic carbocycle (such as (meth) acrylic acid ester derivatives); 5,6-epoxy such as 5,6-epoxy-2-bicyclo [2.2.1] heptyl (meth) acrylate Polymerizable unsaturated compounds containing a 2-bicyclo [2.2.1] heptane ring (such as (meth) acrylic acid ester derivatives); epoxidized dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo [5] 2.1.0 ^2,6 ] decan-9-yl (meth) acrylate; 3,4-epoxytricyclo [5.2.1. 0 ^2,6 ] decan-8-yl (meth) acrylate], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ]] Decan-9-yloxy) ethyl (meth) acrylate; 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl (meth) acrylate], epoxidized di Polymerizable unsaturated compounds containing 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring such as cyclopentenyloxybutyl (meth) acrylate and epoxidized dicyclopentenyloxyhexyl (meth) acrylate ((Meth) acrylic acid ester derivatives and the like). As another oxirane ring (epoxy group) -containing polymerizable unsaturated compound, a vinyl ether compound containing an epoxy group, an allyl ether compound containing an epoxy group, or the like can also be used.

  Examples of the oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound include oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, (3- Methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 2- (3-methyl-3-oxetanyl) ethyl (meth) acrylate, 2- (3-ethyl -3-Oxetanyl) ethyl (meth) acrylate, 2-[(3-methyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 2-[(3-ethyl-3-oxetanyl) methyloxy] ethyl (meta ) Acrylate, 3-[(3-Methyl-3-oxetanyl) methyloxy] propyl Pill (meth) acrylate, 3 - and [(3-ethyl-3-oxetanyl) methyloxy] propyl (meth) acrylate, vinyl ether compounds containing oxetanyl group, and allyl ether compounds containing oxetanyl group.

Examples of the oxolane ring (oxolanyl group) -containing polymerizable unsaturated compound include tetrahydrofurfuryl (meth) acrylate, vinyl ether compounds containing an oxolanyl group, and allyl ether compounds containing an oxolanyl group.
A 3- to 5-membered cyclic ether group [oxirane ring (epoxy group), oxetane ring (oxetanyl group), oxolane ring (oxolanyl group)] acts as a curable group. The 3- to 5-membered cyclic ether group mainly contributes to improvement of chemical resistance (solvent resistance, alkali resistance, etc.).

(Monomer unit corresponding to macromonomer D)
The macromonomer D has a polymer chain containing the repeating unit represented by the formula (2) or (3) as a main structural unit, and has a (meth) acryloyloxy group at the end of the polymer chain. is doing. The (meth) acryloyloxy group and the repeating unit represented by formula (2) or formula (3) may be directly bonded, but may be bonded via an appropriate linking group depending on the synthesis method of the macromonomer. It may be. The terminal of the polymer chain may be a hydrogen atom, but may have an appropriate terminal group depending on the synthesis method of the macromonomer.
The macromonomer D may have one or more repeating units represented by the formula (2) in the polymer chain, and one or two repeating units represented by the formula (3). You may have more than one seed. Moreover, you may have both the repeating unit represented by Formula (2) and the repeating unit represented by Formula (3).

In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a phenyl group or a cyano group which may have a substituent. In Formula (3), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrocarbon group-substituted oxy group.
In the formula (2), examples of the substituent in the “optionally substituted phenyl group” of R ⁵ include halogen atoms such as fluorine atom, chlorine atom and bromine atom; methyl, ethyl, propyl, isopropyl Alkyl groups having 1 to 6 carbon atoms such as butyl, isobutyl, s-butyl, t-butyl, pentyl and hexyl groups; hydroxyl groups; methoxy, ethoxy, propoxy, isopropyloxy, butoxy, pentyloxy, hexyloxy groups and the like Alkoxy groups having 1 to 6 carbon atoms; aryloxy groups such as phenoxy groups; aralkyloxy groups such as benzyloxy groups; acyloxy groups having 1 to 10 carbon atoms such as acetoxy, propionyloxy, benzoyloxy groups; acetyl, propionyl, benzoyl C1-C10 acyl group such as a group; carboxyl group; methoxycal C1-C7 alkoxycarbonyl groups such as bonyl, ethoxycarbonyl, propoxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups; aralkyloxycarbonyl groups such as benzyloxycarbonyl groups; cyano groups; nitro groups; amino groups; Examples thereof include mono- or dialkylamino groups such as methylamino, ethylamino, dimethylamino and diethylamino groups; cyclic amino groups such as piperidino and morpholino groups. The number of substituents can be suitably selected from the range of 0-5.

In formula (3), examples of the hydrocarbon group having 1 to 25 carbon atoms represented by R ⁷ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, 2 -An alkyl group such as ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, docosyl group; an alicyclic hydrocarbon group such as cyclohexyl, dicyclopentanyl, isobornyl group; an aryl group such as phenyl group; benzyl, 1 -Aralkyl groups such as phenylethyl and 2-phenylethyl groups; groups in which two or more of these are bonded. Among the hydrocarbon groups having 1 to 25 carbon atoms, hydrocarbon groups having 1 to 20 carbon atoms, particularly hydrocarbon groups having 1 to 12 carbon atoms are preferable.

Examples of the “hydrocarbon group-substituted oxy group” that the hydrocarbon group having 1 to 25 carbon atoms may have include, for example, alkoxy groups such as methoxy and ethoxy groups (for example, alkoxy groups having 1 to 10 carbon atoms); Aryloxy group such as phenoxy group; alicyclic hydrocarbon group-substituted oxy group such as cyclohexyloxy group and dicyclopentanyloxy group; 1 to 15 carbon atoms such as aralkyloxy group such as benzyloxy group (preferably carbon Examples thereof include hydrocarbon group-substituted oxy groups represented by formulas 1 to 12.
The weight average molecular weight of the macromonomer D is 500 or more and 30000 or less, preferably 1000 or more and 25000 or less, and more preferably 2000 or more and 20000 or less.

The polymer chain portion of the macromonomer D includes a repeating unit represented by the formula (2) or a repeating unit represented by the formula (3) as a main structural unit.
In the macromonomer having a polymer chain containing the repeating unit represented by the formula (2) as a main structural unit, the polymer chain is composed only of one or more repeating units represented by the formula (2). However, it may have other structural units (repeating units). In such a macromonomer, the ratio of the repeating unit represented by the formula (2) to the entire repeating unit (monomer unit) constituting the polymer chain is, for example, 30% by weight to 100% by weight, preferably 50%. % By weight or more and 100% by weight or less, more preferably 80% by weight or more and 100% by weight or less.

As a macromonomer having a polymer chain containing a repeating unit represented by the formula (2) as a main structural unit, a repeating unit in which R ⁵ is a phenyl group which may have a substituent in the formula (2). macromonomer having a polymer chain comprising as a main structural unit, and a repeating unit R ⁵ in formula (2) is a phenyl group which may have a substituent, in the formula (2) R ⁵ is a cyano group A macromonomer having a polymer chain part containing both repeating units of a certain repeating unit as a main structural unit is preferred.

The macromonomer having a polymer chain containing the repeating unit represented by the formula (2) as a main structural unit is a vinyl monomer corresponding to the repeating unit represented by the formula (2), that is, the following formula (a) Can be produced by a known method using a vinyl monomer represented by the formula (1) and, if necessary, another vinyl monomer as a monomer raw material.
CH ₂ = CR ⁴ R ⁵ (a)
(Wherein R ⁴ and R ⁵ are the same as above)

Examples of the vinyl monomer represented by the formula (a) include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, methacrylonitrile, and the like.
As said other vinyl monomer, (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic, such as a vinyl monomer corresponding to the repeating unit represented by Formula (3) mentioned later, for example Examples include acid amides and vinyl acetate.

  In the macromonomer having a polymer chain containing the repeating unit represented by the formula (3) as a main structural unit, the polymer chain is composed only of one or more repeating units represented by the formula (3). However, it may have other structural units (repeating units). In such a macromonomer, the ratio of the repeating unit represented by the formula (3) to the entire repeating unit (monomer unit) constituting the polymer chain is, for example, 30% by weight or more and 100% by weight or less, preferably 50%. % By weight or more and 100% by weight or less, more preferably 80% by weight or more and 100% by weight or less.

The macromonomer having a polymer chain containing the repeating unit represented by the formula (3) as a main structural unit is a vinyl monomer corresponding to the repeating unit represented by the formula (3), that is, the following formula (b) (Meth) acrylic acid ester represented by the above, and if necessary, other vinyl monomers can be used as monomer raw materials, and can be produced by a known method.
^{_{CH 2 = C (R 6)}} COOR 7 (b)
(Wherein R ⁶ and R ⁷ are the same as above)

Examples of the (meth) acrylic acid ester represented by the formula (b) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, Dodecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, Examples include benzyl (meth) acrylate and phenylethyl (meth) acrylate.
Examples of the other vinyl monomer include a vinyl monomer corresponding to the repeating unit represented by the above formula (2), (meth) acrylic acid, (meth) acrylic acid amide, and vinyl acetate. It is done.

A commercially available product can be used as the macromonomer D. As the commercially available product, for example, trade name “AS-6” (a macromonomer having a polymer chain containing a repeating unit corresponding to styrene as a main structural unit and having a methacryloyloxy group at the terminal of the polymer chain) , “AB-6” (a macromonomer having a polymer chain containing a repeating unit corresponding to butyl acrylate as a main structural unit and having an acryloyloxy group at the terminal of the polymer chain), “AA-6” (A macromonomer having a polymer chain containing a repeating unit corresponding to methyl methacrylate as a main structural unit and having a methacryloyloxy group at the terminal of the polymer chain), “AN-6” (repeating corresponding to styrene) A polymer chain containing a repeating unit corresponding to the unit and acrylonitrile as a main structural unit, and methacryloyloxy at the end of the polymer chain. Macromonomer) (or with a group, all manufactured by Toagosei Co., Ltd.). These macromonomers have a weight average molecular weight of about 6000.
The polymer chain part derived from the macromonomer D constituting the branch part of the graft copolymer contributes to the improvement of the solvent resistance and the adhesion of the colored part formed using the color filter ink to the substrate and the like. To do.

The monomer unit corresponding to vinyl monomer A, the monomer unit corresponding to vinyl monomer B, the monomer unit corresponding to vinyl monomer C, and the monomer unit corresponding to macromonomer D were each one type. Or two or more of them may be present.
The proportion of the monomer unit corresponding to the vinyl monomer A in the graft copolymer is, for example, 1% by weight or more and 90% by weight or less, preferably 3 to 70% with respect to all the monomer units constituting the graft copolymer. % By weight, more preferably 5% by weight or more and 50% by weight or less, and particularly preferably 6% by weight or more and 35% by weight or less. If this ratio is too small, the adhesion of the colored portion formed using the color filter ink to the substrate or the like tends to be lowered, and if it is too large, the ratio of the monomer units corresponding to the vinyl monomer C is relatively small. As a result, the solvent resistance tends to decrease.

  The proportion of the monomer unit corresponding to the vinyl monomer B in the graft copolymer is, for example, 1% by weight or more and 90% by weight or less, preferably 3% by weight, based on all monomer units constituting the graft copolymer. It is 70 wt% or less, more preferably 5 wt% or more and 50 wt% or less, and particularly preferably 6 wt% or more and 35 wt% or less. If this ratio is too small, the heat resistance tends to be lowered, and if it is too much, the ratio of the monomer units corresponding to the vinyl monomer C is relatively reduced, so that the solvent resistance tends to be lowered.

  The proportion of the monomer units corresponding to the vinyl monomer C in the graft copolymer is, for example, 5% by weight or more and 99% by weight or less, preferably 20% by weight with respect to all the monomer units constituting the graft copolymer. It is 95% by weight or less, more preferably 30% by weight or more and 90% by weight or less, and particularly preferably 35% by weight or more and 70% by weight or less. If this ratio is too small, chemical resistance such as solvent resistance tends to decrease, and if it is too large, the ratio of monomer units corresponding to vinyl monomer A is relatively small. The adhesion of the colored portion to the substrate or the like tends to decrease.

  The proportion of the monomer unit corresponding to the macromonomer D in the graft copolymer is, for example, 1% by weight or more and 60% by weight or less, preferably 1.5% by weight, based on all monomer units constituting the graft copolymer. It is 50 wt% or less, more preferably 2 wt% or more and 40 wt% or less, and particularly preferably 2.5 wt% or more and 30 wt% or less. If this ratio is too small, the solvent resistance and the adhesion of the colored part formed using the color filter ink to the substrate or the like are likely to be lowered, and if it is too much, the residual monomer is increased, so that the solvent resistance is lowered. It becomes easy.

  The total of the monomer unit corresponding to the vinyl monomer A, the monomer unit corresponding to the vinyl monomer B, the monomer unit corresponding to the vinyl monomer C, and the monomer unit corresponding to the macromonomer D occupies the graft copolymer. The ratio is, for example, 40% by weight to 100% by weight, preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, based on all monomer units constituting the graft copolymer. It is.

(Other monomer units)
The graft copolymer constituting the color filter ink is composed of a monomer unit corresponding to vinyl monomer A, a monomer unit corresponding to vinyl monomer B, a monomer unit corresponding to vinyl monomer C, and macromonomer D. Although it may be composed only of the corresponding monomer units, it may contain other monomer units (repeating units) in addition to these monomer units.
As a monomer capable of forming another monomer unit that may be contained in such a graft copolymer, a (meth) acrylic acid ester represented by the following formula (4), an aromatic vinyl compound, and a hydroxyl group-containing Monomers, and these monomers can be used alone or in combination of two or more.

（式中、Ｒ^８は水素原子又はメチル基を示し、Ｒ^９は炭化水素基置換オキシ基を有していてもよい炭素数１〜２５の炭化水素基を示す）

(Wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrocarbon-substituted oxy group)

  In addition to the monomer unit corresponding to the vinyl monomer A, the monomer unit corresponding to the vinyl monomer B, the monomer unit corresponding to the vinyl monomer C, and the monomer unit corresponding to the macromonomer D. And a monomer unit corresponding to at least one monomer selected from the group consisting of (meth) acrylic acid ester represented by formula (4), an aromatic vinyl compound, and a hydroxyl group-containing monomer. As a result, the discharge stability is further improved by lowering the viscosity of the color filter ink, while further improving the solvent resistance of the formed colored portion, and the surface flatness of the formed colored portion. The brightness and contrast of the display image can be further improved by the improvement.

In the (meth) acrylic acid ester represented by the formula (4), R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ may have a hydrocarbon group-substituted oxy group having 1 to 25 carbon atoms. A hydrocarbon group is shown. Examples of the hydrocarbon group having 1 to 25 carbon atoms for R ⁹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, Alkyl groups such as dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and docosyl groups; alicyclic hydrocarbon groups such as cyclohexyl, dicyclopentanyl and isobornyl groups; aryl groups such as phenyl groups; benzyl, 1-phenylethyl, 2 An aralkyl group such as a phenylethyl group; a group in which two or more of these are bonded.

  Examples of the “hydrocarbon group-substituted oxy group” that the hydrocarbon group having 1 to 25 carbon atoms may have include, for example, alkoxy groups such as methoxy and ethoxy groups (for example, alkoxy groups having 1 to 10 carbon atoms) ); Aryloxy group such as phenoxy group; alicyclic hydrocarbon group-substituted oxy group such as cyclohexyloxy group and dicyclopentanyloxy group; 1 to 15 carbon atoms such as aralkyloxy group such as benzyloxy group (preferably Is a hydrocarbon group-substituted oxy group having 1 to 12 carbon atoms.

As typical examples of the (meth) acrylic acid ester represented by the formula (4), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (Meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl Examples include (meth) acrylate, benzyl (meth) acrylate, and phenylethyl (meth) acrylate.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, vinyl biphenyl, and the like.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxy. Polyhydric alcohol and acrylic acid such as hexyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 8-hydroxyoctyl (meth) acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, etc. Alternatively, a compound obtained by ring-opening polymerization of ε-caprolactone to a monoesterified product with methacrylic acid, or a monoesterified product of the above polyhydric alcohol with acrylic acid or methacrylic acid (manufactured by Daicel Chemical Industries, Ltd. FA series, PLACCEL FM series, etc.), ethylene oxide, or propylene oxide ring-opening polymerization with hydroxyl group-containing compounds, and the like.

  Graft copolymerization of monomer units corresponding to at least one monomer selected from the group consisting of (meth) acrylic acid esters represented by formula (4), aromatic vinyl compounds, and hydroxyl group-containing monomers The proportion in the coalescence is generally 0% by weight or more and 60% by weight or less (for example, 1% by weight or more and 60% by weight or less), preferably 0% by weight or more and 50% by weight or less with respect to all monomer units constituting the graft copolymer. % By weight or less (eg, 2% by weight or more and 50% by weight or less), more preferably 0% by weight or more and 40% by weight or less (eg, 2% by weight or more and 40% by weight or less).

  The graft copolymer constituting the color filter ink of the present invention includes a vinyl monomer A having a blocked isocyanate group represented by the formula (1) and a vinyl monomer having a carboxyl group or an acid anhydride group. A monomer mixture containing B, a vinyl monomer C having a 3- to 5-membered cyclic ether group, a macromonomer D, and another copolymerizable monomer as necessary is copolymerized (vinyl copolymer). (Polymerization).

As the polymerization initiator used for polymerization, a normal radical initiator can be used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), Dimethyl-2,2'-azobis (2-methylpropionate), 2,2-azobis (isobutyric acid) dimethyl, diethyl-2,2'-azobis (2-methylpropionate), dibutyl-2,2 Azo compounds such as' -azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, organic peroxides such as 1,1-bis (t-butylperoxy) cyclohexane, peroxide Examples thereof include inorganic peroxides such as hydrogen and ammonium persulfate. When a peroxide is used as a radical polymerization initiator, a redox initiator may be combined with a reducing agent. Of these, azo compounds are preferred, and in particular, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2-azobis (isobutyric acid) dimethyl. preferable.
The amount of the polymerization initiator used can be appropriately selected within a range that does not impair smooth copolymerization, but is usually about 1% by weight to 30% by weight with respect to the total amount of all monomer components and polymerization initiator. Preferably, it is about 5 wt% or more and 25 wt% or less.

  In the present invention, a chain transfer agent generally used in radical polymerization may be used in combination. Specific examples include thiols (such as n-dodecyl mercaptan, n-octyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethylene glycol dimercaptan). Mercaptopropionic acid, thiobenzoic acid, thioglycolic acid, thiomalic acid, etc.), alcohols (isopropyl alcohol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.), α-methylstyrene dimer , Terbinolene, myrcene, limonene, α-pinene, β-pinene and the like. The amount of the chain transfer agent is preferably 0.001% by weight or more and 3% by weight based on the amount of the total radical polymerizable monomer. % Or less. When using a chain transfer agent, it is preferable to mix with a polymerizable vinyl monomer in advance.

  The polymerization can be performed by a conventional method used for producing a styrene polymer or an acrylic polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. Among these, solution polymerization is preferable. The monomer and the polymerization initiator may be supplied all at once to the reaction system, or a part or all of them may be dropped into the reaction system. For example, a method in which a solution in which a polymerization initiator is dissolved in a polymerization solvent is dropped into a mixed solution of a monomer and a polymerization solvent kept at a constant temperature, or the monomer and the polymerization initiator are dissolved in the polymerization solvent in advance. A method in which the solution is dropped into a polymerization solvent maintained at a constant temperature for polymerization (drop polymerization method) can be employed.

The polymerization solvent can be appropriately selected according to the monomer composition and the like. As a polymerization solvent, for example, ether (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether, propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, dipropylene glycol mono or dialkyl ether, tripropylene glycol mono Or glycol ethers such as dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerol mono, di or trialkyl ether Chain ethers such as tetrahydrofuran, cyclic ethers such as dioxane, etc.), esters (methyl acetate, ethyl acetate) , Butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C _5-6 cycloalkane diol mono- or diacetate, C _5-6, such as cycloalkane monovinyl or diacetate Carboxylic acid esters; ethylene glycol monoalkyl ether acetate, ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono or diacetate, dipropylene glycol monoalkyl Ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate 1,3-propanediol mono or diacetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4 -Glycol acetates such as butanediol mono or diacetate, glycerol mono, di or triacetate, glycerol mono or di _C1-4 alkyl ether di or monoacetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono or diacetate Or glycol ether acetates), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.), amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkanedimethanol, etc.) Hydrocarbons (aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane), and mixed solvents thereof. The polymerization temperature can be appropriately selected within a range of, for example, 30 ° C. or more and 150 ° C. or less.

  The graft copolymer which comprises the color filter ink of this invention can be produced | generated by the said method. The weight average molecular weight of the graft copolymer is, for example, 1000 or more and 100,000 or less, preferably 1500 or more and 40000 or less, and more preferably 2500 or more and 30000 or less. The degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer is 1 or more and 3 or less.

The content of the graft copolymer in the color filter ink is preferably 1.8% by weight or more and 10.5% by weight or less, and more preferably 2.0% by weight or more and 8.0% by weight or less. More preferred. Thereby, the effects as described above can be more reliably exhibited.
As described above, in the present invention, the resin material includes the above-described graft copolymer, but may further include another resin component (polymer).
Examples of such a resin component (polymer) include polymer X and polymer Y as described below.

[Polymer X]
Polymer X includes monomer component x1 represented by the following formula (11), monomer component x3 represented by the following formula (13), monomer component x4 represented by the following formula (14), and Is included. Examples of the polymer X include those represented by the following formula (17).

By including such a polymer X, the switching characteristic of the curing reaction as a whole resin material (the curing reaction is not allowed to proceed substantially at a predetermined temperature or lower, and the curing reaction can be efficiently performed at a temperature higher than that). Characteristics) and the affinity and compatibility of each polymer component in the color filter ink are sufficiently excellent, while the solvent resistance of the colored portion formed using the color filter ink is particularly excellent. In addition, the flatness of the surface of the colored portion to be formed can be made particularly high. As a result, it is possible to more reliably prevent color unevenness, density unevenness, contrast reduction, etc. at each part of the color filter manufactured using the color filter ink, and durability and reliability of the color filter. Can be made particularly excellent.
In addition, the polymer X may consist essentially of a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer X is a mixture of a plurality of types of compounds, each compound contains monomer components x1, x3, and x4.

(Monomer component x1)
The polymer X contains the monomer component x1 represented by the formula (11) as a monomer component.
By containing such a monomer component x1 as a monomer component, an unintentional reaction (polymerization reaction) of the resin material can be reliably prevented during storage of the color filter ink or in the ink application step described later. On the other hand, in the colored part forming step (curing step) performed in a heating environment, the curing reaction (polymerization reaction) of the resin material can be more suitably progressed. That is, by including the monomer component x1, the switching characteristics of the curing reaction for the resin material can be made particularly excellent. Further, by containing the monomer component x1 as the monomer component, for example, the dispersion stability of the pigment particles in the color filter ink can be improved, and the long-term storage stability of the color filter ink. The discharge stability can be made excellent. Moreover, the hardness etc. of the colored part formed can be made excellent by containing the monomer component x1 as a monomer component.

  The content of the monomer component x1 in the polymer X (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is preferably 30% by weight or more and 90% by weight or less. It is more preferable that the weight is not less than 80% by weight. When the content of the monomer component x1 in the polymer X is a value within the above range, the above-described effects can be achieved without inhibiting the functions of the monomer components x2, x3, and x4 described in detail later. It can be expressed more significantly. On the other hand, if the content of the monomer component x1 in the polymer X is less than the lower limit value, the effect of including the monomer component x1 may not be sufficiently exhibited. On the other hand, when the content of the monomer component x1 in the polymer X exceeds the upper limit, the content of the monomer components x2, x3, and x4 is relatively lowered, and these functions are not sufficiently exhibited. there is a possibility. Further, the reaction rate of the polymer X at a high temperature decreases, and it becomes difficult to produce a color filter with sufficiently excellent productivity. In addition, when the polymer X is a mixture of plural kinds of compounds, the weighted average value (weighted average value based on the weight ratio) of these compounds is adopted as the content value of the monomer component x1. can do. Moreover, when the polymer X is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component x1 at the content as described above.

(Monomer component x2)
The polymer X may contain the monomer component x2 represented by the following formula (12) as a monomer component.

Containing such a monomer component x2 as a monomer component (particularly, together with the monomer component x1 described above and the monomer component x3 described in detail later) can preserve the color filter ink. In the colored part formation process (curing process) performed in a heating environment while reliably preventing unintentional reaction (polymerization reaction) of the resin material in the ink application process or the like described later, the resin material curing reaction (polymerization) Reaction) can proceed more suitably. In particular, in the colored portion forming step (curing step) under a heating environment, the rising of the polymerization reaction of the resin material can be improved, and the polymerization reaction can be continuously advanced. Further, by containing the monomer component x2 as the monomer component, the hardness of the colored portion to be formed can be made particularly excellent.
Examples of the polymer X containing the monomer component x2 as a monomer component include those represented by the following formula (18).

  The content of the monomer component x2 in the polymer X (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is preferably 5% by weight or more and 60% by weight or less. It is more preferable that the amount is not less than 50% by weight. When the content of the monomer component x2 in the polymer X is a value within the above range, without inhibiting the functions of the monomer component x1 and the monomer components x3 and x4 described in detail later, The effects as described above can be expressed more remarkably. On the other hand, when the content of the monomer component x2 in the polymer X is less than the lower limit, the effect of including the monomer component x2 may not be sufficiently exhibited. On the other hand, when the content of the monomer component x2 in the polymer X exceeds the upper limit, the content of the monomer components x1, x3, and x4 is relatively lowered, and these functions are not sufficiently exhibited. there is a possibility. In addition, the reactivity of the polymer X at a relatively low temperature increases, and the storage stability of the color filter ink tends to decrease. In addition, when the polymer X is a mixture of a plurality of kinds of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is adopted as the content value of the monomer component x2. can do. Moreover, when the polymer X is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component x2 at the above-described content.

(Monomer component x3)
The polymer X contains the monomer component x3 represented by the above formula (13) as a monomer component.
By containing the monomer component x3 as the monomer component, the chemical resistance, solvent resistance, and the like of the colored portion to be formed can be made particularly excellent. Thus, after the colored portion forming step (curing step), chemical application and washing (especially washing with N-methyl-2-pyrrolidone, γ-butyrolactone, isopropyl alcohol, hydrochloric acid, aqueous sodium hydroxide, etc.), etc. Even when post-processing is performed, the occurrence of adverse effects due to these can be reliably prevented.

Further, the monomer component x3 has a sufficiently low reactivity at a relatively low temperature (for example, 100 ° C. or lower) in the polymer X, similarly to the monomer component x1 described above. Under a heating environment such as a heat treatment applied in the forming step (curing step), the substrate exhibits sufficient reactivity. For this reason, in the coloring part formation process (curing process) performed in a heating environment while reliably preventing unintentional reaction (polymerization reaction) of the resin material during storage of the color filter ink or in the ink application process described later. Can suitably advance the curing reaction (polymerization reaction) of the resin material.
Further, by containing the monomer component x3 as a monomer component, for example, the dispersion stability of the pigment particles in the color filter ink can be made particularly excellent, and the color filter ink can be stored for a long time. And discharge stability can be made particularly excellent.

  The content of the monomer component x3 in the polymer X (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is preferably 2% by weight or more and 20% by weight or less. It is more preferable that the amount is not less than 15% by weight. When the content of the monomer component x3 in the polymer X is a value within the above range, without inhibiting the functions of the monomer components x1 and x2 described above and the monomer component x4 described in detail later, The effects as described above can be expressed more remarkably. On the other hand, when the content of the monomer component x3 in the polymer X is less than the lower limit, the effect of including the monomer component x3 may not be sufficiently exhibited. On the other hand, when the content of the monomer component x3 in the polymer X exceeds the upper limit, the content of the monomer components x1, x2, and x4 is relatively decreased, and these functions are not sufficiently exhibited. there is a possibility. In addition, the colored portion formed using the color filter ink becomes too hard, and the tendency to follow the deformation of the substrate or the like accompanying a temperature change appears. In addition, when the polymer X is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) of these compounds is adopted as the content value of the monomer component x3. can do. Moreover, when the polymer X is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component x3 with the content as described above.

(Monomer component x4)
The polymer X contains the monomer component x4 represented by the formula (14) as a monomer component.
By containing such a monomer component x4 as a monomer component, the solid content concentration is increased when the dispersion medium is removed from the color filter ink applied on the substrate during the formation of the colored portion. Along with this, the thixotropic property and viscosity of the color filter ink are increased, and it is possible to more reliably prevent the occurrence of unintentional irregularities on the surface of the formed colored portion.

Moreover, the monomer component x4 has a hydroxyl group at the terminal. By having such a structure, the reaction at a relatively low temperature (for example, 100 ° C. or less) is sufficiently low, and the reaction is performed in a heating environment such as a heat treatment performed in the colored portion forming step (curing step). The sex can be further enhanced. By this, in the colored part forming step (curing step) performed in a heating environment while reliably preventing unintentional reaction (polymerization reaction) of the resin material during storage of the color filter ink or in the ink application step described later Can advance the curing reaction (polymerization reaction) of the resin material more suitably.
Further, by containing the monomer component x4 as the monomer component, for example, the dispersion stability of the pigment particles in the color filter ink can be made particularly excellent, and the color filter ink can be stored for a long time. And discharge stability can be made particularly excellent.

  The content of the monomer component x4 in the polymer X (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is preferably 2% by weight or more and 20% by weight or less. It is more preferable that the amount is not less than 15% by weight. When the content of the monomer component x4 in the polymer X is a value within the above range, the above-described effects are more remarkable without inhibiting the functions of the monomer components x1, x2, and x3. Can be expressed. On the other hand, when the content of the monomer component x4 in the polymer X is less than the lower limit, the effect due to the inclusion of the monomer component x4 may not be sufficiently exhibited. On the other hand, when the content of the monomer component x4 in the polymer X exceeds the upper limit, the content of the monomer components x1, x2, and x3 is relatively lowered, and these functions are not sufficiently exhibited. there is a possibility. Moreover, the tendency for the hardness of the colored part formed using the ink for color filters to fall appears. In addition, when the polymer X is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) of these compounds is used as the content value of the monomer component x4. can do. Moreover, when the polymer X is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component x4 with the content as described above.

The polymer X may include a monomer component (other monomer component) other than the monomer components x1, x2, x3, and x4 described above. Thereby, for example, the effects derived from the chemical structures of other monomer components can be obtained while exhibiting the above-described characteristics.
When the polymer X contains other monomer components (monomer components other than the monomer components x1, x2, x3, x4), the content of other monomer components in the polymer X ( When a plurality of other monomer components are included, the sum of these contents) is preferably 15% by weight or less, and more preferably 10% by weight or less.

The weight average molecular weight of the polymer X is preferably 1000 or more and 50000 or less, more preferably 1200 or more and 10,000 or less, and further preferably 1500 or more and 5000 or less. As a result, it is possible to make the color filter ink stable over time (long-term storage stability), the discharge stability of the color filter ink, and the color filter productivity sufficiently. Furthermore, the flatness of the colored portion formed using the color filter ink can be made more reliable, and the occurrence of color unevenness in the image displayed using the color filter can be more effectively achieved. Can be prevented.
Further, the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer X is preferably 1 or more and 3 or less.

[Polymer Y]
The polymer Y includes a monomer component y1 represented by the following formula (15). Examples of the polymer Y include those represented by the following formula (19).

By including such a polymer Y, the discharge stability of the color filter ink, the dispersion stability of the pigment in the color filter, and the like can be improved, while the colored portion formed using the color filter ink The adhesion to the substrate can be made particularly excellent, and the durability and reliability of the produced color filter can be made particularly excellent.
The polymer Y may be substantially composed of a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer Y is a mixture of a plurality of types of compounds, each compound contains the monomer component y1.

(Monomer component y1)
The polymer Y contains the monomer component y1 represented by the formula (15) as a monomer component.
By including such a monomer component y1 as the monomer component, the adhesion of the formed colored portion to the substrate can be made particularly excellent. As a result, the durability of the color filter can be made particularly excellent.

  The content of the monomer component y1 in the polymer Y (value obtained by conversion in terms of the weight of the monomer used for polymer synthesis) is preferably 30% by weight to 90% by weight, It is more preferable that the weight is not less than 80% by weight. When the content of the monomer component y1 in the polymer Y is a value within the above range, for example, when the polymer Y includes the monomer component y2 described in detail later as the monomer component, the unit The effects as described above can be expressed more significantly without inhibiting the function of the monomer component y2. On the other hand, when the content of the monomer component y1 in the polymer Y is less than the lower limit value, the effect of including the monomer component y1 may not be sufficiently exhibited. On the other hand, when the content of the monomer component y1 in the polymer Y exceeds the upper limit, for example, when the polymer Y includes the monomer component y2 described in detail later as the monomer component, Accordingly, the content of the monomer component y2 may be reduced, and the function of the monomer component y2 may not be sufficiently exhibited. In addition, when the colored portion is formed, when the dispersion medium is removed from the color filter ink applied on the substrate, the viscosity of the color filter ink tends to increase with an increase in the solid content concentration. Involuntary unevenness is likely to occur on the surface of the colored portion. In addition, when the polymer Y is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is adopted as the content value of the monomer component y1. can do. Moreover, when the polymer Y is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component y1 at the content as described above.

(Monomer component y2)
The polymer Y may contain the monomer component y2 represented by the following formula (16) as a monomer component.

  By containing such a monomer component y2 as a monomer component (particularly, together with the monomer component y1 described above), the resin in the storage of the color filter ink or in the ink application step described later, etc. In the colored part forming step (curing step) performed in a heating environment, the unintentional reaction (polymerization reaction) of the material can be prevented more reliably, and the curing reaction (polymerization reaction) of the resin material can be suitably advanced. it can. In particular, in the colored portion forming step (curing step) under a heating environment, the rising of the polymerization reaction of the resin material can be improved, and the polymerization reaction can be continuously advanced. Moreover, the hardness etc. of the colored part formed can be made excellent by containing the monomer component y2 as a monomer component.

Further, when the polymer Y contains the monomer component y2, the affinity and compatibility with the graft copolymer G and the polymer X can be sufficiently improved. As a result, the discharge stability of the color filter ink can be made excellent, and the colored portion formed using the color filter ink has excellent transparency (light transmission due to the opacity of the resin material). Rate is prevented), adhesion to the substrate is particularly excellent, and problems such as cracks are less likely to occur. On the other hand, when the monomer component y2 is not contained as a monomer component, the affinity and compatibility with the graft copolymer G and the like cannot be sufficiently improved, and the color filter ink is In addition, the color filter produced is inferior in discharge stability, and color unevenness and density unevenness are likely to occur, making it difficult to sufficiently improve contrast, durability, reliability, and the like. .
An example of the polymer Y containing the monomer component y2 as a monomer component is represented by the following formula (20).

  The content of the monomer component y2 in the polymer Y (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is preferably 10% by weight or more and 70% by weight or less. More preferably, it is at least 60% by weight. When the content of the monomer component y2 in the polymer Y is a value within the above range, the above-described effects can be expressed more significantly without inhibiting the function of the monomer component y1 described above. Can do. On the other hand, when the content of the monomer component y2 in the polymer Y is less than the lower limit value, the effect of including the monomer component y2 may not be sufficiently exhibited. On the other hand, when the content of the monomer component y2 in the polymer Y exceeds the upper limit, the content of the monomer component y1 is relatively lowered, and the function of the monomer component y1 is not sufficiently exhibited. there is a possibility. In addition, the reactivity of the polymer Y at a relatively low temperature increases, and the storage stability of the color filter ink tends to decrease. In addition, when the polymer Y is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is adopted as the content value of the monomer component y2. can do. Moreover, when the polymer Y is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component y2 with the content as described above.

In addition, the polymer Y may contain monomer components (other monomer components) other than the monomer components y1 and y2 described above. Thereby, for example, the effects derived from the chemical structures of other monomer components can be obtained while exhibiting the above-described characteristics.
When the polymer Y contains other monomer components (monomer components other than the monomer components y1 and y2), the content of other monomer components in the polymer Y (multiple types of other components) When the monomer component is included, the sum of these contents) is preferably 15% by weight or less, more preferably 10% by weight or less.

The weight average molecular weight of the polymer Y is preferably 1000 or more and 50000 or less, more preferably 1200 or more and 10,000 or less, and further preferably 1500 or more and 5000 or less. As a result, it is possible to make the color filter ink stable over time (long-term storage stability), the discharge stability of the color filter ink, and the color filter productivity sufficiently. Furthermore, the flatness of the colored portion formed using the color filter ink can be made more reliable, and the occurrence of color unevenness in the image displayed using the color filter can be more effectively achieved. Can be prevented.
Moreover, it is preferable that the dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of the polymer Y is 1 or more and 3 or less.

<Liquid medium>
The liquid medium (liquid medium) has a function of dissolving and / or dispersing the colorant and the like as described above. That is, the liquid medium functions as a solvent and / or a dispersion medium. In general, most of the liquid medium is removed in the process of manufacturing the color filter.

As the liquid medium constituting the color filter ink, for example, ester compounds, ether compounds, hydroxy ketones, carbonic acid diesters, cyclic amide compounds and the like can be used. Among them, [1] polyhydric alcohols (for example, ethylene glycol) , Propylene glycol, butylene glycol, glycerin, etc.) condensates (polyhydric alcohol ethers), polyhydric alcohols or alkyl ethers of polyhydric alcohol ethers (eg, methyl ether, ethyl ether, butyl ether, hexyl ether, etc.) , Esters (eg, formate, acetate, propionate, etc.), [2] esters of polyvalent carboxylic acids (eg, succinic acid, glutaric acid, etc.) (eg, methyl esters), [3] at least one hydroxyl group in the molecule When Ether compounds having one carboxyl group even without (hydroxy acid), esters and the like, (4) polyhydric alcohol and carbonic acid diester having a chemical structure as obtained in the reaction with phosgene is preferred. Examples of the compound that can be used as the liquid medium include 2- (2-methoxy-1-methylethoxy) -1-methylethyl 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-butylate, 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-ethoxypropionate, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, diethylene glycol diethyl ether, octane Ethyl acid, 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 Recall 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 Examples include 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 one or two selected from these A combination of more than one species can be used.
Among these, as the liquid medium, 1,3-butylene glycol diacetate, bis (2-butoxyethyl) ether, 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate and diethylene glycol monobutyl ether acetate It is preferable that 1 type or 2 types or more selected from the group which consists of is included.

  As a result, the state of dissolution of the graft copolymer in the color filter ink can be made more uniform, and the discharge stability of the color filter ink becomes particularly excellent, and the manufactured color filter is used. The contrast ratio and brightness of the displayed image can be made particularly excellent. Further, when the color filter ink contains a pigment as a colorant, the dispersion stability of the pigment particles in the color filter ink can be made particularly excellent. Even when a relatively large amount of a colorant, a resin material, or the like is contained in the color filter ink, the change in the physical properties of the color filter ink is relatively small. In addition, when the liquid medium is composed of the above-described compound, in the color filter manufacturing method as described later, the color filter ink is more reliably spread throughout the cell. Can do.

  Among the above, when the liquid medium contains diethylene glycol monobutyl ether acetate, the viscosity of the color filter ink can be made particularly low, and the discharge stability of the color filter ink droplets is particularly excellent. Can be. In addition, since the color filter ink spreads quickly and everywhere on the substrate, the uniformity of the thickness of the colored portion to be formed can be increased, and color reproducibility and depolarization (contrast ratio) can be achieved. Can be made particularly excellent. Moreover, when a liquid medium contains diethylene glycol monobutyl ether acetate, the solubility to the liquid medium of water can be made moderate. For this reason, the liquid medium constituting the color filter ink can reliably prevent moisture absorption from the outside. Further, even when water is mixed into the color filter ink flow path or the like of the droplet discharge device, the water can be suitably dissolved and removed. As a result, the discharge stability of the color filter ink droplets from the droplet discharge head (for example, the uniformity of the droplet discharge amount) can be made particularly excellent over a longer period of time.

  In addition, among the above, when the liquid medium contains bis (2-butoxyethyl) ether and 1,3-butylene glycol diacetate, the color filter ink becomes very difficult to dry in the vicinity of the nozzle, and the ink is applied. Occurrence of flight bends in the process is more effectively suppressed. In addition, in the flushing process that is performed to periodically discharge a small amount of color filter ink to prevent nozzle clogging, it is possible to prevent the color filter ink from drying near the nozzle while moving the head over a long distance. A discarded area such as a dummy pixel provided is unnecessary. In addition, since the color filter ink is difficult to dry, deterioration, aggregation, and segregation of components such as a colorant and a resin material can be more reliably prevented.

  In particular, when the liquid medium contains 1,3-butylene glycol diacetate, the solubility of water in the liquid medium can be made appropriate. For this reason, the liquid medium constituting the color filter ink surely prevents the absorption of excessive moisture from the outside, while some moisture is inside the color filter ink flow path of the droplet discharge device. Even when it is mixed, it is possible to move in the flow path while maintaining dispersion stability and fluidity by suitably dissolving water.

  The boiling point of the liquid medium under atmospheric pressure (1 atm) is preferably 160 ° C. or higher and 300 ° C. or lower, more preferably 180 ° C. or higher and 290 ° C. or lower, and 200 ° C. or higher and 280 ° C. or lower. Further preferred. When the boiling point of the liquid medium under atmospheric pressure is a value within the above range, clogging or the like in the droplet discharge head that discharges the color filter ink can be more effectively prevented, and the productivity of the color filter is improved. Can be made particularly excellent.

  The vapor pressure at 25 ° C. of the liquid medium is preferably 0.7 mmHg or less, and more preferably 0.1 mmHg or less. When the vapor pressure of the liquid medium is within the above range, it is possible to more effectively prevent clogging and the like in the droplet discharge head that discharges the color filter ink, and the color filter productivity is particularly excellent. Can be.

  The content of the liquid medium in the color filter ink is preferably 50% by weight to 98% by weight, more preferably 70% by weight to 95% by weight, and more preferably 80% by weight to 93% by weight. More preferably, it is as follows. When the content of the liquid medium is a value within the above range, the color filter ink is excellent in the discharge property from the droplet discharge head, and the manufactured color filter has excellent durability. can do. Further, a sufficient color density can be secured in the manufactured color filter.

<Dispersant>
The color filter ink may contain a dispersant. Thereby, for example, even when the color filter ink contains a pigment having low dispersibility, the dispersion stability of the pigment can be made excellent, and the storage stability of the color filter ink is excellent. Can be.

Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl Polyoxyethylene alkyl phenyl ethers such as phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; polyethyleneimines In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by Tochem Products), Mega Pack (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (above, Asahi Glass Co., Ltd.), Disperbyk (Bicchemy Japan Co., Ltd.), Sol Sparse 3000 , 5000, 11200, 12000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 22000, 24000SC, 24000GR (manufactured by Nippon Lubrizol Co., Ltd.).
The content of the dispersant in the color filter ink is preferably from 0.5% by weight to 15% by weight, and more preferably from 0.5% by weight to 8% by weight.

<Other ingredients>
The color filter ink may contain various other components as required. Examples of such components (other additives) include various crosslinking agents; onium salts such as diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts, and benzothiazolium salts. Photoacid generators such as diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts; various polymerization initiators; acid crosslinking agents; sensitizers; light stabilizers; Adhesion improver; Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives; Fillers such as glass and alumina; Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ether and polyfluoroalkyl acrylate; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Lutris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxy Adhesion promoters such as silane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol Antioxidants such as 2- (3- UV absorbers such as -butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; aggregation inhibitors such as sodium polyacrylate; methanol, ethanol, i-propanol, n-butanol, glycerin Inkjet ejection performance stabilizers such as: Ftop EF301, EF303, EF352 (above, Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F172, F173, F178K (above, Dainippon Ink & Chemicals, Inc.), FLORAD FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103 SC-104, SC-105, SC-106 (hereinafter Asahi Glass Co., Ltd.), KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and the like.

  As the crosslinking agent, for example, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid, polyfunctional epoxy monomer, polyfunctional acrylic monomer, polyfunctional vinyl ether monomer, polyfunctional oxetane monomer and the like can be used. Specific examples of polycarboxylic anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbaric anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; Fats such as 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride Polyhydric carboxylic acid dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tristrimitate Examples of the acid anhydrides include aromatic polycarboxylic anhydrides. Masui. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably. Specific examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid; hexahydrophthalic acid, 1,2-cyclohexane Aliphatic polycarboxylic acids such as dicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid and cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5 , 8-Naphthalenetetracarboxylic acid, benzophenonetetracarboxylic acid, and other aromatic polyvalent carboxylic acids, among which aromatic polyvalent carboxylic acids are preferred. Specific examples of the polyfunctional epoxy monomer include Daicel Chemical Industries, Ltd., trade name Celoxide 2021, Daicel Chemical Industries, Ltd., trade name Epolide GT401, Daicel Chemical Industries, Ltd., trade name Epolide PB3600, and Bisphenol A. , Hydrogenated bisphenol A, triglycidyl isocyanurate, and the like. Specific examples of the polyfunctional acrylic monomer include pentaerythritol ethoxytetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxytriacrylate, dipentaerythritol. Examples include hexaacrylate trimethallyl isocyanurate and triallyl isocyanurate. Specific examples of the polyfunctional vinyl ether monomer include 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and triethylene. Examples include glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and the like. Specific examples of the polyfunctional oxetane monomer include xylylene oxetane, biphenyl type oxetane, novolak type oxetane and the like.

  The thermal acid generator is a component that generates an acid by heating, and among them, a sulfonium salt and a benzothiazolium salt are particularly preferable. As more specific examples of thermal acid generators, as trade names, Sun-Aid SI-45, Same as left SI-47, Same as left SI-60, Same as left SI-60L, Same as left SI-80, Same as left SI-80L, Same as left SI- 100, same left SI-100L, same left SI-145, same left SI-150, same left SI-160, same left SI-110L, same left SI-180L (above, Sanshin Chemical Co., Ltd., product name), CI-2921, CI -2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (Nippon Soda Co., Ltd. product, trade name), CP-66, CP-77 (Asahi Denka Kogyo Co., Ltd. products) , Product name), FC-520 (product of 3M company, product name) and the like.

  The photoacid generator is a component that generates an acid by light, and more specific examples include, as trade names, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, US Union Carbide, trade name), Irgacure 261 (Ciba Specialty Chemicals, trade name), SP-150, SP-151, SP-170, Optmer SP-171 (above, manufactured by Asahi Denka Kogyo Co., Ltd.) , Product name), CG-24-61 (product name, manufactured by Ciba Specialty Chemicals Co., Ltd.), DAICATII (product name, manufactured by Daicel Chemical Industries, Ltd.), UVAC1591 (product name, manufactured by Daicel UCB Co., Ltd.) CI-2064, CI-2639, CI-2624, CI-2481, CI-2 34, CI-2855, CI-2823, CI-2758 (Nippon Soda Co., Ltd., trade name), PI-2074 (Rhone-Poulenc, trade name, pentafluorophenylborate toluylcumyl iodonium salt), FFC509 ( 3M company product, trade name), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (Midori Chemical Co., Ltd., product) Name), CD-1012 (trade name, manufactured by Sartomer, USA) and the like.

The viscosity at 25 ° C. of the color filter ink (viscosity measured using a vibration viscometer) is not particularly limited, but is preferably 4 mPa · s or more and 12 mPa · s or less, preferably 5 mPa · s or more and 11 mPa · s. The following is more preferable. When the viscosity of the color filter ink is within the above-mentioned range, in the droplet discharge by the ink jet method as described later, the droplet discharge is performed while the variation in the appropriate amount of the color filter ink to be discharged is particularly small. The occurrence of clogging in the head can be prevented more reliably. The viscosity of the color filter ink can be measured using, for example, a vibration viscometer, and can be performed in particular in accordance with JIS Z8809.
<Ink set for color filter>
The color filter ink as described above is used for manufacturing a color filter by an ink jet method. Since the color filter usually corresponds to full color display, it has a plurality of colored portions (usually, three RGB colors corresponding to the three primary colors of light). For forming the colored portions of the plurality of colors, a plurality of types of color filter inks of corresponding colors are used. That is, for the production of a color filter, an ink set (color filter ink set) including a plurality of color filter inks is used. In the present invention, in the production of the color filter, the color filter ink as described above may be used as long as it can be used for forming at least one colored portion, but it can be used for forming all types of colored portions. It is preferable. Thereby, the effects as described above are more remarkably exhibited, and the reliability of the manufactured color filter can be made particularly high.

"Color filter"
Next, an example of a color filter manufactured using the color filter ink (ink set) as described above will be described.
FIG. 1 is a cross-sectional view showing a preferred embodiment of the color filter of the present invention.
As shown in FIG. 1, the color filter 1 includes a substrate 11 and a colored portion 12 formed using the color filter ink described above. As the coloring portion 12, a first coloring portion 12A, a second coloring portion 12B, and a third coloring portion 12C having different colors are provided. A partition wall 13 is provided between the adjacent colored portions 12.

<Board>
The substrate 11 is a plate-like member having optical transparency, and has a function of holding the colored portion 12 and the partition wall 13.
The substrate 11 is preferably made of a substantially transparent material. Thereby, a clearer image can be formed by the light transmitted through the color filter 1.

  The substrate 11 is preferably excellent in heat resistance and mechanical strength. Thereby, for example, deformation due to heat applied during the manufacture of the color filter 1 can be reliably prevented. Examples of the constituent material of the substrate 11 that satisfies such conditions include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, norbornene-based ring-opening polymer, and hydrogenated products thereof.

<Coloring part>
The colored portion 12 is formed using the color filter ink (color filter ink set) as described above.
Since the colored portion 12 is formed using the color filter ink (color filter ink set) as described above, the occurrence of uneven color and uneven density is effectively prevented. In addition, an image excellent in contrast ratio and brightness can be suitably displayed. Further, with respect to the colored portion 12 of the same color, the characteristic difference (variation in density or the like) between the individual color filters 1 is small.
Each colored portion 12 is provided in a cell 14 which is a region surrounded by a partition wall 13 which will be described later.

The first colored portion 12A, the second colored portion 12B, and the third colored portion 12C are of different colors. For example, the first colored portion 12A can be a red filter region (R), the second colored portion 12B can be a green filter region (G), and the third colored portion 12C can be a blue filter region (B).
One set of colored portions 12A, 12B, and 12C of different colors constitutes one pixel. In the color filter 1, a predetermined number of colored portions 12 are arranged in the horizontal direction and the vertical direction. For example, when the color filter 1 is a high-definition color filter, 1366 × 768 pixels are arranged, and when the color filter 1 is a full high-definition color filter, 1920 × 1080 pixels are arranged. In the case of a super high vision color filter, 7680 × 4320 pixels are arranged. Note that the color filter 1 may be provided with a spare pixel outside the effective area, for example.

<Partition wall>
A partition wall (bank) 13 is provided between the adjacent colored portions 12. Thereby, it can prevent reliably that the adjacent coloring parts 12 will mix colors, As a result, a clear image can be displayed reliably.
The partition wall 13 may be made of a transparent material, but is preferably made of a light-shielding material. Thereby, an image with excellent contrast can be displayed. The color of the partition wall (light shielding part) 13 is not particularly limited, but is preferably black. Thereby, the contrast of the displayed image can be made particularly excellent.

  The height of the partition wall 13 is not particularly limited, but is preferably substantially the same as the film thickness of the colored portion 12. Thereby, the color mixture between the adjacent coloring parts 12 can be prevented reliably. The specific thickness of the partition wall 13 is preferably 0.1 μm or more and 10 μm or less, and more preferably 0.5 μm or more and 3.5 μm or less. As a result, color mixing between the adjacent colored portions 12 can be reliably prevented, and the viewing angle characteristics of the image display device and electronic apparatus including the color filter 1 can be improved.

  The partition wall 13 may be made of any material, but for example, is preferably made mainly of a resin material. Thereby, the partition wall 13 can be easily formed as having a desired shape by a method as described later. Moreover, when the partition 13 has a function as a light-shielding part, it may include a light-absorbing material such as carbon black as a constituent material.

《Color filter manufacturing method》
Next, an example of a method for manufacturing the color filter 1 as described above will be described.
FIG. 2 is a cross-sectional view illustrating a method for manufacturing a color filter, and FIG. 3 is a perspective view illustrating a droplet discharge device used for manufacturing the color filter.
As shown in FIG. 2, in this embodiment, a substrate preparation step (1a) for preparing a substrate 11, a partition formation step (1b, 1c) for forming a partition 13 on the substrate 11, and a color filter by an ink jet method. An ink application step (1d) for applying the ink 2 to the region surrounded by the partition wall 13, and removing the liquid medium from the color filter ink 2 and curing the resin material to form a solid colored portion 12 Part forming step (1e).

<Board preparation process>
First, the substrate 11 is prepared (1a). The substrate 11 prepared in this step is preferably subjected to a cleaning process. In addition, the substrate 11 prepared in this step has been subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, and the like. Also good.

<Partition forming process>
Next, the radiation-sensitive composition for forming the partition walls of the substrate 11 is applied to almost the entire one surface of the substrate 11 to form the coating film 3 (1b). In addition, after giving a radiation sensitive composition on the board | substrate 11, you may perform a prebaking process as needed.
Then, the partition 13 is formed by performing a post-exposure baking process (PEB) by irradiating with a radiation through a photomask, and further performing a developing process using an alkaline developer (1c).

  Moreover, you may perform a liquid-repellent process with respect to the coating film 3 before image development processing. For example, before the development treatment, a fluororesin may be applied to the coating film 3 by a stamp method or the like, and fluorine is doped on the surface of the coating film 3 (radiation sensitive composition) by plasma polymerization treatment. Also good. By performing such a treatment, only the bank surface (upper surface in the drawing, the portion excluding the inner wall surface) is made liquid repellent, contributing to the flattening of the surface of the colored portion 12 formed in a later step. Further, a fluororesin having a light specific gravity may be added to the radiation-sensitive composition so as to be oriented only on the surface.

<Ink application process>
Next, the color filter ink 2 is applied to the cell 14 surrounded by the partition wall 13 by an inkjet method (1d).
This step is performed using a plurality of types of color filter inks 2 corresponding to the plurality of colored portions 12 to be formed. At this time, since the partition wall 13 is provided, it is reliably prevented that two or more kinds of color filter inks 2 are mixed.
The color filter ink 2 is discharged by using a droplet discharge device as shown in FIG.

  As shown in FIG. 3, the droplet discharge device 100 used in this step is supplied with the color filter ink 2 from the tank 101 that holds the color filter ink 2, the tube 110, and the tube 110. A discharge scanning unit 102. The ejection scanning unit 102 includes a droplet ejection unit 103 in which a plurality of droplet ejection heads (inkjet heads) are mounted on a carriage, and a first position control device 104 (moving unit) that controls the position of the droplet ejection unit 103. A stage 106 that holds the substrate 11 (hereinafter also simply referred to as “substrate 11”) on which the partition wall 13 is formed in the above-described process, and a second position control device 108 (moving means) that controls the position of the stage 106. The control means 112 is provided. The tank 101 and the plurality of droplet discharge heads in the droplet discharge means 103 are connected by a tube 110, and the color filter ink 2 is supplied from the tank 101 to each of the plurality of droplet discharge heads by compressed air. The

The first position control device 104 moves the droplet discharge means 103 along the X-axis direction and the Z-axis direction orthogonal to the X-axis direction in response to a signal from the control means 112. Further, the first position control device 104 also has a function of rotating the droplet discharge means 103 around an axis parallel to the Z axis. In the present embodiment, the Z-axis direction is a direction parallel to the vertical direction (that is, the direction of gravitational acceleration). The second position controller 108 moves the stage 106 along the Y-axis direction orthogonal to both the X-axis direction and the Z-axis direction in response to a signal from the control unit 112. Further, the second position control device 108 also has a function of rotating the stage 106 around an axis parallel to the Z axis.
The stage 106 has a plane parallel to both the X-axis direction and the Y-axis direction. The stage 106 is configured so that the substrate 11 having the cells 14 to which the color filter ink 2 is to be applied can be fixed or held on the plane.

As described above, the droplet discharge means 103 is moved in the X-axis direction by the first position control device 104. On the other hand, the stage 106 is moved in the Y-axis direction by the second position control device 108. That is, the first position control device 104 and the second position control device 108 change the relative position of the droplet discharge head with respect to the stage 106 (the substrate 11 held on the stage 106 and the droplet discharge means 103 are relatively Moving).
The control unit 112 is configured to receive ejection data representing a relative position where the color filter ink 2 is to be ejected from an external information processing apparatus.

Using the droplet discharge device 100 as described above, the color filter ink 2 corresponding to the colored portions 12 of the plurality of colors of the color filter 1 is applied to the cells 14. By using the apparatus as described above, the color filter ink 2 can be efficiently and selectively applied to the cells 14. In addition, as described above, the color filter ink 2 has excellent ejection stability, and even when droplets are ejected for a long period of time, the flight curve and the droplet ejection amount are low. Problems such as destabilization are extremely unlikely to occur. Accordingly, a plurality of types of ink used to form colored portions of different colors are mixed (mixed) or between a plurality of colored portions that are originally required to have the same color density. Problems such as the occurrence of variations in color density can be reliably prevented. In the illustrated configuration, the droplet discharge device 100 has only one tank 101 for holding the color filter ink 2, a tube 110, etc., but the color filter 1 has a plurality of these members. It may have a plurality of colors corresponding to the colored portion 12. In manufacturing 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 head may use a piezo element or an electrostatic actuator as a drive element. In addition, the droplet discharge head may be configured to use an electrothermal conversion element as a drive element and discharge the color filter ink by utilizing thermal expansion of a material by the electrothermal conversion element.

<Colored part forming step (curing step)>
Next, the liquid medium is removed from the color filter ink 2 in the cell 14 and the resin material is cured to form a solid colored portion 12 (1e). Thereby, the color filter 1 is obtained.
This step is usually performed by heating. By performing this step by heating, the adhesion of the colored portion 12 to be formed to the substrate 11 can be made particularly excellent. Moreover, it can prevent reliably that a liquid medium remains in the colored part 12 formed. As a result, the durability and reliability of the color filter 1 can be made particularly excellent. Also, the productivity of the color filter 1 is improved.

The heating temperature in this step (the temperature of the heated substrate 11) is not particularly limited, but is preferably 100 ° C. or higher and 280 ° C. or lower, and more preferably 110 ° C. or higher and 250 ° C. or lower. Thereby, the curing reaction of the resin material can be efficiently advanced while preventing the unintentional deterioration / decomposition of the constituent material of the colored portion 12, and the liquid medium can be suitably removed from the color filter ink 2.
Moreover, the heating time in this step is not particularly limited, but is preferably 30 minutes or longer and 190 minutes or shorter, and more preferably 40 minutes or longer and 130 minutes or shorter.

In this step, a plurality of heat treatments with different temperatures may be performed. Specifically, in this step, a first heat treatment that heats the substrate 11 at a relatively low temperature and a second heat treatment that heats the substrate 11 at a temperature higher than the first heat treatment are performed. May be.
As a result, unintentional deterioration / decomposition of the constituent material of the colored portion 12 is prevented, the productivity of the color filter 1 is improved, and the liquid medium remains in the formed colored portion 12. Can be prevented.

Further, in this step, by performing a first heat treatment for heating the substrate 11 at a relatively low temperature and a second heat treatment for heating the substrate 11 at a temperature higher than the first heat treatment, The flatness of the surface of the coloring part 12 can be made higher.
In such a case, by heating the substrate 11 at a relatively low temperature in the first heat treatment, the liquid medium is gently removed while preventing the convection of the color filter ink 2, and the color filter ink 2. The fluidity can be lost or reduced in a state in which the surface is flat. Moreover, the unintentional curing reaction of the resin material can be prevented by heating at a relatively low temperature.
In the second heat treatment, the liquid medium that could not be removed by the first heat treatment can be completely removed. In this step, when the color filter ink 2 is cured by reacting the resin material, the color filter ink 2 fixed in a flat state in the first heat treatment is efficiently cured in the shape. Can be made.

As described above, when the first heat treatment and the second heat treatment are performed in this step, the treatment temperature in the first heat treatment (the temperature of the heated substrate 11) is not particularly limited, but is 30 ° C. The temperature is preferably 100 ° C. or lower and more preferably 40 ° C. or higher and 80 ° C. or lower. Accordingly, the liquid medium can be suitably removed from the color filter ink 2 while reliably preventing convection of the color filter ink 2.
The time for the first heat treatment is not particularly limited, but is preferably 3 minutes or longer and 50 minutes or shorter, and more preferably 5 minutes or longer and 40 minutes or shorter.

The treatment temperature in the second heat treatment (the temperature of the heated substrate 11) is not particularly limited, but is preferably 120 ° C. or higher and 280 ° C. or lower, and more preferably 150 ° C. or higher and 250 ° C. or lower. preferable. Thereby, the liquid medium which could not be removed by the first heat treatment can be completely removed. In this step, when the color filter ink 2 is cured by reacting a resin material (curable resin material), the color filter ink 2 fixed in a flat state in the first heat treatment is used. It can be efficiently cured in that shape.
The time for the second heat treatment is not particularly limited, but is preferably 25 minutes or more and 150 minutes or less, and more preferably 30 minutes or more and 100 minutes or less.

Further, in this step, for example, treatment such as irradiation with active energy rays or placing the substrate 11 to which the color filter ink 2 is applied in a reduced pressure environment may be performed.
By irradiating the active energy rays, the curing reaction of the resin material can be efficiently advanced, or even when the heating temperature is relatively low, the curing reaction of the resin material can be reliably advanced, It is possible to obtain such an effect that the adverse effects on the substrate 11 and the like are more reliably prevented. As the active energy ray, light beams having various wavelengths, for example, ultraviolet rays, X-rays, g-rays, i-rays, excimer lasers, and the like can be used.

  Further, by placing the substrate 11 provided with the color filter ink 2 in a reduced pressure environment (depressurization treatment), the liquid medium can be removed more efficiently, or coloring in the pixels (cells). Even if the shape of the portion can be reliably made preferable, or even when the heating temperature is relatively low, the liquid medium can be reliably removed, and the substrate 11, the colored portion to be formed 12 and the like can be reliably prevented from being adversely affected. Moreover, a colored part can be more efficiently formed by using heat processing and pressure reduction processing together.

<Image display device>
Next, a preferred embodiment of a liquid crystal display device that is an image display device (electro-optical device) having the color filter 1 will be described.
FIG. 4 is a cross-sectional view showing a preferred embodiment of the liquid crystal display device. As shown in the figure, the liquid crystal display device 60 includes a color filter 1, a substrate (opposite substrate) 66 disposed on the side of the color filter 1 on which the colored portion 12 is provided, a color filter 1 and a substrate 66. And a polarizing plate 67 provided on the side opposite to the surface of the substrate 11 of the color filter 1 facing the liquid crystal layer 62 (lower side in FIG. 4). And a polarizing plate 68 provided on the side of the substrate 66 opposite to the surface facing the liquid crystal layer 62 (upper side in FIG. 4). A common electrode 61 is provided on the surface of the color filter 1 on which the colored portion 12 and the partition wall 13 are provided (the surface opposite to the surface of the colored portion 12 and the partition wall 13 facing the substrate 11). On the surface of the (opposite substrate) 66 facing the liquid crystal layer 62 and the color filter 1, pixel electrodes 65 are arranged in a matrix at positions corresponding to the colored portions 12 of the color filter 1. Further, an alignment film 64 is provided between the common electrode 61 and the liquid crystal layer 62, and an alignment film 63 is provided between the substrate 66 (pixel electrode 65) and the liquid crystal layer 62.

The substrate 66 is a substrate having optical transparency with respect to visible light, and is, for example, a glass substrate.
The common electrode 61 and the pixel electrode 65 are made of a material having optical transparency to visible light, and are made of, for example, ITO.
Although not shown in the drawing, a plurality of switching elements (for example, TFT: thin film transistor) are provided so as to correspond to each pixel electrode 65. For each pixel electrode 65 corresponding to each coloring portion 12, by controlling the voltage application state between the common electrode 61, in the region corresponding to each coloring portion 12 (each pixel electrode 65), Light transmittance can be controlled.

  In the liquid crystal display device 60, light emitted from a backlight (not shown) enters from the polarizing plate 68 side (upper side in FIG. 4). And the light which permeate | transmitted the liquid crystal layer 62 and entered into each coloring part 12 (12A, 12B, 12C) of the color filter 1 is polarized as light of the color corresponding to each coloring part 12 (12A, 12B, 12C). The light is emitted from the plate 67 (lower side in FIG. 4).

  As described above, since the colored portion 12 is formed using the color filter ink 2 (color filter ink set) of the present invention, the occurrence of uneven color and uneven density is effectively prevented, In addition to suppressing variation in characteristics between pixels, the pixel has excellent durability. As a result, in the liquid crystal display device 60, it is possible to stably display an image in which color unevenness, density unevenness, and the like at each part are suppressed. Moreover, since the coloring part 12 is formed using the color filter ink of the present invention, it is excellent in contrast ratio and brightness.

"Electronics"
An image display device (electro-optical device) 1000 such as a liquid crystal display device having the color filter 1 as described above can be used for display portions of various electronic devices.
FIG. 5 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.
In this figure, a personal computer 1100 includes a main body 1104 having a keyboard 1102 and a display unit 1106. The display unit 1106 is supported by the main body 1104 via a hinge structure so as to be rotatable. Yes.
In the personal computer 1100, the display unit 1106 includes an image display device 1000.
FIG. 6 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the present invention is applied.
In this figure, a cellular phone 1200 is provided with an image display device 1000 in a display unit, together with a plurality of operation buttons 1202, an earpiece 1204, and a mouthpiece 1206.

FIG. 7 is a perspective view showing the configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.
Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an imaging device such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.

On the back of the case (body) 1302 in the digital still camera 1300, an image display device 1000 is provided in the display unit, and is configured to display based on an imaging signal from the CCD, and a finder that displays a subject as an electronic image. Function as.
A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.

A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time 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 an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the input / output terminal 1314 for data communication as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

  The electronic apparatus of the present invention includes, for example, a television (for example, a liquid crystal television), a video camera, a viewfinder type, a monitor in addition to the above-described personal computer (mobile personal computer), mobile phone, and digital still camera. Direct-view video tape recorder, laptop personal computer, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, videophone, security TV monitor , Electronic binoculars, POS terminals, devices equipped with touch panels (for example, cash dispensers of financial institutions, automatic ticket vending machines), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographic display devices, ultrasonic diagnostic devices, endoscopy) Mirror display device), Group detector, various measuring instruments, gages (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors such, can be applied to the projection type display device such as a projector. In particular, televisions have a remarkable tendency to increase the size of display portions in recent years. However, in electronic devices having such a large display portion (for example, a display portion having a diagonal length of 80 cm or more), conventional color filter inks are used. When the color filter manufactured using the above is applied, problems such as uneven color and uneven density are particularly likely to occur. However, if the present invention is applied, such problems can be reliably prevented. That is, when applied to an electronic device having a large display unit as described above, the effects of the present invention are more remarkably exhibited.

As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, in the above-described embodiment, after applying the color filter ink corresponding to the colored portion of each color into the cell, the liquid medium is removed from the color filter ink of each color in the cell in a lump, and the resin Although it has been described that the material is cured, that is, the colored portion forming step (curing step) is performed only once, the ink application step and the colored portion forming step may be repeatedly performed corresponding to each color. Good.

  In addition, each unit constituting the color filter, the image display device, and the electronic device can be replaced with an arbitrary one that exhibits the same function, or another configuration can be added. For example, in the present invention, the color filter may be provided with a protective film covering the colored portion on the side of the colored portion opposite to the surface facing the substrate. Thereby, damage, deterioration, etc. of a coloring part can be prevented more effectively.

  In the above-described embodiment, the case where the color filter ink set includes the three types (three colors) of color filter inks corresponding to the three primary colors of light has been mainly described, but the color filter ink set is configured. The number and type (color) of the color filter ink to be performed are not limited to those described above. For example, in the present invention, the color filter ink set may include four or more color filter inks.

Next, specific examples of the present invention will be described.
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the weight average molecular weight (polystyrene conversion) and dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of the produced | generated copolymer were measured on condition of the following.

Device: Detector: RID-10A (Shimadzu Corporation)
Pump: LC-10ADVP (Shimadzu Corporation)
System controller: SCL-10AVP (Shimadzu Corporation)
Degasser: DGU-14A (Shimadzu Corporation)
Autoinjector: SIL-10AF (Shimadzu Corporation)
Column: Waters Styragel HR3, Styragel HR4, Styragel HR5, 3 in total Mobile phase: THF
Flow rate: 1mL / min
Temperature: Oven (40 ° C), RI (40 ° C)
Detector: RI POLARITY (+)
Injection volume: 50μL

[1] Synthesis of polymer (Synthesis Example 1)
An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 100 parts by weight of diethylene glycol monobutyl ether acetate was added and heated to 80 ° C. with stirring. Next, in the flask, 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, Showa Denko KK): 40 parts by weight, methacrylic acid : 30 parts by weight, epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Chemical Industries, Ltd.): 100 parts by weight, butyl acrylate macromonomer (trade name “AB-6”, Toagosei Co., Ltd.) Manufactured): 10 parts by weight, butyl acrylate: 10 parts by weight, a solution of diethylene glycol monobutyl ether acetate: 50 parts by weight was added dropwise over about 5 hours using a dropping pump. On the other hand, a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile): 30 parts by weight of diethylene glycol monobutyl ether acetate: 260 parts by weight of a solution was added for about 5 hours using another dropping pump. It was dripped in the flask. After completion of the dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 4 hours, and then cooled to room temperature to obtain a graft copolymer G1. The resulting graft copolymer G1 had a weight average molecular weight Mw of 12000 and a dispersity of 2.52.

(Synthesis Example 2)
The monomer composition is 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, Showa Denko KK): 40 parts by weight, methacrylic acid: 30 parts by weight, epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Chemical Industries, Ltd.): 100 parts by weight, styrenic macromonomer (trade name “AS-6”, manufactured by Toagosei Co., Ltd.) : Graft copolymer G2 was obtained in the same manner as in Synthesis Example 1 except that the content was changed to 10 parts by weight and styrene: 10 parts by weight. The resulting graft copolymer G2 had a weight average molecular weight Mw of 10500 and a dispersity of 2.29.

(Synthesis Example 3)
The monomer composition is 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, manufactured by Showa Denko KK): 20 parts by weight, methacrylic acid: 25 parts by weight, epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Chemical Industries, Ltd.): 100 parts by weight, butyl acrylate macromonomer (trade name “AB-6”, manufactured by Toagosei Co., Ltd.) ): 20 parts by weight, stearyl methacrylate: Except for changing to 40 parts by weight, the same operation as in Synthesis Example 1 was performed to obtain a graft copolymer G3. The resulting graft copolymer G3 had a weight average molecular weight Mw of 12400 and a dispersity of 2.50.

(Synthesis Example 4)
The monomer composition is 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, manufactured by Showa Denko KK): 20 parts by weight, methacrylic acid: 25 parts by weight, epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Chemical Industries, Ltd.): 100 parts by weight, styrenic macromonomer (trade name “AS-6”, manufactured by Toagosei Co., Ltd.) : 20 parts by weight, stearyl methacrylate: Except for changing to 40 parts by weight, the same operation as in Synthesis Example 1 was performed to obtain a graft copolymer G4. The resulting graft copolymer G4 had a weight average molecular weight Mw of 11800 and a dispersity of 2.31.

(Synthesis Example 5)
The monomer composition is 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, Showa Denko KK): 40 parts by weight, methacrylic acid: 30 parts by weight, epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Chemical Industries, Ltd.): 100 parts by weight, butyl acrylate: the same operation as in Synthesis Example 1 except for changing to 30 parts by weight To obtain a copolymer G′1. The produced copolymer G′1 had a weight average molecular weight Mw of 11900 and a dispersity of 2.55.

(Synthesis Example 6)
The monomer composition is 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, Showa Denko KK): 40 parts by weight, methacrylic acid: 30 parts by weight, epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Chemical Industries, Ltd.): 100 parts by weight, styrene: 30 parts by weight And a copolymer G′2 was obtained. The produced copolymer G′2 had a weight average molecular weight Mw of 11000 and a dispersity of 2.39.

(Synthesis Example 7)
The monomer composition is 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, Showa Denko KK): 25 parts by weight, methacrylic acid: 30 parts by weight, epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Chemical Industries, Ltd.): 100 parts by weight, stearyl methacrylate: the same operation as in Synthesis Example 1 except for changing to 40 parts by weight To obtain a copolymer G′3. The produced copolymer G′3 had a weight average molecular weight Mw of 12100 and a degree of dispersion of 2.43.

(Synthesis Example 8)
In a reaction vessel (flask) equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer, 314 parts by weight of diethylene glycol monobutyl ether acetate as a solvent (solvent) was added and heated to 90 ° C. Subsequently, 2,2′-azobis (isobutyronitrile) (AIBN) as a radical initiator: 20 parts by weight and diethylene glycol monobutyl ether acetate (solvent): 30 parts by weight were added to the flask. The monomer component (compound) represented by the formula (11) x1: 180 parts by weight, the monomer component (compound) x2 represented by the formula (12): 90 parts by weight, the formula (13) Monomer component (compound) x3: 15 parts by weight, monomer component (compound) x4: 15 parts by weight represented by the above formula (14), 2,2'-azobis (isobutyronitrile) ) (AIBN): A solution prepared by dissolving 50 parts by weight of diethylene glycol monobutyl ether acetate: 200 parts by weight was added dropwise using a dropping pump over 5 hours, and further aged for 4 hours. Then, it cooled to room temperature and obtained the polymer X1 as the polymer X represented by the said Formula (18) including the monomer components x1, x2, x3, x4.
(Synthesis Examples 9 to 15)
The same operation as in Synthesis Example 8 was performed except that the type of solvent (solvent) used in the synthesis of the polymer and the ratio of each component were adjusted and the composition of the polymer was changed as shown in Table 1. As a result, seven types of polymers X (polymers X2 to X8) were obtained.

(Synthesis Example 16)
In a reaction vessel (flask) equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer, 314 parts by weight of diethylene glycol monobutyl ether acetate as a solvent (solvent) was added and heated to 90 ° C. Subsequently, 2,2′-azobis (isobutyronitrile) (AIBN) as a radical initiator: 20 parts by weight and diethylene glycol monobutyl ether acetate (solvent): 30 parts by weight were added to the flask. , Monomer component (compound) y1: 200 parts by weight represented by formula (15), monomer component (compound) y2 represented by formula (16): 100 parts by weight, 2,2′- A solution prepared by dissolving 50 parts by weight of azobis (isobutyronitrile) (AIBN) in 200 parts by weight of diethylene glycol monobutyl ether acetate was added dropwise over 5 hours using a dropping pump, and further aged for 4 hours. Then, it cooled to room temperature and obtained the polymer Y1 as the polymer Y containing the monomer components y1 and y2 and represented by the said Formula (20).
(Synthesis Examples 17 and 18)
The same operation as in Synthesis Example 16 was performed except that the type of solvent (solvent) used in the synthesis of the polymer and the ratio of each component were adjusted and the composition of the polymer was changed as shown in Table 1. As a result, two types of polymers Y (polymers Y2 and Y3) were obtained.

  In Table 1, the ratio of each monomer component which comprises each resin component synthesize | combined in the synthesis examples 1-18, and the weight average molecular weight Mw of each resin component were shown collectively. In the table, "g1" represents 2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl methacrylate (= 2- (1-methylpropylideneaminooxycarbonylaminoethyl) methacrylate), and "g2 "" Indicates methacrylic acid, "g3" indicates epoxidized dicyclopentenyl acrylate, "g4" indicates a butyl acrylate macromonomer (trade name "AB-6", manufactured by Toagosei Co., Ltd.), and "g5" Represents butyl acrylate, “g6” represents a styrenic macromonomer (trade name “AS-6”, manufactured by Toagosei Co., Ltd.), “g7” represents styrene, and “g8” represents stearyl methacrylate. The polymers synthesized as described above all had a dispersity (weight average molecular weight Mw / number average molecular weight Mn) in the range of 1 or more and 3 or less.

[2] Preparation of color filter ink (color filter ink set) (Example 1)
Dispersic 166 as a dispersant, graft copolymer G1, and diethylene glycol monobutyl ether acetate functioning as a solvent for dissolving graft copolymer G1 (component of liquid medium in color filter ink) A graft copolymer G solution in which the graft copolymer G1 was dissolved in a solvent was obtained by adding it to a uniaxial mixer and stirring with a disper mill for 10 minutes (graft copolymer G solution preparation step). At this time, the rotation speed of the stirring blade of the stirrer was set to 2000 rpm.

Next, as described below, a pigment is added to the graft copolymer G solution obtained in the graft copolymer G solution preparation step, and inorganic beads are added in multiple stages using a stirrer (bead mill). A fine dispersion process for fine dispersion treatment was performed.
First, a pigment was added to the obtained graft copolymer G solution and stirred for 10 minutes. At this time, the rotation speed of the stirring blade of the bead mill (stirrer) was set to 2000 rpm. In addition, as the pigment, a halogenated phthalocyanine zinc complex represented by the above formula (8) (however, of 16 X in the molecule, 2 are hydrogen atoms, 4 are chlorine atoms, 10 are bromine) Atom) powder, a sulfonated pigment derivative (sub-pigment) powder having the chemical structure represented by the above formula (9), and C.I. I. A mixture with Pigment Yellow 150 was used.
Next, inorganic beads having an average particle size of 0.8 mm (first inorganic beads, manufactured by Zirconia, “Toray ceramic pulverized ball” (trade name), manufactured by Toray Industries, Inc.) are added and stirred at room temperature for 30 minutes. First-stage distributed processing (first processing) was performed. At this time, the rotation speed of the stirring blade of the bead mill (stirrer) was set to 2000 rpm.

Next, the inorganic beads (first inorganic beads) are removed by filtration using a filter (“PALL HDCII Membrane Filter”, manufactured by PALL), and then inorganic beads having a mean particle diameter of 0.1 mm (second Inorganic beads, made of zirconia, “Toray ceramic pulverized ball” (trade name), manufactured by Toray Industries, Inc.) were added, and the mixture was further stirred for 30 minutes to perform the second stage dispersion treatment (second treatment). At this time, the rotation speed of the stirring blade of the bead mill (stirrer) was set to 2000 rpm.
Thereafter, the inorganic beads (second inorganic beads) were removed by filtration using a filter (“PALL HDCII Membrane Filter” (trade name), manufactured by PALL) to obtain a pigment dispersion.

Next, to the pigment dispersion obtained as described above, a polymer X1, a polymer Y1, a leveling agent (Surfinol DF58, manufactured by Nissin Chemical Industry Co., Ltd.), an antioxidant (TINUVIN 152, Ciba Japan Co., Ltd.), diethylene glycol monobutyl ether acetate and diethylene glycol methyl ethyl ether as liquid media were added and mixed (dilution step). This step was performed by putting each of the above materials into a stirrer (uniaxial mixer) having an internal capacity of 400 cc and stirring for 10 minutes with a disper mill. At this time, the rotation speed of the stirring blade of the stirrer was set to 2000 rpm. As a result, the intended green color filter ink (G ink) was obtained.
In addition, the color filter ink (R ink) and the blue color filter ink (B ink) are the same as the green color filter ink except that the type of pigment and the amount of each component used are changed. Was prepared. As a result, an ink set for a color filter composed of three colors of R, G, and B was obtained.

(Examples 2 to 11)
A color filter ink (color filter ink set) was prepared in the same manner as in Example 1 except that the types and amounts of materials used for preparing the color filter ink were changed as shown in Tables 2 and 3. did.
(Comparative Examples 1-4)
A color filter ink (color filter ink set) was prepared in the same manner as in the above Example, except that the types and amounts of materials used for preparing the color filter ink were changed as shown in Table 3.

  Tables 2 and 3 collectively show the types and contents of the components of the color filter ink in each of the above Examples and Comparative Examples. In the table, the graft copolymers G1 to G4 are indicated by G1 to G4, the copolymers G′1 to G′3 are respectively indicated by G′1 to G′3, and resins as thermosetting acrylic resins A (trade name: ACRYDIC A-430-60, manufactured by DIC Corporation) is “A”, a zinc complex of a halogenated phthalocyanine represented by the above formula (8) (however, of 16 X in the molecule, 2 powders of hydrogen atoms, 4 chlorine atoms, and 10 bromine atoms) are referred to as “HPZC1”, C.I. I. Pigment Green 36 is “PG36”, a powder composed of a pigment derivative represented by the above formula (9) (one sulfo group in the molecule) is “SPD1”, and a pigment derivative represented by the following formula (10) (SPD2), a powder composed of (two sulfo groups in the molecule), C.I. I. Pigment Red 177 is “PR177”, C.I. I. Pigment Red 254 is "PR254", C.I. I. Pigment Red 177 and a pigment derivative represented by the formula (6) are referred to as “PR177D”, C.I. I. Pigment Red 254 and a pigment derivative represented by the formula (7) are mixed in “PR254D”, C.I. I. Pigment Blue 15: 6 is changed to “PB15: 6”, C.I. I. Pigment Yellow 150 is changed to “PY150”, C.I. I. Pigment Violet 23 is "PV23", Dispersic 111 (acid value: 50 KOHmg / g) is "DA1", Dispersic 166 (amine value: 115 KOHmg / g) is "DA2", Hinoact T8000E is "DA3", antioxidant (TINUVIN 152, manufactured by Ciba Japan Co., Ltd.) is “T152”, leveling agent (Surfinol DF58, manufactured by Nissin Chemical Industry Co., Ltd.) is “DF58”, diethylene glycol monobutyl ether acetate is “S1”, 1, 3 -Butylene glycol diacetate as "S2", 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate as "S3", bis (2-butoxyethyl) ether as "S4", and ethyl octoate as "S5", diethylene glycol mononormal “S6”, triethylene glycol mono-normal butyl ether “S7”, ethyl 3-ethoxypropionate “S8”, methylpropylene triglycol “S9”, diethylene glycol methyl ethyl ether “S10”, diethylene glycol dimethyl ether “ “S11”, diethylene glycol diethyl ether as “S12”, ethylene glycol monobutyl ether acetate as “S13”, dipropylene glycol dimethyl ether as “S14”, and 3-methoxybutyl acetate as “S15”.

  The C.I. used in each of the above examples. I. The content of the pigment derivative represented by the formula (6) in the mixture of Pigment Red 177 and the pigment derivative represented by the formula (6) was 0.1% by weight or more and 10% by weight or less. . The C.I. used in each of the above examples. I. The content of the pigment derivative represented by the formula (7) in the mixture of Pigment Red 254 and the pigment derivative represented by the formula (7) was 0.1% by weight or more and 10% by weight or less. . In addition, the viscosity at 25 ° C. of the color filter inks of each of the examples measured using a vibration viscometer in accordance with JIS Z8809 is in the range of 5 mPa · s to 11 mPa · s. Value.

[3] Storage stability evaluation of color filter ink (long-term stability evaluation)
The color filter inks of the respective Examples and Comparative Examples were left to stand for 70 days in an environment of 50 ° C., then visually observed and evaluated according to the following five-stage criteria.
A: No change from before heating is observed.
B: Almost no aggregation or sedimentation of pigment particles is observed.
C: Slight aggregation / precipitation of pigment particles is observed.
D: Aggregation / sedimentation of pigment particles is clearly observed.
E: Aggregation / sedimentation of pigment particles is noticeable.

[4] Droplet discharge stability evaluation (discharge stability evaluation)
Color filter inks obtained in the above Examples and Comparative Examples (color filter inks immediately after manufacture), and color filter inks left in a 55 ° C. environment for 28 days (colors left in a heated environment) The following tests were performed using the filter ink).

[4.1] Evaluation of accuracy of landing position Prepared are a droplet discharge device as shown in FIG. 3 installed in a chamber (thermal chamber) and color filter ink sets of the respective examples and comparative examples. With the drive waveform optimized, 3 million droplets (3,000,000 drops) are continuously discharged from each nozzle of the droplet discharge head for each color filter ink in an environment of 25 ° C. and 40% RH. It was. For the 3000000 droplets ejected from the specified nozzle near the center of the droplet ejection head, the average value of the deviation amounts d from the center aiming position of the center position of each landed droplet is obtained, and the following five steps Evaluation was performed according to the criteria of It can be said that the smaller the value is, the more effectively the occurrence of flight bending is prevented.

A: The average value of the shift amounts d is less than 0.5 μm.
B: The average value of the shift amount d is 0.5 μm or more and less than 1 μm.
C: The average value of the shift amount d is 1 μm or more and less than 3 μm.
D: The average value of the shift amount d is 3 μm or more and less than 5 μm.
E: The average value of the shift amounts d is 5 μm or more.

[4.2] Stability evaluation of droplet discharge amount Prepared are a droplet discharge device as shown in FIG. 3 installed in a chamber (thermal chamber), and an ink set for a color filter of each of the above examples and comparative examples. In the state where the driving waveform of the piezo element is optimized, each color filter ink is subjected to 3000000 droplets (3,000,000 droplets) from each nozzle of the droplet discharge head in an environment of 25 ° C. and 40% RH. Continuous discharge was performed. For the two specified nozzles on the left and right ends of the droplet discharge head, the total weight of the discharged droplets is obtained, and the absolute value ΔW [ng] of the difference between the average discharge amounts of the droplets discharged from the two nozzles is calculated. Asked. A ratio (ΔW / W _T ) of ΔW with respect to the target discharge amount W _T [ng] of the droplet was obtained and evaluated according to the following five-stage criteria. As the value of [Delta] W / W _T is small, it can be said that the greater the stability of the droplet discharge amount.

A: The value of ΔW / _{W T} is less than 0.026.
B: The value of ΔW / _{W T} is less than 0.026 than 0.270.
C: The value of ΔW / _{W T} is less than 0.270 than 0.470.
D: The value of ΔW / _{W T} is less than 0.470 than 0.790.
E: The value of ΔW / _{W T} is 0.790 or more.

[5] Production of color filter Color filter ink (color filter ink immediately after production) obtained in each of the above Examples and Comparative Examples, and color filter ink left in a 55 ° C. environment for 28 days ( A color filter was produced in the following manner using a color filter ink left in a heating environment.

First, a soda glass substrate (G5 size: 1100 × 1300 mm) on which a silica (SiO ₂ ) film for preventing elution of sodium ions was formed on both surfaces was prepared and subjected to a cleaning treatment.
Next, the radiation-sensitive composition for forming partition walls containing carbon black was applied to the entire surface of one of the cleaned substrates to form a coating film.

Next, prebaking was performed under the conditions of heating temperature: 110 ° C. and heating time: 120 seconds. Thereafter, radiation is applied through a photomask, post-exposure baking (PEB) is performed, and subsequently, atmospheric pressure in which a gas in which CF ₄ and He gas are mixed at a volume ratio of 1: 9 is introduced. Only on the surface of the coating film that has been pre-baked and post-exposure baked under the conditions of a plasma polymerization apparatus with an output of 600 W, a distance from the plasma generator to the table: 0.5 mm, and a processing table speed of 5 mm / s. Fluorine doped. Thereafter, development processing using an alkali developer was performed, and further, post-baking processing was performed to form partition walls. PEB was performed under the conditions of heating temperature: 110 ° C., heating time: 120 seconds, and radiation irradiation intensity: 150 mJ / cm ² . The development process was performed by, for example, a vibration dipping method. The development processing time was 60 seconds. The post-bake treatment was performed under the conditions of heating temperature: 150 ° C. and heating time: 5 minutes. The formed partition wall had a thickness of 2.0 μm.

  Next, using a droplet discharge device as shown in FIG. 3, the color filter ink was discharged into a cell as a region surrounded by a partition wall. At this time, three color filter inks were used so that the color filter inks of the respective colors were not mixed. In each cell, the color filter ink was applied in such an amount that the average thickness of the colored portion to be formed was 2.0 μm.

Thereafter, heat treatment was performed on a hot plate at 80 ° C. for 20 minutes (first heat treatment). Further, by performing heat treatment in an oven at 230 ° C. for 60 minutes (second heat treatment), colored portions of three colors (red (R), green (G), and blue (B)) were formed. Thereafter, washing with N-methyl-2-pyrrolidone and γ-butyrolactone was performed, and a color filter as shown in FIG. 1 was obtained.
Using the method as described above, the color filter ink of each example and each comparative example (the color filter ink immediately after manufacture and the color filter ink left in a heating environment) was used, respectively, and 8000. A sheet of color filter was manufactured.

[6] Evaluation of color filter The following evaluation was performed using each color filter obtained as described above.
[6.1] Flatness of the colored portion Each of the color filters manufactured using the color filter inks (color filter ink sets) of the respective Examples and Comparative Examples was manufactured on the 6000th sheet. A color filter was prepared.
About these color filters, the difference (DELTA) D of the maximum height and the minimum height of a coloring part was calculated | required using the stylus type roughness meter (the Tencor company make, P-15), and it evaluated in accordance with the following five steps | standards. .

A: ΔD is less than 0.14 μm.
B: ΔD is 0.14 μm or more and less than 0.23 μm.
C: ΔD is 0.23 μm or more and less than 0.40 μm.
D: ΔD is 0.40 μm or more and less than 0.50 μm.
E: ΔD is 0.50 μm or more.

[6.2] Evaluation of contrast ratio Among the color filters manufactured using the color filter inks (color filter ink sets) of the respective Examples and Comparative Examples, each color manufactured on the 8000th sheet Using the filter, a liquid crystal display device as shown in FIG. 4 was manufactured under the same conditions.
When these liquid crystal display devices are used, a red single color display, a green single color display, and a blue single color display are performed, and a single color display is not performed using a contrast tester (CT-1 manufactured by Aisaka Electric Co., Ltd.). The contrast ratio (CR) in comparison with was calculated and evaluated as follows.

In the case of a red single color display, evaluation was performed according to the following five-stage criteria.
A: CR is 2900 or more.
B: CR is 2400 or more and less than 2900.
C: CR is 2000 or more and less than 2400.
D: CR is 1700 or more and less than 2000.
E: CR is less than 1700.

In the case of green single color display, evaluation was performed according to the following four-stage criteria.
A: CR is 3800 or more.
B: CR is 3500 or more and less than 3800.
C: CR is 3200 or more and less than 3500.
D: CR is 2800 or more and less than 3200.
E: CR is less than 2800.

In the case of blue single color display, evaluation was performed according to the following four-stage criteria.
A: CR is 3100 or more.
B: CR is 2700 or more and less than 3100.
C: CR is 2400 or more and less than 2700.
D: CR is 2200 or more and less than 2400.
E: CR is less than 2200.

[6.3] Evaluation of lightness The liquid crystal display devices of the Examples and Comparative Examples manufactured in [6.2] were evaluated as shown below. The liquid crystal display device performs red single color display, green single color display, and blue single color display, and a chromaticity meter (manufactured by Minolta, CM-3700d, using a C light source as a light source) and three by the xyY color system. Stimulus values were determined, and the average of the Y values of the three colors of red light, green light, and blue light was used as the brightness Y of white light, and evaluated according to the following five-step criteria.

A: Brightness Y is 29.2 or more.
B: Brightness Y is 28.5 or more and less than 29.2.
C: Brightness Y is 27.9 or more and less than 28.5.
D: Brightness Y is 27.2 or more and less than 27.9.
E: Lightness Y is less than 27.2.

[6.4] Color unevenness and density unevenness About the liquid crystal display devices of the above-described Examples and Comparative Examples manufactured in [6.2], in the dark room, red single color display, green single color display, blue single color display Then, visual observation was performed in a state where white single color display was performed, and the occurrence of color unevenness and density unevenness (including those caused by light leakage) in each part was evaluated according to the following five criteria.

A: Color unevenness and density unevenness are not recognized at all.
B: Color unevenness and density unevenness are hardly recognized.
C: Color unevenness and density unevenness are slightly recognized.
D: Color unevenness and density unevenness are clearly recognized.
E: Color unevenness and density unevenness are noticeable.

[6.5] Characteristic difference among individuals Among the color filters manufactured using the color filter inks (color filter ink sets) of the respective examples and comparative examples, 1 to 20th sheet, In addition, a color filter manufactured for the 7980th to 7999th sheets is prepared, and in a dark room, a red single color display, a green single color display, a blue single color display, and a white single color display are performed. A spectrophotometer (manufactured by Otsuka Electronics Co., Ltd.) , MCPD3000). From the results, for each example and each comparative example, the color difference (in the Lab display system) that is the largest among the color filters manufactured in the 1st to 20th sheets and 7980 to 7999th sheets (total 40 color filters), respectively. The color difference ΔE) was determined and evaluated according to the following five-step criteria.

A: Color difference (ΔE) is less than 1.3.
B: Color difference (ΔE) is 1.3 or more and less than 2.3.
C: Color difference (ΔE) is 2.3 or more and less than 3.3.
D: Color difference (ΔE) is 3.3 or more and less than 4.3.
E: Color difference (ΔE) is 4.3 or more.

[6.6] Heat cycle test Among the color filters manufactured using the color filter inks (color filter ink sets) of the respective Examples and Comparative Examples, the heat filter was manufactured on the 7001 to 7010th sheets, respectively. Using a color filter, a liquid crystal display device as shown in FIG. 4 was manufactured under the same conditions.
Using these liquid crystal display devices, light leakage (white spots, bright spots) occurs when visual observation is performed in a dark room with red single color display, green single color display, and blue single color display. Confirmed that there is no.

Next, the color filter was removed from the liquid crystal display device.
Each removed color filter was placed in a 20 ° C. environment for 1.5 hours, then in a 75 ° C. environment in 2.5 hours, then in a 20 ° C. environment in 1.5 hours, and then −15 ° C. It was left in the environment for 2.5 hours. Thereafter, the ambient temperature was returned again to 20 ° C., which was set to one cycle (8 hours), and this cycle was repeated 30 times in total (total 240 hours).
Thereafter, using these color filters, a liquid crystal display device as shown in FIG. 4 was assembled again.
Using these liquid crystal display devices, visual observation is performed in a dark room with red single color display, green single color display, and blue single color display, and the occurrence of light leakage (white spots, bright spots) is observed. The evaluation was made according to the following 6-step criteria.

A: There is no color filter in which light leakage (white spots, bright spots) occurs.
B: Light leakage (white spots, bright spots) is observed in one or two color filters.
C: Light leakage (white spots, bright spots) is observed in 3 to 4 color filters.
D: Light leakage (white spots, bright spots) is observed in 5 to 7 color filters.
E: Light leakage (white spots, bright spots) is observed in 8 to 9 color filters.
F: Light leakage (white spots, bright spots) is observed in 10 color filters.

[7] Evaluation of heat resistance Each color filter ink was applied onto a 0.7 mm thick glass substrate by spin coating. The amount of ink applied was set so that the dry film thickness was 2.0 μm.
Next, these test pieces were heated at 220 ° C. for 1 hour in a clean oven.

Next, the color of the test piece subjected to the heat treatment at 220 ° C. was measured using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., MCPD3000).
Thereafter, these test pieces were further heated at 250 ° C. for 1 hour in a clean oven.
Here, the color of the test piece subjected to the heat treatment at 250 ° C. was measured using a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.).
From these results, the color difference (color difference ΔE in the Lab display system) before and after the heat treatment (heat treatment at 250 ° C.) was determined for each test piece and evaluated according to the following five-stage criteria.

A: Color difference (ΔE) is less than 0.9.
B: Color difference (ΔE) is 0.9 or more and less than 1.9.
C: Color difference (ΔE) is 1.9 or more and less than 2.5.
D: Color difference (ΔE) is 2.5 or more and less than 3.1.
E: Color difference (ΔE) is 3.1 or more.

[8] Evaluation of Colored Film Formed Using Color Filter Ink Using each color filter ink, a large number of test pieces (test plates) used for the following tests were prepared.
First, each ink was applied onto a glass substrate having a thickness of 0.7 mm by spin coating. The amount of ink applied was set so that the dry film thickness was 2.0 μm.
Next, pre-baking was performed on a 90 ° C. hot plate for 10 minutes. Thereafter, in a clean oven, post-baking was performed by heating at 200 ° C. for 30 minutes, and further post-baking was performed by heating at 240 ° C. for 30 minutes to obtain a test piece (test plate) having a colored film.

[8.1] Evaluation of solvent resistance The test pieces of the respective colors of the examples and comparative examples were measured using a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.).
Next, these test pieces were immersed in a solvent at 50 ° C. for 10 minutes, and thereafter, colorimetry was similarly performed using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., MCPD3000).
From these results, the color difference before and after the immersion of the solvent (color difference ΔE in the Lab display system) was determined for each test piece and evaluated according to the following four criteria.

A: Color difference (ΔE) is less than 2.5.
B: Color difference (ΔE) is 2.5 or more and less than 3.0.
C: Color difference (ΔE) is 3.0 or more and less than 3.5.
D: Color difference (ΔE) is 3.5 or more.
As a solvent, N-methyl-2-pyrrolidone (NMP) was used.

[8.2] Light resistance evaluation The test pieces of the respective colors of the examples and comparative examples were measured using a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.).
Next, in an environment of 40 ° C. and 60% RH, these test pieces were irradiated with light using a xenon fade meter, and then a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., MCPD3000) was used similarly. And measured the color. Irradiation conditions were 320 W / m ² × 180 hours. The black panel temperature at this time was 50 degreeC.
From these results, the color difference before and after light irradiation (color difference ΔE in the Lab display system) was determined for each test piece, and evaluated according to the following four criteria.
A: Color difference (ΔE) is less than 1.0.
B: Color difference (ΔE) is 1.0 or more and less than 2.8.
C: Color difference (ΔE) is 2.8 or more and less than 3.3.
D: Color difference (ΔE) is 3.3 or more.
These results are shown in Tables 4 and 5. In the table, the color filter ink immediately after production is indicated as “before heating”, and the color filter ink left in a 55 ° C. environment for 28 days (color filter ink left in a heating environment) is “after heating”. "

As is apparent from the table, excellent results were obtained with the present invention, whereas satisfactory results were not obtained with the comparative example.
Further, when a commercially available liquid crystal television was disassembled and the liquid crystal display device part was replaced with one manufactured as described above, and the same evaluation as described above was performed, the same result as above was obtained.

  DESCRIPTION OF SYMBOLS 1 ... Color filter 11 ... Board | substrate 12 ... Colored part 12A ... 1st colored part 12B ... 2nd colored part 12C ... 3rd colored part 13 ... Partition (bank, light-shielding part) 14 ... Cell 2 ... Color filter ink DESCRIPTION OF SYMBOLS 3 ... Coating film 60 ... Liquid crystal display device 61 ... Common electrode 62 ... Liquid crystal layer 63, 64 ... Orientation film 65 ... Pixel electrode 66 ... Substrate (opposite substrate) 67, 68 ... Polarizing plate 100 ... Droplet discharge device 101 ... Tank 102 DESCRIPTION OF SYMBOLS ... Discharge scanning part 103 ... Droplet discharge means 104 ... 1st position control apparatus (moving means) 106 ... Stage 108 ... 2nd position control apparatus (moving means) 110 ... Tube 112 ... Control means 1000 ... Image display apparatus 1100 ... Personal Computer 1102 ... Keyboard 1104 ... Main body 1106 ... Display unit 1200 ... Mobile phone 120 DESCRIPTION OF SYMBOLS 2 ... Operation button 1204 ... Earpiece 1206 ... Mouthpiece 1300 ... Digital still camera 1302 ... Case (body) 1304 ... Light receiving unit 1306 ... Shutter button 1308 ... Circuit board 1312 ... Video signal output terminal 1314 ... Input / output for data communication Terminal 1430 ... TV monitor 1440 ... Personal computer

Claims (10)

A color filter ink used in the production of an ink jet color filter,
A colorant, a resin material, and a liquid medium in which the colorant is dissolved and / or dispersed,
The resin material corresponds to the monomer unit corresponding to the vinyl monomer A having a blocked isocyanate group represented by the following formula (1) and the vinyl monomer B having a carboxyl group or an acid anhydride group. A monomer unit, a monomer unit corresponding to the vinyl monomer C having a 3- to 5-membered cyclic ether group, and a repeating unit represented by the following formula (2) or the following formula (3) as a main structural unit A monomer unit corresponding to a macromonomer D having a polymer chain and having a (meth) acryloyloxy group at the terminal of the polymer chain and having a weight average molecular weight of 500 to 30,000, and is derived from the macromonomer D A color filter ink comprising a graft copolymer in which the polymer chain portion constitutes a branch portion.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. R ³ is a residue of an isocyanate group blocking agent R ³ H. Indicate)

(In formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a phenyl group or a cyano group which may have a substituent. In formula (3), R ⁶ represents a hydrogen atom or Represents a methyl group, and R ⁷ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrocarbon group-substituted oxy group) The graft copolymer includes a monomer unit corresponding to the vinyl monomer A, a monomer unit corresponding to the vinyl monomer B, a monomer unit corresponding to the vinyl monomer C, and a monomer unit corresponding to the macromonomer D. In addition, a monomer unit corresponding to at least one monomer selected from the group consisting of a (meth) acrylic acid ester represented by the following formula (4), an aromatic vinyl compound, and a hydroxyl group-containing monomer The color filter ink according to claim 1, comprising:

(Wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrocarbon-substituted oxy group)   The color filter ink according to claim 1, comprising a halogenated phthalocyanine zinc complex as the colorant.   The liquid medium includes 1,3-butylene glycol diacetate, bis (2-butoxyethyl) ether, 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate and diethylene glycol monobutyl ether acetate. The color filter ink according to claim 1, comprising one or more selected from the group consisting of: In addition to the polymer M, the resin material is represented by a monomer component x1 represented by the following formula (11), a monomer component x3 represented by the following formula (13), and the following formula (14). The color filter ink according to any one of claims 1 to 4, comprising a polymer X containing a monomer component x4.

The color filter ink according to any one of claims 1 to 5, wherein the resin material includes, in addition to the polymer M, a polymer Y containing a monomer component y1 represented by the following formula (15). .

  A color filter manufactured using the color filter ink according to claim 1.   An image display device comprising the color filter according to claim 7.   The image display device according to claim 8, wherein the image display device is a liquid crystal panel.   An electronic apparatus comprising the image display device according to claim 8.

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