JP2006016545A - Colored resin composition, color filter and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored resin composition having good sensitivity and resolution even when a pigment is at a high concentration and suppressing lowering of voltage retention and defective display of the liquid crystal. <P>SOLUTION: The colored resin composition comprises (a) a colorant, (b) a nitrogen atom-noncontaining binder resin, (c) a nitrogen atom-containing dispersing agent, (d) a solvent and (e) a photopolymerization initiator system. The (b) contains a resin having a structure in which the epoxy group of an epoxy group-containing unsaturated compound is added to a carboxy group of a resin having the carboxy group and/or another specific resin and the (e) contains an oxime ester compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a colored resin composition, a color filter, and a liquid crystal display device. More specifically, the present invention relates to a colored resin composition that is excellent in sensitivity and resolution and prevents a decrease in voltage holding ratio of liquid crystal, a high-precision color filter, and a liquid crystal display device.

Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for producing color filters used in liquid crystal display devices and the like. From the viewpoint of spectral characteristics, durability, pattern shape and accuracy, a pigment dispersion method having excellent characteristics on average is most widely used.
Hereinafter, the outline of the pigment dispersion method will be described. Usually, first, a black matrix is formed on a transparent support such as a glass substrate using a metal light-shielding film such as chromium or chromium oxide. Next, for example, a colored resin composition (color resist) in which a red pigment is dispersed is applied to the entire surface by spin coating or the like, and exposed through a mask. When development is performed after exposure, red pixels are obtained. The same method is adopted for the blue and green pixels, and three color pixels are formed.

  Between each pixel, the black matrix part is concave, so the surface is covered with a protective film of transparent resin such as epoxy resin or acrylic resin for smoothing. In some cases, it is not provided. Further, a transparent conductive film such as an ITO film is formed on the protective film by sputtering or vacuum deposition. In recent years, a pigment dispersion method is often employed when forming a black matrix. Specifically, a black matrix is created by applying, exposing and developing a colored resin composition (black resist) in which a black pigment is dispersed.

The color filter obtained as described above is used in a liquid crystal display device as follows. That is, after forming an alignment film and spraying spacers on the alignment film, a liquid crystal cell is formed by bonding to the counter substrate, liquid crystal is injected into the formed liquid crystal cell, and the liquid crystal cell is connected to the counter electrode to be connected to the liquid crystal display device. To complete.
In recent years, the trend of technological innovation is rapid, and there is a strong demand for color liquid crystal display elements that can further widen the color reproducibility of the liquid crystal display elements and can express more vivid color images. If an attempt is made to improve the color purity of the color filter in order to realize a vivid color image, a large amount of pigment is required, which causes a decrease in the photosensitive characteristics of the color resist. That is, as the pigment concentration in each pixel increases, the light transmittance decreases. For example, (1) it is extremely difficult to make a difference in cross-linking density between the exposed portion and the unexposed portion, (2 ) The difference in cross-linking density in the film thickness direction occurs even in the exposed part. That is, even if it is sufficiently cured on the light-irradiated surface, it does not cure on the base surface. It has become.

  A method for improving sensitivity and resolution performance is known for a photosensitive resin having a certain light transmittance. For example, a photosensitive composition containing an initiator composed of a binder resin, a polyfunctional acrylic monomer, and a triazine compound is known as a coloring composition for a color filter in which a pigment is dispersed (see Patent Documents 1 to 4). In addition, it is also known that the initiator is bisimidazole in the same composition (see Patent Documents 5 to 6). However, in the case of the compositions disclosed therein, the polymerization inhibition by oxygen occurs when exposed in air. Therefore, practical sensitivity could not be obtained.

Further, a technique using a specific oxime ester compound as a photopolymerization initiator is known (see Patent Document 7), but a conventional initiator (for example, bisimidazole or triazine-based initiator) is simply used as the oxime compound. However, it was impossible to improve image characteristics required for a resist having a high pigment concentration, that is, sensitivity and resolution, or a decrease in voltage holding ratio described later.

  For the above reasons, in recent years, the colored resin composition is required to have a high transmittance and a high concentration, but in order to form a highly transparent color filter, it is necessary to increase the degree of dispersion of the coloring material, Nitrogen atom-containing dispersants having excellent dispersibility have been widely used. On the other hand, in order to form a color filter having a high transmittance and a high concentration, it is necessary to increase the concentration of the color material in the colored resin composition to be used. There was a need.

In addition, liquid crystal display devices are increasingly demanded for high-speed response due to the support for moving image display, and the cell gap between the color filter and the counter substrate tends to narrow, that is, the amount of liquid crystal per cell area is small. It has become.
When a large amount of the nitrogen atom-containing dispersant is contained in the colored resin composition, elution into the liquid crystal occurs via the ITO film after the liquid crystal cell is formed, and there is a problem that the voltage holding ratio of the liquid crystal is lowered. In addition, as the response speed increases, the amount of liquid crystal per cell area decreases as described above, and the voltage holding ratio further decreases. When the voltage holding ratio of the liquid crystal is lowered, it is said that display defects such as display unevenness and image sticking are caused (see, for example, Patent Documents 8 and 9), and particularly a large problem in a liquid crystal display device with high transmission, high density, and high speed response. It has become.

  In order to solve the problem of display unevenness, a method has been proposed in which a dispersant having a decomposition temperature higher by −20 ° C. or more than the temperature during the colored layer forming step is used as the dispersant contained in the colored resin composition. Then, as the decomposition temperature, when the colored resin composition containing the dispersant is heat-treated to form a colored layer, heating when the extracted amount of organic impurities when the colored layer is extracted with liquid crystal is 100 ppm. It is defined as temperature (see Patent Document 10).

However, when a nitrogen atom-containing dispersant is used, the voltage holding ratio is lowered by this method, and the problem of display unevenness sometimes increases.
Japanese Patent Laid-Open No. 1-152449 JP-A-1-254918 JP-A-2-153353 JP-A-2-804 JP-A-6-75372 JP-A-6-75373 JP 2000-80068 A JP 2000-292920 A Japanese Patent Laid-Open No. 2002-311228 JP 2000-171784 A

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a colored resin composition excellent in sensitivity and resolution even when a high concentration pigment is used. It is another object of the present invention to provide a colored resin composition that satisfies the requirements for high transmission and high density, and suppresses a decrease in voltage holding ratio of liquid crystal and a display defect caused by a material that is in direct and direct contact with the liquid crystal layer. . Another object of the present invention is to provide a high-quality color filter using the colored resin composition, and still another object of the present invention is a high-quality liquid crystal using the color filter substrate. It is to provide a display device.

As a result of intensive studies to solve the above problems, the inventors of the present invention include a binder resin having a specific structure, and a photopolymerization initiator having a specific structure, whereby a high-concentration pigment is obtained. It has been found that even if it is used, it is excellent in sensitivity and resolution, and further it is possible to prevent a decrease in voltage holding ratio of liquid crystal and a display defect, and the present invention has been completed.
That is, the first gist of the present invention is a photopolymerizability containing a) a color material, b) a nitrogen atom-free binder resin, c) a nitrogen atom-containing dispersant, d) a solvent, and e) a photopolymerization initiator system. A resin having a structure in which an epoxy group of an epoxy group-containing unsaturated compound is added to a carboxyl group of a resin having a carboxyl group and / or (A) an epoxy-containing (meth) acrylate 5 to 90 10% to 95% by mole of the other radical polymerizable compound that can be copolymerized with the component (B) (A), and 10% to 100% by mole of the epoxy group contained in the resulting copolymer ( C) a resin obtained by adding an unsaturated monobasic acid and adding (D) a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl group produced when the component (C) is added. And e) is oxime beauty treatment salon It consists in the colored resin composition characterized by containing a system compound.

  The second gist of the present invention resides in a color filter formed by using the above colored resin composition, and the third gist uses the above color filter. It exists in the liquid crystal display device characterized by forming.

  The colored resin composition of the present invention is excellent in sensitivity and resolution even when the pigment concentration is high, and it can form a high-quality color filter in order to prevent a decrease in the voltage holding ratio of the liquid crystal. In addition, the color filter and the liquid crystal display formed using such a colored resin composition are of high quality without display defects such as display unevenness and burn-in because the voltage holding ratio of the liquid crystal is prevented from lowering. .

[1] Constituent Components of Colored Resin Composition (Resist) First, constituent components of the colored resin composition of the present invention will be described. The colored resin composition (resist) of the present invention comprises a) a coloring material, b) a nitrogen atom-free binder resin, c) a nitrogen atom-containing dispersant, d) a solvent, and e) a photopolymerization initiator as essential components. If necessary, additives other than the above components may be blended. Hereinafter, each component will be described.
[1-1] a) Coloring material:
A color material means what colors the colored resin composition which concerns on this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. The structure includes organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can also be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 8
1, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 64,265,266,267,268,269,270,271,272,273,274,275,276 can be mentioned. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, preferably C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

Examples of green pigments include C.I. I. CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. Pigment Green 7 and 36.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, preferably C.I. I. Pigment oranges 38 and 71.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31,
32, 37, 39, 42, 44, 47, 49, 50. Of these, preferably C.I. I. Pigment violet 19 and 23, and more preferably C.I. I. Pigment Violet 23.

Examples of other pigments include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, and chromium oxide.
The above various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination. The average particle size of these pigments is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.

Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
In addition to the above, examples of phthalocyanine dyes include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  Moreover, when forming the resin black matrix of a color filter using a colored resin composition, a black color material can be used. The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, the average particle size is preferably 1 μm or less, preferably 0.5 μm or less.

Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.
Among the above black color materials, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

As products manufactured by Mitsubishi Chemical Corporation, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 3
2, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B etc. are mentioned.

The products made by Degussa include Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex85, Printex85, Printex85, Printex85, Printex85, Printex85, Printex85 PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, ColorBlack FW1Clock 2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black
S170 etc. are mentioned.

  Products manufactured by Cabot Corporation include: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL99R, REGA15R BLACK PEARLS 480, PEARLS 130, VULCAN XC72R, ELFTEX-8, and the like.

  The products manufactured by Colombian Carbon are: Raven11, Raven14, Raven15, Raven16, Raven22Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven10, Raven10, Raven10, V , RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 and the like.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  Furthermore, other pigments that can be used in combination are described in C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  The ratio of the coloring material to the total solid content in the colored resin composition is usually 1 to 70% by weight, preferably 10 to 70% by weight, and more preferably 20 to 60% by weight. When the ratio of the color material is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control when the liquid crystal cell is formed. On the other hand, if the ratio of the color material is too large, sufficient image formability may not be obtained. In the present invention, “total solid content” means all components other than the solvent components described later.

[1-2] b) Nitrogen atom-free binder resin:
In the present invention, b) a nitrogen atom-free binder resin is a resin having a structure in which an epoxy group of an epoxy group-containing unsaturated compound is added to a carboxyl group of a resin having a carboxyl group, and / or (A) an epoxy-containing ( 5) to 90 mol% of (meth) acrylate, 10 to 95 mol% of other radical polymerizable compound that can be copolymerized with the component (B) and (A), and 10 of the epoxy groups contained in the obtained copolymer. (C) Unsaturated monobasic acid is added to 100 mol%, and (D) polybasic acid anhydride is added to 10 to 100 mol% of the hydroxyl group produced when the component (C) is added. It is characterized by containing the resulting resin.

[1-2-1]
In the present invention, the nitrogen atom-free binder resin can be used alone or in combination with a resin having a structure obtained by adding an epoxy part of an epoxy group-containing unsaturated compound to a carboxyl group part of a resin having a carboxyl group. .
Although it does not specifically limit as resin which has a carboxyl group, Usually, it can obtain by superposing | polymerizing the polymerizable monomer which has a carboxyl group. Examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2-acryloyloxy. Ethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxy Propyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl hydrophthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl Maleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxy In addition to butyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- (meth) acryloyloxybutyl maleic acid, (meth) acrylic acid -Monomers added with lactones such as caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, hydroxyalkyl (meth) acrylate, (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) malein And monomers added with an acid (anhydride) such as an acid. Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable. A plurality of these may be used.

Moreover, the resin which has a carboxyl group may copolymerize the other polymerizable monomer which does not have a carboxyl group with the polymerizable monomer which has said carboxyl group. Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (Meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styrene and its derivatives, α-methylstyrene, polymethyl (meth) acrylate Over preparative macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomer, polypropylene glycol macromonomer, macromonomer such as polycaprolactone macro monomers.

  Among the above, preferably, styrene, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate. These may be used in combination.

In the present specification, “(meth) acryl-”, “(meth) acrylate” and the like mean “acryl- or methacryl-”, “acrylate or methacrylate”, for example, “(meth) acryl”. "Acid" shall mean "acrylic acid or methacrylic acid".
The resin having a carboxyl group preferably further has a hydroxyl group from the viewpoint of dispersibility of the pigment. In particular, a copolymer containing 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate as a copolymerization component. Coalescence is preferred.

  Specifically, polymerizable monomers not containing a hydroxyl group such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmaleimide, and 2- Examples thereof include a copolymer of a polymerizable monomer containing a hydroxyl group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic acid.

  Other specific examples of preferred resins include methyl (meth) acrylate, benzyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, ) Acrylic acid ester / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, styrene / α-methylstyrene / (meth) acrylic acid copolymer, and the like.

  The acid value of the “resin having a carboxyl group” in the present invention is usually 30 to 500 KOH mg / g, preferably 40 to 350 KOH mg / g, and more preferably 50 to 300 KOH mg / g. Moreover, when adding the compound which has an ethylenically unsaturated group and an epoxy group, the introduction | transduction rate to the carboxyl group of "resin which has a carboxyl group" is 10-90 mol% normally, Preferably it is 30-80 mol%. If the introduction rate is too small, the side chain having an ethylenically unsaturated double bond cannot be sufficiently introduced, so that there is a tendency that sufficient dispersion performance cannot be obtained. The solubility of the composition tends to deteriorate.

Moreover, the weight average molecular weight of polystyrene conversion measured by GPC of resin which has a carboxyl group in this invention is 2000-100000 normally, Preferably it is 3000-80000, More preferably, it is 4000-50000. When the weight average molecular weight is too small, the liquid stability is poor, and when it is too large, the solubility of the colored resin composition tends to deteriorate.
An epoxy group-containing unsaturated compound is a compound having an ethylenically unsaturated group and an epoxy group in one molecule.

  Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, allyl glycidyl ether, α-ethyl acrylate glycidyl, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl. An acyclic epoxy group-containing unsaturated compound such as ether may be mentioned, but an alicyclic epoxy group-containing unsaturated compound is preferable from the viewpoint of heat resistance and dispersibility.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. The ethylenically unsaturated bond is preferably derived from a (meth) acryloyl group. Specific examples of suitable alicyclic epoxy group-containing ethylenically unsaturated compounds include (3,4-epoxycyclohexyl) methyl (meth) acrylate and the following chemical formulas (1) to (11). And the like.

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group.)

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group, and R ^{2 ′} represents an alkylene group having 1 to 10 carbon atoms.)

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group, and R ^{2 ′} represents an alkylene group having 1 to 10 carbon atoms.)

Wherein R ^{1 ′} is a hydrogen atom or a methyl group, R ^{2 ′} is an alkylene group having 1 to 10 carbon atoms, R ^3
' Represents a hydrocarbon group having 1 to 10 carbon atoms, and k represents 0 or an integer of 1 to 10. )

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group, and R ^{2 ′} represents an alkylene group having 1 to 10 carbon atoms.)

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group, and R ^{2 ′} represents an alkylene group having 1 to 10 carbon atoms.)

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group, and R ^{2 ′} represents an alkylene group having 1 to 10 carbon atoms.)

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group, and R ^{2 ′} represents an alkylene group having 1 to 10 carbon atoms.)

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group, and R ^{2 ′} represents an alkylene group having 1 to 10 carbon atoms.)

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group.)

(In the formula, R ^{1 ′} represents a hydrogen atom or a methyl group.)
In the above formulas (2) to (9), R ^{2 ′} is preferably methylene, ethylene or propylene. In formula (4), R ^{3 ′} is preferably 3 to 6 carbon atoms, and k is preferably 2 to 8. .
Among the above compounds, 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable. These epoxy group-containing unsaturated compounds can be used in combination of two or more.

In the present invention, a resin having a structure obtained by adding an epoxy group of an epoxy group-containing unsaturated compound to a carboxyl group of a resin having a carboxyl group does not necessarily include an epoxy group-containing unsaturated compound in a resin actually having a carboxyl group. It is not necessary to make it react, and as a result, what is necessary is just to have said structure.
As a method of reacting an epoxy group-containing unsaturated compound with a carboxyl group of a resin having a carboxyl group, a known method can be used.

  For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are mixed with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium. Carboxyl group of resin having carboxyl group by reaction in organic solvent at reaction temperature of 50 to 150 ° C. for several hours to several tens of hours in the presence of catalyst such as quaternary ammonium salt such as chloride, pyridine, triphenylphosphine, etc. An epoxy compound can be introduced into the.

  The polystyrene-reduced weight average molecular weight (Mw) measured by GPC of the binder resin produced as described above is usually 3000 to 120,000, preferably 4000 to 90000, and more preferably 5000 to 60000. When the weight average molecular weight is too small, the liquid stability is poor, and when it is too large, the solubility of the colored resin composition tends to deteriorate. The proportion of the binder resin in the total solid content of the colored resin composition is usually 0 to 80% by weight, preferably 20 to 70% by weight. Moreover, as a ratio with respect to a color material, it is 0-300 weight% normally, Preferably it is 30-200 weight%, More preferably, it is 40-100 weight%.

[1-2-2]
In the present invention, the following binder resins can be used alone or in combination as a binder resin not containing nitrogen atoms other than those described above. That is, epoxy group-containing (meth) acrylate (hereinafter abbreviated as component (A)) 5 to 90 mol%, other radical polymerizable compound copolymerizable with component (A) (hereinafter abbreviated as component (B)). 10) to 95 mol% is copolymerized, and an unsaturated monobasic acid (hereinafter abbreviated as component (C)) is added to 10 to 100 mol% of the epoxy group contained in the obtained copolymer, It is a resin obtained by adding a polybasic acid anhydride (hereinafter abbreviated as component (D)) to 10 to 100 mol% of the hydroxyl group produced when component (C) is added. Hereinafter, the binder resin will be described. Examples of the component (A): epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4- Epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether and the like can be mentioned. Among these, glycidyl (meth) acrylate is preferable.

Content of a component (A) becomes like this. Preferably it is 20-80 mol%, More preferably, it is 30-70 mol%. When the amount is too large, other components may be reduced, and heat resistance and strength may be lowered. When the amount is too small, the addition amount of the polymerizable component and the alkali-soluble component becomes insufficient.
Component (B): Other radical polymerizable compounds that can be copolymerized with component (A) are preferably mono (meth) acrylates having a structure represented by the following chemical formula (12).

In the formula (12), R ^{4 ′ to} R ^{9 ′} each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and R ^{10 ′} and R ^{11 ′} each represent , A hydrogen atom, or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or may be linked to form a ring. The ring formed by linking R ^{10 ′} and R ^{11 ′} is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

  In the present invention, mono (meth) acrylate having a structure represented by the following chemical formula (13), (14) or (15) is particularly preferable.

  As the mono (meth) acrylate having the structure represented by the chemical formula (12), various known ones can be used, and those represented by the following chemical formula (16) are particularly preferable.

(In the formula (16), R ^{12 ′} represents a hydrogen atom or a methyl group, and R ^{13 ′} represents the chemical formula (12)).
The content of the mono (meth) acrylate having the structure of the chemical formula (12) in the copolymerization monomer is usually 10 to 90 mol%, preferably 10 to 70 mol%, more preferably 15 to 50 mol%. . By having such a structure, heat resistance and strength can be increased.

  Other radical polymerizable compounds are not particularly limited, but specific examples thereof include styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene; butadiene, 2, Dienes such as 3-dimethylbutadiene, isoprene, chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) Acrylic acid-n-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meta ) Hexyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) ) Dodecyl acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, Allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate , Salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate , (Meta) Cresyl acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro- (meth) acrylate (Meth) acrylates such as iso-propyl, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate Vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconate;

In order to impart more excellent heat resistance and strength, it is effective to use at least one selected from the group of styrene and benzyl (meth) acrylate as the component (B).
Content of the component (B) in a copolymerization monomer becomes like this. Preferably it is 20-80 mol%, More preferably, it is 30-70 mol%. When the component (B) is too much, the proportion of the component (A) is decreased, the addition amount of the polymerizable component and the alkali-soluble component is insufficient, and when the component (B) is too small, the heat resistance and strength are low. descend.

  Component (C): Unsaturated monobasic acid includes, for example, unsaturated carboxylic acid having an ethylenically unsaturated double bond, and specific examples thereof include acrylic acid, methacrylic acid, crotonic acid, o- , M-, p-vinylbenzoic acid, monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of (meth) acrylic acid. Among these, acrylic acid or methacrylic acid is preferable.

The addition rate of component (C) is preferably 30 to 100 mol%, more preferably 50 to 100 mol%. When the addition rate is too small, there is a concern about adverse effects due to residual epoxy groups such as stability over time.
Said component (D): Polybasic acid anhydride is used in order to make the binder resin in this invention alkali-soluble. As the component (D), known compounds can be used, and dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride and the like. And polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride or succinic anhydride is preferred.

The addition ratio of component (D) is preferably 20 to 90 mol%, more preferably 30 to 80 mol%. When the addition ratio of component (D) is too large, the residual film ratio during development may be reduced, and when it is too small, the solubility becomes insufficient.
A known solution polymerization method is applied to the copolymerization reaction between the component (A) and the component (B). The solvent to be used is not limited as long as it is inert to radical polymerization, and a normal organic solvent can be used. Specific examples thereof include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate; propylene Acetic esters such as glycol monoalkyl ether acetates; Dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, and butyl carbitol; Triethylene glycol dialkyl ethers Class: Propylene glycol dialkyl ether Dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane Petroleum petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more.

The usage-amount of a solvent is 30-1000 weight part normally with respect to 100 weight part of binder resin, Preferably it is 50-800 weight part. Outside this range, it is difficult to control the molecular weight.
As the radical polymerization initiator, a normal organic peroxide catalyst or an azo compound can be used. Examples include various ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. An azo compound is also effective.

Specific examples of the radical polymerization initiator include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy. 2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-Butylperoxy) hexyl 3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxy Dicarbonate Diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1 -Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarbonamide and the like. A radical polymerization initiator having an appropriate half-life is selected according to the polymerization temperature.

The usage-amount of a radical polymerization initiator is 0.5-20 weight part normally with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.
The polymerization method may be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or performing the polymerization reaction in the solvent that has been heated and stirred. The monomer added with may be added dropwise. Further, the monomer may be dropped while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions are appropriately selected according to the target molecular weight. The reaction temperature is usually 70 to 150 ° C., preferably 80 to 130 ° C., and the reaction time is usually 2 to 20 hours, preferably 3 to 10 hours.

As a method of adding the polybasic acid (D) after adding the unsaturated monobasic acid (C) to the copolymer, a known method can be adopted.
In the present invention, in order to further improve the photosensitivity, after addition of component (D): polybasic acid anhydride, a part of the generated carboxyl group has glycidyl (meth) acrylate or a polymerizable unsaturated group. In order to add a glycidyl ether compound or improve developability, a glycidyl ether compound having no polymerizable unsaturated group can be added to a part of the generated carboxyl group after the addition of the component (D). Both of these may be used in combination.

  Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Kasei Kogyo Co., Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.

  The polystyrene-reduced weight average molecular weight (Mw) measured by GPC of the binder resin produced as described above is usually 3000 to 100000, preferably 5000 to 50000. When the weight average molecular weight is less than 3000, the heat resistance and film strength are poor, and when it exceeds 100,000, the solubility in the developer is insufficient. The molecular weight distribution (Mw / Mn) is usually 2.0 to 5.0. The proportion of the binder resin in the total solid content of the colored resin composition is usually 0 to 70% by weight, preferably 10 to 60% by weight. Moreover, as a ratio with respect to a color material, it is 0-280 weight% normally, Preferably it is 20-200 weight%, More preferably, it is 30-100 weight%.

Moreover, in this invention, binder resin other than the above can be used together as binder resin. Examples of such a binder resin include the following resins.
Polyolefin polymers such as polyethylene, polypropylene, polyisobutylene;
Diene polymers such as polybutadiene and polyisoprene;
Polymers having a conjugated polyene structure such as polyacetylene-based polymers and polyphenylene-based polymers;
Vinyl polymers such as polyvinyl chloride, polystyrene, vinyl acetate, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polyacrylonitrile, polyvinylphenol;
Polyethers such as polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyetherketone, polyetheretherketone and polyacetal; phenolic resins such as novolac resin and resole resin;
Polyesters such as polyethylene terephthalate, polyphenolphthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin;
Polyamides such as nylon-6, nylon 66, water-soluble nylon and polyphenyleneamide; polypeptides such as gelatin and casein;
Epoxy resins such as novolac epoxy resins, bisphenol epoxy resins, novolac epoxy acrylates and acid anhydrides, and modified products thereof;
In addition, polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline, polysulfide, polysulfone, celluloses and the like.

Among the above resins, vinyl polymers are preferably used, and among them, polyacrylic acid esters and copolymers of polyacrylic acid and polyacrylic acid esters are more preferably used.
The total amount of the binder resin is usually 10 to 80% by weight, preferably 20 to 70% by weight, as a ratio in the total solid content of the colored resin composition. Moreover, as a ratio with respect to a coloring material, it is 20 to 500 weight% normally, Preferably it is 30 to 300 weight%, More preferably, it is 50 to 200 weight%.

  In the nitrogen atom-free binder resin, the proportion of the resin having a structure obtained by adding the epoxy portion of the epoxy group-containing compound to the carboxyl group portion of the resin having a carboxyl group is usually 0% by weight or more, preferably 20 % By weight or more, more preferably 30% by weight or more, and usually 100% by weight or less, preferably 90% by weight or less, more preferably 80% by weight or less.

[1-3] c) Nitrogen atom-containing dispersant:
As the nitrogen atom-containing dispersant in the present invention, the residual ratio of the total nitrogen amount when heated at 230 ° C. for 30 minutes (weight ratio of the total nitrogen amount after heating to the total nitrogen amount before heating) is usually 95% by weight. The dispersant is preferably 90% by weight or less, more preferably 80% by weight or less. Further, the residual ratio of the weight of the nitrogen atom-containing dispersant when heated at 230 ° C. for 30 minutes (weight ratio of the weight after heating to the weight before heating) is preferably 95% by weight or less, and 90% by weight or less. More preferably.

In the present invention, before heating at 230 ° C. for 30 minutes, the solvent component is dried under reduced pressure at 60 ° C. for 48 hours under the conditions of 10 mmHg, and this is set to be before heating. Then, it heats at 230 degreeC for 30 minutes in heating furnaces, such as a circulation type hot stove. The nitrogen amount before and after heating is usually measured using an elemental analyzer such as a CHN meter, and the weight is usually measured using a precision balance.
As the nitrogen atom-containing dispersant, surfactants, polymer dispersants and the like are usually used, and polymer dispersants are particularly preferable. As the polymer dispersant, a urethane dispersant, a graft copolymer type dispersant and / or a block copolymer type dispersant are usually used.

Hereinafter, the polymer dispersant will be described in detail.
[1-3-1] Urethane-based dispersant The urethane-based dispersant includes (1) a polyisocyanate compound, (2) a compound having one or two hydroxyl groups in the same molecule, and (3) active in the same molecule. A dispersion resin obtained by reacting hydrogen with a compound having a tertiary amino group is preferred.

(1) a polyisocyanate compound,
Examples of the polyisocyanate compound include aromatics such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanates such as diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω'- Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanate having an aromatic ring such as silylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, Examples thereof include triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

(2) Compounds having one or two hydroxyl groups in the same molecule As compounds having one or two hydroxyl groups in the same molecule, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and these compounds The one terminal hydroxyl group is alkoxylated with an alkyl group having 1 to 25 carbon atoms, and a mixture of two or more of these.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and the like. The mixture of 2 or more types of these is mentioned. Polyether ester diols include those obtained by reacting mixtures of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol) Propylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2
-Ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonane Polycondensation with aliphatic glycols such as diols, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and N-alkyl dialkanolamines such as N-methyldiethanolamine). For example, polyethylene adipate, polybutylene adipate, polyethylene Hexamethylene adipate, polyethylene / propylene adipate, or the like, or polylactone diol or polylactone monool obtained by using the diol or monohydric alcohol having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol, polymethylvalerolactone And a mixture of two or more of these. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator, and more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. .

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
Examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol.
Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferable.
The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

(3) Compound having active hydrogen and tertiary amino group in the same molecule Active hydrogen, that is, hydrogen atom directly bonded to oxygen atom, nitrogen atom or sulfur atom includes hydroxyl group, amino group, thiol group, etc. The hydrogen atom in a functional group is mentioned, Especially, the hydrogen atom of an amino group, especially a primary amino group is preferable.
The tertiary amino group is not particularly limited. For example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl and n-butyl, or the dialkylamino group is linked to form a heterocyclic structure. The group which forms, More specifically, an imidazole ring or a triazole ring is mentioned.
Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is a nitrogen-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. . Specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H- 1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino- Examples include 1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred.

  A preferable blending ratio of the dispersion resin raw material is usually 10 to 200 parts by weight, preferably 20 to 190 parts by weight, more preferably 20 to 190 parts by weight of the compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 30 to 180 parts by weight of the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

  The polystyrene-reduced weight average molecular weight measured by GPC of the urethane-based dispersion resin of the present invention is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. It is a range. When the molecular weight is 1,000 or less, the dispersibility and dispersion stability are poor, and when it is 200,000 or more, the solubility is lowered and the dispersibility is poor, and at the same time, the reaction is difficult to control.

  Manufacture of the urethane type dispersion resin of this invention is performed in accordance with the well-known method of polyurethane resin manufacture. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

A normal urethanization reaction catalyst is used as a catalyst for production. Examples include tin series such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate, iron series such as iron acetylacetonate and ferric chloride, and tertiary amine series such as triethylamine and triethylenediamine. It is done.
The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g by the amine value of the dispersion resin after the reaction. More preferably, it is the range of 5-95 mgKOH / g. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in the dispersion resin by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the dispersion resin has high temporal stability.

[1-3-2] Graft copolymer containing nitrogen atom The graft copolymer containing nitrogen atom preferably has a repeating unit containing a nitrogen atom in the main chain. Especially, it is preferable to have a repeating unit represented by Formula (I) or / and a repeating unit represented by Formula (II).

(In the formula, R ₁ ″ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any of the following formulas (III) to (V).)
In the above formula (I), R ₁ ″ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, and more preferably. Is an ethylene group. A represents a hydrogen atom or any one of the following formulas (III) to (V), preferably formula (III).

In the formula _{(II), R 1 ''} , A may, R ₁ of formula (I) '', the same meanings as A.

In the above formula (III), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, hexylene and the like is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the above formula (IV), Y ₁ represents a divalent linking group. Among them, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy are included. preferable. W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable. Y ₂ represents a hydrogen atom or —CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among which carbon number 2 such as ethyl, propyl, butyl, pentyl, etc. ~ 5 alkyl groups are preferred). q represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the above formula (V), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, among which an alkyl group having 10 to 20 carbon atoms such as stearyl, A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as monohydroxystearyl is preferred.
The content of the repeating unit represented by the formula (I) or (II) in the graft copolymer of the present invention is preferably higher, and is generally 50 mol% or more in total, preferably 70 mol% or more. . Both of the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) may be included, and the content ratio is not particularly limited, but preferably of the formula (I) It is preferable to contain a larger number of repeating units. The total number of repeating units represented by formula (I) or formula (II) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50. Moreover, repeating units other than Formula (I) and Formula (II) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The graft copolymer of the present invention preferably has a terminal of —NH ₂ and —R ₁ —NH ₂ (R ₁ is as defined above for R ₁ ).

In the graft copolymer of the present invention, the main chain may be linear or branched.
As a weight average molecular weight measured by GPC of the said dispersing agent, 3000-100000 are preferable and 5000-50000 are especially preferable. When the weight average molecular weight is less than 3000, the color material cannot be prevented from agglomerating and may become highly viscous or gelled. When the weight average molecular weight exceeds 100000, the material itself becomes highly viscous and dissolved in an organic solvent. It is not preferable because of lack of properties.

As a method for synthesizing the dispersing agent, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.
[1-3-3] AB block copolymer and / or BAB block comprising A block having quaternary ammonium base in side chain and B block not having quaternary ammonium base Copolymer The A block constituting the block copolymer of the dispersant is a quaternary ammonium base, preferably -N + R _1a R _2a R _3a · Y- (where R _1a , R _2a and R _3a are each Independently, it represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R _1a , R _2a and R _3a are bonded to each other to form a cyclic structure. Y- represents a counter anion.) And has a quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N + R _1a R _2a R _3a , as a cyclic structure formed by combining two or more of R _1a , R _2a and R _3a with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

(In the above formula, R represents any group of R _{1a to} R _3a .)
These cyclic structures may further have a substituent.
As R _1a to R _3a in the _{-N + R 1a R 2a R 3a} , and more preferably it may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group.
As the A block, those containing a partial structure represented by the following general formula (1) are particularly preferable.

(In the above general formula (1), R _1a , R _2a and R _3a each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R _1a , R _2a And two or more of R _3a may be bonded to each other to form a cyclic structure, R _4a represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y − represents Represents a counter anion.)
In the general formula (1), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R _5a —, —COO—R _6a — (provided that R _5a and R _6a represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R _7a —O—R _8a —: R _7a and R _8a are each independently an alkylene group). And the like, and preferably —COO—R _6a —.

As the counter anion ^{Y-, Cl-, Br -, I} -, ClO 4 -, BF 4 -, CH 3 CO
O ^-, PF ₆ ^-, and the like.
Two or more kinds of partial structures containing the specific quaternary ammonium base as described above may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done. The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, it is not included in the A block.

  On the other hand, as the B block constituting the block copolymer of the dispersant, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid Propyl, isopropyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N-dimethylaminoethyl (meth) (Meth) acrylic acid ester monomers such as acrylate; (meth) acrylic acid monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N- Dimethylaminoethyl acrylic Vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether, (meth) acrylamide monomers such as amide N- methacryloyl morpholine, polymer structure obtained by copolymerizing comonomers such.

  The B block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (II). In the present specification, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl or methacryl”, “acrylate or methacrylate” and the like, for example, “(meth) acrylic acid” It shall mean “acrylic acid or methacrylic acid”.

(In the general formula (II), R _9a represents a hydrogen atom or a methyl group. R _10a may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents a good allyl group or an aralkyl group which may have a substituent.)
Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be. When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 50% by weight, more preferably 0 to 20% by weight, but it is most preferable that a partial structure other than the (meth) acrylate monomer is not contained in the B block.

The dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block. Such a block copolymer is, For example, it is prepared by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

In the synthesis of the dispersant used in the present invention, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (
1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be employed.

  Whether the dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio (weight ratio) constituting the copolymer. Is usually in the range of 1/99 or more, especially 5/95 or more, and usually 80/20 or less, especially 60/40 or less. Outside this range, it may not be possible to combine good heat resistance and dispersibility.

In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer used in the present invention is usually preferably 0.1 to 10 mmol. In some cases, good heat resistance and dispersibility cannot be combined.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of a basic amino group with an acid.

  Moreover, although the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, it is generally preferable that the acid value is low, and is usually 10 mg-KOH / g or less, and its molecular weight is A weight average in terms of polystyrene is usually preferably in the range of 1000 or more and 100,000 or less. When the molecular weight of the block copolymer is less than 1,000, the dispersion stability decreases, and when it exceeds 100,000, the developability and resolution tend to decrease. It is essential that the graft copolymer contains a nitrogen atom. In the present invention, by using a combination of this specific dispersant and a specific binder resin described later, while maintaining dispersion stability, the coating film formed from the colored resin composition and the substrate at the time of development. High adhesion and suppression of residual undissolved material can be achieved.

Moreover, it is preferable that the dispersing agent in this invention contains a phosphate ester type dispersing agent in addition to the said block copolymer. This improves the solubility during development.
The phosphate ester may be any of primary to tertiary esters, but primary esters are preferred from the viewpoint of dispersion performance. As for the structure of the part couple | bonded with phosphoric acid, the structure which has a hydroxyl group at the terminal represented by polyethers, such as polyester, such as polycaprolactone and polyethyleneglycol, is mentioned, for example. These may be a copolymer of polyester and polyether. Further, it may have a double bond such as (meth) acrylate at one end of the polyester chain and / or the polyether chain, and may form a copolymer with another radical polymerizable compound.

  Specifically, the phosphate ester preferably has a partial structure represented by the following structural formula (3).

As a method for synthesizing such a phosphate ester, for example, it can be produced by the method described in JP-B-50-22536 and JP-A-58-128393.
The molecular weight Mw of the phosphate ester type dispersant is usually 200 or more, and usually 5000 or less, preferably 1000 or less. Since it is originally added for the purpose of imparting development solubility, it is not preferable to make it high molecular weight.

  The content of the phosphate ester type dispersant is usually 5 parts by weight or more, preferably 10 parts by weight or more, and usually 100 parts by weight or less, preferably 80 parts by weight based on 100 parts by weight of the block copolymer. Less than parts by weight. If the proportion of the phosphate ester is too small, sufficient development solubility may not be exhibited. On the other hand, if the proportion of the phosphate ester is too large, the effect is saturated and the dispersibility may be lowered.

The nitrogen atom-containing dispersant may be used alone or in combination of two or more nitrogen atom-containing dispersants. In the case of mixing two or more types of nitrogen atom-containing dispersants, the above-mentioned residual rate is defined as the total residual rate of each nitrogen atom-containing dispersant combined at each mixing ratio.
The form of the nitrogen atom in the nitrogen atom-containing dispersant is preferably an amino group or a quaternary ammonium salt. This is because these functional groups usually have basicity so that they can easily coordinate with acidic groups such as pigments and pigment derivatives, and as a result, contribute to dispersion stabilization. The amine value of the dispersant is usually 2 to 100 KOH mg / g, preferably 3 to 80 KOH mg / g. When the amine value is too low, the basicity is insufficient and the dispersion stability is poor, and when the amine value is too high, the voltage holding ratio of the liquid crystal is lowered, and as a result, display defects are liable to occur.

  The weight ratio of the nitrogen atom-containing dispersant to the color material is 0.01 or more and 0.5 or less. Preferably it is 0.02 or more, Preferably it is 0.3 or less, More preferably, it is 0.2 or less. When the ratio of the dispersant is too large, there is an adverse effect on the voltage holding ratio, causing display defects such as display unevenness and image sticking. Conversely, when the ratio is too small, the dispersibility is not sufficiently exhibited, high transmittance and high Viscosity stability cannot be achieved.

[1-4] d) Solvent:
d) In the colored resin composition of the present invention, the solvent adjusts the viscosity by dissolving or dispersing a) the coloring material, b) the binder resin, c) the dispersing agent and other components other than the above-mentioned components. It works like this.
Examples of the solvent include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, and apco #. 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino Luketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxy Methyl propionate, 3-ethoxypropyl Ethyl pionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether , Propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight. When the solvent exceeds 99% by weight, the coloring material, the dispersing agent, etc. are too small to be suitable for forming a coating film. On the other hand, the lower limit of the solvent content is usually 75% by weight, preferably 80% by weight, and more preferably 82% by weight in consideration of viscosity suitable for coating.

[1-5] e) Photopolymerization initiator system:
The colored resin composition of the present invention is blended with a photopolymerization initiator component having a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. It is essential. In the present invention, the “photopolymerization initiator system” means a mixture in which an additive such as an accelerator and a sensitizing dye is used in combination with the photopolymerization initiator.

[1-5-1] Oxime Ester Compound The present invention is characterized by containing an oxime ester compound as a photopolymerization initiator e) photopolymerization initiator.
Examples of the oxime ester compound of e) include those having the structure of the following general formula (1).

(In the formula, each R ² represents an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a phenoxycarbonyl group. .)
Moreover, the compound shown by General formula (2) is mentioned as a preferable oxime ester type compound.

(In the formula, each R ¹ is an optionally substituted phenyl group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group, or carbon. An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group, an amide group or a nitro group, wherein R ² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, A benzoyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms or a phenoxycarbonyl group, wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently substituted with a hydrogen atom or a halogen atom; C1-C12 alkyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, carbon Alkanoyl group prime 2-12, alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group, ^{or, -OR 8, -SR 9, -SOR} 9, shows a -SO ₂ R ⁹ or -NR ¹⁰ R ^11, and , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent —OR ⁸ , —SR ⁹ or —NR ¹⁰ R ¹¹ , provided that R ⁸ is a hydrogen atom, each substituted. an alkyl group having 1 to 12 carbon atoms, the alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, alkenoyl of 3 to 6 carbon atoms, a phenyl group or - (CH ₂ CH ₂ O) _{n represents} H (n is an integer of 1 to 20), and R ⁹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or a phenyl group. , R ¹⁰ and R ¹¹ are, independently of one another, hydrogen Child, respectively optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, alkenyl of 3 to 5 carbon atoms represents a phenyl group, and R ^3, R ^4, R ⁵ , R ⁶ and R ⁷ may combine with each other to form a ring structure.)
This oxime ester compound is a compound known per se, and is, for example, one of a series of compounds described in JP-A No. 2000-80068.

Of the oxime ester compounds, preferred substituents of the compounds are shown below.
R ¹ : C 1-10 which may be substituted, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. It is done. The alkyl group is preferably an alkyl group having 2 to 8 carbon atoms, more preferably 5 to 7 carbon atoms, and particularly preferably a hexyl group.

R ^2: an acetyl group, a benzoyl group, 4-methylbenzoyl group, 4-chlorobenzoyl group, 2,4,6-trichloro-benzoyl group or 3-methylbenzoyl group and the like. An acetyl group and a benzoyl group are preferable, and a benzoyl group is particularly preferable.
R ³ , R ⁶ , R ⁷ : hydrogen atom R ⁴ : hydrogen atom or methoxy group R ⁵ : methyl mercapto group, phenyl mercapto group or 1,4-oxazyl group R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ “May be bonded to each other to form a ring structure” means that two or more of R ^{3 to} R ⁷ may be bonded to form a ring structure.

More specific compounds are listed in Table 1 with combinations of substituents R ¹ , R ² , R ⁴ and R ⁵ . R ³ , R ⁶ and R ⁷ not listed in Table 1 are all hydrogen atoms.
In the compounds of Table 1, compounds 21 and 22 are preferred, and compounds 21 are particularly preferred.

  Examples of other oxime ester compounds include compounds represented by the following general formulas (3), (4), and (5).

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as defined in the general formula (2), and R ^{4 to} R ⁶ are bonded to each other to form a ring) A structure may be formed, and M is C ₁ -C _12.
Alkylene group, a cycloalkylene group, a phenylene group, - (CO) O- (C 2 -C 12 alkylene) -O (CO) -, - (CO) O- (CH 2 CH 2 O) n - (CO) - Or-(CO)
- (C ₂ -C ₁₂ alkylene) - (CO) - represents a. )
Among the oxime ester compounds, preferably, an oxime ester compound represented by the general formula (4) is exemplified, and more preferred substituents of the oxime ester compound represented by the general formula (4) are shown below.

R ^{1 is an} optionally substituted alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group Etc. Preferably it is C1-C6, More preferably, it is C1-C3, and especially a methyl group is preferable.
R ^{2 is} an optionally substituted alkanoyl group or benzoyl group having 2 to 10 carbon atoms, and examples of the alkanoyl group having 2 to 10 carbon atoms include ethanoyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, A heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, etc. are mentioned. The number of carbon atoms is preferably 2 to 5, more preferably 2 to 3, and particularly preferably an ethanoyl group.

R ^{3 to} R ⁷ : a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group, a benzyl group, a benzoyl group, or —NR ¹⁰ R ¹¹ And R ^{4 to} R ⁶ may be bonded to each other to form a ring structure. R ³ and R ⁷ are preferably both hydrogen atoms. More preferably, R ³ and R ⁷ are both hydrogen atoms, and at least one of R ⁴ , R ⁵ and R ⁶ is —NR ¹⁰ R ¹¹ . R ³ and R ⁷ are both hydrogen atoms, and at least one of R ⁴ , R ⁵ and R ⁶ is —NR ¹⁰ R ¹¹ and at least one is substituted. Particularly preferred is an optionally substituted phenyl group. In this case, the substituent which may be substituted by the phenyl group is a phenyl group which may be substituted, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 2 to 20 carbon atoms. Alkanoyl group, benzoyl group, C2-C12 alkoxycarbonyl group, phenoxycarbonyl group, amide group or nitro group. A benzoyl group which may be substituted is preferable, but a toluoyl group is more preferable, and an o-toluoyl group is particularly preferable. R ⁴ to R ⁶ ring structure which may be formed bond to each other, two or more any themselves may be bonded among R ⁴ to R ^6. The ring structure may be an aromatic ring, an aliphatic ring or a heterocyclic ring, but is preferably a heterocyclic ring, more preferably a hetero 5-membered ring or 6-membered ring in which the hetero atom is a nitrogen atom, A hetero 5-membered ring is preferred.

  Among the oxime ester compounds, more preferred are oxime ester compounds represented by the following general formula (6).

(In the formula, R ¹ is an optionally substituted alkyl group having 1 to 10 carbon atoms, R ² is an optionally substituted alkanoyl group having 2 to 10 carbon atoms and a benzoyl group, R ¹⁰ independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or a phenyl group. shown, R ¹⁰ is also bonded to one carbon atom of one or both of the further substituents or an aromatic ring of an aromatic ring linked via a nitrogen atom to which R ¹⁰ is bonded to form a ring structure R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a phenyl group which may be substituted, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, carbon An alkanoyl group having a number of 2 to 20, a benzoyl group, Alkoxycarbonyl group prime 2-12, phenoxycarbonyl group, an amide group or a nitro group.)
Of the oxime ester compounds, preferred substituents of the compounds are shown below.

R ^{1 is an} optionally substituted alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group Etc. Preferably it is C1-C6, More preferably, it is C1-C3, and especially a methyl group is preferable.
R ² : an optionally substituted alkanoyl group having 2 to 10 carbon atoms, such as ethanoyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, etc. Can be mentioned. The number of carbon atoms is preferably 2 to 5, more preferably 2 to 3, and particularly preferably an ethanoyl group. R ¹⁰ is an optionally substituted alkyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group , Undecyl group, dodecyl group and the like. Preferably, it has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably an ethyl group.

R ¹² , R ¹⁴ and R ¹⁵ : hydrogen atom R ¹³ : a benzoyl group which may be substituted is exemplified, and a toluoyl group is preferable, and an o-toluoyl group is particularly preferable.
The compounds represented by the above general formulas (3), (4), (5) and (6) are also known per se, for example, a series of compounds described in JP-A-2000-80068. It is a kind of.

Moreover, although the said oxime ester type compound can be used independently as a photoinitiator of this invention, it can also use together with another photoinitiator and can anticipate the high sensitivity by combined use. Examples of such photopolymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, JP-A-58-403023, Hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, and N-aryl-α described in JP-A No. 45-37377 and JP-A-10-39503 -Amino acid salts, radical activators such as N-aryl-α-amino acid esters, “Fine Chemical” (1991, March 1, Vol. 20, No. 4), pages 16 to 26 Dialkyl acetophenone, benzoin, thioxanthone derivatives, JP-A-4-221958, JP-A-4-2 No. 9756, etc., a combination of a titanocene and a xanthene dye, an α-aminoalkylphenone compound, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group, etc. It is done.

Specific examples of the polymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2
-(4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-
Halomethylated triazine derivatives such as ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2'-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3, Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- ( 2'-Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl)
Imidazole derivatives such as -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1
-Anthraquinone derivatives such as chloroanthraquinone;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl -Acetophenone derivatives such as (p-butylphenyl) ketone;
Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2
Thioxanthone derivatives such as 1,4-diisopropylthioxanthone;
Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazines such as 9,10-dimethylbenzphenazine Derivatives;
Anthrone derivatives such as benzanthrone;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl -1 monoyl, di-cyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentagenyl-Ti-2,6-dipuruolophen-1-yl, di-cyclopentagenyl-Ti-2,4-difluorophenyl-1-yl, Di-methylcyclopentaenyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentagenyl-Ti-bis-2,6-di-fluoropheny -1-yl, di-cyclopentagenyl-Ti-2,6-di-fluoro-3- (pi 1-yl) - titanocene derivatives such as 1-yl;
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-
Α-aminoalkylphenone compounds such as dimethylamino-1- (4-morpholinophenyl) -butanone-1.

  Examples of the accelerator constituting the photopolymerization initiator system component include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzoxazole. A mercapto compound having a heterocyclic ring such as 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound is used. Two or more types of mixtures may be sufficient as a photoinitiator and an accelerator, respectively.

  The blending ratio of the photopolymerization initiator system component is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0.7% by weight, based on the total solid content of the colored resin composition of the present invention. In addition, it is usually 30% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less. If the blending ratio is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

These may be used as a mixture of a plurality of photopolymerization initiators and accelerators. Preferred combinations of photopolymerizers and accelerators include combinations of imidazole derivatives and mercapto compounds. A combination of an arylbiimidazole derivative and an aromatic mercapto compound is exemplified. By combining these initiators, the sensitivity (sensitivity) to ultraviolet rays is further increased.

  If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiator system component for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335. 3-ketocoumarin compounds described in JP-A-3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292. JP, 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A Dialkyls described in JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a Minobenzen skeleton.

  Of these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzo Thiazole, 2- (p-die Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds. Most preferred among these is 4,4'-dialkylaminobenzophenone.

The blending ratio of the sensitizing dye in the colored resin composition according to the present invention is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% in the total solid content of the colored resin composition. It is in the range of not less than wt%, usually not more than 20 wt%, preferably not more than 15 wt%, more preferably not more than 10 wt%.
The proportion of the photopolymerization initiator system is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 0.7 to 0%, based on the total solid content in the colored resin composition of the present invention. 10% by weight. If the ratio of the photopolymerization initiator system is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed part in the developer may be reduced, causing development failure. This is not preferable.

[1-6] Other components [1-6-1] Photopolymerizable monomer:
The colored resin composition of the present invention may contain a photopolymerizable monomer. The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but is preferably an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). With such an ethylenic compound, when the colored resin composition of the present invention is irradiated with actinic rays,
It is cured by addition polymerization by the action of the photopolymerization initiation system. In the present invention, the term “monomer” means a concept opposite to a so-called polymer substance, and also a concept including a dimer, trimer, oligomer, etc. in addition to a monomer in a narrow sense. .

  Examples of the ethylenic compound include unsaturated carboxylic acids, esters thereof with monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, aromatic polyhydroxy compounds and unsaturated carboxylic acids, and the like. Esters obtained by esterification reaction with unsaturated carboxylic acid and polyhydric carboxylic acid and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds mentioned above, polyisocyanate compounds and (meta ) An ethylenic compound having a urethane skeleton obtained by reacting an acryloyl-containing hydroxy compound.

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Examples thereof include acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. Furthermore, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
The esters obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound are not necessarily a single substance, and may be a mixture. Typical examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, and fats such as cyclohexane diisocyanate and isophorone diisocyanate. Aromatic diisocyanates such as cyclic diisocyanates, tolylene diisocyanate, diphenylmethane diisocyanate and the like, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- Reaction with (meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Thing, and the like.

Examples of ethylenic compounds other than those described above include acrylamides such as ethylene bisacrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate.
The compounding ratio of the ethylenic compound is usually 0 to 50% by weight, preferably 10 to 40% by weight, as a ratio in the total solid content of the colored resin composition of the present invention. Moreover, the ratio with respect to a coloring material is 0-200 weight% normally, Preferably it is 10-100 weight%, More preferably, it is 20-80 weight%.

[1-6-2] Other solid content:
In addition to the above, the colored resin composition of the present invention, if necessary, a dispersion aid, a surfactant, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protective agent, an adhesion improver, a development improver, etc. Can be added.
Examples of the dispersion aid include pigment derivatives. Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, Examples thereof include derivatives such as dioxazine pigments.
Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group directly on the pigment skeleton or an alkyl group, an aryl group, And those bonded via a heterocyclic group. Among these, a sulfonamide group and a quaternary salt or sulfonic acid group thereof are preferable, and a sulfonic acid group is more preferable. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions.

Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, diketopyrrolopyrrole pigment sulfone. Examples thereof include acid derivatives and sulfonic acid derivatives of dioxazine pigments.
The added amount of the pigment derivative is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, particularly preferably 0.1 to 10% by weight based on the pigment. 5% by weight. When the addition amount is small, the effect is not exhibited. Conversely, when the addition amount is too large, the dispersibility and dispersion stability are worsened.

  As the surfactant, various types such as an anionic, cationic, nonionic and amphoteric surfactants can be used. Among these, nonionic surfactants are preferred because they are less likely to adversely affect various properties. The addition amount of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0.5% by weight, particularly preferably 0, based on the total amount of the composition. 0.03 to 0.3% by weight.

Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like. The blending amount of the thermal polymerization inhibitor is usually 3% by weight or less with respect to the total solid content in the colored resin composition.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. The compounding quantity of a plasticizer is 10 weight% or less normally with respect to the total solid in a colored resin composition.

[2] Characteristics of Colored Resin Composition (Resist) The colored resin composition (resist) according to the present invention is particularly capable of holding a voltage by using the above-mentioned specific nitrogen atom-free binder resin and photopolymerization initiator system. It has the characteristic that the rate is high.
The voltage holding ratio is evaluated by the following method. This will be specifically described below.
An electrode substrate A in which an ITO film is formed on one entire surface of a 2.5 cm square alkali-free glass substrate (AN-100 manufactured by Asahi Glass Co., Ltd.), and a 2 mm width at the center of one surface of the 2.5 cm square glass substrate. An electrode substrate B on which a 1 cm square ITO film with connected take-out electrodes is formed is prepared, and an alignment film agent (Sun Ever 7492 manufactured by Nissan Chemical Industries, Ltd.) is applied onto the electrode substrates A and B by spin coating. After drying at 110 ° C. for 1 minute on a hot plate, in a hot air circulating furnace, 20
A film with a thickness of 70 nm is formed by heating at 0 ° C. for 1 hour.

After applying the coloring composition of each example on the electrode substrate A coated with the alignment film agent by spin coating, heating at 80 ° C. for 3 minutes on a hot plate, and exposing the entire surface at 100 mJ / cm ² , Spray development is performed with a 0.1 wt% sodium carbonate aqueous solution at 23 ° C. at a water pressure of 0.3 MPa for 30 seconds, and then baking is performed at 230 ° C. for 30 minutes in a hot air circulating furnace. The coating conditions are adjusted so that the film thickness of the colored composition after firing is 1.7 μm. After applying an epoxy resin sealant containing silica beads having a diameter of 5 μm on the outer periphery of the electrode substrate B to which the alignment film agent has been applied using a dispenser, the surface of the electrode substrate A to which the coloring composition has been applied Then, the outer edge portions are arranged so as to be shifted by 3 mm, and heated in a hot air circulating furnace at 180 ° C. for 2 hours while being crimped. Liquid crystal (MLC-6846-000 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the periphery was sealed with a UV curable sealant to complete a voltage holding ratio liquid crystal cell. The liquid crystal cell was annealed (heated at 105 ° C. for 2.5 hours in a hot air circulating furnace), and then a pulse voltage was applied to the electrode substrates A and B under the conditions of an applied voltage of 5 V and a pulse frequency of 60 Hz, and the voltage holding ratio Measure.
In the present invention, the voltage holding ratio is 80% or more, preferably 85% or more.
The color filter formed of the colored resin composition having a high voltage holding ratio according to the present invention is less likely to cause display defects when incorporated in a liquid crystal display device, and has high quality.

[3] Preparation of Colored Resin Composition (Coating Solution for Color Filter) Next, a method for preparing a colored resin composition according to the first aspect of the present invention will be described. First, a predetermined amount of each of the coloring material, the solvent, and the nitrogen atom-containing dispersant is weighed, and in the dispersion treatment step, the coloring material is dispersed to obtain a liquid colored resin composition (ink-like liquid). When dispersing the color material, it is preferable to appropriately use a binder resin, a dispersion aid and the like. As the binder resin, it is particularly preferable to use a resin having a structure in which an epoxy part of an epoxy group-containing unsaturated compound is added to a carboxyl group part of a resin having a carboxyl group.

  In the dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. Since the color material is finely divided by performing the dispersion treatment, the coating characteristics of the colored resin composition are improved, and the transmittance of the product color filter substrate is improved. For example, when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually 0 to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink-like liquid (coloring material, solvent, dispersant having a nitrogen-containing functional group), the size of the sand grinder apparatus, and the like.

The ink-like liquid obtained by the above dispersion treatment is mixed with a solvent, a nitrogen-free binder resin, and in some cases, a predetermined amount of a photopolymerizable monomer, a photopolymerization initiator system component, components other than the above, and the like. Use a suitable dispersion solution. As the binder resin containing no nitrogen atom to be mixed with the ink-like liquid, the aforementioned “epoxy group-containing (meth) acrylate (hereinafter abbreviated as component (A)) 5 to 90 mol%, copolymerized with component (A)” 10 to 95 mol% of other radical polymerizable compounds (hereinafter abbreviated as component (B)) that can be obtained, and 10 to 100 mol% of the epoxy groups contained in the obtained copolymer are unsaturated. A basic acid (hereinafter abbreviated as component (C)) is added, and polybasic acid anhydride (hereinafter referred to as component (D) is added to 10 to 100 mol% of the hydroxyl group produced when component (C) is added. The resin obtained by adding (abbreviated) ”is preferable. In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.

Next, the color filter of the present invention will be described. The color filter of the present invention is formed using the above colored resin composition.
The material of the transparent substrate for the color filter is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, sheet made of thermoplastic resin such as polycarbonate, polymethyl methacrylate, polysulfone, epoxy resin, unsaturated polyester resin, poly (meth) acrylic resin, etc. Thermosetting resin sheets, various glasses, and the like. Among these, from the viewpoint of heat resistance, glass or a resin excellent in heat resistance is preferable.

  To improve surface properties such as adhesiveness, transparent substrates and black matrix forming substrates are subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins as necessary. You may go. The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

A color filter is manufactured by providing a black matrix on a transparent substrate and forming red, green, and blue pixel images. The colored resin composition of the present invention described above is used as at least one resist forming coating solution of black, red, green, and blue.
The black resist is formed on the transparent substrate (on the raw glass surface) by applying, heating and drying, image exposure, development and thermosetting. For red, green, and blue, coating, heating and drying on a resin black matrix forming surface formed on a transparent substrate or a metal black matrix forming surface formed using a chromium compound or other light shielding metal material Then, image exposure, development, and thermosetting are performed to form pixel images of each color.

  As the light shielding metal material used for forming the metal black matrix, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloys, etc. are used, and these may be laminated in a plurality of layers. Good. The light shielding metal thin film is generally formed by a sputtering method. Then, after forming a desired pattern in a film shape with a positive photoresist, an etchant mixed with ceric ammonium nitrate and perchloric acid is used for chromium, and for other materials The black matrix can be formed by etching using an etching solution according to the material and finally stripping the positive photoresist with a dedicated stripper.

The colored resin composition can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred.
If the thickness of the coating film is too large, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming step. If it is too small, it is difficult to increase the pigment concentration and the desired value. Color expression may be impossible. Therefore, the thickness of the coating film is usually in the range of 0.2 to 20 μm, preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm as the film thickness after drying.

  The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent in the colored resin composition, the performance of the dryer to be used, and the like. Usually, it is selected at a temperature of 40 to 80 ° C. for 15 seconds to 5 minutes, preferably at a temperature of 50 to 70 ° C. for 30 seconds to 3 minutes.

  The temperature condition of the reheating drying is 50 to 200 ° C., preferably 70 to 160 ° C., more preferably 70 to 130 ° C. higher than the preliminary drying temperature. Further, although depending on the heating temperature, the time is usually 10 seconds to 10 minutes, preferably 15 seconds to 5 minutes. The higher the temperature is, the better the adhesion to the transparent substrate is. However, when the temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. The thickness of the photosensitive colored resin composition coating film after drying is usually in the range of 0.5 to 3 μm, preferably 1 to 2 μm. In this step, a vacuum drying method may be used, which is performed in a vacuum chamber without increasing the temperature.

Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet light source or a visible light source through this matrix risk pattern. Under the present circumstances, in order to prevent the fall of the sensitivity by the oxygen of a photoinitiator type | system | group at this time, you may expose, after forming oxygen barrier layers, such as a polyvinyl alcohol layer, on the coating film of a colored resin composition.
Examples of the light source used for the above image exposure include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a lamp light source such as a carbon arc, a fluorescent lamp, Examples thereof include laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can be used when irradiating and using light of a specific wavelength.

Development can be performed using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. This developer may contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, phosphorus Inorganic alkaline compounds such as potassium acid, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or Trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Yes And alkali compounds. These alkaline compounds may be used as a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzenes. Examples thereof include anionic surfactants such as sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate salts, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used by mixing with water.
The temperature of development processing is 10-50 degreeC normally, Preferably it is 15-45 degreeC, More preferably, it is 20-40 degreeC. Further, the developing method may be any of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like. After the development process, a thermosetting process is performed. The temperature at this time is usually 100 to 280 ° C., preferably 150 to 250 ° C., and the time is usually in the range of 5 to 60 minutes.

The patterning image formation for one color is completed through the above series of steps. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.
In the present invention, a color filter can also be produced using a colored resin composition that does not contain a photopolymerization initiation system. In this case, the colored resin composition is applied to the substrate, and a pixel image is formed by an etching method.

  The color filter of the present invention forms a transparent electrode such as ITO on the image as it is, and is used as a part of components such as a color display and a liquid crystal display device, in order to improve surface smoothness and durability. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

Next, the liquid crystal display device (panel) of the present invention will be described. The liquid crystal display device of the present invention is characterized by using the color filter. And it can manufacture as follows.
First, an alignment film is formed on the color filter, a spacer is disposed on the alignment film, and then a liquid crystal cell is formed by bonding to the counter substrate. Next, liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode to complete.

The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method or a flexographic printing method is usually employed, and the thickness of the alignment film is usually several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state capable of adjusting the tilt of the liquid crystal.
A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film is formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. To do. The degree of vacuum in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, Preferably it is 50-90 degreeC. The warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of the liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of a lyotropic liquid crystal, a thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of these may be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “part” represents “part by weight”.

<Synthesis of Binder Resin (a)>
A reaction vessel was charged with 35 parts of propylene glycol monomethyl ether acetate, 8.8 parts of 1-methoxy-2-propanol, and 1.5 parts of an azo polymerization initiator (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.). In an atmosphere, the temperature was raised to 80 ° C., 9.5 parts of benzyl methacrylate, 6.5 parts of methyl methacrylate, 3.5 parts of 2-hydroxyethyl methacrylate, and 10.7 parts of methacrylic acid were added dropwise over 2 hours. Stirring was performed for 4 hours to obtain a polymerization reaction solution.

  After adding 25.5 parts of propylene glycol monomethyl ether acetate, 0.05 part of p-methoxyphenol and 0.3 part of triphenylphosphine to the above polymerization reaction solution, (3,4-epoxycyclohexyl) 17.5 parts of methyl acrylate was added dropwise and reacted at 85 ° C. for 24 hours to obtain a resin solution having an ethylenically unsaturated group in the side chain (hereinafter referred to as binder resin (a)). The polymerization average molecular weight by GPC of the obtained binder resin (a) was 18000 in terms of polystyrene, and when the neutralization titration with KOH was performed, the acid value was 50. The introduction rate into the carboxylic acid by (3,4-epoxycyclohexyl) methyl acrylate was 66% from the acid value before and after the reaction.

<Synthesis of Binder Resin (b)>
First, 145 parts of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120 ° C. 20 parts of styrene, 57 parts of glycidyl methacrylate, and 82 parts of monoacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 120 ° C. for 2 hours.

Next, the inside of the reaction vessel was purged with air, 27.0 parts of acrylic acid, 0.7 part of trisdimethylaminomethylphenol and 0.12 part of hydroquinone were added, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52.0 parts of tetrahydrophthalic anhydride (THPA) and 0.7 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a polymerization reaction liquid (hereinafter referred to as binder resin (c)). The polymerization average molecular weight by GPC of the obtained binder resin (c) was about 15000 in terms of polystyrene.
The types of dispersant used in the following examples are as shown in Table 1 below. Moreover, the heating nitrogen loss measurement of a dispersing agent and a heating weight loss measurement were performed with the following method, and the result is shown in Table 1.

<Measurement of heating nitrogen loss of dispersant>
About 50 to 100 mg of the dispersant is measured in a 50 ml beaker, dried under reduced pressure for 48 hours under conditions of 60 ° C. and 10 mmHg. This is used as a sample before heating. The dried dispersant is heated in a hot air circulating furnace at 230 ° C. for 30 minutes. This is used as a sample after heating. The dispersant before and after the heating is subjected to elemental analysis with “PE2400Series • CHNS / O Analyzer” manufactured by PERKIN ELMER, and the total amount of nitrogen is measured. The amount of nitrogen is a ratio in the total amount, and the absolute amount is calculated by multiplying the weight before and after heating measured by the following method.

<Measurement of heat loss of dispersant>
The weight of the dispersant before and after heating obtained by the same method as described above is measured with a precision balance.

<Preparation of pigment dispersion>
As a coloring material, C.I. I. Pigment Green (CIPG) 36 and C.I. I. Pigment Yellow (CIPY) 138, propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the dispersant described in Table 1, the binder resins (a) and (b) described above, and the weight ratios described in Tables 2 and 3 Mixed. A zirconia bead (0.5 mm diameter) of 3 times the total weight was mixed here, and then filled in a stainless steel container and dispersed for 6 hours with a paint shaker to prepare a green pigment dispersion.

<Preparation of colored resin composition>
Other components were mixed with each of the above pigment dispersions to prepare a colored resin composition having a solid content ratio shown in Table 4. The colored resin composition was prepared so that the whole was diluted with propylene glycol monomethyl ether acetate to a total solid content concentration of 20% by weight.

<Measurement of voltage holding ratio>
An electrode substrate A in which an ITO film is formed on the entire surface of a 2.5 cm square non-alkali glass substrate (“AN-100” manufactured by Asahi Glass Co., Ltd.), and a 2 mm wide takeout at the center of one surface of the 2.5 cm square glass substrate. An electrode substrate B on which a 1 cm square ITO film with electrodes connected was formed.
An alignment film agent (“Sun Ever 7492” manufactured by Nissan Chemical Co., Ltd.) is applied onto the electrode substrates A and B by spin coating, and dried at 110 ° C. for 1 minute on a hot plate, and then 200 ° C. in a hot air circulating furnace. Heated for 1 hour to form a coating film having a thickness of 70 nm.

An alignment film agent is applied by spin coating, and the colored resin compositions of the examples and comparative examples are applied on the electrode substrate A, heated on a hot plate at 80 ° C. for 3 minutes, and the entire surface is 30 or 60 mJ / cm ^2. And exposed. And 0.3M in 0.1 wt% sodium carbonate aqueous solution at 23 ° C
Spray development was performed at a water pressure of Pa for 30 seconds. Thereafter, baking was performed at 230 ° C. for 30 minutes in a hot air circulating furnace. The coating conditions were adjusted so that the film thickness of the colored resin composition after firing was 1.7 μm.

The surface on which the colored resin composition of the electrode substrate A is applied after applying an epoxy resin-based sealant containing silica beads having a diameter of 5 μm on the outer periphery of the electrode substrate B to which the alignment film agent has been applied. Were placed facing each other so that the outer edge portion was shifted by 3 mm, and heated in a hot air circulating furnace at 180 ° C. for 2 hours while being crimped.
A liquid crystal ("MLC-6846-000" manufactured by Merck Japan Co., Ltd.) was injected into the empty cell obtained as described above, the periphery was sealed with a UV curable sealant, and a liquid crystal cell for measuring voltage holding ratio was obtained. completed.

  Next, the liquid crystal cell was heated at 105 ° C. for 2.5 hours in a hot air circulating furnace. Thereafter, a pulse voltage was applied to the electrode substrates A and B under conditions of an applied voltage of 5 V and a pulse frequency of 60 Hz, and the voltage holding ratio was measured. In addition, the voltage holding ratio was evaluated as ○ when the voltage holding ratio was 85% or more and less than 85%. Table 4 shows the voltage holding ratio and evaluation results of each colored resin composition.

<Evaluation of sensitivity (measurement of line width)>
(1) Determination of coating conditions The colored resin compositions of Examples and Comparative Examples were applied to a 10 cm square glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) by spin coating and dried on a hot plate at 70 ° C. for 2.5 minutes. Thereafter, the entire surface was exposed to 60 mJ / cm ^{2 with} a high-pressure mercury lamp, and post-baked in an oven at 230 ° C. for 30 minutes. Then, it measured with the Hitachi Ltd. spectrophotometer (U-3500), and calculated | required the spin coat application | coating conditions which match y = 0.552 (C light source) by the color coordinate represented by a CIE surface pigment | dye.
(2) Preparation of pattern sample Using Cr glass substrate (Asahi Glass Co., Ltd., low reflection Cr AN100) as in (1) (
It apply | coated on the application | coating conditions calculated | required by 1), and prebaked and dried.

Next, 30 or 60 mJ / cm ^{2 was} exposed with a high-pressure mercury lamp through a pattern mask.
Thereafter, a resist pattern sample was prepared by spray development using a sodium hydroxide aqueous solution having a temperature of 23 ° C. and a concentration of 0.1%.
(3) Evaluation of sensitivity (measurement of line width)
The line width of the 25 μm mask pattern portion was measured using a Nikon optical microscope (OPTI PHOT-2), a Tokyo Denki Kogyo CCD camera (CS5720 C series), and a Flove major unit (MC-50K). Went.

Evaluation was carried out with sensitivity ○ when the pattern having a line width of 30 μm or more was formed, and sensitivity x when the pattern was less than 30 μm or when the pattern was not formed and the image flowed out.
Table 5 shows the evaluation results of the line width and sensitivity of each resin composition.

note)
1) CGI242: “CGI-242” manufactured by Ciba Specialty Chemicals Co., Ltd., ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), oxime ester compound 2) BI: “Biimidazole”, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetra, manufactured by Kurokin Kasei Co., Ltd. Phenyl-biimidazole, biimidazole compound 3) EABF: “EAB-F” manufactured by Hodogaya Chemical Co., Ltd. -G ", 2-mercaptobenzothiazol 5) I369:" IRGACURE369 "manufactured by Ciba Specialty Chemicals Co., Ltd., 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, α-aminoa Kirphenone compound 6) I907: “IRGACURE907” manufactured by Ciba Specialty Chemicals Co., Ltd., 2-methyl-1- (4-methylthiophenyl) -2-morpholinofluoro-1-one, α-aminoalkylphenone From the above results, since the colored resin composition of the present invention forms a pattern with an appropriate line width with a small exposure amount, it has high sensitivity and high resolution, and has an extremely bad influence on the voltage holding ratio of the liquid crystal. Clearly less.

  The colored resin composition of the present invention and a color filter using the same can be used for a color television, a liquid crystal display element, a solid-state imaging element, a camera, and the like.

Claims (10)

a) a coloring material, b) a nitrogen atom-free binder resin, c) a nitrogen atom-containing dispersant, d) a solvent, e) a colored resin composition containing a photopolymerization initiator system, and b) having a carboxyl group Resin having a structure in which an epoxy group of an epoxy group-containing unsaturated compound is added to a carboxyl group of the resin and / or (A) 5 to 90 mol% of an epoxy-containing (meth) acrylate, (B) (A) and a component 10 to 95 mol% of another radical polymerizable compound that can be polymerized is copolymerized, and (C) an unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group contained in the obtained copolymer, (C) containing a resin obtained by adding (D) a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl group produced when the component is added, and e) containing an oxime ester compound With features Colored resin composition that. The colored resin composition according to claim 1, wherein the oxime ester compound of e) has a structure represented by the following general formula (1).

(In the formula, each R ² represents an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a phenoxycarbonyl group. .) The colored resin composition according to claim 1, wherein the oxime ester compound of e) is represented by the following general formula (4).

(In the formula, each R ¹ is an optionally substituted phenyl group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group, or carbon. An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group, an amide group or a nitro group, wherein R ² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, A benzoyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms or a phenoxycarbonyl group, wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently substituted with a hydrogen atom or a halogen atom; May be an alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, phenyl , A benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group, ^{or, -OR 8, -SR 9, -SOR} 9, -SO 2 R 9 or - NR ¹⁰ R ¹¹ , and at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents —OR ⁸ , —SR ⁹ or —NR ¹⁰ R ¹¹ , where R ⁸ represents , A hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a phenyl group, or — (CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20), R ⁹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or 3 to 12 carbon atoms. An alkenyl group or a phenyl group, and R ¹⁰ and And R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or a phenyl group. R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure. 4. The colored resin composition according to claim 3, wherein in the general formula (4), R ³ and R ⁷ are both hydrogen atoms. In General Formula (4), R ¹ is an optionally substituted alkyl group having 1 to 10 carbon atoms, and R ² is an optionally substituted alkanoyl group having 2 to 10 carbon atoms and a benzoyl group. , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group, a benzyl group, or benzoyl. a group or -NR ¹⁰ R ^11, and at least one of R ^4, R ⁵ and R ⁶ represents an -NR ¹⁰ R ^11, and the R ^4, R ⁵ and R ⁶ are bonded to ring structure The colored resin composition according to claim 4, which may be formed. The colored resin composition according to claim 5, wherein the oxime ester compound of e) is represented by the following general formula (6).

(In the formula, R ¹ is an optionally substituted alkyl group having 1 to 10 carbon atoms, R ² is an optionally substituted alkanoyl group having 2 to 10 carbon atoms and a benzoyl group, R ¹⁰ independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or a phenyl group. shown, R ¹⁰ combines with one of the carbon atoms of one or both of the further substituents or an aromatic ring of an aromatic ring linked via a nitrogen atom to which R ¹⁰ is bonded to form a ring structure R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be independently of each other a hydrogen atom, an optionally substituted phenyl group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 5 to 8 carbon atoms. A cycloalkyl group, an alkanoyl group having 2 to 20 carbon atoms, Nzoiru shown group, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group, an amide group or a nitro group.)   The colored resin composition according to any one of claims 1 to 6, wherein e) contains, in addition to the oxime ester-based compound, a hexaarylbiimidazole derivative and an aromatic mercapto compound which is a hydrogen donor.   The colored resin composition according to any one of claims 1 to 7, wherein the coating film formed by the colored resin composition is annealed in a state of being in contact with liquid crystal, and then the colored resin layer is formed. A colored resin composition having a voltage holding ratio of 80% or more when a voltage is applied to the liquid crystal.   A color filter formed using the colored resin composition according to any one of claims 1 to 8.   A liquid crystal display device comprising the color filter according to claim 9.