JP2004219979A - Colored photosensitive composition, color filter, and liquid crystal display device formed by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive composition for color filters which is free of staining on the composition and is free of uneven thickness of coating films. <P>SOLUTION: The colored photosensitive composition for the colored filters contains a photopolymerizable polymeric compound (1) having unsaturated double bonds, a photopolymerization initiator (2), an alkali-soluble resin (3), a polymerizable monomer or oligomer (4), a color material (5), and a solvent (6). The photopolymerizable polymeric compound having a carboxylic acid branched alkyl ester group and methacryloyl oxy group at its side chain and having an acid value of 10 to 300 mg KOH/g is used as the above (1) and/or (3). The colored photosensitive composition can be utilized as the colored photosensitive composition for the color filters used for a liquid crystal display device or solid-state image sensor etc. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a colored photosensitive composition for a color filter used for a liquid crystal display device or a solid-state imaging device, and a method for producing the same. Further, the present invention relates to a color filter formed using the colored photosensitive composition and a liquid crystal display device formed using the color filter.

  Generally, a color filter is formed by dispersing a black pigment-dispersed resist or a color pigment-dispersed resist on a transparent substrate such as glass (hereinafter, these colored photosensitive (radiation-sensitive) compositions for color filters are sometimes simply referred to as “resist”). It is produced by coating a thin film of

  A color filter is an important element for a display device such as a liquid crystal display device to provide a bright and lively image. In particular, when the applications of the above display devices were limited to small TVs and game TVs, not so high-quality displays were required. However, in recent years, with the expanded use of liquid crystal display devices and the like, laptop computers, large TVs, etc. As a result, a display screen with high definition and high image quality has been demanded.

  When producing a color filter, development is carried out using an alkaline aqueous solution. At this time, undissolved matter of the radiation-sensitive composition remains on the substrate surface of the non-image area, which is referred to as "ground fouling". Phenomena occurred. Then, when the undissolved substance of the radiation-sensitive composition remains in the non-image area on the substrate, the resulting color filter may have reduced transmittance or reduced contrast.

  In addition, the color filter is usually formed on the substrate radiation-sensitive composition of any one of red, blue, green hue sequentially to form three color pixels, when forming a certain color pixel, When such background contamination occurs, the other color pixels formed on the substrate on which the undissolved matter remains may be peeled off due to poor adhesion to the substrate. As described above, the undissolved material of the radiation-sensitive composition remaining on the substrate surface in the non-pixel portion was one of the causes of lowering the yield of the color filter production.

  On the other hand, if the color filter resist is excessively soluble in the developing solution in order to avoid background contamination, on the other hand, the phenomenon of "film thinning" occurs, in which the coating film surface in the image area dissolves. When the film is reduced, the surface roughness of the coating film increases, and after the final processing as a color filter, the transparency of the color originally possessed by the resist is reduced, and further, rubbing failure or the like is likely to be caused in the panel assembly process. In order to accurately control the thickness of the liquid crystal layer, it is important to accurately maintain the cell gap between the upper and lower substrates, that is, the cell gap. In this case, unevenness on the surface of the color filter becomes a problem.

  As the applications of liquid crystal display devices are expanded and a display screen comparable to a CRT is required, the demand for a coating film for a color filter resist has been particularly severe in recent years. Achieving this is one key to the widespread use of LCDs in various multimedia display materials.

As a resin used for color resist, it has no tackiness even after solvent removal, does not stain the photomask at the exposure stage, and has high sensitivity and high resolution. There is known an unsaturated group-containing acrylic resin (C) obtained by a reaction with a compound (B) having both an alicyclic epoxy group and an unsaturated bond (for example, see Patent Document 1). In addition, as a curable resin with improved development failure and film residue during development, a modified copolymer in which an epoxy group-containing unsaturated compound is added to some of the acid groups of a copolymer of acrylic acid ester and acrylic acid Is known (for example, see Patent Document 2). In addition, a high sensitivity, a solvent resistance at a low exposure dose, as a photopolymerizable composition excellent in scratch resistance, including a photopolymerizable polymer having an acryloyloxy group, a carboxyl group and a carboxylic ester group in the side chain. A composition is known (for example, see Patent Document 3).
JP-A-8-262221 JP 2000-72814 A JP 2000-154207 A

  However, the above-described various color filter compositions still have a problem. Specifically, when the development is strengthened to avoid background fouling, the film is reduced, and the two performances cannot be simultaneously achieved. Did not.

  An object of the present invention is to provide a resist in which undissolved matter of the radiation-sensitive composition does not remain on a substrate that can be used for a display device having high definition and high image quality as described above.

  The present inventors have made intensive efforts to elucidate the structure of a photopolymerizable polymer that does not cause background fouling, and as a result, have developed a photopolymerizable polymer compound having a carboxylic acid branched alkyl ester group and a methacryloyloxy group in a side chain to obtain a colored photosensitive polymer. The inventors have found that the above object can be achieved by using the composition as one component of the composition, and have accomplished the present invention.

  That is, the gist of the present invention is to provide a photopolymerizable polymer compound having an unsaturated double bond (1), a photopolymerization initiator (2), an alkali-soluble resin (3), a polymerizable monomer or oligomer (4), and a color. The composition for a color filter containing the material (5) and the solvent (6), wherein the (1) is a polymer having a repeating unit represented by the following general formulas (I) and (II). In the colored photosensitive composition.

（一般式（Ｉ）及び（II）中、Ｘ¹及びＸ²は、各々独立に、水素原子又はメチル基を表す。Ｒ¹は分岐状アルキル基を表す。Ｚは２価の連結基を表す。）
又、本発明の他の要旨は、不飽和二重結合を有する光重合性高分子化合物（１）、光重合開始剤（２）、アルカリ可溶性樹脂（３）、重合性モノマー又はオリゴマー（４）、色材（５）及び溶剤（６）を含むカラーフィルター用組成物において、前記（３）が、前記一般式（Ｉ）及び（II）で表される繰り返し単位を有し、酸価が１０〜３００ｍｇＫＯＨ／ｇの重合体であることを特徴とする着色感光性組成物に存する。

(In the general formulas (I) and (II), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. R ¹ represents a branched alkyl group. Z represents a divalent linking group.) .)
Another gist of the present invention is to provide a photopolymerizable polymer compound having an unsaturated double bond (1), a photopolymerization initiator (2), an alkali-soluble resin (3), a polymerizable monomer or oligomer (4). In the composition for a color filter containing a coloring material (5) and a solvent (6), the (3) has a repeating unit represented by the general formulas (I) and (II), and has an acid value of 10 A colored photosensitive composition characterized by being a polymer of about 300 mgKOH / g.

  Another gist of the present invention is to provide a photopolymerizable polymer compound having an unsaturated double bond (1), a photopolymerization initiator (2), an alkali-soluble resin (3), a polymerizable monomer or oligomer (4). A color filter composition comprising a coloring material (5) and a solvent (6), wherein (1) and (3) have a repeating unit represented by the general formulas (I) and (II), The present invention relates to a colored photosensitive composition characterized by being a polymer having an acid value of 10 to 300 mgKOH / g.

  Another gist of the present invention is to provide a coloring material-dispersed composition containing a coloring material (5) and a solvent (6), and optionally a photopolymerizable polymer compound (1) further having an unsaturated double bond. Coloring by mixing a photopolymerizable polymer compound having an unsaturated double bond (1), a photopolymerization initiator (2), an alkali-soluble resin (3), a polymerizable monomer or oligomer (4), and a solvent (6) In the method for producing a photosensitive composition, (1) and / or (3) have a repeating unit represented by the general formula (I) or (II), and have an acid value of 10 to 300 mgKOH / g. The present invention relates to a method for producing a colored photosensitive composition, characterized by using the polymer of (1).

  Another aspect of the present invention resides in a color filter formed using the colored photosensitive composition and a liquid crystal display device formed using the color filter.

  According to the present invention, a colored photosensitive composition for a color filter which is free from background stains and free from coating film is obtained.

  The colored photosensitive composition of the present invention contains the following six components (1) to (6) as essential components, and may contain other optional components (7). Hereinafter, the content and the amount of each component will be described in detail.

(1) Photopolymerizable polymer compound having an unsaturated double bond (2) Photopolymerization initiator (3) Alkali-soluble resin (4) Polymerizable monomer or oligomer (5) Colorant (6) Solvent (7) Optional component.

(1) Photopolymerizable Polymer Compound Having Unsaturated Double Bond The photopolymerizable polymer compound having an unsaturated double bond of the present invention comprises repeating units represented by the following general formulas (I) and (II). It is a polymer having.

（一般式（Ｉ）及び（II）中、Ｘ¹及びＸ²は、各々独立に、水素原子又はメチル基を表す。Ｒ¹は分岐状アルキル基を表す。Ｚは２価の連結基を表す。）
Ｘ¹及びＸ²は、各々独立に、水素原子又はメチル基を表す。Ｒ¹は分岐状アルキル基であり、具体的には、ｉ−プロピル基、ｉ−ブチル基、ｔ−ブチル基、２−ブチル基、２−ペンチル基、２，２−ジメチルプロピル基、２−メチルブチル基、３−メチルブチル基、１−メチルペンチル基、１−エチルブチル基、２−メチルペンチル基、２−エチルブチル基、３−メチルペンチル基等をあげることができる。

(In the general formulas (I) and (II), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. R ¹ represents a branched alkyl group. Z represents a divalent linking group.) .)
X ¹ and X ² each independently represent a hydrogen atom or a methyl group. R ¹ is a branched alkyl group, specifically, i-propyl, i-butyl, t-butyl, 2-butyl, 2-pentyl, 2,2-dimethylpropyl, Examples include a methylbutyl group, a 3-methylbutyl group, a 1-methylpentyl group, a 1-ethylbutyl group, a 2-methylpentyl group, a 2-ethylbutyl group, and a 3-methylpentyl group.

R ¹ is preferably an i-butyl group, a t-butyl group, a 2,2-dimethylpropyl group or a 3-methylbutyl group. If the carbon number of R ¹ is too large, the resin itself becomes a plasticizer, and the strength of the resulting coating film is weak, so that the resist may not be used as a highly durable resist. In addition, since it acts as a plasticizer, the developability during image formation becomes too large, resulting in a thinned image or reduced film thickness.

Further, R ¹ preferably has a structure in which the terminal is branched. This is because at the time of development, it functions as a dissolution inhibiting group for a developing solution. An appropriate dissolution inhibiting group has the effect of improving the linearity of the image and preventing film roughness.

  Z in the general formula (II) is a divalent linking group for extending the chain length of the ester bond. The divalent linking group may be a hydrocarbon group, may be composed of a hetero atom, or may be a combination of a hydrocarbon group and a hetero atom.

Examples of the divalent hydrocarbon group include an alkylene group having 1 to 12 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group; a cyclohexylene group, a cyclopentylene group, a cyclobutylene group; Examples include hydrocarbon groups having an alicyclic structure and the like exemplified in the following [Formula 7]; and arylene groups such as a phenylene group and a xylylene group. Further, these hydrocarbon groups, an alkyl group having 1 to 10 carbon ^{atoms, -OH, -OR 2, -SR 3} , -NR 4 R 5, -SH, may be substituted by -NH _2, and halogen atoms such as . Here, R ^{2 to} R ⁵ represent an alkyl group having 1 to 20 carbon atoms.

ヘテロ原子から構成される２価の連結基としては、−ＣＯ₂−、−ＮＨ−、−ＮＲ−、−ＣＯＮＨ−、−Ｏ−、−ＣＯ−、−ＳＯ₂−等を挙げることができる。また、炭化水素基とヘテロ原子から構成される２価の連結基が組み合わされた連結基としては、下記［化８］に示す構造を挙げることができる。

Examples of the divalent linking group composed of a hetero _{atom, -CO 2 -, - NH -} , - NR -, - CONH -, - O -, - CO -, - SO 2 - and the like. In addition, examples of the linking group in which a divalent linking group composed of a hydrocarbon group and a hetero atom are combined include a structure represented by the following [Chemical Formula 8].

上記連結基のうち好ましくは、構造内に水酸基を有する脂環式構造を有する炭素数６〜１２の２価の連結基である。水酸基を有することで画像形成時、アルカリ現像液に樹脂が溶解しやすくなり、また脂環式構造を有することで膜強度が大きくなる。

Among these linking groups, a divalent linking group having 6 to 12 carbon atoms and having an alicyclic structure having a hydroxyl group in the structure is preferable. Having an hydroxyl group makes it easier for the resin to be dissolved in an alkaline developer during image formation, and having an alicyclic structure increases the film strength.

  The repeating unit of the general formula (I) is contained in the polymer in an amount of usually 10 to 90 mol%, preferably 10 to 70 mol%, more preferably 10 to 50 mol%, especially 15 to 30 mol%. If the amount is too large, the solubility in the developing solution is deteriorated, resulting in poor development. Conversely, if the amount is too small, it will dissolve and become thin, leading to a decrease in film thickness.

  The repeating unit represented by the general formula (II) is contained in the polymer in an amount of usually 10 to 90 mol%, preferably 10 to 70 mol%, more preferably 10 to 50 mol%, particularly preferably 15 to 40 mol%. If the amount is too small, the sensitivity is low, and the strength of the completed color filter coating film is low. If the amount is too large, it is difficult to synthesize the resin.

  The weight average molecular weight of the polymer containing the repeating units of the general formulas (I) and (II) is 5,000 or more, preferably 5,000 to 60,000, and more preferably 6,000 to 30,000. If the thickness is less than the above range, the film is liable to be reduced. If the thickness exceeds this range, development becomes difficult.

  The acid value of the polymer containing the repeating units of the general formulas (I) and (II) is preferably from 10 to 300 mgKOH / g. More preferably, it is 30 to 200 mgKOH / g. This makes it possible to achieve both substrate adhesion and developability with an alkali developing solution. Since the polymer composed of only the repeating units of the general formulas (I) and (II) has no acid group, the acid value is substantially zero. Therefore, in order to satisfy the above acid value, it is necessary to introduce, for example, one or more repeating units represented by the following general formula (III).

（一般式（III）中、Ｘ³は、各々独立に、水素原子又はメチル基を表す。Ｚは２価の連結基を表し、一般式(II)で定義されるものと同義である。Ｒ⁶はアルキル基、アルコキシ基又はハロゲン原子を表し、ベンゼン環の置換数は０〜４である。ｎは１又は２を表す。）
一般式（Ｉ）及び(II)、場合によっては更に一般式(III)で表される繰り返し単位を有する重合体を製造するには、それぞれの繰り返し単位に相当するモノマーを所定の割合で重合すればよい。また、（メタ）アクリル酸、（メタ）アクリル酸エステル、（メタ）アクリル酸アミド、（メタ）アクリロニトリルなどを重合又は共重合した後、特定の側鎖を、所望の程度変性する方法によっても製造できる。

(In the general formula (III), X ³ each independently represents a hydrogen atom or a methyl group. Z represents a divalent linking group and has the same meaning as defined in the general formula (II). R ⁶ represents an alkyl group, an alkoxy group, or a halogen atom, and the number of substituents on the benzene ring is 0 to 4. n represents 1 or 2.)
In order to produce a polymer having the repeating units represented by the general formulas (I) and (II) and, in some cases, the general formula (III), a monomer corresponding to each of the repeating units is polymerized at a predetermined ratio. Just fine. Further, it is also produced by a method of polymerizing or copolymerizing (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic amide, (meth) acrylonitrile, etc., and then modifying a specific side chain to a desired degree. it can.

  The synthesis of the main chain may be either condensation polymerization or addition polymerization. However, since condensation polymerization tends to vary in the degree of polymerization of molecules, addition polymerization in which a polymer having a low degree of polymerization is difficult to form is preferable. The polymerization mode may be any of bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and the like. Generally, polymerization is carried out by mixing a raw material monomer constituting the main chain, an initiator, and further, if necessary, a solution and the like, and adjusting the temperature. The initiator is determined by its decomposition rate and the ease with which it reacts with the monomers, for example, potassium peroxodisulfate, ammonium peroxodisulfate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, acetyl peroxide , Benzoyl peroxide, peroxides such as lauroyl peroxide, azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane / HCl salt Is used. The solvent only needs to dissolve the monomer and the produced polymer well. For example, toluene, ethyl acetate, methanol, ethanol, acetone, dimethylformamide, cellosolve solvents, and the like. The polymerization temperature is set by a temperature that gives an appropriate rate of primary radical generation of the initiator and a desired molecular weight of the produced polymer, and is usually -10 to 120C, preferably 40 to 100C. In addition, a chain transfer agent and a polymerization inhibitor can be used as necessary.

The repeating unit of the general formula (I) can be easily introduced by selecting a (meth) acrylate having R ¹ as a monomer.

  In order to make Z in the general formula (II) a linking group containing a structure having a hydroxyl group, a method of ring-opening addition of a compound having both an unsaturated bond and an epoxy group to a side chain carboxyl group is used. The ring-opening addition is carried out at a reaction temperature of 50 to 150 ° C. by mixing an acrylic resin having a carboxyl group, an epoxy compound, a solvent, a ring-opening addition catalyst, and optionally a polymerization inhibitor. In order to prevent gelation, it is desirable to carry out the reaction in the presence of a molecular oxygen-containing gas.

  Examples of catalysts that promote ring-opening addition include tertiary amines such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine and tri-n-octylamine, and quaternary amines such as tetramethylammonium chloride, tetramethylammonium bromide and tetrabutylammonium bromide. Examples thereof include ammonium salts, alkyl ureas such as tetramethyl urea, alkyl guanidines such as tetramethyl guanidine, and tertiary phosphines such as triphenyl phosphine. The catalyst is used in an amount of 0.01 to 10% by weight, preferably 0.5 to 4.0% by weight based on the epoxy compound.

  As the epoxy compound, (3,4-epoxycyclohexyl) methyl methacrylate, glycidyl methacrylate, β-methyl glycidyl methacrylate and the like are used.

  The repeating unit of the general formula (III) includes (meth) acrylic acid, vinylphenol, vinylbenzenesulfonic acid, a modified unsaturated monocarboxylic acid having a chain extended between an unsaturated group and a carboxylic acid, for example, β-carboxyethyl ( (Meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, lactone-modified unsaturated monocarboxylic acid having an ester bond, modified unsaturated having an ether bond It can be introduced by selecting a compound such as a monocarboxylic acid as a monomer.

  The photopolymerizable polymer compound (1) having an unsaturated double bond of the present invention is a polymer having a repeating unit represented by the general formulas (I) and (II) and, in some cases, further represented by the general formula (III) However, this does not preclude the inclusion of another repeating unit. For example, a polymerizable monomer or oligomer (4) described below can be copolymerized.

  The photopolymerizable polymer compound (1) having a repeating unit represented by the general formulas (I) and (II), and optionally the general formula (III), has a content in the colored photosensitive composition of: Usually, it is adjusted to be in the range of 0.5 to 30% by weight, preferably 1 to 15% by weight. When the amount is less than 0.5% by weight, the coating film for forming an image becomes brittle and the impact resistance is poor. On the other hand, when the amount exceeds 30% by weight, the linearity of the pixel deteriorates, and in some cases, scum is easily generated in the pixel.

(2) Photopolymerization initiator The polymerization initiator used in the colored photosensitive composition of the present invention is not particularly limited as long as the monomer or the like causes a polymerization reaction. That is, a compound having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical can be used.

Specific examples are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-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-oxadiazole Diazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-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) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5 Imidazole derivatives such as diphenylimidazole dimer; benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-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-hydroxycyclohexylphenyl 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 derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzuanthrone;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentagenenyl-Ti-bis-phenyl, di-cyclopentagenenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl -11-yl, di-cyclopentagenenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenenyl-Ti-bis-2,4,6-tri Fluorophenyl-1-yl, di-cyclopentagenenyl-Ti-2,61-difluorophenyl-1-yl, di-cyclopentagenyl-Ti-2,4-di-fluorophenyl-1-yl, Di-methylcyclopentagenenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentagenenyl-Ti-bis-2,6-di-fluorophenyl 1-yl, di-cyclopentagenenyl-Ti-2,6-di-fluoro-3- (pi 1-yl) - phenylcarbamoyl-1-titanocene derivatives such as yl.

  In addition, photopolymerization initiators that can be used in the present invention are described in Fine Chemicals, March 1, 1991, Vol. 20, no. 4, p. 16-P26, JP-A-59-152396, JP-A-61-151197, JP-B-45-37377, JP-A-58-40302, and JP-A-10-39503. Have been.

  The compounding ratio of the photopolymerization initiator 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 photosensitive composition of the present invention. It is usually at most 30% by weight, preferably at most 20% by weight, more preferably at most 10% by weight. If the blending ratio is extremely low, the sensitivity may be lowered. On the contrary, if the blending ratio is extremely high, the solubility of the unexposed portion in the developing solution is lowered, and poor development is likely to be induced.

(3) Alkali-soluble resin The alkali-soluble resin used in the colored photosensitive composition of the present invention has a carboxyl group or a phenolic hydroxyl group in a side chain or a main chain. Use of a resin having these functional groups enables development with an alkaline solution. Preferably, a resin having a carboxyl group, which is a resin exhibiting high alkali developability, such as a (meth) acrylic acid (co) polymer, a styrene / maleic anhydride resin, and an acid anhydride-modified resin of novolak epoxy acrylate. preferable. Particularly preferred are (co) polymers containing (meth) acrylic acid or (meth) acrylate having a carboxyl group. Since this resin has excellent developability and transparency, and can obtain various copolymers by selecting various monomers, it is extremely advantageous in that the performance and the production method can be easily controlled. .

  In the present invention, as the alkali-soluble resin, a polymer having a repeating unit represented by the aforementioned general formulas (I) and (II) and having an acid value of 3 to 200 mgKOH / g can be used. Since such a polymer is the same as the photopolymerizable polymer compound (1) having an unsaturated double bond, it also functions as a photopolymerizable polymer compound. In this case, the same substance simultaneously exerts the function of the photopolymerizable polymer compound (1) having an unsaturated double bond and the function of the alkali-soluble resin (3), has excellent compatibility, and has excellent transparency. This is the most preferred embodiment of the present invention, since it also has excellent properties.

  In the present invention, a known alkali-soluble resin can also be used. The known alkali-soluble resin is used alone or in combination with a polymer having a repeating unit represented by the general formulas (I) and (II) and having an acid value of 10 to 300 mgKOH / g, Can be used.

  Monomers that can be used to produce the (co) polymer containing (meth) acrylic acid esters include, for example, (meth) acrylic acid, succinic acid (2- (meth) acryloyloxyethyl) ester, adipine Acid (2-acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meta) ) Acryloyloxyethyl) ester, succinic acid (2- (meth) acryloyloxypropyl) ester, adipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyl) Loxypropyl) ester, phthalic acid (2- (meth) acryloyloxypropyl) ester, maleic acid (2- ( (T) Acryloyloxypropyl) ester, succinic acid (2- (meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2- (meth) acrylic acid) Hydroxyalkyl (meth) acrylates (anhydride) succinic acid, such as (loyloxybutyl) ester, phthalic acid (2- (meth) acryloyloxybutyl) ester, and maleic acid (2- (meth) acryloyloxybutyl) ester A compound to which an acid (anhydride) such as phthalic acid (anhydride) or maleic anhydride (anhydride) has been added as an essential component, and styrene monomers such as styrene, α-methyl-styrene, and vinyltoluene as required; Acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid and other unsaturated group-containing carboxylic acids; methyl (meta A) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (Meth) acrylates such as (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, cyclohexyl (meth) acrylate, and adamantyl (meth) acrylate; ε-caprolactone to (meth) acrylic acid; Compounds to which lactones such as β-propiolactone, γ-butyrolactone, δ-valerolactone are added; acrylonitrile; (meth) acrylamide, N-methylolacrylamide, N, Acrylamides such as -dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethylacrylamide; vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate, pivalic acid Resins obtained by copolymerizing various monomers such as vinyl carboxylate such as vinyl, acrylonitrile, vinylidene chloride, and maleimide are exemplified.

  Further, in order to increase the strength of the coating film, styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (meth) 10 to 98 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol% of a monomer having a phenyl group such as acrylsulfonamide, and (meth) acrylic acid or succinic acid (2- (meth) ) Acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) Ester, maleic acid (2- (meth) acryloyloxy 2 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol% of at least one monomer selected from the group consisting of (meth) acrylates having a carboxyl group such as tyl) ester % Acrylic resin is also preferably used.

  In addition, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetylcellulose, novolak resin, resole resin, polyvinyl phenol, polyvinyl butyral, or the like can be mixed with these acrylic resins.

  The molecular weight of the alkali-soluble resin is usually selected from the range of 3000 to 100,000, and the acid value is selected from the range of 10 to 300 mgKOH / g.

  In this specification, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”, and (meth) acrylate, (meth) acryloyl group, and the like are described as having the same meaning.

  The content of the alkali-soluble resin (3) is adjusted so that the content in the colored photosensitive composition is usually in the range of 0.5 to 30% by weight, preferably 1 to 15% by weight. If it is less than 0.5% by weight, the developability is insufficient, and if it exceeds 30% by weight, the surface of the coating film is roughened by the developer, the roughness increases, and as a result, the color deteriorates.

(4) Polymerizable monomer or oligomer The polymerizable monomer or oligomer used in the colored photosensitive composition of the present invention is not particularly limited as long as it is a polymerizable low molecular compound. For example, an addition-polymerizable compound having at least one ethylenic double bond (hereinafter, referred to as “ethylenic compound”) is preferable. The ethylenic compound is a compound having an ethylenic double bond such that when the colored photosensitive composition of the present invention is irradiated with actinic rays, it undergoes addition polymerization by the action of a photopolymerization initiator and is cured. The term “monomer or oligomer” in the present invention means a concept corresponding to a so-called polymer substance, and means a concept containing dimers, trimers and oligomers in addition to monomers in a narrow sense. The weight average molecular weight is selected from a range of less than 5000, preferably less than 3000, and more preferably 50 to 2000.

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

  Esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, and pentaerythritol. Acrylic esters such as erythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate are exemplified. Also, the acrylate portion of these acrylates is replaced with a methacrylic acid portion, a methacrylic acid ester, an itaconic acid ester, which is replaced with an itaconic acid portion, a crotonic acid ester, which is replaced with a crotonic acid portion, or a maleic acid, which is replaced with a maleic acid portion. Esters and the like.

  Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

  The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance, but may be a mixture. Representative 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; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate and the like, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3-hydroxy ( Reaction product with (meth) acryloyl group-containing hydroxy compound such as 1,1,1-trimethacryloyloxymethyl) propane And the like.

  Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.

  The content of the polymerizable monomer or oligomer (4) is adjusted so that the content in the colored photosensitive composition is usually in the range of 0.2 to 30% by weight, preferably 1 to 20% by weight. If the amount is less than 0.2% by weight, the sensitivity of the photosensitive composition is low, and the curing of the coating film is insufficient. As a result, the coating film is weak and too soft. On the other hand, if it exceeds 30% by weight, the coating film is brittle and easily formed into a coating film having low impact resistance.

(5) Coloring material As the coloring material used in the colored photosensitive composition of the present invention, various dyes and pigments can be used, but pigments are preferable in terms of heat resistance, light resistance and the like.

  As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a violet pigment, an orange pigment, a brown pigment, and a black pigment can be used. Also, as its structure, various inorganic pigments are used in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perinone. It is possible.

  Hereinafter, specific examples of pigments that can be used are shown by pigment numbers. Terms such as “CI Pigment Red 2” below refer to the color index (CI).

  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, 81, 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, 17 , 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, 264, 265, 266, 267 , 268, 269, 270, 271, 272, 273, 274, 275, 276. Among them, 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.

  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. Among them, 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.

  Green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among them, C.I. I. Pigment Green 7 and 36.

  As the yellow pigment, 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. Among them, 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, and 180.

  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. Among these, C.I. I. Pigment Orange 38 and 71.

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

  When a resin black matrix of a color filter is formed using the photosensitive coloring composition, a black coloring material can be used. As the black color material, a color material that shows black alone can be used alone or in combination. Alternatively, a black color material obtained by mixing red, green, blue and the like can be used. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic or organic pigments, it is preferable to use them dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Examples of the black coloring 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 these, carbon black is preferable from the viewpoint of the light blocking ratio and image characteristics. Examples of the carbon black include the following carbon blacks.

  Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 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.

  Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex, Printex, Printex, Printex, Printex, Printex, Printex, Printex L , Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2 Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170.

  Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8.

  Colombian Carbon: RAVEN11, RAVE14, RAVE15, RAVE16, RAVE22RAVE30, RAVE35, RAVE40, RAVE410, RAVE420, RAVE450, RAVE500, RAVE780, RAVE850, RAVE890H, RAVE50, RAVE10, RAVE10, RAVE50, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE50, RAVE10, RAVE10, RAVE10, RAVE10, RAVE10, RAVE50, RAVE50 , RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

  Specific examples of colorants that can be used in combination include Victoria Pure Blue (42595), Auramine O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK 70: 100. (50240), Erioglaucine X (42080), 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7B4401 (15850), First 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 indicate the color index (CI)).

  Further, regarding other pigments that can be used in combination, C.I. I. The number is, 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. Brown pigments 23, 25, 26 and the like can be mentioned.

  As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green and blue can be mixed and used as black pigments. In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide, and the like can be used as the pigment. These various pigments may be used in combination of two or more. For example, in order to adjust the chromaticity, it is possible to use a green pigment and a yellow pigment in combination, or to use a blue pigment and a violet pigment in combination.

  These pigments preferably have an average particle size of 1 μm, preferably 0.5 μm or less, and more preferably 0.25 μm or less.

  The content of the coloring material (5) is adjusted so that the content of the colored photosensitive composition in the solid content is usually in the range of 5 to 60% by weight, preferably 10 to 50% by weight. If it is less than 5% by weight, it is difficult to obtain a sufficient color density as a color filter, and if it is more than 60% by weight, the resin component becomes insufficient and it becomes difficult to form pixels.

(6) Solvent In the colored photosensitive composition of the present invention, a solvent is used. As such a solvent, those which can dissolve components in a composition such as a binder resin, a monomer or an oligomer, a photopolymerization initiator, an accelerator, a sensitizing dye, and a surfactant as a photosensitive material are usually used. There is no particular limitation as long as it is not particularly limited. In particular, in addition to the above, generally, a property capable of dissolving or stably retaining a dye or pigment dispersion as a colorant is required.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-t-butyl ether, and diethylene glycol monomethyl. Glycol mono such as ether, diethylene glycol monoethyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, and tripropylene glycol methyl ether Alkyl ethers;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, dipropylene glycol monomethyl ether acetate, 3- Glycol alkyl ether acetates such as methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate Rate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy Linear or cyclic esters such as propyl propionate, butyl 3-methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.

  Examples of the solvent corresponding to the above include mineral spirit, Valsol # 2, Apco # 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 1 2, commercially available products with trade names such as Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, diglyme.

  One of these solvents may be used alone, or two or more thereof may be used in combination. Further, the colored photosensitive composition of the present invention may be used by dividing into a plurality of steps for preparing the colored photosensitive composition.

  The amount of the solvent (6) used is adjusted so that the solid content in the colored photosensitive composition is usually in the range of 60 to 90% by weight, preferably 70 to 85% by weight. If the content is less than 60% by weight, it is difficult to sufficiently dissolve the components constituting the photosensitive composition and to maintain a stable dispersion state, while if it exceeds 90% by weight, the coating efficiency is deteriorated.

(7) Optional component The colored photosensitive composition of the present invention contains the above-mentioned components (1) to (6) as essential components. Can be mixed.

<A> Sensitizing dye (accelerator)
For the purpose of increasing the sensitivity of the colored photosensitive composition according to the present invention, a sensitizing dye corresponding to the wavelength of the image forming exposure light source can be blended.

  Examples of these sensitizing dyes include xanthene dyes, coumarin dyes having a heterocyclic ring, 3-ketocoumarin compounds, pyromethene dyes, and dyes having a dialkylaminobenzene skeleton.

  Preferred sensitizing dyes are compounds containing an amino group, 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, 4,4'-methylethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'- Benzophenone-based compounds such as diaminobenzophenone, 3,3′-diaminobenzophenone, and 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-dimethylamino Phenyl) benzothiazole, 2- (p-diethylaminophenyl) 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) P-dialkylaminophenyl group-containing compounds such as pyrimidine and (p-diethylaminophenyl) pyrimidine; and N, N-dialkylaminobenzoic acid alkyl esters such as ethyl N, N-dimethylaminobenzoate. The most preferred of these is 4,4'-dialkylaminobenzophenone.

  The compounding ratio of the sensitizing dye is usually 0.05% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, based on the total solid content of the colored photosensitive composition. Further, it is usually at most 20% by weight, preferably at most 15% by weight, more preferably at most 10% by weight. If the amount is too large, the pattern accuracy may decrease, while if it is too small, the pattern itself is difficult to form. The sensitizing dye is sometimes called an accelerator, and the compound is the same.

<A> Thermal polymerization inhibitor As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used.

  The amount of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight based on the total solid content of the composition.

<C> Plasticizer As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like are used.

  The amount of these plasticizers is preferably in the range of 10% by weight or less based on the total solid content of the composition.

<D> Storage stabilizer <e> Surface protectant <f> Adhesion improver <g> Development improver <h> Dispersant (dispersion aid, surfactant)
<K> Coatability improving agent An example of the method for producing the colored photosensitive composition according to the present invention and the method for producing the color filter of the present invention using the same will be described below.

[Production of colored photosensitive composition]
In order to produce the composition of the present invention, first, a coloring material is subjected to a dispersion treatment and adjusted to an ink state. The dispersion treatment is performed using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the coloring material becomes fine particles by the dispersion treatment, the transmittance of transmitted light and the coating characteristics are improved.

  The dispersion treatment is preferably performed in a system in which a binder resin having a dispersing function, a dispersant such as a surfactant, a dispersing aid, and the like are appropriately used in combination with a coloring material and a solvent. It is effective to use the photopolymerizable polymer compound (1) having an unsaturated double bond of the present invention in this system. Particularly, it is preferable to use a polymer dispersant since the dispersion stability with time is excellent. 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 millimeters as a medium. The temperature during the dispersion treatment is usually set in the range of 0 to 100 ° C, preferably room temperature to 80 ° C. The appropriate dispersion time depends on the composition of the ink (colorant, solvent, dispersant), the size of the sand grinder, and the like.

  Next, an alkali-soluble resin, a monomer, a photopolymerization initiator, and the like are mixed with the colored ink obtained by the dispersion treatment to form a uniform solution. It is effective to use the photopolymerizable polymer compound of the present invention as the alkali-soluble resin. In each step of the dispersion treatment and the mixing, fine dust is often mixed, so that the obtained solution is preferably filtered by a filter or the like.

[Manufacture of color filters]
The color filter of the present invention can be usually manufactured by forming red, green, and blue pixel images on a transparent substrate provided with a black matrix.

  The material of the transparent substrate is not particularly limited. Examples of the material include polyesters such as polyethylene terephthalate, polypropylene, polyolefins such as polyethylene, thermoplastic plastic sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic resins. Thermosetting plastic sheets, various glass plates, and the like can be given. Among them, a glass plate and a heat-resistant plastic sheet are preferable from the viewpoint of heat resistance.

  Prior to the formation of the black matrix, the transparent substrate is subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as silane coupling agents and urethane polymers, etc. in order to improve the physical properties such as surface adhesion. You may keep it. The black matrix is formed on a transparent substrate using a metal thin film or a black matrix pigment dispersion.

  A black matrix using a metal thin film is formed of, for example, a single layer of chromium or two layers of chromium and chromium oxide. In this case, first, a thin film of these metals or metal / metal oxides is formed on a transparent substrate by vapor deposition or sputtering. Subsequently, after a photosensitive film is formed thereon, the photosensitive film is exposed and developed using a photomask having a repetitive pattern such as stripes, mosaics, and triangles to form a resist image. Thereafter, the thin film is etched to form a black matrix.

  On a transparent substrate provided with a black matrix, a composition for a color filter containing one of red, green and blue coloring materials is applied and dried, and then a photomask is placed on the composition, A pixel image is formed by image exposure, development, and, if necessary, heat curing or light curing through a mask to form a colored layer. This operation is performed for each of the three color filter compositions of red, green and blue to form a color filter image.

  The application of the composition for a color filter can be performed by a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, and a spray.

  Drying after application may be performed using a hot plate, an IR oven, a convection oven, or the like. The drying temperature is such that the higher the temperature, the better the adhesion to the transparent substrate. However, if the temperature is too high, the photopolymerization initiation system is decomposed, and thermal polymerization is liable to occur, resulting in poor development. The range is 150 ° C. The drying time is in the range of 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes.

  The film thickness of the composition for a color filter after drying is preferably in the range of 0.5 to 5 μm, particularly preferably 1 to 3 μm.

  Exposure light sources that can be applied to the color filter composition of the present invention are not particularly limited, but include, for example, xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, Lamp light sources such as a low-pressure mercury lamp, carbon arc, and fluorescent lamp, and laser light sources such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser are used. When only a specific wavelength is used, an optical filter can be used.

  The composition for a color filter of the present invention forms an image on a substrate by performing image exposure with such a light source and then developing with an organic solvent or an aqueous solution containing a surfactant and an alkali agent. be able to. The aqueous solution may further contain an organic solvent, a buffer, a dye or a pigment.

  Although there is no particular limitation on the developing method, a method such as immersion development, spray development, brush development, or ultrasonic development is usually used at a development temperature of 10 to 50 ° C, preferably 15 to 45 ° C.

  As an alkaline agent of the developer, inorganic agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, etc. And organic amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, and tetraalkylammonium hydroxide. These may be used alone or in combination of two or more. Can be used.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonic acid Anionic surfactants such as salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts; and amphoteric surfactants such as alkyl betaines and amino acids can be used. Or a combination of two or more.

  As the organic solvent, both when used alone and when used in combination with an aqueous solution, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like, and these are used alone. Alternatively, two or more kinds can be used in combination.

  In addition, the color filter of the present invention can also be manufactured by a method of applying a polyimide resin composition and forming a pixel image by an etching method, in addition to the above method. Further, a method of directly forming a pixel image on a transparent substrate by a printing machine using a resin composition as a coloring ink, or a method of immersing the resin composition in an electrodeposition liquid to form a colored film on an ITO electrode having a predetermined pattern. It can also be produced by a precipitation method. Further, it can also be produced by a method in which a film coated with a resin composition is adhered to a transparent substrate, peeled off, image-exposed and developed to form a pixel image, or a method in which a pixel image is formed by an ink-jet printer using ink. As the production method, a method more suitable for the composition of the composition for a color filter is used.

  Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto. The following “parts” represent “parts by weight” unless otherwise specified. The weight average molecular weight was measured by gel permeation chromatography (GPC), and the acid value was measured by neutralization titration.

[Resin Production Example 1]
57.0 g of propylene glycol monomethyl ether acetate and 57.0 g of 1-ethoxy-2-propanol were placed in a 500 ml four-necked flask, and heated to 85 ° C. while performing nitrogen bubbling.

  There, 32.7 g (0.23 mol) of isobutyl methacrylate, 37.0 g (0.37 mol) of methyl methacrylate, 34.4 g (0.40 mol) of methacrylic acid and 2,2′-azobis (isobutyronitrile) A solution of 9.9 g (0.06 mol) in 57.0 g of propylene glycol monomethyl ether acetate was added dropwise over 4 hours.

  After the dropwise addition, the mixture was further stirred for 2 hours while maintaining the reaction solution at 85 ° C, and then nitrogen bubbling was stopped, the temperature was raised to 100 ° C, and the mixture was stirred for 1 hour.

Thereto, 0.66 g (4 × 10 ⁻³ mol) of tetraethylammonium chloride was added and dissolved with stirring at 80 ° C., and 39.2 g (0.2 mol of (3,4-epoxycyclohexyl) methyl methacrylate) was added thereto. ) And 58.8 g of propylene glycol monomethyl ether acetate were added dropwise over 1 hour. The reaction solution was stirred while being kept at 80 ° C., to obtain 384 g of a photopolymerizable polymer compound A solution having an unsaturated double bond.

  The molar ratio of the monomers constituting the polymer compound A was as follows, the weight average molecular weight was 8,000, and the acid value was 100 mgKOH / g.

[(2-hydroxy-4-methacryloyloxymethyl) cyclohexyl] methacrylate 20
Isobutyl methacrylate 23
Methyl methacrylate 37
Methacrylic acid 20.

[Resin Production Example 2]
Photopolymerization was performed in the same manner as in Resin Production Example 1 except that an equimolar amount of (3,4-epoxycyclohexyl) methyl acrylate was used instead of (3,4-epoxycyclohexyl) methyl methacrylate. A high molecular compound B was obtained.

  The molar ratio of the monomers constituting the polymer compound B was as follows, the weight average molecular weight was 8,000, and the acid value was 100 mgKOH / g.

[(2-hydroxy-4-acryloyloxymethyl) cyclohexyl] methacrylate 20
t-butyl methacrylate 23
Methyl methacrylate 37
Methacrylic acid 20.

[Example 1]
Polymer Compound A (Resin Production Example 1) 40 parts Blue coloring material (CI Pigment Blue 15: 6) 40 parts Propylene glycol monomethyl ether acetate 100 parts These were mixed and kneaded with a three-roll mill to form a mixture having a pore size of 5 μm. The coarse particles were filtered with a filter to obtain a blue pigment dispersion for a color filter. Next, using the pigment dispersion, the following components were blended to obtain a photopolymerizable composition for a color filter.

Blue pigment dispersion 130 parts Dipentaerythritol hexaacrylate 40 parts Polymer compound A (Resin Production Example 1) 80 parts
2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer 8 parts Photopolymerization initiator (Michler's ketone) 20 parts Propylene glycol monomethyl ether acetate 1000 parts This composition is applied to a glass substrate for a color filter by a spin coater. It is applied, dried at 80 ° C. for 3 minutes, further exposed to 100 mJ / cm ² through a mask using a 2.5 kW ultra-high pressure mercury lamp, immersed in a 0.04 wt% potassium hydroxide aqueous solution, and An image according to the pattern was obtained. No residue of the color resist containing the pigment dispersion was observed in the portion where no image was formed. When observed with a scanning microscope, no surface roughness was observed.

[Comparative Example 1]
Polymer compound B (Resin Production Example 2) 40 parts Blue colorant (CI Pigment Blue 15: 6) 40 parts Propylene glycol monomethyl ether acetate 100 parts These are mixed, kneaded with a three-roll mill, and mixed with a pore diameter of 5 μm. The coarse particles were filtered with a filter to obtain a blue pigment dispersion for a color filter. Next, using the pigment dispersion, the following components were blended to obtain a photopolymerizable composition for a color filter.

Blue pigment dispersion 130 parts Dipentaerythritol hexaacrylate 40 parts Polymer compound B (Resin Production Example 2) 80 parts
2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer 8 parts Photopolymerization initiator (Michler's ketone) 20 parts Propylene glycol monomethyl ether acetate 1000 parts This composition was coated and dried in the same manner as in Example 1. Exposure and development were performed to obtain an image according to the mask pattern. A small amount of color resist residue was observed in the portion where no image was formed. When the resulting image was observed by SEM, irregularities were recognized on the image surface.

[Example 2]
10.0 parts of a blue colorant (CI Pigment Blue 15: 6) was mixed with 33.4 parts of a polymer dispersant (BYK161 manufactured by Big Chemical Co., solid content concentration: 30% by weight) and 36.6 parts of propylene glycol monomethyl ether acetate. Was dispersed for 8 hours with a paint conditioner to obtain a blue colorant-dispersed ink 5.

  A photopolymerizable composition for a color filter was similarly obtained using the blue colorant-dispersed ink 5 obtained above in place of the “blue pigment dispersion” used in Example 1.

  Thereafter, an image according to the mask pattern was obtained in the same manner as in Example 1. No residue of the color resist containing the pigment dispersion was observed in the portion where no image was formed. When observed with a scanning microscope, no surface roughness was observed.

[Example 3]
A color was obtained in the same manner as in Example 2 except that a mixed pigment of 9.0 parts of a blue color material (CI Pigment Blue 15: 6) and 1.0 part of a copper phthalocyanine pigment (S-5000, manufactured by Avicia) was used. A photopolymerizable composition for a filter was obtained. Thereafter, an image according to the mask pattern was obtained in the same manner as in Example 1. No residue of the color resist containing the pigment dispersion was observed in the portion where no image was formed. When observed with a scanning microscope, no surface roughness was observed.

It can be used as a colored photosensitive composition for a color filter used in a liquid crystal display device or a solid-state imaging device.

Claims (9)

Photopolymerizable polymer compound having an unsaturated double bond (1), photopolymerization initiator (2), alkali-soluble resin (3), polymerizable monomer or oligomer (4), coloring material (5) and solvent (6) ), Wherein (1) is a polymer having a repeating unit represented by the following general formulas (I) and (II).

(In the general formulas (I) and (II), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. R ¹ represents a branched alkyl group. Z represents a divalent linking group.) .) Photopolymerizable polymer compound having an unsaturated double bond (1), photopolymerization initiator (2), alkali-soluble resin (3), polymerizable monomer or oligomer (4), coloring material (5) and solvent (6) And (3) is a polymer having a repeating unit represented by the following general formulas (I) and (II) and having an acid value of 10 to 300 mgKOH / g. A colored photosensitive composition comprising:

(In the general formulas (I) and (II), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. R ¹ represents a branched alkyl group. Z represents a divalent linking group.) .) Photopolymerizable polymer compound having an unsaturated double bond (1), photopolymerization initiator (2), alkali-soluble resin (3), polymerizable monomer or oligomer (4), coloring material (5) and solvent (6) ), The above (1) and (3) each have a repeating unit represented by the following general formulas (I) and (II), and have an acid value of 10 to 300 mgKOH / g. A colored photosensitive composition, which is a united product.

(In the general formulas (I) and (II), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. R ¹ represents a branched alkyl group. Z represents a divalent linking group.) .) The colored photosensitive composition according to any one of claims 1 to 3, wherein R ¹ in the general formula (I) is a terminally branched alkyl group.   5. The colored photosensitive composition according to claim 1, wherein Z in the general formula (II) is a divalent linking group containing an alicyclic structure having a hydroxyl group. 6.   The colored photosensitive composition according to any one of claims 1 to 5, wherein the polymer having a repeating unit represented by the general formulas (I) and (II) has a weight average molecular weight of 5,000 or more. The colorant dispersion composition containing the colorant (5) and the solvent (6), and optionally the photopolymerizable polymer compound (1) further having an unsaturated double bond, is added with a photopolymerizable compound having an unsaturated double bond. A method for producing a colored photosensitive composition by mixing a polymer compound (1), a photopolymerization initiator (2), an alkali-soluble resin (3), a polymerizable monomer or oligomer (4) and a solvent (6), As the above (1) and / or (3), a polymer having a repeating unit represented by the following general formulas (I) and (II) and having an acid value of 10 to 300 mgKOH / g is used. For producing a colored photosensitive composition.

(In the general formulas (I) and (II), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. R ¹ represents a branched alkyl group. Z represents a divalent linking group.) .)   A color filter formed using the colored photosensitive composition according to claim 1. A liquid crystal display device formed using the color filter according to claim 8.