JP2015176152A - colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition.SOLUTION: The colored photosensitive resin composition comprises an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D), and a solvent (E). The colorant (D) comprises a pigment (d1) and a dye (d2). The alkali-soluble resin (A) contains a repeating unit represented by chemical formula 1. The glass transition temperature of the alkali-soluble resin (A) is controlled to be lower than 0°C, which significantly improves a development rate, sensitivity and adhesion strength of the composition, and which also minimizes a level difference in a pattern that may be increased by the colorant, and can significantly improve the transmittance of the pattern.

Description

  The present invention relates to a colored photosensitive resin composition (A COLORED PHOTOSENSITIVE RESIN COMPOSITION) capable of significantly improving development speed, sensitivity, and adhesion during the development process.

  The color filter is widely used in an image sensor, a liquid crystal display device, and the like, and its application range is rapidly expanding. A color filter used in a color liquid crystal display device or an image pickup device is usually a spin coating of a colored photosensitive resin composition containing a colorant corresponding to each color of red, green, and blue on a substrate on which a black matrix is patterned. After the coating is uniformly applied, the conductive film formed by heating and drying (hereinafter sometimes referred to as pre-plasticity) is exposed and developed, and further heat-cured (hereinafter referred to as post-plasticity as required). ) Is repeated for each color, and each color pixel is formed.

  A pigment is used as a colorant, but recently there has been an attempt to use a brighter dye having excellent heat resistance. When using only a dye as a colorant, it is preferable because all the excellent properties of the dye can be realized, but the dye is not compatible with the other components of the composition than the pigment and has a large color change at high temperatures. , Its use is limited.

  Therefore, a method using a hybrid type colorant that uses both a pigment and a dye as a colorant has been attempted. However, it is still not possible to completely solve the problem when a colorant containing a dye is used.

  When a color filter is produced using a colored photosensitive resin composition containing a dye as a colorant, decolorization or color change occurs during a post process at a high temperature, and foreign matter is not formed when forming a colored layer due to lack of compatibility with the materials used. Occur. Further, when manufacturing a color filter, there is a problem that the development speed is slow, the sensitivity is insufficient, and the pattern formed during the development process with an alkaline developer frequently peels off. Therefore, development of a colored photosensitive resin composition suitable for the litho process has been sought that can eliminate the problems associated with containing a dye as a colorant or using a dye alone as a colorant.

  Korean Patent Application Publication No. 2012-80123 discloses a colored photosensitive composition, a method for producing a color filter, a color filter, a liquid crystal display device, and an organic EL display device, but an alternative to the above problem is presented. Not done.

Republic of Korea Patent Application Publication No. 2012-80123

  An object of the present invention is to provide a colored photosensitive resin composition having excellent development speed and adhesion.

  Furthermore, another object of the present invention is to provide a color filter formed using the photosensitive resin composition.

  1. It contains an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D) and a solvent (E). The colorant (D) is a pigment (d1) and a dye ( d2), the alkali-soluble resin (A) includes a repeating unit represented by the following chemical formula 1, and the alkali-soluble resin (A) has a glass transition temperature of less than 0 ° C .:

(In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,
R ₃ is a residue containing a carboxylic acid derived from an acid anhydride).

  2. In the above 1, the acid anhydride may be phthalic anhydride, (2-dodecen-1-yl) succinic anhydride ((2-Dodecen-1-yl) succinic anhydride, or maleic anhydride). anhydride), succinic anhydride, citraconic anhydride, glutaric anhydride, methyl succinic anhydride 3, dimethyl succinic anhydride 3, methyl succinic anhydride 3, dimethyl succinic anhydride 3, -Dimethylsulfuric anhydride), phenylsuccinic anhydride Itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride (3,4,5,6-tetrahydrophthalic anhydride), trimellitic anhydride, hexahydrophthalic anhydride A colored photosensitive resin composition selected from the group consisting of (Hexahydrophthalic anhydride) and Carbic anhydride.

  3. 2. The colored photosensitive resin composition according to 1, wherein the repeating unit of Chemical Formula 1 is contained in an amount of 50 to 90 mol% with respect to the entire alkali-soluble resin.

  4). In 1 above, the alkali-soluble resin (A) is copolymerized by further including a monomer having an unsaturated double bond in addition to the monomer for realizing the repeating unit of the chemical formula 1. Colored photosensitive resin composition.

  5. 2. The colored photosensitive resin composition according to 1, wherein the alkali-soluble resin (A) is contained in an amount of 10 to 80% by weight based on the total solid powder content in the composition.

  6). The color filter formed using the coloring photosensitive resin composition by any one of said 1-5.

  7). An image display device comprising the color filter according to 6 above.

  The colored photosensitive resin composition of the present invention can further improve the development speed, improve the sensitivity and adhesion, and suppress a pattern short circuit.

  Furthermore, when a pattern is formed using the colored photosensitive resin composition of the present invention, the level difference can be minimized and the transmittance can be further improved.

  The present invention includes an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D), and a solvent (E), and the colorant (D) is a pigment (d1). ) And a dye (d2), the alkali-soluble resin (A) includes a repeating unit of the following chemical formula 1, and the glass transition temperature of the resin is maintained at less than 0 ° C. The present invention relates to a colored photosensitive resin composition capable of remarkably improving adhesion and minimizing a pattern step that can be increased by a colorant and remarkably improving transmittance.

  The colored photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D), and a solvent (E).

<Alkali-soluble resin (A)>
The alkali-soluble resin (A) used in the present invention contains a repeating unit represented by the following chemical formula 1 and exhibits a glass transition temperature of less than 0 ° C.

In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and R ₃ is a residue containing a carboxylic acid derived from an acid anhydride.

  The alkali-soluble resin (A) according to the present invention includes the above-mentioned repeating unit and exhibits a glass transition temperature of less than 0 ° C., thereby significantly improving the development speed of the composition and improving the sensitivity and adhesion. It is possible to suppress the short circuit problem of the pattern due to the increase in speed.

  Furthermore, when forming a pattern using the composition containing the alkali-soluble resin (A), the level difference of the pattern that can be increased by the colorant in the composition can be minimized, and the smoothness can be remarkably improved. The transmittance is also improved, so that a color filter with excellent quality can be manufactured.

  The content of the repeating unit shown in the chemical formula 1 is not particularly limited. For example, it can be contained at 50 to 90 mol%, preferably 50 to 75 mol%, based on the entire alkali-soluble resin. Is good. When the above range is satisfied, the glass transition temperature of the polymerized resin is more preferably less than 0 ° C. When the repeating unit is included in less than 50 mol%, the sensitivity may be reduced and a pattern short circuit may occur. When the repeating unit is included in an amount exceeding 90 mol%, gelation or polymerization may occur during the polymerization process. However, the storage safety of the resin can be reduced.

  On the other hand, when the glass transition temperature (Tg) of the polymerized alkali-soluble resin (A) is 0 ° C. or higher, a level difference occurs due to the colorant content in the composition, and it becomes difficult to ensure flatness.

  The alkali-soluble resin (A) of the present invention further comprises a monomer (a2) having an unsaturated double bond in addition to the monomer (a1) for realizing the repeating unit of Chemical Formula 1 Can be manufactured.

  The kind of the monomer having an unsaturated double bond capable of copolymerization is not particularly limited, and specifically, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene. , M-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl Includes aromatic vinyl compounds such as glycidyl ether.

  N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N N-substituted maleimide compounds such as -m-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide.

  Moreover, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl ( Examples include alkyl (meth) acrylates such as (meth) acrylate and t-butyl (meth) acrylate.

  Also, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylhexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl ( Examples thereof include alicyclic (meth) acrylates such as (meth) acrylate, 2-dicyclofentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate.

  Further, hydroxy such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethylacrylamide, etc. Examples include ethyl (meth) acrylates.

  Furthermore, allyl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate are exemplified.

  Also, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl And unsaturated oxetane compounds such as oxetane, 2- (methacryloyloxymethyl) oxetane, and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane. The monomers can be used alone or in combination of two or more.

  The content of the compound having an unsaturated double bond capable of copolymerization is not particularly limited. For example, it may be contained in an amount of 10 to 50 mol% with respect to the total monomer content for polymerizing the alkali-soluble resin. Preferably 30 to 40 mol%. When the above range is satisfied, the glass transition temperature of the resin is less than 0 ° C. and the step can be minimized.

  Below, it demonstrates in detail about the manufacturing method of alkali-soluble resin (A) which concerns on this invention.

  Conventionally, an alkali-soluble resin of a colored photosensitive resin composition must have an ethylenically unsaturated monomer having a carboxy group in order to be soluble in an alkali developer used in a development processing step when forming a pattern. Copolymerized as a component. However, the alkali-soluble resin formed by such a production method has a problem that it is difficult to produce a resin having a carboxy group in the main chain and a glass transition temperature of less than 0 ° C.

  However, the alkali-soluble resin (A) of the present invention is produced so that a carboxy group is contained in a side chain that is not a main chain in which a polymerization reaction occurs, thereby providing appropriate developability and a glass transition temperature of 0. Indicates less than ° C.

  Meanwhile, one embodiment of the production method of the present invention includes (S1) a step of copolymerizing glycidyl (meth) acrylate and a monomer (a2) having an unsaturated double bond; (S2) the produced copolymer Reacting the polymer with an ethylenically unsaturated monomer having a carboxy group; and (S3) reacting the copolymer having undergone the reaction with an acid anhydride.

  The step (S2) is a step for imparting photocurability to the alkali-soluble resin (A) of the present invention. In the step (S2), the type of ethylenically unsaturated monomer having a carboxy group is used. Although it will not specifically limit if it is in the range which performs the function, For example, (meth) acrylic acid, ethylacrylic acid, butylacrylic acid etc. are mentioned, Preferably it can be set to methacrylic acid.

  The step (S3) is a step for imparting an appropriate acid value to the alkali-soluble resin (A) of the present invention. More specifically, the hydroxyl group derived from the glycidyl group of the alkali-soluble resin is converted into an acid. This is a step of reacting with an anhydride to introduce a carboxy group into the side chain of the alkali-soluble resin.

  The type of the acid anhydride used in the step (S3) is not particularly limited as long as the function is within the range of performing the function. For example, phthalic anhydride, (2-dodec-1-yl) succinate Acid anhydride ((2-Dodecen-1-yl) succinic anhydride, Maleic anhydride, Succinic anhydride, Citriconic anhydride, Glutaric anhydride, Glutaric anhydride, Glutaric anhydride Methylsuccinic anhydride, 3,3-dimethylglutaric anhydride, 3,3-dimethylglutanic anhydride Phenylsuccinic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride (3,4,5,6-tetrahydrophthalic anhydride), trimellitic anhydride (Trimellitic anhydride) anhydride), hexahydrophthalic anhydride, carbic anhydride, and the like. In view of cost and ease of reaction, maleic anhydride, phthalic anhydride, trimellitic anhydride, succinic anhydride, hexhydrophthalic anhydride Anhydride and carbic anhydride are preferable, and trimellitic anhydride, succinic anhydride, and hexahydrophthalic anhydride are more preferable than hexahydrophthalic anhydride.

  The acid value of the alkali-soluble resin (A) according to the present invention produced by the production method described above is 30 to 150 mgKOH / in order to ensure compatibility with the dye contained in the composition and the storage safety of the composition. g. When the acid value of the alkali-soluble resin (A) is less than 30 mgKOH / g, it may be difficult for the colored photosensitive resin composition to ensure a sufficient development speed. In addition, when the acid value exceeds 150 mgKOH / g, the adhesion to the substrate is reduced, pattern short circuit is likely to occur, and there is a problem in compatibility with the dye, and the dye in the colored photosensitive resin composition May precipitate, or the storage safety of the colored photosensitive resin composition may decrease and the viscosity may increase.

  The content of the alkali-soluble resin (A) according to the present invention is not particularly limited. For example, it can be 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the solid powder in the composition. It can be. When the above range is satisfied, the solubility in the developer is sufficient and pattern formation is facilitated, and the development is prevented from decreasing the film thickness of the pixel portion of the exposed portion, and the omission degree of the non-image portion is improved. preferable.

<Photopolymerizable compound (B)>
The photopolymerizable compound (B) according to the present invention is a compound that can be polymerized by the action of the following photopolymerization initiator (C), and is a monofunctional monomer, bifunctional monomer, or polyfunctional monomer. A polyfunctional monomer having two or more functional groups is preferably used.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl pyrrolidone. However, it is not limited to this.

  Specific examples of the bifunctional monomer include 1,6-hexanediol (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth). Examples include, but are not limited to, acrylate, bis (acryloyloxyethyl) ether of bisphenol A, or 3-methylpentanedioldi (meth) acrylate.

  Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated (ethoxylated) trimethylolpropane tri (meth) acrylate, propoxylated (propoxylated) trimethylolpropane tri (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated (ethoxylated) dipentaerythritol hexa (meth) acrylate, propoxylated (propoxylated) di Examples include but are not limited to pentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

  The content of the photopolymerizable compound (B) is not particularly limited. For example, the content of the photopolymerizable compound (B) can be included at 5 to 45% by weight, preferably 7 to 45% by weight, based on the total weight of the solid powder in the composition. can do. When the above range is satisfied, it is preferable because the strength and smoothness of the pixel portion are improved.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) is not particularly limited as long as the photopolymerizable compound (B) can be polymerized. In particular, the photopolymerization initiator (C) includes an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. It is preferable to use one or more compounds selected from the group consisting of thioxanthone compounds.

  Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Ethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (4- Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone and the like.

  As a specific example of the triazine compound, 2,4-bis (卜 lichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (卜 trichloromethyl) -6 -(4-Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (卜 lichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (卜 lichloromethyl) -6 (4-Methoxystyryl) -1,3,5-triazine, 2,4-bis (卜 lichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine 2,4-bis (卜 lichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (卜 trichloromethyl) -6- [2- (4 -Diethylamino-2-methyl Enyl) ethenyl] -1,3,5-triazine, 2,4-bis (卜 trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like. .

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3- Dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2, 2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, 4′5, 5 ′ -Tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4, 4 ', 5, 5' position is substituted with a carboalkoxy group. Among them, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4, 4′5, 5′-tetraphenyl-1,2′-biimidazole is preferably used.

  Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and OXE01 and OXE02 manufactured by BASF are typical.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  The photopolymerization initiator (C) can further contain a photopolymerization initiation auxiliary agent (c1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention includes the photopolymerization initiation auxiliary agent (c1), so that the sensitivity becomes the highest and the productivity can be improved.

  As the (c1), for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

  As the amine compound, an aromatic amine compound is preferably used. Specifically, an aliphatic amine compound such as triethyl alcohol amine, methyl diethanol amine, triisopropane olamine, methyl 4-dimethylaminobenzoate, 4-dimethyl Ethyl aminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl p-toluidine, 4,4'-bis (dimethylamino) Benzophenone (common name: Michler's ketone), 4,4′-bis (diethylamino) benzophenone, or the like is used.

  The carboxylic acid compound is preferably aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxy. Examples include phenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

  Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mogabutopropionate), pentaerythritol tetrakis (3-mercaptobutylate) , Pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like.

  The content of the photopolymerization initiator (C) is not particularly limited. For example, the content of the alkali-soluble resin (A) and the photopolymerizable compound (B) with respect to the total weight of the solid powder in the composition, It can be contained at 0.1 to 40% by weight, preferably 0.1 to 30% by weight. When the above range is satisfied, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained.

  In addition, when the photopolymerization initiation auxiliary (d2) is further used, the content of the photopolymerization initiation auxiliary (d2) is not particularly limited. For example, the total weight of the solid powder in the composition may be an alkali-soluble resin ( The content of A) and the photopolymerizable compound (B) can be 0.1 to 40% by weight, preferably 0.1 to 30% by weight. When the range is satisfied, the sensitivity of the colored photosensitive resin is the highest, and the effect of improving the productivity of the color filter formed using the composition is provided.

<Colorant (D)>
The colorant (D) used in the present invention contains one or more pigments (d1) and one or more dyes (d2).

  The photosensitive resin composition of the present invention contains the above-described alkali-soluble resin (A), so that excellent developability and adhesion can be obtained even when the pigment (d1) and the dye (d2) are used simultaneously as the colorant (D). Can be shown.

Pigment (d1)
As the pigment, an organic pigment or an inorganic pigment generally used in this field is used. As the pigment, various pigments used for printing inks, inkjet inks and the like are used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylenes. Pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavantron pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, etc. Can be mentioned. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, and the like. And metal oxides or composite metal oxides. In particular, examples of the organic pigment and the inorganic pigment include compounds classified as pigments in the color index (published by The society of Dyers and Colorists). More specifically, the following color index (C I.) number pigments, but are not necessarily limited thereto.

  For example, C.I. I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185, C.I. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71.

  In addition, C.I. I. And CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264.

  In addition, C.I. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38.

  Furthermore, C.I. I. Pigment blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76.

  Furthermore, C.I. I. Pigment green 7, 10, 15, 25, 36, 47, and 58.

  In addition, C.I. I. And CI Pigment Brown 28.

  In addition, C.I. I. And CI pigment black 1 and 7.

  The pigments (a1) are used alone or in combination of two or more.

  The exemplified C.I. I. Among pigment pigments, C.I. I. Pigment orange 38, C.I. I. Pigment red 122, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 208, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment violet 23, C.I. I. Pigments selected from Pigment Blue 15: 3 and Pigment Blue 15: 6 may be preferably used.

  As the pigment, it is preferable to use a pigment dispersion in which the particle diameter is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing by adding a pigment dispersant (d3). According to this method, the pigment is uniformly dispersed in the solution. A pigment dispersion is obtained.

  Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants. These may be used alone or in combination of two or more. They can be used in combination.

  The content of the pigment (d1) is 20 to 90% by mass, preferably 30 to 70% by mass with respect to the total solid powder in the pigment dispersion composition. If the content of the pigment is in the range of 20 to 90% by mass based on the above, it is preferable because the viscosity is low, the storage safety is excellent, the dispersion efficiency is high, and the light / dark ratio is effective.

  As the dispersant (d3), in addition to the acrylic dispersant as described above, a pigment dispersant of another resin type is used. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylates, polycarboxylates (partially A) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and their modified products, or free (Free) Milky dispersants such as amides formed by the reaction of polyesters having carboxy groups with poly (lower alkyleneimines) or salts thereof; (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- ( (Meth) acrylates Water-soluble resins or water-soluble polymer compounds such as polyethylene copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; polyesters; modified polyacrylates; ethylene oxide / propylene oxide addition products and phosphate esters. . As a commercially available product of the above-mentioned resin-type dispersant, as a cationic resin dispersant, for example, trade names of BYK (Big) Chemi: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163 , DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's trade names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA- 4010, EFKA-4050, EFKA-40505, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-451 , EFKA-4800; trade names of Lubilzol: SOLPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; trade names of Kawaken Fine Chemicals: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000 Trade names of Ajinomoto Co., Inc .: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; trade names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, Florence DOPA-15BHF, Florence DOPA-33, Florence DOPA-44 etc. are mentioned. In addition to the acrylic dispersants described above, other resin-type pigment dispersants can be used alone or in combination of two or more, and can also be used in combination with acrylic dispersion.

  The usage-amount of the said dispersing agent (d3) is 5-60 mass parts with respect to 100 mass parts of solid powder of the pigment (d1) used, More preferably, it is the range of 15-50 mass parts. If the content of the dispersant (d3) exceeds 60 parts by mass based on the above, the viscosity can be increased, and if it is less than 5 parts by mass, it becomes difficult to atomize the pigment, Can cause problems.

Dye (d2)
The dye is used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye that can ensure the solubility in an alkali developer, the heat resistance, the solvent resistance, and the like while having solubility in an organic solvent.

  Examples of the dye include those selected from acidic dyes having an acidic group such as sulfonic acid and carboxylic acid, salts of acidic dyes and nitrogen-containing compounds, sulfonamides of acidic dyes, and derivatives thereof. In addition, azo, xanthene, and phthalocyanine acid dyes and derivatives thereof can also be selected. Preferably, the dye includes a compound classified as a dye in the color index (published by The Society of Dyersand Colorists), and a known dye described in a dye note (color dye company).

  Specific examples of the dye include C.I. I. Examples of the solvent dye include the following dyes.

  For example, C.I. I. Examples include red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, and 179.

  In addition, C.I. I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 59, 67, 70 are listed.

  In addition, C.I. I. And violet dyes such as Solvent Violet 8, 9, 13, 14, 36, 37, 47, 49.

  Furthermore, C.I. I. And yellow dyes such as Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162.

  Furthermore, C.I. I. And orange dyes such as Solvent Orange 2, 7, 11, 15, 26, 56.

  In addition, C.I. I. Examples include green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

  C. I. Excellent solubility in organic solvents in solvent dyes, C.I. I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; I. Solvent Blue 35, 36, 44, 45, 70; C.I. I. Solvent violet 13 is preferable, and among these, C.I. I. Solvent red 8, 122, 132 are more preferable.

  Furthermore, C.I. I. Examples of the acid dye include the following dyes.

  For example, C.I. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, And red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426.

  In addition, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251 etc. Can be mentioned.

  In addition, C.I. I. Examples include orange dyes such as Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, and 173. It is done.

  Furthermore, C.I. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, And blue dyes such as 335 and 340.

  Furthermore, C.I. I. Examples thereof include violet dyes such as Acid Violet 6B, 7, 9, 17, 19, 66.

  In addition, C.I. I. And green dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109.

  Excellent solubility in organic solvents among acid dyes, C.I. I. Acid Red 92; I. Acid Blue 80, 90; I. Acid violet 66 is preferred.

  Furthermore, C.I. I. Examples of the direct dye include the following dyes.

  C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 and the like.

  In addition, C.I. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, And yellow dyes such as 136, 138, and 141.

  In addition, C.I. I. Examples include orange dyes such as direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, and 107.

  Furthermore, C.I. I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc. It includes the color dye.

  Furthermore, C.I. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like can be mentioned.

  In addition, C.I. I. Examples thereof include green dyes such as direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82.

  In addition, C.I. I. And yellow dyes such as Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65.

  In addition, C.I. I. Modern tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, Examples include red dyes such as 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, and 95.

  In addition, C.I. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. Dyes.

  Furthermore, C.I. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like.

  Furthermore, C.I. I. Violet color dyes such as modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 .

  In addition, C.I. I. Green dyes such as Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53 can be used.

  These dyes can be used alone or in combination of two or more.

  The dye content in the colorant (D) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, based on the solid powder in the colorant (D). Preferably, 1 to 50% by weight is particularly preferable. If the content of the dye in the colorant (D) is within the above range, it is possible to prevent the problem of lowering reliability in which the dye is eluted by the organic solvent after pattern formation, and the sensitivity is excellent.

  The content of the colorant (D) including the pigment and the dye according to the present invention is not particularly limited, but may be included at, for example, 5 to 60% by weight based on the total weight of the solid powder in the composition, preferably 10 to 45% by weight. If the above range is satisfied, the color density of the pixels is sufficient even if a thin film is formed, and the degree of omission of the non-image area is not lowered during development, so that it is preferable that no residue is generated.

<Solvent (E)>
The solvent (E) used in the present invention can be used without particular limitation as long as it is effective for dissolving other components contained in the colored photosensitive resin composition, and particularly ethers and aromatics. Hydrocarbons, ketones, alcohols, esters or amides are preferred.

  Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether.

  In addition, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether are listed.

  Moreover, ethylene glycol alkyl ether acetates, such as methyl cellosolve acetate and ethyl cellosolve acetate, are mentioned.

  Further, alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate can be mentioned.

  Furthermore, aromatic hydrocarbons, such as benzene, toluene, xylene, mesitylene, are mentioned.

  Furthermore, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone can be mentioned.

  Also, alcohols such as ethyl alcohol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 4-hydroxy-4-methly-2-pentanone, etc. may be mentioned. .

  Moreover, ester, such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, cyclic esters, such as (gamma) -butyrolactone, etc. are mentioned.

  The solvent (E) is preferably an organic solvent having a boiling point of 100 to 200 ° C. in view of coating properties and drying properties, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butane Lulactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like are used. Can be mixed with alcoholic solvents such as 4-hydroxy-4-methly-2-pentanone, which can suppress the precipitation of dyes and improve storage safety preferable.

  The exemplified solvent (E) can be used alone or in combination of two or more, and is 60 to 90% by weight, preferably 70 to 85% based on the total weight of the colored photosensitive resin composition of the present invention. % By weight. When the above range is satisfied, when coating is performed by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an ink jet, an effect of improving the coatability is provided.

  The colored photosensitive resin composition of the present invention can optionally further contain an additive as necessary, for example, other polymer compound, curing agent, surfactant, adhesion promoter, antioxidant, ultraviolet absorption. Examples thereof include, but are not limited to, an aggregation inhibitor and the like.

  Specific examples of the other polymer compounds include thermoplastic resins such as curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Resin etc. are mentioned.

  The curing agent is used to enhance deep curing and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.

  Specific examples of the epoxy compound as the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, Aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of such epoxy resins, aliphatics other than epoxy resins and brominated derivatives thereof, alicyclic Alternatively, aromatic epoxy compounds, butadiene (co) polymer epoxidized products, isoprene (co) polymer epoxidized products, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate and the like can be mentioned.

  Specific examples of the oxetane compound as the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  The curing agent can be used in combination with a curing auxiliary compound so as to ring-open polymerization the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. As the polyvalent carboxylic acid anhydrides, those commercially available as epoxy resin curing agents are used. Specific examples of the epoxy resin curing agent include a trade name (Adeka Hadna EH-700) (manufactured by Adeka Industries Co., Ltd.), a trade name (Rikacid HH) (manufactured by Shin Nippon Chemical Co., Ltd.), and a trade name (MH-700). ) (Manufactured by Shin Nippon Rika Co., Ltd.). The curing agents exemplified above are used alone or in admixture of two or more.

  The surfactant can be used to further improve the film-forming property of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant can be preferably used.

  Examples of the commercially available silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc., manufactured by Dow Corning Dray Silicone Co., Ltd., and TSF-4440, TSF-4445, TSF-4445, TSF of GE Toshiba Silicone Co., Ltd. -4446, TSF-4460, TSF-4442, and the like. Examples of the fluorosurfactant include MegaFace F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals, Inc. as commercially available products. The exemplified surfactants can be used alone or in combination of two or more.

  Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxy Run, 3-isocyanate propyl triethoxysilane and the like. The adhesion promoters exemplified above can be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solid powder of the colored photosensitive resin composition.

  Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

  Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.

  Specific examples of the aggregation inhibitor include sodium polyacrylate.

Synthesis Example 1: Synthesis of Colorant Composition (1) Colorant Composition (M1)
As a pigment, C.I. I. Pigment Red 177 12.0 parts by mass, as a pigment dispersant, DISPERBYK-2001 (manufactured by BYK) 4.0 parts by mass, as a dye, 1.2 parts by mass of Acid Red 52, and as a solvent, 44 parts by mass of propylene glycol methyl ether acetate And 20 parts by mass of 4-hydroxy-4-methly-2-pentanone were mixed / dispersed in a bead mill for 12 hours to produce a colorant composition (M1). did.

(2) Colorant composition (M2)
As a pigment, C.I. I. Pigment Red 177 13.2 parts by mass, DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 4.0 parts by mass, and as a solvent, 44 parts by mass of propylene glycol methyl ether acetate and 4-hydroxy-4-methyl-2- A colorant composition (M2) was produced by mixing / dispersing 20 parts by mass of 4-hydroxy-4-methly-2-pentanone with a bead mill for 12 hours.

Synthesis Example 2: Synthesis of Alkali-Soluble Resin (1) Synthesis of Alkali-Soluble Resin (A-1) 100 parts of propylene glycol monomethyl ether acetate in a flask equipped with a stirrer, thermometer reflux condenser, cargo lot, and nitrogen inlet tube ( Parts by mass), 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, 23.0 parts of 2-ethylhexyl acrylate, 1.6 parts of 4-methylstyrene, 46.0 parts of glycidyl methacrylate, 3 parts of n-dodecyl mercapto, and nitrogen Replaced. Thereafter, the temperature of the reaction solution was increased to 80 ° C. by stirring and reacted for 4 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the atmosphere in the flask was replaced with nitrogen. Then, 0.2 part of triethylamine, 0.1 part of 4-methoxyphenol, and 23.3 parts of acrylic acid were added to 100 ° C. For 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 parts of succinic anhydride was added, and the reaction was carried out at 80 ° C. for 6 hours.

  The solid powder acid value of the alkali-soluble resin thus synthesized was 32.8 mgKOH / g, the weight average molecular weight Mw measured by GPC was about 6350, and the repeating unit shown in Chemical Formula 1 was 70 mol%. .

  The glass transition temperature measured with a differential scanning calorimeter was -12 ° C.

(2) Synthesis of alkali-soluble resin (A-2) 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN in a flask equipped with a stirrer, thermometer reflux condenser, cargo lot and nitrogen introduction pipe , 21.4 parts of 2-ethylhexyl acrylate, 1.5 parts of 4-methylstyrene, 42.8 parts of glycidyl methacrylate, and 3 parts of n-dodecyl mercapto were added, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was stirred to raise the temperature of the reaction solution to 80 ° C. and reacted for 4 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the flask atmosphere was replaced with nitrogen to air. Then, 0.2 part of triethylamine, 0.1 part of 4-methoxyphenol, and 21.7 parts of acrylic acid were added to 100 ° C. For 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 12.5 parts of succinic anhydride was added, and the reaction was carried out at 80 ° C. for 6 hours.

  The solid powder acid value of the alkali-soluble resin thus synthesized was 68.6 mgKOH / g, the weight average molecular weight Mw measured by GPC was about 5570, and the repeating unit shown in Chemical Formula 1 was 70 mol%. It was.

  The glass transition temperature measured with a differential scanning calorimeter was -8.3 ° C.

(3) Synthesis of alkali-soluble resin (A-3) 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN in a flask equipped with a stirrer, thermometer reflux condenser, cargo lot and nitrogen introduction pipe , 17.3 parts of 2-ethylhexyl acrylate, 1.2 parts of 4-methylstyrene, 59.4 parts of glycidyl methacrylate and 3 parts of n-dodecyl mercapto were added, and the atmosphere was replaced with nitrogen. Thereafter, the temperature of the reaction solution was increased to 80 ° C. by stirring and reacted for 4 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the flask atmosphere was replaced with nitrogen to air. Then, 0.2 part of triethylamine, 0.1 part of 4-methoxyphenol, and 17.6 parts of acrylic acid were added, and 100 ° C. For 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 4.5 parts of succinic anhydride was added, and the reaction was carried out at 80 ° C. for 6 hours.

  The solid powder acid value of the alkali-soluble resin thus synthesized was 24.98 mg KOH / g, the weight average molecular weight Mw measured by GPC was about 5950, and the repeating unit shown in Chemical Formula 1 was 80 mol%. It was. The glass transition temperature measured with a differential scanning calorimeter was −20.4 ° C.

(4) Synthesis of alkali-soluble resin (A-4) In a flask equipped with a stirrer, a thermometer reflux condenser, a cargo lot and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, AIBN5 Parts, 2-ethylhexyl acrylate 10.2 parts, 4-methylstyrene 0.7 part, glycidyl methacrylate 76.0 parts, n-dodecyl mercapto 3 parts were added, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was stirred to raise the temperature of the reaction solution to 80 ° C. and reacted for 4 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the atmosphere in the flask was replaced with nitrogen. Then, 0.2 part of triethylamine, 0.1 part of 4-methoxyphenol, and 10.4 parts of acrylic acid were added, and 100 ° C. For 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 2.7 parts of succinic anhydride was added, and the reaction was carried out at 80 ° C. for 6 hours.

  The solid powder acid value of the alkali-soluble resin thus synthesized was 16.45 mgKOH / g, the weight average molecular weight Mw measured by GPC was about 5450, and the repeating unit represented by Chemical Formula 1 was 90 mol%. . The result of measuring the glass transition temperature with a differential scanning calorimeter was −28.4 ° C.

(5) Synthesis of alkali-soluble resin (A-5) In a flask equipped with a stirrer, a thermometer reflux condenser, a cargo lot and a nitrogen introduction pipe, 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, AIBN2 Parts, 13.0 parts of the acrylic acid, 10 parts of benzyl methacrylate, 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate, and 3 parts of n-dodecyl mercapto were substituted with nitrogen. Thereafter, the temperature of the reaction solution was increased to 80 ° C. by stirring and reacted for 8 hours. The solid powder acid value of the alkali-soluble resin thus synthesized was 98.2 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 14950.

  The glass transition temperature measured with a differential scanning calorimeter was 95 ° C.

(6) Synthesis of alkali-soluble resin (A-6) In a flask equipped with a stirrer, a thermometer reflux condenser, a cargo lot and a nitrogen introduction pipe, 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, AIBN2 Parts, 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 67.0 parts of 4-methylstyrene, 10 parts of methyl methacrylate, and 3 parts of n-dodecyl mercapto were substituted with nitrogen. Thereafter, the temperature of the reaction solution was increased to 80 ° C. by stirring and reacted for 8 hours. The solid powder acid value of the alkali-soluble resin thus synthesized was 81.6 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 16110.

  The glass transition temperature measured with a differential scanning calorimeter was 85 ° C.

(7) Synthesis of alkali-soluble resin (A-7) In a flask equipped with a stirrer, a thermometer reflux condenser, a cargo lot and a nitrogen introduction pipe, 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, AIBN2 Parts, 5.0 parts of the acrylic acid, 20 parts of benzyl methacrylate, 55.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercapto were substituted with nitrogen. Thereafter, the temperature of the reaction solution was increased to 80 ° C. by stirring and reacted for 8 hours. The solid powder acid value of the alkali-soluble resin thus synthesized was 17.4 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 17370.

  The glass transition temperature measured with a differential scanning calorimeter was 82 ° C.

Examples and Comparative Examples Photosensitive resin compositions were produced using the components and contents shown in Table 1 below.

Test Method (1) Evaluation of Development Speed and Adhesion Color filters were produced using the colored photosensitive resin compositions produced in the examples and comparative examples.

Specifically, each of the colored photosensitive resin compositions is applied onto a 2 inch square glass substrate (manufactured by Konin, “EAGLE XG”) by spin coating, and then heated at 100 ° C. on a heating plate. A thin film was formed by maintaining for a minute. Subsequently, a test photomask having a pattern for changing the transmittance on the staircase in a range of 1 to 100% and a line / space pattern of 1 to 100 μm is placed on the thin film, and the distance from the test photomask is set. Ultraviolet rays were irradiated at 300 μm. At this time, the ultraviolet light source is irradiated with an illuminance of 60 mJ / cm ² using a 1 KW high-pressure mercury lamp including all of g, h, and i rays, and no special optical filter is used. The thin film irradiated with the ultraviolet rays was developed for 2 minutes in a KOH aqueous solution having a pH of 10.5. The glass plate coated with the thin film was washed with distilled water, dried by spraying nitrogen gas, and heated in a heating oven at 200 ° C. for 25 minutes to produce a color filter.

  The film thickness of the color filter manufactured above was 2.4 μm.

  The time (development speed) required for the unexposed area to be completely dissolved in the developer during development during the development was measured and listed in Table 2 below.

  Moreover, when the produced | generated pattern was evaluated with the optical microscope, adhesiveness was evaluated in the peeling phenomenon level of the following 20 micrometers pattern, and it showed in following Table 2.

<Evaluation criteria>
○: No pattern peeling △: Pattern peeling 1 to 3 ×: Pattern peeling 4 or more

(2) Transmittance measurement (%)
A color filter was manufactured by the same method as Test Method (1) except that the test photomask was not used.

  Among the formed patterns, the transmittance of a line pattern portion of 100 μm was measured using a chromaticity meter (manufactured by Olympus, OSP-200) and shown in Table 2 below.

(3) Step measurement (Å)
The colored photosensitive resin compositions of Examples and Comparative Examples were applied by spin coating on a 2-inch substrate patterned with a black matrix of 1.5 μm-thick lines / spaces, and then 65 Pa with vacuum drying equipment. The solution was vacuumed and dried until Thereafter, the substrate was maintained on a heating plate at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, ultraviolet rays were irradiated on the thin film without a photomask. At this time, the ultraviolet light source was irradiated at 40 mJ / cm ² using a 1 KW high-pressure mercury lamp including all g, h, and i rays, and no special optical filter was used. The thin film irradiated with the ultraviolet rays was developed for 2 minutes in a KOH aqueous solution having a pH of 10.5. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C. for 25 minutes to produce a color filter. The difference in level between the color resist portion formed on the BM pattern and the color resist formed on the glass was measured using Surface Profiler (Veeco Dektak 6M). The results are shown in Table 2 below.

  Referring to Table 2, in the case of the colored photosensitive resin composition according to the present invention (Examples 1-4), it shows excellent adhesion even though the development speed is very fast, and the step value is It was confirmed that it is very small and has a high transmittance and is suitable for producing a color filter of excellent quality.

  However, in the case of Example 4 in which the alkali-soluble resin contains a slightly excessive amount of the repeating unit of Chemical Formula 1, it was confirmed that the development speed and the adhesion force were slightly reduced as compared with the other examples.

  In the case of Comparative Example 2 in which the alkali-soluble resin of the present invention was used but only the pigment was used as the colorant, the development speed and the adhesion were the same as those in the Examples, but the transmittance reduction and the step value were remarkably high. We were able to confirm that it increased.

  In Comparative Examples 1, 3, and 4 in which the alkali-soluble resin of the present invention was not used, it was confirmed that the development speed and the adhesion were significantly reduced and the step value was also increased. In particular, Comparative Examples 3 and 4 were able to confirm that the transmittance value was significantly reduced by using only the pigment as the colorant.

Claims (7)

Including an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D) and a solvent (E);
The colorant (D) includes a pigment (d1) and a dye (d2),
The alkali-soluble resin (A) includes a repeating unit represented by the following chemical formula 1,
Colored photosensitive resin composition in which the glass transition temperature of the alkali-soluble resin (A) is less than 0 ° C .:

(In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and R ₃ is a residue containing a carboxylic acid derived from an acid anhydride).   Examples of the acid anhydride include phthalic anhydride, (2-dodecen-1-yl) succinic anhydride ((2-Dodecen-1-yl) succinic anhydride, maleic anhydride, and anhydride). Succinic anhydride, Citraconic anhydride, Glutaric anhydride, Methylsuccinic anhydride, 3,3-dimethylgluthydric anhydride, 3,3-dimethylgluthydric anhydride , Phenylsuccinic anhydride, itaconic anhydride (Itaconic anhydride), 3,4,5,6-tetrahydrophthalic anhydride (3,4,5,6-tetrahydrophthalic anhydride), trimellitic anhydride, hexahydrophthalic anhydride The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition is selected from the group consisting of carboxylic acid anhydride and carbic anhydride.   The colored photosensitive resin composition according to claim 1 or 2, wherein the repeating unit of the chemical formula 1 is contained in an amount of 50 to 90 mol% with respect to the entire alkali-soluble resin (A).   The alkali-soluble resin (A) is copolymerized by further including a monomer having an unsaturated double bond in addition to the monomer for realizing the repeating unit of Formula 1. The colored photosensitive resin composition according to any one of 3 above.   The colored photosensitive resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin (A) is contained in an amount of 10 to 80% by weight based on the total solid powder content in the composition.   The color filter formed using the colored photosensitive resin composition as described in any one of Claims 1-5.   An image display device comprising the color filter according to claim 6.