JP5250888B2 - Colored photosensitive resin composition, color filter obtained by using the colored photosensitive resin composition, and liquid crystal display device including the color filter - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition, a color filter obtained using the colored photosensitive resin composition, and a liquid crystal display device including the color filter.

  Color filters are widely used in image sensors, liquid crystal display devices (LCDs), and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device or an image pickup element is usually formed by spin coating a colored photosensitive resin composition containing pigments corresponding to red, green and blue colors on a substrate on which a black matrix is formed. After uniformly coating, the coating film formed by heating and drying (hereinafter sometimes referred to as pre-baking) is exposed and developed, and further heat-cured as necessary (hereinafter also referred to as post-baking). This operation is repeated for each color to produce pixels of each color. Thereafter, a step of forming an ITO electrode on the surface of the color filter for a liquid crystal display device is performed. In this step, the color filter is exposed to a high temperature of about 200 ° C. or more. Also, the alignment film is exposed to a high temperature of 200 ° C. or higher.

  In such a photosensitive coloring composition, an acrylic resin having a carboxyl group in the side chain is used as a resin having excellent light resistance and little color change. For example, a colored photosensitive resin composition using an acrylic resin containing a carboxyl group in the side chain, a pigment, and a polyfunctional acrylate is known.

  However, when forming a pixel using a conventional composition, if the colored layer formed on the base is a photosensitive resin composition that is inferior in heat resistance, brightness and color due to insufficient heat resistance during high-temperature processing. There is a problem that the image and color purity are deteriorated, such as deterioration of characteristics and generation of an afterimage due to outgas generated by decomposition of the photosensitive resin composition.

  In order to improve the above problems, Patent Document 1 and Patent Document 2 use a curable resin having a high Tg (glass transition temperature) containing a tetrahydropyran group or an N-substituted maleimide group in the curable resin structure. Although this improves the transparency and heat-resistant yellowing performance, the outgas is the same as that generated with a low-Tg curable resin, although the substituents contained in the side chain are decomposed in the high-temperature process. Occurs and has a problem that causes afterimages. Further, when the hydrophobicity of the curable resin composition is high, there is a problem that developability is extremely deteriorated with an equivalent acid value.

JP 2004-300204 A Japanese Patent Laid-Open No. 10-300922

  The present invention has been devised to solve the above-mentioned problems of the prior art, and its purpose is to generate a development residue on a substrate when a pixel is formed using a colored photosensitive resin composition. In other words, the present invention provides a photosensitive resin composition in which the pixel portion is free from surface defects and the like, the pencil hardness and sensitivity are excellent, there is no problem during development, the outgassing is significantly reduced, and the afterimage problem is solved.

  Another object of the present invention is to provide a high-quality color filter and a liquid crystal display device including the color filter using the colored photosensitive resin composition according to the present invention.

The colored photosensitive resin composition according to the present invention for achieving the above object is a colored photosensitive resin composition comprising a curable resin A, a photopolymerizable compound B, a photopolymerization initiator C, a coloring material D, and a solvent E. The curable resin A is an unsaturated group-containing colored photosensitive resin composition obtained by further reacting the compound A4 with a copolymer obtained by copolymerizing the following compounds A1 to A3. The following compound A1 is characterized in that it is at least one selected from the compounds represented by the following chemical formulas 1 and 2.
Compound A1: Compound having an unsaturated bond capable of forming a cyclic structure in the main chain Compound A2: Vinyltoluene Compound A3: Compound having an unsaturated carboxyl group Compound A4: Having an unsaturated bond and an epoxy group in one molecule Compound.

  Moreover, it is preferable that the compound A3 provided with the said unsaturated carboxyl group is acrylic acid.

The ratio of the component derived from each of the compounds A1 to A3 is based on the total number of moles of the curable resin component,
Constituent units derived from compound A1: 2 mol% to 50 mol%
Structural units derived from compound A2: 2 mol% to 60 mol%
Structural units derived from compound A3: 2 mol% to 70 mol%
It is also preferable that the compound A4 is obtained by reacting 5 mol% to 80 mol% of the component derived from the compound A3.

  In addition, the color filter according to the present invention is characterized by including a color layer formed by applying the colored photosensitive resin composition on an upper portion of a substrate, exposing and developing it in a predetermined pattern.

  In addition, a liquid crystal display device according to the present invention includes the color filter.

  If pixels are formed using the colored photosensitive resin composition according to the present invention, development residues are not generated on the substrate, surface defects are not generated on the pixel portions, and the pencil hardness and sensitivity are excellent, and there is a problem during development. And significantly reduce outgassing. As a result, a colored photosensitive resin composition capable of solving the afterimage problem can be provided, and a high-quality color filter can be provided.

  Hereinafter, the present invention will be described in detail. The following specific description is an explanation of one embodiment of the present invention, and even if expressed in a limited manner, the scope of rights determined from the scope of claims. Note that this is not a limitation.

  The colored photosensitive resin composition in one embodiment of the present invention is a colored photosensitive resin composition comprising a curable resin A, a photopolymerizable compound B, a photopolymerization initiator C, a coloring material D, and a solvent E. The curable resin A is an unsaturated group-containing resin obtained by further reacting the compound A4 with a copolymer obtained by copolymerizing the following compounds A1 to A3.

Compound A1: Compound provided with an unsaturated bond capable of forming a cyclic structure in the main chain Compound A2: Vinyltoluene Compound A3: Compound provided with an unsaturated carboxyl group Compound A4: Provided with an unsaturated bond and an epoxy group in one molecule Compound

  The curable resin A usually has reactivity and alkali solubility due to the action of light and heat, and functions as a dispersion medium for the coloring material.

  In addition to the above monomers, the present invention may further include other monomers as necessary for copolymerization.

  Specific examples include unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, aminoethyl (meth) acrylate;

  Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclo Hexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pinenyl Unsaturated carboxylic acid ester compounds containing an alicyclic substituent such as (meth) acrylate;

  Monounsaturated carboxylic acid ester compounds of glycols such as unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate; oligoethylene glycol monoalkyl (meth) acrylate; Etc. can be used.

  In the embodiment of the present invention, examples of the compound A1 having an unsaturated bond capable of forming a cyclic structure in the main chain include a compound capable of forming a tetrahydropyran ring at the time of polymerization, an N-substituted maleimide compound, and the like. Compound A1 having an unsaturated bond capable of forming a cyclic structure in the chain can be used alone or in combination of two or more of tetrahydropyran and N-substituted maleimides.

  The compound capable of forming a tetrahydropyran ring at the time of polymerization can be exemplified as a compound represented by Chemical Formula 5 shown below.

Specific examples of R ₁ and R ₂ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, and cyclohexane. There are a xyl group, an ethylhexyl group, a methoxyethyl group, an ethoxyethyl group, a benzyl group and the like, and among them, a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group are more preferable. These can be used alone or in combination of two or more.

  If the compound shown in Chemical Formula 5 is polymerized, a resin formed by mixing two repeating unit structures according to the polymerization reaction formula shown in Chemical Formula 6 below can be obtained, or any one major repeating unit can be used. A formed resin is obtained.

  Examples of the N-substituted maleimide compound include compounds represented by Chemical Formula 7 shown below.

In the above formula, R ₃ is a phenyl group, a benzyl group, a naphthal group, a cyclohexyl group, a methyl group, an ethyl group, a propyl group or the like, and particularly excellent in heat resistance when benzyl maleimide, which is a benzyl group, is used. Therefore, it is preferable. These can be used alone or in combination of two or more. And if vinyl toluene is used as a monomer as compound A2 contained in one molecule, and a curable resin is produced as a colored photosensitive resin composition, it is excellent in effects such as reduction in outgas generation. Become.

  If the compound A3 having an unsaturated carboxyl group is a carboxyl group-containing monomer, the compound A3 has one or more carboxyl groups in a molecule such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid. Unsaturated carboxylic acids such as unsaturated polyvalent carboxylic acids can be used. Here, as the unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid and the like can be used. As the unsaturated dicarboxylic acid, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like can be used. Unsaturated polyvalent carboxylic acid is also an acid anhydride, and specifically, maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride and the like can be used. Unsaturated polyvalent carboxylic acids are mono (2-methacryloyloxyalkyl) esters such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), and phthalic acid mono (2 -Acryloyloxyethyl), mono (2-methacryloyloxyethyl) phthalate and the like can be used.

  The unsaturated polyvalent carboxylic acid is a mono (meth) acrylate of a dicarboxy polymer at both ends, and for example, ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, and the like can be used. These carboxyl group-containing monomers can be used alone or in admixture of two or more.

  In the composition containing the compound having an unsaturated bond capable of forming a cyclic structure in the main chain and the aromatic vinyl compound, it is more preferable to use acrylic acid because there is no problem of developability and development residue on the substrate. .

  In the embodiment of the present invention, in the copolymer obtained by copolymerizing the compounds A1 to A3 used in the present invention, the ratio of the constituent components derived from each of the compounds A1 to A3 constitutes the copolymer. It is preferable that it exists in the range below a mole fraction with respect to the total number of moles of the component to perform.

  It is preferable that the ratio of the component derived from each of the compound A1 to the compound A3 is in the following range with respect to the total number of moles of the copolymer component. If the said composition ratio exists in the following range, since the balance of developability, solubility, and heat resistance is favorable, the preferable curable resin A is obtained.

Constituent units derived from compound A1: 2 mol% to 50 mol%
Structural units derived from compound A2: 2 mol% to 60 mol%
Structural units derived from compound A3: 2 mol% to 70 mol%

  In the embodiment of the present invention, the method for producing the copolymer by copolymerizing the compounds A1 to A3 is not particularly limited, and various known polymerization methods can be employed. However, a more preferable method is a solution polymerization method. The polymerization temperature and polymerization time vary depending on the type and ratio of monomer components used, the molecular weight and acid value of the target copolymer, and preferably maintained at 60 to 130 ° C. for 1 to 10 hours. It can be polymerized. In the production of the copolymer, one part or the whole amount of the polymerization initiator may be charged into the reaction vessel, and one part or the whole amount of the compound A1, compound A2, and compound A3 may be charged into the reaction vessel. .

  Moreover, when using a solvent for manufacture of the said copolymer, the solvent used at the time of normal radical polymerization reaction can be utilized as a solvent. Specific examples include tetrahydrofuran, dioxan, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, Ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like can be used. These solvents can be used alone or in combination of two or more.

  Moreover, as a polymerization initiator used for manufacture of the said copolymer, the polymerization initiator used normally can be added and it does not need to specifically limit. Specific examples include diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl. Organic peroxides such as peroxy-2-ethylhexanoate, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2 Nitrogen compounds such as' -azobis (2-methylpropionate) can be used. These can be used alone or in combination of two or more.

  In order to control the molecular weight and molecular weight distribution, mercapto chain transfer agents such as n-dodecyl mercapto, mercaptoacetic acid and methyl mercaptoacetate, α-methylstyrene dimer, and the like can also be used as the chain transfer agent. The amount of α-methylstyrene dimer or mercapto compound used is 0.005% to 5% on a mass basis with respect to the total amount of Compound A1, Compound A2, Compound A3 and Compound A4. In addition, the polymerization conditions may be adjusted as appropriate depending on the production equipment and the amount of heat generated by the polymerization.

  As compound A4 having an unsaturated bond and an epoxy group in one molecule, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, Methyl glycidyl (meth) acrylate or the like can be used. Among these, glycidyl (meth) acrylate can be preferably used. These can be used alone or in combination of two or more. The compound A4 having an unsaturated bond and an epoxy group is preferably reacted at 5 to 80 mol% with respect to the number of moles of the compound A3 having an unsaturated carboxyl group contained in the copolymer. 10 mol% to 80 mol% is particularly preferable. If the composition ratio of the compound A4 is within the above range, sufficient photocurability and thermosetting can be obtained, and both sensitivity and pencil hardness can be achieved, and the reliability is excellent.

  In the present invention, the curable resin A can be produced by reacting the copolymer and the compound A4 by, for example, the following method.

  The atmosphere in the reaction vessel is replaced from nitrogen to air, and 5 mol% to 80 mol% of the compound A4, carboxyl group and epoxy with respect to the component derived from the compound A3 having the unsaturated carboxyl group As a group reaction catalyst, for example, trisdimethylaminomethylphenol is 0.01% to 5% on a mass basis with respect to the total amount of Compound A1 to Compound A4, and as a polymerization inhibitor, for example, hydroquinone is the sum of Compound A1 to Compound A4. If 0.001% -5% is thrown into a reaction container on the mass basis with respect to quantity, and if it maintains at 60 degreeC-130 degreeC for 1 hour-10 hours, the said copolymer and compound A4 can be made to react. Similarly to the polymerization conditions, the charging method and reaction temperature may be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization.

  In the embodiment of the present invention, the curable resin A preferably has a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. preferable. When the weight average molecular weight of the curable resin A is in the range of 3,000 to 100,000, film reduction is unlikely to occur during development, and the non-pixel portion can be easily removed during development.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the curable resin A is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. If the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5 to 6.0, the developability is excellent.

  The content of the curable resin A is usually 5% by mass to 85% by mass, preferably 10% by mass to 70% by mass with respect to the solid content in the colored photosensitive resin composition. If the content of the curable resin A is 5% by mass to 85% by mass on the basis of the above, the solubility in the developer is sufficient, and a development residue is hardly generated on the substrate of the non-pixel part. It is difficult for the film reduction of the pixel portion of the exposed portion to occur during development, so that the non-pixel portion can be easily removed.

  The photopolymerizable compound B contained in the colored photosensitive resin composition according to the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and is a monofunctional monomer, a bifunctional monomer, Other polyfunctional monomers can be used. The photopolymerizable compound B comprises two or more photopolymerizable compounds having different functional group structures and functional group numbers in order to improve the developability, sensitivity, adhesion, surface problems, etc. of the colored photosensitive resin composition. They can be mixed and used, and the range is not limited.

  As the monofunctional monomer, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, or the like may be used. it can.

  Bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol. A bis (acryloyloxyethyl) ether of A, 3-methylpentanediol di (meth) acrylate, or the like can be used.

  Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa ( A (meth) acrylate etc. can be used. Among these, a polyfunctional monomer having two or more functions can be preferably used.

  The photopolymerizable compound B is used in a mass fraction of usually 5% to 50% by mass, preferably 7% to 45% by mass, based on the solid content in the colored photosensitive resin composition. When the photopolymerizable compound B is in the range of 5% by mass to 50% by mass on the basis of the above, the strength and smoothness of the pixel portion are improved.

  The photopolymerization initiator C contained in the colored photosensitive resin composition according to the present invention is not limited, but one or more compounds selected from the group consisting of triazine compounds, acetophenone compounds, biimidazole compounds, and oxime compounds. Can be preferably used. The colored photosensitive resin composition containing the photopolymerization initiator C has high sensitivity, and the film formed using this composition has good strength and surface smoothness of the pixel portion. If the photopolymerization initiator auxiliary agent (C-1) is used in combination with the photopolymerization initiator C, the colored photosensitive resin composition containing them becomes more sensitive, and a color filter is formed using this composition. Increases productivity at the time.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-Methylfe E) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. Can do.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy). ) Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- It is possible to use an oligomer of dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, or the like. it can. The acetophenone compound is, for example, a compound represented by the following chemical formula 8.

Of the reduction _8, R 1 to R ₄ are substituted each independently, a hydrogen atom, a halogen atom, a hydroxyl _group, a substitutable phenyl group by an alkyl group of C 1 _{-C 12,} with an alkyl group of C 1 _{-C 12} possible benzyl or an alkyl group of C ₁ -C _12, either of the substitutable naphthalic group.

  Examples of the compound represented by the formula 8 include 2-methyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1-one, 2- Propyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-methyl-2-amino (4-morpholinophenyl) propane -1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propane-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) can be used propan-1-one and the like.

  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, an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted by a carboalkoxy group Etc. can be used. Of these, 2,2′bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5, 5′-tetraphenylbiimidazole can be preferably used.

  As the oxime compound, the compounds shown in the following chemical formula 9, chemical formula 10 and chemical formula 11 can be used.

  Moreover, as long as the effect of the present invention is not impaired, other photopolymerization initiators that are usually used in this field can be used in combination. As other photopolymerization initiators, for example, benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, and the like can be used. These can be used alone or in combination of two or more.

  Examples of benzoin compounds that can be used include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone, etc. can be used.

  As the thioxanthone compound, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like can be used.

  As the anthracene compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like can be used. . In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound Etc. can also be used as a photopolymerization initiator.

  Further, the photopolymerization initiator C can be used in combination with a photopolymerization initiation auxiliary agent (C-1).

  As the photopolymerization initiation auxiliary agent (C-1), amine compounds and carboxylic acid compounds can be preferably used. Among the photopolymerization initiation aids, amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate. Acid isoamyl, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4 ′ Aromatic amine compounds such as -di (N, N'-dimethylamino) -benzophenone and 4,4'-bis (diethylamino) benzophenone can be used. Among the amine compounds, an aromatic amine compound can be preferably used.

  Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid. , Aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid can be used.

  The amount of the photopolymerization initiator C used is usually 0.1% by mass to 40% by mass in terms of a mass fraction with respect to the total amount of the curable resin A and the photopolymerizable compound B based on the solid content, preferably Is 1% by mass to 30% by mass. And the usage-amount of a photoinitiation adjuvant (C-1) is 0.1 mass%-50 mass% normally by the said reference | standard, Preferably you may be 1 mass%-40 mass%. If the use amount of the photopolymerization initiator C is within the above range, the sensitivity of the colored photosensitive resin composition is enhanced, and the strength of the pixel portion formed using this composition and the smoothness on the surface of the pixel portion are increased. Property is improved. Moreover, if the usage-amount of photoinitiator adjuvant (C-1) exists in the said range, the sensitivity of a colored photosensitive resin composition will become still higher, and the production of the color filter formed using this composition will be carried out. Improves.

  The coloring material D used in the present invention is preferably an organic pigment or an inorganic pigment usually used in a pigment dispersion resist as a normal pigment. A dye can be used as necessary.

  As the inorganic pigment, a metal compound such as a metal oxide or a metal complex salt can be used. Specifically, a metal compound such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony is used. An oxide, a composite metal oxide, or the like can be used.

  The organic pigment and the inorganic pigment are compounds classified as pigments according to a color index (published by The Society of Dyer's and Colorists). More specifically, pigments having the following color index (CI) numbers can be used. However, it is not necessarily limited to these.

  C. I. Pigment yellow 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. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;

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

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

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

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

  C. I. Pigment brown 28;

  C. I. Pigment Black 1 and 7, etc.

  The coloring material D can be used alone or in combination of two or more. Content of the coloring material D is 3 mass%-60 mass% normally with respect to solid content in a colored photosensitive resin composition, Preferably you may be 5 mass%-55 mass%. If the content of the coloring material D is in the range of 3% by mass to 60% by mass on the basis of the above, the color density of the pixel is sufficient even if a thin film is formed, and the omission of the non-pixel part during development does not deteriorate Therefore, it is difficult to generate a residue.

  There is no restriction | limiting in particular in the solvent E which the colored photosensitive resin composition which concerns on this invention contains, The various organic solvent currently used in the field | area of the colored photosensitive resin composition can be used.

  Specifically, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether Diethylene glycol dialkyl ethers such as methyl cellosolve acetate, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Alkylene glycol alkyl ether acetates such as methoxybutyl acetate, methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol and other alcohols, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, cyclic esters such as γ-butyrolactone, etc. Can be used.

  Among the above solvents, from the viewpoints of coating properties and drying properties, it is preferable to use an organic solvent having a boiling point of 100 ° C. to 200 ° C., more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid. Esters such as ethyl and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. are preferably used. .

  These solvents E can be used alone or in admixture of two or more.

  Content of the solvent E in the colored photosensitive resin composition which concerns on this invention is a mass fraction with respect to the total amount of the solvent E and a colored photosensitive resin composition, and is normally 60 mass%-90 mass%, Preferably it is set as 70 mass%-85 mass%. If the content of the solvent E is in the range of 60% by mass to 90% by mass on the basis of the above, a roll coater, a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater), an inkjet, etc. Applicability when applied by a coating apparatus is improved.

  In the colored photosensitive resin composition according to the present invention, as necessary, a filler, other polymer compound, a curing agent, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like. Additive F can be used in combination.

  As the filler, glass, silica, alumina or the like can be used.

  As other polymer compounds, curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane can be used. .

  A hardening | curing agent is used in order to make deep part hardening and mechanical strength favorable, and an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound etc. can be used.

  Examples of the epoxy compound in 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, and other aromatic epoxy resins. , Alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin, or brominated derivatives of this epoxy resin, aliphatic resins other than epoxy resins and brominated derivatives thereof, alicyclic or 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 used.

  In the curing agent, as the oxetane compound, for example, carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylate bisoxetane, or the like can be used.

  The curing agent may include a curing auxiliary compound that enables ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. As the curing auxiliary compound, for example, polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, acid generators and the like can be used.

  As the carboxylic acid anhydrides, commercially available epoxy resin curing agents can be used. Specifically, the brand name (ADEKA HARDNA EH-700) (manufactured by ADEKA INDUSTRY CO., LTD.), The brand name (Rikasit HH) (manufactured by Shin Nippon Rika Co., Ltd.), and the brand name (MH-700) (Shin Nippon Rika ( Etc.) can be used. The said hardening | curing agent can be used individually or in mixture of 2 or more types.

  As the pigment dispersant, a commercially available surfactant can be used. For example, surfactants such as silicon-based, fluorine-based, ester-based, anionic-based, nonionic-based, cationic-based, and amphoteric. These can be used alone or in combination of two or more. These surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethane systems, and polyethyleneimines. . Specific products include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (MEGAFAC) ( Dainippon Ink Chemical Co., Ltd.), Florad (Sumitomo Suriem Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (SOLPERSE) ( Zeneka Co., Ltd.), EFKA (manufactured by EFKA Chemicals), PB821 (manufactured by Ajinomoto Co., Inc.) and the like can be used.

  As adhesion promoters, 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) ethyl Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-iso It can be used A titanate-propyl triethoxysilane. These adhesion promoters can be used alone or in combination of two or more.

  As the antioxidant, hindered phenol-based antioxidants such as 2,2′-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol are used. be able to.

  As the ultraviolet absorber, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, or the like can be used.

  As the aggregation inhibitor, sodium polyacrylate or the like can be used.

  These additives contain 0.01 mass%-10 mass% normally with respect to solid content in a coloring photosensitive resin composition, and preferably 0.05 mass%-5 mass%. If it is this range, the performance of an additive can be exhibited, without impairing the basic physical property of a coloring photosensitive resin composition.

  The colored photosensitive resin composition according to the present invention can be prepared, for example, by the following method. The coloring material D is mixed with the solvent E in advance, and is dispersed using a bead mill or the like until the average particle size of the coloring material is about 0.2 μm or less. Under the present circumstances, you may mix | blend 1 part or all of curable resin A using a pigment dispersant as needed. To the obtained dispersion (hereinafter sometimes referred to as mill base), the remainder of the curable resin A, the photopolymerizable compound B and the photopolymerization initiator C, other components used as necessary, and added as necessary If the solvent is further added to a predetermined concentration, the desired colored photosensitive resin composition can be obtained.

  Hereinafter, the pattern forming method of the colored photosensitive resin composition according to the present invention will be described.

  The pattern formation method of the colored photosensitive resin composition according to the present invention includes a step of applying the colored photosensitive resin composition onto a substrate, and a step of selectively exposing a one-part region of the colored photosensitive resin composition. And a step of removing an exposed region or a non-exposed region of the colored photosensitive resin composition.

  As one example, if a pattern is formed by applying onto a substrate as described below and performing photocuring and development, it can be used as a black matrix or a colored pixel (colored image).

  This composition is applied onto a substrate (no particular limitation, but usually a glass or silicon wafer is used) or a layer already formed with a solid content of a colored photosensitive resin composition. To dry a volatile component such as a solvent to obtain a smooth coating film. In this case, the thickness of the coating film is about 1 to 4 μm. A mask having a target pattern is placed on the coating film thus obtained, and a specific region is irradiated with ultraviolet rays. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper in order to uniformly irradiate the entire exposure unit with parallel light rays and enable accurate alignment between the mask and the substrate. Further, after the cured coating is brought into contact with an alkaline aqueous solution to develop the unexposed areas, a desired pattern can be obtained. After development, if necessary, post-drying may be performed at 150 to 230 ° C. for about 10 to 60 minutes.

  As a developer used for development after pattern exposure, an aqueous solution containing an alkaline compound and a surfactant is usually used.

  As the alkaline compound, both inorganic and organic alkaline compounds can be used.

  Inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, silicic acid Potassium, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like can be used.

  Further, as the organic alkaline compound, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc. are used. be able to. These inorganic and organic alkaline compounds can be used alone or in combination of two or more.

  The concentration of the alkaline compound in the alkaline developer is preferably 0.01% by mass to 10% by mass, and more preferably 0.03% by mass to 5% by mass.

  As the surfactant in the alkaline developer, any of a nonionic surfactant, an anionic surfactant or a cationic surfactant can be used.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxy Ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be used.

  Anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate. Alkyl aryl sulfonates such as can be used.

  As the cationic surfactant, an amine salt such as stearylamine hydrochloride or lauryltrimethylammonium chloride, or a quaternary ammonium salt can be used.

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

  The concentration of the surfactant in the alkali developer is usually in the range of 0.01% by mass to 10% by mass, preferably 0.05% by mass to 8% by mass, more preferably 0.1% by mass to 5% by mass. And

  Hereinafter, the color filter according to the present invention will be described. The color filter according to the present invention is a color filter including a color layer formed by exposing and developing the colored photosensitive resin composition in a predetermined pattern.

  Since the pattern of the colored photosensitive resin composition is the same as that obtained from the forming method, detailed description of the pattern forming method is omitted. As a general rule, a pixel or black matrix corresponding to the color of the coloring material in the photosensitive resin composition can be obtained by applying a colored photosensitive resin solution and drying it, exposing the pattern to the resulting dried coating film and developing it. Is obtained. Further, if such an operation is repeated for the number of colors required for the color filter, a color filter can be obtained. Since the configuration and the manufacturing method of the color filter are known techniques in the present technical field, detailed description thereof is omitted.

  The color filter usually has a black matrix and red, green, and blue primary color pixels arranged on a substrate. However, if the above-described operation is performed using the colored photosensitive resin composition according to the present invention containing a coloring material corresponding to a certain color, a black matrix or pixel of the target color can be obtained. When the same operation is performed using the colored photosensitive resin composition according to the present invention including a coloring material corresponding to a desired color for other colors, a black matrix and three primary color pixels are arranged on the substrate. can do. Moreover, it is also possible to apply the photosensitive resin composition according to the present invention to any one of the black matrix and the three primary colors, two colors, or three colors.

  In addition, the coloring (colored with black) photosensitive resin which concerns on this invention can be used for the black matrix which is a light shielding layer. However, since it can also be formed of, for example, a chromium layer, it is not essential to use the colored photosensitive resin composition according to the present invention in forming the black matrix.

  The color filter manufactured using the colored photosensitive resin composition according to the present invention has a small in-plane film thickness difference. If the film thickness is 1 to 4 μm, the in-plane film thickness difference can be 0.15 μm or less, and further 0.05 μm or less. Therefore, the color filter according to the invention of the main building is excellent in flatness. If this color filter is incorporated in a color liquid crystal display device, a liquid crystal display device of excellent quality can be manufactured with a high yield.

  The present invention also includes a liquid crystal display device including the color filter.

  The liquid crystal display device according to the present invention has a configuration known in the technical field except that it includes the color filter according to the present invention. That is, all liquid crystal display devices to which the color filter according to the present invention can be applied are included. As one example, a transmissive liquid crystal display in which a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode, and an alignment layer is opposed to each other at a predetermined interval, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Device. In addition, a reflective liquid crystal display device in which a reflective layer is provided between a color filter substrate and a colored layer can be provided.

  In addition, a TFT (Thin Film Transistor) substrate aligned on the transparent electrode of the color filter, and a liquid crystal display device including a backlight in which the TFT substrate is fixed at a position overlapping the color filter can be provided. The TFT substrate is arranged for each region of an outer frame made of light-proof resin surrounding a peripheral surface of the color filter, a liquid crystal layer made of nematic liquid crystal attached to the outer frame, and a liquid crystal layer. It can also be set as the structure provided with a polarizing plate on the surface which exposed the transparent glass substrate in which many pixel electrodes and pixel electrodes were formed, and a transparent glass substrate.

  The polarizing plate has a polarization direction that crosses vertically and is made of an organic material such as polyvinyl alcohol. A large number of pixel electrodes are connected to a plurality of thin film transistors formed on the glass substrate of the TFT substrate. Therefore, if a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage is applied between the specific pixel electrode and the transparent electrode. Therefore, the electric field formed by the voltage changes the alignment of the liquid crystal layer in a region corresponding to the specific pixel electrode.

  Hereinafter, although this invention is further explained in full detail based on an experiment example and an Example, it is an illustration to the last and the range of this invention is not limited to these embodiment. The scope of the present invention is described in the scope of claims, and further includes meanings equivalent to the description of the scope of claims and all modifications within the scope. In the following, “%” and “part” indicating the content are based on mass unless otherwise specified.

[Experimental example]
In the experimental example, as the curable resin according to the present invention, the resin a, the resin b, and the resin c used in the examples and the resin d, the resin e, the resin f, and the resin g used in the comparative example were synthesized.

<Synthesis of Resin a>
As the reaction vessel, a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen inlet was used. In the funnel for dropping the monomer, 85.6 parts (0.2 mol) of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate and 43.2 parts (0.3 mol) of acrylic acid were added. Mol), 118.0 parts (0.5 mol) of vinyl toluene, 4.0 parts of t-butylperoxy-2-ethylhexanoate, and 40.0 parts of propylene glycol monomethyl ether acetate (PGMEA). , Stirred and mixed. Further, 6.0 parts of n-dodecanethiol and 24.0 parts of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring. And after putting 395 parts of PGMEA into the flask and substituting the air in a flask with nitrogen, the temperature in a flask was heated up to 90 degreeC, stirring. Thereafter, the monomer and the chain transfer agent were dropped into the flask. The dropwise addition was performed over 2 hours while maintaining the temperature at 90 ° C., and after 1 hour from the completion of the dropwise addition, the temperature was raised to 110 ° C. and maintained for 3 hours. = 5/95 (v / v) Bubbling of gas mixture was started. Subsequently, 28.4 parts (0.1 mol) of glycidyl methacrylate (33 mol% based on the carboxyl group of acrylic acid used in the reaction), 2,2′-methylenebis (4-methyl-6-tert-butylphenol) ) And 0.4 parts of triethylamine were charged into a flask, and the reaction was continued at 110 ° C. for 8 hours to obtain a resin a having a solid content acid value of 71 mgKOH / g. The polystyrene-reduced weight average molecular weight measured by GPC was 17,000, and the molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of Resin b>
As the reaction vessel, a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen inlet was used. In the dropping funnel, 85.6 parts (0.2 mol) of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate and 74.8 parts of benzylmaleimide (0.2 Mol), 43.2 parts (0.3 mol) of acrylic acid, 35.4 parts (0.3 mol) of vinyltoluene, 4.0 parts of t-butylperoxy-2-ethylhexanoate, propylene 40.0 parts of glycol monomethyl ether acetate was added and mixed with stirring. Further, 6.0 parts of n-dodecanethiol and 24.0 parts of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring. And after putting 395 parts of PGMEA into the flask and substituting the air in a flask with nitrogen, the temperature in a flask was heated up to 90 degreeC, stirring. Thereafter, the monomer and the chain transfer agent were dropped into the flask. The dropwise addition was performed over 2 hours while maintaining the temperature at 90 ° C., and after 1 hour from the completion of the dropwise addition, the temperature was raised to 110 ° C. and maintained for 3 hours. = 5/95 (v / v) Bubbling of gas mixture was started. Next, 28.4 parts (0.1 mol) of glycidyl methacrylate (33 mol% with respect to the carboxyl group of acrylic acid used in this reaction), 2,2′-methylenebis (4-methyl-6-t-). Butylphenol) and 0.4 parts of triethylamine were put into a flask and the reaction was continued at 110 ° C. for 8 hours to obtain a resin b having a solid content acid value of 73 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 17,500, and the molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of Resin c>
As a reaction vessel, a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet was used. In the monomer dropping funnel, 74.8 parts (0.2 mol) of benzylmaleimide, 43.2 parts (0.3 mol) of acrylic acid, 118.0 parts (0.5 mol) of vinyltoluene, 4.0 parts of t-butylperoxy-2-ethylhexanoate and 40.0 parts of propylene glycol monomethyl ether acetate were added and mixed with stirring. Further, 6.0 parts of n-dodecanethiol and 24.0 parts of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring. Then, 395.0 parts of PGMEA was charged into the flask, and the air in the flask was replaced with nitrogen, and then the temperature in the flask was raised to 90 ° C. while stirring. Thereafter, the monomer and the chain transfer agent were dropped into the flask. The dropwise addition was performed over 2 hours while maintaining the temperature at 90 ° C., and after 1 hour from the completion of the dropwise addition, the temperature was raised to 110 ° C. and maintained for 3 hours. = 5/95 (v / v) Bubbling of gas mixture was started. Next, 28.4 parts (0.1 mol) of glycidyl methacrylate (33 mol% with respect to the carboxyl group of acrylic acid used in this reaction), 2,2′-methylenebis (4-methyl-6-t-). Butylphenol) and 0.4 parts of triethylamine were charged into a flask, and the reaction was continued at 110 ° C. for 8 hours to obtain a resin c having a solid content acid value of 70 mgKOH / g. The polystyrene-reduced weight average molecular weight measured by GPC was 16,000, and the molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of Resin d>
As a reaction vessel, a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet was used. In the monomer dropping funnel, 176.0 parts (0.5 mol) of benzyl methacrylate, 43.2 parts (0.3 mol) of acrylic acid, 47.2 parts (0.2 mol) of vinyltoluene, 4.0 parts of t-butylperoxy-2-ethylhexanoate and 40.0 parts of propylene glycol monomethyl ether acetate were added and mixed with stirring. Further, 6.0 parts of n-dodecanethiol and 24.0 parts of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring. Then, 395.0 parts of PGMEA was charged into the flask, and the air in the flask was replaced with nitrogen, and then the temperature in the flask was raised to 90 ° C. while stirring. Thereafter, the monomer and the chain transfer agent were dropped into the flask. The dropwise addition was performed over 2 hours while maintaining the temperature at 90 ° C., and after 1 hour from the completion of the dropwise addition, the temperature was raised to 110 ° C. and maintained for 3 hours. = 5/95 (v / v) Bubbling of gas mixture was started. Next, 28.4 parts (0.1 mol) of glycidyl methacrylate (33 mol% with respect to the carboxyl group of acrylic acid used in this reaction), 2,2′-methylenebis (4-methyl-6-t-). Butylphenol) and 0.4 parts of triethylamine were charged into a flask, and the reaction was continued at 110 ° C. for 8 hours to obtain a resin d having a solid content acid value of 75 mgKOH / g. The polystyrene-reduced weight average molecular weight measured by GPC was 17,000, and the molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of resin e>
As a reaction vessel, a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet was used. In the monomer dropping funnel, 74.8 parts (0.2 mol) of benzyl maleimide, 43.2 parts (0.3 mol) of acrylic acid, 176.0 parts (0.5 mol) of benzyl methacrylate, After adding 4.0 parts of t-butylperoxy-2-ethylhexanoate and 40.0 parts of propylene glycol monomethyl ether acetate, they were mixed with stirring. Further, 6.0 parts of n-dodecanethiol and 24.0 parts of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring. Then, 395.0 parts of PGMEA was charged into the flask, and the air in the flask was replaced with nitrogen, and then the temperature in the flask was raised to 90 ° C. while stirring. Thereafter, the monomer and the chain transfer agent were dropped into the flask. The dropwise addition was performed over 2 hours while maintaining the temperature at 90 ° C., and after 1 hour from the completion of the dropwise addition, the temperature was raised to 110 ° C. and maintained for 3 hours. = 5/95 (v / v) Bubbling of gas mixture was started. Next, 28.4 parts (0.1 mol) of glycidyl methacrylate (33 mol% with respect to the carboxyl group of acrylic acid used in this reaction), 2,2′-methylenebis (4-methyl-6-t-). Butylphenol) and 0.4 parts of triethylamine were charged into a flask, and the reaction was continued at 110 ° C. for 8 hours to obtain a resin e having a solid content acid value of 73 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 17,300, and the molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of Resin f>
As a reaction vessel, a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet was used. In the monomer dropping funnel, 74.8 parts (0.2 mol) of benzylmaleimide, 51.6 parts (0.3 mol) of methacrylic acid, 118.0 parts (0.5 mol) of vinyltoluene, After adding 4.0 parts of t-butylperoxy-2-ethylhexanoate and 40.0 parts of propylene glycol monomethyl ether acetate, they were mixed with stirring. Further, 6.0 parts of n-dodecanethiol and 24.0 parts of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring. Then, 395.0 parts of PGMEA was charged into the flask, and the air in the flask was replaced with nitrogen, and then the temperature in the flask was raised to 90 ° C. while stirring. Thereafter, the monomer and the chain transfer agent were dropped into the flask. The dropwise addition was carried out over 2 hours while maintaining the temperature at 90 ° C. After 1 hour from the completion of the dropwise addition, the temperature was raised to 110 ° C. and maintained for 5 hours, and then the resin f having a solid content acid value of 85 mgKOH / g Got. The weight average molecular weight in terms of polystyrene measured by GPC was 13,000, and the molecular weight distribution (Mw / Mn) was 2.2.

<Synthesis of Resin g>
As a reaction vessel, a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet was used. In the monomer dropping funnel, 85.6 parts (0.2 mol) of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate and 43.2 parts (0.3 mol) of acrylic acid were added. ), 104.0 parts (0.5 mol) of styrene, 4.0 parts of t-butylperoxy-2-ethylhexanoate, and 40.0 parts of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred. Mixed. Further, 6.0 parts of n-dodecanethiol and 24.0 parts of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring. Then, 395.0 parts of PGMEA was charged into the flask, and the air in the flask was replaced with nitrogen, and then the temperature in the flask was raised to 90 ° C. while stirring. Thereafter, the monomer and the chain transfer agent were dropped into the flask. The dropwise addition was performed over 2 hours while maintaining the temperature at 90 ° C., and after 1 hour from the completion of the dropwise addition, the temperature was raised to 110 ° C. and maintained for 3 hours. = 5/95 (v / v) Bubbling of gas mixture was started. Next, 28.4 parts (0.1 mol) of glycidyl methacrylate (33 mol% with respect to the carboxyl group of acrylic acid used in this reaction), 2,2′-methylenebis (4-methyl-6-t-). Butylphenol) and 0.4 parts of triethylamine were charged into a flask, and the reaction was continued at 110 ° C. for 8 hours to obtain a resin g having a solid content acid value of 71 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 23,000, and the molecular weight distribution (Mw / Mn) was 2.5.

<Measurement of molecular weight>
The GPC method was used for the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the curable resin obtained above, and the following conditions were set.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Injection volume: 50 μl
Detector: RI
Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran)
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

  The ratio of the weight average molecular weight and the number average molecular weight obtained above was defined as molecular weight distribution (Mw / Mn).

  In Example 1, the resin a adjusted as described above was used as the curable resin A, and among the components described in Table 1 below, the total of the pigment as the coloring material D and the pigment dispersant as the additive F in advance. After mixing the pigment, pigment dispersant and propylene glycol monomethyl ether acetate in an amount of 20% by mass, sufficiently dispersing the pigment using a bead mill, separating the bead mill, and further propylene The remaining components including the remaining amount of glycol monomethyl ether acetate were added and mixed to obtain a colored photosensitive resin composition.

Thereafter, a 2-inch square glass substrate (Corning Corp., # 1737) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the colored photosensitive resin composition (Table 1) was exposed at an exposure amount (365 nm) of 100 mJ / cm ² and the development step was omitted, and the film thickness after firing was 3.0 μm. And then pre-dried at 100 ° C. for 3 minutes in a clean oven. After cooling, a substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 μm to 50 μm) And an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Electric Co., Ltd., and irradiated with light at an exposure dose (365 nm) of 100 mJ / cm ^{2 in} an air atmosphere. Thereafter, the coating film was developed by being immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, washed with water, and then post-washed at 220 ° C. for 30 minutes. Bake was done. No surface roughness was observed in the obtained pixel portion. Further, development residues and undeveloped defects did not occur on the non-pixel portion on the substrate. The minimum necessary exposure amount required to form a pattern having no surface roughness even when developed was 40 mJ / cm ² . The evaluation results are shown in Table 2 below.

  In Example 2, the same operation as in Example 1 was performed except that the resin a in Example 1 was changed to the resin b. The evaluation results are shown in Table 2 below.

  In Example 3, the same operation as in Example 1 was performed except that the resin a in Example 1 was changed to the resin c. The evaluation results are shown in Table 2 below.

Comparative example

<Comparative Example 1>
In Comparative Example 1, the same operation as in Example 1 was performed except that the resin a in Example 1 was changed to the resin d. The evaluation results are shown in Table 2 below.

<Comparative example 2>
In Comparative Example 3, the same operation as in Example 1 was performed except that the resin a in Example 1 was changed to the resin e. The evaluation results are shown in Table 2 below.

<Comparative Example 3>
In Comparative Example 3, the same operation as in Example 1 was performed except that the resin a in Example 1 was changed to the resin f. The evaluation results are shown in Table 2 below.

<Comparative example 4>
In Comparative Example 4, the same operation as in Example 1 was performed except that the resin a in Example 1 was changed to the resin g. The evaluation results are shown in Table 2 below.

  From Table 2, the colored photosensitive resin compositions of Examples 1, 2, and 3 containing the curable resin A according to the present invention have high sensitivity and excellent development speed and pencil hardness, and the outgas generation is extremely reduced, resulting in an afterimage problem. It was found that a color filter that can solve the above problem can be obtained.

  The colored photosensitive resin composition according to the present invention is not limited to the color filter and black matrix provided in the liquid crystal display panel, and can be preferably used for applications that hate the generation of outgas.

Claims (5)

A colored photosensitive resin composition comprising a curable resin A, a photopolymerizable compound B, a photopolymerization initiator C, a coloring material D and a solvent E,
The curable resin A is an unsaturated group-containing resin obtained by further reacting a compound A4 with a copolymer obtained by copolymerizing the following compounds A1 to A3. The following compound A1 is shown below. A colored photosensitive resin composition, which is at least one selected from the compounds represented by Chemical formula 1 and Chemical formula 2.
Compound A1: Compound Compound in the main chain comprises a formation unsaturated bond cyclic structure A2: vinyltoluene Compound A3: includes mosquitoes carboxyl group unsaturated compound Compound A4: 1 single and unsaturated bond and an epoxy group in the molecule Compound provided

[R ₃ is a phenyl group, a benzyl group, a naphthal group, a cyclohexyl group, a methyl group, an ethyl group, or a propyl group. ] Unsaturated compound comprises a pre-listen carboxyl group A3 is colored photosensitive resin composition according to claim 1 is an acrylic acid. The ratio of the component derived from each of the compound A1, the compound A2 and the compound A3 to the total number of moles of the curable resin component,
Constituents derived from compound A1: 2 mol% to 50 mol%
Components derived from Compound A2: 2 mol% to 60 mol%
Components derived from Compound A3: 2 mol% to 70 mol%
The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition is obtained by reacting 5 mol% to 80 mol% of compound A4 with a component derived from compound A3. A color filter comprising: a color layer formed by applying the colored photosensitive resin composition according to any one of claims 1 to 3 on an upper portion of a substrate, and exposing and developing a predetermined pattern. A liquid crystal display device comprising the color filter according to claim 4.