JP2009075591A - Colored photosensitive resin composition, color filter, and liquid crystal display device equipped with color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition which contains a coloring material in high concentration and which, when used to form pixels, causes no development residue on a substrate and causes no surface defect on a pixel part, and a high-quality color filter excellent in sensitivity. <P>SOLUTION: The colored photosensitive resin composition comprises a binder resin A, a photopolymerizable compound B, a photopolymerization initiator C, the coloring material D, and a solvent E, wherein the binder resin A is a copolymer obtained by copolymerizing the following compounds A1, A2 and A3; compound A1: a compound having general formula (1), compound A2: a compound having an unsaturated bond capable of copolymerizing with the compounds A1 and A3, compound A3: an unsaturated carboxylic acid. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  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 in a color liquid crystal display device or an image pickup device is usually formed by spin coating a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is patterned. 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 form pixels of each color. A color filter using such a colored photosensitive resin composition is required to have high resolution during image formation, excellent adhesion to a substrate, low development residue, and the like. Recently, a pixel having a high color density has been demanded, and the pigment and carbon black used in the colored photosensitive resin composition are increasing.

  On the other hand, as described above, when forming a pixel using a colored photosensitive resin composition having a high colorant content, a development residue is generated on the unexposed part of the substrate during the development process, or the unexposed part is completely dissolved. However, by developing to a peeling type, there is a problem that the developer filter is clogged, or impurities that are left undissolved during the process stick to the substrate of the pixel and non-pixel portions. In addition, since the sensitivity of the pixels formed in the exposed area is insufficient, there are problems in that the surface of the coating film is defective or the film hardness is insufficient.

  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 in order to solve the above-described conventional problems, and an object thereof is to provide a colored photosensitive resin composition having excellent developability even when a high-concentration colored material is contained. .

  Another object of the present invention is to use the above-described colored photosensitive resin composition to produce a high-quality color filter having excellent sensitivity without causing surface defects in the pixel portion when pixels are formed. It is to provide.

  The present invention for achieving the above-described object is a colored photosensitive resin composition containing a binder resin A, a photopolymerizable compound B, a photopolymerization initiator C, a coloring material D, and a solvent E, The agent resin A is a copolymer obtained by copolymerizing the following compounds A1 to A3, and provides a colored photosensitive resin composition.

Compound A1: A compound represented by the general formula of Chemical Formula 3 below. In the compound represented by Chemical Formula 3, R ₁ is hydrogen or a methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ -C ₆ alkyl group or alkenyl group, and A is substituted or unsubstituted. Benzene group, cyclohexyl group, C ₁ -C ₆ alkyl group or alkenyl group, wherein the substituents of R ₂ and A are independently fluorine, chlorine, bromine, iodo, C ₁ -C ₆ alkyl group C ₁ -C ₃ perhalogenated alkyl group, hydroxy group, C ₁ -C ₆ ketone group, C ₁ -C ₆ ester group, N, N- (C ₁ -C ₃ ) alkyl-substituted amide A formulation comprising one or more of the groups or substituents.

Compound A2: Compound A2 is a compound having an unsaturated bond that can be copolymerized with Compound A1 and Compound A3.

Compound A3: Compound A3 is an unsaturated carboxylic acid.

In addition, as the compound A1 used in the colored photosensitive resin composition according to the present invention, it is also preferable to use one or more compounds selected from compounds of the general formula represented by the following chemical formula 4. In this Chemical Formula 4, R ₁ is hydrogen or a methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ -C ₆ alkyl group or alkenyl group, and the substituents of R ₂ are independently fluorine, chlorine, bromine, _iodine, an alkyl group of _{C 1 ~C 6, C 1 ~C} 3 perhalogenated alkyl group, hydroxy _group, a ketone group of C 1 -C _6, ester groups C 1 -C _6, N, N- (C ₁ -C ₃ ) alkyl-substituted amide groups or formulations containing one or more of these substituents.

  Further, the binder resin A is an unsaturated group-containing resin obtained by further reacting the copolymer with a compound A4 having an unsaturated bond and an epoxy group in one molecule. A functional resin composition is provided.

  The colored photosensitive resin composition is characterized in that the compound A2 having an unsaturated bond copolymerizable with the compound A1 and the compound A3 is an aromatic vinyl compound or an N-substituted maleimide.

  The ratio of the structural component derived from each of the compound A1, the compound A2, and the compound A3 to the total number of moles of the structural component of the binder resin A is 2 to 50 mol% of the structural unit derived from the compound A1. The colored photosensitive resin composition is characterized in that the structural unit derived from the compound A2 is 2 to 50 mol% and the structural unit derived from the compound A3 is 2 to 70 mol%.

  Further, the ratio of the component derived from the compound A4 is 5 to 80 mol% with respect to the number of moles of the component derived from (Compound A3) in the binder resin A. A colored photosensitive resin composition is provided.

  Further, the present invention provides a color filter comprising a color layer formed by applying a colored photosensitive resin composition on an upper portion of a substrate and exposing and developing it into a predetermined pattern, wherein the colored photosensitive resin composition is described above. Provided is a color filter which is a colored photosensitive resin composition.

  The present invention provides a liquid crystal display device including the color filter described above.

  According to the present invention, it is possible to provide a colored photosensitive resin composition excellent in developability even when it contains a high-concentration colored material. Moreover, when forming a pixel using the said colored photosensitive resin composition, surface defect etc. do not generate | occur | produce in a pixel part, but the colored photosensitive resin composition excellent in the sensitivity can be provided.

The present invention is described in detail below. The present invention is a colored photosensitive resin composition containing a binder resin A, a photopolymerizable compound B, a photopolymerization initiator C, a coloring material D and a solvent E, wherein the binder resin A includes the following compound A1, The present invention relates to a colored photosensitive resin composition, which is a copolymer obtained by copolymerizing compound A2 and compound A3. Although it does not restrict | limit in particular, It is preferable that the other additive F is arbitrarily melt | dissolved or disperse | distributed to the solvent E contained in the said colored photosensitive resin composition. Hereinafter, the binder resin A, the photopolymerizable compound B, the photopolymerization initiator C, the coloring material D, and the solvent E will be described in this order.

Binder resin A: The binder 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 the present invention, the binder resin A is a copolymer containing structural units that can be obtained by polymerization of the compound A1, the compound A2, and the compound A3 (this is a concept that includes copolymerization), and is a major feature of the present invention. Part.

  The binder resin A according to the present invention is a copolymer containing structural units that can be obtained by polymerization of the compound A1, compound A2, and compound A3 (this is a concept that includes copolymerization). . The binder resin A can be polymerized together with another monomer other than the monomer. That is, the present invention includes a case where a monomer other than the compounds A1 to A3 is further included and copolymerized. Hereinafter, Compound A1, Compound A2, and Compound A3 will be described in order.

[Compound A1]
This compound A1 is a compound represented by the general formula of Chemical Formula 5 below. In this Chemical Formula 5, R ₁ is hydrogen or a methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ -C ₆ alkyl group or alkenyl group, A is a substituted or unsubstituted benzene group, cyclohexyl A C ₁ -C ₆ alkyl group or alkenyl group, wherein the substituents of R ₂ and A are independently fluorine, chlorine, bromine, iodo, C ₁ -C ₆ alkyl groups, C ₁ -C ₃ perhalogenated alkyl group, hydroxy _group, a ketone group of C 1 -C _6, ester groups _{C 1 ~C 6, N, N-} (C 1 ~C 3) alkyl-substituted amide group or substitution of these A formulation containing one or more of the groups.

  In the embodiment of the present invention, specific examples of Compound A1 represented by Chemical Formula 5 (= Chemical Formula 1) are shown in Chemical Formulas 6 to 9 below.

  More specific examples of the compound A1 include 2-phenylthioethyl (meth) acrylate and hexylthioethyl (meth) acrylate. These can be used alone or in combination of two or more.

In particular, it is more preferable that at least one compound A1 represented by the chemical formula 1 is selected from the compounds represented by the following chemical formula 10. This is because developability and surface development are further improved when a pixel is formed using a compound of the following chemical formula 10. In this chemical formula 10, R ₁ and R ₂ are the same as the alkyl group described in chemical formula 1.

  More specific examples include 2-phenylthioethyl (meth) acrylate.

[Compound A2]
As the compound A2, a compound having an unsaturated bond that can be copolymerized with the compound A1 and the compound A3 is used. As the compound A2 in the present invention, an aromatic vinyl compound, an N-substituted maleimide compound, an unsubstituted or substituted alkyl ester of an unsaturated carboxylic acid, an unsaturated carboxylic ester compound containing an alicyclic substituent, a carboxylic acid vinyl ester And unsaturated oxetanyl group containing an oxetane group. Among the compounds, aromatic vinyl compounds and N-substituted maleimide compounds are more preferable in terms of improving sensitivity and adhesion. These can be used alone or in combination of two or more.

  Among the compounds A2, examples of the aromatic vinyl compound include vinyl toluene, styrene, α-methyl styrene, α-chlorostyrene, divinylbenzene, and the like. These may be used alone or in combination of two or more. it can. In the present invention, a binder resin was produced using the vinyl toluene as an additional monomer, and the performance of the colored photosensitive resin composition containing the produced binder resin was tested. It was found that the effect is excellent.

  In addition, examples of the N-substituted maleimide compound include compounds represented by the following chemical formula 11.

In this Formula 11, R ₃ is a C _{1 to} C ₂₀ aliphatic or aromatic hydrocarbon with or without heteroatoms. Specific examples of R ₃ include a phenyl group, a benzyl group, a naphthyl group, a cyclohexyl group, a methyl group, an ethyl group, and a propyl group. Particularly, a benzyl group and a cyclohexyl group are preferable, and these are each independently , Or a combination of two or more.

  The unsaturated or substituted alkyl ester compound system of the unsaturated carboxylic acid includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) ) Acrylate and the like. These can be used alone or in combination of two or more.

  The unsaturated carboxylic acid ester compound system containing the alicyclic substituent includes cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) ) Acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, pentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl ( And (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pinenyl (meth) acrylate. These can be used alone or in combination of two or more.

  Examples of the carboxylic acid vinyl ester compounds include vinyl acetoate and vinyl propionate. These can be used alone or in combination of two or more.

  Examples of the unsaturated oxetanyl-based compound containing an oxetane group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (Methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2 , 2-Difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxy) Ethyl) Tan, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) 2-pentafluoroethyl oxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4- Examples include trifluorooxetane and 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane. These can be used alone or in combination of two or more.

[Compound A3]
Compound A3 is a compound having an unsaturated carboxyl group, and is not particularly limited as long as it is a carboxylic acid compound having a polymerizable unsaturated double bond, and may be used alone or in combination of two or more. it can. Specific examples include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids; ω-carboxypolycaprolactone mono (meta And mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends, such as acrylate). Of these, acrylic acid and methacrylic acid are preferred because they are excellent in copolymerization reactivity and solubility in a developer.

[Structural Unit Derived from Each Compound in Binder Resin A]
The binder resin A used in the present invention is a copolymer obtained by copolymerizing the compounds A1 to A3, and the ratio of the structural units derived from the respective compounds of the compounds A1 to A3 is as described above. The thing of the following composition ranges is desirable with a mole fraction with respect to the total number of moles of the constituent components constituting the copolymer.

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

[Method for preparing binder resin A for copolymerizing compound A1 to compound A3]
In the embodiment of the present invention, the method for producing the copolymer is not particularly limited as long as it is obtained as described above, and various conventionally known polymerization methods can be used. Legal is more preferred. The polymerization temperature and polymerization time vary depending on the type and ratio of the monomer to be introduced, the target binder resin molecular weight, and the acid value, but the polymerization is preferably performed at 60 to 130 ° C. for 1 to 10 hours. And in the said process, a part or whole quantity of a polymerization initiator can also be thrown into a flask, and a part or whole quantity of compound A1, compound A2, and compound A3 can also be thrown into a flask.

  In the case of using a solvent in the above step, a solvent used in a normal radical polymerization reaction can be used, specifically, tetrahydrofuran, dioxane, 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, Examples include dimethyl sulfoxide. These solvents can be used alone or in combination of two or more.

  Moreover, as a polymerization initiator used for the said process, the polymerization initiator used normally can be added and it does not restrict | limit separately. Specifically, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy Organic peroxides such as 2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis And nitrogen compounds such as (2-methylpropionate). 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 the α-methylstyrene dimer or mercapto compound used is 0.005 to 5% based on the mass with respect to the total amount of Compound A1, Compound A2 and Compound A3. In addition, the polymerization conditions can be appropriately adjusted in terms of the charging method and the reaction temperature in consideration of the production equipment and the amount of heat generated by the polymerization.

[Compound A4]
The binder resin A contained in the colored photosensitive resin composition of the embodiment of the present invention is unsaturated in one molecule with respect to the copolymer obtained by copolymerizing the compound A1, the compound A2, and the compound A3. It is also preferable to use a compound obtained by further reacting a compound A4 having a bond and an epoxy group. By adding the compound A4 to the copolymer, it is possible to impart photocurability / thermosetting to the binder resin.

  Specific examples of the compound A4 having an unsaturated bond and an epoxy group in one molecule of the present invention include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxy. Examples thereof include cyclohexylmethyl (meth) acrylate and methyl glycidyl (meth) acrylate. Of these, glycidyl (meth) acrylate is more preferably used. These can be used alone or in combination of two or more.

[Structural Unit Derived from Each Compound in Binder Resin A Containing Compound A4]
The ratio of the structural unit derived from the compound A4 in the binder resin A is 5 to 80 mol% with respect to the number of moles of the structural component derived from the compound A3 in the binder resin A. Is preferable, and 10-70 mol% is more preferable. If the composition ratio of compound A4 is within the above range, sufficient photocurability and thermosetting properties can be obtained, and both sensitivity and pencil hardness are compatible and excellent in reliability.

[Method for preparing binder resin A in which compound A4 is added to the copolymer of compound A1 to compound A3]
In an embodiment of the present invention, the binder resin A is produced by reacting a copolymer obtained by copolymerizing the compound A1, the compound A2, and the compound A3 with the compound A4, for example, by the following method. be able to.

  The atmosphere in the flask is changed from nitrogen to air, and the compound A4 having a molar fraction of 5 to 80 mol% with respect to the structural unit derived from the photopolymer compound A3, as a reaction catalyst for carboxyl group and epoxy group, for example, Trisdimethylaminomethylphenol is 0.01 to 5% based on the total amount of Compound A1 to Compound A4 and a polymerization inhibitor, for example, hydroquinone is 0 based on the total amount of Compound A1 to Compound A4. By putting 0.001 to 5% in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours, the copolymer and compound A4 can be reacted. In addition, similarly to the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization.

  The binder resin A of the present invention is preferably contained in an amount of 10 to 80 parts by mass, more preferably 20 to 70 parts by mass with respect to the total solid content of 100 parts by mass of the colored photosensitive resin composition. If it is the said range, since the coating film calculated | required without a residue remaining in image development can be formed, it is preferable.

  Further, the binder resin A of the present invention is not particularly limited, but the polystyrene-equivalent weight average molecular weight is preferably in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the binder 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 is liable to be easily removed, which is preferable.

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

Photopolymerizable compound B: The photopolymerizable compound B contained in the colored photosensitive resin composition of 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, etc. are mentioned.

  The photopolymerizable compound B used in the present invention contains two or more light 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. A polymerizable compound can be mixed and used, and the range is not limited.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. .

  Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate and the like can be mentioned.

  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 (meth) ) Acrylate and the like. Among these, polyfunctional monomers having two or more functions are preferably used.

  The photopolymerizable compound B is usually used in the range of 1 to 60 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass in total of the binder resin A and the photopolymerizable compound B. If the photopolymerizable compound B is in the range of 1 to 60 parts by mass based on the above criteria, the strength and smoothness of the pixel part tend to be good, which is preferable.

Photopolymerization initiator C: The photopolymerization initiator C contained in the colored photosensitive resin composition of the present invention is not limited, but is selected from the group consisting of triazine compounds, acetophenone compounds, biimitazole compounds, and oxime compounds. One or more compounds. The colored photosensitive resin composition containing the photopolymerization initiator C has high sensitivity, and a film formed using this composition has good strength and surface smoothness of the pixel portion.

  Further, 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 this composition is used for the color filter. It is preferable because the productivity when forming is improved.

  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 Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like. .

  Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy). Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- Examples include oligomers of 1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one. Examples of the acetophenone compound include compounds represented by the following chemical formula 12.

Of the above reduction _12, each R 1 to R ₄ are independently a hydrogen atom, a halogen atom, a hydroxyl _group, C 1 _{-C 12} optionally substituted phenyl group by an alkyl _group, an alkyl group of C 1 _{-C 12} It shows the optionally substituted naphthyl group with an alkyl group optionally substituted benzyl group or C ₁ -C ₁₂ through.

  Specific examples of the compound represented by the above formula 12 include 2-methyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1- ON, 2-propyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-methyl-2-amino (4- Morpholinophenyl) propan-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, such as 2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-one and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 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, imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted by a carboalkoxy group, etc. Is mentioned. Of these, 2,2′bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5, 5′-tetraphenylbiimidazole is preferably used.

  Examples of the oxime compound include compounds represented by the following chemical formula 13, chemical formula 14, and chemical formula 15.

  Moreover, as long as the effect of the present invention is not impaired, other photopolymerization initiators or the like usually used in this field can be further used in combination. Examples of other photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, and polyfunctional thiol compounds. These may be used alone or in combination of two or more.

  Examples of the benzoin compound 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 and the like.

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

  Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like.

  Examples of the polyfunctional thiol compound include tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis. -3-mercaptopropionate and the like.

  In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. Examples of other photopolymerization initiators.

  Photopolymerization initiator C can also be used in combination with photopolymerization initiation auxiliary (C-1), and amine compounds and carboxylic acid compounds are preferably used.

  Specific examples of the amine compound among the photopolymerization initiation assistants include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone) Aromatic amine compounds such as 4,4′-bis (diethylamino) benzophenone. An aromatic amine compound is preferably used as the amine compound.

  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.

  The usage-amount of the photoinitiator C is 0.1-40 mass parts normally with respect to a total of 100 mass parts of binder resin A and the photopolymerizable compound B, Preferably it is 1-30 mass parts, and photopolymerization is carried out. The usage-amount of a start adjuvant (C-1) is 0.1-50 mass parts normally on the said reference | standard, Preferably it is 1-40 mass parts.

  When the amount of the photopolymerization initiator C is within the above range, the colored photosensitive resin composition is highly sensitive, and the strength of the pixel portion formed using this composition and the smoothness on the surface of the pixel portion are increased. It tends to be favorable and is preferable. Moreover, if the usage-amount of photoinitiator adjuvant (C-1) is in the said range, the sensitivity of a colored photosensitive resin composition will become still higher, and the productivity of the color filter formed using this composition will be improved. It tends to be improved and is preferable.

Coloring material D: The coloring material D used in the present invention is preferably an organic pigment or an inorganic pigment that is usually used in a pigment dispersion resist as a normal pigment. Dyes can be used as needed and are included in the present invention.

  Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Or a composite metal oxide etc. are mentioned.

  Specific examples of the organic pigment and the inorganic pigment include compounds classified as pigments by color index (published by The Society of Dyers and Colorists), and more specifically, the following color index (C.I. I.) numbered pigments, but not necessarily limited thereto.

  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.

  These coloring materials D can be used alone or in combination of two or more. Content of the coloring material D is 3-60 mass% normally on the basis of the total amount of solid content in a coloring photosensitive resin composition, Preferably it is the range of 5-55 mass%. If the content of the coloring material D is in the range of 3 to 60% by mass based on the above criteria, the color density of the pixel is sufficient even when a thin film is formed, and the omission of non-pixel portions does not deteriorate during development. It tends to be difficult to generate a residue, which is preferable.

Solvent E: The solvent E contained in the colored photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of the colored photosensitive resin composition can be used.

  Specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol diethylene ether. Diethylen glycol dialkyl ethers such as butyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Alkylene glycol alkyl ether acetates such as acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone , Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone It is done.

  Among the above solvents, an organic solvent having a boiling point of 100 ° C. to 200 ° C. in the solvent is preferable from the viewpoint of coating property and drying property, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid. And 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 and the like. Can be mentioned. 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 of this invention is a mass fraction with respect to the whole colored photosensitive resin composition containing it, and is 60-90 mass% normally, Preferably it is 70-85. % By mass. When the content of the solvent E is in the range of 60 to 90% by mass based on the above standard, it is applied when applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes called a die coater), or an ink jet. There is a tendency for the properties to be favorable, which is preferable.

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

  Specific examples of the filler mentioned here include glass, silica, alumina and the like.

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

  The curing agent is used to increase the deep curing and mechanical strength, and examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

  Examples of the epoxy compound in the curing agent include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolac-type epoxy resins, and other aromatic epoxy resins. Alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, 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) ) Polymer epoxidized product, isoprene (co) polymer epoxidized product, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.

  Examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  The curing agent includes a curing auxiliary compound that enables ring-reversal polymerization of 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 carboxylic acid anhydride, commercially available epoxy resin curing agents can be used. As the epoxy resin curing agent, for example, trade name (ADEKA HARDNA EH-700) (manufactured by ADEKA INDUSTRY CO., LTD.), Trade name (Rikasit HH) (manufactured by Shin Nippon Rika Co., Ltd.), trade name (MH-700) ( New Nippon Rika Co., Ltd.). The said hardening | curing agent can be used individually or in mixture of 2 or more types.

  Commercially available surfactants can be used as the pigment dispersant, and examples thereof include silicon-based, fluorine-based, ester-based, anionic-based, nonionic-based, cationic-based, and amphoteric surfactants. These can be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethylene amines. Other product names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (MEGAFAC) (large) Nippon Ink Chemical Co., Ltd.), Florad (Sumitomo Suriem Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), Solsperse (SOLSPERSE) Zeneka Co., Ltd.), EFKA (manufactured by EFKA Chemicals), PB821 (manufactured by Ajinomoto Co., Inc.), and the like.

  As an adhesion promoter, for example, 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- Such Socia sulphonate propyl triethoxy silane. These adhesion promoters can be used alone or in combination of two or more.

  The resist solid content concentration is usually 0.01 to 10% by mass, preferably 0.05 to 2% by mass.

  Specific examples of the antioxidant include hindered phenols such as 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

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

  Specific examples of the aggregation inhibitor include sodium polyacrylate.

  The colored photosensitive resin composition of the present invention can be prepared, for example, based on 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 diameter of the coloring material is about 0.2 μm or less. At this time, a pigment dispersant is used as necessary, and a part or all of the binder resin A may be blended. In the obtained dispersion (hereinafter sometimes referred to as mill base), the remainder of the binder resin A, the photopolymerizable compound B and the photopolymerization initiator C, other components used as necessary, and as necessary. An additional solvent is further added so as to have a predetermined concentration to obtain a target colored photosensitive resin composition.

[Pattern forming method of colored photosensitive resin composition]
Hereinafter, the pattern formation method of the colored photosensitive resin composition concerning this invention is demonstrated. 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 described above on a substrate, and selectively exposing a partial region of the colored photosensitive resin composition. And a step of removing an exposed area or an unexposed area of the colored photosensitive resin composition.

  As an example, it is applied onto a substrate as described below, followed by photocuring and development to form a pattern, which can be used in a black matrix or colored pixels (colored image).

  First, the composition of the present invention is applied to a base material (not limited, usually glass or silicon wafer) or a layer containing a solid content of a colored photosensitive resin composition previously formed, and then pre-dried to form a solvent. A smooth coating film is obtained by removing volatile components such as. In this case, the thickness of the coating film is about 1 to 3 μm. In order to obtain a target pattern on the coating film thus obtained, a specific region is irradiated with ultraviolet rays through a mask. At this time, it is desirable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel light rays and the mask and the substrate are accurately aligned. Further, the target pattern can be produced by bringing the coating film, which has been cured, into contact with an alkaline aqueous solution to dissolve the unexposed area and developing. After development, post-drying can be performed at 150 to 230 ° C. for about 10 to 60 minutes as necessary.

  The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound.

  Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, Examples include potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

  Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc. These inorganic and organic alkaline compounds can be used alone or in combination of two or more.

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

  Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

  Specific examples of 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 dodecylnaphthalene. And alkylaryl sulfonates such as sodium sulfonate.

  Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts. These surfactants can be used alone or in combination of two or more.

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

[Color filter according to the present invention]
The color filter according to the present invention will be described below. The color filter according to the present invention includes a color layer formed by exposing and developing the above-described colored photosensitive resin composition in a predetermined pattern.

  The pattern forming method of the colored photosensitive resin composition is as described above, and detailed description thereof is omitted. As described above, the pixel corresponding to the color of the coloring material in the photosensitive resin composition through the operations of application of the colored photosensitive resin solution, drying, patterning exposure to the resulting dried coating film, and development, or A black matrix is obtained, and a color filter is obtained by repeating such an operation for the number of colors required for the color filter. Since the configuration and manufacturing method of the color filter are known in the art, a detailed description thereof will be omitted.

  The color filter is usually a black matrix and three primary color pixels of red, green, and blue arranged on a substrate, but the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color is used. By performing the above operation, a black matrix or a pixel of that color is obtained, and the same operation is performed using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to the target color for other colors. The black matrix and the three primary color pixels can be arranged on the substrate. Of course, the photosensitive resin composition of the present invention can be applied to only one, two or three of the black matrix and the three primary colors.

  In addition, the black matrix that is the light shielding layer can use the colored photosensitive resin of the present invention (colored in black), but may be formed of, for example, a chromium layer. It is not necessary to use the colored photosensitive resin composition.

  The color filter manufactured using the colored photosensitive resin composition of the present invention has a small in-plane film thickness difference, for example, a film thickness of 1 to 3 μm, and an in-plane film thickness difference of 0.15 μm or less. It can be 0.05 μm or less. Therefore, the color filter obtained in this way is excellent in smoothness, and an excellent quality liquid crystal display device can be manufactured with a high yield by incorporating it into the color liquid crystal display device.

  The present invention also includes a liquid crystal display device including the color filter described above. The liquid crystal display device of the present invention includes a configuration known in this technical field except that the above-described color filter is provided. That is, all liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. As an example, a transmissive liquid crystal display device in which a counter electrode substrate including 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 portion to form a liquid crystal layer. It is done. There is also a reflective liquid crystal display device in which a reflective layer is provided between a color filter substrate and a colored layer.

  Another example is a liquid crystal display device including a TFT (Thin Film Transistor) substrate aligned on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate is provided with an outer frame made of light-proof resin surrounding the peripheral surface of the color filter, a liquid crystal layer made of nematic liquid crystal attached to the outer frame, and a large number provided for each region of the liquid crystal layer. Pixel electrodes, a transparent glass substrate on which the pixel electrodes are formed, and a polarizing plate formed on the exposed surface of the 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 a glass substrate of the TFT substrate. 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 orientation of the region corresponding to the specific pixel electrode of the liquid crystal layer.

  As described below, the present invention will be described in more detail based on examples, but are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is described in the claims, and includes all modifications within the meaning and scope equivalent to the description of the claims. In the following, “%” and “part” indicating the content are based on mass unless otherwise specified.

<Synthesis of Resin A>
A flask equipped with a stirrer, a reflux condenser with a thermometer, a dropping funnel and a nitrogen introducing tube was prepared. On the other hand, as a monomer dropping funnel, 52 g (0.25 mol) of 2-phenylthioethyl acrylate, 44 g of benzyl methacrylate (0.25) Mol), 12.9 g (0.15 mol) of methacrylic acid, 41.3 g (0.35 mol) of vinyl toluene, 4 g of t-butylperoxy-2-ethylhexanoate, 40 g of propylene glycol monomethyl ether acetate (PGMEA) Then, 6 g of n-dodecanethiol and 24 g of PGMEA were added and stirred and mixed as a chain transfer agent dropping tank. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ° C. while stirring. Next, the dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dropwise addition was carried out for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature was raised to 110 ° C. and the reaction was continued for 8 hours to obtain Resin A having a solid content acid value of 70 mgKOH / g. The polystyrene-equivalent weight average molecular weight measured by GPC was 23,000, and the molecular weight distribution (Mw / Mn) was 2.4.

<Synthesis of Resin B>
A flask equipped with a stirrer, a reflux condenser with a thermometer, a dropping funnel and a nitrogen introducing tube was prepared. On the other hand, as a monomer dropping funnel, 52 g (0.25 mol) of 2-phenylthioethyl acrylate, 26.4 g of benzyl methacrylate ( 0.15 mol), methacrylic acid 21.5 g (0.25 mol), vinyl toluene 41.3 g (0.35 mol), t-butylperoxy-2-ethylhexanoate 4 g, propylene glycol monomethyl ether acetate ( 40 g of PGMEA) was added, and the mixture was prepared by stirring and mixing. As the chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added and mixed by stirring. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ° C. while stirring. Next, the dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dropwise addition is performed for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature is raised to 110 ° C. and maintained for 5 hours, and then a gas introduction pipe is introduced to mix oxygen / nitrogen = 5/95 (v / v) Gas bubbling started. Next, 21.3 g (0.15 mol) of glycidyl methacrylate, 0.4 g of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 g of triethylamine were put into the flask, and the mixture was heated at 110 ° C. for 8 hours. The reaction was continued for a while to obtain Resin B having a solid content acid value of 75 mgKOH / g. The polystyrene-reduced weight average molecular weight measured by GPC was 19,000, and the molecular weight distribution (Mw / Mn) was 2.4.

<Synthesis of Resin C>
A flask equipped with a stirrer, a reflux condenser with a thermometer, a dropping funnel and a nitrogen introducing tube was prepared. On the other hand, as a monomer dropping funnel, 52 g (0.25 mol) of 2-phenylthioethyl acrylate, 15 g of methyl methacrylate (0.15) Mol), 21.5 g (0.25 mol) of methacrylic acid, 65.4 g (0.35 mol) of benzylmaleimide, 4 g of t-butylperoxy-2-ethylhexanoate, 40 g of propylene glycol monomethyl ether acetate (PGMEA) Then, 6 g of n-dodecanethiol and 24 g of PGMEA were added and stirred and mixed as a chain transfer agent dropping tank. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ° C. while stirring. Next, the dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dropwise addition is performed for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature is raised to 110 ° C. and maintained for 5 hours. Then, a gas introduction pipe is introduced, and oxygen / nitrogen = 5/95 (v / v) Bubbling of the mixed gas was started. Next, 21.3 g (0.15 mol) of glycidyl methacrylate, 0.4 g of 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and 0.8 g of triethylamine were charged into the flask, and the mixture was heated at 110 ° C. for 8 hours. The reaction was continued for a while to obtain Resin C having a solid content acid value of 73 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 18,000, and the molecular weight distribution (Mw / Mn) was 2.2.

<Synthesis of Resin D>
A flask equipped with a stirrer, a reflux condenser with a thermometer, a dropping funnel and a nitrogen introducing tube was prepared. On the other hand, 88 g (0.5 mol) of benzyl methacrylate and 12.9 g (0.15 mol) of methacrylic acid were used as the monomer dropping funnel. ), 41.3 g (0.35 mol) of vinyltoluene, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) are prepared by stirring and mixing. As a transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ° C. while stirring. Next, the dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dropwise addition was performed for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature was raised to 110 ° C. and reacted for 8 hours to obtain Resin D having a solid content acid value of 70 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 21,000, and the molecular weight distribution (Mw / Mn) was 2.2.

<Synthesis of Resin E>
A flask equipped with a stirrer, a reflux condenser with a thermometer, a dropping funnel and a nitrogen introducing tube was prepared. On the other hand, 70.4 g (0.4 mol) of benzyl methacrylate and 21.5 g (0. 25 mol), 41.3 g (0.35 mol) of vinyl toluene, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) are prepared by stirring and mixing. As a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ° C. while stirring. Next, the dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dropwise addition is performed for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature is raised to 110 ° C. and maintained for 5 hours. Then, a gas introduction pipe is introduced, and oxygen / nitrogen = 5/95 (v / v) Bubbling of the mixed gas was started. Next, 21.3 g (0.15 mol) of glycidyl methacrylate, 0.4 g of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 g of triethylamine were put into the flask, and the mixture was heated at 110 ° C. for 8 hours. The reaction was continued for a while to obtain a resin E having a solid content acid value of 75 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 16,300, and the molecular weight distribution (Mw / Mn) was 2.2.

  The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder polymer were measured using the GPC method under the following conditions.

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 substance 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).

[Example 1]
Of the components described in Table 1 below, the total amount of the pigment dispersant, which is the pigment of the coloring material D and the additive F, is 20 masses based on the mixture of the pigment, the pigment dispersant, and propylene glycol monomethyl ether acetate. After mixing the pigments sufficiently using a bead mill, the bead mill is separated, and then the remaining components including the remaining amount of propylene glycol monomethyl ether acetate are added and mixed. A resin composition was obtained.

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) according to the present invention is exposed at an exposure amount (365 nm) of 100 mJ / cm ² , and the film thickness after baking when the developing step is omitted is 2. It spin-coated so that it might be set to 0 micrometer, and preliminarily dried for 3 minutes at 100 degreeC in the clean oven then. After cooling, the substrate coated with the colored photosensitive resin composition and a photomask made of quartz glass (having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line / space pattern from 1 μm to 50 μm ) Was set to 100 μm and irradiated with light at an exposure dose (365 nm) of 100 mJ / cm ^{2 in} an air atmosphere using an ultrahigh pressure mercury lamp (trade name USH-250D) manufactured by USHIO INC. Thereafter, the coating film is immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide for a predetermined time at 26 ° C., developed, washed with water, and dried at 220 ° C. for 30 minutes. did. In the obtained pixel portion, no surface roughness was observed. Further, development residues and undeveloped defects did not occur on the non-pixel portion on the substrate. And the minimum required exposure amount required in order to form a pattern without surface roughness even if it developed was 60 mJ / cm < ² >.

[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.

[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.

Comparative example

[Comparative Example 1]
Example 1 The same operation as in Example 1 was performed except that the resin A was changed to the resin D. The evaluation results are shown in Table 2.

[Comparative Example 2]
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.

  From Table 2, it was found that the colored photosensitive resin compositions of Examples containing the binder resin of the present invention can obtain a color filter having high sensitivity and excellent developability. On the other hand, in the case of the colored photosensitive resin composition of the comparative example, a high-quality color filter could not be obtained due to poor sensitivity and developability.

According to the present invention, a colored photosensitive resin composition having excellent developability and excellent sensitivity can be provided even if it contains a high-concentration colored material. It is not limited to a color filter such as a device.

Claims (8)

A colored photosensitive resin composition containing a binder resin A, a photopolymerizable compound B, a photopolymerization initiator C, a coloring material D and a solvent E,
The colored photosensitive resin composition, wherein the binder resin A is a copolymer obtained by copolymerizing the compound A1, the compound A2, and the compound A3 shown in the following chemical formula 1.
Compound A1: A compound represented by the general formula shown in Chemical Formula 1 below.

(In Chemical Formula 1, R ₁ is hydrogen or a methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ -C ₆ alkyl group or alkenyl group, and A is a substituted or unsubstituted benzene group, cyclohexyl. A C ₁ -C ₆ alkyl group or alkenyl group, wherein the substituents of R ₂ and A are independently fluorine, chlorine, bromine, iodo, C ₁ -C ₆ alkyl groups, C ₁ -C ₃ perhalogenated alkyl groups, hydroxy groups, C ₁ -C ₆ ketone groups, C ₁ -C ₆ ester groups, N, N- (C ₁ -C ₃ ) alkyl-substituted amide groups or these substituents A formulation containing one or more of the following.)
Compound A2: Compound A3 having an unsaturated bond copolymerizable with Compound A1 and Compound A3 Compound A3: Unsaturated carboxylic acid 2. The colored photosensitive resin composition according to claim 1, wherein at least one of the compounds A1 is selected from compounds represented by the general formula of Chemical Formula 2 below.

(In Chemical Formula 2, R ₁ is hydrogen or a methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ -C ₆ alkyl group or alkenyl group, and in this case, the substituent of R ₂ is independently fluorine, chlorine, bromine, _iodine, an alkyl group of _{C 1 ~C 6, C 1 ~C} 3 perhalogenated alkyl group, hydroxy _group, a ketone group of C 1 -C _6, ester groups C 1 -C _6, N, N- (C ₁ -C ₃ ) alkyl substituted amide groups or formulations containing one or more of these substituents.) The binder resin A is an unsaturated group-containing resin obtained by further reacting the copolymer with a compound A4 having an unsaturated bond and an epoxy group in one molecule. Item 3. The colored photosensitive resin composition according to Item 2. The compound A2 having an unsaturated bond capable of copolymerization with the compound A1 and the compound A3 is an aromatic vinyl compound or an N-substituted maleimide, according to any one of claims 1 to 3. The colored photosensitive resin composition as described. The ratio of the structural component derived from each of the compound A1, the compound A2, and the compound A3 to the total number of moles of the structural component of the binder resin A is 2 to 50 mol% of the structural unit derived from the compound A1. The structural unit derived from Compound A2 is 2 to 50 mol%, and the structural unit derived from Compound A3 is 2 to 70 mol%. The colored photosensitive resin composition according to Item. The ratio of the component derived from the compound A4 is 5 to 80 mol% with respect to the number of moles of the component derived from the compound A3 in the binder resin A. The colored photosensitive resin composition of any one of Claim 5. In a color filter comprising a color layer formed by applying a colored photosensitive resin composition on an upper portion of a substrate and exposing and developing it into a predetermined pattern.
The said color photosensitive resin composition is a color photosensitive resin composition of any one of Claims 1-6, The color filter characterized by the above-mentioned. A liquid crystal display device comprising the color filter according to claim 7.