KR101405765B1 - Addition copolymer, photosensitive resin composition, and color filter - Google Patents

Abstract

(식중에서, X 및 Y는 각각 독립적으로, 수소원자, 또는 탄소수 1~4의 직쇄 또는 분기쇄의 탄화수소기를 나타내고, R¹ 및 R²는 각각 독립적으로, 수소원자, 탄소수 1~20의 탄화수소기 또는 카복실기를 나타내고, R¹ 및 R²가 연결된 고리상 구조를 형성하여도 좋음)로 표시되는 모노머(a-1') 2~60 몰%, 불포화 다염기산 무수물(a-2) 30~88 몰%, 및 (a-1), (a-1') 및 (a-2) 이외의 공중합 가능한 모노머(a-3) 10~68 몰%를 공중합시킨 공중합체에, 수산기를 갖는 모노머(a-4)를 부가시킨 부가 공중합체(A), 용매(B)를 함유하는 것을 특징으로 하는 감광성 수지 조성물에 관한 것으로, 이 감광성 수지 조성물은, 감도나 현상성이 양호한 것과 함께, 내열분해성 및 내용매성이 우수한 착색 패턴을 나타낼 수 있다. The present invention relates to a monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a monomer (a-1)
(1)

(Wherein X and Y each independently represent a hydrogen atom or a straight or branched chain hydrocarbon group having 1 to 4 carbon atoms; R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or it denotes a carboxyl group, R ¹ and R ² is good to form a cyclic structure linked) monomer (a-1 ') 2 ~ 60% by mole represented by, an unsaturated polybasic acid anhydride (a-2) 30 ~ 88 mol% And 10 to 68 mol% of a copolymerizable monomer (a-3) other than the monomer (a-1), (a-1 ' And a solvent (B). The photosensitive resin composition is excellent in sensitivity and developability, and is excellent in heat resistance and solvent resistance. An excellent coloring pattern can be exhibited.

Description

A photosensitive resin composition, and a color filter,

The present invention relates to an addition copolymer, a photosensitive resin composition and a color filter, and more particularly to an addition copolymer and a photosensitive resin composition used for producing a color filter to be combined with an organic EL display, a liquid crystal display, and a solid- And a color filter manufactured by using the above-described addition copolymer and photosensitive resin composition.

In recent years, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams are widely used in the fields of various coatings, printing, paints, and adhesives from the viewpoints of resource saving and energy saving. Also in the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be cured by active energy rays are used for solder resists, resists for color filters, and the like.

The color filter generally includes a transparent substrate such as a glass substrate, a red (R), green (G), and blue (B) pixel formed on the transparent substrate, a black matrix formed in the pixel environment, And a protective film formed on the matrix. A color filter having such a configuration is usually manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. Various methods of forming pixels and black matrix (hereinafter, referred to as pixel and black matrix) are proposed. However, the photosensitive resin composition may be used as a resist to perform coating, exposure, development and baking Repeated photolithography is the current mainstream because it provides a coloring pattern with excellent durability such as light resistance and heat resistance and less defects such as pinholes.

Generally, the photosensitive resin composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. As the alkali-soluble resin, it has been proposed to use a copolymer obtained by copolymerizing a carboxyl group-containing unsaturated monomer, maleic anhydride, a carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer other than maleic anhydride at a predetermined ratio (for example, see Patent Document 1). It has also been proposed to use a copolymer obtained by adding a hydroxyl group-containing compound to a copolymer obtainable by a monomer copolymerizable with maleic anhydride and maleic anhydride (see, for example, Patent Documents 2 to 5).

Patent Document 1: JP-A-2005-148720 Patent Document 2: JP-A-10-293402 Patent Document 3: JP-A 2007-79294 Patent Document 4: JP-A 2007-133032 Patent Document 5: JP-A-2009-223127

However, the conventional photosensitive resin composition may not be sufficient in sensitivity and developability, and may fail to obtain a coloring pattern excellent in heat resistance decomposability and solvent resistance.

Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a photosensitive resin composition which exhibits good sensitivity and developability, and exhibits a coloring pattern excellent in heat resistance decomposability and solvent resistance. It is another object of the present invention to provide an alkali-soluble resin (addition copolymer) for use in a photosensitive resin composition exhibiting good sensitivity and developability as well as exhibiting a coloring pattern excellent in heat resistance decomposability and solvent resistance. It is another object of the present invention to provide a color filter having a coloring pattern excellent in heat resistance and solvent resistance.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to solve the above problems and found that a specific addition copolymer is optimal as an alkali-soluble resin to be used in a photosensitive resin composition, and have reached the present invention.

That is, the present invention is the following [1] to [13].

(1) a monomer having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a monomer represented by the following formula (1):

(1)

(Wherein X and Y each independently represent a hydrogen atom or a straight or branched chain hydrocarbon group having 1 to 4 carbon atoms; R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or it denotes a carboxyl group, R ¹ and R ² is good to form a cyclic structure linked) monomer (a-1 ') 2 ~ 60% by mole represented by, an unsaturated polybasic acid anhydride (a-2) 30 ~ 88 mol% And 10 to 68 mol% of a copolymerizable monomer (a-3) other than the monomer (a-1), (a-1 ' ) Added thereto, and a solvent (B).

[2] The photosensitive resin composition according to [1], wherein the monomer (a-1) is dicyclopentanyl methacrylate.

[3] The photosensitive resin composition according to [1] or [2], wherein the unsaturated polybasic acid anhydride (a-2) is maleic anhydride.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the monomer (a-3) comprises 10 to 40 mol% of vinyl toluene.

[5] The composition according to any one of [1] to [4], wherein the monomer (a-4) is at least one monomer selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di [1] to [4] above, wherein the photosensitive resin composition is at least one selected from the group consisting of alkali,

[6] The photosensitive resin according to any one of [1] to [5], which further comprises at least one member selected from the group consisting of a reactive diluent (C), a photopolymerization initiator (D) Composition.

[7] The photosensitive resin composition according to [6], wherein the colorant (E) comprises a dye.

(8) a monomer having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms (a-1) and / or a monomer represented by the following formula (1):

(Wherein X and Y each independently represent a hydrogen atom or a straight or branched chain hydrocarbon group having 1 to 4 carbon atoms; R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or it denotes a carboxyl group, R ¹ and R ² is good to form a cyclic structure linked) monomer (a-1 ') 2 ~ 60% by mole represented by, an unsaturated polybasic acid anhydride (a-2) 30 ~ 88 mol% And 10 to 68 mol% of a copolymerizable monomer (a-3) other than the monomer (a-1), (a-1 ' ) Is added to the addition copolymer (A).

[9] The addition copolymer (A) according to [8], wherein the monomer (a-1) is dicyclopentanyl methacrylate.

[10] The additional copolymer (A) according to [8] or [9], wherein the unsaturated polybasic acid anhydride (a-2) is maleic anhydride.

[11] The addition copolymer (A) according to any one of [8] to [10], wherein the monomer (a-3) comprises 10 to 40 mol% of vinyltoluene.

The monomer (a-4) is at least one monomer selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) (A) according to any one of [8] to [11], characterized in that the addition copolymer (A) is at least one selected from the group consisting of ethylene glycol,

[13] A color filter having a coloring pattern formed from the photosensitive resin composition according to any one of [1] to [7].

According to the present invention, it is possible to provide a photosensitive resin composition which exhibits good sensitivity and developability, and exhibits a coloring pattern excellent in heat resistance decomposability and solvent resistance. Further, according to the present invention, it is possible to provide an alkali-soluble resin (addition copolymer) used in a photosensitive resin composition exhibiting good sensitivity and developability and exhibiting a coloring pattern excellent in heat-resistant decomposability and solvent resistance. Further, according to the present invention, it is possible to provide a color filter having a coloring pattern excellent in thermal decomposition resistance and solvent resistance.

1 is a cross-sectional view of a color filter according to a third embodiment.

Carrying out the invention  Form for

Embodiment 1

The addition copolymer (A) of the present embodiment comprises a monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a monomer (a)

(Wherein X and Y each independently represent a hydrogen atom or a straight or branched chain hydrocarbon group having 1 to 4 carbon atoms; R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or it denotes a carboxyl group, R ¹ and R ² is connected to the monomer represented by the good to form a cyclic structure) (a-1 '), an unsaturated polybasic acid anhydride (a-2), and (a-1), (a (A-4) is added to a copolymer obtained by copolymerizing a copolymerizable monomer (a-3) other than the monomer (a-1)

The monomer (a-1) is not particularly limited as long as it has a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. The term "bridged cyclic hydrocarbon" as used herein means having a structure represented by the following formula (2) or (3) represented by adamantane or norbornane, and the term "bridged cyclic hydrocarbon group" , And a group corresponding to the remaining part of the structure in which part of hydrogen is removed.

(2)

(3)

In formula (2), A ¹ and B ¹ may be the same or different and each represents a straight chain or branched alkylene group (including cyclic group), and R ³ represents a hydrogen atom or a methyl group. The branches of A ¹ and B ¹ may be combined to form an annular shape. In formula (3), A ² , B ² and L may be the same or different and each represents a straight chain or branched alkylene group (including cyclic group), and R ⁴ represents a hydrogen atom or a methyl group . A ² , B ^2, and L may be combined to form an annular shape.

Examples of the monomer (a-1) include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl . Of these, dicyclopentyl methacrylate is preferable from the viewpoints of heat decomposition resistance, adhesion, developability and the like. These may be used alone or in combination of two or more.

The monomer (a-1 ') is not particularly limited as long as it has the chemical structure represented by the above formula (1). Examples of X and Y representing a linear or branched hydrocarbon group having 1 to 4 carbon atoms in the formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Butyl group and the like. Examples of R ¹ and R ² which represent a hydrocarbon group of 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, A straight chain or branched chain alkyl group such as a stearyl group, a lauryl group and a 2-ethylhexyl group; An aryl group such as phenyl; Alicyclic groups such as a cyclohexyl group, a t-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group and a 2-methyl-2-adamantyl group; An alkyl group substituted by an alkoxy such as a 1-methoxyethyl group or a 1-ethoxyethyl group; And an alkyl group substituted with an aryl group such as benzyl.

Examples of the monomer (a-1 ') having a chemical structure represented by the chemical formula (1) include norbornene (bicyclo [2.2.1] hepto-2-ene), 5-methylbicyclo [2.2.1] 2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, tetracyclo 4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, 8-methyl tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, dicyclopentadiene, tricyclo [ 5.2.1.0 ^2,6 ] deca-8-ene, tricyclo [5.2.1.0 ^2,6 ] dec-3-ene, tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene, tricyclo [6.2 .1.0 ^1,8] undec-9-ene, tricyclo [6.2.1.0 ^1,8] undec-4-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] Ene, 8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^{2,5 -7,12} ] dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, pentacyclo [ ^{3.6, 2.0, 2.7, 9, 13} ] Pentadeca-4-ene, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] ^pentadec -3-ene, 5-norbornene-2-carboxy acid, 5-norbornene -2,3-dicarboxylic acid, and 5-norbornene-2,3-dicarboxylic anhydride. Among them, norbornene, dicyclopentadiene and 5-norbornene-2,3-dicarboxylic anhydride are preferable from the standpoint of heat decomposition resistance, adhesion, development characteristics and the like. These may be used alone or in combination of two or more.

The blending ratio of the monomer (a-1) and / or the monomer (a-1 ') is preferably in the range of 0.1 to 10 parts by mass, is 2 to 60 mol%, preferably 5 to 20 mol%, based on 100 mol% of the total of (a-3). If the blending ratio of the monomer (a-1) and / or the monomer (a-1 ') is less than 2 mol%, the desired thermal decomposition resistance can not be obtained. On the other hand, when the blend ratio exceeds 60 mol%, the blending ratio of the unsaturated polybasic acid anhydride (a-2) becomes small, and the desired sensitivity and developability can not be obtained.

The unsaturated polybasic acid anhydride (a-2) is not particularly limited and those known in the art can be used. Examples of the unsaturated polybasic acid anhydride (a-2) include maleic anhydride, itaconic anhydride, and citraconic anhydride. Of these, maleic anhydride is preferable from the viewpoints of availability, polymerizability, reactivity, and the like.

The blending ratio of the unsaturated polybasic acid anhydride (a-2) is preferably from 100 to 100 such that the total amount of the monomer (a-1) and / or the monomer (a-1 '), the unsaturated polybasic acid anhydride (a- Mol%, it is 30 to 88 mol%, preferably 35 to 70 mol%. If the blend ratio of the unsaturated polybasic acid anhydride (a-2) is less than 30 mol%, the amount of the double bonds in the addition copolymer (A) becomes small and the desired sensitivity can not be obtained. On the other hand, when the blend ratio exceeds 88 mol%, many unreacted unsaturated polybasic acid anhydrides (a-2) remain.

The monomer (a-3) is not particularly limited as long as it can be copolymerized in addition to (a-1), (a-1 ') and (a-2). The monomer (a-3) is generally a radically polymerizable compound having an ethylenic unsaturated group, and examples thereof include dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; Butyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) Butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, (Meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl Acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (Meth) acrylate (Meth) acrylate, 5-ethyl norbornyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, (Meth) acrylate, cresyl (meth) acrylate, 1,1,1-tetramethylbutyl (meth) acrylate, (Meth) acrylate, perfluoro (meth) acrylate, perfluoro (meth) acrylate, perfluoro (meth) acrylate, perfluoro (Meth) acrylate, butanetriol mono (meth) acrylate, cumyl (meth) acrylate, cumyl (meth) acrylate, 3- Mono (meth) acrylate, naphthalene (meth) acrylate, (Meth) acrylates such as acrylate and anthracene (meth) acrylate; (Meth) acrylic acid amide, N, N-dimethyl amide, N, N-diethyl amide, N, N-dipropyl amide, (Meth) acrylamide such as isopropylamide and isobutyl (meth) acrylate; (Meth) acrylic acid anilide, vinyl (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate and vinyltoluene compound; Styrene,? -, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene; Unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; And compounds having a carboxyl group such as N- (meth) acryloyl phthalimide, (meth) acrylic acid, crotonic acid, and cinnamic acid. These may be used alone or in combination of two or more.

In particular, when maleic anhydride is used as the unsaturated polybasic acid anhydride (a-2), the maleic anhydride is a compound having a strong electron-accepting property, and therefore the monomer (a-3) is preferably an electron-donating monomer. By using such electron-donating monomers, alternate copolymerization takes place with maleic anhydride and the like, and each unit is disposed more randomly. As a result, developability, sensitivity and the like are improved and at the same time, A pattern can be formed. Examples of the electron-donating monomers include vinyl ethers, vinyl sulfides, styrenes, and the like. Of these, styrenes are preferred from the viewpoint of copolymerization, and vinyltoluene is more preferable from the viewpoint of decomposition resistance. When vinyl toluene is used, the (meth) acrylic acid ester is used, and the developability can be further improved.

The blend ratio of the monomer (a-3) is preferably 100 mol% or more, more preferably 100 mol% or more, more preferably 100 mol% or less, , It is 10 to 68 mol%, preferably 20 to 50 mol%. If the blend ratio of the monomer (a-3) is less than 10 mol%, a balance between heat resistance and developability can not be obtained. On the other hand, when the blend ratio exceeds 68 mol%, the sensitivity and heat resistance deteriorate.

Particularly, when vinyl toluene is used as the monomer (a-3), the amount of the monomer (a-1) and / or the monomer (a-1 '), the unsaturated polybasic acid anhydride (a- When the total amount is 100 mol%, the monomer (a-3) preferably contains 10 to 40 mol% of vinyltoluene.

The copolymerization reaction using the monomer (a-1) and / or the monomer (a-1 '), the unsaturated polybasic acid anhydride (a-2), and the monomer (a-3) as raw materials can be carried out by radical polymerization Can be carried out according to the method. For example, after a monomer (a-1) and / or a monomer (a-1 '), an unsaturated polybasic acid anhydride (a-2), and a monomer (a-3) are dissolved in a solvent, , And 50 to 130 ° C for 1 to 20 hours.

Examples of the solvent that can be used in the copolymerization reaction include, but are not limited to, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Hydrocarbon solvents such as toluene and xylene, and solvents having no reactive functional groups such as ethyl acetate. These may be used alone or in combination of two or more. Among them, a glycol ether-based solvent is preferable.

The blending amount of the solvent is not particularly limited as long as it is an amount capable of dissolving the raw material, but the amount of the monomer (a-1) and / or the monomer (a-1 '), the unsaturated polybasic acid anhydride (a- ) Is 100 parts by mass, it is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. Particularly, when the blending amount of the solvent is 1000 parts by mass or less, it is possible to suppress the decrease of the molecular weight of the copolymer by the chain transfer action, and to control the viscosity of the copolymer to an appropriate range. In addition, by setting the amount of the solvent to 30 parts by mass or more, abnormal polymerization reaction can be prevented, polymerization reaction can be stably performed, and coloring and gelation of the copolymer can be prevented.

The polymerization initiator that can be used in the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisobalonitrile, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate And the like. These may be used alone or in combination of two or more.

When the total amount of the monomer (a-1) and / or the monomer (a-1 '), the unsaturated polybasic acid anhydride (a-2), and the monomer (a-3) is 100 parts by mass, 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass.

Bulk polymerization is carried out using the monomer (a-1) and / or the monomer (a-1 '), the unsaturated polybasic acid anhydride (a-2), the monomer (a-3) and a polymerization initiator without using an organic solvent .

In the copolymer obtained by the copolymerization reaction, a carboxyl group and a double bond are introduced into the side chain of the copolymer by adding the monomer (a-4) having a hydroxyl group. This improves the sensitivity and developability of the photosensitive resin composition.

Examples of the monomer (a-4) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (Meth) acrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, trimethylolpropane di Methacrylate, pentaerythritol triacrylate, and the like. These may be used alone or in combination of two or more.

In particular, in consideration of the reactivity with the acid anhydride group in the copolymer, the monomer (a-4) preferably has a primary hydroxyl group. In consideration of the sensitivity of the photosensitive resin composition, the monomer (a-4) is preferably a monomer having a small molecular weight or a multifunctional (meth) acrylate in order to increase the amount of double bonds in the addition copolymer (A) desirable. Examples of the monomer satisfying these conditions include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol triacrylate. have.

The addition ratio of the monomer (a-4) to the acid anhydride group in the copolymer is preferably 10 to 100%. In order to carry out the addition reaction of the monomer (a-4), the molar equivalent of the hydroxyl group of the monomer (a-4) should be in the range of 0.1 to 1, when the molar equivalent of the acid anhydride group of the copolymer is 1. The monomer (a-4) may be added and reacted. If the addition ratio is less than 10%, the amount of the carboxyl group and the double bond introduced into the side chain of the copolymer is too small, and the desired sensitivity and developability can not be obtained.

The addition reaction of the monomer (a-4) to the acid anhydride group in the copolymer is carried out by adding the monomer (a-4), a polymerization inhibitor and a catalyst to the copolymer and heating at 50 to 150 ° C, The reaction may be carried out. In this addition reaction, there is no particular problem even if the solvent used in the copolymerization reaction is included, so that the addition reaction can be carried out without removing the solvent after completion of the copolymerization reaction.

Here, the polymerization inhibitor is added in order to prevent gelation by polymerization of the copolymer. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether and the like. Examples of the catalyst include, but are not limited to, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelate compounds of chromium. . Among them, it is preferable to use tertiary amines such as triethylamine, triethylenediamine, 4-dimethylaminopyridine and dimethylaminoethyl methacrylate in the reaction of the acid anhydride with the hydroxyl group.

The acid value of the addition copolymer (A) thus obtained is preferably 50 to 400 KOH mg / g, and more preferably 150 to 300 KOH mg / g. If the acid value is less than 50 KOH mg / g, the developability of the photosensitive resin composition may be deteriorated. On the other hand, if the acid value exceeds 400 KOH mg / g, the exposed portion (light-cured portion) tends to dissolve in the alkaline developer.

The molecular weight (weight average molecular weight in terms of polystyrene) of the addition copolymer (A) is preferably 1,000 to 40,000, more preferably 3,000 to 20,000. If the molecular weight is less than 1000, defects of the coloring pattern may easily occur after development. On the other hand, if the molecular weight exceeds 40,000, the development time becomes too long, and practicality may be lost.

The addition copolymer (A) of the present embodiment is a photosensitive resin composition which is optimal as an alkali-soluble resin for use in a photosensitive resin composition and which is excellent in sensitivity and developability and exhibits a coloring pattern excellent in heat resistance and solvent resistance can do.

Embodiment 2 Fig.

The photosensitive resin composition of this embodiment contains the addition copolymer (A) of the first embodiment and the solvent (B).

The solvent (B) is not particularly limited as long as it is an inert solvent that does not react with the addition copolymer (A).

As the solvent (B), the same solvent as that used in the production of the addition copolymer (A) (copolymerization reaction) can be used. Specific examples of the solvent (B) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, Propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl Ether acetate and the like. These may be used alone or in combination of two or more. Of these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, which are used in the production of the addition copolymer (A) (copolymerization reaction), are preferred.

The blending amount of the solvent (B) in the photosensitive resin composition of the present embodiment is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, per 100 parts by mass of the solid component (that is, the component excluding the solvent) in the photosensitive resin composition Mass part, and more preferably 100 to 700 mass parts. When the amount is within this range, a photosensitive resin composition having an appropriate viscosity is obtained.

The photosensitive resin composition of the present embodiment may contain a reactive diluent (C), a photopolymerization initiator (D) and a colorant (E) in addition to the above components.

The reactive diluent (C) is not particularly limited as long as it reacts with the addition copolymer (A). Examples of the reactive diluent include aromatic vinyl monomers such as styrene,? -Methylstyrene,? -Chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzenephosphonate; Polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; (Meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl Acrylates such as di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane di (Meth) acrylate monomers such as tri (meth) acrylate of pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and tris (hydroxyethyl) isocyanurate ; Triallyl cyanurate and the like. These may be used alone or in combination of two or more.

The amount of the reactive diluent (C) to be added in the photosensitive resin composition of the present embodiment is generally 10 to 90 parts by mass, preferably 20 to 90 parts by mass, per 100 parts by mass of the solid component (that is, 80 parts by mass, and more preferably 25 to 70 parts by mass. When the amount is within this range, a photosensitive resin composition having appropriate photocurability and viscosity is obtained.

Examples of the photopolymerization initiator (D) include, but are not limited to, benzoin and alkyl ethers thereof such as benzoin, benzoin methyl ether, and benzoin ethyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; Anthraquinones such as 2-methyl anthraquinone, 2-amylanthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone ; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; Acylphosphine oxides; And xanthones. These may be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator (D) in the photosensitive resin composition of the present embodiment is generally from 0.1 to 30 parts by mass, preferably from 0.5 to 30 parts by mass, per 100 parts by mass of the solid component (that is, 20 parts by mass, and more preferably 1 to 10 parts by mass. When the amount is within this range, a photosensitive resin composition having appropriate photo-curability can be obtained.

The colorant (E) is not particularly limited as long as it is soluble in the solvent (B), and examples thereof include a dye and a pigment.

Particularly, in the conventional photosensitive resin composition, when a dye is used, a coloring pattern having a high luminance can be obtained, but there is a problem that the heat resistance of the coloring pattern is lowered as compared with the case of using a pigment. On the other hand, in the photosensitive resin composition of the present embodiment, since the pure salt of the dye is good, a coloring pattern excellent in heat resistance can be obtained even by using a dye.

From the viewpoints of solubility in solvents (B) and alkali developers, interaction with other components in the photosensitive resin composition, heat resistance, etc., the dyes include acid dyes having an acidic group such as carboxylic acid, salts with nitrogen compounds of acid dyes, A sulfonamide form of an acidic dye or the like is preferably used. Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3, and derivatives thereof. Among them, azo dyes, xanthan dyes, anthraquinone dyes or phthalocyanine dyes are preferable. These can be used alone or in combination of two or more kinds, depending on the color of a target pixel.

Examples of the pigment include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214; C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ; C.I. Blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments such as Pigment Green 7, 36, 58; C.I. Brown pigments such as Pigment Brown 23 and 25; C.I. Pigments black 1, black pigments such as carbon black, titanium black and iron oxide, and the like. These can be used alone or in combination of two or more kinds, depending on the color of a target pixel.

The dye and the pigment may be used in combination according to the color of the target pixel.

The blending amount of the colorant (E) in the photosensitive resin composition of the present embodiment is generally 5 to 80 parts by mass, preferably 5 to 70 parts by mass, per 100 parts by mass of the solid component (that is, the component excluding the solvent) in the photosensitive resin composition Mass part, and more preferably 10 to 60 mass parts.

When a pigment is used as the colorant (E), a known dispersant may be added to the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersing agent, it is preferable to use a polymer dispersing agent having excellent dispersion stability over time. Examples of the polymer dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, a sorbitan aliphatic ester-based dispersant, and an aliphatic modified ester-based dispersant. Examples of such polymer dispersing agents include trade names such as EFKA (manufactured by EFKA), Disperbyk (manufactured by BICKEMISA), DIPERRON (manufactured by Kusumoto Chemical Co., Ltd.) and SOLSPERSE (manufactured by Geneca) May be used.

The blending amount of the dispersing agent in the photosensitive resin composition of the present embodiment may be suitably set in accordance with the kind of the pigment to be used.

The photosensitive resin composition of the present embodiment may be blended with known additives such as known coupling agents, leveling agents, and thermosetting agents in addition to the above components in order to impart predetermined characteristics. The blending amount of these additives is not particularly limited as long as the effect of the present invention is not impaired.

The photosensitive resin composition of the present embodiment can be produced by mixing the above components using a known mixing apparatus.

The photosensitive resin composition of the present embodiment, which can be obtained in the above-described manner, has alkali developability, so that development can be easily carried out by using an aqueous alkali solution. In particular, the photosensitive resin composition of the present embodiment can exhibit a coloring pattern excellent in heat resistance and solvent resistance as well as excellent in sensitivity and developability. For this reason, the photosensitive resin composition of the present embodiment is suitable for use as a resist used for producing a color filter to be combined with various resists, particularly organic EL displays, liquid crystal displays, and solid-state image pickup devices. The photosensitive resin composition of the present embodiment can be used for various coatings, adhesives, binders for printing inks, and the like because it can provide a cured film excellent in various properties such as heat resistance decomposability and solvent resistance.

Embodiment 3:

The color filter of the present embodiment has a coloring pattern obtainable from the photosensitive resin composition.

Hereinafter, the color filter of this embodiment will be described with reference to the drawings.

1 is a cross-sectional view of a color filter of the present embodiment. 1, the color filter includes a substrate 1, a black matrix 3 formed on the boundary between the RGB pixels 2 and the pixels 2 formed on the substrate 1, a pixel 2, And a protective film (4) formed on the matrix (3). In this configuration, other known structures can be employed, except that the pixel 2 and the black matrix 3 (coloring pattern) are formed using the photosensitive resin composition described above. The color filter shown in Fig. 1 is an example, and is not limited to this configuration.

Next, a method of manufacturing the color filter of the present embodiment will be described.

First, a colored pattern is formed on the substrate 1. Specifically, a black matrix 3 and a pixel 2 are formed on a substrate 1 in sequence. The substrate 1 is not particularly limited, and examples thereof include a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, Can be used.

The coloring pattern can be formed by photolithography. Specifically, the photosensitive resin composition is coated on the substrate 1 to form a coating film, and then the coating film is exposed through a photomask of a predetermined pattern to photo-cure the exposed portion. Then, the unexposed portions are developed with an aqueous alkaline solution and then baked to form a predetermined pattern.

The method of applying the photosensitive resin composition is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, or the like can be used. After the application of the photosensitive resin composition, the solvent (B) may be volatilized by heating using a heating means such as a circulating oven, an infrared heater, or a hot plate, if necessary. The heating conditions are not particularly limited and may be appropriately set according to the type of the photosensitive resin composition to be used. Generally, heating may be performed at a temperature of 50 to 120 DEG C for 30 seconds to 30 minutes.

As a light source used for exposure, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp and the like can be used although there is no particular limitation. The amount of exposure is not particularly limited, and may be suitably adjusted according to the type of the photosensitive resin composition to be used.

The alkali aqueous solution used for the development is not particularly limited, and examples thereof include aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like; An aqueous solution of an amine compound such as ethylamine, diethylamine or dimethylethanolamine; 3-methyl-4-amino-N, N-diethylaniline, 3-methyl- -methanesulfonamide ethyl aniline, 3-methyl-4-amino-N-ethyl-N -? - methoxyethylaniline and p-phenylenediamine compounds such as sulfate, hydrochloride or p- And the like can be used. Among them, it is preferable to use an aqueous solution of a p-phenylenediamine compound. To these aqueous solutions, a defoaming agent or a surfactant may be added as required. Further, after development with the above-mentioned alkali aqueous solution, it is preferable to wash with water and dry.

The baking conditions are not particularly limited, and heat treatment may be performed depending on the type of the photosensitive resin composition to be used. Generally, heating at 130 ° C to 250 ° C for 10 to 60 minutes is sufficient.

By repeating the above-mentioned application, exposure, development and baking in sequence using the photosensitive resin composition for the black matrix 3 and the photosensitive resin composition for the pixel 2, a desired coloring pattern can be formed have.

In the above description, a method of forming a colored pattern by photo-curing has been described. However, when a photosensitive resin composition containing a curing accelerator and a known epoxy resin is used in place of the photopolymerization initiator (D) , A desired coloring pattern can be formed.

Next, the protective film 4 is formed on the colored patterns (the pixel 2 and the black matrix 3). The protective film 4 is not particularly limited and may be formed using a known film.

The color filter thus produced is excellent in sensitivity and developability and is manufactured using a photosensitive resin composition exhibiting a coloring pattern excellent in heat resistance decomposability and solvent resistance. Therefore, a coloring pattern having excellent heat resistance and solvent resistance can be obtained .

Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In this embodiment, parts and percentages are based on total mass unless otherwise specified.

≪ Preparation of Photosensitive Resin Composition >

426.1 g of propylene glycol monomethyl ether acetate (solvent 1) and 176.4 g of maleic anhydride (a-2) were placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube, And the temperature was raised to 120 ° C. Subsequently, 24.4 g of t-butylperoxy-2-ethylhexanoate (polymerization) was added to a monomer mixture composed of 66.0 g of dicyclopentanyl methacrylate (a-1) and 106.2 g of vinyltoluene Initiator) was added to the flask from the dropping funnel. After completion of the dropwise addition, the mixture was stirred at 120 DEG C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

Then, the flask was purged with air, and then 139.2 g of 2-hydroxyethyl acrylate (a-4), 1.5 g of triethylamine (catalyst) and 1.5 g of methylhydroquinone And the addition reaction was carried out at 120 DEG C for 6 hours to produce the addition copolymer (A).

Subsequently, 305.6 g of propylene glycol monomethyl ether (solvent 2) was added to this addition copolymer (A) to obtain a photosensitive resin composition (sample No. 1).

Several kinds of photosensitive resin compositions (Sample Nos. 2 to 19) were prepared in the same manner as above except that the kinds and amounts of raw materials were changed.

Table 1 shows the raw materials used in the production of the photosensitive resin compositions (Sample Nos. 1 to 19) and their blending amounts.

In Table 1, the molar percentages of the respective raw materials of (a-1), (a-1 '), (a-2) and (a- means the mol% of each raw material when the total amount of the raw materials of (a-2) and (a-3) is 100 mol%. The molar equivalent of (a-4) means the molar equivalent of the hydroxyl group of the monomer (a-4) when the molar equivalent of the acid anhydride group of the copolymer is 1. The acid value is the acid value of the addition copolymer (A) measured according to JIS K6901 5.3, which means the number of mg of potassium hydroxide necessary for neutralizing the acidic component contained in 1 g of the addition copolymer (A). Further, the molecular weight (Mw) means the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography under the following conditions.

<Molecular Weight Measurement Conditions>

Column: Showdix LF-804 + LF-804 (manufactured by Digo Co., Ltd.)

Column temperature: 40 ° C

Sample: 0.2% tetrahydrofuran solution of the addition copolymer (A)

Developing solvent: tetrahydrofuran

Detector: Differential refractometer (Showidix RI-71S) (manufactured by Digo Co., Ltd.)

Flow rate: 1 mL / min

A transparent resist, a color resist (pigment type) and a color resist (dye type) were prepared using the photosensitive resin compositions of Sample Nos. 1 to 19.

&Lt; Preparation of transparent resist &

30 parts by mass of pentaerythritol tetraacrylate (reactive diluent) and 4 parts by mass of 2,2-dimethoxy-2-phenylacetophenone (photopolymerization initiator) were added to 100 parts by mass of the solid content of the photosensitive resin compositions of Sample Nos. To thereby prepare a transparent resist (Examples 1 to 14 and Comparative Examples 1 to 5).

&Lt; Formation of cured coating film by transparent resist &

The prepared transparent resist was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the final cured coating film had a thickness of 2.5 m and then heated at 90 占 폚 for 30 minutes to volatilize the solvent. Then, the entire surface of the resultant coating film was exposed to light (exposure dose: 50 mJ / cm ² ) to be photo-cured, and further baked at 230 ° C for 30 minutes to obtain a cured film.

&Lt; Evaluation of cured coating film formed from transparent resist &

The cured coating film formed from the transparent resist was evaluated for thermal decomposition resistance, transparency and adhesion.

(1) Evaluation of thermal decomposition resistance

The thermal decomposition resistance was evaluated by thermogravimetric analysis (TGA) using a sample from which a cured film formed from a transparent resist was discharged. In this analysis, the weight change rate between the sample and the sample heated to 220 DEG C for 2 hours was obtained. The criteria for this evaluation are as follows.

○: less than -2.0%

×: -2.0% or more

(2) Evaluation of transparency

The transparency was measured by measuring a light transmittance of 400 nm with respect to the cured coating film formed from a transparent resist and heating the cured film at 230 DEG C for 1 hour in a drier by using a spectrophotometer and examining the rate of change of the transmittance Respectively. The criteria for this evaluation are as follows.

?: The rate of change of transmittance is less than 1%

X: Change rate of transmittance is 1% or more

(3) Evaluation of adhesion

The adhesiveness was evaluated by subjecting the cured coating film formed from the transparent resist to a scratch test according to JIS K5400 and visually observing the peeling state of 100 scratch marks. The evaluation criteria are as follows.

○: No peeling at all

X: peeling is visible

The evaluation results of the heat-decomposability, transparency and adhesiveness are shown in Table 2.

As can be seen from the results shown in Table 2, the transparent resist of Examples 1 to 14 exhibits a cured film excellent in all of heat resistance, transparency and adhesion, whereas the transparent resist of Comparative Examples 1 to 5 has heat resistance , And the adhesion was not sufficient.

&Lt; Preparation of color resist (pigment type) >

To an SUS container filled with 180 parts by mass of zirconia beads having a diameter of 0.5 mm, 10.00 parts by mass of C.I. Pigment Green 36, 33.75 parts by mass of PGMEA (solvent) and 6.25 parts by mass of a dispersant (Disperbyk-161 manufactured by Big Chem Co., Ltd.) were mixed and dispersed for 3 hours with a paint shaker to obtain a green pigment dispersion .

Next, a color resist (pigment type) was prepared by mixing the green pigment dispersion thus prepared, the photosensitive resin composition of Sample Nos. 1 to 19, and other components (Examples 15 to 28 and Comparative Examples 6 to 10). Table 3 shows the blending components of the color resist (pigment type) and their blending amounts.

Compounding ingredient Formulation amount (parts by mass)
Green pigment dispersion 50 Photosensitive resin composition 8.03 Trimethylolpropane triacrylate
(Reactive diluent) 6.5 Irgacure 907
(Photopolymerization initiator, manufactured by Ciba Specialty Chemicals) 1.66 High Cure ABP
(Photopolymerization initiator, manufactured by Kawaguchi Pharmaceutical Co., Ltd.) 0.83 Propylene glycol monomethyl ether acetate
(menstruum) 52.6 Sum 119.62

&Lt; Pattern formation by color resist (pigment type) >

The prepared color resist (pigment type) was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness upon drying would be 2.2 μm and then heated at 80 ° C. for 3 minutes to volatilize the solvent , And dried. Subsequently, a photomask of a predetermined pattern was disposed at a distance of 100 mu m from the coated film, and the coated film was exposed (exposure amount: 150 mJ / cm &lt; ² &gt;) through the photomask. Subsequently, an unexposed portion was dissolved and developed by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23 캜 and a pressure of 0.3 MPa, and then baked at 230 캜 for 30 minutes to form a predetermined pattern .

&Lt; Evaluation of color resist (pigment type) and pattern >

With regard to the color resist (pigment type) and the pattern, the alkalinity developing property, the sensitivity and the solvent resistance were evaluated.

(4) Evaluation of alkali developability

The alkali developability was evaluated by the time of alkali development, the residue after alkaline development, and the development form.

The alkali development time was measured by the time when the pattern was completely visually recognized by the alkali development using the spray.

The residue after the alkali development was evaluated by observing the pattern after the alkali development using an electron microscope. The criteria for this evaluation are as follows.

○: No residue

X: Residual

In the form of development, the form of removal of the unexposed portion due to the alkali development was visually evaluated. Here, in the development process of negative resist, unexposed unexposed portions are dissolved by the alkali developing solution to be separated from the substrate. In the developing mode, however, the detached thinned portion mainly becomes a large lump, , And a dissolving type that dissolves and diffuses gradually. The exfoliation type of the former is not preferable because the agglomerates remain in the system as foreign matters and easily contaminate pixels of different colors. In short, since the latter dissolution type is not preferable, the criteria for this evaluation are as follows.

○: Dissolution type

×: peeling type

(5) Evaluation of sensitivity

The sensitivity was evaluated by the alkali development using the above spray for 30 seconds to measure the amount of decrease in the pattern thickness before and after the alkali development. Since this pattern thickness can be said to have a better sensitivity as the reduction amount is smaller, the criterion for this evaluation is as follows.

○: less than 0.20 μm

×: 0.20 μm or more

(6) Evaluation

The solvent resistance was measured by using a pattern sample formed by photocuring in the same manner as described above except that the entire surface was exposed without using a photomask, and 200 mL of n-methyl-2-pyrrolidone was added to a cover glass having a capacity of 500 mL After the pattern sample was immersed in the sample, the color change after 60 minutes at 23 ° C was measured by a colorimeter. The criteria for this evaluation are as follows.

?:? E * ab is less than 0.3

×: ΔE * ab is 0.3 or more

The evaluation results of the alkali developability, the sensitivity and the solvent resistance are shown in Table 4.

As can be seen from the results in Table 4, the color resist (pigment type) of Examples 15 to 28 exhibited good alkali developability and sensitivity, and excellent solvent resistance, while Comparative Examples 6 to 10 The color resist (pigment type) exhibited a pattern in which the alkali developability or sensitivity was poor or the solvent resistance was insufficient.

 &Lt; Preparation of color resist (dye type) >

A color resist (dye type) was prepared by mixing the dye (acid green 3), the photosensitive resin composition of Sample Nos. 1 to 19, and other components (Examples 29 to 42 and Comparative Examples 11 to 15). Table 5 shows the blending components of the color resist (dye type) and their blending amounts.

Compounding ingredient Formulation amount (parts by mass) acid green 3 5.2 Photosensitive resin composition 32.5 Trimethylolpropane triacrylate
(Reactive diluent) 15.6 Irgacure 907
(Photopolymerization initiator, manufactured by Ciba Specialty Chemicals) 1.3 Propylene glycol monomethyl ether
(menstruum) 45.4 Sum 100.0

&Lt; Pattern formation by color resist (dye type) >

Except that a color resist (dye type) was used, a predetermined pattern was formed in the same manner as the pattern formation by a color resist (pigment type).

&Lt; Evaluation of color resist (dye type) and pattern >

The alkali developability, sensitivity and solvent resistance were evaluated by the same method as that of the color resist (pigment type).

The evaluation results of the alkali developability, sensitivity and solvent resistance are shown in Table 6.

As can be seen from the results of Table 6, the color resist (dye type) of Examples 29 to 42 exhibited good alkali developability and sensitivity and excellent solvent resistance, while Comparative Examples 11 to 15 The color resist (dye type) exhibited a pattern in which the alkali developability or sensitivity was not good, and the solvent resistance was insufficient.

As can be seen from the above results, according to the present invention, an alkali-soluble resin (addition copolymer) used in the production of a photosensitive resin composition exhibiting good sensitivity and developability as well as a coloring pattern excellent in heat- Can be provided. Further, according to the present invention, it is possible to provide a photosensitive resin composition which exhibits good sensitivity and developability and exhibits a coloring pattern excellent in heat resistance decomposability and solvent resistance. Further, according to the present invention, it is possible to provide a color filter having a coloring pattern excellent in thermal decomposition resistance and solvent resistance.

This international application claims priority based on Japanese Patent Application No. 2010-092286 filed on April 13, 2010, and the entire content of this Japanese patent application is incorporated in the present international application.

Claims (13)

(A-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a monomer (a-1)
(1)

(Wherein X and Y each independently represent a hydrogen atom or a straight or branched chain hydrocarbon group having 1 to 4 carbon atoms; R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or it denotes a carboxyl group, R ¹ and R ² is good to form a cyclic structure linked) monomer (a-1 ') 2 ~ 60% by mole represented by, an unsaturated polybasic acid anhydride (a-2) 30 ~ 88 mol% And 10 to 68 mol% of a copolymerizable monomer (a-3) other than the monomer (a-1), (a-1 ' ) Added thereto, and a solvent (B). The photosensitive resin composition according to claim 1, wherein the monomer (a-1) is dicyclopentanyl methacrylate. The photosensitive resin composition according to claim 1 or 2, wherein the unsaturated polybasic acid anhydride (a-2) is maleic anhydride. The photosensitive resin composition according to claim 1 or 2, wherein the monomer (a-3) comprises 10 to 40 mol% of vinyl toluene. The positive resist composition according to claim 1 or 2, wherein the monomer (a-4) is at least one monomer selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di , And pentaerythritol triacrylate. The photosensitive resin composition according to claim 1, The photosensitive resin composition according to claim 1 or 2, further comprising at least one member selected from the group consisting of a reactive diluent (C), a photopolymerization initiator (D), and a colorant (E). The photosensitive resin composition according to claim 6, wherein the colorant (E) comprises a dye. (A-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a monomer (a-1)

(Wherein X and Y each independently represent a hydrogen atom or a straight or branched chain hydrocarbon group having 1 to 4 carbon atoms; R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or it denotes a carboxyl group, R ¹ and R ² is good to form a cyclic structure linked) monomer (a-1 ') 2 ~ 60% by mole represented by, an unsaturated polybasic acid anhydride (a-2) 30 ~ 88 mol% And 10 to 68 mol% of a copolymerizable monomer (a-3) other than the monomer (a-1), (a-1 ' ) Is added to the addition copolymer (A). The addition copolymer (A) according to claim 8, wherein the monomer (a-1) is dicyclopentanyl methacrylate. The addition copolymer (A) according to claim 8 or 9, wherein the unsaturated polybasic acid anhydride (a-2) is maleic anhydride. The addition copolymer (A) according to claim 8 or 9, wherein the monomer (a-3) comprises 10 to 40 mol% of vinyltoluene. The thermoplastic resin composition according to claim 8 or 9, wherein the monomer (a-4) is at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di , And pentaerythritol triacrylate. The addition copolymer (A) is characterized in that the addition copolymer A color filter having a coloring pattern formed from the photosensitive resin composition according to any one of claims 1 to 5.

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