KR20120125511A - 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 provides a monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or the following general formula (1):
Formula (1)

(Wherein X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) Or 2 to 60 mol% of a monomer (a-1 ') represented by a carboxyl group, which may form a cyclic structure to which R ¹ and R ² are linked, and 30 to 88 mol% of an unsaturated polybasic acid anhydride (a-2). And monomer (a-4) having a hydroxyl group in a copolymer obtained by copolymerizing 10 to 68 mol% of copolymerizable monomers (a-3) other than (a-1), (a-1 ') and (a-2). The addition photopolymer (A) and the solvent (B) which added ()) are related, The photosensitive resin composition is a thing with favorable sensitivity and developability, and thermal decomposition resistance and solvent resistance Excellent coloring patterns can be exhibited.

Description

Addition copolymer, photosensitive resin composition, and color filter

The present invention relates to an addition copolymer, a photosensitive resin composition and a color filter, and in particular, an addition copolymer and a photosensitive resin composition used in the production of color filters combined with an organic EL display, a liquid crystal display device, and a solid-state image sensor, and The color filter manufactured using these addition copolymers and the photosensitive resin composition.

In recent years, from the viewpoint of resource saving and energy saving, photosensitive resin compositions curable by active energy rays such as ultraviolet rays and electron beams have been widely used in various coatings, printing, coating materials, adhesives and the like. Moreover, also in the field of electronic materials, such as a printed wiring board, the photosensitive resin composition which can be hardened by an active energy ray is used for a soldering resist, a color filter resist, etc.

The color filter is generally a transparent substrate such as a glass substrate, pixels of red (R), green (G), and blue (B) formed on the transparent substrate, and a black matrix, pixels, and black formed in the pixel environment. It consists of a protective film formed on a matrix. The color filter which has such a structure is normally manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. As a method for forming the pixel and the black matrix (hereinafter, referred to as the "coloring pattern" of the pixel and the black matrix), various manufacturing methods have been proposed, but application, exposure, development and baking are carried out using the photosensitive resin composition as a resist. The repeating photolithography method has become a mainstream because it provides excellent coloring resistance, heat resistance, and the like, and provides a colored pattern with few defects such as pinholes.

Generally, the photosensitive resin composition used for the photolithographic method contains alkali-soluble resin, a reactive diluent, a photoinitiator, a coloring agent, and a solvent. As alkali-soluble resin, what copolymerized the carboxyl group-containing unsaturated monomer, maleic anhydride, a carboxyl group-containing unsaturated monomer, and copolymerizable unsaturated monomers other than maleic anhydride in predetermined ratio is proposed (for example, refer patent document 1). Moreover, the thing which added the hydroxyl group containing compound to the copolymer obtained by the monomer copolymerizable with maleic anhydride and maleic anhydride is also proposed (for example, refer patent documents 2-5).

Patent Document 1: Japanese Patent Application Laid-Open No. 2005-148720 Patent Document 2: Japanese Patent Application Laid-Open No. 10-293402 Patent Document 3: Japanese Patent Application Laid-Open No. 2007-79294 Patent Document 4: Japanese Patent Application Laid-Open No. 2007-133032 Patent Document 5: Japanese Patent Application Laid-Open No. 2009-223127

However, the conventional photosensitive resin composition may not be able to obtain the case where sensitivity and developability are not enough, and the coloring pattern excellent in thermal decomposition resistance and solvent resistance.

Therefore, an object of the present invention is to provide a photosensitive resin composition exhibiting a coloring pattern excellent in thermal decomposition resistance and solvent resistance, in addition to having good sensitivity and developability. Moreover, an object of this invention is to provide alkali-soluble resin (addition copolymer) used for the photosensitive resin composition which shows the coloring pattern excellent in thermal decomposition resistance and solvent resistance while being excellent in sensitivity and developability. Moreover, an object of this invention is to provide the color filter which has a coloring pattern excellent in thermal decomposition resistance and solvent resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the above subjects, the present inventors discovered that the specific addition copolymer was optimal as alkali-soluble resin used for the photosensitive resin composition, and came to this invention.

That is, this invention is the following [1]-[13].

[1] A monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or the following general formula (1):

(1)

(Wherein X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) Or 2 to 60 mol% of a monomer (a-1 ') represented by a carboxyl group, which may form a cyclic structure to which R ¹ and R ² are linked, and 30 to 88 mol% of an unsaturated polybasic acid anhydride (a-2). And monomer (a-4) having a hydroxyl group in a copolymer obtained by copolymerizing 10 to 68 mol% of copolymerizable monomers (a-3) other than (a-1), (a-1 ') and (a-2). The addition copolymer (A) and the solvent (B) which added () are contained, The photosensitive resin composition characterized by the above-mentioned.

[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) contains 10 to 40 mol% of vinyltoluene.

[5] The monomer (a-4) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, and pentaerythritol triacryl. It is 1 or more types chosen from the group which consists of a rate, The photosensitive resin composition in any one of [1]-[4] characterized by the above-mentioned.

[6] The photosensitive resin according to any one of [1] to [5], further comprising one or more selected from the group consisting of a reactive diluent (C), a photopolymerization initiator (D) and a colorant (E). Composition.

[7] The photosensitive resin composition according to [6], wherein the coloring agent (E) contains a dye.

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

(Wherein X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) Or 2 to 60 mol% of a monomer (a-1 ') represented by a carboxyl group, which may form a cyclic structure to which R ¹ and R ² are linked, and 30 to 88 mol% of an unsaturated polybasic acid anhydride (a-2). And monomer (a-4) having a hydroxyl group in a copolymer obtained by copolymerizing 10 to 68 mol% of copolymerizable monomers (a-3) other than (a-1), (a-1 ') and (a-2). ) Is an addition copolymer (A).

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

[10] The addition 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) contains 10 to 40 mol% of vinyltoluene.

[12] The monomer (a-4) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, and pentaerythritol triacryl. It is 1 or more types chosen from the group which consists of a rate, The addition copolymer (A) in any one of [8]-[11] characterized by the above-mentioned.

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

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which shows the coloring pattern excellent in thermal decomposition resistance and solvent resistance while being excellent in sensitivity and developability can be provided. Moreover, according to this invention, alkali-soluble resin (addition copolymer) used for the photosensitive resin composition which shows the coloring pattern excellent in thermal decomposition resistance and solvent resistance while being excellent in sensitivity and developability can be provided. Moreover, according to this invention, the color filter which has a coloring pattern excellent in thermal decomposition resistance and solvent resistance can be provided.

1 is a cross-sectional view of a color filter of Embodiment 3. FIG.

Carrying out the invention  Form for

Embodiment 1

The addition copolymer (A) of this embodiment is a monomer (a-1) which has a C10-C20 bridged cyclic hydrocarbon group, and / or following General formula (1):

(Wherein X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) Or a carboxyl group, which may form a cyclic structure in which R ¹ and R ² are connected), a monomer (a-1 '), an unsaturated polybasic acid anhydride (a-2), and (a-1), (a It is obtained by adding the monomer (a-4) which has a hydroxyl group to the copolymer which copolymerized the copolymerizable monomer (a-3) other than -1 ') and (a-2).

Monomer (a-1) will not be specifically limited if it has a C10-20 bridged cyclic hydrocarbon group. Here, the bridged cyclic hydrocarbon means having a structure represented by the following formula (2) or (3), represented by adamantane or norbornane, and being bridged cyclic hydrocarbon group In the above structure, a group corresponding to the remaining portion from which some hydrogen has been removed.

(2)

Formula (3)

In Formula (2), A ¹ and X ¹ may be the same or different, and each represents a straight chain or branched alkylene group (including cyclic), and R ³ represents a hydrogen atom or a methyl group. Branches of A ¹ and X ¹ may be bonded to each other to form an annular shape. In Formula (3), A ² , X ² and L may be the same or different, and each represents a straight chain or branched alkylene group (including cyclic), and R ⁴ represents a hydrogen atom or a methyl group. . Branches of A ² , X ² and L may be bonded to each other to form an annular shape.

Examples of the monomer (a-1) include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and the like. . Among these, dicyclopentanyl methacrylate is preferable from a viewpoint of thermal decomposition resistance, adhesiveness, developability, etc. These can be used individually or in combination of 2 or more types.

Monomer (a-1 ') will not be specifically limited if it has a chemical structure represented by the said General formula (1). In Formula (1), as an example of X and Y which show a C1-C4 linear or branched hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t- Butyl group etc. are mentioned. Moreover, as an example of R <^1> and R <^2> which represents a C1-C20 hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, Linear or branched alkyl groups such as stearyl group, lauryl group and 2-ethylhexyl group; Aryl groups such as phenyl; Alicyclic groups such as cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, and 2-methyl-2-adamantyl group; Alkyl group substituted by alkoxy, such as 1-methoxyethyl group and 1-ethoxyethyl group; Alkyl groups substituted by aryl groups, such as benzyl, etc. are mentioned.

Examples of the monomer (a-1 ′) having the chemical structure represented by the formula (1) include norbornene (bicyclo [2.2.1] hepto-2-ene) and 5-methylbicyclo [2.2.1] hepto 2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, tetracyclo 4.4.0.1 ^2,5 .1, ¹⁰ ] dodeca-3-ene, 8-methyltetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, 8-ethyltetracyclo [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 ] deca-3-ene, tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene, tricyclo [6.2 .1.0 ^1,8 ] undeca-9-ene, tricyclo [6.2.1.0 ^1,8 ] undeca-4-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 .1 ^7,12 ] dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] Pentadeca-4-ene, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] ^pentadeca -3-ene, 5-norbornene-2-carboxylic acid, 5-norbornene -2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, etc. are mentioned. Among these, norbornene, dicyclopentadiene, 5-norbornene-2,3-dicarboxylic acid anhydride is preferable from a viewpoint of thermal decomposition resistance, adhesiveness, image development characteristics, etc. These can be used individually or in combination of 2 or more types.

The compounding ratio of monomer (a-1) and / or monomer (a-1 ') is monomer (a-1) and / or monomer (a-1'), unsaturated polybasic acid anhydride (a-2), and monomer ( When the sum total of a-3) is 100 mol%, it is 2-60 mol%, Preferably it is 5-20 mol%. If the compounding ratio of monomer (a-1) and / or monomer (a-1 ') is less than 2 mol%, desired thermal decomposition resistance cannot be obtained. On the other hand, when this compounding ratio exceeds 60 mol%, the compounding ratio of unsaturated polybasic acid anhydride (a-2) will become small, and desired sensitivity and developability cannot be acquired.

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, citraconic anhydride, and the like. Among these, maleic anhydride is preferable from the viewpoint of availability, polymerizability, reactivity, and the like.

The compounding ratio of unsaturated polybasic acid anhydride (a-2) is 100 the sum total of monomer (a-1) and / or monomer (a-1 '), unsaturated polybasic acid anhydride (a-2), and monomer (a-3). When it is set as mol%, it is 30-88 mol%, Preferably it is 35-70 mol%. When the compounding ratio of unsaturated polybasic anhydride (a-2) is less than 30 mol%, the amount of the double bond in the addition copolymer (A) decreases, and the desired sensitivity cannot be obtained. On the other hand, when this compounding ratio exceeds 88 mol%, many of unreacted unsaturated polybasic acid anhydride (a-2) will remain.

Monomer (a-3) will not be specifically limited if it is copolymerizable other than (a-1), (a-1 '), and (a-2). The monomer (a-3) is generally a radically polymerizable compound having an ethylenically unsaturated group, and examples thereof include dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso Butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth ) Acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (Meth) acrylate , 5-ethylnorbornyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, piperonyl (meth) acrylate, salicylic (meth) acrylate, furyl (meth) acrylic Latex, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, pyranyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1- Trifluoroethyl (meth) acrylate, perfluoroluethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth ) Acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, glycerylol mono (meth) acrylate, butanetriol mono (meth) acrylate, pentanetriol Mono (meth) acrylate, naphthalene (meth) (Meth) acrylic acid esters such as acrylate and anthracene (meth) acrylate; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di (Meth) acrylic acid amides such as iso-propylamide and (meth) acrylate anthracenyl amide; Vinyl such as (meth) aniline acrylate, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene compound; Styrene, α-,-, 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-cyclohexyl maleimide, N-lauryl maleimide, and N- (4-hydroxyphenyl) maleimide; The compound which has carboxyl groups, such as N- (meth) acryloyl phthalimide, (meth) acrylic acid, crotonic acid, cinnamic acid, etc. are mentioned. These can be used individually or in combination of 2 or more types.

In particular, when maleic anhydride is used as the unsaturated polybasic acid anhydride (a-2), since maleic anhydride is a compound having strong electron acceptability, the monomer (a-3) is preferably an electron donating monomer. By using such an electron donating monomer, alternating copolymerization property is produced between maleic anhydride and the like, and each unit is randomly arranged, resulting in improved developability, sensitivity, and the like, and excellent coloration in thermal decomposition. Patterns can be formed. Examples of the electron donating monomers include vinyl ethers, vinyl sulfides and styrenes. Among these, styrene is preferable from a copolymerization viewpoint, and vinyltoluene is more preferable from a decomposition resistance viewpoint. When vinyltoluene is used, developability can be further improved by using (meth) acrylic acid esters.

The compounding ratio of monomer (a-3) is 100 mol% of the sum total of monomer (a-1) and / or monomer (a-1 '), unsaturated polybasic acid anhydride (a-2), and monomer (a-3). In the case of using, it is 10-68 mol%, Preferably it is 20-50 mol%. If the compounding ratio of monomer (a-3) is less than 10 mol%, the thermal decomposition resistance and developability cannot be balanced. On the other hand, when this compounding ratio exceeds 68 mol%, a sensitivity and heat resistance will fall.

In particular, when vinyltoluene is used as the monomer (a-3), the monomer (a-1) and / or monomer (a-1 '), unsaturated polybasic anhydride (a-2), and monomer (a-3) When total is 100 mol%, it is preferable that monomer (a-3) contains 10-40 mol% of vinyltoluene.

The copolymerization reaction which uses a monomer (a-1) and / or a monomer (a-1 '), an unsaturated polybasic acid anhydride (a-2), and a monomer (a-3) as a raw material is radical polymerization known in the art. It can carry out according to a method. For example, after dissolving the monomer (a-1) and / or the monomer (a-1 '), the unsaturated polybasic acid anhydride (a-2), and the monomer (a-3) in a solvent, a polymerization initiator is added to the solution. What is necessary is just to react at 50-130 degreeC for 1 to 20 hours.

Although it does not specifically limit as a solvent which can be used for this copolymerization reaction, For example, Glycol ether solvent, such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; The solvent which does not have reactive functional groups, such as hydrocarbon solvents, such as toluene and xylene, and ethyl acetate, is mentioned. These can be used individually or in combination of 2 or more types. Moreover, a glycol ether solvent is preferable among these.

Although the compounding quantity of a solvent will not be specifically limited if it is an amount which can melt | dissolve a raw material, A monomer (a-1) and / or a monomer (a-1 '), an unsaturated polybasic acid anhydride (a-2), and a monomer (a-3) In the case of making the total of) 100 parts by mass, it is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. In particular, by adjusting the blending amount of the solvent to 1000 parts by mass or less, a decrease in the molecular weight of the copolymer can be suppressed by the chain transfer action, and the viscosity of the copolymer can be controlled in an appropriate range. Moreover, by making the compounding quantity of a solvent into 30 mass parts or more, abnormal polymerization reaction can be prevented, a polymerization reaction can be stabilized and performed, and coloring and gelation of a copolymer can be prevented.

In addition, the polymerization initiator that can be used in this copolymerization reaction is not particularly limited, and for example, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate Etc. can be mentioned. These can be used individually or in combination of 2 or more types.

When the compounding quantity of a polymerization initiator makes the sum total of a monomer (a-1) and / or a monomer (a-1 '), an unsaturated polybasic acid anhydride (a-2), and a monomer (a-3) 100 mass parts, Is 0.5-20 mass parts, Preferably it is 1.0-10 mass parts.

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

In the copolymer obtained by the said copolymerization reaction, a carboxyl group and a double bond are introduce | transduced into the side chain of a copolymer by adding the monomer (a-4) which has a hydroxyl group. Thereby, the sensitivity and developability of the photosensitive resin composition improve.

Examples of the monomer (a-4) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2,3-dihydroxypropyl (Meth) acrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, trimethylolpropanedi ( Meta) acrylate, pentaerythritol triacrylate, and the like. These can be used individually or in combination of 2 or more types.

In particular, when considering the reactivity with the acid anhydride group in the copolymer, the monomer (a-4) preferably has a primary hydroxyl group. In addition, when considering the sensitivity of the photosensitive resin composition, in order that the monomer (a-4) may increase the quantity of the double bond in an addition copolymer (A), it is a thing with a small molecular weight or a polyfunctional (meth) acrylate. desirable. As a monomer which satisfy | fills these conditions, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritol triacrylate, etc. are mentioned. have.

It is preferable that the addition ratio of the monomer (a-4) with respect to the acid anhydride group in a copolymer is 10 to 100%. In order to perform the addition reaction of such a monomer (a-4), when the molar equivalent of the acid anhydride group of a copolymer is set to 1, the molar equivalent of the hydroxyl group of a monomer (a-4) may be in the range of 0.1-1. It is good to make it react by adding a monomer (a-4). When 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 cannot be obtained.

Addition reaction of the monomer (a-4) with respect to the acid anhydride group in a copolymer adds a monomer (a-4), a polymerization inhibitor, and a catalyst to a copolymer, and is 50-150 degreeC, Preferably it is 80-130 degreeC The reaction may be performed. In this addition reaction, even if the solvent used for the copolymerization reaction is contained, there is no problem. Therefore, the addition reaction can be carried out without removing the solvent after the completion of the copolymerization reaction.

Here, a polymerization inhibitor is added in order to prevent gelation by superposition | polymerization of a copolymer. Although it does not specifically limit as a polymerization inhibitor, For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, etc. are mentioned. Further, the catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, phosphorus compounds such as triphenylphosphine, chelate compounds of chromium, and the like. Can be. Among these, in reaction of an acid anhydride and a hydroxyl group, it is preferable to use tertiary amines, such as a triethylamine, a triethylenediamine, 4-dimethylaminopyridine, and dimethylaminoethyl methacrylate.

The acid value of the addition copolymer (A) obtained as mentioned above becomes like this. Preferably it is 50-400 KOH mg / g, More preferably, it is 150-300 KOH mg / g. When this acid value is less than 50 KOH mg / g, the developability of the photosensitive resin composition may fall. On the other hand, when this acid value exceeds 400 KOH mg / g, an exposure part (photocuring part) may become easy to melt | dissolve with an alkaline developing solution.

In addition, the molecular weight (weight average molecular weight in terms of polystyrene) of the addition copolymer (A) is preferably 1000 to 40000, and more preferably 3000 to 20000. If the molecular weight is less than 1000, defects of the coloring pattern may easily occur after development. On the other hand, when this molecular weight exceeds 40000, developing time may become too long and may lack utility.

The addition copolymer (A) of this embodiment is optimal as alkali-soluble resin used for the photosensitive resin composition, and since it has a favorable sensitivity and developability, it produces the photosensitive resin composition which shows the coloring pattern excellent in thermal decomposition resistance and solvent resistance. can do.

Embodiment 2 Fig.

The photosensitive resin composition of this embodiment contains the addition copolymer (A) and solvent (B) of Embodiment 1.

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 a solvent (B), the same thing as the solvent used at the time of manufacturing an addition copolymer (A) (copolymerization reaction) can be used. Specifically, 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, di 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 can be used individually or in combination of 2 or more types. Among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate used in producing the addition copolymer (A) are preferable.

In the photosensitive resin composition of this embodiment, the compounding quantity of a solvent (B) is 30-1000 mass parts normally with respect to 100 mass parts of solid content (ie, the component except a solvent) in the photosensitive resin composition, Preferably it is 50-800 It is mass parts, More preferably, it is 100-700 mass parts. If it is a compounding quantity of this range, it will become the photosensitive resin composition which has an appropriate viscosity.

In addition to the said component, the photosensitive resin composition of this embodiment can contain a reactive diluent (C), a photoinitiator (D), and a coloring agent (E).

The reactive diluent (C) is not particularly limited as long as it reacts with the addition copolymer (A). As an example of a reaction diluent, Aromatic vinyl monomers, such as styrene, (alpha) -methylstyrene, (alpha)-chloromethyl styrene, vinyltoluene, divinyl benzene, diallyl phthalate, and diallylbenzene phosphonate; Polycarboxylic acid monomers such as vinyl acetate and vinyl adipic acid; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropane tree ( (Meth) acrylic monomers such as meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tri (meth) acrylate of tris (hydroxyethyl) isocyanurate ; Triallyl cyanurate, etc. are mentioned. These can be used individually or in combination of 2 or more types.

In the photosensitive resin composition of this embodiment, the compounding quantity of the reactive diluent (C) is 10-90 mass parts normally with respect to 100 mass parts of solid content (that is, components except a solvent) in the photosensitive resin composition, Preferably it is 20- 80 mass parts, More preferably, it is 25-70 mass parts. If it is a compounding quantity of this range, it will become the photosensitive resin composition which has suitable photocurability and viscosity.

Although it does not specifically limit as a photoinitiator (D), For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and its alkyl 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-methylanthraquinone, 2-amyl anthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones, such as 2, 4- dimethyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2-chloro thioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 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; Acyl phosphine oxides; And xanthones. These can be used individually or in combination of 2 or more types.

In the photosensitive resin composition of this embodiment, the compounding quantity of a photoinitiator (D) is generally 0.1-30 mass parts with respect to 100 mass parts of solid content (that is, components except a solvent) in the photosensitive resin composition, Preferably it is 0.5- It is 20 mass parts, More preferably, it is 1-10 mass parts. If it is a compounding quantity of this range, it will become the photosensitive resin composition which has appropriate photocurability.

The coloring agent (E) is not particularly limited as long as it is dissolved in the solvent (B), and examples thereof include dyes and pigments.

In particular, as a conventional photosensitive resin composition, when a dye is used, a colored pattern with high luminance can be obtained, but there is a problem that the heat resistance of the colored pattern is lower than that in the case of using a pigment. On the other hand, as the photosensitive resin composition of this embodiment, since the pure salt of dye is favorable, the coloring pattern excellent in heat resistance can be obtained even if dye is used.

Examples of the dyes include acidic dyes having acidic groups such as carboxylic acid, salts with nitrogen compounds of acidic dyes, from the viewpoints of solubility in solvents (B) and alkaline developing solutions, interaction with other components in the photosensitive resin composition, heat resistance, and the like, It is preferable to use sulfonamide bodies of acid dyes and the like. 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, 80, 87, 88, 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 these, acidic dyes of azo, xanthene, anthraquinone or phthalocyanine are preferred. These can be used individually or in combination of 2 or more types according to the color of the pixel made into the objective.

Examples of pigments 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 Yellow pigments such as, 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 and the like; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ; 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 and 38; C.I. Green pigments such as pigment green 7, 36 and 58; C.I. Brown pigments such as pigment brown 23 and 25; C.I. Pigment black 1, 7, black pigments, such as carbon black, titanium black, iron oxide, etc. are mentioned. These can be used individually or in combination of 2 or more types according to the color of the pixel made into the objective.

According to the color of the pixel made into the objective, the said dye and pigment can be used in combination.

In the photosensitive resin composition of this embodiment, the compounding quantity of a coloring agent (E) is 5-80 mass parts normally with respect to 100 mass parts of solid content (ie, the component except a solvent) in the photosensitive resin composition, Preferably it is 5-70 A mass part, More preferably, it is 10-60 mass parts.

When using a pigment as a coloring agent (E), you may mix | blend a well-known dispersing agent with the photosensitive resin composition from a viewpoint of improving the dispersibility of a pigment. As a dispersing agent, it is preferable to use the polymeric dispersing agent which was excellent in dispersion stability with time. Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified ester dispersants, and the like. As such a polymer dispersing agent, EFKA (made by Efka Chemicals Viv (EFKA) company), Disperbyk (made by BICKEM Corporation), disparon (made by Kusumoto Kasei Co., Ltd.), SOLSPERSE (made by Genca company), etc. What is marketed may be used.

What is necessary is just to set the compounding quantity of a dispersing agent suitably according to the kind of pigment etc. to be used in the photosensitive resin composition of this embodiment.

In addition to the said component, the photosensitive resin composition of this embodiment may mix | blend well-known additives, such as a well-known coupling agent, a leveling agent, and a thermal polymerization inhibitor, in order to provide a predetermined characteristic. The compounding quantity of these additives will not be specifically limited if it is a range which does not impair the result of this invention.

The photosensitive resin composition of this embodiment can be manufactured by mixing the said component using a well-known mixing apparatus.

Since the photosensitive resin composition of this embodiment obtained as mentioned above has alkali developability, image development can be performed easily by using aqueous alkali solution. In particular, the photosensitive resin composition of this embodiment can exhibit the coloring pattern excellent in the thermal decomposition resistance and solvent resistance while being excellent in the sensitivity and developability. For this reason, the photosensitive resin composition of this embodiment is suitable for using as a resist used for manufacturing various resists, especially the color filter combined with organic electroluminescent display, a liquid crystal display device, and a solid-state image sensor. Moreover, since the photosensitive resin composition of this embodiment can provide the cured film excellent in various characteristics, such as thermal decomposition resistance and solvent resistance, it can be used for various coatings, adhesives, binders for printing inks, etc.

Embodiment 3．

The color filter of this embodiment has the coloring pattern obtained from the said photosensitive resin composition.

Hereinafter, the color filter of this embodiment is demonstrated using drawing.

1 is a cross-sectional view of the color filter of the present embodiment. In FIG. 1, the color filter includes a substrate 1, a black matrix 3 formed on the substrate 1, a black matrix 3 formed at a boundary between the pixel 2, and a pixel 2, and a black. It consists of the protective film 4 formed on the matrix 3. In this structure, a well-known thing can be employ | adopted for the other structure except that the pixel 2 and the black matrix 3 (coloring pattern) are formed using the said photosensitive resin composition. The color filter shown in FIG. 1 is an example, and is not limited only to this structure.

Next, the manufacturing method of the color filter of this embodiment is demonstrated.

First, a coloring pattern is formed on the board | substrate 1. Specifically, the black matrix 3 and the pixels 2 are sequentially formed on the substrate 1. Here, the substrate 1 is not particularly limited, but may be 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 board, an array substrate, or the like. Can be used.

A coloring pattern can be formed by the photolithographic method. Specifically, after applying the said photosensitive resin composition on the board | substrate 1 to form a coating film, a coating film is exposed through the photomask of a predetermined pattern, and an exposure part is photocured. And after developing an unexposed part with aqueous alkali solution, baking can form a predetermined pattern.

Although it does not specifically limit as a coating method of the photosensitive resin composition, The screen printing method, the roll coat method, the curtain coat method, the spray coat method, the spin coat method, etc. can be used. In addition, after application | coating of the photosensitive resin composition, you may volatilize the solvent (B) by heating using heating means, such as a circulating oven, an infrared heater, and a hotplate, as needed. Heating conditions are not specifically limited, What is necessary is just to set suitably according to the kind of photosensitive resin composition to be used. Generally, what is necessary is just to heat for 30 second-30 minutes at the temperature of 50 degreeC-120 degreeC.

Although it does not specifically limit 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, etc. can be used. Moreover, exposure amount is not specifically limited, either, According to the kind of photosensitive resin composition to be used, it may adjust suitably.

Although it does not specifically limit as aqueous alkali solution used for image development, aqueous solution, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide; Aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N ｐ-phenylenediamine compounds such as -β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or ｐ-toluenesulfonate salts thereof The aqueous solution of etc. can be used. Among these, it is preferable to use the aqueous solution of a X-phenylenediamine type compound. You may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, after image development by the said aqueous alkali solution, it is preferable to wash with water and to dry.

The conditions of baking are not specifically limited, What is necessary is just to heat-process according to the kind of photosensitive resin composition to be used. Generally, what is necessary is just to heat for 10 to 60 minutes at 130 degreeC-250 degreeC.

By repeating the above application | coating, exposure, image development, and baking 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.

Although the formation method of the coloring pattern by photocuring was demonstrated above, when using the photosensitive resin composition which mix | blended the hardening accelerator and a well-known epoxy resin instead of a photoinitiator (D), after apply | coating by the inkjet method, it heats. By doing this, a desired coloring pattern can be formed.

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

Since the color filter manufactured in this way is manufactured using the photosensitive resin composition which shows the coloring pattern excellent in the thermal decomposition resistance and solvent resistance while being excellent in the sensitivity and developability, it is excellent in coloring pattern excellent in the thermal decomposition resistance and solvent resistance. Have

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples. In this example, parts and percentages are by mass, unless otherwise specified.

<Production 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 added to a flask equipped with a stirring device, a dropping lot, a condenser, a thermometer, and a gas introduction tube, followed by nitrogen substitution. It stirred and heated up at 120 degreeC. Next, 24.4 g of t-butylperoxy-2-ethylhexanoate (polymerized) in a monomer mixture composed of 66.0 g of dicyclopentanyl methacrylate (a-1) and 106.2 g of vinyltoluene (a-3) The initiator) was added dropwise into the flask from the dropping lot. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

Subsequently, after replacing the flask with air, 139.2 g of 2-hydroxyethyl acrylate (a-4), 1.5 g of triethylamine (catalyst), and 1.5 g of methylhydroquinone (polymerization inhibitor) Was added and addition reaction was performed at 120 degreeC for 6 hours, and the addition copolymer (A) was produced.

Next, 305.6 g of propylene glycol monomethyl ether (solvent 2) was added to this addition copolymer (A), and the photosensitive resin composition (sample number 1) was obtained.

Except having changed the kind and quantity of a raw material, many kinds of photosensitive resin compositions (sample numbers 2-19) were produced similarly to the above.

The raw material used for manufacture of the photosensitive resin composition (sample numbers 1-19), and its compounding quantity are shown in Table 1.

In Table 1, the mole% of each raw material of (a-1), (a-1 '), (a-2) and (a-3) is (a-1), (a-1'), ( It means mol% of each raw material when the sum total of the raw material of a-2) and (a-3) is 100 mol%. In addition, the molar equivalent of (a-4) means the molar equivalent of the hydroxyl group of monomer (a-4) when the molar equivalent of the acid anhydride group of a copolymer is set to one. In addition, an acid value means the acid value of the addition copolymer (A) measured according to JISK6901x5.3, and means the mg number of potassium hydroxide required to neutralize the acidic component contained in 1 g of addition copolymers (A). In addition, molecular weight (MV) means the standard polystyrene conversion weight average molecular weight measured on the following conditions by the gel permeation chromatography.

<Molecular Weight Measurement Conditions>

Column: Shodix LF-804 + LF-804 (manufactured by Sowa Electric Co., Ltd.)

Column temperature: 40 ° C

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

Developing Solvent: Tetrahydrofuran

Detector: Differential Refractometer (Show Dix RI-71S)

Flow rate: 1 mL / min

Using the photosensitive resin composition of sample numbers 1-19, the transparent resist, the color resist (pigment type), and the color resist (dye type) were manufactured.

<Production of Transparent Resist>

30 mass parts of pentaerythritol tetraacrylate (reactive diluent) and 4 mass parts of 2, 2- dimethoxy- 2-phenylacetophenone (photoinitiator) with respect to 100 mass parts of solid content of the photosensitive resin composition of sample numbers 1-19. It added and manufactured the transparent resist (Examples 1-14 and Comparative Examples 1-5).

<Formation of Cured Coating Film by Transparent Resist>

The prepared transparent resist was spin-coated on each 5 cm glass substrate (alkali-free glass substrate) so that the thickness of a final cured coating film might be 2.5 micrometers, and the solvent was volatilized by heating at 90 degreeC for 30 minutes. Subsequently, after exposing the whole surface of the obtained coating film (exposure amount 50mJ / cm <^2> ) and photocuring, the cured coating film was obtained by baking at 230 degreeC for 30 minutes.

<Evaluation of Cured Coating Film Formed from Transparent Resist>

About the cured coating film formed from the transparent resist, thermal decomposition resistance, transparency, and adhesiveness were evaluated.

(1) Evaluation of thermal decomposition resistance

Thermal decomposition resistance was evaluated by performing thermogravimetric analysis (TGA) using the sample which cut out the cured coating film formed from the transparent resist. In this analysis, the weight change rate between this sample and the sample heated to 220 degreeC and hold | maintained for 2 hours was calculated | required. The criteria of this evaluation are as follows.

○: less than -2.0%

×: -2.0% or more

(2) evaluation of transparency

Transparency was measured by measuring the light transmittance of 400 nm with a spectrophotometer and investigating the change rate of the transmittance | permeability with respect to the cured coating film formed from the transparent resist, and this cured coating film heated at 230 degreeC in the dryer, and standing for 1 hour. Evaluated. The criteria of this evaluation are as follows.

○: change rate of transmittance is less than 1%

×: change rate of transmittance is 1% or more

(3) Evaluation of adhesiveness

The adhesiveness was evaluated by performing a checkerboard scale test in accordance with JIS K5400 with respect to the cured coating film formed from a transparent resist, and visually observing the peeling state of 100 checkerboard scales. This evaluation criteria are as follows.

○: no peeling at all

X: peeling is seen

Table 2 shows the evaluation results of the thermal decomposition resistance, transparency and adhesion.

As can be seen from the results in Table 2, the transparent resists of Examples 1 to 14 exhibit cured coating films excellent in all of thermal decomposition resistance, transparency and adhesion, whereas the transparent resists of Comparative Examples 1 to 5 exhibit thermal decomposition resistance and transparency. The cured coating film in which neither of adhesiveness was enough was shown.

<Production of Color Resist (Pigment Type)>

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 (Bikkemi Japan Co., Ltd. Disperbyk-161) were added, and the mixture was dispersed for 3 hours with a paint shaker to obtain a green pigment dispersion. .

Next, the color resist (pigment type) was manufactured by mixing the produced green pigment dispersion liquid, the photosensitive resin composition of sample numbers 1-19, and other components (Examples 15-28 and Comparative Examples 6-10). Table 3 shows the blending components of the color resist (pigment type) and the blending amount thereof.

Compounding ingredient Compounding amount (mass part)
Green pigment dispersion 50 Photosensitive resin composition 8.03 Trimethylolpropanetriacrylate
(Reactive diluent) 6.5 Irgacure 907
(Photoinitiator, Ciba Specialty Chemicals) 1.66 Hi Cure ABP
(Photoinitiator, Kawaguchi Chemical Manufacturing) 0.83 Propylene Glycol Monomethyl Ether Acetate
(menstruum) 52.6 Sum 119.62

<Pattern formation by color resist (pigment type)>

The coated color resist (pigment type) is spin-coated on each 5 cm glass substrate (alkali-free glass substrate) so as to have a thickness of 2.2 탆 upon drying, and then the solvent is evaporated by heating at 80 ° C. for 3 minutes. And dried. Next, the photomask of a predetermined pattern was arrange | positioned at the distance of 100 micrometers from a coating film, the coating film was exposed (exposure amount 150mJ / cm <^2> ) through this photomask, and the exposure part was photocured. Subsequently, an unexposed portion is dissolved and developed by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23 ° C. and a pressure of 0.3 MPa, and then a predetermined pattern is formed by baking at 230 ° C. for 30 minutes. I was.

<Evaluation of color resist (pigment type) and pattern>

The alkali developability, sensitivity, and solvent resistance were evaluated with respect to the color resist (pigment type) and pattern.

(4) evaluation of alkali developability

Alkali developability was evaluated by alkali developing time, residue after alkali developing, and developing form.

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

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

○: no residue

×: There is residue

The developing form evaluated visually the removal form of the unexposed part by alkali image development. Here, in the developing step of the negative resist, the uncured unexposed portion is dissolved by the alkaline developer and is separated from the substrate, but as the developing form, the peeling type is mainly separated into large chunks and peeled off. There is a dissolution type that gradually dissolves and diffuses. The former peeling type is not preferable because agglomerates become foreign matter and remain in the system, and are likely to contaminate pixels of different colors. In short, since the latter dissolution type is not preferable, the criteria for this evaluation are as follows.

○: melting

X: peeling type

(5) evaluation of sensitivity

As for sensitivity, alkali image development using the said spray was performed for 30 second, and the amount of reduction of the pattern thickness before and after alkali image development was measured. Since this pattern thickness can be said that sensitivity is so good that there is little decrease amount, the criteria of this evaluation were made as follows.

○: less than 0.20 μm

×: 0.20 μm or more

(6) Evaluation of content selling

Solvent resistance was obtained 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. The pattern sample was immersed in it, and the color change after 60 minutes at 23 degreeC was measured with the colorimeter. The criteria of this evaluation are as follows.

○: ΔE * ａｂ is less than 0.3

X: ΔE * a * is 0.3 or more

Table 4 shows the evaluation results of the alkali developability, sensitivity, and solvent resistance.

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

 <Production of Color Resist (Dye Type)>

Color resist (dye type) was manufactured by mixing dye (acid green 3), the photosensitive resin composition of sample numbers 1-19, and other components (Examples 29-42 and Comparative Examples 11-15). Table 5 shows the blending components of the color resist (dye type) and the blending amounts thereof.

Compounding ingredient Compounding amount (mass part) acid green 3 5.2 Photosensitive resin composition 32.5 Trimethylolpropanetriacrylate
(Reactive diluent) 15.6 Irgacure 907
(Photoinitiator, Ciba Specialty Chemicals) 1.3 Propylene Glycol Monomethyl Ether
(menstruum) 45.4 Sum 100.0

<Pattern formation by color resist (dye type)>

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

<Evaluation of color resist (dye type) and pattern>

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

Table 6 shows the evaluation results of the alkali developability, sensitivity, and solvent resistance.

As can be seen from the results in Table 6, the color resists (dye types) of Examples 29 to 42 exhibit good patterns of alkali developability and sensitivity, and exhibit excellent patterns of solvent resistance. The color resist (dye type) exhibited a pattern in which alkali developability or sensitivity was not good or solvent resistance was not sufficient.

As can be seen from the above results, according to the present invention, the alkali-soluble resin (added copolymer) used in the production of the photosensitive resin composition exhibiting a coloring pattern excellent in thermal decomposition resistance and solvent resistance while having good sensitivity and developability. Can be provided. Moreover, according to this invention, the photosensitive resin composition which shows the coloring pattern which is excellent in thermal decomposition resistance and solvent resistance while being excellent in sensitivity and developability can be provided. Moreover, according to this invention, the color filter which has a coloring pattern excellent in thermal decomposition resistance and solvent resistance can be provided.

This international application claims priority based on Japanese Patent Application No. 2010-092286 for which it applied on April 13, 2010, and employ | adopts the whole content of this Japanese patent application for this international application.

Claims (13)

Monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or the following general formula (1):
Formula (1)

(Wherein X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) Or 2 to 60 mol% of a monomer (a-1 ') represented by a carboxyl group, which may form a cyclic structure to which R ¹ and R ² are linked, and 30 to 88 mol% of an unsaturated polybasic acid anhydride (a-2). And monomer (a-4) having a hydroxyl group in a copolymer obtained by copolymerizing 10 to 68 mol% of copolymerizable monomers (a-3) other than (a-1), (a-1 ') and (a-2). The addition copolymer (A) and the solvent (B) which added () are contained, The photosensitive resin composition characterized by the above-mentioned. The said monomer (a-1) is dicyclopentanyl methacrylate, The photosensitive resin composition of Claim 1 characterized by the above-mentioned. The said unsaturated polybasic acid anhydride (a-2) is maleic anhydride, The photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned. The said monomer (a-3) contains 10-40 mol% of vinyltoluene, The photosensitive resin composition of any one of Claims 1-3 characterized by the above-mentioned. The said monomer (a-4) is a 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and a trimethylolpropanedi (A) in any one of Claims 1-4. It is at least 1 type selected from the group which consists of a meta) acrylate and pentaerythritol triacrylate. The photosensitive resin composition characterized by the above-mentioned. The photosensitive resin composition of any one of Claims 1-5 which further contains 1 or more types chosen from the group which consists of a reactive diluent (C), a photoinitiator (D), and a coloring agent (E). . The said coloring agent (E) contains dye, The photosensitive resin composition of Claim 6 characterized by the above-mentioned. Monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or the following general formula (1):

(Wherein X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) Or 2 to 60 mol% of a monomer (a-1 ') represented by a carboxyl group, which may form a cyclic structure to which R ¹ and R ² are linked, and 30 to 88 mol% of an unsaturated polybasic acid anhydride (a-2). And monomer (a-4) having a hydroxyl group in a copolymer obtained by copolymerizing 10 to 68 mol% of copolymerizable monomers (a-3) other than (a-1), (a-1 ') and (a-2). ) Is an 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 any one of claims 8 to 10, wherein the monomer (a-3) contains 10 to 40 mol% of vinyltoluene. The monomer (a-4) according to any one of claims 8 to 11, wherein 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropanedi ( Meta) acrylate, and pentaerythritol triacrylate, at least one member selected from the group consisting of addition copolymer (A). It has a coloring pattern formed from the photosensitive resin composition of any one of Claims 1-7, The color filter characterized by the above-mentioned.

Images