KR20130132639A - Copolymer, resin composition and photosensitive resin composition each containing said copolymer, and color filter - Google Patents

Abstract

(식(1) 중의 Ｘ 및 Ｙ는, 각각 독립하여, 수소 원자, 직쇄 또는 분기되어 있어도 좋은 탄소수 1~4의 탄화수소기를 나타내고, R¹ 및 R²는 각각 독립하여 수소 원자, 치환기를 가지고 있어도 좋은 탄소수 1~20의 탄화수소기 또는 카르복실기이고, R¹ 및 R²를 연결하는 환상구조를 취하고 있어도 좋다.)

(식(2) 중의 R³은 수소 원자 또는 메틸기이고, n은 1~4의 정수를 나타낸다.)An object of this invention is to provide the copolymer which gives the coloring pattern excellent in thermal decomposition resistance and thermal yellowing resistance, the resin composition containing this copolymer, or the photosensitive resin composition with the favorable sensitivity and developability. Moreover, an object of this invention is to provide the color filter using the said photosensitive resin composition. The copolymer of the present invention is a polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a polymerizable monomer (a-1 ') represented by the following formula (1), It is a copolymer (A) which consists of superposing | polymerizing the polymerizable monomer (a-2) represented by 2) and whose weight average molecular weight (weight average molecular weight of polystyrene conversion) is 1000-50000:

(Ｘ and 중의 in Formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ And R ² are each independently a hydrogen atom, a C1-C20 hydrocarbon group or carboxyl group which may have a substituent, and R ¹ And an annular structure connecting R ² .

(R <^3> in Formula (2) is a hydrogen atom or a methyl group, n shows the integer of 1-4.)

Description

Copolymer, the resin composition containing the copolymer, and the photosensitive resin composition, and a color filter TECHNICAL FIELD [COPOLYMER, RESIN COMPOSITION AND PHOTOSENSITIVE RESIN COMPOSITION EACH CONTAINING SAID COPOLYMER, AND COLOR FILTER}

The present invention relates to a copolymer, a resin composition containing the copolymer, a photosensitive resin composition, and a color filter. In particular, the present invention relates to a copolymer as a material used for producing a color filter to be incorporated into an organic EL display, a liquid crystal display device, and a solid state image pickup device, a resin composition and a photosensitive resin composition containing the copolymer, and the photosensitive resin composition. It relates to a color filter produced using.

In recent years, the photosensitive resin composition which can harden | cure by active energy rays, such as an ultraviolet-ray and an electron beam, is widely used in the field of various coatings, printing, coatings, adhesives, etc. from a viewpoint of resource saving and energy saving. 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 formed on a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, on a black matrix formed at the boundary of the pixels, on the pixels and the black matrix. It consists of a protective film formed. 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 pigment / dye dispersion method produced by the repeating photolithography method is presently mainstream because it is excellent in durability, such as exposure property and heat resistance, and gives a coloring 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. In the pigment / dye dispersion method, while having the above-mentioned advantages, since the patterns of the black matrix, R, G, and B are repeatedly formed, high thermal decomposition resistance and thermal yellowing resistance of the alkali-soluble resin serving as the binder of the coating film Required. As a method of improving thermal decomposition resistance, the resin composition (for example, patent document 1) etc. which use the monomer containing maleimide as a copolymerization component is proposed conventionally. However, in the resin composition which uses the monomer containing maleimide as a copolymerization component, it has yellow to yellowish-brown coloring which caused the nitrogen atom contained in a molecule | numerator, and worsens transparency of a coating film. Moreover, there existed a problem that coloring advances at the time of post-cure at which heat processing is performed. In addition, although acrylic copolymers containing methacrylic acid, benzyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, and the like are known, thermally decomposable products are not sufficiently thermally decomposed. It occurs as outgassing and contaminates a board | substrate or an apparatus, and has become a problem.

In addition, when an acrylic copolymer using an alicyclic cyclohexyl methacrylate or the like is used to improve the heat yellowing resistance, the thermal decomposition resistance is not sufficient. Moreover, it is proposed to use ethylene oxide (EO) modification or propylene oxide (PO) modification (meth) acrylate of paracumyl phenol as a means of improving patterning property and a sensitivity (for example, patent document 2, 3). In addition, it is proposed to use hydroxyethylated phenylphenol (meth) acrylate as a negative resist for forming a projection for liquid crystal alignment (for example, Patent Document 4). However, it is not made to satisfy the thermal decomposition resistance and the thermal yellowing resistance as a binder for color filters.

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-29018 Patent Document 2: Japanese Patent Application Laid-Open No. 2004-101728 Patent Document 3: Japanese Patent Application Laid-Open No. 2006-215452 Patent Document 4: Japanese Patent Application Laid-Open No. 2009-109879

As mentioned above, the conventional photosensitive resin composition may not be able to obtain the coloring pattern which is excellent in thermal decomposition resistance and thermal yellowing resistance, or when sensitivity and developability are not enough.

Therefore, this invention was implemented in order to solve the above subjects, The copolymer as photosensitive resin which gives the coloring pattern excellent in thermal decomposition resistance and thermal yellowing resistance while being excellent in sensitivity and developability, resin containing it It is an object to provide a composition and a photosensitive resin composition. Moreover, it aims at providing the color filter which has a coloring pattern excellent in thermal decomposition resistance and thermal yellowing 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 said subject can be solved by using a specific copolymer for the photosensitive resin composition, and came to this invention.

That is, this invention is a polymerizable monomer (a-1) which has [1] a C10-C20 bridged cyclic hydrocarbon group, and / or the polymerizable monomer (a-1 ') represented by following General formula (1), and It is a copolymer (A) which polymerizes the polymerizable monomer (a-2) represented by General formula (2), and whose weight average molecular weight (weight average molecular weight of polystyrene conversion) is 1000-50000.

(Ｘ and 중의 in Formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ And R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom, a carboxyl group, or a substituent, and R ¹ And an annular structure connecting R ² .

(R <^3> in Formula (2) is a hydrogen atom or a methyl group, n shows the integer of 1-4.)

Moreover, this invention contains the copolymer (A) of [1] which contains a [2] carboxyl group and whose acid value is 20-300 KOH mg / g,

[3] The copolymer (A) of [1] or [2] containing an unsaturated group,

[4] The polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and isobornyl (meth) acrylic. Copolymer (A) in any one of [1]-[3] containing at least 1 sort (s) chosen from a rate and adamantyl (meth) acrylate,

[5] The copolymer (A) of any of [1] to [4], further obtained by polymerizing a radically polymerizable monomer (a-3) having an ethylenically unsaturated group;

[6] The polymerizable monomer (a-1) and / or (a-1 ') is 2 to 50% by molar ratio, the polymerizable monomer (a-2) is 10 to 80%, and the polymerizable monomer (a The copolymer (A) of [5], in which -3) is polymerized at a ratio of 18 to 88%,

[7] The radical polymerizable monomer having an ethylenically unsaturated group is one or two or more selected from unsaturated monobasic acids, unsaturated polybasic anhydrides, or glycidyl (meth) acrylates [5] or [6] Copolymer (A),

[8] a resin composition containing any one of the copolymers (A) and (B) of [1] to [7];

[9] The resin composition of [8], further containing a reactive diluent (C);

[10] A photosensitive resin composition containing the copolymer (A) of any of [1] to [7], a solvent (B), a reactive diluent (C) and a photopolymerization initiator (D);

[11] The photosensitive resin composition of [10], further comprising a colorant (E) made of a dye and / or a pigment;

[12] The photosensitive resin composition of [11], which is a photosensitive resin composition for color filters,

[13] A color filter formed by curing a resist coating film containing the photosensitive resin composition of [12].

ADVANTAGE OF THE INVENTION According to this invention, the copolymer which can form the cured coating film excellent in thermal decomposition resistance and thermal yellowing resistance, and the photosensitive resin composition containing this copolymer can be provided with favorable sensitivity and developability. Moreover, since the cured coating film formed from the photosensitive resin composition of this invention is excellent in heat resistance and sensitivity, and has developability, it is extremely high in the use value in various resist fields, and especially the coloring which is excellent in thermal decomposition resistance and heat yellowing resistance A color filter having a pattern can be provided.

1 is a cross-sectional view of a color filter of one embodiment of the present invention.

Carrying out the invention  Form for

First, the copolymer (A) of this invention is demonstrated.

The copolymer (A) of the present invention is a polymerizable monomer (a-1) having a C10-C20 bridged cyclic hydrocarbon group and / or a polymerizable monomer (a-1 ') represented by the general formula (1), or a general formula It is made by superposing | polymerizing the polymerizable monomer (a-2) represented by (2), and the weight average molecular weight (weight average molecular weight of polystyrene conversion) is 1000-50000.

(Ｘ and 중의 in Formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ And R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom, a carboxyl group, or a substituent, and R ¹ And an annular structure connecting R ² .

(R <^3> in Formula (2) is a hydrogen atom or a methyl group, n shows the integer of 1-4.)

The polymerizable monomer (a-1) which comprises a copolymer (A) has a C10-C20 bridged cyclic hydrocarbon group. Here, a bridged cyclic hydrocarbon means the thing which has a structure represented by following formula (3) or (4) represented by adamantane and norbornane, and a bridged cyclic hydrocarbon group means Group corresponding to remainder except a part of hydrogen in a structure.

(In Formula (3), A <^1> , B <^1> represents a linear or branched alkylene group (including cyclic), respectively, and R <^4> represents a hydrogen atom or a methyl group. Even if A <^1> , B <^1> is the same, It may differ, and the branches of A ¹ and B ¹ may be connected to each other to form an annular shape.)

(In Formula (4), A <^2> , B <^2> , L represents a linear or branched alkylene group (including cyclic.), Respectively, R <^5> represents a hydrogen atom or a methyl group. A <^2> , B <^2> , L May be the same or different, and the branches of A ² , B ² , and L may be connected to each other to form an annular shape.)

As a monomer (a-1), the (meth) acrylate which has a C10-C20 bridged cyclic hydrocarbon group is preferable, and has a structure represented by adamantyl (meth) acrylate or following formula (5) (meth) ) Acrylate is more preferred.

(In formula (5), R <^6> -R <^8> represents a hydrogen atom or a methyl group, respectively. R <^9> , R <^10> may connect with a hydrogen atom or a methyl group, or may mutually form the saturated or unsaturated ring, The said ring is preferable. Preferably it is a 5-membered ring or a 6-membered ring. * Indicates the bond number connected to a (meth) acrylate group.)

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

Moreover, as another structural monomer of the copolymer (A) of this invention, following General formula (1):

(Ｘ and 중의 in Formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ And R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom, a carboxyl group, or a substituent, and R ¹ And R ² may be formed to form a cyclic structure.).

Monomer (a-1 ') will not be specifically limited if it has a chemical structure represented by General formula (1). In Formula (1), as an example of V and V which represent 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, an alkoxy group, an aryl group, etc. are mentioned as a substituent in the C1-C20 hydrocarbon group which may have a substituent. R ¹ And examples of R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhex Linear or branched alkyl groups, such as actual groups; An aryl group 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 groups substituted with alkoxy groups such as 1-methoxyethyl group and 1-ethoxyethyl group; And an alkyl group substituted with an aryl group such as benzyl.

As an example of the monomer (a-1 ') which has a chemical structure represented by General formula (1), norbornene (bicyclo [2.2.1] hepto-2-ene) and 5-methylbicyclo [2.2.1] hepto 2-en, 5-ethyl-bicyclo [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-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-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] dodeca-3-ene, Other cyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] -4-penta-deca-yen, penta-cyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] deca-penta- 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.

As an essential structural monomer of this invention, the polymeric monomer (a-2) represented by following General formula (2) is used.

(R <^3> in Formula (2) is a hydrogen atom or a methyl group, n shows the integer of 1-4.)

The polymerizable monomer (a-2) is not particularly limited and may be a mixture of n = 1 to 4 in the chemical formula, but in order to obtain desired thermal decomposition resistance, n = 1 ethoxylated o-phenylphenol (meth) acryl in the chemical formula Rate is preferred. As a commercial item, Toagosei Co., Ltd. Aronix TO-1463, Shin-Nakamura Kagaku Kogyo Co., Ltd. NK ester A-LEN-10, Nippon Kayaku Co., Ltd. KAYARAD @ OPP-1, etc. exist.

Moreover, it is also possible to superpose | polymerize the monomer (a-3) copolymerizable other than (a-1), (a-1 '), and (a-2) as another monomer. The polymerizable monomer (a-3) is generally a radically polymerizable compound having an ethylenically unsaturated group, and examples thereof include dienes such as butadiene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (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-cyclohexane dimethanol mono (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate, 5-methylnor Bornyl (meth) acrylic , 5-ethylnorbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (Meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, glycerol mono (meth) acrylate, butanetriol mono (meth) acrylate, pentanetriol mono (meth) acrylate, naphthalene (meth) acrylate (Meth) acrylic acid esters such as 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 anthracenylamide (meth) acrylic acid; Vinyl, such as (meth) anilic acid acrylate, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene compound; Styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene; Unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate and diethyl itaconic acid; Monomaleimides such as N-phenylmaleimide, N-cyclohexyl maleimide, N-lauryl maleimide and N- (4-hydroxyphenyl) maleimide; Unsaturated monobasic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid; Glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate having an alicyclic epoxy, and its lactone adducts (e.g., Daicel Kagaku Kogyo Cymer A200, M100), Mono (meth) acrylic acid ester of 3,4-epoxycyclohexyl methyl-3 ', 4'-epoxycyclohexane carboxylate, epoxide of dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth Radical polymerizable monomers having epoxy groups such as epoxides of acrylates; And unsaturated polybasic acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride. These can be used individually or in combination of 2 or more types.

It is preferable that this copolymer (A) has a carboxyl group in order to improve developability. As a method of adding carboxyl to a copolymer (A), copolymerizing the monomer which has a carboxyl group as a polymerizable monomer (a-3) is mentioned. Moreover, in order to improve photosensitivity, it is preferable to add the monomer which has an epoxy group to a part of its carboxyl group, and introduce a double bond. Alternatively, the carboxyl group and the double bond may also be added by copolymerizing a monomer having an epoxy group as the polymerizable monomer (a-3) and adding an acid anhydride to the hydroxyl group produced by adding the monomer having a carboxyl group. Or a carboxyl group and a double bond can also be added by copolymerizing unsaturated polybasic acid anhydride as a polymerizable monomer (a-3), and adding the monomer which has a hydroxyl group to the acid anhydride.

The monomer (a-1) and the monomer (a-1 ') may use either one, or both may be used, but this is collectively referred to as "monomer (a-1) and / or monomer (a-1')". In terms of the amount, the total ratio of the monomer (a-1) and / or monomer (a-1 ') is not particularly limited, but the monomer (a-1) and / or When the sum total of a monomer (a-1 '), a monomer (a-2), and a polymerizable monomer (a-3) is 100 mol%, Preferably it is 2-50 mol%, More preferably, it is 2-30 Molar%. When the compounding ratio of monomer (a-1) and / or monomer (a-1 ') is less than 2 mol%, there is a possibility that desired heat yellowing resistance cannot be obtained. On the other hand, when this compounding ratio exceeds 50 mol%, there is a possibility that the compounding ratio of monomer (a-2) becomes small and desired thermal decomposition resistance cannot be obtained.

In addition, the compounding ratio of monomer (a-2) is not particularly limited, but monomer (a-1) and / or monomer (a-1 '), monomer (a-2), and polymerizable monomer (a-3) When sum total is 100 mol%, Preferably it is 10-80 mol%, More preferably, it is 20-70 mol%. When the compounding ratio of monomer (a-2) is less than 10 mol%, there is a possibility that desired thermal decomposition resistance may not be obtained. On the other hand, when this compounding ratio exceeds 80 mol%, the compounding ratio of monomer (a-1) and / or monomer (a-1 ') decreases, and it may become impossible to obtain desired thermal yellowing resistance.

In the case of adding the monomer (a-3), the mixing ratio thereof is not particularly limited, but the monomer (a-1) and / or the monomer (a-1 '), the monomer (a-2), and the polymerizable monomer (a) When the sum total of -3) is 100 mol%, Preferably it is 18-88 mol%, More preferably, it is 25-70 mol%. It is effective for the compounding ratio of monomer (a-3) to 18 mol% or more to further improve developability and sensitivity. On the other hand, when this compounding ratio exceeds 88 mol%, the compounding ratio of monomer (a-1) and / or monomer (a-1 ') and monomer (a-2) will become small, and desired thermal decomposition resistance and heat-sulfur resistance There is a possibility that degeneration cannot be obtained.

Copolymerization reaction using a monomer (a-1) and / or a monomer (a-1 '), a monomer (a-2), and a polymerizable monomer (a-3) (optional) as a raw material is in the art. It can carry out by a well-known radical polymerization method. For example, after dissolving the monomer (a-1) and / or the monomer (a-1 '), the monomer (a-2) and any monomer in a solvent, a polymerization initiator is added to the solution, and the solution is heated at 50 to 130 ° C. It is good to react 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 solvents, such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Hydrocarbon solvents, such as toluene and xylene, and the solvent which does not have reactive functional groups, such as ethyl acetate, are 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 is not specifically limited, The sum total of a monomer (a-1) and / or a monomer (a-1 '), a monomer (a-2), and a polymerizable monomer (a-3) is 100 mass parts. In this case, 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 stopped, a polymerization reaction can be stabilized and performed, and coloring and gelation of a copolymer can be prevented.

Moreover, it does not specifically limit as a polymerization initiator which can be used for this copolymerization reaction, For example, Azobisisobutyronitrile, Azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2-ethyl hexanoate 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 '), a monomer (a-2), and a polymerizable monomer (a-3) 100 mass parts, Is 0.5-20 mass parts, Preferably it is 1.0-10 mass parts.

Without using an organic solvent, the monomer (a-1) and / or monomer (a-1 '), monomer (a-2), and a polymerizable monomer (a-3) (optional) and a polymerization initiator are used to form a block. You may superpose | polymerize.

When a carboxyl group, an epoxy group, or an acid anhydride group exists in the copolymer (A) obtained by the said copolymerization reaction, a double bond can also be introduce | transduced. This improves the sensitivity and developability of the photosensitive resin composition.

Reaction which adds a double bond to the carboxyl group, an epoxy group, or an acid anhydride group in a copolymer (A) adds an epoxy group containing monomer, a carboxyl group containing monomer, a hydroxyl group containing monomer, a polymerization inhibitor, and a catalyst, respectively, at 50-150 degreeC Preferably, the reaction may be carried out at 80 to 130 ° C. 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.

In addition, the compound listed by the said polymerizable monomer (a-3) can be used here.

Here, the polymerization inhibitor is added in order to prevent gelation by polymerization of the copolymer. Although it does not specifically limit as a polymerization inhibitor, For example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, etc. are mentioned. The catalyst is not particularly limited, and examples thereof include tertiary amines such as triethyl amine, quaternary ammonium salts such as triethyl benzyl ammonium chloride, phosphorus compounds such as triphenyl phosphine, chelate compounds of chromium and the like. Can be.

Although the acid value (JIS K6901-5.3) of the copolymer (A) obtained by the above is not restrict | limited, When used for photosensitive resin, it is 20-300 KOH mg / g normally, Preferably it is 30-200 KOH mg / g. . When this acid value is less than 20 KOH mg / g, developability as photosensitive resin may fall. On the other hand, when this acid value exceeds 300 KOH mg / g, an exposure part (photocuring part) may become easy to melt | dissolve with an alkaline developing solution.

Moreover, the molecular weight (weight average molecular weight of polystyrene conversion) of a copolymer (A) is 1000-50000 normally, Preferably it is 3000-40000. When this molecular weight is less than 1000, the lack of a coloring pattern may arise easily after image development. On the other hand, when this molecular weight exceeds 50000, image development time may become too long and a practicality may be lacking.

Moreover, when a copolymer (A) has an unsaturated group, the unsaturated group equivalent is although it does not restrict | limit, Usually, it is 100-4000 g / mol, Preferably it is 200-3000 g / mol. The amount of this unsaturated group equivalent of 100 g / mol or more is effective to further increase the thermal decomposition resistance and heat yellowing resistance. On the other hand, the unsaturated group equivalent of less than 4000 g / mol is effective to further increase the sensitivity.

Moreover, this invention relates to the resin composition containing a copolymer (A), a solvent (B), and arbitrary reactive diluents (C). Moreover, the photosensitive resin composition of this invention contains a copolymer (A), a solvent (B), a reactive diluent (C), a photoinitiator (D), and arbitrary coloring agents (E).

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

As a solvent (B), the same thing as the solvent used at the time of manufacturing a copolymer (A) can be used, The solvent contained after a copolymerization reaction can be used as it is, and can also be added. Moreover, when adding another component, it may coexist. 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, and 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. Moreover, glycol ether type solvents, such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, used in manufacturing a copolymer (A) (copolymerization reaction) are preferable among these.

When the compounding quantity of the solvent (B) in the resin composition or photosensitive resin composition of this embodiment makes the total of the component except the solvent (B) in the said composition 100 mass parts, it is generally 30-1000 mass parts, Preferably It is 50-800 mass parts, More preferably, it is 100-700 mass parts. If it is a compounding quantity of this range, it will become a resin composition or photosensitive resin composition which has a suitable viscosity.

Although it does not specifically limit as a reactive diluent (C), For example, aromatic vinyl type monomers, such as styrene, (alpha) -methylstyrene, (alpha)-chloromethylstyrene, vinyl toluene, divinyl benzene, diallyl phthalate, diallyl benzene phosphonate, etc. ; Polycarboxylic acid monomers such as vinyl acetate and vinyl adipic acid; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxy ethyl (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, trimethylol propane di (meth) acrylate, trimethylol propane tri ( (Meth) acrylic monomers such as tri (meth) acrylate of meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tris (hydroxyethyl) isocyanurate ; Triallyl cyanurate and the like. These can be used individually or in combination of 2 or more types.

When the compounding quantity of the reactive diluent (C) in the resin composition or photosensitive resin composition of this embodiment makes the total of the component except the solvent (B) in the said composition 100 mass parts, generally 10-90 mass parts, Preferably 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 a resin composition or photosensitive resin composition which has a suitable viscosity, and the photosensitive resin composition has suitable photocurability.

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-methyl anthraquinone, 2-amylanthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals 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 can be used individually or in combination of 2 or more types.

When the compounding quantity of the photoinitiator (D) in the photosensitive resin composition of this embodiment makes the total of the component except the solvent (B) in the photosensitive resin composition 100 mass parts, it is generally 0.1-30 mass parts, Preferably it is 0.5- It is 20 mass parts, More preferably, it is 1-15 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 or dispersed in the solvent (B), and examples thereof include dyes and pigments.

In particular, in the conventional photosensitive resin composition, when a dye is used, the coloring pattern with high brightness was obtained, but there existed a problem that the heat resistance of a coloring pattern becomes low compared with the case of using a pigment. On the other hand, in the photosensitive resin composition of this embodiment, even if dye is used, the coloring pattern excellent in heat resistance can be obtained.

Examples of the dyes include acidic dyes having acidic groups such as carboxylic acids, salts with nitrogen compounds of acidic dyes, and acidic acids from the viewpoints of solubility in solvents (B) and alkaline developing solutions, interaction with other components in the photosensitive resin composition, and heat resistance. It is preferable to use sulfonamide bodies of 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 the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, Yellow pigments such as 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; Brown pigments such as C.I. pigment orange 13, 31, 36, 38, 40, 42,43, 51, 55, 59, 61, 64, 65, 71, 73 and the like; CI 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. Pigments; Blue pigments such as C.I. pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and the like; Violet pigments such as C.I. pigment violet 1, 19, 23, 29, 32, 36, 38; Green pigments such as C.I. Pigment Green 7, 36 and 58; Color difference pigments such as C.I. Pigment Brown 23, 25; Black pigments, such as C.I. pigment black 1, 7, carbon black, titanium black, and 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.

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

In the photosensitive resin composition of this embodiment, when the compounding quantity is mix | blended with a coloring agent (E), when the sum total of the component except the solvent (B) in the photosensitive resin composition is 100 mass parts, it is generally 5-80 mass parts, Preferably Is 5-70 mass parts, More preferably, it is 10-60 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 dispersant, it is preferable to use a polymer dispersant having a dispersion stability over time. Examples of the polymer dispersant include urethane dispersants, polyethylene imine 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, it is marketed under brand names, such as EFKA (made by Efka Chemical Spirai Co., Ltd.), Disper byk (made by Bikkemi Co., Ltd.), Disperon (made by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (made by Geneca Co., Ltd.). You may use what has become.

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

When the photosensitive resin composition of this embodiment contains a coloring agent (E), the compounding quantity of a copolymer (A), a solvent (B), a reactive diluent (C), a photoinitiator (D), and a coloring agent (E) is generally, When the sum total of the component except the solvent (B) in the photosensitive resin composition is 100 mass parts, 5-80 mass parts of copolymers (A), 30-1000 mass parts of solvents (B), and 10-1000 mass parts of reactive diluents (C) 90 mass parts, a photoinitiator (D) is 0.1-30 mass parts, a coloring agent (E) is 5-80 mass parts, Preferably, the copolymer (A) is 8-70 mass parts and the solvent (B) is 50 It is -800 mass parts, 20-80 mass parts of reactive diluents (C), 0.5-20 mass parts of photoinitiators (D), and 5-70 mass parts of coloring agents (E), More preferably, a copolymer (A 10-60 parts by mass of the solvent, 100-700 parts of the solvent (B), 25-70 parts by mass of the reactive diluent (C), 1-15 parts by mass of the photopolymerization initiator (D), and 10-60 parts of the coloring agent (E). It is a mass part.

Even when the photosensitive resin composition of this embodiment does not contain a coloring agent (E), the said numerical value is applicable for the compounding quantity of a copolymer (A), a solvent (B), a reactive diluent (C), and a photoinitiator (D). Do.

When the compounding quantity of the copolymer (A) and the solvent (B) in the resin composition of this embodiment makes the total of the component except the solvent (B) in a resin composition 100 mass parts, a copolymer (A) is 50- It is 100 mass parts, 30-1000 mass parts of solvents (B), Preferably it is 50-800 mass parts, More preferably, it is 100-700 mass parts.

When the resin composition of this embodiment contains a reactive diluent (C), the compounding quantity of a copolymer (A), a solvent (B), and a reactive diluent (C) is the sum total of the component except the solvent (B) in a resin composition. When it is 100 mass parts, the copolymer (A) is 10-90 mass parts, 30-1000 mass parts of solvents (B), and 10-90 mass parts of reactive diluents (C), Preferably, it is a copolymer (A ) Is 20 to 80 parts by mass, 50 to 800 parts by mass of the solvent (B) and 20 to 80 parts by mass of the reactive diluent (C). More preferably, the copolymer (A) is 30 to 75 parts by mass. , Solvent (B) is 100 to 700 parts by mass, and reactive diluent (C) is 25 to 70 parts by mass.

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 predetermined characteristics. The compounding quantity of these additives will not be specifically limited if it is a range which does not impair the effect of this invention.

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 this embodiment first manufactures the resin composition containing a copolymer (A) and a solvent (B), and then uses a reactive diluent (C), a photoinitiator (D), and arbitrary coloring agents (E). It is also possible to manufacture by mixing. The resin composition can be used in other applications, in addition to being usable for producing the photosensitive resin composition of the present embodiment.

Since the photosensitive resin composition of this embodiment obtained as mentioned above has alkali developability, it can develop by using aqueous alkali solution. In particular, the photosensitive resin composition of this embodiment can provide the coloring pattern excellent in the thermal decomposition resistance and the yellowing resistance of heat while being excellent in sensitivity and developability. Therefore, the photosensitive resin composition of this embodiment is suitable for using as a resist used in order to manufacture the various filters, especially the color filter assembled in an organic electroluminescent display, a liquid crystal display device, and a solid-state image sensor. Moreover, since the photosensitive resin composition of this embodiment gives the cured film excellent in various characteristics, such as thermal decomposition resistance and thermal yellowing resistance, it can be used for various coatings, adhesives, binders for printing inks, etc.

Next, the color filter manufactured using the photosensitive resin composition of this invention is demonstrated. The color filter of this invention has the coloring pattern obtained from the said photosensitive resin composition.

EMBODIMENT OF THE INVENTION Hereinafter, the color filter of one Embodiment of this invention is demonstrated using drawing.

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

Next, the manufacturing method of the color filter of one Embodiment of this invention is demonstrated.

First, a coloring pattern is formed on the base material 1. Specifically, the black matrix 3 and the pixel 2 are sequentially formed on the base material 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 polyamide imide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, or an array substrate. Etc. can be used.

The coloring pattern can be formed by photolithography. 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. Therefore, a predetermined pattern can be formed by baking an unexposed part with aqueous alkali solution, and baking.

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. Moreover, after application | coating of the photosensitive resin composition, you may volatilize a 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, an exposure amount is not specifically limited, either, What is necessary is just to adjust suitably according to the kind of photosensitive resin composition to be used.

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 dimethyl ethanolamine; 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N p-phenylene diamine compounds such as -β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluene sulfonates thereof The aqueous solution of etc. can be used. Among these, it is preferable to use the aqueous solution of a p-phenylene diamine type compound. To these aqueous solutions, a defoaming agent or a surfactant may be added as required. Moreover, it is preferable to wash with water and to dry after image development by the said aqueous alkali solution.

Baking conditions 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 130-250 degreeC.

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). It does not specifically limit as the protective film 4, A well-known thing may be used.

Since the color filter manufactured in this way is manufactured using the photosensitive resin composition which gives the coloring pattern excellent in the thermal decomposition resistance and the thermal yellowing resistance, while being excellent in the sensitivity and developability, coloring excellent in the thermal decomposition resistance and the thermal decomposition resistance Has a pattern.

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 example, parts and percentages are all based on mass, unless particularly limited. In addition, an acid value is an acid value of the copolymer (A) measured according to JIS # 69015.3, and means the mg number of potassium hydroxide required to neutralize the acidic component contained in 1 g of copolymers (A). In addition, molecular weight (MV) means the standard polystyrene conversion weight average molecular weight measured on condition of the following using gel permeation chromatography (GPC).

Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.)

Column temperature: 40 ° C

Sample: 0.2% tetrahydrofuran solution of copolymer

Developing solvent: tetrahydrofuran

Detector: Differential Refractometer (Showdex RI-71S) (Showa Denko Corporation)

Flow rate: 1 ml / min

The manufacture example of the copolymer (A) of this invention is shown below.

<Production Example 1>

189.7 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were placed in a flask equipped with a stirring device, a dropping lot, a condenser, a thermometer, and a gas inlet tube, followed by nitrogen. It stirred, replacing, and heated up at 120 degreeC. Subsequently, 0.9 g of t-butylperoxy-2-ethyl hexanoate was added to a monomer mixture composed of 4.4 g of dicyclopentanyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3). The addition of the polymerization 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 (A).

Subsequently, 94.9 g of propylene glycol monomethyl ether was added to this copolymer, and the sample number (No.) 1 (solid content acid value 126 mg KOH / g, weight average molecular weight 20000) was obtained.

<Production Example 2>

In the same manner, 189.7 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, followed by stirring while replacing with nitrogen, and the temperature was raised to 120 ° C. Subsequently, 0.9 g of t-butylperoxy-2-ethyl hexanoate was added to a monomer mixture consisting of 4.4 g of dicyclopentanyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3). The addition was dripped in the said 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 inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenyl phosphine (catalyst), and 0.6 g of hydroquinone (polymerization inhibitor) were added thereto at 120 ° C. The addition reaction was carried out for 6 hours to produce a copolymer (A).

Subsequently, 116.2 g of propylene glycol monomethyl ether was added to this copolymer, and the sample number 2 (solid content acid value 90 mg KOH / g, weight average molecular weight 22000) was obtained.

<Production Example 3>

In the same manner, 160.5 g of propylene glycol monomethyl ether acetate and 99.2 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, followed by stirring with nitrogen substitution, and the temperature was raised to 120 ° C. Next, 5.3 g of t-butylperoxy-2-ethyl hexa was added to the monomer mixture consisting of 6.6 g of dicyclopentanyl methacrylate (a-1) and 85.2 g of glycidyl methacrylate (a-3). What added noate was dripped in the said 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, 41.9 g of acrylic acid, 0.7 g of triphenyl phosphine, and 0.7 g of hydroquinone were added thereto, followed by addition reaction at 120 ° C. for 6 hours to produce a copolymer. .

Subsequently, 60.8 g of tetrahydro phthalic anhydride was added to this copolymer, and addition reaction was performed at 115 degreeC for 1 hour, and the copolymer (A) was produced.

Next, 287.8 g of propylene glycol monomethyl ether was added to this copolymer (A), and the sample number 3 (solid content acid value 75 mg KOH / g, weight average molecular weight 21000) was obtained.

Production Example 4

In the same flask, 215.1 g of propylene glycol monomethyl ether acetate, 91.8 g of ethoxylated o-phenylphenol acrylate (a-2), and 41.7 g of maleic anhydride (a-3) were added thereto, followed by stirring with nitrogen substitution. It heated up at 120 degreeC. Subsequently, 13.0 g of t-butylperoxy-2-ethyl hexanoate is added to a monomer mixture composed of 4.4 g of dicyclopentanyl methacrylate (a-1) and 25.1 g of vinyl toluene (a-3). One was dripped in the said 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 inside of the flask with air, 40.6 g of 2-hydroxy ethyl acrylate, 1.0 g of triethyl amine (catalyst), and 1.0 g of hydroquinone were added thereto, followed by addition reaction at 120 ° C. for 6 hours. It carried out and produced the copolymer (A).

Next, 109.8 g of propylene glycol monomethyl ether was added to this copolymer (A), and sample number 4 (solid content acid value 110 mg KOH / g, weight average molecular weight 5800) was obtained.

Production Example 5

In the same manner, 217.2 g of propylene glycol monomethyl ether acetate and 187.6 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, followed by stirring while replacing with nitrogen, and the temperature was increased to 120 ° C. Subsequently, 1.1 g of t-butylperoxy-2-ethyl hexanoate was added to a monomer mixture composed of 4.4 g of dicyclopentanyl methacrylate (a-1) and 24.1 g of methacrylic acid (a-3). The addition was dripped in the said 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 inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.7 g of triphenyl phosphine, and 0.7 g of hydroquinone were added thereto, followed by addition reaction at 120 ° C. for 6 hours. Copolymer (A) was produced.

Next, 129.9 g of propylene glycol monomethyl ether was added to this copolymer to obtain Sample No. 5 (Solid acid value 43 mg KOH / g, Weight average molecular weight 13900).

Production Example 6

In the same manner, 170.1 g of propylene glycol monomethyl ether acetate and 53.6 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, followed by stirring with nitrogen substitution, followed by heating to 120 ° C. Subsequently, 0.8 g of t-butylperoxy-2-ethyl hexanoate was added to a monomer mixture composed of 66.0 g of dicyclopentanyl methacrylate (a-1) and 43.0 g of methacrylic acid (a-3). The addition was dripped in the said 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 inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.5 g of triphenyl phosphine (catalyst), and 0.5 g of hydroquinone (polymerization inhibitor) were added at 120 ° C. The addition reaction was carried out for 6 hours to produce a copolymer (A).

Subsequently, 96.3 g of propylene glycol monomethyl ether was added to this copolymer (A), and the sample number 6 (solid content acid value 125 mg KOH / g, weight average molecular weight 25600) was obtained.

Production Example 7

In the same flask, 187.2 g of propylene glycol monomethyl ether acetate, 1.9 g of norbornene (a-1 '), and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were added, followed by nitrogen replacement. It stirred, heating up at 120 degreeC. Next, what added 0.9 g of t-butylperoxy-2-ethyl hexanoate to 37.0 g of methacrylic acid (a-3) was dripped in the said 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 inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenyl phosphine, and 0.6 g of hydroquinone were added, followed by addition reaction at 120 ° C. for 6 hours. Copolymer (A) was produced.

Next, 114.9 g of propylene glycol monomethyl ether was added to this copolymer (A), and the sample number 7 (solid content acid value 91 mg KOH / g, weight average molecular weight 21500) was obtained.

Production Example 8

In the same manner, 189.8 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, followed by stirring while replacing with nitrogen, and the temperature was raised to 120 ° C. Subsequently, the addition of 0.9 g of t-butylperoxy-2-ethyl hexanoate was added dropwise to 4.4 g of isobornyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3). It was dripped in the said flask from the 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 inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenyl phosphine, and 0.6 g of hydroquinone were added, followed by addition reaction at 120 ° C. for 6 hours. Copolymer (A) was produced.

Subsequently, 116.2 g of propylene glycol monomethyl ether was added to this copolymer (A), and the sample number 8 (solid content acid value 90 mg KOH / g, weight average molecular weight 21800) was obtained.

Production Example 9

In the same manner, 197.8 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, followed by stirring while replacing with nitrogen, and the temperature was raised to 120 ° C. Subsequently, 0.9 g of t-butylperoxy-2-ethyl hexano was added to 4.7 g of 2-methyl-2-adamantyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3). What was added 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 inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenyl phosphine, and 0.6 g of hydroquinone were added, followed by addition reaction at 120 ° C. for 6 hours. Copolymer (A) was produced.

Next, 108.5 g of propylene glycol monomethyl ether was added to this copolymer (A), and the sample number 9 (solid content acid value 90 mg KOH / g, weight average molecular weight 22500) was obtained.

Below, the manufacture example of the copolymer which is a comparative product is shown.

<Production Comparative Example 1>

In the same manner, 218.1 g of propylene glycol monomethyl ether acetate and 193.0 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, followed by stirring while replacing with nitrogen, and the temperature was increased to 120 ° C. Subsequently, what added 0.9 g of t-butylperoxy-2-ethyl hexanoate to 24.1 g of methacrylic acid (a-3) was dripped in the said 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 inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenyl phosphine, and 0.6 g of hydroquinone were added, followed by addition reaction at 120 ° C. for 6 hours. The copolymer was produced.

Subsequently, 130.4 g of propylene glycol monomethyl ether was added to this copolymer to obtain Sample No. 10 (Solid acid value 44 mg KOH / g, Weight average molecular weight 24800).

<Production Comparative Example 2>

In the same manner, 160.0 g of propylene glycol monomethyl ether acetate was added to the flask, followed by stirring while replacing with nitrogen, and the temperature was raised to 120 ° C. Subsequently, what added 0.8 g of t-butylperoxy-2-ethyl hexanoate to 110.0 g dicyclopentanyl methacrylate (a-1) and 43.0 g methacrylic acid (a-3) was dripped. It was dripped in the said flask from the 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 inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.5 g of triphenyl phosphine, and 0.5 g of hydroquinone were added thereto, followed by addition reaction at 120 ° C. for 6 hours. The copolymer was produced.

Subsequently, 91.9 g of propylene glycol monomethyl ether was added to this copolymer to obtain Sample No. 11 (Solid acid value 132 mg KOH / g, Weight average molecular weight 26300).

Using sample numbers 1 to 11, a transparent resist, a color resist (pigment type) and a color resist (dye type) were prepared.

&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 Sample Nos. 1 to 11 to form a photosensitive resin. A composition was prepared and a transparent resist was prepared using this (Examples 1 to 9 and Comparative Examples 1 and 2).

<Pattern Formation 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 set to 2.5 micrometers, and the solvent was volatilized by heating at 90 degreeC for 3 minutes. Subsequently, the whole surface of a coating film was exposed (exposure amount 50mJ / cm <^2> ), and photocured, and also the cured coating film was obtained by baking at 230 degreeC for 30 minutes.

<Evaluation of Coating Film Formed from Transparent Resist>

With respect to the coating film formed from the transparent resist, thermal decomposition resistance, thermal yellowing resistance and transparency were evaluated.

(1) Evaluation of thermal decomposition resistance

It evaluated by performing thermogravimetric analysis (TGA) using the sample which cut out the coating film formed into a film on the glass substrate. In this analysis, the weight change rate between this sample and the sample which heated the sample to 220 degreeC and hold | maintained for 2 hours was calculated | required. The criteria for this evaluation are as follows.

○: less than -2.0%

× ： -2.0% or more

(2) Evaluation of heat resistant yellowing

The coating film formed on the glass substrate was left to stand in a 230 degreeC dryer for 1 hour, and the coloring of the coating film before and behind heat processing was compared with Japan Color Corporation Ltd. color difference meter SE2000. The criteria for this evaluation are as follows.

○: ΔE * a 'is less than 0.3

X: ΔE * a 'is 0.3 or more

(3) evaluation of transparency

The coating film formed on a glass substrate was left to stand in a 230 degreeC dryer for 1 hour, 400 nm light transmittance of the coating film after heat processing was measured by the Shimadzu Corporation spectrophotometer UV-1650PC, and the change rate of the transmittance | permeability is measured. It evaluated by examining. The criteria for this evaluation are as follows.

○: Change rate of transmittance is less than 1%

X: The rate of change of the transmittance is 1% or more

Table 1 shows the evaluation results of the thermal decomposition resistance, thermal yellowing resistance and transparency.

As can be seen from the results in Table 1, the transparent resists of Comparative Examples 1 and 2 are heat-resistant, whereas the transparent resists of Examples 1 to 9 give excellent patterns of thermal decomposition resistance, thermal yellowing resistance and overall transparency. Degradability, heat yellowing resistance, and transparency all showed insufficient patterns.

<Production of Color Resist (Pigment Type)>

In a 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. Pigment Green 36, 33.75 parts by mass of PGMEA (solvent), and 6.25 parts by mass of dispersant (Disperbyk-161 manufactured by BICKEMY Japan) Was added, the mixture was dispersed for 3 hours with a paint shaker and dispersed to obtain a green pigment dispersion.

Next, the photosensitive resin composition was manufactured by mixing the prepared green pigment dispersion liquid, sample numbers 1-11, and other components, and the color resist (pigment type) was produced using this (Examples 10-18 and a comparison). Example 3-4). Table 2 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 Sample Nos. 1 to 9 8.03 Trimethylolpropane triacrylate
(Reactive diluent) 6.5 Irgacure 907
(Photoinitiator, Ciba Specialty Chemicals) 1.66 High Cure ABP
(Photoinitiator, Kawaguchi Pharmaceutical Co., Ltd.) 0.83 Propylene Glycol Monomethyl Ether Acetate
(solvent) 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 glass substrate) so as to have a thickness of 1.5 μm after exposure, and then the solvent is volatilized by heating at 90 ° C. for 3 minutes to dry. I was. 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. It was.

<Checking color resist (pigment type) and pattern>

About the color resist (pigment type) and the pattern, alkali developability, sensitivity, heat yellowing resistance and solvent resistance were confirmed.

(4) Evaluation of alkali developability

Alkali developability was confirmed by the residue after alkali image development, and the image development form. The residue after alkali image development was confirmed by observing the pattern after alkali image development using the Hitachi High-Technologies Corporation electron microscope S-3400. 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 type resist, the uncured unexposed portion is dissolved by the alkaline developer and separated from the substrate, but as the developing form, the peeling type in which the separated and thin portions are mainly large lumps and peels off is removed. And a dissolution type that gradually dissolves and disperses. 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, the latter dissolution type is preferable.

○: Melt type

× ： Peeling type

(5) Evaluation of sensitivity

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

○: less than 0.20 μm

×: 0.20 μm or more

(6) Evaluation of heat resistant yellowing

Heat-resistant yellowing was carried out in a 230 ° C. dryer using a coating film formed by photocuring in the same manner as above, except that the entire film was exposed to light without using a photomask and the film thickness of the cured final coating film was changed to 2.5 μm. The coloring of the coating film after leaving to stand for time and heat-processing was compared with Japan Color Industry Co., Ltd. color difference meter SE2000. The criteria for this evaluation are as follows.

○: ΔE * a 'is less than 0.3

Δ: E * a 'is 0.3 or more

(7) Evaluation of solvent resistance

Using a coating film prepared in the same manner as the solvent resistance and heat yellowing resistance evaluation sample, 200 ml of n-methyl-2-pyrrolidone was placed in a glass bottle with a capacity of 500 ml, and the pattern sample was immersed therein. The color change after 1 hour at 23 ° C. was measured by a spectrophotometer UV-1650PC manufactured by Shimadzu Corporation. The criteria for this evaluation are as follows.

○: ΔE * a 'is less than 0.3

X: ΔE * a 'is 0.3 or more

Table 3 shows the evaluation results of the alkali developability, sensitivity, heat yellowing resistance and solvent resistance.

As can be seen from the results in Table 3, the color resists (pigment type) of Examples 10 to 18 have good alkali developability and sensitivity, and can provide a pattern excellent in heat yellowing resistance and solvent resistance. In the color resists (pigment type) of Comparative Examples 3 to 4, alkali developability and sensitivity were not good and heat-yellowing resistance or solvent resistance were provided.

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

The photosensitive resin composition was manufactured by mixing dye (acid green 3), sample numbers 1-11, and other components, and the color resist (dye type) was produced using this composition (Examples 19-27, and Comparative Examples 5-6). The blending component of this color resist (dye type) and its compounding quantity are shown in Table 4.

Compounding ingredient Compounding amount (mass part) acid green 3 5.2 Sample Nos. 1 to 9 32.5 Trimethylolpropane triacrylate
(Reactive diluent) 15.6 Irgacure 907
(Photoinitiator, Ciba Specialty Chemicals) 1.3 Propylene Glycol Monomethyl Ether Acetate
(solvent) 45.4 Sum 100.0

&Lt; 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.

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

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

Table 5 shows the evaluation results of the alkali developability, sensitivity, heat yellowing resistance and solvent resistance.

As can be seen from the results in Table 5, the color resists (dye types) of Examples 19 to 27 have good alkali developability and sensitivity, and give a pattern excellent in solvent resistance. The color resist (dye type) showed a pattern in which alkali developability and sensitivity were not good and heat resistance yellowing resistance or solvent resistance was not enough.

As can be seen from the above results, according to the present invention, it is possible to provide a photosensitive resin composition that provides a coloring pattern excellent in thermal decomposition resistance, thermal yellowing resistance and solvent resistance while having good sensitivity and developability. Moreover, according to this invention, the color filter which has a coloring pattern excellent in thermal decomposition resistance and thermal yellowing resistance can be provided.

1: Substrate 2: Pixel 3: Black Matrix 4: Protective Film

Claims (13)

Polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or polymerizable monomer (a-1 ') represented by the following general formula (1), and polymerizable represented by the following general formula (2) Copolymer (A) which polymerizes monomer (a-2) and whose weight average molecular weight (weight average molecular weight of polystyrene conversion) is 1000-50000:

(Ｘ and 중의 in Formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ And R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom, a carboxyl group or a substituent, and may have a cyclic structure connecting R ¹ and R ² .

(R <^3> in Formula (2) is a hydrogen atom or a methyl group, n shows the integer of 1-4.) The copolymer (A) according to claim 1, which contains a carboxyl group and has an acid value of 20 to 300 KOH mg / g. The copolymer (A) according to claim 1 or 2, which contains an unsaturated group. The polymerizable monomer (a-1) according to any one of claims 1 to 3, wherein the polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is dicyclopentenyl (meth) acrylate and dicyclopentanyl (meth). A copolymer (A) containing at least 1 sort (s) chosen from an acrylate, an isobornyl (meth) acrylate, and adamantyl (meth) acrylate. Copolymer (A) in any one of Claims 1-4 which superposes | polymerizes the radically polymerizable monomer (a-3) which has an ethylenically unsaturated group. The said polymerizable monomer (a-1) and / or (a-1 ') is 2 to 50% by molar ratio, The said polymerizable monomer (a-2) is 10 to 80%, The said polymerizable property of Claim 5 characterized by the above-mentioned. A copolymer (A) in which the monomer (a-3) is polymerized at a ratio of 18 to 88%. The copolymer according to claim 5 or 6, wherein the polymerizable monomer (a-3) is one or two or more selected from unsaturated monobasic acids, unsaturated polybasic anhydrides, or glycidyl (meth) acrylates. A). The resin composition containing the copolymer (A) and solvent (B) in any one of Claims 1-7. The resin composition of Claim 8 which further contains a reactive diluent (C). The photosensitive resin composition containing the copolymer (A), the solvent (B), the reactive diluent (C), and the photoinitiator (D) in any one of Claims 1-7. The photosensitive resin composition of Claim 10 which further contains the coloring agent (E) which consists of a dye and / or a pigment. The photosensitive resin composition of Claim 11 which is the photosensitive resin composition for color filters. The color filter formed by hardening the resist coating film containing the photosensitive resin composition of Claim 12.

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