JP5736038B2 - Copolymer, resin composition and photosensitive resin composition containing the copolymer, and color filter - Google Patents

Description

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

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

  The color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, a black matrix formed at the pixel boundary, It is comprised from the protective film formed on a pixel and a black matrix. A color filter having such a configuration is usually manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. Various manufacturing methods have been proposed as a method for forming a pixel and a black matrix (hereinafter, the pixel and the black matrix are referred to as a “colored pattern”). The pigment / dye dispersion method created by a photolithographic method that repeats exposure, development and baking is superior in durability such as light resistance and heat resistance, and gives a colored pattern with few defects such as pinholes. It has become.

  Generally, the photosensitive resin composition used for the photolithographic method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The pigment / dye dispersion method has the above-mentioned advantages, but the pattern of black matrix, R, G, and B is repeatedly formed. Therefore, the alkali-soluble resin serving as the binder of the coating film has high heat decomposition resistance and heat resistance. Yellowing is required. As a method for improving the thermal decomposition resistance, a resin composition (for example, Patent Document 1) using a monomer containing maleimide as a copolymerization component has been proposed. However, a resin composition having a monomer containing maleimide as a copolymerization component has a yellow to tan coloration caused by nitrogen atoms contained in the molecule, and deteriorates the transparency of the coating film. . Furthermore, there has been a problem that coloring progresses during post-curing after heat treatment. In addition, those using acrylic copolymers containing methacrylic acid and benzyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, etc. are known, but the thermal decomposition is not sufficient and the thermal decomposition products in the heating process at the time of pattern fixation Is generated as an outgas, which contaminates the substrate and the device.

  Further, when an acrylic copolymer using alicyclic cyclohexyl methacrylate or the like is used for improving heat yellowing resistance, the heat decomposability is not sufficient. Further, it has been proposed to use ethylene oxide (EO) modification or propylene oxide (PO) modification (meth) acrylate of paracumylphenol as means for improving patterning property and sensitivity (for example, Patent Documents 2 and 3). In addition, it has been proposed to use hydroxyethylated phenylphenol (meth) acrylate as a negative resist for forming liquid crystal alignment protrusions (for example, Patent Document 4). However, a binder for color filters that satisfies heat-resistant decomposition and heat-resistant yellowing has not been made.

JP 2003-29018 A JP 2004-101728 A JP 2006-215451 A JP 2009-109879 A

As described above, the conventional photosensitive resin composition may not have sufficient sensitivity and developability, or a colored pattern excellent in heat decomposition resistance and heat yellowing may not be obtained.
Accordingly, the present invention has been made to solve the above-mentioned problems, and as a photosensitive resin that gives a colored pattern that has good sensitivity and developability and is excellent in heat decomposition and heat yellowing. It is an object to provide a copolymer of the above, a resin composition containing the copolymer, and a photosensitive resin composition. It is another object of the present invention to provide a color filter having a coloring pattern excellent in heat decomposability and heat yellowing.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific copolymer in the photosensitive resin composition, and the present invention has been achieved. It was.
That is, the present invention provides [1] a polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a polymerizable monomer represented by the following chemical formula (1) (a-1 '), A polymerizable monomer (a-2) represented by the following chemical formula (2), and a radical polymerizable monomer (a-3) having an ethylenically unsaturated group, and having a weight average molecular weight (polystyrene). It is a copolymer (A) having a weight average molecular weight (converted) of 1,000 to 50,000, further containing a carboxyl group, and having an acid value of 20 to 300 KOHmg / g .

(X and Y 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 carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may have a cyclic structure connecting R ¹ and R ^2. )

（式（２）中のＲ³は水素原子またはメチル基でｎは１〜４の整数を表す。）

(R ³ in the formula (2) is a hydrogen atom or a methyl group, and n represents an integer of 1 to 4.)

The present invention also provides [2 ] a copolymer (A) of [1 ] containing an unsaturated group,
[3] before Symbol polymerizable monomer (a-1) is dicyclopentenyl (meth) acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, dicyclopentanyl (meth) acrylate, isobornyl (meth) [1] or [2] copolymer (A) containing at least one selected from acrylate and adamantyl (meth) acrylate,
[4] before Symbol polymerizable monomer (a-1) and / or (a-1 ') 2 to 50 percent by molar ratio, the polymerizable monomer (a-2) 10 to 80% of the polymerizable monomer (A-3) is polymerized in a proportion of 18 to 88%, the copolymer (A) according to any one of [1] to [3] ,
[5] radical polymerizable monomer having a pre-Symbol ethylenically unsaturated group, the unsaturated monobasic acid is the unsaturated polybasic acid anhydride, or glycidyl (meth) one or more members selected from acrylate Copolymer (A) of any one of [1] to [4]
[6] [1] to one of the copolymer (A) and Solvent (B) a resin composition containing the [5],
[7] A further reactive diluent containing (C) a resin composition of [6]
[8 ] A photosensitive resin composition containing the copolymer (A) of any one of [ 1] to [ 5 ], a solvent (B), a reactive diluent (C), and a photopolymerization initiator (D),
[9] further to a coloring agent comprising a dye and / or pigment (E), the photosensitive resin composition of [8],
[10] Color is a filter for a photosensitive resin composition, the photosensitive resin composition of [9],
[11 ] A color filter obtained by curing a resist coating film containing the photosensitive resin composition according to [10] .

  ADVANTAGE OF THE INVENTION According to this invention, the sensitivity and developability are favorable, and the copolymer which can form the cured coating film excellent in heat-resistant decomposability | degradability and heat-resistant yellowing, or the photosensitive resin composition containing the copolymer Things can be provided. In addition, the cured coating film formed from the photosensitive resin composition of the present invention is excellent in heat resistance and sensitivity, and has developability, so it has extremely high utility value in various resist fields. And a color filter having a coloring pattern excellent in heat-resistant yellowing.

It is sectional drawing of the color filter which is one Embodiment of this invention.

First, the copolymer (A) of the present invention will be described.
The copolymer (A) of the present invention comprises a polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a polymerizable monomer represented by the chemical formula (1) (a- 1 ') and the polymerizable monomer (a-2) represented by the chemical formula (2) are polymerized, and the weight average molecular weight (polystyrene equivalent weight average molecular weight) is 1000 to 50000.

(X and Y 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 carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may have a cyclic structure connecting R ¹ and R ^2. )

（式（２）中のＲ³は水素原子またはメチル基でｎは１〜４の整数を表す。）

(R ³ in the formula (2) is a hydrogen atom or a methyl group, and n represents an integer of 1 to 4.)

  The polymerizable monomer (a-1) constituting the copolymer (A) has a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. Here, the bridged cyclic hydrocarbon means one having a structure represented by the following formula (3) or (4) represented by adamantane and norbornane, and the bridged cyclic hydrocarbon group: And a group corresponding to the remaining part of the structure excluding part of hydrogen.

(In Formula (3), A ¹ and B ¹ each represent a linear or branched alkylene group (including a cyclic group), R ⁴ represents a hydrogen atom or a methyl group, and A ¹ and B ¹ are the same. Or they may be different, and the branches of A ¹ and B ¹ may be connected to form a ring.)

(In the formula (4), A ² , B ² and L each represent a linear or branched alkylene group (including a cyclic group), and R ⁵ represents a hydrogen atom or a methyl group. A ² and B ² , L may be the same or different, and the branches of A ² , B ² , and L may be connected to form a ring.)

  The monomer (a-1) is preferably a (meth) acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and has a structure represented by adamantyl (meth) acrylate or the following formula (5) ( More preferred is (meth) acrylate.

(In the formula (5), R ^{6 to} R ⁸ each represent a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group, or are linked to each other to form a saturated or unsaturated ring. The ring is preferably a 5-membered ring or a 6-membered ring. * Represents a bond connected to the (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. Among these, dicyclopentanyl methacrylate is more preferable from the viewpoint of thermal decomposition resistance, adhesion, developability, and the like. These can be used alone or in combination of two or more.

  Further, as another constituent monomer of the copolymer (A) of the present invention, the following general formula (1):

(In the formula, X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms; R ¹ and R ² each independently represent a hydrogen atom, a carboxyl group; Represents a hydrocarbon group having 1 to 20 carbon atoms which may have a group or a substituent, and may form a cyclic structure in which R ¹ and R ² are linked).

The monomer (a-1 ′) is not particularly limited as long as it has a chemical structure represented by the general formula (1). In the general formula (1), examples of X and Y representing a linear or branched hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Isobutyl group, t-butyl group and the like. Moreover, an alkoxy group, an aryl group, etc. are mentioned as a substituent in a C1-C20 hydrocarbon group which may have a substituent. Examples of R ¹ and R ² are 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- Linear or branched alkyl group such as ethylhexyl group; aryl group such as phenyl; cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl Examples include alicyclic groups such as a 2-adamantyl group; alkyl groups substituted with an alkoxy group such as 1-methoxyethyl group and 1-ethoxyethyl group; alkyl groups substituted with an aryl group such as benzyl.

Examples of the monomer (a-1 ′) having the chemical structure represented by the general formula (1) include norbornene (bicyclo [2.2.1] hept-2-ene) and 5-methylbicyclo [2.2. 1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tricyclo [5.2.1.0 ^2,6 ] dec-3 -Ene, tricyclo [4.4.0.1 ^2,5 ] undec-3-ene, tricyclo [6.2.1.0 ^1,8 ] undec-9-ene, tricyclo [6.2.1.0 ^1,8 ] undec-4-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,12 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-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, and 5-norbornene-2,3-dicarboxylic anhydride. Among these, norbornene, dicyclopentadiene, and 5-norbornene-2,3-dicarboxylic acid anhydride are preferable from the viewpoints of thermal decomposition resistance, adhesion, development characteristics, and the like. These can be used alone or in combination of two or more.

  As an essential constituent monomer of the present invention, a polymerizable monomer (a-2) represented by the following chemical formula (2) is used.

(R ^{3 in} formula (2) is a hydrogen atom or a methyl group, and n represents an integer of 1 to 4.)

  The polymerizable monomer (a-2) is not particularly limited, and may be a mixture of n = 1 to 4 in the general formula. However, in order to obtain a desired thermal decomposition resistance, n = 1 in the general formula. o-Phenylphenol (meth) acrylate is preferred. Examples of commercially available products include Aronix TO-1463 manufactured by Toa Gosei Co., Ltd., NK Ester A-LEN-10 manufactured by Shin-Nakamura Chemical Co., Ltd., KAYARAD OPP-1 manufactured by Nippon Kayaku Co., Ltd.

  Moreover, it is also possible to polymerize the copolymerizable monomer (a-3) other than (a-1), (a-1 ′) and (a-2) as other monomers. The polymerizable monomer (a-3) is generally a radically polymerizable compound having an ethylenically unsaturated group. 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, cyclopent (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, 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 ( Acrylate), 3- (N, N-dimethylamino) propyl (meth) acrylate, glyceryl 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 (Meth) acrylic amides such as N, N-dipropylamide, (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide; (meth) acrylic acid anilide, ( (Meth) acryloylnitrile, acrolein, vinyl chloride, salt Vinyl compounds such as vinylidene fluoride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene; styrene, α-, o-, m-, p-alkyl of styrene, nitro, cyano, Amide derivatives; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide Monomaleimides such as; (meth) acrylic acid, crotonic acid, cinnamic acid and other unsaturated monobasic acids; glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having alicyclic epoxy, and the like Lactone adduct [eg , Daicel Chemical Industries, Ltd., Cyclomer A200, M100], 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate mono (meth) acrylate, dicyclopentenyl (meth) acrylate Radical polymerizable monomers having an epoxy group such as an epoxidized product and an epoxidized product of dicyclopentenyloxyethyl (meth) acrylate; unsaturated polybasic acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. These can be used alone or in combination of two or more.

  The copolymer (A) preferably has a carboxyl group in order to improve developability. As a method for adding carboxyl to the copolymer (A), a monomer having a carboxyl group may be copolymerized as the polymerizable monomer (a-3). In order to further improve the photosensitivity, it is preferable to add a monomer having an epoxy group to a part of the carboxyl group and introduce a double bond. Alternatively, a carboxyl group and a double bond can be obtained by copolymerizing a monomer having an epoxy group as the polymerizable monomer (a-3) and adding an acid anhydride to a hydroxyl group generated by adding a monomer having a carboxyl group. Can be added. Alternatively, a carboxyl group and a double bond can be added by copolymerizing an unsaturated polybasic acid anhydride as the polymerizable monomer (a-3) and adding a monomer having a hydroxyl group to the acid anhydride.

  One of the monomer (a-1) and the monomer (a-1 ′) may be used, or both of them may be used, but these may be collectively referred to as “monomer (a-1) and / or monomer (a-1 ′). ) ", And the amount means the whole of the monomer (a-1) and / or the monomer (a-1 ') is not particularly limited, the monomer (a-1) And / or when the total of the monomer (a-1 ′), the monomer (a-2), and the polymerizable monomer (a-3) is 100 mol%, preferably 2 to 50 mol%, more preferably 2 to 30 mol%. When the blending ratio of the monomer (a-1) and / or the monomer (a-1 ′) is less than 2 mol%, the desired heat-resistant yellowing may not be obtained. On the other hand, when the blending ratio exceeds 50 mol%, the blending ratio of the monomer (a-2) decreases, and the desired heat decomposability may not be obtained.

  The mixing ratio of the monomer (a-2) is not particularly limited, but the monomer (a-1) and / or monomer (a-1 ′), monomer (a-2), and polymerizable monomer (a-3) ) Is preferably 10 to 80 mol%, more preferably 20 to 70 mol%. When the blending ratio of the monomer (a-2) is less than 10 mol%, desired heat decomposability may not be obtained. On the other hand, when the blending ratio exceeds 80 mol%, the blending ratio of the monomer (a-1) and / or the monomer (a-1 ′) decreases, and the desired heat-resistant yellowing may not be obtained.

  When the monomer (a-3) is added, the blending ratio is not particularly limited, but the monomer (a-1) and / or monomer (a-1 ′), monomer (a-2), and polymerizable monomer (a When the sum of -3) is 100 mol%, it is preferably 18 to 88 mol%, more preferably 25 to 70 mol%. A compounding ratio of the monomer (a-3) of 18 mol% or more is more effective for further improving developability and sensitivity. On the other hand, when the blending ratio exceeds 88 mol%, the blending ratio of the monomer (a-1) and / or the monomer (a-1 ′) and the monomer (a-2) decreases, and the desired thermal decomposition resistance and heat resistance. Yellowing may not be obtained.

  Copolymerization reaction using monomer (a-1) and / or monomer (a-1 ′), monomer (a-2), and polymerizable monomer (a-3) (optional) as raw materials is known in the art. The radical polymerization method can be used. For example, the monomer (a-1) and / or the monomer (a-1 ′), the monomer (a-2), and an arbitrary monomer are dissolved in a solvent, and then a polymerization initiator is added to the solution. What is necessary is just to make it react at 1 degreeC for 20 hours.

  Solvents that can be used for this copolymerization reaction are not particularly limited. For example, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; hydrocarbon solvents such as toluene and xylene; ethyl acetate Examples thereof include a solvent having no reactive functional group. These can be used alone or in combination of two or more. Of these, glycol ether solvents are preferred.

  Although the compounding quantity of a solvent is not specifically limited, The total of a monomer (a-1) and / or monomer (a-1 '), a monomer (a-2), and a polymerizable monomer (a-3) is 100 mass parts. In general, it is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. In particular, by setting the blending amount of the solvent to 1000 parts by mass or less, it is possible to suppress a decrease in the molecular weight of the copolymer by a chain transfer action and to control the viscosity of the copolymer within an appropriate range. Further, by setting the blending amount of the solvent to 30 parts by mass or more, an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably performed, and the coloring and gelation of the copolymer can also be prevented. .

In addition, the polymerization initiator that can be used for the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2- Examples include ethyl hexanoate. These can be used alone or in combination of two or more.
The amount of the polymerization initiator is 100 parts by mass of the total of the monomer (a-1) and / or the monomer (a-1 ′), the monomer (a-2), and the polymerizable monomer (a-3). Generally, it is 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass.
In addition, a monomer (a-1) and / or a monomer (a-1 '), a monomer (a-2), a polymerizable monomer (a-3) (optional), and a polymerization initiator are used without using an organic solvent. And bulk polymerization may be performed.

When a carboxyl group, an epoxy group, or an acid anhydride group is present in the copolymer (A) obtained by the above copolymerization reaction, a double bond can be further introduced. Thereby, the sensitivity and developability of the photosensitive resin composition are improved.
The reaction of adding a double bond to the carboxyl group, epoxy group or acid anhydride group in the copolymer (A) is carried out by adding an epoxy group-containing monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer and a polymerization inhibitor to the copolymer And a catalyst may be added, and the reaction may be carried out at 50 to 150 ° C, preferably 80 to 130 ° C. In this addition reaction, there is no particular problem even if the solvent used in the copolymerization reaction is included. Therefore, the addition reaction can be carried out without removing the solvent after the completion of the copolymerization reaction.
Moreover, the compound quoted by said polymerizable monomer (a-3) can be used here.
Here, the polymerization inhibitor is added to prevent gelation due to polymerization of the copolymer. Although it does not specifically limit as a polymerization inhibitor, For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, etc. are mentioned. The catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelate compounds of chromium. Can be mentioned.

The acid value (JIS K6901 5.3) of the copolymer (A) obtained as described above is not limited, but when used in a photosensitive resin, it is usually 20 to 300 KOHmg / g, preferably 30 to 200 KOHmg. / G. If the acid value is less than 20 KOHmg / g, the developability as a photosensitive resin may be lowered. On the other hand, when the acid value exceeds 300 KOHmg / g, the exposed portion (photocured portion) may be easily dissolved in the alkali developer.
Moreover, the molecular weight (polystyrene conversion weight average molecular weight) of a copolymer (A) is 1000-50000 normally, Preferably it is 3000-40000. If the molecular weight is less than 1000, a lack of a colored pattern may easily occur after development. On the other hand, if the molecular weight exceeds 50,000, the development time becomes too long, and the practicality may be lacking.
Moreover, when a copolymer (A) has an unsaturated group, the unsaturated group equivalent is although there is no restriction | limiting, Usually, it is 100-4000 g / mol, Preferably it is 200-3000 g / mol. When the unsaturated group equivalent is 100 g / mol or more, it is more effective to further improve the heat decomposition resistance and heat yellowing. On the other hand, when the unsaturated group equivalent is less than 4000 g / mol, it is effective to further increase the sensitivity.

  The present invention further relates to a resin composition comprising a copolymer (A), a solvent (B) and optionally a reactive diluent (C). Moreover, the photosensitive resin composition of this invention contains a copolymer (A), a solvent (B), a reactive diluent (C), a photoinitiator (D), and the coloring agent (E) arbitrarily.

The solvent (B) is not particularly limited as long as it is an inert solvent that does not react with the copolymer (A).
As the solvent (B), the same solvent as used in the production of the copolymer (A) (copolymerization reaction) can be used, and the solvent contained after the copolymerization reaction can be used as it is. You can add more. Further, when other components are added, they may coexist there. Specific examples of the solvent (B) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene 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 alone or in combination of two or more. Among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate used in producing the copolymer (A) (copolymerization reaction) are preferable.

  The compounding amount of the solvent (B) in the resin composition or photosensitive resin composition of the present embodiment is generally 30 to 1000 masses when the total of the components excluding the solvent (B) in the composition is 100 mass parts. Parts, preferably 50 to 800 parts by mass, more preferably 100 to 700 parts by mass. If it is the compounding quantity of this range, it will become the 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-methyl styrene, alpha-chloromethyl styrene, vinyl toluene, divinyl benzene, diallyl phthalate, diallyl benzene phosphonate; Polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; 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, trimethylol group (Meth) such as pandi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate Acrylic monomers; triallyl cyanurate and the like. These can be used alone or in combination of two or more.

The amount of the reactive diluent in the resin composition or photosensitive resin composition of the present embodiment (C), when the sum of the components excluding the solvent (B) in the composition is 100 parts by weight, generally 10 It is -90 mass parts, Preferably it is 20-80 mass parts, More preferably, it is 25-70 mass parts. If it is the compounding quantity of this range, it will become the resin composition or photosensitive resin composition which has an appropriate viscosity, and the photosensitive resin composition has appropriate 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 ethers; acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 1, Acetophenones such as 1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone 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 zophenone, 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; acylphosphine oxides; and xanthones It is done. These can be used alone or in combination of two or more.

  The blending amount of the photopolymerization initiator (D) in the photosensitive resin composition of the present embodiment is generally 0.1 when the sum of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. -30 mass parts, Preferably it is 0.5-20 mass parts, More preferably, it is 1-15 mass parts. If it is the compounding quantity of this range, it will become the photosensitive resin composition which has appropriate photocurability.

The colorant (E) is not particularly limited as long as it dissolves or disperses in the solvent (B), and examples thereof include dyes and pigments.
In particular, in the conventional photosensitive resin composition, when a dye is used, a colored pattern having high luminance can be obtained, but there is a problem that the heat resistance of the colored pattern is lower than that when a pigment is used. On the other hand, in the photosensitive resin composition of this Embodiment, even if it uses dye, the coloring pattern excellent in heat resistance can be obtained.

  Examples of the dye include acidic dyes having acidic groups such as carboxylic acid, acidic acids, from the viewpoints of solubility in the solvent (B) and the alkaline developer, interaction with other components in the photosensitive resin composition, and heat resistance. It is preferable to use a salt of a dye with a nitrogen compound, a sulfonamide of an acidic dye, or 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 chroma 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 red1, 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, 38, 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 yellow1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow3 and these Derivatives and the like. Among these, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These can be used alone or in combination of two or more depending on the color of the target pixel.

Examples of pigments include C.I. 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, 214; I. CI orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I. Red pigments such as 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; C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as C.I. Pigment Green 7, 36, 58; I. Brown pigments such as C.I. Pigment Brown 23 and 25; I. And black pigments such as CI pigment blacks 1 and 7, carbon black, titanium black, and iron oxide. These can be used alone or in combination of two or more depending on the color of the target pixel.
Note that the above dyes and pigments may be used in combination depending on the target pixel color.

  In the photosensitive resin composition of the present embodiment, when the colorant (E) is blended, the amount of the component excluding the solvent (B) in the photosensitive resin composition is generally 5 parts by mass. -80 mass parts, preferably 5-70 mass parts, more preferably 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 excellent in dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. System dispersants and the like. As such a polymer dispersant, commercially available under trade names such as EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by GENEKA). You may use what is done.
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 kinds, such as a pigment to be used.

  When the photosensitive resin composition of this Embodiment contains a coloring agent (E), a copolymer (A), a solvent (B), a reactive diluent (C), a photoinitiator (D), a coloring agent In general, the blending amount of (E) is 5 to 80 parts by mass of the copolymer (A) and the solvent (B) when the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. 30-1000 parts by mass, reactive diluent (C) is 10-90 parts by mass, photopolymerization initiator (D) is 0.1-30 parts by mass, and colorant (E) is 5-80 parts by mass, Preferably, the copolymer (A) is 8 to 70 parts by mass, the solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) is 20 to 80 parts by mass, and the photopolymerization initiator (D) is 0. 5 to 20 parts by mass, the colorant (E) is 5 to 70 parts by mass, and more preferably, the copolymer (A) is 10 to 60 parts by mass and the solvent (B) is 100 to 7 parts. 0 parts by weight reactive diluent (C) 25 to 70 parts by weight, the photopolymerization initiator (D) is 1 to 15 parts by weight, the coloring agent (E) is 10 to 60 parts by weight.

Even when the photosensitive resin composition of the present embodiment does not contain the colorant (E), the copolymer (A), the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D). The above numerical values can be applied to the blending amount.
In the resin composition of the present embodiment, the amount of copolymer (A) and solvent (B) is such that the total amount of components excluding solvent (B) in the resin composition is 100 parts by mass. (A) is 50 to 100 parts by mass, and the solvent (B) is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, and more preferably 100 to 700 parts by mass.
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 solvent in a resin composition. When the total sum of the components excluding (B) is 100 parts by mass, the copolymer (A) is 10 to 90 parts by mass, the solvent (B) is 30 to 1000 parts by mass, and the reactive diluent (C) is 10 to 10 parts by mass. 90 parts by mass, preferably, the copolymer (A) is 20-80 parts by mass, the solvent (B) is 50-800 parts by mass, and the reactive diluent (C) is 20-80 parts by mass, More preferably, the copolymer (A) is 30 to 75 parts by mass, the solvent (B) is 100 to 700 parts by mass, and the reactive diluent (C) is 25 to 70 parts by mass.

  In addition to the above components, the photosensitive resin composition of the present embodiment contains known additives such as known coupling agents, leveling agents, thermal polymerization inhibitors, etc., in order to impart predetermined characteristics. May be. The amount of these additives is not particularly limited as long as it does not impair the effects of the present invention.

The photosensitive resin composition of this Embodiment can be manufactured by mixing said component using a well-known mixing apparatus.
In addition, the photosensitive resin composition of this Embodiment prepares the resin composition containing a copolymer (A) and a solvent (B) previously, Then, a reactive diluent (C), a photoinitiator ( It is also possible to produce a mixture of D) and an optional colorant (E). In addition, the said resin composition can be used for preparing the photosensitive resin composition of this Embodiment, and can also be used for another use.

  Since the photosensitive resin composition of the present embodiment obtained as described above has alkali developability, it can be developed by using an alkaline aqueous solution. In particular, the photosensitive resin composition of the present embodiment is excellent in sensitivity and developability, and can give a colored pattern excellent in heat decomposition resistance and heat yellowing resistance. Therefore, the photosensitive resin composition of the present embodiment is suitable for use as various resists, particularly as resists used for manufacturing color filters incorporated in organic EL displays, liquid crystal display devices, and solid-state imaging devices. . In addition, since the photosensitive resin composition of the present embodiment gives a cured film excellent in various properties such as heat decomposability and heat yellowing resistance, it can be used for various coatings, adhesives, binders for printing inks, and the like. it can.

Next, a color filter prepared using the photosensitive resin composition of the present invention will be described. The color filter of the present invention has a colored pattern obtained from the photosensitive resin composition.
Hereinafter, a color filter according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 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 boundary between the RGB pixels 2 and the pixels 2 formed on the substrate 1, and a protection formed on the pixels 2 and the black matrix 3. And the membrane 4. In this configuration, known configurations can be adopted as the other configurations except that the pixels 2 and the black matrix 3 (colored pattern) are formed using the above-described photosensitive resin composition. The color filter shown in FIG. 1 is an example, and the present invention is not limited to this configuration.

Next, the manufacturing method of the color filter of one Embodiment of this invention is demonstrated.
First, a colored pattern is formed on the 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 a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, or the like may be used. it can.

The colored pattern can be formed by a photolithography method. Specifically, after the photosensitive resin composition is applied onto the substrate 1 to form a coating film, the coating film is exposed through a photomask having a predetermined pattern, and the exposed portion is photocured. And a predetermined pattern can be formed by developing after 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, A screen printing method, a roll coat method, a curtain coat method, a spray coat method, a 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 circulation type oven, an infrared heater, a hotplate, as needed. The heating conditions are not particularly limited, and may be set as appropriate according to the type of photosensitive resin composition to be used. In general, heating may be performed at a temperature of 50 ° C. to 120 ° C. for 30 seconds to 30 minutes.

The light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. Further, the exposure amount is not particularly limited, and may be appropriately adjusted according to the type of the photosensitive resin composition to be used.
The aqueous alkali solution used for development is not particularly limited, but an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc .; an aqueous solution of an amine compound such as ethylamine, diethylamine, dimethylethanolamine; 3 -Methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β- Aqueous solutions of methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and p-phenylenediamine compounds such as sulfate, hydrochloride or p-toluenesulfonate Etc. can be used. Among these, it is preferable to use an aqueous solution of a p-phenylenediamine compound. In addition, you may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash and dry after development with the above-mentioned alkaline aqueous solution.
The baking conditions are not particularly limited, and heat treatment may be performed according to the type of the photosensitive resin composition to be used. In general, it may be heated at 130 to 250 ° C. for 10 to 60 minutes.

Forming a desired coloring pattern by sequentially repeating the coating, exposure, development and baking as described above using the photosensitive resin composition for the black matrix 3 and the photosensitive resin composition for the pixel 2. Can do.
In addition, although the formation method of the coloring pattern by photocuring was demonstrated above, if the photosensitive resin composition which mix | blended the hardening accelerator and the well-known epoxy resin was used instead of a photoinitiator (D), it will be inkjet. A desired coloring pattern can also be formed by heating after coating by the method.
Next, the protective film 4 is formed on the colored pattern (pixel 2 and black matrix 3). The protective film 4 is not particularly limited, and may be formed using a known film.

  The color filter produced in this way is excellent in sensitivity and developability, and is manufactured using a photosensitive resin composition that gives a coloring pattern excellent in heat decomposition resistance and heat yellowing resistance. In addition, it has a coloring pattern excellent in thermal decomposition resistance.

EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples. In this example, all parts and percentages are based on mass unless otherwise specified. The acid value is the acid value of the copolymer (A) measured according to JIS K6901 5.3, and is the water required to neutralize the acidic component contained in 1 g of the copolymer (A). It means the number of mg of potassium oxide. Moreover, molecular weight (Mw) 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 KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of copolymer Development solvent: Tetrahydrofuran Detector: Differential refractometer (Showex RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1mL / min

Production examples of the copolymer (A) of the present invention are shown below.
<Production Example 1>
After placing 189.7 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) in a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube The mixture was stirred while replacing with nitrogen and heated to 120 ° C. Next, 0.9 g of t-butylperoxy-2-ethylhexano 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). What added the acid (polymerization initiator) was dropped into the flask from the dropping funnel. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer (A).
Next, 94.9 g of propylene glycol monomethyl ether was added to this copolymer. 1 (solid content acid value 126 mgKOH / g, weight average molecular weight 20000) was obtained.

<Production Example 2>
Similarly, 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, and the mixture was stirred while replacing with nitrogen and heated to 120 ° C. Next, 0.9 g of t-butylperoxy-2-ethylhexano 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). What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of hydroquinone (polymerization inhibitor) were added, and the mixture was heated at 120 ° C. for 6 hours. An addition reaction was performed to produce a copolymer (A).
Next, 116.2 g of propylene glycol monomethyl ether was added to this copolymer. 2 (solid content acid value 90 mgKOH / g, weight average molecular weight 22000) was obtained.

<Production Example 3>
Similarly, after putting 160.5 g of propylene glycol monomethyl ether acetate and 99.2 g of ethoxylated o-phenylphenol acrylate (a-2) into the flask, the mixture was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Next, a monomer mixture composed of 6.6 g of dicyclopentanyl methacrylate (a-1) and 85.2 g of glycidyl methacrylate (a-3) was added to 5.3 g of t-butylperoxy-2-ethylhexano. What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 41.9 g of acrylic acid, 0.7 g of triphenylphosphine, and 0.7 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. Was generated.
Next, 60.8 g of tetrahydrophthalic anhydride was added to the copolymer, and an addition reaction was performed at 115 ° C. for 1 hour to produce a copolymer (A).
Next, 287.8 g of propylene glycol monomethyl ether was added to the copolymer (A). 3 (solid content acid value 75 mgKOH / g, weight average molecular weight 21000) was obtained.

<Production Example 4>
Similarly, after putting 215.1 g of propylene glycol monomethyl ether acetate and 91.8 g of ethoxylated o-phenylphenol acrylate (a-2) and 41.7 g of maleic anhydride (a-3) into a flask, nitrogen was added. The mixture was stirred while being replaced and heated to 120 ° C. Next, 13.0 g of t-butylperoxy-2-ethylhexano was added to a monomer mixture consisting of 4.4 g of dicyclopentanyl methacrylate (a-1) and 25.1 g of vinyltoluene (a-3). What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after replacing the inside of the flask with air, 40.6 g of 2-hydroxyethyl acrylate, 1.0 g of triethylamine (catalyst), and 1.0 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours. A copolymer (A) was produced.
Next, 109.8 g of propylene glycol monomethyl ether was added to the copolymer (A). 4 (solid content acid value 110 mgKOH / g, weight average molecular weight 5800) was obtained.

<Production Example 5>
Similarly, 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, and the mixture was stirred while replacing with nitrogen and heated to 120 ° C. Next, 1.1 g of t-butylperoxy-2-ethylhexano was added to a monomer mixture consisting of 4.4 g of dicyclopentanyl methacrylate (a-1) and 24.1 g of methacrylic acid (a-3). What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.7 g of triphenylphosphine, and 0.7 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. (A) was generated.
Next, 129.9 g of propylene glycol monomethyl ether was added to this copolymer. 5 (solid content acid value 43 mgKOH / g, weight average molecular weight 13900) was obtained.

<Production Example 6>
Similarly, after putting 170.1 g of propylene glycol monomethyl ether acetate and 53.6 g of ethoxylated o-phenylphenol acrylate (a-2) into the flask, the mixture was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Next, 0.8 g of t-butylperoxy-2-ethylhexano was added to a monomer mixture consisting of 66.0 g of dicyclopentanyl methacrylate (a-1) and 43.0 g of methacrylic acid (a-3). What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.5 g of triphenylphosphine (catalyst), and 0.5 g of hydroquinone (polymerization inhibitor) were added, and the mixture was heated at 120 ° C. for 6 hours. An addition reaction was performed to produce a copolymer (A).
Next, 96.3 g of propylene glycol monomethyl ether was added to this copolymer (A). 6 (solid content acid value 125 mgKOH / g, weight average molecular weight 25600) was obtained.

<Production Example 7>
In the same manner, 187.2 g of propylene glycol monomethyl ether acetate and 1.9 g of norbornene (a-1 ′) and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were put into a flask, and then replaced with nitrogen. The mixture was stirred and heated to 120 ° C. Next, a solution obtained by adding 0.9 g of t-butylperoxy-2-ethylhexanoate to 37.0 g of methacrylic acid (a-3) was dropped into the flask from a dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. (A) was generated.
Next, 114.9 g of propylene glycol monomethyl ether was added to this copolymer (A). 7 (solid content acid value 91 mgKOH / g, weight average molecular weight 21500) was obtained.

<Production Example 8>
Similarly, 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, and the mixture was stirred while purging with nitrogen and heated to 120 ° C. Next, 4.4 g of isobornyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3) added with 0.9 g of t-butylperoxy-2-ethylhexanoate Was dropped from the dropping funnel into the flask. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. (A) was generated.
Next, 116.2 g of propylene glycol monomethyl ether was added to this copolymer (A). 8 (solid content acid value 90 mgKOH / g, weight average molecular weight 21800) was obtained.

<Production Example 9>
Similarly, after placing 197.8 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) in a flask, the mixture was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Next, 4.7 g of 2-methyl-2-adamantyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3) were added to 0.9 g of t-butylperoxy-2-ethylhexanoate. Was added dropwise from the dropping funnel into the flask. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. (A) was generated.
Next, 108.5 g of propylene glycol monomethyl ether was added to this copolymer (A). 9 (solid content acid value 90 mgKOH / 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>
Similarly, 218.1 g of propylene glycol monomethyl ether acetate and 193.0 g of ethoxylated o-phenylphenol acrylate (a-2) were placed in a flask, and the mixture was stirred while purging with nitrogen and heated to 120 ° C. Next, what added 0.9 g of t-butylperoxy-2-ethylhexanoate to 24.1 g of methacrylic acid (a-3) was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. Was generated.
Next, 130.4 g of propylene glycol monomethyl ether was added to this copolymer. 10 (solid content acid value 44 mgKOH / g, weight average molecular weight 24800) was obtained.

<Production Comparative Example 2>
Similarly, after putting 160.0 g of propylene glycol monomethyl ether acetate into the flask, the mixture was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Next, 0.8 g of t-butylperoxy-2-ethylhexanoate was added to 110.0 g of dicyclopentanyl methacrylate (a-1) and 43.0 g of methacrylic acid (a-3). Things were dropped from the dropping funnel into the flask. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.5 g of triphenylphosphine, and 0.5 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. Was generated.
Next, 91.9 g of propylene glycol monomethyl ether was added to this copolymer. 11 (solid content acid value 132 mgKOH / g, weight average molecular weight 26300) was obtained.

Sample No. A transparent resist, a color resist (pigment type), and a color resist (dye type) were prepared using 1-11.
<Preparation of transparent resist>
Sample No. To 100 parts by mass of solids 1 to 11, 30 parts by mass of pentaerythritol tetraacrylate (reactive diluent) and 4 parts by mass of 2,2-dimethoxy-2-phenylacetophenone (photopolymerization initiator) were added. The photosensitive resin composition was prepared and the transparent resist was prepared using this (Examples 1-9 and Comparative Examples 1 and 2).

<Pattern formation with transparent resist>
The prepared transparent resist is spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the final cured coating thickness is 2.5 μm, and then heated at 90 ° C. for 3 minutes. The solvent was volatilized. Next, the entire surface of the coating film was exposed (exposure amount 50 mJ / cm ² ), photocured, and then baked at 230 ° C. for 30 minutes to obtain a cured coating film.

<Evaluation of coating film formed from transparent resist>
About the coating film formed from the transparent resist, heat-resistant decomposability, heat-resistant yellowing, and transparency were evaluated.
(1) Evaluation of heat decomposability Evaluation was performed by performing thermogravimetric analysis (TGA) using a sample obtained by cutting out a coating film formed on a glass substrate. In this analysis, the rate of weight change between this sample and the sample heated to 220 ° C. and held for 2 hours was determined. The criteria for this evaluation are as follows.
○: Less than −2.0% ×: −2.0% or more

(2) Evaluation of heat-resistant yellowing property The coating film formed on the glass substrate was left in a dryer at 230 ° C. for 1 hour, and the coating film before and after the heat treatment was colored by a color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. Compared. The criteria for this evaluation are as follows.
○: ΔE ^* ab is less than 0.3 ×: ΔE ^* ab is 0.3 or more

(3) Evaluation of transparency The coating film formed on the glass substrate was left in a dryer at 230 ° C. for 1 hour, and the light transmittance at 400 nm of the coating film before and after the heat treatment was measured by Shimadzu Corporation. The measurement was carried out with a total of UV-1650PC, and the change rate of the transmittance was evaluated. The criteria for this evaluation are as follows.
○: Change rate of transmittance is less than 1% ×: Change rate of transmittance is 1% or more Table 1 shows the evaluation results of the above heat decomposition resistance, heat yellowing resistance, and transparency.

  As can be seen from the results in Table 1, the transparent resists of Examples 1 to 9 gave excellent patterns in all of the heat decomposition resistance, heat yellowing resistance and transparency, whereas the transparent resists of Comparative Examples 1 and 2 Gave a pattern with insufficient thermal decomposition, heat yellowing and transparency.

<Preparation 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.I. Add I Pigment Green 36, 33.75 parts by weight of PGMEA (solvent), and 6.25 parts by weight of a dispersant (Disperbyk-161 manufactured by Big Chemie Japan Co., Ltd.), and mix and disperse in a paint shaker for 3 hours. As a result, a green pigment dispersion was obtained.
Next, the prepared green pigment dispersion, Sample No. The photosensitive resin composition was prepared by mixing 1-11 and another component, and the color resist (pigment type) was prepared using this (Examples 10-18 and Comparative Examples 3-4). Table 2 shows the blending components and blending amounts of this color resist (pigment type).

<Pattern formation with color resist (pigment type)>
The prepared color resist (pigment type) is spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the thickness after exposure is 1.5 μm, and then heated at 90 ° C. for 3 minutes. The solvent was volatilized and dried. Next, a photomask having a predetermined pattern was disposed at a distance of 100 μm from the coating film, and the coating film was exposed through this photomask (exposure amount 150 mJ / cm ² ), and the exposed portion was photocured. Next, an unexposed part was 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 baked at 230 ° C. for 30 minutes. A predetermined pattern was formed.

<Confirmation of color resist (pigment type) and pattern>
The color resist (pigment type) and the pattern were confirmed for alkali developability, sensitivity, heat yellowing and solvent resistance.
(4) Evaluation of alkali developability Alkali developability was confirmed by the residue after alkali development and the development form.
The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The criteria for this evaluation are as follows.
○: No residue ×: Residue With respect to the development form, the removal form of the unexposed part by alkali development was visually evaluated. Here, in the development process of the negative resist, the uncured unexposed part is dissolved by the alkali developer and is detached from the substrate. However, as the development form, the part to be detached is mainly large. There are a peeling type that peels off as a lump and a dissolving type that gradually dissolves and diffuses. The former peeling type is not preferred because the lump becomes a foreign substance and remains in the system and easily contaminates other color pixels. That is, the latter dissolution type is preferable.
○: Dissolution type ×: Peeling type

(5) Evaluation of sensitivity For sensitivity, alkali development using the above spray was performed for 30 seconds, and the amount of decrease in pattern thickness before and after alkali development was measured. Since it can be said that the sensitivity of this pattern thickness is better as the amount of decrease is smaller, the criteria for this evaluation were as follows.
○: Less than 0.20 μm ×: 0.20 μm or more

(6) Evaluation of heat-resistant yellowing The heat-resistant yellowing was photocured in the same manner as above except that the entire film was exposed without using a photomask and the film thickness of the cured final coating was changed to 2.5 μm. The coating film formed in this manner was left in a dryer at 230 ° C. for 1 hour, and the coloring of the coating film before and after the heat treatment was compared with a color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. The criteria for this evaluation are as follows.
○: ΔE ^* ab is less than 0.3 ×: ΔE ^* ab is 0.3 or more

(7) Evaluation of solvent resistance Solvent resistance is obtained by using a coating film prepared in the same manner as the heat-resistant yellowing evaluation sample, putting 200 mL of n-methyl-2-pyrrolidone in a 500 mL lidded glass bottle, After dipping the pattern sample, the color change after 1 hour at 23 ° C. was measured with a spectrophotometer UV-1650PC manufactured by Shimadzu Corporation. The criteria for this evaluation are as follows.
○: ΔE ^* ab is less than 0.3 ×: ΔE ^* ab is 0.3 or more Table 3 shows the evaluation results of the above alkali developability, sensitivity, heat yellowing resistance, and solvent resistance.

  As can be seen from the results in Table 3, the color resists (pigment types) of Examples 10 to 18 had good alkali developability and sensitivity, and gave a pattern excellent in heat yellowing and solvent resistance. The color resists (pigment types) of Comparative Examples 3 to 4 gave a pattern with poor alkali developability and sensitivity and insufficient heat yellowing or solvent resistance.

<Preparation of color resist (dye type)>
Dye (acid green 3), sample no. A photosensitive resin composition was prepared by mixing 1 to 11 and other components, and a color resist (dye type) was prepared using this composition (Examples 19 to 27 and Comparative Examples 5 to 6). . Table 4 shows the blending components and blending amounts of this color resist (dye type).

<Pattern formation with 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 the color resist (dye type) was used.
<Evaluation of color resist (dye type) and pattern>
Alkali developability, sensitivity, heat yellowing resistance, and solvent resistance were evaluated in the same manner as the color resist (pigment type).
Table 5 shows the evaluation results of the alkali developability, sensitivity, heat-resistant yellowing and solvent resistance.

  As can be seen from the results in Table 5, the color resists (dye types) of Examples 19 to 27 had good alkali developability and sensitivity and gave a pattern excellent in solvent resistance, whereas Comparative Examples 5 to The color resist (dye type) of No. 6 gave a pattern with poor alkali developability and sensitivity and insufficient heat-resistant yellowing or solvent resistance.

  As can be seen from the above results, according to the present invention, there is provided a photosensitive resin composition that has a good sensitivity and developability and gives a colored pattern excellent in heat decomposition resistance, heat yellowing resistance and solvent resistance. be able to. Moreover, according to this invention, the color filter which has a coloring pattern excellent in heat-resistant decomposability and heat-resistant yellowing can be provided.

  1 substrate, 2 pixels, 3 black matrix, 4 protective film.

Claims (11)

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 chemical formula (1) and the following chemical formula (2) And a radically polymerizable monomer (a-3) having an ethylenically unsaturated group, and having a weight average molecular weight (polystyrene equivalent weight average molecular weight) of 1,000 to 1,000. Copolymer (A) which is 50,000 , further contains a carboxyl group, and has an acid value of 20 to 300 KOHmg / g .

(X and Y 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 carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may have a cyclic structure connecting R ¹ and R ^2. )

(R ³ in the formula (2) is a hydrogen atom or a methyl group, and n represents an integer of 1 to 4.) The copolymer (A) according to claim 1, which contains an unsaturated group. The polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl ( The copolymer (A) according to claim 1 or 2 , comprising at least one selected from (meth) acrylates. The polymerizable monomer (a-1) and / or (a-1 ′) is 2 to 50% in molar ratio, the polymerizable monomer (a-2) is 10 to 80%, the polymerizable monomer (a-3 The copolymer (A) according to any one of claims 1 to 3 , wherein 18) to 88% are polymerized. The said polymerizable monomer (a-3) is 1 type, or 2 or more types selected from unsaturated monobasic acid, unsaturated polybasic acid anhydride, or glycidyl (meth) acrylate of Claims 1-4. The copolymer (A) according to any one of the above. The resin composition containing the copolymer (A) and solvent (B) of any one of Claims 1-5 . The resin composition according to claim 6, further comprising a reactive diluent (C). The photosensitive resin composition containing the copolymer (A) of any one of Claims 1-5 , a solvent (B), a reactive diluent (C), and a photoinitiator (D). Furthermore, the photosensitive resin composition of Claim 8 containing the coloring agent (E) which consists of dye and / or a pigment. The photosensitive resin composition of Claim 9 which is a photosensitive resin composition for color filters. The color filter formed by hardening | curing the resist coating film containing the photosensitive resin composition of Claim 10 .

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