JP7318533B2 - Photosensitive resin composition for color filter, color filter, image display device, and method for producing color filter - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition for color filters, a color filter, an image display element having the same, and a method for producing a color filter.

In recent years, from the viewpoint of saving resources and energy, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams are widely used in various fields such as coatings, printing, paints, and adhesives. Also in the field of electronic materials such as printed wiring boards, photosensitive resin compositions curable by active energy rays are used for solder resists, color filter resists, and the like. Furthermore, the properties required for curable photosensitive resin compositions are becoming more and more diverse and sophisticated. is required.

A 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 boundaries of the pixels, It is composed of pixels and a protective film formed on the black matrix. A color filter having such a structure is generally manufactured by sequentially forming a black matrix, pixels and a protective film on a transparent substrate. Various methods have been proposed as methods for forming pixels and black matrices (pixels and black matrices are hereinafter referred to as “coloring patterns”). Among them, the pigment / dye dispersion method, which uses a photosensitive resin composition as a resist and is produced by a photolithography method that repeats coating, exposure, development and baking, has excellent durability and has few defects such as pinholes. It is the current mainstream because it gives a pattern.

Generally, a photosensitive resin composition used in photolithography contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a coloring agent and a solvent. The pigment/dye dispersion method has the above advantages, but on the other hand, since the black matrix, R, G, and B patterns are repeatedly formed, high heat resistance is required, and it is a coloring agent that can withstand high baking temperatures. However, limitations such as limited types of colorants that can be used are often problematic.

Patent Document 1 discloses that low-temperature curing is possible by using an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a radiation-sensitive polymerization initiator, a coloring agent, and a compound such as ethyl 3-aminobenzenesulfonate. A coloring composition with improved storage stability is disclosed.

Patent Document 2 describes a polymer precursor whose reaction to the final product is promoted by a basic substance or by heating in the presence of a basic substance, and a specific base generator that generates a base by irradiation with electromagnetic waves and heating. Low-temperature curing is made possible by using a photosensitive resin composition containing an agent.

JP 2013-68843 A JP 2014-70148 A

In recent years, flexible displays such as electronic paper have become popular. As a substrate for this flexible display, a plastic substrate such as polyethylene terephthalate is being studied. This substrate has the property of stretching or shrinking during baking, and it is necessary to lower the temperature of the baking process. However, the levels achieved in US Pat. Moreover, in Patent Document 2, although the low-temperature curability is improved, the storage stability is low, and it is difficult to put it into practical use.

The present invention has been made to solve the above problems, and provides a colored pattern having good developability and storage stability and excellent solvent resistance even when cured at a low temperature of about 100 ° C. An object of the present invention is to provide a photosensitive resin composition for color filters and a copolymer useful for preparing the photosensitive resin composition.
Another object of the present invention is to provide a color filter having a colored pattern with excellent solvent resistance, a method for producing the same, and an image display device having the color filter.

That is, the present invention is represented by the following [1] to [16].
[1] A copolymer (A) containing a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, and a compound (B) that generates an acid by heat and/or ultraviolet irradiation. , a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F).
[2] The photosensitive resin composition for color filters according to [1], wherein the structural unit (a) having an acid group is a structural unit derived from a carboxy group-containing ethylenically unsaturated compound.
[3] The structural unit (b) having a cyclic ether group is a structural unit derived from at least one selected from the group consisting of epoxy group-containing (meth)acrylates and oxetanyl group-containing (meth)acrylates [1] Or the photosensitive resin composition for color filters according to [2].
[4] The ratio of the structural unit (a) having the acid group contained in the copolymer (A) is 5 mol% to 40 mol%, and the structural unit (b) having the cyclic ether group The photosensitive resin composition for color filters according to any one of [1] to [3], wherein the proportion is 60 mol % to 95 mol %.
[5] The color filter according to any one of [1] to [3], wherein the copolymer (A) further contains a structural unit (c) derived from a radically polymerizable compound having an ethylenically unsaturated group. Photosensitive resin composition for
[6] The proportion of the structural unit (a) having an acid group contained in the copolymer (A) is 5 mol% to 60 mol%, and the proportion of the structural unit (b) having a cyclic ether group is 5 mol% to 70 mol%, and the proportion of the structural unit (c) derived from the radically polymerizable compound having an ethylenically unsaturated group is more than 0 mol% to 80 mol%. A photosensitive resin composition for a color filter.
[7] The photosensitive resin composition for color filters according to any one of [1] to [6], wherein the acid group of the structural unit (a) having an acid group is a carboxy group.
[8] The cyclic ether group of the structural unit (b) having a cyclic ether group is at least one selected from the group consisting of an epoxy group and an oxetanyl group, according to any one of [1] to [7]. A photosensitive resin composition for color filters.
[9] Polymerizability in which the compound (B) that generates an acid by heat and/or ultraviolet irradiation gives the structural unit (b) having the cyclic ether group used in synthesizing the copolymer (A) The photosensitive resin composition for color filters according to any one of [1] to [8], which is 0.05 parts by mass to 20 parts by mass with respect to 100 parts by mass of the monomer.
[10] The photosensitive resin composition for color filters according to any one of [1] to [9], wherein the compound (B) that generates an acid by heat and/or ultraviolet irradiation is a sulfonium salt.
[11] The color filter according to any one of [1] to [10], wherein the copolymer (A) has a weight average molecular weight of 1,000 to 50,000 and an acid value of 20 to 300 KOHmg/g. Photosensitive resin composition for
[12] The photosensitive resin composition for color filters according to any one of [1] to [11], wherein the coloring agent (F) contains a pigment.
[13] When the total amount of the components excluding the solvent (C) in the color filter photosensitive resin composition is 100% by mass, the copolymer (A) and the heat and / or ultraviolet irradiation are subjected to acid 1% by mass to 50% by mass of the compound (B) that generates the reactive diluent (D) is 1% by mass to 60% by mass, and the photopolymerization initiator (E) is 0.01% by mass. 15% by mass, the coloring agent (F) is 20% by mass to 80% by mass, and the total of the components excluding the solvent (C) in the color filter photosensitive resin composition is 100 parts by mass. 2. The photosensitive resin composition for color filters according to any one of [1] to [12], wherein the solvent (C) is 10 parts by mass to 800 parts by mass.

[14] A color filter comprising a colored pattern comprising a cured product of the photosensitive resin composition for a color filter according to any one of [1] to [13].

[15] An image display device comprising the color filter of [14].

[16] The photosensitive resin composition for color filters according to any one of [1] to [13] is applied to a substrate, exposed to light, alkali developed, and baked at a temperature of 150° C. or less to form a colored pattern. A method for manufacturing a color filter, comprising a step of forming.

According to the present invention, a photosensitive resin composition for a color filter which has good developability and storage stability and gives a colored pattern with excellent solvent resistance even when cured at a low temperature of about 100° C., and the photosensitive resin composition. It is possible to provide a copolymer useful for preparing a flexible resin composition.
Further, according to the present invention, it is possible to provide a color filter having a colored pattern with excellent solvent resistance, a method for producing the same, and an image display element having the color filter.

<Photosensitive resin composition for color filter>
The photosensitive resin composition for a color filter of the present invention comprises a copolymer (A) containing a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, and heat and/or ultraviolet irradiation. It contains a compound (B) that generates an acid by reaction, a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F).

<Copolymer (A)>
<Structural unit (a) having an acid group>
The structural unit (a) having an acid group contained in the copolymer (A) is a structural unit derived from an acid group-containing polymerizable monomer. The acid group includes a carboxy group (--COOH), a phospho group (--PO(OH) ₂ ), a sulfo group (--SO ₃ H) and the like. Among these, a carboxy group is preferable from the viewpoint of the ease of raw material availability and the solvent resistance when used in the production of color filters. Examples of the polymerizable monomer that provides the structural unit (a) having an acid group include (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth) ) carboxy group-containing ethylenically unsaturated compounds such as acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and 2-(meth)acryloyloxyethyl acid phosphate. These polymerizable monomers may be used alone or in combination of two or more. Among these, (meth)acrylic acid is preferable from the viewpoint of availability and reactivity. In addition, a structural unit is also called a monomer unit.

In the present invention, the inclusion of the structural unit (a) having an acid group in the copolymer (A) greatly improves alkali developability when the copolymer (A) is used as a photosensitive material.

When the copolymer (A) consists of a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, the structural unit (a) having an acid group contained in the copolymer (A) is preferably 5 mol % to 40 mol %, more preferably 10 mol % to 35 mol %, most preferably 15 mol % to 30 mol %. When the proportion of the structural unit (a) having an acid group is 5 mol % to 40 mol %, an appropriate alkali development rate can be obtained and a fine colored pattern can be formed.
When the copolymer (A) further contains another structural unit (c) described later, the proportion of the structural unit (a) having an acid group contained in the copolymer (A) is preferably 5 mol%. ~60 mol%, more preferably 8 mol% to 50 mol%, most preferably 10 mol% to 40 mol%. When the proportion of the structural unit (a) having an acid group is 5 mol % to 60 mol %, an appropriate alkali development rate can be obtained and a fine colored pattern can be formed.

<Structural unit (b) having a cyclic ether group>
The structural unit (b) having a cyclic ether group contained in the copolymer (A) is a structural unit derived from a cyclic ether group-containing polymerizable monomer (however, it corresponds to the structural unit (a) having an acid group except those that do). Cyclic ether groups include epoxy groups and oxetanyl groups. Specific examples of polymerizable monomers containing an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy group, and lactone adducts thereof (for example, Daicel Co., Ltd. Cychromer (registered trademark) A200, M100), 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate mono (meth) acrylic acid ester, dicyclopentenyl (meth) acrylate epoxide, di Examples thereof include epoxidized cyclopentenyloxyethyl (meth)acrylate. Among these, epoxy group-containing (meth)acrylates are preferred, and glycidyl (meth)acrylates are more preferred, from the viewpoint of availability and reactivity. Further, specific examples of polymerizable monomers having an oxetanyl group include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, 2-vinyl-2-methyloxetane and the like mentioned. Among these, oxetanyl group-containing (meth)acrylates are preferred, and (3-ethyloxetan-3-yl)methyl (meth)acrylate is more preferred, from the viewpoint of availability and reactivity. These polymerizable monomers may be used alone or in combination of two or more.

In the present invention, by including the structural unit (b) having a cyclic ether group in the copolymer (A), the solvent resistance when the copolymer (A) is used as a photosensitive material is greatly improved. .

When the copolymer (A) consists of a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, the structural unit (b) having a cyclic ether group contained in the copolymer (A) ) is preferably 60 mol % to 95 mol %, more preferably 65 mol % to 90 mol %, most preferably 70 mol % to 85 mol %. When the ratio of the structural unit (b) having a cyclic ether group is 60 mol % to 95 mol %, both the solvent resistance of the cured coating film and the storage stability of the copolymer (A) are achieved.
When the copolymer (A) further contains another structural unit (c) described later, the ratio of the structural unit (b) having a cyclic ether group contained in the copolymer (A) is preferably 5 mol. % to 70 mol %, more preferably 8 mol % to 60 mol %, most preferably 10 mol % to 50 mol %. When the ratio of the structural unit (b) having a cyclic ether group is 5 mol % to 70 mol %, both the solvent resistance of the cured coating film and the storage stability of the copolymer (A) are achieved.

<Other structural units (c)>
In the present invention, the copolymer (A) is a structural unit (c) other than the structural unit (a) having an acid group and the structural unit (b) having a cyclic ether group (however, the structural unit having an acid group ( It is also possible to contain a) and structural units (b) having a cyclic ether group). Polymerizable monomers that give other structural units (c) are generally radically polymerizable compounds having an ethylenically unsaturated group, examples of which include dienes such as butadiene; methyl (meth) acrylate, ethyl (meth) ) acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate , dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth) acrylates, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl ( meth) acrylate, glycerol mono (meth) acrylate, butanetriol mono (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) (Meth)acrylic acid esters such as acrylates; norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4 .0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]dec-8-ene, tetracyclo[4.4.0.1 ^2,5 . ^17,10 . 0 ^1,6 ]dodeca-3-ene, pentacyclo[6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]pentadeca-4-ene, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, (meth)acrylic acid amide, (meth)acrylic acid N,N - (meth)acrylic acid amides, such as dimethylamide, (meth)acrylic anthracenylamide, N-isopropyl (meth)acrylamide, (meth)acrylmorpholine, diacetone (meth)acrylamide; (meth)acrylic acid Vinyl compounds such as anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene; styrene, styrene α-, o-, m- , p-alkyl, nitro, cyano, amide derivatives; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, monomaleimides such as N-(4-hydroxyphenyl)maleimide; and unsaturated polybasic acid anhydrides such as maleic anhydride and itaconic anhydride. These radically polymerizable compounds having an ethylenically unsaturated group may be used alone or in combination of two or more. Among these, from the viewpoint of heat resistance and transparency, methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, styrene, vinyl toluene, isobornyl (meth) acrylate, adamantyl (meth) acrylate , norbornene, N-isopropyl (meth)acrylamide, (meth)acrylmorpholine and diacetone (meth)acrylamide are preferred, methyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, Vinyl toluene, isobornyl (meth)acrylate, adamantyl (meth)acrylate and norbornene are more preferred.

The ratio of other structural units (c) contained in the copolymer (A) is not particularly limited, but is preferably more than 0 mol% to 80 mol%, more preferably 5 mol% to 70 mol%, most It is preferably 10 mol % to 60 mol %. In the present invention, the other structural unit (c) is not essential, but by containing the other structural unit (c) in the copolymer (A), the solvent resistance and the properties of the coating film can be appropriately improved. can be done.

In this specification, the notation of (meth)acrylate means either acrylate or methacrylate, and the notation of (meth)acrylic acid refers to either acrylic acid or methacrylic acid. It means that it is okay.

<Method for producing copolymer (A)>
Acid group-containing polymerization that gives the structural unit (a) having an acid group used in the production of a copolymer (A) consisting of a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group The ratio of the cyclic ether group-containing polymerizable monomer (b0) that gives the structural unit (b) having a cyclic ether group and the cyclic ether group-containing polymerizable monomer (a0) is not particularly limited, but preferably (a0) is 5 mol% to 40 mol. % and (b0) 60 mol % to 95 mol %, more preferably (a0) 10 mol % to 35 mol % and (b0) 65 mol % to 90 mol %, most preferably (a0) 15 mol % to 30 mol % and (b0) 70 mol % to 85 mol %.
Structural unit having an acid group ( an acid group-containing polymerizable monomer (a0) that gives a), a cyclic ether group-containing polymerizable monomer (b0) that gives a structural unit (b) having a cyclic ether group, and a polymerizable monomer that gives another structural unit (c) ( The proportion of c0) is not particularly limited, but is preferably (a0) 5 mol% to 60 mol%, (b0) 5 mol% to 70 mol% and (c0) more than 0 mol% to 80 mol%, and more Preferably (a0) 8 mol % to 50 mol %, (b0) 8 mol % to 60 mol % and (c0) 5 mol % to 70 mol %, most preferably (a0) 10 mol % to 40 mol % , (b0) 10 mol % to 50 mol % and (c0) 10 mol % to 60 mol %.

The copolymerization reaction of the acid group-containing polymerizable monomer (a0), the cyclic ether group-containing polymerizable monomer (b0), and the polymerizable monomer (c0) to give the other structural unit (c) is a known radical polymerization reaction in the art. It can be carried out in the presence or absence of a polymerization solvent according to the method. For example, after dissolving these polymerizable monomers in a solvent as desired, a polymerization initiator is added to the solution, and the polymerization reaction is carried out at 50° C. to 130° C. for 1 hour to 20 hours.

The solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inert to the reaction. - n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, (Poly)alkylene glycol monoalkyl ethers such as dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene (Poly)alkylene glycol monoalkyl ether acetates such as glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran ; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropion ethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3 -methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetic acid n-amyl, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate , Esters such as ethyl acetoacetate and ethyl 2-oxobutyrate; Aromatic hydrocarbons such as toluene and xylene; Carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide ; diethylene glycol and the like can be mentioned. These solvents may be used alone or in combination of two or more.

Among these solvents, ether-based solvents are preferable because they can be used as the component (C) of the photosensitive resin composition for color filters of the present invention without removing the solvent after the copolymerization reaction is completed. , propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether and ethylene glycol monomethyl ether are more preferred.

The amount of the solvent used in the copolymerization reaction is not particularly limited. 800 parts by mass. In particular, by setting the amount of the solvent to 1,000 parts by mass or less, the decrease in the molecular weight of the copolymer (A) due to the chain transfer effect is suppressed, and the viscosity of the copolymer (A) is controlled within an appropriate range. can do. In addition, by setting the 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 coloring and gelation of the copolymer (A) can be prevented. can also

Further, the radical polymerization initiator that can be used in this copolymerization reaction is not particularly limited, but examples thereof include azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), and the like. Examples include azo radical polymerization initiators, organic peroxide radical polymerization initiators such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. These radical polymerization initiators may be used alone or in combination of two or more. The amount of the radical polymerization initiator used is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, when the total amount of polymerizable monomers charged is 100 parts by mass. be.

The polystyrene equivalent weight average molecular weight of the copolymer (A) is preferably from 1,000 to 50,000, more preferably from 3,000 to 40,000. When the weight average molecular weight of the copolymer (A) is 1,000 or more, chipping of the colored pattern is less likely to occur after alkali development when used as a photosensitive resin composition. On the other hand, when the weight-average molecular weight of the copolymer (A) is 50,000 or less, the development time becomes appropriate and practicality is ensured.

The acid value (JIS K6901 5.3) of the copolymer (A) is preferably 20 mg KOH/g to 300 mg KOH/g, more preferably 30 mg KOH/g to 200 mg KOH/g. When the acid value of the copolymer (A) is 20 KOHmg/g or more, the alkali developability of the photosensitive resin composition for color filters is improved. On the other hand, when the acid value of the copolymer (A) is 300 KOHmg/g or less, the exposed portion (photocured portion) is difficult to dissolve in an alkaline developer, resulting in a favorable pattern shape.

Furthermore, the cyclic ether group equivalent of copolymer (A) is not particularly limited, but is usually 200 g/mol to 2,000 g/mol, preferably 300 g/mol to 1,500 g/mol, more preferably 480 g/mol. It ranges from ~900 g/mol. When the cyclic ether group equivalent of the copolymer (A) is 200 g/mol or more, the stability becomes good. On the other hand, when the cyclic ether group equivalent of the copolymer (A) is 2,000 g/mol or less, the solvent resistance is sufficiently ensured. The cyclic ether group equivalent is the mass of the polymer per mole of the cyclic ether group of the polymer, and can be obtained by dividing the mass of the polymer by the amount of the cyclic ether group of the polymer ( g/mol). In the present invention, the cyclic ether group equivalent of the copolymer (A) is a theoretical value calculated from the charged amount of the polymerizable monomer.

<Compound (B) that generates an acid by heat and/or ultraviolet irradiation>
Hereinafter, the compound that generates acid by heat is abbreviated as "(B-1) thermal acid generator", and the compound that generates acid by UV irradiation is abbreviated as "(B-2) photoacid generator". There is The (B-1) thermal acid generator and (B-2) photoacid generator are not particularly limited as long as they can generate an acid by heat and/or ultraviolet irradiation. Examples include iodonium salts, Onium salts such as sulfonium salts, phosphonium salts and diazonium salts can be mentioned, with sulfonium salts being preferred. Among these, TA-100 and TA-120 manufactured by San-Apro Co., Ltd. are preferable as the thermal acid generator (B-1), which generates an acid when heated at 100° C. or more and is available. In addition, (B-2) photoacid generators are preferably triarylsulfonium salt-based photoacid generators with few impurities and high sensitivity to i-line. CPI-300 series and CPI-400 series are more preferred. These (B-1) thermal acid generator and (B-2) photoacid generator may be used alone or in combination of two or more.

The compounding amount of the compound (B) that generates an acid by heat and/or ultraviolet irradiation is the polymerizable monomer (b0 ) With respect to 100 parts by mass, it is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and 1 to 10 parts by mass. Most preferred. When the compounding amount of the compound (B) is 0.05 parts by mass or more, the curing reaction of the photosensitive resin composition proceeds easily. On the other hand, when the compounding amount of the compound (B) is 20 parts by mass or less, the storage stability of the photosensitive resin composition is enhanced.
The total sum of the copolymer (A) and the compound (B) that generates an acid by heat and/or ultraviolet irradiation is 100% by mass of the total of the components excluding the solvent (C) in the photosensitive resin composition for color filters. , the content is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and most preferably 10% by mass to 30% by mass. When the amount is within this range, the solvent resistance of the cured coating film can be improved and the storage stability can be maintained.

<Solvent (C)>
The photosensitive resin composition for a color filter of the present invention can be prepared by appropriately mixing a desired solvent (C) with the copolymer (A) isolated from the copolymerization reaction system, but the copolymer It is not necessary to isolate (A), and the solvent contained at the end of the copolymerization reaction can be used as it is as solvent (C), and a desired solvent can be added as necessary. can. Moreover, the solvent contained in the other component used when preparing the photosensitive resin composition for color filters can also be used as a solvent (C).

The amount of the solvent (C) compounded is generally 10 parts by mass to 800 parts by mass, preferably 100 parts by mass, when the total of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 parts by mass. It is 50 parts by mass to 500 parts by mass, more preferably 100 parts by mass to 300 parts by mass. A blending amount within this range results in a photosensitive resin composition for a color filter having an appropriate viscosity.

<Reactive diluent (D)>
The reactive diluent (D) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule, preferably a compound having a plurality of polymerizable functional groups. By including the reactive diluent (D) in the photosensitive resin composition for color filters, the strength of the cured product formed and the adhesion to the substrate are improved.

Monofunctional monomers used as reactive diluents (D) include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy Methyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) Acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth)acrylate, tetrahydrofurfuryl (meth)acrylate ) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid derivative half (meth) acrylate, etc. (meth)acrylates; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene and vinyltoluene; carboxylic acid esters such as vinyl acetate and vinyl propionate; Moreover, these monomers may be used alone or in combination of two or more.

Polyfunctional monomers used as reactive diluents (D) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and polypropylene glycol. Di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate acrylates, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydi ethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth) acrylates, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e. tolylene diisocyanate), Reaction products of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, etc., and 2-hydroxyethyl (meth)acrylate, (meth)acrylates such as tris(hydroxyethyl)isocyanurate tri(meth)acrylate; divinylbenzene, diallyl phthalate, diallyl Aromatic vinyl compounds such as benzene phosphonate; Dicarboxylic acid esters such as divinyl adipate; and condensates of. These monomers may be used alone or in combination of two or more.

The amount of the reactive diluent (D) compounded is generally 1% by mass to 60% by mass when the total amount of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100% by mass. , preferably 5% to 50% by mass, more preferably 10% to 40% by mass. If it is the compounding quantity of this range, it will have a suitable viscosity and photocurability as a photosensitive resin composition for color filters.

<Photoinitiator (E)>
Examples of the photopolymerization initiator (E) include, but are not limited to, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; -dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2 - acetophenones such as dimethylamino-1-(4-morpholinophenyl)butanone-1; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, 4-(1-t-butyldioxy-1-methylethyl ) benzophenone, benzophenones such as 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone; acylphosphine oxides; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(0-benzoyloxime)] and other oxime esters. These photoinitiators (E) may be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator (E) is generally 0.01% by mass to 15% by mass when the sum of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100% by mass. , preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass. If it is the compounding quantity of this range, it will become the photosensitive resin composition for color filters which has suitable photocurability.

In addition to the above components, the photosensitive resin composition for color filters of the present invention contains known additives such as known coupling agents, leveling agents, and thermal polymerization inhibitors in order to impart predetermined properties. You may The blending amount of these additives is not particularly limited as long as it does not impair the effects of the present invention.

<Colorant (F)>
The coloring agent (F) is not particularly limited as long as it dissolves or disperses in the solvent (C), and examples thereof include dyes and pigments. As the dye, from the viewpoint of solubility in the solvent (C) and alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., acidic dyes having an acidic group such as carboxylic acid and sulfonic acid It is preferable to use a dye, a salt of an acid dye with a nitrogen compound, a sulfonamide of an acid 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 chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; 56, 63, 74, 95; , 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, azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferred. These dyes may be used alone or in combination of two or more depending on the desired pixel color.

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, 147, 148, 150, 153, 154, 166, 173, 194, 214; C.I. I. C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I. red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60; C.I. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. I. Green pigments such as Pigment Green 7, 36, 58, 59; C.I. I. Brown pigments such as Pigment Brown 23, 25; C.I. I. Pigment Black 1, 7, carbon black, titanium black, black pigments such as iron oxide, and the like. These pigments may be used alone or in combination of two or more, depending on the desired pixel color.

As the colorant (F), the above dyes and pigments can be used in combination depending on the desired pixel color.

When a pigment is used as the colorant (F), a known dispersant may be added to the photosensitive resin composition for color filters from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant that exhibits excellent dispersion stability over time. Examples of polymeric dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified esters. system dispersants and the like. Such polymeric dispersants are commercially available under trade names such as EFKA (manufactured by EFKA Chemicals B.V. (EFKA)), Disperbyk (manufactured by BYK-Chemie), Disparlon (manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (manufactured by Zeneca). You can use what is provided. The blending amount of the dispersant may be appropriately set according to the type of pigment used.
The content of the coloring agent (F) is appropriately adjusted depending on the dye and pigment used. It is preferably 20% to 80% by mass, more preferably 30% to 75% by mass, and most preferably 40% to 70% by mass. If it is the compounding quantity of this range, it will become the photosensitive resin composition for color filters which has suitable photocurability.

The copolymer (A) in the photosensitive resin composition for color filters, the compound (B) that generates an acid upon exposure to heat and/or ultraviolet rays, the solvent (C), the reactive diluent (D), the photopolymerization initiator ( E) and the amount of the colorant (F) to be blended is the amount of the copolymer (A) and heat and / Or the sum of the compound (B) that generates an acid by ultraviolet irradiation is 1% to 50% by mass, the reactive diluent (D) is 1% to 60% by mass, and the photoinitiator (E) is 0 .01% by mass to 15% by mass, the colorant (F) is 20% by mass to 80% by mass, and the total amount of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 parts by mass. Sometimes the solvent (C) is 10 parts by mass to 800 parts by mass, and the compounding amount of the compound (B) that generates an acid by heat and / or ultraviolet irradiation is used when synthesizing the copolymer (A). 0.05 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer (b0) that gives the structural unit (b) having a cyclic ether group. Preferably, when the total amount of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100% by mass, the copolymer (A) and a compound that generates an acid by heat and/or ultraviolet irradiation. (B) is 5% to 40% by mass, the reactive diluent (D) is 5% to 50% by mass, the photopolymerization initiator (E) is 0.05% to 10% by mass, coloring The agent (F) is 30% by mass to 75% by mass, and the solvent (C) is 50 parts by mass when the total of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 parts by mass. 500 parts by mass, and the compounding amount of the compound (B) that generates an acid by heat and/or ultraviolet irradiation is 0.1 parts by mass to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer (b0). be. More preferably, when the total amount of components excluding the solvent (C) in the photosensitive resin composition for color filters is 100% by mass, the copolymer (A) and heat and/or ultraviolet irradiation generate an acid. 10% to 30% by mass of the total amount of the compound (B), 10% to 40% by mass of the reactive diluent (D), 0.1% to 5% by mass of the photopolymerization initiator (E), The colorant (F) is 40% by mass to 70% by mass, and the solvent (C) is 100% by mass when the total of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 parts by mass. parts to 300 parts by mass, and the amount of the compound (B) that generates an acid by heat and/or ultraviolet irradiation is 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer (b0). . A blending amount within this range results in a photosensitive resin composition for a color filter having an appropriate viscosity. In addition, even in the case of a photosensitive resin composition that does not contain a coloring agent (F), the copolymer (A), the compound (B) that generates an acid by heat and/or ultraviolet irradiation, the solvent (C), the reactive dilution The amounts of the agent (D) and the photopolymerization initiator (E) are applicable within the above numerical range, and can be used for various coatings, adhesives, binders for printing inks, and the like.

<Production of photosensitive resin composition for color filter>
The photosensitive resin composition for color filters of the present invention can be produced by mixing the above components using a known mixing device. Further, if desired, after preparing a polymer composition containing the copolymer (A), the compound (B) that generates an acid by heat and/or ultraviolet irradiation, and the solvent (C), a reactive diluent ( D), a photopolymerization initiator (E) and a colorant (F) can also be mixed for production.

Since the photosensitive resin composition for color filters obtained as described above has alkali developability, it is suitable as a resist. Curing of the photosensitive resin composition for color filters may be performed by appropriately selecting a baking temperature within the range of 250° C. or less, and the copolymer (A) used in the present invention has excellent curability at low temperatures. , the baking temperature can be lowered compared to conventional materials. When a pigment is used as the colorant (F) in the photosensitive resin composition for color filters, curing proceeds sufficiently even at a baking temperature of 150° C. or lower. The photosensitive resin composition for color filters of the present invention is advantageous in terms of energy consumption because the crosslinking reaction proceeds sufficiently even at a low baking temperature. In addition, even a coloring agent (F) or a substrate having poor heat resistance can be used, the original properties of the coloring agent can be obtained, and application to various substrates becomes possible. From this point of view, the baking temperature is preferably 80°C to 210°C, more preferably 90°C to 180°C, and most preferably 100°C to 150°C. If the baking temperature is too low, it will be difficult to sufficiently improve the solvent resistance of the coating film. Also, the baking time can be selected as appropriate, but it is usually 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

The photosensitive resin composition for color filters of the present invention is suitable as a resist used for producing color filters incorporated in organic EL displays, liquid crystal displays, solid-state imaging devices such as CCDs and CMOSs, and the like.

INDUSTRIAL APPLICABILITY The photosensitive resin composition for color filters of the present invention has good developability and storage stability, and can form a colored pattern with excellent solvent resistance even if the baking temperature during pattern formation is lowered. Therefore, it is extremely useful as a photosensitive material for color filters. In addition, the photosensitive resin composition for color filters of the present invention can contribute to the development of flexible displays, the reduction of energy consumption in the manufacturing process, and the relaxation of restrictions on the colorants used as a result of low-temperature curing.

<Color filter>
Next, a color filter having a colored pattern made of a cured product of the photosensitive resin composition for color filters of the present invention will be described. The color filter of the present invention has a colored pattern formed using the above photosensitive resin composition for color filters. A color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix formed at the boundaries of each pixel, and a protective film formed over the pixels and the black matrix. In this configuration, one or more colored patterns selected from R, G and B and a black matrix (colored pattern) constituting pixels are formed using the above photosensitive resin composition for a color filter. Except for this, other configurations can employ known ones.

Next, an embodiment of a method for manufacturing a color filter will be described. First, a colored pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, printed wiring substrates, array substrates, etc. can be used as appropriate. can.

A colored pattern can be formed by a photolithographic method. Specifically, after the above photosensitive resin composition for a color filter is coated on a substrate to form a coating film, the coating film is exposed through a photomask having a predetermined pattern, and the exposed portion is photocured. . By developing the unexposed portion with an alkaline aqueous solution and then baking, a predetermined colored pattern can be formed.

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

Then, the formed coating film is partially exposed by irradiation with active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The energy dose to be irradiated may be appropriately selected according to the composition of the photosensitive resin composition for color filters, and is preferably, for example, 30 mJ/cm ² to 2000 mJ/cm ² . The light source used for exposure is not particularly limited, but low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like can be used.

The alkaline aqueous solution used for development is not particularly limited, but aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; methylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl- p-Phenylenediamines such as N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates An aqueous solution of the base compound or the like can be used. In addition, you may add a defoaming agent and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash with water and dry after the development with the above alkaline aqueous solution.

Baking conditions are not particularly limited, and heat treatment may be performed according to the composition of the photosensitive resin composition for color filters to be used. In conventional photosensitive resin compositions, when the baking temperature is 200° C. or lower, the solvent resistance of the colored pattern is insufficient. Even if it is, a colored pattern showing sufficient solvent resistance can be formed. Therefore, the baking temperature can be lowered, and when baking at a high temperature, the processing time can be shortened, which is a great advantage in manufacturing. From this point of view, the baking temperature is usually 210° C. or less, preferably 180° C. or less, more preferably 150° C. or less, most preferably 120° C. or less, and the baking time is usually 10 minutes to 4 hours, preferably is performed for 20 minutes to 2 hours.

By sequentially repeating the coating, exposure, development and baking as described above using the photosensitive resin composition for the black matrix of the color filter and the photosensitive resin composition for the red, green and blue pixels of the color filter, A desired colored pattern can be formed. In the above, the method for forming a colored pattern by photocuring was described, but instead of the photopolymerization initiator (E), if a photosensitive resin composition containing a curing accelerator and a known epoxy resin is used, inkjet A desired colored pattern can also be formed by heating after application by a method. Finally, a protective film is formed on the colored patterns (RGB pixels and black matrix). The protective film is not particularly limited, and may be formed using a known film.

The color filter produced in this way is produced using a photosensitive resin composition for color filters that gives a colored pattern with excellent sensitivity and developability and excellent solvent resistance, so it is excellent with little color change. It has a colored pattern.

<Image display device>
The image display device of the present invention is an image display device equipped with the color filter described above, and specific examples include a liquid crystal display device, an organic EL display device, a solid-state imaging device such as a CCD device and a CMOS device, and the like. The image display device of the present invention may be produced in accordance with conventional methods except for using the color filter described above. For example, when manufacturing a liquid crystal display device, the above color filter is formed on a substrate, and then electrodes, spacers and the like are sequentially formed. Then, an electrode or the like is formed on another substrate, the two substrates are pasted together, a predetermined amount of liquid crystal is injected, and the substrate is sealed.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited by these examples. In the examples, all parts and percentages are based on mass unless otherwise specified. Moreover, the methods for measuring the acid value and the weight average molecular weight are as follows.
(1) Acid value: Acid value of copolymer (A) measured according to JIS K6901 5.3, water required to neutralize acidic components contained in 1 g of copolymer (A) It means the number of mg of potassium oxide.
(2) The weight average molecular weight (Mw) means the standard polystyrene equivalent weight average molecular weight measured under the following conditions using gel permeation chromatography (GPC).
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko K.K.)
Column temperature: 40°C
Sample: 0.2% tetrahydrofuran solution of copolymer Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showdex RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1 mL/min

[Synthesis Example 1]
After putting 175.5 g of propylene glycol monomethyl ether into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, the mixture was stirred under nitrogen substitution and heated to 78°C. Next, from 128.9 g of (3-ethyloxetan-3-yl)methyl methacrylate as a cyclic ether group-containing polymerizable monomer (b0) and 25.8 g of methacrylic acid as an acid group-containing polymerizable monomer (a0) A monomer mixture and 13.9 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (radical polymerization initiator) were added and dissolved in 54.3 g of propylene glycol monomethyl ether, respectively. Dropped into the flask from the dropping funnel. After completion of dropping, 10.3 g of propylene glycol monomethyl ether is added and stirred at 78° C. for 3 hours to carry out a copolymerization reaction to produce a copolymer. Finally, CPI-210S manufactured by San-Apro Co., Ltd. 1 part by mass was added to 100 parts by mass of the ether group-containing polymerizable monomer (b0) to obtain sample No. A polymer composition No. 1 (concentration of components other than the solvent: 35% by mass) was obtained. The obtained polymer composition was diluted about 100 times, and the weight average molecular weight of the copolymer in the polymer composition measured using the GPC was 6,800. The acid value of the copolymer in the polymer composition measured according to JIS K6901 5.3 was 120.5 KOHmg/g.

[Synthesis Examples 2 to 8 and Comparative Synthesis Examples 1 to 3]
A copolymerization reaction was carried out under the same conditions as in Synthesis Example 1 except that the starting materials shown in Tables 1 and 2 were used. Polymer compositions 2 to 11 (concentration of components other than solvent: 35% by mass) were obtained. However, since the cyclic ether group-containing polymerizable monomer (b0) is not added in Comparative Synthesis Example 2, the added amount of the compound (B) that generates acid by heat and/or ultraviolet irradiation is the same as in Synthesis Example 3 (sample The amount was the same as No. 3). Tables 1 and 2 show the weight-average molecular weight and acid value of the copolymer in the obtained polymer composition. Tables 1 and 2 also show the cyclic ether group equivalent calculated from the charged amount of the polymerizable monomer.

[Examples 1 to 8 and Comparative Examples 1 to 3]
<Preparation of photosensitive resin composition for color filter (pigment type)>
A C.I. 100 parts by mass of I Pigment Green 36 (colorant), 45 parts by mass of propylene glycol monomethyl ether acetate (solvent), and 25 parts by mass of Disperbyk-161 (dispersant) manufactured by Big Chemie Japan Co., Ltd. are added, and a paint shaker is used. A green pigment dispersion was prepared by mixing and dispersing for 2 hours.
This green pigment dispersion was mixed with a polymer composition, a reactive diluent, a photopolymerization initiator and a solvent to prepare a photosensitive resin composition for a color filter so that the blending amounts shown in Table 3 were obtained. In addition, the blending amount of the polymer composition in Table 3 excludes the solvent used in preparing the polymer composition (copolymer (A) and a compound that generates an acid by heat and / or ultraviolet irradiation (B)), and the blending amount of the solvent in Table 3 is used when preparing the propylene glycol monomethyl ether and the green pigment dispersion additionally blended with the solvent used when preparing the polymer composition It is the sum of the solvent used. As can be seen from the blending amounts in Table 3, when the sum of the components excluding the solvent (C) in the color filter photosensitive resin composition is 100% by mass, the copolymer (A) and heat and/or ultraviolet rays The total sum of the compound (B) that generates an acid upon irradiation is 24.4% by mass, the reactive diluent (D) is 24.4% by mass, the photopolymerization initiator (E) is 1.2% by mass, and the colorant (F) is 40.0% by mass, and the solvent (C) is 130.2 parts by mass when the total of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 parts by mass. be.
The photosensitive resin compositions for color filters of Examples 1 to 8 were sample Nos. 1 to 8, and the photosensitive resin compositions for color filters of Comparative Examples 1 to 3 were sample Nos. 1 to 8, respectively. 9-11 were prepared using each of the polymer compositions.

<Evaluation of photosensitive resin composition for color filter>
(1) Alkaline developability Each of the photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 3 was placed on a 5 cm square glass substrate (non-alkali glass substrate) to a thickness of 2 after exposure. After spin coating to a thickness of 0.5 μm, the solvent was volatilized by heating at 90° C. for 3 minutes. Next, a photomask with a predetermined pattern was placed at a distance of 100 μm from the coating film, and the coating film was exposed to light (exposure amount: 150 mJ/cm ² ) through this photomask to photocure the exposed portion. Next, an aqueous solution containing 0.1% by mass of sodium carbonate is sprayed at a temperature of 23° C. and a pressure of 0.3 MPa to dissolve and develop the unexposed portions, and then baked at 100° C. for 20 minutes. A predetermined pattern was formed. 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 present Table 4 shows the evaluation results of alkali developability.

(2) Evaluation of solvent resistance On a 5 cm square glass substrate (non-alkali glass substrate), each of the photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 3 was baked. After spin-coating to a thickness of 2.5 μm, the solvent was volatilized by heating at 90° C. for 3 minutes. Next, the coating film was exposed to light having a wavelength of 365 nm to photo-cure the exposed portion, and then left in a drying oven at a baking temperature of 100° C. for 20 minutes to prepare a cured coating film. 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL capacity glass bottle with a lid and allowed to stand at 80°C. After the test piece with the cured coating film was immersed therein, it was allowed to stand for 5 minutes while maintaining the temperature at 80°C. The color change (ΔE ^* ab) of the test piece before and after immersion in propylene glycol monomethyl ether acetate was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). Table 4 shows the measurement results of ΔE ^* ab. If ΔE ^* ab is 1.5 or less, it can be said that the solvent resistance is excellent.

(3) Evaluation of storage stability Equal amounts of the photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 3 were weighed into a glass container, and sealed with aluminum foil to prevent dust from entering. closed. Next, each of these samples was placed in a constant temperature chamber maintained at 23° C., and the weight average molecular weight (Mw) of the sample was measured after one month, and the storage stability was evaluated according to the following criteria.
Mw change rate (%) = 100 × (Mw before storage - Mw after storage) / Mw before storage
○: The rate of change in Mw after 1 month relative to Mw before storage is within ±20% ×: The rate of change in Mw after 1 month relative to Mw before storage is greater than ±20% Table 4 shows the storage stability evaluation results. show.

As shown in Table 4, the photosensitive resin compositions for color filters of Examples 1 to 8 were all excellent in alkali developability, solvent resistance and storage stability. In contrast, the photosensitive resin compositions for color filters of Comparative Examples 1 to 3 do not have sufficient solvent resistance, and the photosensitive resin composition for color filters of Comparative Example 3 has sufficient alkali developability. it wasn't

As can be seen from the above results, according to the present invention, it is possible to provide a photosensitive resin composition for color filters that has good developability and excellent solvent resistance and storage stability under low-temperature curing conditions. .

Claims (10)

A copolymer (A) consisting of a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, a compound (B) that generates an acid by heat and/or ultraviolet irradiation, and a solvent (C ), a reactive diluent (D), a photoinitiator (E), and a coloring agent (F),
The structural unit (b) having a cyclic ether group is a structural unit derived from glycidyl (meth)acrylate,
The ratio of the structural unit (a) having the acid group contained in the copolymer (A) is 5 mol% to 40 mol%, and the ratio of the structural unit (b) having the cyclic ether group is 60. mol% to 95 mol%,
100 masses of a polymerizable monomer in which the compound (B) that generates an acid by heat and/or ultraviolet irradiation provides the structural unit (b) having the cyclic ether group used in synthesizing the copolymer (A). 0.05 parts by mass to 20 parts by mass of the negative photosensitive resin composition for color filters. 2. The negative photosensitive resin composition for a color filter according to claim 1, wherein the structural unit (a) having an acid group is a structural unit derived from a carboxy group-containing ethylenically unsaturated compound. a copolymer (A) comprising a structural unit (a) having an acid group, a structural unit (b) having a cyclic ether group, and a structural unit (c) derived from a radically polymerizable compound having an ethylenically unsaturated group; Contains a compound (B) that generates an acid by heat and/or ultraviolet irradiation, a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F) ,
The structural unit (b) having a cyclic ether group is a structural unit derived from glycidyl (meth)acrylate,
The structural unit (c) derived from the radically polymerizable compound having an ethylenically unsaturated group is methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, styrene, vinyl toluene, isobornyl ( A structural unit derived from at least one selected from the group consisting of meth)acrylate, adamantyl (meth)acrylate and norbornene ,
The proportion of the structural unit (a) having the acid group contained in the copolymer (A) is 5 mol% to 60 mol%, and the proportion of the structural unit (b) having the cyclic ether group is 5 mol. % to 70 mol%, and the proportion of the structural unit (c) derived from the radical polymerizable compound having an ethylenically unsaturated group is more than 0 mol% to 80 mol%,
100 masses of a polymerizable monomer in which the compound (B) that generates an acid by heat and/or ultraviolet irradiation provides the structural unit (b) having the cyclic ether group used in synthesizing the copolymer (A). 0.05 parts by mass to 20 parts by mass of the negative photosensitive resin composition for color filters. 4. The negative photosensitive resin composition for color filters according to any one of claims 1 to 3, wherein the compound (B) that generates an acid by heat and/or ultraviolet irradiation is a sulfonium salt. 5. The negative type for color filters according to any one of claims 1 to 4, wherein the copolymer (A) has a weight average molecular weight of 1,000 to 50,000 and an acid value of 20 to 300 KOHmg/g. A photosensitive resin composition. The negative photosensitive resin composition for color filters according to any one of claims 1 to 5, wherein the colorant (F) contains a pigment. When the total amount of the components excluding the solvent (C) in the negative photosensitive resin composition for a color filter is 100% by mass, the copolymer (A) and the heat and / or ultraviolet irradiation to produce an acid The total amount of the generated compound (B) is 1% by mass to 50% by mass, the reactive diluent (D) is 1% by mass to 60% by mass, and the photopolymerization initiator (E) is 0.01% by mass to 15% by mass, the coloring agent (F) is 20% by mass to 80% by mass, and the total amount of the components excluding the solvent (C) in the negative photosensitive resin composition for a color filter is 100 parts by mass. The negative photosensitive resin composition for color filters according to any one of claims 1 to 6, wherein the solvent (C) is sometimes 10 parts by mass to 800 parts by mass. A color filter comprising a colored pattern comprising a cured product of the negative photosensitive resin composition for a color filter according to any one of claims 1 to 7. An image display device comprising the color filter according to claim 8 . The negative type photosensitive resin composition for color filters according to any one of claims 1 to 7 is applied to a substrate, exposed to light, alkali developed, and baked at a temperature of 150° C. or less to form a colored pattern. A method for manufacturing a color filter, comprising the step of: