KR20200091483A - Photosensitive resin composition for color filter, color filter, image display element, and manufacturing method of color filter - Google Patents

Abstract

A copolymer (A) containing a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, a compound (B) for generating an acid by heat and/or ultraviolet irradiation, and a solvent (C) ), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F).

Description

Photosensitive resin composition for color filter, color filter, image display element, and manufacturing method of color filter

The present invention relates to a photosensitive resin composition for color filters, a color filter, an image display element provided with the same, and a method for manufacturing a color filter.

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 various coating, printing, coating, and adhesive fields from the viewpoint of resource saving and energy saving. Further, 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. In addition, the required properties for the photosensitive resin composition that can be cured are increasingly diverse and high in degree. Among them, short-time curability in consideration of productivity and low-temperature curability that suppresses thermal damage of the applied member are required.

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, and It consists of a protective film formed on the black matrix. A color filter having such a configuration is usually produced by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. As a method of forming a pixel and a black matrix (hereinafter, a pixel and black matrix are referred to as "colored patterns"), various methods have been proposed. Among them, a pigment/dye dispersion method produced by a photolithography method that repeats coating, exposure, development and baking using a photosensitive resin composition as a resist provides excellent durability and provides a coloring pattern with few defects such as pinholes. Therefore, it has become the current mainstream.

Generally, the photosensitive resin composition used for the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. In the pigment/dye dispersion method, while having the above advantages, a high heat resistance is required in that it repeatedly forms a pattern of a black matrix, R, G, B, and a colorant that can be used as a colorant capable of withstanding high baking temperatures It is often a problem that there are limitations, such as the type of being limited.

Patent Literature 1 uses a compound such as an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a radiation-sensitive polymerization initiator, a colorant, and ethyl 3-aminobenzenesulfonate, which can be cured at a low temperature and improve storage stability. Coloring compositions are disclosed.

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

Japanese Patent Application Publication No. 2013-68843 Japanese Patent Application Publication No. 2014-70148

In recent years, flexible displays, such as electronic paper, have been popularized. As a substrate of this flexible display, plastic substrates such as polyethylene terephthalate have been studied. This substrate has a property of stretching or shrinking during baking, and it is necessary to lower the baking process. However, the level achieved in Patent Literature 1 is insufficient to satisfy the above requirements. Moreover, in patent document 2, while low-temperature hardenability was improved, storage stability was low, and practical use was difficult.

The present invention has been made to solve the above problems, and has good developability and storage stability, and a photosensitive resin composition for a color filter that provides a coloring pattern excellent in solvent resistance even when cured at a low temperature of around 100°C, and It is an object to provide a copolymer useful for preparing the photosensitive resin composition.

Moreover, an object of this invention is to provide the color filter which has a coloring pattern excellent in solvent resistance, its manufacturing method, and the image display element provided with 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) generating an acid by heat and/or ultraviolet irradiation, A photosensitive resin composition for a color filter, comprising a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F).

[2] The photosensitive resin composition for a color filter according to [1], wherein the structural unit (a) having the acid group is a structural unit derived from a carboxyl group-containing ethylenically unsaturated compound.

[3] The structural unit (b) having the cyclic ether group is a structural unit derived from at least one member selected from the group consisting of an epoxy group-containing (meth)acrylate and an oxetanyl group-containing (meth)acrylate [1] Or the photosensitive resin composition for color filters described in [2].

[4] The proportion of the structural unit (a) having the acid group contained in the copolymer (A) is 5 mol% to 40 mol%, and the proportion of the structural unit (b) having the cyclic ether group is 60 mol. The photosensitive resin composition for color filters according to any one of [1] to [3], which is% to 95 mol%.

[5] The photosensitive resin for color filters 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. Composition.

[6] 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% The photosensitive resin composition for color filters according to [5], wherein 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%.

[7] The photosensitive resin composition for a color filter according to any one of [1] to [6], wherein the acid group of the structural unit (a) having the acid group is a carboxy group.

[8] The photosensitive property for color filters according to any one of [1] to [7], wherein the cyclic ether group of the structural unit (b) having the cyclic ether group is at least one member selected from the group consisting of an epoxy group and an oxetanyl group. Resin composition.

[9] A polymerizable monomer that gives the structural unit (b) having the cyclic ether group used when synthesizing the copolymer (A) by the compound (B) generating an acid upon irradiation with heat and/or ultraviolet rays The photosensitive resin composition for color filters in any one of [1]-[8] which is 0.05 mass parts-20 mass parts with respect to 100 mass parts.

[10] The photosensitive resin composition for a color filter according to any one of [1] to [9], wherein the compound (B) that generates an acid by irradiation with heat and/or ultraviolet rays is a sulfonium salt.

[11] The photosensitive resin composition for a 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.

[12] The photosensitive resin composition for a color filter according to any one of [1] to [11], in which the coloring agent (F) contains a pigment.

[13] A compound which generates an acid by irradiation of the copolymer (A) and the heat and/or ultraviolet rays when the total sum of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100% by mass The sum of (B) is 1 mass% to 50 mass%, the reactive diluent (D) is 1 mass% to 60 mass%, the photopolymerization initiator (E) is 0.01 mass% to 15 mass%, and the colorant (F) is When the total amount of the components except for the solvent (C) in the photosensitive resin composition for color filters is 20 mass% to 80 mass%, the solvent (C) is 10 mass parts to 800 mass parts [1] -The photosensitive resin composition for color filters in any one of [12].

[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 element comprising the color filter according to [14].

[16] A step of applying a photosensitive resin composition for a color filter according to any one of [1] to [13] to a substrate, exposing it, developing alkali, and then baking at a temperature of 150° C. or lower to form a colored pattern. The manufacturing method of the color filter characterized by including.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition for color filters which provides a coloring pattern excellent in solvent resistance, even when it is hardened at low temperature of around 100 degreeC, while having a good developability and storage stability, and the aerial useful for the preparation of the photosensitive resin composition Coalescence can be provided.

Moreover, according to this invention, the color filter which has a coloring pattern excellent in solvent resistance, its manufacturing method, and the image display element provided with the color filter can be provided.

<Photosensitive resin composition for color filters>

The photosensitive resin composition for color filters 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 an acid by heat and/or ultraviolet irradiation. It contains the compound (B) to be generated, a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F).

<Copolymer (A)>

<Structural unit having acid group (a)>

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. Examples of the acid group include a carboxy group (-COOH), a phospho group (-PO(OH) ₂ ), and a sulfo group (-SO ₃ H). Among these, a carboxyl group is preferred from the viewpoint of ease of raw material availability and solvent resistance when used for color filter production. As a polymerizable monomer which gives the structural unit (a) which has an acidic radical, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-( And ethylenically unsaturated compounds containing carboxyl groups such as meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic 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 preferred from the viewpoint of availability and reactivity. Moreover, a structural unit is also called a monomer unit.

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

When the copolymer (A) is composed of a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, the proportion of the structural unit (a) having an acid group contained in the copolymer (A) is preferable. It is 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%, a moderate alkali development rate is achieved, and a precise colored pattern can be formed.

When the copolymer (A) further contains other structural units (c) described later, the proportion of the structural unit (a) having an acid group contained in the copolymer (A) is preferably 5 mol% to 60 Molar%, 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%, a suitable alkali development rate is achieved, and a precise colored pattern can be formed.

<Structural unit having a cyclic ether group (b)>

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, except for the structural unit (a) having the acid group) do). An epoxy group, an oxetanyl group, etc. are mentioned as a cyclic ether group. Specific examples of the polymerizable monomer containing an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate having an alicyclic epoxy group, and lactone adducts (for example, Daicel Corporation Cyclomer (registered trademark) A200, M100), mono(meth)acrylic acid ester of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, dicyclopentenyl (meth) Epoxides of acrylates, epoxides of dicyclopentenyloxyethyl (meth)acrylate, and the like. Among these, an epoxy group-containing (meth)acrylate is preferable, and a glycidyl (meth)acrylate is more preferable from the viewpoint of availability and reactivity. Moreover, as a specific example of a polymerizable monomer which has an oxetanyl group, (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 And 2-vinyl-2-methyloxetane. Among these, oxetanyl group-containing (meth)acrylate is 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, the structural unit (b) having a cyclic ether group is contained in the copolymer (A), whereby solvent resistance when the copolymer (A) is used as a photosensitive material is greatly improved.

When the copolymer (A) is composed of a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, the proportion of the structural unit (b) having a cyclic ether group contained in the copolymer (A) is , Preferably it is 60 mol%-95 mol%, More preferably, it is 65 mol%-90 mol%, Most preferably, it is 70 mol%-85 mol%. When the proportion of the structural unit (b) having a cyclic ether group is 60 mol% to 95 mol%, the solvent resistance of the cured coating film and storage stability of the copolymer (A) are compatible.

When the copolymer (A) further contains other structural units (c) to be described later, the proportion of the structural unit (b) having a cyclic ether group contained in the copolymer (A) is preferably 5 mol% It is -70 mol%, More preferably, it is 8 mol%-60 mol%, Most preferably, it is 10 mol%-50 mol%. When the proportion of the structural unit (b) having a cyclic ether group is 5 mol% to 70 mol%, the solvent resistance of the cured coating film and storage stability of the copolymer (A) are compatible.

<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 (a) having the acid group and It is also possible to contain the said structural unit (b) except the said cyclic ether group). The polymerizable monomer that gives the other structural unit (c) is generally a radically polymerizable compound having an ethylenically unsaturated group, and examples thereof include dienes such as butadiene; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, 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)acrylate, 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)acrylic acid esters such as meth)acrylate; 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 ]dode Car-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]deca-8-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodeca- 3-ene, pentacyclo[6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] ^pentadeca -4-ene, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene Nen-2,3-dicarboxylic acid anhydride, (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid anthracenylamide, N-isopropyl (meth)acrylamide, (meth) (Meth)acrylic acid amides, such as acrylic morpholine and diacetone (meth)acrylamide; Vinyl compounds such as (meth)acrylic acid anilide, (meth)acryloyl nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyl toluene; Styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene; Unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, and diethyl itaconic acid; Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; And unsaturated polybasic acid anhydrides such as maleic anhydride and itaconic anhydride. The radically polymerizable compounds having these ethylenically unsaturated groups 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, vinyltoluene, isobornyl (meth)acrylate, adamantyl (Meth)acrylate, norbornene, N-isopropyl (meth)acrylamide, (meth)acrylic morpholine and diacetone (meth)acrylamide are preferred, methyl (meth)acrylate, benzyl (meth)acrylic Late, dicyclopentanyl (meth)acrylate, styrene, vinyl toluene, isobornyl (meth)acrylate, adamantyl (meth)acrylate and norbornene are more preferred.

The proportion of the other structural unit (c) contained in the copolymer (A) is not particularly limited, but is preferably greater than 0 mol% to 80 mol%, more preferably 5 mol% to 70 mol%, most preferably It is 10 mol%-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 properties of the coating film can be appropriately improved.

In addition, in this specification, the expression (meth)acrylate means that any of acrylate and methacrylate may be used, and the expression (meth)acrylic acid is any of acrylic acid and methacrylic acid. It means that it may be.

<Method for producing copolymer (A)>

An acid group-containing polymerizable monomer (a0) that gives a structural unit (a) having an acid group used in the production of the copolymer (A) consisting of a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group ) And the proportion of the cyclic ether group-containing polymerizable monomer (b0) to give the structural unit (b) having a cyclic ether group is not particularly limited, but is preferably (a0) 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%.

A structural unit (a) having an acid group used in the production of the copolymer (A) consisting of a structural unit (a) having an acid group, a structural unit (b) having a cyclic ether group, and other structural units (c) is given The acidic group-containing polymerizable monomer (a0), the cyclic ether group-containing polymerizable monomer (b0) to give the structural unit (b) having a cyclic ether group, and the other polymerizable monomer (c0) to give the structural unit (c) The ratio of) 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%, more preferably Is (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 acidic group-containing polymerizable monomer (a0), the cyclic ether group-containing polymerizable monomer (b0), and other polymerizable monomer (c0) to give the structural unit (c) is a radical known in the art. Depending on the polymerization method, it can be carried out in the presence or absence of a polymerization solvent. For example, after dissolving these polymerizable monomers in a solvent as desired, a polymerization initiator may be added to the solution, and a polymerization reaction may be performed at 50°C to 130°C for 1 hour to 20 hours.

The solvent that can be used for this copolymerization reaction is not particularly limited as long as it is inert to the reaction, but is not limited to, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. , Diethylene glycol mono-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 (Poly)alkyl such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Renglycol monoalkyl ethers; (Poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 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-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-propionic acid Esters such as butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, 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 etc. are mentioned. These solvents may be used alone or in combination of two or more.

Among these solvents, an ether-based solvent is preferable, and a propylene glycol monomethyl ether is preferred because it 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 acetate, diethylene glycol methyl ethyl ether, and ethylene glycol monomethyl ether are more preferable.

The amount of the solvent used for the copolymerization reaction is not particularly limited, but when the total amount of the polymerizable monomer is 100 parts by mass, it is generally 30 parts by mass to 1,000 parts by mass, preferably 50 parts by mass to 800 parts by mass . In particular, by setting the amount of the solvent to 1,000 parts by mass or less, a decrease in the molecular weight of the copolymer (A) due to the chain transfer action can be suppressed, and the viscosity of the copolymer (A) can be controlled within an appropriate range. Moreover, by making the amount of a solvent 30 mass parts or more, an abnormal polymerization reaction can be prevented and a polymerization reaction can be performed stably, and coloring and gelation of the copolymer (A) can also be prevented.

Moreover, although it does not specifically limit as a radical polymerization initiator which can be used for this copolymerization reaction, For example, azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc. And azo-based radical polymerization initiators, organic peroxide-based 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 parts by mass to 20 parts by mass, and preferably 1.0 parts by mass to 10 parts by mass, when the total amount of the polymerizable monomer is 100 parts by mass.

The weight average molecular weight in terms of polystyrene of the copolymer (A) is preferably 1,000 to 50,000, and more preferably 3,000 to 40,000. When the weight average molecular weight of the copolymer (A) is 1,000 or more, defects in the colored pattern are 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, development time becomes appropriate and practicality is secured.

Moreover, the acid value (JIS K6901 5.3) of the copolymer (A) is preferably 20 KOHmg/g to 300 KOHmg/g, and more preferably 30 KOHmg/g to 200 KOHmg/g. When the acid value of the copolymer (A) is 20 KOH mg/g or more, the alkali developability of the photosensitive resin composition for color filters becomes good. On the other hand, if the acid value of the copolymer (A) is 300 KOHmg/g or less, the pattern shape is good because the exposed portion (photocured portion) is poorly dissolved in the alkali developer.

In addition, the cyclic ether group equivalent of the 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 It is in the range of g/mol to 900 g/mol. When the cyclic ether group equivalent of the copolymer (A) is 200 g/mol or more, stability is improved. On the other hand, when the cyclic ether group equivalent of the copolymer (A) is 2,000 g/mol or less, solvent resistance is sufficiently secured. In addition, 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 equivalent weight of the cyclic ether group of the copolymer (A) is a theoretical value calculated from the input amount of the polymerizable monomer.

<The compound (B) which generates an acid by heat and/or ultraviolet irradiation>

Hereinafter, a compound that generates acid by heat is abbreviated as "(B-1) thermal acid generator", and a compound that generates acid by ultraviolet irradiation is abbreviated as "(B-2) photoacid generator". have. The (B-1) thermal acid generator and (B-2) photoacid generator are not particularly limited as long as the acid can be generated by heat and/or ultraviolet irradiation, for example, iodonium salt, sulfonium salt, and phos. And onium salts such as phonium salts and diazonium salts, and sulfonium salts are preferred. Among these, as the thermal acid generator (B-1), TA-100 and TA-120 manufactured by San Afro Co., Ltd., which can be obtained by generating an acid by heating at 100°C or higher, are preferable. In addition, in the (B-2) photoacid generator, a triarylsulfonium salt-based photoacid generator with low impurities and high sensitivity is preferred, and among them, CPI-210 series and CPI-100 series, CPI- manufactured by San Afro Co., Ltd. 300 series and CPI-400 series are more preferable. These (B-1) thermal acid generators and (B-2) photoacid generators may be used alone or in combination of two or more.

The compounding amount of the compound (B) which generates an acid by heat and/or ultraviolet irradiation is a polymerizable monomer (b0) 100 that provides a structural unit (b) having a cyclic ether group used when synthesizing the copolymer (A) 100 It is preferable that it is 0.05 mass parts-20 mass parts with respect to a mass part, it is more preferable that it is 0.1 mass parts-15 mass parts, and it is most preferable that it is 1 mass part-10 mass parts. When the compounding amount of the compound (B) is 0.05 parts by mass or more, the curing reaction of the photosensitive resin composition tends to proceed. 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 increased.

When the total amount of the component (B) in the photosensitive resin composition for color filters was 100% by mass, the total amount of the copolymer (A) and the compound (B) generating an acid upon irradiation with heat and/or ultraviolet rays was 100% by mass. It is preferably 1 mass% to 50 mass%, more preferably 5 mass% to 40 mass%, and most preferably 10 mass% to 30 mass%. If the compounding amount in this range, the solvent resistance of the cured coating film can be improved and storage stability can be maintained.

<Solvent (C)>

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

When the total amount of components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 parts by mass, the compounding amount of the solvent (C) is generally 10 parts by mass to 800 parts by mass, preferably 50 parts by mass to 500 parts by mass It is a mass part, More preferably, it is 100 mass parts-300 mass parts. If it is the compounding quantity in this range, it will become a photosensitive resin composition for color filters which has 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, and among them, a compound having a plurality of polymerizable functional groups is preferable. By containing the reactive diluent (D) in the photosensitive resin composition for color filters, the strength of the formed cured product and adhesion to the substrate are improved.

As the monofunctional monomer used as the reactive diluent (D), (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl ( Meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydride Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth) )Acryloyloxy-2-hydroxypropylphthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl (Meth)acrylates such as (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylate of phthalic acid derivatives; Aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene; And carboxylic acid esters such as vinyl acetate and vinyl propionate. Moreover, these monomers may be used individually or may be used in combination of 2 or more type.

Examples of the polyfunctional monomer used as the reactive diluent (D) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylic. Rate, 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, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( Meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3 -(Meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate Di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. (Meth)acrylates, such as reactants of 2-hydroxyethyl (meth)acrylate and tri(meth)acrylate of tris(hydroxyethyl)isocyanurate; Aromatic vinyl compounds such as divinylbenzene, diallylphthalate and diallylbenzenephosphonate; Dicarboxylic acid esters such as divinyl adipate; And triallyl cyanurate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, and condensates of polyhydric alcohols and N-methylol (meth)acrylamide. These monomers may be used alone, or two or more of them may be used in combination.

When the total amount of components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 mass%, the blending amount of the reactive diluent (D) is generally 1 mass% to 60 mass%, preferably 5 mass%. It is 50 mass %, More preferably, it is 10 mass%-40 mass %. If it is a compounding quantity in this range, it has viscosity and photocurability suitable as a photosensitive resin composition for color filters.

<Photopolymerization initiator (E)>

Although it does not specifically limit as a photoinitiator (E), For example, Benzoins, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[ Acetophenones such as 4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones such as xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone ; Acylphosphine oxides; And oxime esters such as 1,2-octanedione and 1-[4-(phenylthio)-,2-(0-benzoyloxime)]. These photopolymerization initiators (E) may be used alone or in combination of two or more.

When the total amount of components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 mass%, the blending amount of the photopolymerization initiator (E) is generally 0.01 mass% to 15 mass%, preferably 0.05 mass%. It is -10 mass %, More preferably, it is 0.1 mass%-5 mass %. If it is the compounding quantity in this range, it will become a photosensitive resin composition for color filters which has appropriate photocurability.

The photosensitive resin composition for a color filter of the present invention may contain, in addition to the above-mentioned components, known additives such as known coupling agents, leveling agents, and thermal polymerization inhibitors to impart predetermined characteristics. 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 is dissolved or dispersed in the solvent (C), and examples thereof include dyes and pigments. As a dye, an acidic dye having an acidic group such as carboxylic acid or sulfonic acid, nitrogen compound of acidic dye, from the viewpoint of solubility in solvent (C) or alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, and the like It is preferable to use a salt of a family, a sulfonamide body 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; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and derivatives thereof. Among these, azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acidic dyes are preferred. These dyes may be used alone or in combination of two or more depending on the color of the target pixel.

Examples of pigments include CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 Yellow pigments such as, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; Orange pigments such as C.I. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red 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 Pigment; Blue pigments such as C.I. pigment blue 15, 15: 3, 15: 4, 15: 6, 60; Violet pigments such as C.I. pigment violet 1, 19, 23, 29, 32, 36, 38; Green pigments such as C.I. pigment green 7, 36, 58, 59; Color pigments such as C.I. pigment brown 23 and 25; And black pigments such as C.I. pigment black 1, 7, carbon black, titanium black, and iron oxide. These pigments may be used alone or in combination of two or more depending on the color of the target pixel.

The coloring agent (F) may be used in combination of the dyes and pigments described above depending on the color of the target pixel.

When using a pigment as a coloring agent (F), you may mix|blend a well-known dispersing agent in the photosensitive resin composition for color filters from a viewpoint of improving the dispersibility of a pigment. As the dispersant, it is preferable to use a polymer dispersant with excellent dispersion stability over time. Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified ester dispersants. As such a polymer dispersing agent, commercially available products such as EFKA (manufactured by Efka Chemicals BV (EFKA)), Disperbyk (manufactured by Bickemi), Dispalon (manufactured by Kusumoto Hwasung Co., Ltd.), SOLSPERSE (manufactured by Geneca) You may use The compounding amount of the dispersant may be appropriately set depending on the type of the pigment or the like used.

The content of the colorant (F) is appropriately adjusted depending on the dye and pigment used, but when the total amount of components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 mass%, it is generally 20 mass% to 80 It is preferably mass%, more preferably 30 mass% to 75 mass%, and most preferably 40 mass% to 70 mass%. If it is the compounding quantity in this range, it will become a photosensitive resin composition for color filters which has appropriate photocurability.

Copolymer (A), compound (B), solvent (C), reactive diluent (D), photopolymerization initiator (E) and colorant in the photosensitive resin composition for color filters to generate an acid upon irradiation with heat and/or ultraviolet light The compounding amount of (F) is a compound which generates an acid by copolymer (A) and heat and/or ultraviolet irradiation when the sum of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 mass%. The sum of (B) is 1 mass% to 50 mass%, the reactive diluent (D) is 1 mass% to 60 mass%, the photopolymerization initiator (E) is 0.01 mass% to 15 mass%, and the colorant (F) is 20 mass% ∼80 mass%, when the total sum of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 parts by mass, the solvent (C) is 10 parts by mass to 800 parts by mass, and is also used for heat and/or ultraviolet irradiation. The compounding amount of the compound (B) for generating an acid is 0.05 mass based on 100 parts by mass of the polymerizable monomer (b0) which gives the structural unit (b) having a cyclic ether group used when synthesizing the copolymer (A). Parts to 20 parts by mass. Preferably, when the total sum of the components excluding the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass, the copolymer (A) and the compound (B) which generates an acid by heat and/or ultraviolet irradiation Of 5 mass% to 40 mass %, reactive diluent (D) 5 mass% to 50 mass %, photopolymerization initiator (E) 0.05 mass% to 10 mass %, and colorant (F) 30 mass% to 75 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, the solvent (C) is 50 parts by mass to 500 parts by mass, and the acid is The compounding amount of the compound (B) to be generated is 0.1 to 15 parts by mass based on 100 parts by mass of the polymerizable monomer (b0). More preferably, when the total sum of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 mass%, the copolymer (A) and a compound that generates an acid by heat and/or ultraviolet irradiation (B) ) Is 10 mass% to 30 mass%, the reactive diluent (D) is 10 mass% to 40 mass%, the photopolymerization initiator (E) is 0.1 mass% to 5 mass%, and the colorant (F) is 40 mass% to 70 When it is mass% and the sum total of the components except the solvent (C) in the photosensitive resin composition for color filters is 100 mass parts, the solvent (C) is 100 mass parts-300 mass parts, and it is acid by heat and/or ultraviolet irradiation The compounding amount of the compound (B) that generates is 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer (b0). If it is the compounding quantity in this range, it will become a photosensitive resin composition for color filters which has an appropriate viscosity. Moreover, also in the case of the photosensitive resin composition which does not contain a coloring agent (F), copolymer (A), the compound (B) which produces|generates an acid by heat and/or ultraviolet irradiation, a solvent (C), and a reactive diluent (D) And the photopolymerization initiator (E), the above numerical range is applicable, 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 this invention can be manufactured by mixing the said component using a well-known mixing apparatus. Further, if desired, a polymer composition containing a copolymer (A), a compound (B) generating an acid by heat and/or ultraviolet irradiation, and a solvent (C) is prepared first, and then a reactive diluent (D) and photopolymerization The initiator (E) and the colorant (F) can also be prepared by mixing.

The photosensitive resin composition for color filters obtained as described above has alkali developability, and is therefore preferable as a resist. The curing of the photosensitive resin composition for color filters may be appropriately selected from a baking temperature of 250° C. or lower, but the copolymer (A) used in the present invention is excellent in curing at low temperatures, and thus is baked in comparison with conventional materials. You can lower the temperature. When a pigment is used as the colorant (F) in the photosensitive resin composition for color filters, curing proceeds sufficiently even if the baking temperature is 150°C or lower. The photosensitive resin composition for color filters of the present invention is advantageous in terms of energy consumption since the crosslinking reaction proceeds sufficiently even when the baking temperature is lowered. Moreover, it is possible to use even the colorant (F) and the substrate having poor heat resistance, so that the original characteristics of the colorant can be obtained, and application to various substrates is also possible. From such a viewpoint, 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. When the baking temperature is too low, it becomes difficult to sufficiently improve the solvent resistance of the coating film. Moreover, although baking time can be selected suitably, it is 10 minutes-4 hours normally, Preferably it is 20 minutes-2 hours.

The photosensitive resin composition for color filters of the present invention is preferable as a resist used for manufacturing a color filter mounted on an organic EL display, a liquid crystal display device, a solid-state imaging device such as a CCD or CMOS, or the like.

The photosensitive resin composition for color filters of the present invention has good developability and storage stability, and can form a colored pattern excellent in solvent resistance even when the baking temperature at the time of pattern formation is low. As a photosensitive material for color filters, Very useful. Moreover, the photosensitive resin composition for color filters of this invention can contribute also to power generation of a flexible display, reduction of energy consumption in a manufacturing process, and relaxation of the limitation of the colorant to be used with low temperature curing.

<color filter>

Next, the color filter which has a coloring pattern which consists of hardened|cured material of the photosensitive resin composition for color filters of this invention is demonstrated. The color filter of this invention has a coloring pattern formed using the photosensitive resin composition for color filters mentioned above. The color filter is usually composed of a substrate, RGB pixels formed thereon, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixel and black matrix. In this configuration, other than R, G and B constituting the pixel, and one or more coloring patterns selected from the black matrix (coloring pattern) are formed using the photosensitive resin composition for color filters described above. Known configurations can be employed.

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

The coloring pattern can be formed by a photolithography method. Specifically, after applying the photosensitive resin composition for a color filter on a substrate to form a coating film, the coating film is exposed through a photomask of a predetermined pattern to photocur the exposed portion. And a predetermined coloring pattern can be formed by baking an unexposed part with an aqueous alkali solution, and baking it.

Although it does not specifically limit as a coating method of the photosensitive resin composition for color filters, 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 apply|coating the photosensitive resin composition for color filters, you may volatilize the solvent (C) by heating using heating means, such as a circulating oven, an infrared heater, and a hot plate, as needed. The heating conditions are not particularly limited, and may be appropriately set depending on the composition of the photosensitive resin composition for color filters used. Generally, it is sufficient to heat at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

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

Although it does not specifically limit as an alkali aqueous solution used for image development, 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; Tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N -Ethyl-N-β-methanesulfonamide ethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl aniline and p-phenyl such as sulfate, hydrochloride or p-toluenesulfonate An aqueous solution of the rendamine compound can be used. Moreover, you may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash with water and dry after image development by the said aqueous alkali solution.

The conditions for baking are not particularly limited, and heat treatment may be performed depending on the composition of the photosensitive resin composition for color filters used. In the conventional photosensitive resin composition, when the baking temperature is 200°C or less, the solvent resistance of the colored pattern is insufficient, but in the photosensitive resin composition for color filters of the present invention, even when baked at a temperature of 150°C or less, sufficient solvent resistance is exhibited. A coloring pattern 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 such a viewpoint, 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. -4 hours, preferably 20 minutes-2 hours.

The above-mentioned coating, exposure, development and baking are sequentially repeated using a photosensitive resin composition for a black matrix of a color filter and a photosensitive resin composition for red, green, and blue pixels of a color filter to form a desired coloring pattern. Can. In addition, although the method of forming a colored pattern by photocuring was described above, if a photosensitive resin composition containing a curing accelerator and a known epoxy resin is used instead of the photopolymerization initiator (E), after coating by an inkjet method By heating, it is also possible to form a desired coloring pattern. Finally, a protective film is formed on the coloring pattern (each pixel and black matrix of RGB). The protective film is not particularly limited and may be formed using a known one.

Since the color filter manufactured in this way is manufactured using a photosensitive resin composition for color filters which gives a coloring pattern excellent in sensitivity and developability and excellent solvent resistance, it has an excellent coloring pattern with little color change.

<image display element>

The image display element of the present invention is an image display element provided with the above color filter, and specific examples thereof include liquid crystal display elements, organic EL display elements, solid-state imaging elements such as CCD elements and CMOS elements. Production of the image display element of the present invention may be performed in accordance with a conventional method in addition to the use of the above color filters. For example, when manufacturing a liquid crystal display element, the above-mentioned 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, and both are attached to inject and seal a predetermined amount of liquid crystal.

Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by these Examples. In addition, in this Example, what is described in parts and percentages are all on a mass basis unless otherwise specified. Moreover, the measuring method of an acid value and weight average molecular weight is as follows.

(1) Acid value: As the acid value of the copolymer (A) measured according to JIS K6901 5.3, it means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the copolymer (A).

(2) Weight average molecular weight (Mw) means the weight average molecular weight equivalent to standard polystyrene measured under the following conditions using gel permeation chromatography (GPC).

Column: Showdex (registered trademark) LF-804+LF-804 (manufactured by Showa Electric Corporation)

Column temperature: 40 ℃

Sample: 0.2% tetrahydrofuran solution of copolymer

Development solvent: tetrahydrofuran

Detector: Differential refractometer (Showdex RI-71S) (manufactured by Showa Electric Co., Ltd.)

Flow rate: 1 ml/min

[Synthesis Example 1]

After adding 175.5 g of propylene glycol monomethyl ether to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, the mixture was stirred with nitrogen substitution and heated to 78°C. Next, 128.9 g of (3-ethyloxetan-3-yl)methyl methacrylate as the cyclic ether group-containing polymerizable monomer (b0) and 25.8 g of methacrylic acid as the acid group-containing polymerizable monomer (a0) The resulting monomer mixture and 13.9 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (radical polymerization initiator) were added to and dissolved in 54.3 g of propylene glycol monomethyl ether. Dropped in the middle. After completion of the dropwise addition, 10.3 g of propylene glycol monomethyl ether was added, and the mixture was stirred at 78° C. for 3 hours to undergo a copolymerization reaction to produce a copolymer. Finally, CPI-210S manufactured by San Afro Co., Ltd., was cyclic ether. 1 mass part was added to 100 mass parts of the group-containing polymerizable monomer (b0) to obtain a polymer composition (component concentration of 35 mass% other than solvent) of Sample No. 1. 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 above GPC was 6,800. Moreover, using the obtained polymer composition, the acid value of the copolymer in the polymer composition measured according to JIS K6901 5.3 was 120.5 KOH mg/g.

[Synthesis Examples 2 to 8 and Comparative Synthesis Examples 1 to 3]

A copolymerization reaction was performed under the same conditions as in Synthesis Example 1, except that the raw materials shown in Tables 1 and 2 were used to obtain polymer compositions (component concentrations of 35 mass% other than the solvent) of Samples Nos. 2 to 11. However, in Comparative Synthesis Example 2, since the cyclic ether group-containing polymerizable monomer (b0) was not added, the addition amount of the compound (B) generating acid by heat and/or ultraviolet irradiation was obtained in Synthesis Example 3 ( Sample No. 3). Table 1 and Table 2 show the weight average molecular weight and acid value of the copolymer in the obtained polymer composition. Moreover, Table 1 and 2 also show the equivalent of the cyclic ether group calculated from the input amount of a polymerizable monomer.

[Examples 1 to 8 and Comparative Examples 1 to 3]

<Preparation of photosensitive resin composition for color filters (pigment type)>

In a container made of stainless steel filled with 200 parts by mass of zirconia beads having a diameter of 0.5 mm, 100 parts by mass of CI Pigment Green 36 (colorant), 45 parts by mass of propylene glycol monomethyl ether acetate (solvent), Disperbyk, manufactured by Big Chemical Japan Co., Ltd. A green pigment dispersion was prepared by adding -161 (dispersant) of 25 parts by mass and mixing and dispersing with a paint shaker for 2 hours.

The green pigment dispersion liquid 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 to have a blending amount shown in Table 3. In addition, the compounding amount of the polymer composition in Table 3 excluded the solvent used when preparing the polymer composition (total of the copolymer (A) and the compound (B) generating acid by irradiation with heat and/or ultraviolet rays) , And the amount of the solvent in Table 3 is the sum of the solvents used in preparing the polymer composition, and the solvents used in preparing the propylene glycol monomethyl ether and green pigment dispersion further formulated. As can be seen from the blending amounts in Table 3, when the total amount of components excluding the solvent (C) in the photosensitive resin composition for color filters was 100% by mass, the copolymer (A) and the acid were subjected to heat and/or ultraviolet irradiation. The total amount of the compound (B) generating 24.4 mass%, the reactive diluent (D) is 24.4 mass%, the photopolymerization initiator (E) is 1.2 mass%, the colorant (F) is 40.0 mass%, and the photosensitive resin composition for color filters The solvent (C) is 130.2 parts by mass when the sum of the components excluding the solvent (C) in the total is 100 parts by mass.

The photosensitive resin compositions for color filters of Examples 1-8 were prepared using each of the polymer compositions of Sample Nos. 1 to 8, and the photosensitive resin compositions for color filters of Comparative Examples 1 to 3 were sample Nos. 9 to 11 It was prepared using each of the polymer composition.

<Evaluation of the photosensitive resin composition for color filters>

(1) alkali developability

Each of the photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 3 was spin-coated on a 5 cm wide glass substrate (alkali-free glass substrate) so that the thickness after exposure was 2.5 µm, The solvent was volatilized by heating at 90°C for 3 minutes. Next, a photomask of a predetermined pattern was placed at a distance of 100 µm from the coating film, and the coating film was exposed (exposure amount: 150 mJ/cm 2) through the photomask, and the exposed portion was photocured. Next, an unexposed portion was dissolved and developed by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23°C and a pressure of 0.3 MPa, and then baking at 100°C for 20 minutes to form a predetermined pattern. 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

×: There is residue

Table 4 shows the evaluation results of alkali developability.

(2) Evaluation of solvent resistance

After spin coating each of the photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 3 on a 5 cm wide glass substrate (alkali-free glass substrate) to a thickness of 2.5 µm after baking, The solvent was volatilized by heating at 90°C for 3 minutes. Next, a light having a wavelength of 365 nm was exposed to the coating film, the exposed portion was photocured, and then left in a dryer at a baking temperature of 100°C for 20 minutes to produce a cured coating film. 200 ml of propylene glycol monomethyl ether acetate was placed in a glass bottle with a cap of 500 ml, and the mixture was left standing at 80°C. After immersing the test piece with the cured coating film therein, it was left standing at 80°C for 5 minutes. The color change (ΔE ^* ab) before and after immersion of the test piece 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. When ΔE ^* ab is 1.5 or less, it can be said that the solvent resistance is excellent.

(3) Evaluation of storage stability

The photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 3 were weighed in equal amounts in a glass container, and the opening was closed with aluminum foil to prevent dust and the like from entering. Next, these samples were each left in a thermostat maintained at 23°C, and the weight average molecular weight (Mw) of the sample after 1 month was measured, and 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 of Mw after 1 month with respect to Mw before storage is within ±20%.

X: The rate of change of Mw after 1 month with respect to Mw before storage is more than ±20%

Table 4 shows the evaluation results of storage stability.

As shown in Table 4, in the photosensitive resin composition for color filters of Examples 1 to 8, all of alkali developability, solvent resistance, and storage stability were satisfactory. In contrast, the photosensitive resin composition for color filters of Comparative Examples 1 to 3 had insufficient solvent resistance, and the photosensitive resin composition for color filters of Comparative Example 3 also had insufficient alkali developability.

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

Claims (16)

A copolymer (A) containing a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group, a compound (B) for generating an acid by heat and/or ultraviolet irradiation, and a solvent (C) ), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F). According to claim 1,
The photosensitive resin composition for color filters whose structural unit (a) which has the said acidic radical is a structural unit derived from the ethylenically unsaturated compound containing a carboxyl group. The method of claim 1 or 2,
The photosensitive resin composition for color filters, wherein the structural unit (b) having the cyclic ether group is a structural unit derived from at least one member selected from the group consisting of epoxy group-containing (meth)acrylate and oxetanyl group-containing (meth)acrylate. . The method according to any one of claims 1 to 3,
The proportion of the structural unit (a) having the acid group contained in the copolymer (A) is 5 mol% to 40 mol%, and the proportion of the structural unit (b) having the cyclic ether group is 60 mol% to 95 Photosensitive resin composition for color filter which is mol%. The method according to any one of claims 1 to 3,
The photosensitive resin composition for color filters in which the said copolymer (A) further contains the structural unit (c) derived from the radically polymerizable compound which has an ethylenic unsaturated group. The method of claim 5,
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 radically polymerizable compound having the ethylenically unsaturated group is more than 0 mol% to 80 mol%. The photosensitive resin composition for color filters. The method according to any one of claims 1 to 6,
The photosensitive resin composition for color filters whose acid value of the structural unit (a) which has the said acid group is a carboxy group. The method according to any one of claims 1 to 7,
The photosensitive resin composition for color filters which is at least 1 sort(s) chosen from the group which consists of an epoxy group and oxetanyl group of the cyclic ether group of the structural unit (b) which has the said cyclic ether group. The method according to any one of claims 1 to 8,
100 parts by mass of a polymerizable monomer that gives the structural unit (b) having the cyclic ether group used when synthesizing the copolymer (A), the compound (B) generating an acid by the heat and/or ultraviolet irradiation The photosensitive resin composition for color filters which is 0.05 mass parts-20 mass parts with respect to. The method according to any one of claims 1 to 9,
The photosensitive resin composition for color filters in which the compound (B) which generates an acid by the heat and/or ultraviolet irradiation is a sulfonium salt. The method according to any one of claims 1 to 10,
The photosensitive resin composition for color filters whose weight average molecular weight of said copolymer (A) is 1,000-50,000, and an acid value is 20-300 KOHmg/g. The method according to any one of claims 1 to 11,
The colorant (F) is a photosensitive resin composition for a color filter containing a pigment. The method according to any one of claims 1 to 12,
The compound (B) which generates an acid by irradiation with the copolymer (A) and the heat and/or ultraviolet rays when the total sum of the components excluding the solvent (C) in the photosensitive resin composition for color filters is 100% by mass Of 1 mass% to 50 mass%, the reactive diluent (D) is 1 mass% to 60 mass%, the photopolymerization initiator (E) is 0.01 mass% to 15 mass%, and the colorant (F) is 20 mass% The photosensitive resin composition for color filters having a solvent (C) of 10 parts by mass to 800 parts by mass when the total amount of components excluding the solvent (C) in the photosensitive resin composition for color filters is 100 parts by mass is 80% by mass . The color filter which has a coloring pattern which consists of hardened|cured material of the photosensitive resin composition for color filters of any one of Claims 1-13. An image display element comprising the color filter according to claim 14. A process comprising applying the photosensitive resin composition for a color filter according to any one of claims 1 to 13 to a substrate, exposing it, alkali developing and baking at a temperature of 150° C. or lower to form a colored pattern. Method of manufacturing a color filter, characterized in that.