TWI778376B - Coloring resin composition, and color filter and display device using the same - Google Patents

Abstract

A coloring resin composition, and a color filter and a display device using the same are provided. The coloring resin composition includes a colorant, a photo-polymerizable monomer, a photo initiator, a solvent, a first binder polymer and a second binder polymer. The colorant includes a green pigment and/or a yellow pigment. The first binder polymer includes a resin monomer unit. The resin monomer unit contains an unsaturated double bond and/or an epoxy group. The second binder polymer includes a silicon alkyl monomer unit.

Description

Colored resin composition, color filter using the same, and display device

The present invention relates to a colored resin composition, a color filter and a display device using the same.

In displays, color filters are commonly used to control the color of each pixel. For example, in earlier liquid crystal displays, color filters were formed on a substrate opposite to a thin film transistor substrate, and the overall structure of the substrate and the color filters disposed thereon was often referred to as a color filter. Optical substrate. The photoresist structure of the color filter can be formed using the resin composition.

In general, for various types of display applications, the composition of the colored resin composition can be adjusted and optimized to form various color filters with predetermined characteristics.

The present invention relates to a colored resin composition, a color filter and a display device using the same.

According to one aspect of the present invention, a colored resin composition is provided, which includes a colorant, a photopolymerizable monomer, a photopolymerization initiator, a solvent, a first adhesive polymer and a second adhesive polymer. Colorants include green pigments and/or yellow pigments. The first adhesive polymer includes a resin monomer unit. The resin monomer unit contains an unsaturated double bond and/or an epoxy group. The second adhesive polymer includes silane-based monomer units.

According to another aspect of the present invention, there is provided a color filter formed of the above-mentioned colored resin composition.

According to yet another aspect of the present invention, a display device is provided, comprising the above-mentioned color filter.

In order to have a better understanding of the above-mentioned and other aspects of the present invention, the following specific examples are given and described in detail in conjunction with the accompanying drawings as follows:

In the embodiments of the present disclosure, the resin of the colored resin composition includes a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) and a solvent (E). Here, the terms of the colorant (A), resin (B), photopolymerizable monomer (C), photopolymerization initiator (D), solvent (E) and other components may independently include a single one or a plurality of Colorant (A), Resin (B), photopolymerizable monomer (C), photopolymerization initiator (D), solvent (E) and other components.

Colorants (A) may contain pigments and dyes. The pigment of the colorant (A) is not particularly limited, and known pigments can be used, and examples thereof include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists). According to some embodiments, the dye of the colorant (A) is not particularly limited as long as it can be appropriately selected in accordance with the desired spectral spectrum of the color filter. In some embodiments, the colorant (A) may account for, for example, more than 3 wt % of the colored resin composition. In some embodiments, the colorant (A) may account for, for example, 5-50 wt % of the colored resin composition.

In an embodiment, the colorant (A) includes a green pigment and/or a yellow pigment.

In some embodiments, colorant (A) pigment refers to a dispersion including green pigment and/or yellow pigment. In the embodiment, the dispersion liquid of green pigment and/or yellow pigment comprises a mixture of propylene pigment dispersant, pigment dispersing resin and propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate), which is prepared by uniform dispersion through a bead mill.

In some embodiments, from the viewpoint of improving time stability by suppressing pigment aggregation, in addition to the above-mentioned dispersing agent, a pigment dispersing resin may be used to further disperse the pigment. Pigment dispersing resins include generally known Linear organic polymers are not particularly limited. Specified examples of linear organic polymers include free-radical polymers having carboxylic acid groups in the side chains, that is, resins obtained by homopolymerization or copolymerization of monomers having carboxyl groups; Resins obtained by hydrolysis or half-esterification or half-amidation of acid anhydride units obtained by polymerization or copolymerization; epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides, etc. Monomers having carboxyl groups include acrylic acid, methacrylic acid, itonic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like. The monomer having an acid anhydride includes maleic anhydride and the like.

Pigment dispersing resins usable in the present invention can be synthesized by known methods. Examples of solvents that can be used in the synthesis include tetrahydrofuran, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, Ethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethylacetate Amine, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethylsulfite, water, etc. These solvents may be used alone or in combination of two or more. In some embodiments, the pigment dispersion resin can be made of a material similar to the resin (B), for example, a material similar to the first adhesive polymer (B1).

In the examples, as green pigments in the coloring agent (A) of the present invention, phthalocyanine pigments, methanimine metal complex pigments, etc. can be mentioned. Specifically, for example, C.I. Pigment Green 1, C.I. Pigment Green 4 can be used. , C.I. Pigment Green 7, C.I. Pigment Green 8, C.I. Pigment Green 36, C.I. Pigment Green 58, etc. In one embodiment, the colorant (A) of the present invention may include a halogenated metal phthalocyanine pigment as a pigment. Halogenated metal phthalocyanine pigments include halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments, and it is particularly preferable to contain halogenated zinc phthalocyanine pigments such as C.I. Pigment Green 58 and C.I. Pigment Green 59. In the present invention, C.I. Pigment Green 58 is particularly preferred.

In embodiments, the coloring agent (A) of the present invention may include yellow pigments, such as monoazo pigments, monoazo lake pigments, disazo pigments, anthracene pigments. anthraquinone pigment, monoazo pyrazolone pigment, condensed azo pigment, isoindoline pigment, benzimidazolone pigment , azomethine metal complex pigment (azomethine metal complex pigment), quinophthalone pigment (quinophthalone pigment), quinoxaline pigment (quinoxaline pigment), etc. Specifically, for example, can be used: C.I. Pigment Yellow 1, C.I. Pigment Pigment Yellow 2, C.I. Pigment Yellow 3, C.I. Pigment Yellow 4, C.I. Pigment Yellow 5, C.I. Pigment Yellow 6, C.I. Pigment Yellow 10, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Pigment Yellow 16, C.I. Pigment Yellow 17, C.I. Pigment Yellow 18, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 32, C.I. Pigment Yellow 34, C.I. Pigment Yellow 35, C.I. Pigment Yellow 35:1, C.I. Pigments Pigment Yellow 36, C.I. Pigment Yellow 36:1, C.I. Pigment Yellow 37, C.I. Pigment Yellow 37:1, C.I. Pigment Yellow 40, C.I. Pigment Yellow 42, C.I. Pigment Yellow 43, C.I. Pigment Yellow 53, C.I. Pigment Yellow 55, C.I. Pigment Yellow 60, C.I. Pigment Yellow 61, C.I. Pigment Yellow 62, C.I. Pigment Yellow 63, C.I. Pigment Yellow 65, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74, C.I. Pigment Yellow 77, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86. C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 98, C.I. Pigment Yellow 100, C.I. Pigment Yellow 101, C.I. Pigment Yellow 104, C.I. Pigment Yellow 106, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 113, C.I. Pigment Yellow 114, C.I. Pigment Yellow 115, C.I. Pigment Yellow 116, C.I. Pigment Yellow 117, C.I. Pigment Yellow 118, C.I. Pigment Yellow 119, C.I. 120, C.I. Pigment Yellow 123, C.I. Pigment Yellow 125, C.I. Pigment Yellow 126, C.I. Pigment Yellow 127, C.I. Pigment Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 152, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 156, C.I. Pigment Yellow 161, C.I. Pigment Yellow 162, C.I. Pigment Yellow 164, C.I. Pigment Yellow 166, C.I. Pigment Yellow 167, C.I. Pigment Yellow 168, C.I. Pigment Yellow 169, C.I. Pigment Yellow 170, C.I. Pigment Yellow 171, C.I. Pigment Yellow 172, C.I. Pigment Yellow 173, C.I. 174, C.I. Pigment Yellow 175, C.I. Pigment Yellow 176, C.I. Pigment Yellow 177, C.I. Pigment Yellow 170, C.I. Pigment Yellow 180, C.I. Pigment Yellow 181, C.I. Pigment Yellow 182, C.I. Pigment Yellow 185, C.I. Pigment Yellow 187, C.I. Pigment Yellow 188, C.I. Pigment Yellow 193, C.I. Pigment Yellow 194, C.I. Pigment Yellow 199, C.I. Pigment Yellow 213, C.I. pigment. In the present invention, C.I. Pigment Yellow 138 is particularly preferred.

According to some embodiments of the present disclosure, it is found that when the colorant (A) includes only one of the green pigment and the yellow pigment, that is, only the green pigment, or only the yellow pigment, the patterned color formed by the coloring resin composition is Filters have fewer residual particles in their holes

According to some embodiments of the present disclosure, the colorant (A) includes green pigments and yellow pigments. According to some examples of the present disclosure, it is found that when the colorant (A) includes both green pigment and yellow pigment, the patterned color filter formed from the colored resin composition may have more residual particles in the pores. However, if the number of residual particles in the holes of the patterned color filter is too large, it is easy to cause the problem that the structure of the electrode material layer filled in the holes and used to form the conductive vias (via) is incomplete or discontinuous. This increases the probability of circuit breakage and reduces product yield. According to some embodiments of the present disclosure, when the colorant (A) includes both the green pigment and the yellow pigment, the content of the green pigment and the yellow pigment, the composition and the content of the resin (B) and other factors, can be obtained in the pores. Patterned color filters with low amounts of residual particles.

According to some embodiments of the present disclosure, the content of the yellow pigment is less than the content of the green pigment. For example, green pigments can account for the coloring tree 17~30wt% of lipid composition. The yellow pigment may account for 5-17 wt % of the colored resin composition.

In some embodiments, in addition to the green pigment and the yellow pigment, the colorant resin composition may include other colorants other than the green pigment and the yellow pigment, such as dyes or pigments other than the green pigment and the yellow pigment, according to actual needs.

In the present invention, pigments and dyes may be used alone or in combination of two or more. As another pigment, a yellow pigment, a brown pigment, a purple pigment, etc. can be illustrated.

Dyes other than green pigments and yellow pigments are not particularly limited, and well-known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dyes include compounds classified as substances having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (Shiyesha). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, square dyes Acid dyes, acridine dyes, styryl dyes, coumarin dyes, cyanine dyes, anthraquinone dyes, azo dyes, squaraine dyes, dipyrromethene dyes, quinoline dyes, porphyrin dyes, quinoline dyes Fluorine dyes and nitro dyes, etc. The pigment is also not particularly limited, and known pigments can be used, for example, the Color Index (The Society of Pigments classified as pigments in Dyers and Colourists Publishing). In some embodiments, if the solid component of the colorant in the colored resin composition is 100 parts by weight, preferably 5 to 50 parts by weight, more preferably 30 to 45 parts by weight. The "solid component" in this case refers to the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid component and the content of each component relative thereto can be measured by an appropriate analytical method such as liquid chromatography or gas chromatography, for example.

According to actual needs, the solid component may contain a dispersant, so that the colorant can be uniformly dispersed in the solution. As said dispersing agent, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. surfactants are mentioned, for example. These dispersants may be used alone or in combination of two or more. The pigment dispersant is represented by a trade name, and examples include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOREN (manufactured by Kyōeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), and EFKA (manufactured by CIBA Corporation) , Adisper (manufactured by Ajinomoto fine-techno Co., Ltd.), Disperbyk (manufactured by BYK Chemicals), and the like.

The resin (B) contains a resin monomer unit and a silane-based monomer unit. The resin monomer unit contains an unsaturated double bond and/or an epoxy group.

According to an embodiment of the present disclosure, the resin (B) includes a first binding polymer (B1). The first binding polymer (B1) may for example account for the coloring 0.2~2.9wt% of the resin composition. The first adhesive polymer (B1) contains resin monomer units. The resin monomer unit contains an unsaturated double bond and/or an epoxy group.

The resin monomer unit of the first adhesive polymer (B1) contains an epoxy dicyclopentenyl (EDCP) monomer unit.

Furthermore, according to an embodiment of the present disclosure, the resin (B) further includes a second adhesive polymer (B2). The second binding polymer may account for 0.2-2.9 wt % of the colored resin composition. The second adhesive polymer (B2) contains a silane-based monomer unit. Compared with the carbon atom in the polymer structure, the silicon atom in the silane-based monomer unit has a larger size and forms a longer bond length. Therefore, the resin ( The silane-based monomer unit in B) is matched with the epoxy dicyclopentenyl monomer unit, which can further help reduce the volume shrinkage when heated, and help improve the heat resistance and stability of the overall structure.

According to the embodiment of the present disclosure, the weight ratio of the first binding polymer (B1): the second binding polymer (B2) of the resin (B) is 0.1˜3.5:1.

In some embodiments, the resin (B) may comprise an alkali-soluble resin such as, but not limited to, a (meth)acrylic acid derived structural unit.

In some embodiments, the epoxydicyclopentenyl monomer unit of the first adhesive polymer (B1) may include a first monomer unit having a structure as shown in Chemical Formula 1, and a first monomer unit having a structure as shown in Chemical Formula 2 at least one of the second monomer units of:

Wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group, and X1 represents a single bond, -R3-, -R3-O-, -R3- S-, or -R3-NH-, wherein R3 represents an alkylene group having 1 to 6 carbon atoms, and n is a positive integer;

Wherein, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group, and X2 represents a single bond, -R3-, -R3-O-, -R3- S-, or -R3-NH-, m is a positive integer.

In some embodiments, the epoxydicyclopentenyl monomer unit of the first adhesive polymer (B1) may include a monomer unit having a structure as shown in Chemical Formula 1A and a monomer having a structure as shown in Chemical Formula 2A unit:

In some embodiments, the unsaturated double bond-containing resin monomer unit of the first adhesive polymer (B1) may contain at least one monomer from unsaturated carboxylic acid and unsaturated carboxylic acid anhydride.

In some embodiments, the first adhesive polymer (B1) may have a structural unit derived from a monomer (m2-1), and a monolithic unit having a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond. A copolymer of structural units derived from a monomer (hereinafter referred to as "monomer (m2-2)"). The above-mentioned copolymer may contain other constituent units. As the other structural unit, for example, a structural unit derived from a monomer (hereinafter referred to as "monomer (m2-3)") different from the monomer (m2-1) and the monomer (m2-2), or having an alkene It is a structural unit of unsaturated bonds, etc. In the copolymer, each of the above-mentioned structural units contains only one type, but may contain two or more types.

Examples of the monomer (m2-1) include (1) acrylic acid, methacrylic acid (MAA), succinic acid (SA), crotonic acid, o-, m-, p-vinyl benzoic acid, etc. Saturated monocarboxylic acids; (2) maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4, 5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids Carboxylic acids; (3) methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1] Hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy- Bicyclic unsaturated compounds containing carboxyl groups such as 6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc.; (4) Maleate Acid anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4- Vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride , 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic acid anhydrides; (5) succinate mono[2-(meth)acryloyloxyethyl]ester, ortho Unsaturated mono[(meth)acrylooxyalkyl]esters of polyvalent carboxylic acids having a valence of 2 or more such as mono[2-(meth)acryloyloxyethyl]phthalate; or (6) Unsaturated acrylates and the like containing a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymeth)acrylic acid.

Among these, acrylic acid (AA), methacrylic acid (MAA), maleic anhydride, etc. are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

The monomer (m2-2) refers to, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (eg, an oxirane ring, an oxetane ring, or a tetrahydrofuran ring) and an ethylenically unsaturated bond. The monomer (m2-2) may preferably be a monomer having a cyclic ether having a carbon number of 2 to 4 and a (meth)acryloyloxy group.

Examples of the monomer (m2-2) include a monomer (m2-2-1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-1)" "), a monomer (m2-2-2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-2)"), or A monomer (m2-2-3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-3)") and the like.

Examples of the monomer (m2-2-1) include monomers (m2-2-1a) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "" Monomer (m2-2-1a)"), monomer (m2-2-1b) having a structure in which alicyclic unsaturated hydrocarbons are epoxidized (hereinafter sometimes referred to as "monomer (m2-2-1b)" ”).

As the monomer (m2-2-1a), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Examples of the monomer (m2-2-1a) include glycidyl (meth)acrylate (GMA), β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl (meth)acrylate, and glycidyl (meth)acrylate. Glyceryl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, alpha-methyl-o-vinylbenzyl Glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl) Styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene , 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl) base) styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

As the monomer (m2-2-1b), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMERA400; manufactured by Daicel Co., Ltd.), 3,4-epoxy (meth)acrylate Cyclohexyl methyl ester (for example, CYCLOMERM100; manufactured by Daicel Co., Ltd.), a compound represented by the following formula (III), a compound represented by the formula (IV), and the like.

In formula (III) and formula (V), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. X ^a and X ^b represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-. R ^c represents an alkylene group having 1 to 6 carbon atoms. * indicates the bonding end with O.

As the compound represented by the formula (III), the compound represented by any one of the formula (III-1) to the formula (III-15), and the like can be exemplified. Among them, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) to formula (III) are preferred The compound represented by -15).

As the compound represented by the formula (IV), the compound represented by any one of the formula (IV-1) to the formula (IV-15), and the like can be exemplified. Among them, formula (IV-1), formula (IV-3), formula (IV-5), formula (IV-7), formula (IV-9) or formula (IV-11) to formula (IV) are preferred. The compound represented by -15) is more preferably a compound represented by formula (IV-1), formula (IV-7), formula (IV-9) or formula (IV-15).

The compound represented by the formula (III) and the compound represented by the formula (IV) may each be used alone, or two or more of them may be used in combination. When the compound represented by the formula (III) and the compound represented by the formula (IV) are used in combination, their content ratio [the compound represented by the formula (III): the compound represented by the formula (IV)] is on a molar basis , preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

Examples of the monomer (m2-3) include methyl (meth)acrylate (MMA), ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, 2-ethylhexyl acrylate (2-Ethylhexyl acrylate; 2HEA), 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, ( Lauryl meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, (meth)acrylate ) Tricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate (in this technical field, it is called "dicyclopentyl (meth)acrylate" as a common name. In addition, it is sometimes called " (meth)acrylate tricyclodecyl”), (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decen-8-yl ester (in this technical field, as a common name, referred to as “(methyl) ) Dicyclopentenyl acrylate”), Dicyclopentyloxyethyl (meth)acrylate, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, Allyl (meth)acrylate, (meth)acrylate (meth)acrylates such as propargyl acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate (BZMA); 2-hydroxy (meth)acrylate Ethyl ester (HEMA), 2-hydroxypropyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. Carboxylic acid diesters; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5 -Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept -2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2- alkene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2- 2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl Bicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo [2.2.1] Bicyclic unsaturated compounds such as hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide (CHMI), N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-methylene Dicarbonyl imine derivatives such as lyimide caproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl) maleimide; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride , acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, and 2-hydroxy (meth)acrylic acid are preferred. ethyl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and benzyl (methyl base) acrylate, etc.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group. The first adhesive polymer (B1) having such a structural unit can be obtained by making a polymer containing a structural unit derived from the monomer (m2-1) and a structural unit derived from the monomer (m2-2) , and react with monomers having reactive groups and ethylenically unsaturated bonds with the aforementioned constituent units.

As a constitutional unit having an ethylenically unsaturated bond, for example, a constitutional unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, or by adding 2 to a maleic anhydride unit can be used. - A structural unit obtained by hydroxyethyl (meth)acrylate, a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, and in a structural unit having a hydroxyl group A structural unit obtained by adding a carboxylic acid anhydride, etc.

The polymer containing the structural unit derived from the monomer (m2-1) can be produced by, for example, polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, solvent, etc. are not particularly limited, and those generally used in this field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic The peroxide (benzyl peroxide, etc.) may be used as a solvent if each monomer of the first binder polymer (B1) is dissolved, and examples thereof include the solvent used for the colored resin composition of the present invention, which will be described later.

In the production of a polymer containing a constituent unit derived from the monomer (m2-1), as the monomer, a carboxylic acid anhydride having an ethylenically unsaturated bond can be used. As the carboxylic acid anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydro Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]heptyl-2- Olefins, etc.

The weight average molecular weight (Mw) of the first adhesive polymer (B1) is preferably 1,500 to 100,000, more preferably 1,750 to 50,000, further preferably 2,000 to 20,000.

The first adhesive polymer (B1) can be, for example, commercially available product "E-DCPA"/(meth)acrylic acid (AA)/N-cyclohexylmaleimide (CHMI)/(meth)acrylic acid 2 - Copolymer of hydroxyethyl ester (HEMA), the trade name of which is "E-DCPA" (manufactured by Daicel Co., Ltd.) is 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 containing acrylic acid - 50:50 mixture of acrylic acid ester and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl acrylate in molar ratio, of E-DCPA, AA, CHMI and HEMA The weight relationship is E-DCPA(5~60 parts by weight)/AA(5~30 parts by weight)/CHMI(10~70 parts by weight)/HEMA(5~30 parts by weight), for example, E-DCPA:AA:CHMI : The weight ratio of HEMA is 9.9:15.1:55:20, and the weight-average molecular weight (Mw) of the copolymer can be 5,000 to 10,000, such as about 8,000; the trade name is "EHPE-3150", which is 2,2-bis(hydroxyl) The condensation product of 1,2-epoxy-4-(2-oxacyclopropyl)cyclohexane of methyl)-1-butanol, manufactured by Daicel Co., Ltd.; Dicyclopentyl (meth)acrylate Copolymer of (TCDMA)/(meth)benzyl acrylate (BZMA)/methacrylic acid (MAA), wherein the weight relationship between TCDMA, BZMA and MAA is TCDMA (2~40 parts by weight)/BZMA (10~70 parts by weight) parts)/MAA (10~70 parts by weight), for example, the weight ratio of TCDMA:BZMA:MAA is 10:59.6:30.4, and the weight average molecular weight (Mw) of the copolymer can be 10,000 to 12,000, such as about 11,000; TCDMA/ A copolymer of glycidyl (meth)acrylate (GMA)/2HEA/AA/SA, such as a copolymer of TCDMA/GMA/2HEA copolymerized with AA and SA in sequence, wherein TCDMA, GMA, 2HEA, AA and SA weight relationship is TCDMA (2~10 parts by weight)/GMA (50~90 parts by weight)/2HEA (10~50 parts by weight)/(AA (50~90 parts by weight)/SA (5~90 parts by weight) 20 parts by weight), for example, the weight ratio of TCDMA:GMA:2HEA:AA:SA is 3:70:27:70:13, and the weight average molecular weight (Mw) of the copolymer may be 5,400 to 7,000, such as about 6,000; TCDMA A copolymer of /GMA/2HEA/MMA/AA/SA, such as a copolymer of TCDMA/GMA/2HEA/MMA copolymerized with AA and SA in sequence, wherein TCDMA, GMA, 2HEA, MMA, AA The weight relationship with SA is TCDMA (2~10 parts by weight)/GMA ( 20~50 parts by weight)/2HEA(10~50 parts by weight)/MMA(20~50 parts by weight)/AA(20~50 parts by weight)/SA(5~20 parts by weight), for example, TCDMA:GMA:2HEA : The weight ratio of MMA:AA:SA is 3:30:30:37:30:10.9, and the weight average molecular weight (Mw) of the copolymer can be 8,500 to 11,500, such as about 9,700; or other suitable copolymers can be used. as the first adhesive polymer (B1).

In some embodiments, the silane-based monomer unit of the second adhesive polymer (B2) may have the structure shown in Chemical Formula 3:

Wherein, R4 represents a hydrogen atom or a methyl group; R5~R7 each independently represents a hydrogen atom, an alkyl group with a carbon number of 1~6 or an alkoxy group with a carbon number of 1~6, but at least one of R5~R7 is a carbon number 1-6 alkoxy groups; p is a positive integer, q is an integer of 1-10.

By using a silicone resin having a silane-based monomer unit as shown in Chemical Formula 3 in combination with the first colorant, the formed colored resin composition film layer can still be formed with good resolution under high exposure. Micro hole pattern.

Examples of the alkyl group having 1 to 6 carbon atoms in R5 to R7 include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, and neopentyl. .

Examples of alkoxy groups having 1 to 6 carbon atoms in R5 to R7 include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, isopropoxy, isobutoxy The oxy group includes isopentyloxy and neopentyloxy.

R5 to R7 may each independently be methoxy, ethoxy or propoxy, more preferably methoxy or ethoxy. q is an integer that may be 1 to 6, or an integer that may be 1 to 3.

In some embodiments, the silane-based monomer unit may have the structure shown in Formula 3A:

In some embodiments, the silane-based monomer unit may have the structure shown in Formula 3B:

In some embodiments, the second adhesive polymer (B2) comprising a silane-based monomer unit may further comprise a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter referred to as “constitutive unit (b1-2)”. b1-2)"), and a copolymer of other constituent units (b1-3) (hereinafter referred to as "constituent units (b1-3)"). In this case, the other constitutional unit (b1-3) represents a constitutional unit different from the silyl monomer unit and the constitutional unit (b1-2). In (B-2), each of the silyl group monomer unit, the structural unit (b1-2) and the structural unit (b1-3) may contain only one kind of each, or two or more kinds of each may be contained.

Examples of the acidic group contained in the constituent unit (b1-2) include a carboxyl group, a phosphoric acid group (-OP(=O)(OH) ₂ ), and a sulfo group (-S(=O) ₂ OH), and among them, preferred are carboxyl.

The weight average molecular weight (Mw) of the second adhesive polymer (B2) may be 1,000 to 50,000, or 2,000 to 40,000, or 4,000 to 7,000. The above-mentioned weight average molecular weight (Mw) can be obtained by converting from the value of polystyrene by Gel Permeation Chromatography (GPC).

In some embodiments, the second adhesive polymer (B2) can be formed with the compound (m1-1) represented by the formula (2b), or the compound (m1-1) and other compounds in the presence of a polymerization solvent. The monomer mixture is obtained by free-radical polymerization or copolymerization by other suitable methods.

[The meanings of the symbols in the formula (2b) are as described above]

In some embodiments, the second adhesive polymer (B2) can be prepared by dissolving compound (m1-1) and other compounds according to actual needs in a solvent for polymerization to form a solution, and then adding a polymerization initiator to the solution. The reaction is obtained.

In some embodiments, the second adhesive polymer (B2) containing a silane-based monomer unit, a structural unit (b1-2) and a structural unit (b1-3) can be prepared by compounding the compound (m1) in the presence of a polymerization solvent. -1), polymerizable unsaturated compounds (m1-2) having acidic groups (hereinafter referred to as "compounds (m1-2)"), and other polymerizable unsaturated compounds (m1-3) (hereinafter referred to as "compounds (m1-3)" The monomer mixture composed of compound (m1-3)") is obtained by copolymerization by known free radical polymerization method. Here, other polymerizable unsaturated And compound (m1-3) means a polymerizable unsaturated compound different from compound (m1-1) and compound (m1-2). In addition, the silyl monomer unit is derived from the compound (m1-1), the structural unit (b1-2) is derived from the compound (m1-2), and the structural unit (b1-3) is derived from the compound (m1-3) .

In some embodiments, the second adhesive polymer (B2) can be formed by dissolving compound (m1-1), compound (m1-2), and compound (m1-3) in a solvent for polymerization to form a solution, The solution is obtained by adding a polymerization initiator to react.

As the compound (m1-1), for example, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, , 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxy propylpropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, etc. Among them, 3-(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acrylooxypropyltriethoxysilane are from the viewpoints of availability and reactivity. better. In this case, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid. Other similar recording methods have the same meaning as this.

The acidic group possessed by the compound (m1-2) may be, for example, a carboxyl group, a phosphoric acid group (-OP(=O)(OH) ₂ ), or a sulfo group (-S(=O) ₂ OH), among which a carboxyl group is preferred.

Specific examples of the compound (m1-2) are, for example, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acrylooxyethylsuccinic acid, 2-acryloyloxy Ethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. Among these, (meth)acrylic acid is preferable from the viewpoint of easiness of acquisition and reactivity.

Examples of the compound (m1-3) include (1) dienes such as butadiene; (2) methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid Amyl, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2 -Ethylhexyl acrylate (2-Ethylhexyl acrylate; 2HEA), benzyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate , cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, ( Rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, allyl (meth)acrylate , tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoron-propyl (meth)acrylate, (meth)acrylate (methyl) perfluoroisopropyl acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate (cumyl), (meth)acrylate 3-(N,N-dimethylamino) Propyl ester, glycerol mono(meth)acrylate, butanetriol mono(meth)acrylate, pentanetriol mono(meth)acrylate, dicyclopentenyl (meth)acrylate, (meth) Dicyclopentyl acrylate (TCDMA), Isobornyl (meth)acrylate, adamantyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, (meth)acrylic acid 2-(2-Vinyloxyethoxy)ethyl ester, Glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyl) (meth)acrylate Oxetan-3-yl) methyl ester, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanato (meth)acrylate Propyl acid, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, (methyl) 4-Isocyanatocyclohexyl acrylate, the isocyanate group of the ethylenically unsaturated compound of the aforementioned isocyanato group, and the compound having a blocked isocyanate group which is blocked by using a blocking agent, ( N,N-dimethylaminoethyl meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, (meth)acrylate (meth)acrylates such as tetramethylpiperidyl acrylate, hexamethylpiperidinyl (meth)acrylate, etc.; (3) (meth)acrylamide, (meth)acrylate N, N-dimethylamide, (meth)acrylic acid N,N-diethylamide , (meth)acrylate N,N-dipropylamide, (meth)acrylate N,N-diisopropylamide, (meth)acrylate anthrylamide, N-isopropyl (methyl) (Meth) Acrylic amides such as acrylamide, (meth) morpholine, diacetone (meth) acrylamide, etc.; (4) Norbornene (bicyclo[2.2.1]hept-2 -ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]hept-3 -ene, 8-methyltetracyclo[4.4.0.12,5.17,10]hept-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]hept-3-ene, dicyclopentadiene, Tricyclo[5.2.1.0 ^2,6 ]dec-8-ene, tricyclo[5.2.1.0 ^2,6 ]dec-3-ene, tricyclo[4.4.0.12,5]undec-3-ene, tricyclo [6.2.1.01,8]undec-9-ene, tricyclo[6.2.1.01,8]undec-4-ene, tetracyclo[4.4.0.12,5.17,10.01,6]hept-3-ene, 8 -Methyltetracyclo[4.4.0.12,5.17,10.01,6]hept-3-ene, 8-ethylenetetracyclo[4.4.0.12,5.17,12]hept-3-ene, 8-ethylenetetra Cyclo[4.4.0.12,5.17,10.01,6]hept-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadec-4-ene, pentacyclo[7.4.0.12,5.19,12.08, 13] Pentadec-3-ene, 5-norbornene-2,3-dicarboxylic acid anhydride, (meth)acrylic acid-aniline, (meth)acrylonitrile, acrolein, vinyl chloride, dichloride Vinyl compounds of ethylene, vinyl fluoride, vinylidene fluoride, vinyl pyridine, vinyl acetate, vinyl toluene, etc.; (5) styrene, α-, o-, m-, p-alkyl, Nitro, cyano, amide derivatives; (6) unsaturated dicarboxylic acid diesters of diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. ; (7) Unsaturated polybasic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc.

Among these, from the viewpoint of availability and reactivity, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and (meth)acrylic acid Dicyclopentyl ester, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, N,N-diethylamino (meth)acrylate Ethyl ester, N,N-dimethylamide (meth)acrylate, morpholine (meth)acrylate, styrene, vinyltoluene and norbornene are preferred, methyl (meth)acrylate, (methyl) ) benzyl acrylate, dicyclopentyl (meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, styrene and Vinyltoluene is preferred. The compound (m1-3) may be used alone or in two or more. Among them, from the viewpoint of thermal decomposition resistance and thermal yellow discoloration, alkyl (meth)acrylate is preferred, methyl (meth)acrylate, benzyl (meth)acrylate, and dicyclopentyl (methyl) Acrylates are preferred.

Also, from the viewpoint of improving solvent resistance, a polymerizable compound having a functional group reactive with an acid group is preferable, and specifically, a glycidyl group, an oxetanyl group, an isocyanate group, Or a polymerizable compound with a blocked isocyanate. From the viewpoints of easiness of acquisition and reactivity, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methylmethacrylate, etc. are preferably mentioned.

As the blocking agent used for the above-mentioned isocyanate group block, ε-caprolactam, δ-valerolactam, γ-butyrolactam, β- Propionamide and other lactamides; methanol, ethanol, propanol, butanol, ethylene glycol, methyl celex, butyl cel, methyl carbitol, benzyl alcohol, benzyl alcohol Alcohols such as threo, sugar alcohols, cyclohexanol, etc.; butylphenol, p-tert- Phenols such as octylphenol, nonylphenol, dinonylphenol, styrene phenol, hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol, etc.; Methyl ester, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetone acetone, etc.; butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc. thiol series; amine series such as diphenylamine, phenylnaphthylamine, aniline, carbazole; ; Acid imide series such as succinimide, maleate imide, etc.; imidazole series such as imidazole, 2-methyl imidazole, 2-ethyl imidazole, etc.; urea series such as urea, thiourea, ethylene urea ; Carbamate series of N-phenylcarbamate, 2-oxazolidinone, etc.; imine series of ethylene imine, polyethylene imine, etc.; formaldehyde oxime, acetaldoxime, acetone oxime, Ketone oxime series such as methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, etc.; bisulfite series such as sodium bisulfite, potassium bisulfite, etc.

In order to control the weight molecular weight and molecular weight distribution (Mw/Mn) of the second adhesive polymer (B2) in a specific range, and at the same time to obtain a color pattern with the desired solvent resistance, the polymer used in the copolymerization reaction is used. The solvent is preferably a hydroxyl-containing solvent having 3 to 10 carbon atoms. as Specific examples of the hydroxyl-containing solvent having 3 to 10 carbon atoms include monoalcohols such as propanol, butanol, pentanol, hexanol, octanol, nonanol, tridecanol, dodecanol, benzyl alcohol, etc. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-propyl ether 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, dipropylene glycol Mono-n-propyl ether, dipropylene glycol mono-n-dibutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly) polyolefin glycol monoalkyl ethers, etc. These C3-C10 hydroxyl-containing solvent systems can be used individually by 1 type or in combination of 2 or more types.

The polymerization solvent used in the copolymerization reaction may contain other solvents other than the aforementioned polymerization solvent. Examples of other solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like (polyethylene glycol monoethyl ether acetate). ) polyolefin glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ether Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate Ester, Ethyl 2-Hydroxy-2-Methylpropionate, Methyl 3-Methoxypropionate, Ethyl 3-Methoxypropionate, Methyl 3-Ethoxypropionate, 3-Ethoxypropionate Ethyl propionate, ethyl ethoxyacetate, ethyl glycolate ester, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate , n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Propyl, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate Esters, etc.; Aromatic hydrocarbons such as toluene and xylene; Carboxylic amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Wait. Among these, from the viewpoint of reactivity, (poly)polyolefin glycol monoalkyl ether acetate-based solvents such as propylene glycol monomethyl ether acetate are preferable.

For the polymerization solvent used in the copolymerization reaction, the content ratio of the hydroxyl group-containing solvent having 3 to 10 carbon atoms is preferably 10 wt % to 100 wt %, preferably 20 wt % to 100 wt %.

The amount of the polymerization solvent used in the copolymerization reaction is not particularly limited. Preferably, when the total amount of compound (m1-1), compound (m1-2) and compound (m1-3) added is 100 parts by weight, it is preferably 30 parts by weight to 1000 parts by weight, or 50 parts by weight ~800 parts by weight.

The polymerization initiator that can be used in this copolymerization reaction is not particularly limited, and examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylene) valeronitrile), 2,2'-azobis(isobutyric acid) dimethyl ester, benzyl peroxide, tert-butylperoxy-2-ethylhexanoate, etc. Should Such polymerization initiators may be used alone or in combination of two or more. The usage amount of the polymerization initiator is not particularly limited, but when the total amount of the compound (m1-1), the compound (m1-2) and the compound (m1-3) added is 100 parts by weight, it is preferably 0.5 Parts by weight to 20 parts by weight, more preferably 1.0 parts by weight to 10 parts by weight.

In some embodiments, the resin (B) may further comprise at least one structural unit having an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and/or having a (meth)acrylate and/or a (meth)acrylate. A copolymer formed from at least one structural unit of a derivative.

In some embodiments, the resin (B) may account for about 0.1-10 wt % of the colored resin composition, for example, about 0.4-5.8 wt %.

In some embodiments, the photopolymerizable monomer (C) is a monomer that can be polymerized by reactive radicals and/or acids generated by the photopolymerization initiator (D), such as, but not limited to, polymerizable ethylene. Sexually unsaturated bonds, such as (meth)acrylate compounds. Here, the compound described using parentheses means including the presence or absence of the characters in the parentheses, such as the aforementioned (meth)acrylate compound, the case of including an acrylate compound, and a methacrylate compound. The photopolymerizable monomer (C) may also be referred to as a polymerizable compound.

For example, the photopolymerizable monomer (C) may include, but is not limited to, at least one selected from the group consisting of: nonylphenyl carbitol acrylate, 2-hydroxy- 3-phenoxypropyl ester, Polymerizable compounds with one ethylenically unsaturated bond, such as 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc.; 1,6-hexanedi(meth)acrylate Alcohol esters, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl of bisphenol A) ) ether, 3-methylpentanediol di(meth)acrylate and other polymerizable compounds having two ethylenically unsaturated bonds; and trimethylolpropane tri(meth)acrylate, tri(methyl) ) pentaerythritol acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(methyl) ) acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol ten(meth)acrylate, pentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanate , ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol hexa(meth)acrylate modified dipentaerythritol, propylene glycol tetra(meth)acrylate modified pentaerythritol, propylene glycol hexa(meth)acrylate modified A polymerizable compound having three ethylenically unsaturated bonds, such as sex dipentaerythritol ester, caprolactone tetra (meth)acrylate-modified pentaerythritol, and caprolactone hexa (meth)acrylate-modified dipentaerythritol. In some embodiments, the photopolymerizable monomer (C) is, for example, a compound having an ethylenically unsaturated double bond. In some embodiments, the photopolymerizable monomer (C) is, for example, a polymerizable compound having three ethylenically unsaturated double bonds.

Commercially available products of the photopolymerizable monomer (C) include KAYARAD (registered trademark) DPHA (Nihon Kayaku Co., Ltd.), trade name "A-TMM-3LM-N" (pentaerythritol triacrylate; Shin-Nakamura Chemical Industry Co., Ltd. Co., Ltd.), and the trade name "A9550" (dipivalerythritol hexaacrylate; Shin-Nakamura Chemical Industry Co., Ltd.).

The weight average molecular weight of the photopolymerizable monomer (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

According to some embodiments, the photopolymerization initiator (D) can be any compound that can generate active radicals, acids, etc. by the action of light, thereby starting the photopolymerization reaction, and is not particularly limited.

In some embodiments, the photopolymerizable monomer (C) may account for about 1-10 wt % of the colored resin composition.

For example, the photopolymerization initiator (D) may include, but is not limited to, at least one selected from the group consisting of: O-acyloxime (O-acyloxime) compound, alkyl group Phenyl ketone compound, bisimidazole compound, triazine compound, acyl phosphine oxide, benzoin compound, diphenyl ketone compound, quinone compound, 10-butyl-2-chloroacridone, benzyl base, methyl phenylformate, acetophenone, and titanocene compounds.

In some embodiments, the photopolymerization initiator (D) preferably comprises at least one selected from the group consisting of: O-acyl oxime compounds, alkyl phenyl ketone compounds, bis imidazole compound compounds, acetophenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds. For example, in the case of using an O-acyl oxime compound as the photopolymerization initiator (D), Irgacure® OXE-01 (BASF Corporation), Irgacure® OXE-02 (BASF Corporation), N-1919 ( ADEKA Corporation) and other commercially available products.

The above-mentioned O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bonding end.

Examples of the above-mentioned O-acyl oxime compound include N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, Oxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)- 3-Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3 -yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxolatylmethoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6- (2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as IRGACURE OXE01 and OXE02 (the above are manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) can be used. That Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, yl-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3 -At least one of cyclopentylpropan-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one- 2-Imine. In the case of these O-acyl oxime compounds, a high-brightness color filter tends to be obtained.

The above-mentioned alkyl phenyl ketone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

As a compound having a partial structure represented by formula (d2), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl base]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercially available products such as IRGACURE 369, 907, and 379 (the above are manufactured by BASF Corporation) can be used.

As a compound having a partial structure represented by formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4- (2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxy Cyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propan-1-one, α,α-diethoxyacetophenone, benzoyl Acetyl dimethyl ketal, etc.

In terms of sensitivity, as the alkyl phenyl ketone compound, a compound having a partial structure represented by the formula (d2) is preferable.

Examples of the above-mentioned triazine compound include 2,4-bis-trichloromethyl-6--4-methoxyphenyl-1,3,5-triazine, 2,4-bis-trichloromethyl-6 -4-Methoxynaphthyl-1,3,5-triazine, 2,4-bistrichloromethyl-6-pipronyl-1,3,5-triazine, 2,4-bistrichloromethane yl-6-4-methoxystyryl-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(5-methylfuran-2-yl)vinyl ]-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4- Bistrichloromethyl-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bistrichloromethyl- 6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

As said acyl phosphine oxide compound, 2, 4, 6- trimethylbenzyl diphenyl phosphine oxide etc. are mentioned. Commercially available products such as IRGACURE (registered trademark) 819 (manufactured by BASF) can be used.

As said biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis (Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62- 174204 Gazette, etc.), imidazole compounds in which the phenyl group at the 4,4', 5,5'-position is substituted with an alkoxycarbonyl group (for example, see Japanese Patent Laid-Open No. 7-10913, etc.), and the like.

Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Esters, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(3-butylperoxycarbonyl) Benzophenone compounds such as benzophenone and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthraquinone, 2-ethylanthraquinone and camphorquinone; 10-butyl- 2-Chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. Preferably, these polymerization initiators may be used in combination with a polymerization initiator (especially amines) described later.

The acid generators include 4-hydroxyphenyldimethyl perylene-p-toluenesulfonate, 4-hydroxyphenyldimethyl perylene hexafluoroantimonate, and 4-acetoxyphenyldimethylene Acetyl-p-toluenesulfonate, 4-Acetyloxyphenylmethylbenzyl-hexafluoroantimonate, triphenyl-p-toluenesulfonate, triphenyl-perylene hexafluoroantimonate , diphenyliodonium-p-toluenesulfonate, diphenyliodonium Onium salts such as phenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

In some embodiments, the photopolymerization initiator (D) may account for about 0.1-2.5 wt % of the colored resin composition.

In some embodiments, solvent (E) may include, but is not limited to, at least one selected from the group consisting of: an ester solvent (herein meant to contain -COO- in the molecule but not -O- solvent), ether solvent (here means a solvent containing -O- but not -COO- in the molecule), ether ester solvent (here means containing -COO- and -O- in the molecule solvent), ketone solvent (here means a solvent containing -CO- but not -COO- in the molecule), alcohol solvent (here means containing OH in the molecule but not -O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclic Hexanol acetate and γ-butyrolactone, etc.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl butanol, tetrahydrofuran , diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl ether Anisole, etc.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone (cyclohexanone, CHN) and isophorone, etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

As the aromatic hydrocarbon solvent, benzene, toluene, xylene, 1,3,5-trimethylbenzene and the like can be mentioned.

As an amide solvent, N,N- dimethylformamide, N,N- dimethylacetamide, N-methylpyrrolidone, etc. are mentioned.

Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120° C. or higher and 180° C. or lower is preferable from the viewpoint of coatability and drying properties. As the solvent, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, and diethylene glycol monomethyl ether are preferable ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether Acetate, Propylene Glycol Monomethyl ether, N-methylpyrrolidone, ethyl lactate and ethyl 3-ethoxypropionate.

The content rate of the solvent (E) may be 30 to 95 wt %, or 70 to 95 wt %, more preferably 80 to 90 wt %, relative to the total amount of the colored resin composition of the present invention. In other words, the total content rate of the solid components of the colored resin composition may be 5 to 70 wt %, or 5 to 30 wt %, and more preferably 10 to 20 wt %. When the content of the solvent (E) is within the above-mentioned range, the flatness at the time of coating becomes favorable, and the color density does not become insufficient when the color filter is formed, so that the display characteristics tend to become favorable.

In some embodiments, the colored resin composition may further include antioxidants. In some embodiments, the antioxidant may include phenolic type compounds and/or bisphenolic type compounds, but is not limited thereto.

In some embodiments, the colored resin composition may further include a leveling agent (F). Leveling agent (F) is a commonly used coating additive, which can promote the formation of a smooth, smooth and uniform coating film during the drying process of the coating. As a leveling agent, a silicone-based surfactant, a fluorine-based surfactant, a silicone-based surfactant having a fluorine atom, and the like are exemplified. These may have a polymerizable group in the side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray-Dow Corning Corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd. (LLC)) and the like.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray-Dow Corning Corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 ( manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd. (LLC)), and the like.

As said fluorochemical surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, FLUORAD (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (DIC shares have Co., Ltd.), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), SURFLON (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), etc.

As the organosilicon-based surfactant having the above-mentioned fluorine atom, a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like can be exemplified. Specifically, MEGAFACE (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Co., Ltd.), etc. are mentioned.

The content of the leveling agent may be 0.001 wt % or more and 0.2 wt % or less, preferably 0.002 wt % or more and 0.1 wt % or less, and more preferably 0.005 wt % with respect to the total amount of the colored resin composition. More than 0.05wt% or less.

In some embodiments, the colored resin composition may further include other additives such as surfactants, polymerization initiation assistants, fillers, adhesion promoters, light stabilizers, etc., but is not limited thereto. Additives can account for 0~1wt% of the colored resin composition

A polymerization initiator is a compound or a sensitizer for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator. When a polymerization initiator is included, it is usually used in combination with a polymerization initiator. As a polymerization initiation aid, an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine; 4, 4'-bis(dimethylamino)benzophenone (commonly known as MichleRketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl) among them, 4,4'-bis(diethylamino)benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

As said alkoxyanthracene compound, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, and dimethylphenylsulfanyl acetic acid. Alkyl Acetic Acid, Methoxy Phenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine acid, phenoxyacetic acid, thionaphthalene acetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

Another embodiment of the present disclosure is directed to a color filter formed from the colored resin composition according to any of the foregoing embodiments. For example, the coloring resin composition according to any of the foregoing embodiments can be used to form the color filter by a photolithography method, an inkjet method, or a printing method, but the present disclosure is not limited thereto.

As a method of producing a color filter (color filter pattern) from the coloring resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, the photolithography method is preferable. The photolithography method is a method in which the above-mentioned colored resin composition is applied to a substrate, dried to form a colored composition layer, and developed by exposing the colored composition layer through a photomask. In the photolithography method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask and/or not developing during exposure. The colored pattern and colored coating film thus formed can be used as the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose, application, etc., for example, it is 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm, and more preferably 2.5 μm to 3.5 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass whose surface is coated with silica, polycarbonate, polymethyl methacrylate, polyparaphenylene can be used Resin sheets such as ethylene dicarboxylate, silicon, and aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the above-mentioned substrates. Additional color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The formation of various color patterns (pixels) by photolithography can be performed under known or conventional apparatus and conditions. For example, it can be produced as follows.

First, the colored curable resin composition is applied on a substrate, and dried by heating (prebaking) and/or under reduced pressure to remove volatile components such as a solvent and dry to obtain a smooth colored composition layer. As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned.

Next, the coloring composition layer is exposed to light through a photomask for forming a target coloring pattern. It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, since parallel light rays can be uniformly irradiated to the whole exposure surface, and a photomask and the board|substrate on which the coloring composition layer is formed can be correctly aligned.

A coloring pattern is formed on a board|substrate by making the exposed coloring composition layer contact with a developing solution, and developing. By developing, the unexposed portion of the coloring composition layer is dissolved in the developing solution and removed. as The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10 wt %, and more preferably 0.03 to 5 wt %. Furthermore, the developer may contain a surfactant. The development method may be any of a spin dipping method, a dipping method, a spray method, and the like. Furthermore, the substrate can be inclined at an arbitrary angle during development. It can be washed with water after developing.

In some embodiments, the present case can be exposed with an exposure dose of 50 to 100 mJ. In some embodiments, the gap between the edge of the hole and the hole after exposure and development may be only 1 to 50 μm , or may be 3 to 40 μm .

Furthermore, it is preferable to post-bake the obtained coloring pattern. The post-baking temperature is preferably 90°C to 250°C, or may be 100°C to 240°C. The post-baking time is preferably 1 to 120 minutes.

With the colored resin composition of the present application, a color filter with a fine hole pattern can be produced. This color filter can be used as a color filter or a color filter for display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state photographing elements.

Yet another embodiment of the present disclosure relates to a display device, which may include the aforementioned color filter, but the present disclosure is not limited thereto. According to some embodiments of the present disclosure, the display device It can be a display such as a liquid crystal display device, an organic electroluminescence display device, or a plasma display device.

For example, a display device may have a backlight, a TFT substrate, a color filter substrate, and a display medium (such as liquid crystal) disposed between the TFT substrate and the color filter substrate, and the color filter substrate of which can use the A filter formed of a colored resin composition.

Hereinafter, the present disclosure will provide several examples and comparative examples to more specifically illustrate the effects that can be achieved by the colored resin compositions according to the embodiments of the present disclosure, and the colored resin compositions obtained by applying the present disclosure. characteristics. However, the following examples and comparative examples are only used for illustration, and should not be construed as a limitation of the implementation of the present disclosure.

Tables 1 to 3 show the compositions of the colored resin compositions of the respective examples and comparative examples, and the types selected for each component of the composition are described below. The unit "parts" used below means parts by weight unless otherwise specified.

Green Pigment (G58): 16 parts by weight of C.I. Pigment Green 58, 4 parts by weight of acrylic pigment dispersant, 2.3 parts by weight (solid content) of pigment dispersing resin (the first binding polymer (B1- 4)) The mixture with 77.7 parts by weight of propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate) was uniformly dispersed by a bead mill.

Yellow Pigment (Y138): 12 parts by weight of C.I. Pigment Yellow 138, 4.8 parts by weight (solid content) of acrylic pigment dispersant, 4.8 parts by weight (solid content) of pigment dispersing resin (such as the first adhesive polymerization described below Compound (B1-4)), 5 parts by weight of diacetone alcohol (DAA) and 73.4 parts by weight of propylene glycol methyl ether acetate are uniformly dispersed in a bead mill.

First adhesive polymer (B1-1): copolymer of E-DCPA (9.9 parts by weight)/AA (15.1 parts by weight)/CHMI (55 parts by weight)/HEMA (20 parts by weight), weight average molecular weight (Mw) About 8,000.

First adhesive polymer (B1-2): trade name "EHPE-3150".

The first adhesive polymer (B1-3): a copolymer of TCDMA (10 parts by weight)/BZMA (59.6 parts by weight)/MAA (30.4 parts by weight), with a weight average molecular weight (Mw) of about 11,000.

The first adhesive polymer (B1-4): a copolymer of (TCDMA (3 parts by weight)/GMA (70 parts by weight)/2HEA (27 parts by weight)) sequentially combined with AA (70 parts by weight) and SA (13 parts by weight) part) of the copolymer formed by the copolymerization reaction, the weight average molecular weight (Mw) is about 6,000.

The first adhesive polymer (B1-5): a copolymer of (TCDMA (3 parts by weight)/GMA (30 parts by weight)/2HEA (30 parts by weight)/MMA (37 parts by weight)) sequentially mixed with AA (30 parts by weight) parts) and SA (10.9 parts by weight) were copolymerized to form a copolymer with a weight-average molecular weight (Mw) of about 9,700.

Second adhesive polymer (B2): a copolymer of MAA (40 parts by weight)/TCDMA (20 parts by weight)/3-(meth)acrylooxypropyltriethoxysilane (40 parts by weight).

Photopolymerizable monomer (C1): Dipivalerythritol hexaacrylate ("A9550" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., in terms of solid content).

Photopolymerizable monomer (C2): tripentaerythritol octaacrylate.

Photopolymerization initiator (D): acetophenone compound (trade name: Trolly PBG327).

Additive: Trimethylolpropane tris(3-mercaptopropionate) (TMMP) manufactured by SC Organic Chemicals.

Leveling agent: F554 (manufactured by DIC Co., Ltd.).

Solvent: Propylene Glycol Monomethyl Ether Acetate (PGMEA).

Tables 1 to 3 also list the patterned color filters observed with an optical microscope using the colored resin composition through exposure and development processes to form patterned color filters on the substrate, and the patterned color filters were baked at 280°C for 20 minutes. The residual particle results of the tablet. The film thickness of the patterned color filter was about 3 μm, the hole diameter was about 30 μm, and the evaluation was the average number of residual particles observed in two holes. "◎" indicates that the average number of remaining fine particles in the pores is 0 or more and less than 5, which is an excellent case. "X" indicates that the average number of remaining fine particles in the pores is 5 or more, and this is evaluated as a defective product.

According to Example 14 and Example 15, it can be found that when the colorant (A) of the coloring resin composition only uses green pigment and yellow pigment, among them In one case, the patterned color filter formed from the colored resin composition has fewer residual particles in the holes.

When the coloring agent (A) of the coloring resin composition includes both green pigment and yellow pigment, compared with the comparative example, the coloring resin compositions of the remaining Examples 4~6, 10~13, 17~18 and 21 formed The patterned color filter has fewer residual particles in the holes, thus helping to improve product yield.

To sum up, although the present invention has been disclosed by the above embodiments, it is not intended to limit the present invention. Those skilled in the art to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope of the appended patent application.

Claims (11)

A colored resin composition, comprising: colorants, including green pigments and/or yellow pigments; photopolymerization monomers; photopolymerization initiators; solvents; ,4-Epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl ester/3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl acrylate/(methyl acrylate Copolymer of acrylic acid (AA)/N-cyclohexylmaleimide (CHMI)/(meth)acrylic acid 2-hydroxyethyl ester (HEMA); (meth)acrylic acid dicyclopentyl ester (TCDMA)/ Glycidyl (meth)acrylate (GMA)/2-ethylhexylacrylate (2HEA)/(meth)acrylic acid (AA)/succinic acid (SA) copolymer; and dicyclopentane (meth)acrylate Esters (TCDMA)/Glycidyl(Meth)acrylate(GMA)/2-Ethylhexylacrylate(2HEA)/Methyl(Meth)acrylate(MMA)/(Meth)acrylic acid(AA)/Succinic acid (SA) copolymer, and the first adhesive polymer accounts for 0.2-2.6wt% of the colored resin composition; and the second adhesive polymer includes silane-based monomer units, wherein the first adhesive polymer The total content with the second adhesive polymer accounts for 0.4-5.8 wt % of the colored resin composition. The colored resin composition according to claim 1, wherein the silane-based monomer unit has the structure shown below:

Wherein, R4 represents a hydrogen atom or a methyl group; R5~R7 each independently represents a hydrogen atom, an alkyl group with a carbon number of 1~6 or an alkoxy group with a carbon number of 1~6, but at least one of R5~R7 is a carbon number 1-6 alkoxy groups; p is a positive integer, q is an integer of 1-10. The colored resin composition according to claim 1, wherein the colorant accounts for 5-50 wt % of the colored resin composition. The colored resin composition according to claim 1, wherein the colorant comprises the green pigment and the yellow pigment, and the content of the yellow pigment is less than the content of the green pigment. The colored resin composition according to claim 1, wherein the green pigment accounts for 17-30 wt % of the colored resin composition. The colored resin composition according to claim 1, wherein the yellow pigment accounts for 5-17 wt % of the colored resin composition. The colored resin composition according to claim 1, wherein the second adhesive polymer accounts for 0.2-2.9 wt % of the colored resin composition. The colored resin composition according to claim 1, wherein the weight ratio of the first adhesive polymer: the second adhesive polymer is 0.1-3.5:1. The colored resin composition of claim 1, wherein the green pigment comprises C.I. Pigment Green 58 (G58), and/or the yellow pigment comprises C.I. Pigment Yellow 138 (Y138). A color filter formed of the colored resin composition according to any one of claims 1 to 9. A display device comprising the color filter of claim 10.