TWI908979B - Color-curable resin compositions, color filters, display devices, and solid-state imaging elements. - Google Patents

Abstract

The purpose of this invention is to provide a color-curing resin composition useful for manufacturing color filters with good contrast. The color-curing resin composition of this invention is characterized by comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) comprises a squaric acid innerium dye, the polymerizable compound (C) has an average vinyl unsaturated group equivalent number represented by formula (1) of less than 96.0, and the content of the squaric acid innerium dye is 3 to 140 parts by weight relative to 100 parts by weight of the polymerization initiator (D).

Description

Color-curable resin compositions, color filters, display devices, and solid-state imaging elements

This invention relates to a color-curing resin composition, a color filter, a display device, and a solid-state imaging element.

Color filters used in display devices such as liquid crystal displays, electroluminescence displays, and plasma displays, or in solid-state imaging elements such as charge-coupled devices (CCDs) or complementary metal-oxide-semiconductor (CMOS) sensors, are manufactured from color-curing resin compositions. In the embodiments of Patents 1 to 2, dipentaerythritol hexaacrylate is primarily used as the polymeric compound used in these color-curing resin compositions.

[Existing technical literature]

[Patent Documents]

[Patent Document 1] Japanese Patent Application Publication No. 2020-055956

[Patent Document 2] Japanese Patent Application Publication No. 2019-163233

However, color filters made from color-curing resins containing dipentaerythritol hexaacrylate sometimes lack sufficient contrast.

The purpose of this invention is to provide a color-curing resin composition useful for manufacturing color filters with good contrast.

In other words, the main points of this invention are as follows.

[1] A color-curing resin composition comprising a colorant (A), a resin (B), a polymeric compound (C), and a polymerization initiator (D), wherein the colorant (A) comprises a squaric acid inneron dye, the average ethylene unsaturated base equivalent number of the polymeric compound (C) represented by formula (1) is less than 96.0, and the content of the squaric acid inneron dye is 3 to 140 parts by mass relative to 100 parts by mass of the polymerization initiator (D), and the average ethylene unsaturated base equivalent number of the polymeric compound (C) is ΣK _{i mi} ... (1) [In formula (1), _Ki : represents the value of component i in all polymeric compounds (C) contained in the color-curing resin composition (molecular weight/number of ethylene unsaturated bonds).

_mi : represents the molar fraction of component i.

[2] A color-curing resin composition as described in [1], wherein the squaric acid inneron dye comprises at least one of the group consisting of compounds represented by formula (I) and compounds represented by formula (III).

[In formula (I), ^R1 to ^R8 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon with 1 to 20 carbon atoms that may have substituents, or an alkoxy group with 1 to 20 carbon atoms that may have substituents; ^R9 and ^R10 independently represent a divalent aliphatic hydrocarbon with 1 to 20 carbon atoms that may have substituents, wherein the methylene group contained in the aliphatic hydrocarbon may be substituted to -O-; ^R11 and ^R12 independently represent a hydrocarbon with 6 to 20 carbon atoms having an aromatic hydrocarbon ring, wherein the hydrocarbon may have substituents, and the methylene group contained in the hydrocarbon may be substituted to -O-; ^R13 represents a hydrogen atom or a saturated hydrocarbon with 1 to 8 carbon atoms.]

[In formula (III), R ³¹ to R ³⁸ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms that may have substituents, or an alkoxy group having 1 to 20 carbon atoms that may have substituents; R ³⁹ to R ⁴² each independently represent an hydrocarbon having 1 to 20 carbon atoms that may have substituents; at least one of R ³⁹ to R ⁴² is an aliphatic hydrocarbon having 1 to 20 carbon atoms that has a carboxyl group as a substituent; and at least one of R ³⁹ to R ⁴² is an aromatic hydrocarbon having 6 to 20 carbon atoms that may have substituents; the methylene group contained in the aliphatic hydrocarbon may be substituted with -O-].

[3] A color-curing resin composition as described in [1] or [2], wherein the average vinyl unsaturated base equivalent number is 83.0 or higher.

[4] A color-curing resin composition as described in any one of [1] to [3], wherein the polymeric compound (C) comprises a polymeric compound having three or more but no more than five ethylene unsaturated bonds.

[5] A color-curing resin composition as described in any one of [1] to [4], wherein the polymeric compound (C) comprises at least one selected from pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and glycerol tri(meth)acrylate.

[6] A color-curing resin composition as described in any one of [1] to [5], wherein the polymerization initiator (D) comprises an O-acetylgimide compound.

[7] A color filter formed from a color-curing resin composition as described in any one of [1] to [6].

[8] A display device comprising a color filter as described in [7].

[9] A solid-state imaging element comprising a color filter as described in [7].

According to the present invention, a color-curing resin composition useful for manufacturing color filters with good contrast can be provided.

The color-curing resin composition of this invention comprises: a colorant (hereinafter, there may be a case referred to as colorant (A)), a resin (hereinafter, there may be a case referred to as resin (B)), a polymerizable compound (hereinafter, there may be a case referred to as polymerizable compound (C)) and a polymerization initiator (hereinafter, there may be a case referred to as polymerization initiator (D)).

Colorant (A) contains squaric acid-lactone dyes.

The coloring and curing resin composition of this invention may contain a solvent (hereinafter, there exists a case referred to as solvent (E)).

The coloring and curing resin composition of this invention may also contain a leveling agent (hereinafter, there exists a case referred to as leveling agent (F)).

Furthermore, unless otherwise specified, the compounds exemplified as ingredients in this specification may be used alone or in combination.

<Colorant (A)>

Colorant (A) comprises a squaric acid-lactonium dye. There are no particular limitations on the squaric acid-lactonium dye; any known dye may be used.

As a squaric acid inneron dye, it is preferably a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). Furthermore, compound (I) is assumed to include the resonance structure of formula (I), and further includes compounds obtained by rotating the bases of formula (I) or its resonance structure around the bonding axis of a carbon-carbon single bond or a carbon-nitrogen single bond.

[In formula (I), ^R1 to ^R8 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon with 1 to 20 carbon atoms that may have substituents, or an alkoxy group with 1 to 20 carbon atoms that may have substituents; ^R9 and ^R10 independently represent a divalent aliphatic hydrocarbon with 1 to 20 carbon atoms that may have substituents, wherein the methylene group contained in the aliphatic hydrocarbon may be substituted to -O-; ^R11 and ^R12 independently represent a hydrocarbon with 6 to 20 carbon atoms having an aromatic hydrocarbon ring, wherein the hydrocarbon may have substituents, and the methylene group contained in the hydrocarbon may be substituted to -O-; ^R13 represents a hydrogen atom or a saturated hydrocarbon with 1 to 8 carbon atoms.]

The halogen atoms represented by ^R1 to ^R8 include: fluorine, chlorine, bromine, iodine, etc.

The saturated hydrocarbons represented by ^R1 to ^R8 , having 1 to 20 carbon atoms, can be linear, branched, or cyclic. Examples of linear or branched saturated hydrocarbons include: methyl, ethyl, propyl, isobutyl, butyl, tributyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecanyl, undecyl, etc. Examples of cyclic saturated hydrocarbons include: cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1,2-dimethylcyclohexyl, cyclooctyl, 2,4,6-trimethylcyclohexyl, 4-cyclohexylcyclohexyl, etc.

Substituents for saturated hydrocarbons with 1 to 20 carbon atoms, represented by ^R1 to ^R8 , include: halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl groups; ^-NRaRb ( ^Ra and ^Rb are independently hydrogen atoms or alkyl groups with 1 ^to 20 carbon atoms); nitro groups; alkoxy groups with 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups with 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.

As alkoxy groups representing 1 to 20 carbon atoms ( ^R1 to R8 ⁾ , examples include those with -O- groups bonded to the bonding bonds of the saturated hydrocarbons having 1 to 20 carbon atoms. Specifically, examples include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, dibutoxy, tributoxy, pentoxy, hexoxy, heptoxy, octoxy, 2-ethylhexoxy, etc.

Substituents for alkoxy groups with 1 to 20 carbon atoms, represented by ^R1 to ^R8 , include: halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl; ^-NRcRd (where ^Rc and ^Rd are independently hydrogen atoms or alkyl groups with 1 ^to 20 carbon atoms); nitro; alkoxy groups with 1 to 10 carbon atoms such as methoxy and ethoxy; and alkoxycarbonyl groups with 1 to 10 carbon atoms in the alkoxy moiety, such as methoxycarbonyl and ethoxycarbonyl.

The number of carbons in the saturated hydrocarbons represented by ^R1 to ^R8 is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 7, and even more preferably 1 to 4.

The saturated hydrocarbons represented by ^R1 to ^R8 are preferably linear or branched linear saturated hydrocarbons, and more preferably linear saturated hydrocarbons.

Of ^R1 to ^R8 , ^R1 to ^R4 are preferably hydrogen atoms or methyl groups, more preferably hydrogen atoms. Furthermore, if ^R1 to ^R4 are hydrogen atoms or methyl groups, it is even more preferable that ^R5 to ^R8 are each independently preferably hydrogen atoms, hydroxyl groups, saturated hydrocarbons with ¹ to ²⁰ carbon atoms that may have substituents, or alkoxy groups with 1 to 20 carbon atoms that may have substituents, more preferably hydrogen atoms or hydroxyl groups.

Preferably, 2 to 4 of ^R1 to ^R8 (preferably ^R5 to ^R8 ) are each independently hydroxyl groups; more preferably, 2 to 3 of ^R1 to ^R8 (preferably ^R5 to ^R8 ) are each independently hydroxyl groups; and even more preferably, 2 of ^R1 to ^R8 (preferably ^R5 to ^R8 ) are each independently hydroxyl groups.

The divalent aliphatic hydrocarbons with 1 to 20 carbon atoms represented by ^R9 and ^R10 can be either saturated or unsaturated, preferably saturated. In addition, the divalent aliphatic hydrocarbons with 1 to 20 carbon atoms can be any of linear, branched, or cyclic, preferably linear or branched.

Examples of divalent aliphatic hydrocarbons with 1 to 20 carbon atoms include: methylene, ethyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, decadecane... Divalent straight-chain aliphatic hydrocarbons such as hexadecane-1,16-diyl, heptadecane-1,17-diyl, and propenyl; and divalent branched-chain aliphatic hydrocarbons such as ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, 2,2-dimethylpropane-1,3-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl.

Cyclic divalent aliphatic hydrocarbons can be monocyclic or polycyclic. Examples of monocyclic divalent aliphatic hydrocarbons include: cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; and polycyclic divalent aliphatic hydrocarbons include norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl.

The number of carbons in the divalent aliphatic hydrocarbons represented by ^R9 and ^R10 is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 4.

The divalent aliphatic hydrocarbons with 1 to 20 carbon atoms represented by ^R9 and ^R10 are preferably saturated linear or branched aliphatic hydrocarbons, and more preferably saturated linear aliphatic hydrocarbons.

The divalent aliphatic hydrocarbons represented by ^R9 and ^R10 may be the same or different, but it is preferred that they are the same.

The methylene group in the divalent aliphatic hydrocarbon having 1 to 20 carbon atoms can be substituted with -O-. Examples of groups where the methylene group in the divalent aliphatic hydrocarbon is substituted with -O- include those represented by the following formula. In the following formulas, the * on the left indicates a bond with a nitrogen atom, and the * on the right indicates a bond with an oxygen atom.

[Chemistry 4]

The divalent aliphatic hydrocarbons with 1 to 20 carbon atoms represented by ^R9 and ^R10 may have substituents. Examples of such substituents include: halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl groups ^{; -NReRf} (where ^Re and ^Rf are independently hydrogen atoms or alkyl groups with 1 to 20 carbon atoms); nitro groups; alkoxycarbonyl groups with 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.

Among them, the divalent aliphatic hydrocarbons represented by ^R9 and ^R10 are preferably methylene, ethyl, propane-1,3-diyl, or butane-1,4-diyl.

As represented by R ¹¹ and R ¹² , hydrocarbons having an aromatic hydrocarbon ring with 6 to 20 carbon atoms can be listed as groups having a bond on the aromatic hydrocarbon ring (hereinafter referred to as aromatic hydrocarbons) and aralkyl groups having 7 to 20 carbon atoms. These may have substituents.

Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings, with benzene rings being preferred.

Examples of aromatic hydrocarbon groups include: phenyl, naphthyl, anthraceneyl, phenanthryl, tolyl, xylyl, dimethylethylphenyl, dimethylpropylphenyl, dimethylbutylphenyl, trimethylphenyl, diisopropylphenyl, etc. Preferably, these are aromatic hydrocarbon groups having an alkyl group at the adjacent position, such as: 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 2,6-dimethyl-4-ethyl-phenyl, 2,6-dimethyl-4-propyl-phenyl, 2,6-dimethyl-4-butyl-phenyl, etc. Furthermore, a larger volume of the adjacent alkyl group tends to result in better lightfastness.

When an aromatic hydrocarbon has substituents, it may have one or more such substituents. When an aromatic hydrocarbon has multiple substituents, the substituents may be the same or different. Examples of such substituents include: hydroxyl; carboxyl; halogen atoms such as fluorine, chlorine, iodine, and bromine; alkoxy groups with 1 to 6 carbon atoms such as methoxy and ethoxy; alkylsulfonyl groups with 1 to 6 carbon atoms such as aminesulfonyl; alkylsulfonyl groups with 1 to 6 carbon atoms such as methylsulfonyl; alkoxycarbonyl groups with 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.

The aromatic hydrocarbon ring with 6 to 20 carbon atoms may have substituents such as hydroxyl, carboxyl, halogen atom, and alkoxy group, preferably hydroxyl.

In the case where the aromatic hydrocarbon that may have substituents has a methylene group, the methylene group may be substituted to -O-.

The aralkyl group having 7 to 20 carbon atoms can be categorized as having an alkyl dienyllium group having 1 to 5 carbon atoms, such as methylene, ethyl, or propyl, bonded to the aromatic hydrocarbon ring described in the aromatic hydrocarbon group description. Examples of such aralkyl groups include: benzyl, phenylethyl, naphthylmethyl, and naphthylethyl.

The aralkyl group having 7 to 20 carbon atoms may have substituents. When multiple substituents are present, they may be the same or different. These substituents may be bonded to the aromatic hydrocarbon ring or to the alkyl diene group. Substituents capable of bonding to the aromatic hydrocarbon ring are the same as those described for substituents of the aromatic hydrocarbon group.

When the aralkyl group having 7 to 20 carbon atoms has a methylene group, the methylene group can be substituted to -O-.

The hydrocarbon groups with 6 to 20 carbon atoms representing aromatic hydrocarbon rings represented by R ¹¹ and R ¹² may be the same or different, but it is preferred that they are the same.

Among them, the hydrocarbons with 6 to 20 carbon atoms representing the aromatic hydrocarbon rings represented by R ¹¹ and R ¹² are preferably dimethylethylphenyl, dimethylpropylphenyl, dimethylbutylphenyl, dimethylmethoxyphenyl, dimethylethoxyphenyl, or dimethylpropoxyphenyl, more preferably 2,6-dimethyl-4-ethylphenyl, 2,6-dimethyl-4-propylphenyl, 2,6-dimethyl-4-butylphenyl, 2,6-dimethyl-4-methoxyphenyl, 2,6-dimethyl-4-ethoxyphenyl, or 2,6-dimethyl-4-propoxyphenyl, and even more preferably 2,6-dimethyl-4-methoxyphenyl, 2,6-dimethyl-4-ethoxyphenyl, or 2,6-dimethyl-4-propoxyphenyl, and even more preferably 2,6-dimethyl-4-ethoxyphenyl. In addition, it is preferred that the substituents for ethyl, propyl, butyl, methoxy, ethoxy, and propoxy have hydroxyl groups.

The saturated hydrocarbons with 1 to 8 carbon atoms represented by R ¹³ can be linear, branched, or cyclic. Examples of linear or branched saturated hydrocarbons include: methyl, ethyl, propyl, isobutyl, butyl, tributyl, hexyl, heptyl, and octyl. Examples of cyclic saturated hydrocarbons include: cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1,2-dimethylcyclohexyl, and cyclooctyl.

Among them, R ¹³ is particularly good for hydrogen atoms.

As for compound (I), examples include compounds represented by formulas (I-1) to (I-240) shown in Tables 1 to 3.

[Table 1]

[Table 2]

In Tables 1-3, A1-1 to A1-4 represent the bases indicated by the following formulas. In these formulas, the asterisk (*) on the left-hand side indicates a bond with a nitrogen atom, and the asterisk (*) on the right-hand side indicates a bond with an oxygen atom.

In Tables 1-3, A2-1 to A2-5 represent the bases represented by the following formulas. In the following formulas, * indicates a key.

In addition to the compounds represented by formulas (I-1) to (I-240), compounds represented by formula (II) (hereinafter sometimes referred to as compound (II)) are also listed as compound (I), with compound (II) being preferred. Compound (II) exhibits good lightfastness.

[Chemistry 7]

In equation (II), ^R1 ~ ^R10 have the same meaning as ^R1 ~ ^R10 in equation (I).

^X1 and ^X2 independently represent an hydrocarbon, hydroxyl, and carboxyl group having 1 to 14 carbon atoms, having at least one group selected from the group consisting of hydroxyl and carboxyl groups, wherein the methylene group contained in the hydrocarbon group may be substituted with -O-.

^R14 and ^R15 represent hydrogen atoms or hydrocarbons with 1 to 13 carbon atoms, respectively.

n1 and n2 represent integers from 1 to 5 independently.

The total carbon number of ( ^X1 ) _n1 and ( ^R14 ) _5-n1 , and the total carbon number of ( ^X2 ) _n2 and ( ^R15 ) _5-n2 are both 14 or less.

As hydrocarbons with 1 to 14 carbon atoms represented by ^X1 and ^X2 , aliphatic hydrocarbons, aromatic hydrocarbons, and groups formed by combining these can be listed.

Examples of linear aliphatic hydrocarbons include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

Examples of branched, chain-like aliphatic hydrocarbons include: isopropyl, dibutyl, tributyl, methylpentyl, ethylpentyl, methylhexyl, ethylhexyl, propylhexyl, and trioctyl, with isopropyl, dibutyl, tributyl, and ethylhexyl being preferred.

Examples of cyclic aliphatic hydrocarbons include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and diamondyl.

Examples of aromatic hydrocarbons include: phenyl, naphthyl, anthraceneyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, isopropylphenyl, mesitylene, biphenyl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.

Examples of bases that can be used to combine these compounds include: alkyl-cycloalkyl, cycloalkyl-alkyl, aralkyl, etc.

The carbon number of the groups represented by ^X1 and ^X2 with carbon numbers of 1 to 14 is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 4.

The hydrocarbons represented by ^X1 and ^X2 , having 1 to 14 carbon atoms, are preferably linear or branched aliphatic hydrocarbons, more preferably linear aliphatic hydrocarbons, and even more preferably methyl, ethyl, propyl or butyl.

The groups represented by ^X1 and ^X2 , which have 1 to 14 carbon atoms, may be the same or different, but are preferably the same.

Preferably, ^X1 and ^X2 are each independently an hydrocarbon having at least one group selected from the group consisting of hydroxyl and carboxyl groups, having 1 to 10 carbon atoms; more preferably, ^X1 and ^X2 are each independently an hydrocarbon having at least one group selected from the group consisting of hydroxyl and carboxyl groups, having 1 to 7 carbon atoms; even more preferably, ^X1 and ^X2 are each independently an hydrocarbon having at least one group selected from the group consisting of hydroxyl and carboxyl groups, having 1 to 4 carbon atoms; and even more preferably, ^X1 and ^X2 are each independently an hydrocarbon having a hydroxyl group, having 1 to 4 carbon atoms.

The methylene group in the hydrocarbons having 1 to 14 carbon atoms may be substituted with -O-.

Examples of groups ^that are the ^same as those described as groups that are the same as ^{those ...}

R ¹⁴ and R ¹⁵ may be the same or different, but it is better for them to be the same.

Among them, ^R14 and ^R15 are preferably hydrogen atoms.

n1 and n2 independently represent integers from 1 to 5, preferably from 1 to 2, and even better, 1.

The total carbon number of ( ^X1 ) _n1 and ( ^R14 ) _5-n1 , and the total carbon number of ( ^X2 ) _n2 and ( ^R15 ) _5-n2 are 14 or less. In the case of multiple ^X1 , ^X2 , ^R14 and ^R15 , each ^X1 , ^X2 , ^R14 and ^R15 may be the same or different.

As for compound (II), compounds represented by formula (II-a) can be listed, and more specifically, compounds represented by formulas (II-1) to (II-540) shown in Tables 4 to 12 can be listed.

In Tables 4 to 12, A1-1 to A1-4 represent the same bases as described above.

In Tables 4 to 12, A3-1 to A3-3 represent the bases represented by the following formulas. In the following formulas, * indicates a key.

In Tables 4-12, A4-1 to A4-3 represent the bases represented by the following formulas. In the following formulas, * indicates a key.

The compounds represented by formulas (I), (II), and (II-a) preferably have 2 to 10, more preferably 3 to 9, and even more preferably 4 to 8 hydroxyl groups, respectively.

As compound (I), it is preferably a compound represented by formulas (I-1) to (I-180), (II-121) to (II-180), and (II-331) to (II-375), more preferably a compound represented by formulas (I-25) to (I-36), (I-85) to (I-96), (I-145) to (I-156), (I-169) to (I-181), (II-121) to (II-150), and (II-361) to (II-375), further preferably a compound represented by formulas (II-133) to (II-135), and most preferably a compound represented by formula (II-135).

The compound represented by formula (I) can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2020-055956.

As a squaric acid inneron dye, it is preferably a compound comprising formula (III) (hereinafter, sometimes referred to as compound (III)). Furthermore, compound (III) is assumed to contain the resonance structure of formula (III), and further includes compounds obtained by rotating the bases of formula (III) or its resonance structure around the bonding axis of a carbon-carbon single bond or a carbon-nitrogen single bond.

In formula (III), R ³¹ to R ³⁸ represent hydrogen atoms, hydroxyl groups, alkyl groups with 1 to 20 carbon atoms that may have substituents, or alkoxy groups with 1 to 20 carbon atoms that may have substituents.

R ³⁹ to R ⁴² each independently represent an hydrocarbon having 1 to 20 carbon atoms that may have substituents, wherein at least one of R ³⁹ to R ⁴² is an aliphatic hydrocarbon having 1 to 20 carbon atoms with a carboxyl group as a substituent, and at least one of R ³⁹ to R ⁴² is an aromatic hydrocarbon having 6 to 20 carbon atoms that may have substituents, wherein the methylene group contained in the aliphatic hydrocarbon may be substituted with -O-.

The alkyl groups represented by R ³¹ to R ³⁸ , having 1 to 20 carbon atoms, can be linear, branched, or cyclic. Examples of linear or branched alkyl groups include: methyl, ethyl, propyl, isobutyl, butyl, tributyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecanyl, undecyl, etc. Examples of cyclic alkyl groups include: cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1,2-dimethylcyclohexyl, cyclooctyl, 2,4,6-trimethylcyclohexyl, 4-cyclohexylcyclohexyl, etc.

Substituents for alkyl groups with 1 to 20 carbon atoms represented by R ³¹ to R ³⁸ include: halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl; ^-NRkRl (where ^Rk and ^Rl are independently hydrogen atoms or alkyl ^groups with 1 to 20 carbon atoms); nitro; alkoxy groups with 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups with 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.

As alkoxy groups with 1 to 20 carbon atoms represented by R ³¹ to R ³⁸ , examples include those with -O- groups bonded to the bonding bonds of the alkyl groups with 1 to 20 carbon atoms. Specifically, examples include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, dibutoxy, tributoxy, pentoxy, hexoxy, heptoxy, octoxy, 2-ethylhexoxy, etc.

Substituents for alkoxy groups with 1 to 20 carbon atoms, represented by R ³¹ to R ^{38, include} : halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl; ^-NRmRn (where ^Rm and ^Rn are independently hydrogen atoms or alkyl groups with 1 to 20 carbon atoms); nitro; alkoxy groups with 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups with 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.

The alkyl and alkoxy groups represented by R ³¹ to R ³⁸ with 1 to 20 carbon atoms preferably have 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.

Of R ³¹ to R ³⁸ , R ³¹ to R ³⁴ are preferably hydrogen atoms. In addition, R ³⁵ to R ³⁸ are each preferably independently hydrogen atoms, hydroxyl groups, alkyl groups having 1 to 20 carbon atoms that may have substituents, or alkoxy groups having 1 to 20 carbon atoms that may have substituents, and more preferably hydrogen atoms or hydroxyl groups.

Preferably, 2 to 4 of R ³¹ to R ³⁸ (preferably R ³⁵ to R ³⁸ ) are each independently hydroxyl groups; more preferably, 2 to 3 of R ³¹ to R ³⁸ (preferably R ³⁵ to R ³⁸ ) are each independently hydroxyl groups; and even more preferably, 2 of R ³¹ to R ³⁸ (preferably R ³⁵ to R ³⁸ ) are each independently hydroxyl groups.

Examples of hydrocarbons with 1 to 20 carbon atoms, represented by R ³⁹ to R ⁴² , include aliphatic hydrocarbons with 1 to 20 carbon atoms or aromatic hydrocarbons with 6 to 20 carbon atoms.

The aliphatic hydrocarbon with 1 to 20 carbon atoms can be either saturated or unsaturated, preferably saturated. Furthermore, the aliphatic hydrocarbon with 1 to 20 carbon atoms can be any of linear, branched, or cyclic structures, preferably linear or branched.

Examples of aliphatic hydrocarbons with 1 to 20 carbon atoms, either linear or branched, include: linear aliphatic hydrocarbons such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, vinyl, 1-propenyl, and 2-propenyl (allyl); and branched aliphatic hydrocarbons such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The aliphatic hydrocarbon preferably has 1 to 15 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 5.

The cyclic aliphatic hydrocarbon group can be monocyclic or polycyclic. Examples of such cyclic aliphatic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 8, more preferably 3 to 6.

The methylene group in the aliphatic hydrocarbon having 1 to 20 carbon atoms may be substituted with -O-. Examples of groups in which the methylene group in the aliphatic hydrocarbon is substituted with -O- include those represented by the following formulas. In the following formulas, * denotes a bond.

Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include phenyl, xylyl, trimethylphenyl, dipropylphenyl, bis(2,2-dimethylpropyl)phenyl, and naphthyl. The aromatic hydrocarbon preferably has 6 to 16 carbon atoms, more preferably 6 to 12, and even more preferably 6 to 9.

The hydrocarbons with 1 to 20 carbon atoms represented by R ³⁹ to R ⁴² may have substituents. Examples of such substituents include: carboxyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups with 1 to 10 carbon atoms such as methoxy and ethoxy; hydroxyl groups; amine sulfonyl groups; alkoxy carbonyl groups with 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.

At least one of R ³⁹ to R ⁴² is an aliphatic hydrocarbon having 1 to 20 carbon atoms as a carboxyl group as a substituent. Ideally, the aliphatic hydrocarbon having 1 to 20 carbon atoms as a carboxyl group as a substituent has 1 to 2 carboxyl groups, more preferably 1 carboxyl group. Furthermore, it is ideal that the carboxyl group is bonded to at least the end of the aliphatic hydrocarbon having 1 to 20 carbon atoms as a carboxyl group as a substituent. Examples of such aliphatic hydrocarbon having 1 to 20 carbon atoms as a carboxyl group as a substituent include groups represented by the following formula. In the following formula, * indicates a bond.

At least one of R ³⁹ to R ⁴² is an aromatic hydrocarbon with 6 to 20 carbon atoms that may have substituents. Preferably, the aromatic hydrocarbon with 6 to 20 carbon atoms that may have substituents is a phenyl group, such as phenyl, xylyl, trimethylphenyl, dipropylphenyl, bis(2,2-dimethylpropyl)phenyl, or 2,4-difluorophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl, or 2,4-diiodophenyl, having two halogen atoms as substituents; more preferably, it is 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, or 2,4-difluorophenyl.

In compound (III), preferably R ³⁹ and R ⁴² are each independently an aliphatic hydrocarbon with 1 to 20 carbon atoms having a carboxyl group as a substituent, and R ⁴⁰ and R ⁴¹ are each independently an aromatic hydrocarbon with 6 to 20 carbon atoms that may have substituents. More preferably, R ³⁹ and R ⁴² are each independently an aliphatic hydrocarbon with 1 to 10 carbon atoms having a carboxyl group as a substituent, and R 40 and R 41 are each independently an aromatic hydrocarbon with 6 to 16 carbon atoms that may have substituents. Even more preferably, R ³⁹ and R ⁴² are each independently an aliphatic hydrocarbon with 1 to 8 carbon atoms having a carboxyl group as a substituent, and R ⁴⁰ and R ⁴¹ are each independently an aromatic hydrocarbon with 6 to 12 carbon atoms that may have substituents. Even more preferably, R ³⁹ and R 42 are each independently an aliphatic hydrocarbon with 1 to 8 carbon atoms having a carboxyl group as a substituent, and R ⁴⁰ and R ⁴¹ are each independently an aromatic hydrocarbon with 6 to 12 carbon atoms that may have substituents. ^R42 is an aliphatic hydrocarbon with 1 to 5 carbon atoms having a carboxyl group as a substituent, and ^R40 and ^R41 are aromatic hydrocarbons with 6 to 9 carbon atoms that may have substituents.

Compound (III) preferably has 2-4 hydroxyl groups and 2-4 carboxyl groups, more preferably has 2-3 hydroxyl groups and 2-3 carboxyl groups, and even more preferably has 2 hydroxyl groups and 2 carboxyl groups.

As compounds (III), examples include those represented by formulas (III-1) to (III-180) shown in Tables 13 to 15.

Regarding compound (III), it is preferably a compound represented by formulas (III-1) to (III-90), (III-121) to (III-180), more preferably a compound represented by formulas (III-1) to (III-30), (III-121) to (III-150), even more preferably a compound represented by formulas (III-1) to (III-3), (III-19) to (III-21), (III-127) to (III-129), and even more preferably a compound represented by formulas (III-1) to (III-3), and most preferably a compound represented by formula (III-3).

In Tables 13-15, ph1-ph10 represent the bases (* indicates bond bonds) as shown in the following formulas.

In Tables 13-15, ca1-ca6 represent the bases indicated by the following formulas (* refers to the binding bonds).

[Chemistry 15]

The compound represented by formula (III) can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2019-163233.

Squamous acid inneron dyes are preferably those comprising at least one of the group consisting of compounds (I) and (III).

The content of compounds (I) and (III) is preferably 0.1 to 150 parts by weight, more preferably 0.3 to 100 parts by weight, and even more preferably 0.5 to 50 parts by weight, relative to 100 parts by weight of resin (B).

The content of compounds (I) and (III) in the total amount of colorant (A) is preferably 20% by mass or more, more preferably 50% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.

The content of the squaric acid inneron dye is 3 to 140 parts by weight, more preferably 5 to 130 parts by weight, and even more preferably 10 to 120 parts by weight, relative to 100 parts by weight of the polymerization initiator (D). Within this range, a color filter with good contrast is obtained.

Furthermore, when the squaric acid inner-lactonium dye is compound (I) (including compound (II)), the content of compound (I) relative to 100 parts by weight of the polymerization initiator (D) is preferably 3 to 140 parts by weight, more preferably 18 to 135 parts by weight, even more preferably 50 to 130 parts by weight, and even more preferably 90 to 125 parts by weight. When the squaric acid inner-lactonium dye is compound (I), there is a tendency for the contrast to increase as the content of compound (I) relative to the polymerization initiator (D) increases.

Furthermore, when the squaric acid inner-lactonium dye is compound (III), the content of compound (III) relative to 100 parts by weight of the polymerization initiator (D) is preferably 3 to 140 parts by weight, more preferably 18 to 135 parts by weight, even more preferably 50 to 130 parts by weight, and even more preferably 90 to 125 parts by weight. When the squaric acid inner-lactonium dye is compound (III), there is a tendency for the contrast to increase as the content of compound (III) relative to the polymerization initiator (D) increases.

Colorant (A) may contain compounds (I) and (III), as well as colorants different from compounds (I) and (III). The colorant different from compounds (I) and (III) may be either a dye (hereinafter, in some cases, referred to as dye (A1)) or a pigment (hereinafter, in some cases, referred to as pigment (A2)). The colorant different from compounds (I) and (III) may contain one or both of these dyes (A1) and pigments (A2).

There are no particular limitations on the dye (A1) as long as it does not contain compounds (I) and (III). Well-known dyes can be used, such as solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes that can be listed include compounds with hues other than pigments in the Color Index (published by The Society of Dyers and Colourists), or well-known dyes recorded in dyeing notes (Shikisensha Co., Ltd.). In addition, based on their chemical structure, the following can be listed: azo dyes, cyanide dyes, triphenylmethane dyes, oxanthracene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methylene dyes, azomethylene dyes, squaric acid inneron dyes (excluding compounds (I) and (III)), acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes, etc. Among these, organic solvent-soluble dyes are preferred.

Specifically, examples include: C.I. Solvent Yellow 4 (hereinafter, only the numbers are listed), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Solvent Orange... Orange) 2, 7, 11, 15, 26, 56, 77, 86; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59; 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent Green C.I. solvent dyes, including: (green) 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.; C.I. acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160. 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Acid Red (acid red)1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 9 4, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 19 5, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; C.I. Acid Orange Orange) 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; Acid Violet (C.I.) 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; Acid Blue (C.I.) blue)1,3,5,7,9,11,13,15,17,18,22,23,24,25,26,27,29,34,38,40,41,42,43,45,48,51,54,59,60,62,70,72,74,75,78,80,82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 1 27, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324, 1, 335, 340; C.I. Acid Green (acid C.I. acid dyes: 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50; 1, 58, 63, 65, 80, 104, 105, 106, 109, etc.; C.I. direct yellow: 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; C.I. direct red. Red) 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Purple violet) 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. direct blue (direct blue)1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 10 9, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 1 70, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Green C.I. direct dyes, including C.I. (green) 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.; C.I. disperse yellow 51, 54, 76; C.I. disperse violet 26, 27; C.I. disperse blue 1, 14, 56, 60, etc.; C.I. basic red 1, 10; C.I. basic blue... C.I. basic violet 2; C.I. basic red 9; C.I. basic green 1, etc.; C.I. reactive yellow 2, 76, 116; C.I. reactive orange 16; C.I. reactive orange 36, etc.; C.I. mordant yellow Yellow) 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C.I. Mordant Orange Orange) 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C.I. Mordant Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; C.I. Mordant C.I. mordant green dyes include: 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; C.I. mordant green dyes include: 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc.; C.I. vat green dyes include: 1, etc. C.I. mordant green dyes include: 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 84; C.I. vat green dyes include: 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 53, etc.

These dyes can be appropriately selected based on the spectroscopic spectrum of the desired color filter.

As a pigment (A2), there are no particular limitations; any well-known pigment can be used, such as those classified as pigments in the Dye Index (published by The Society of Dyers and Colourists).

As pigments, examples include: C.I. pigment yellow (1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.); C.I. pigment orange (13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.); C.I. pigment red (… C.I. pigments include: 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. (red); C.I. pigment blue (15, 15:3, 15:4, 15:6, 60, etc. (blue); C.I. pigment violet (1, 19, 23, 29, 32, 36, 38, etc. (purple); C.I. pigment green (7, 36, 58, etc. (green); C.I. pigment brown (23, 25, etc. (brown); C.I. pigment black (1, 7, etc. (black)).

As needed, pigments may also undergo surface treatments such as rosin treatment, surface treatment using pigment derivatives with introduced acidic or alkaline groups, grafting treatment using polymeric compounds, micronization treatment using sulfuric acid micronization, cleaning treatment using organic solvents or water to remove impurities, and removal of ionic impurities using ion exchange methods.

The pigment is preferably of uniform particle size. A pigment dispersion, in which the pigment is uniformly dispersed in solution, can be obtained by containing a pigment dispersant and performing dispersion treatment.

Examples of pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants can be used alone or in combination of two or more. Examples of pigment dispersants by trade name include: KP (Shin-Etsu Chemical Co., Ltd.), Flowlen (Kyoei Chemical Co., Ltd.), Solsperse (Zeneca Co., Ltd.), EFKA (CIBA Corporation), Ajisper (Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (BYK-chemie Co., Ltd.).

When using a pigment dispersant, the amount of pigment dispersant used relative to the total amount of pigment (A2) is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less. If the amount of pigment dispersant used is within the aforementioned range, there is a tendency to obtain a pigment dispersion with a uniform dispersion state.

The content of colorant (A) in the color-curing resin composition relative to the total solid content is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass or less, and even more preferably 1% by mass or more and 50% by mass or less.

Furthermore, relative to the total amount of solid components, the content of squaric acid innerium dye in the color-curing resin composition is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, and even more preferably 1% by mass or more and 20% by mass or less.

If the content of the colorant (A) and the squaric acid inneron dye is within the stated range, the color concentration when producing the color filter will be sufficient, and the composition may contain the necessary amount of resin (B) or polymeric compound (C), thus enabling the formation of patterns with sufficient mechanical strength.

Here, the term "total solids" in this specification refers to the amount obtained by removing the solvent content from the total amount of the colored curing resin composition. The total solids and the relative content of each component can be determined using known analytical methods such as liquid chromatography or gas chromatography.

<Resin (B)>

Resin (B) is preferably an alkaline-soluble resin, and more preferably a polymer having structural units derived from at least one monomer (hereinafter, in the case of a monomer (a)) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

Resin (B) is preferably a copolymer comprising structural units derived from a monomer (hereinafter referred to as "monomer (b)") having a cyclic ether structure having 2 to 4 carbon atoms and ethylene-unsaturated bonds, and other structural units.

Other structural units include those derived from monomers that can copolymerize with monomer (a) (wherein, there exists a monomer different from monomer (a) and monomer (b). Hereinafter, there exists a case referred to as "monomer (c)"), and structural units possessing ethylene-unsaturated bonds.

In this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acrylyl" and "(meth)acrylate" have the same meaning.

Examples of monosaturated monocarboxylic acids as simple monoisocyanates (a) include, for example: acrylic acid, methacrylic acid, butenoic acid and unsaturated monocarboxylic acids such as orthovinylbenzoic acid, metavinylbenzoic acid, and paravinylbenzoic acid; and other monocarboxylic acids such as maleic acid, transbutenic acid, leuconic acid, mesocarnic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, and dimethylphthalic acid. Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; 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-6-methyl Bicyclic [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclic [2.2.1]hept-2-ene, and other carboxyl-containing bicyclic unsaturated compounds; cis-butenedioic anhydride, leuconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5 Unsaturated dicarboxylic anhydrides such as 6-dicarboxylic bicyclic [2.2.1]hept-2-ene anhydride; unsaturated mono[(meth)acrylic oxyalkyl] esters of di- or higher polycarboxylic acids such as succinate mono[2-(meth)acrylic oxyethyl] ester and phthalate mono[2-(meth)acrylic oxyethyl] ester; and unsaturated acrylates containing both hydroxyl and carboxyl groups in the same molecule, such as α-(hydroxymethyl)acrylate.

Of these, acrylic acid, methacrylic acid, ortho-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and maleic anhydride are preferred in terms of copolymerization reactivity or the solubility of the obtained resin in alkaline aqueous solutions.

The monomer (b) refers to a polymerizable compound having a cyclic ether structure with 2 to 4 carbon atoms (e.g., selected from at least one of the group consisting of oxocyclopropane, oxocyclobutane, and tetrahydrofuran (oxocyclopentane) rings) and an ethylene-unsaturated bond.

The monomer (b) is preferably a monomer having a cyclic ether with 2 to 4 carbon atoms and a (meth)acrylic acid oxy group.

As a single entity (b), examples include single entities having an oxadicyclopropyl group and an ethylene-unsaturated bond (hereinafter referred to as "single entity (b1)"), single entities having an oxadicyclobutyl group and an ethylene-unsaturated bond (hereinafter referred to as "single entity (b2)"), and single entities having a tetrahydrofuran group and an ethylene-unsaturated bond (hereinafter referred to as "single entity (b3)").

As a monomer (b1), examples include monomers with structures formed by the epoxidation of unsaturated aliphatic hydrocarbons in the form of straight or branched chains (hereinafter referred to as "monomer (b1-1)"), and monomers with structures formed by the epoxidation of unsaturated alicyclic hydrocarbons (hereinafter referred to as "monomer (b1-2)").

As a monomer (b1-1), it is preferably a monomer having a glycidyl group and an ethylene-unsaturated bond.

Examples of monodimers (b1-1) include: (meth)acrylate glycidyl ester, (meth)acrylate β-methyl glycidyl ester, (meth)acrylate β-ethyl glycidyl ester, glycidyl vinyl ether, ortho-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-ortho-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl) 2,4-Bis(glycidyloxymethyl)styrene, 2,5-Bis(glycidyloxymethyl)styrene, 2,6-Bis(glycidyloxymethyl)styrene, 2,3,4-Tris(glycidyloxymethyl)styrene, 2,3,5-Tris(glycidyloxymethyl)styrene, 2,3,6-Tris(glycidyloxymethyl)styrene, 3,4,5-Tris(glycidyloxymethyl)styrene, 2,4,6-Tris(glycidyloxymethyl)styrene, etc.

Examples of monoisocyanates (b1-2) include, for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Inc.), 3,4-epoxycyclohexyl methyl methacrylate (e.g., Cyclomer A400; manufactured by Daicel Inc.), 3,4-epoxycyclohexyl methyl methacrylate (e.g., Cyclomer M100; manufactured by Daicel Inc.), compounds represented by formula (BI), and compounds represented by formula (BII).

[Chemistry 16]

In formulas (BI) and (BII), ^Ra and ^Rb independently represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, wherein the hydrogen atoms contained in the alkyl group may be substituted with hydroxyl groups.

X ^a and X ^b independently represent single keys, *-R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-.

R ^_c represents an alkyldiyl group with 1 to 6 carbon atoms.

* indicates a key binding with 0.

Alkyl groups having 1 to 4 carbon atoms include, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tributyl, etc.

Alkyl groups formed by hydroxyl substitution of a hydrogen atom include, for example: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

As for ^Ra and ^Rb , it is preferable to include hydrogen atoms, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, and more preferably hydrogen atoms and methyl.

Examples of alkyldiyl groups include: methylene, ethyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc.

For ^Xa and ^Xb , it is preferable to list single bonds, methylene, ethyl groups, * _-CH2 -O-, * _{-CH2CH2 -} O-, and more preferably single bonds, * _{-CH2CH2 -} O- (* indicates a bond with O).

Compounds represented by formula (BI) may include compounds represented by any of formulas (BI-1) to (BI-15). Among these, compounds represented by formulas (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), and (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9), and (BI-15) are even more preferred.

As for the compounds represented by formula (BII), compounds represented by any of formulas (BII-1) to (BII-15) may be listed. Preferably, compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), and (BII-11) to (BII-15) may be listed; more preferably, compounds represented by formulas (BII-1), (BII-7), (BII-9), and (BII-15) may be listed.

The compounds represented by formula (BI) and formula (BII) may be used individually or in combination. They may also be used in combination. When using compounds represented by formula (BI) and formula (BII) in combination, the content ratio [compound represented by formula (BI):compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20 on a molar basis.

As a monomer (b2) having an oxocyclobutyl group and an vinyl unsaturated bond, it is more preferably a monomer having an oxocyclobutyl group and a (meth)acrylic acid oxy group.

Examples of the monomer (b2) include: 3-methyl-3-(meth)propenylideneoxymethyloxacyclobutane, 3-ethyl-3-(meth)propenylideneoxymethyloxacyclobutane, 3-methyl-3-(meth)propenylideneoxyethyloxacyclobutane, 3-ethyl-3-(meth)propenylideneoxyethyloxacyclobutane, etc.

As a monomer (b3) having a tetrahydrofuran group and an ethylene-unsaturated bond, it is more preferably a monomer having a tetrahydrofuran group and a (meth)acrylic acid oxy group.

Examples of monomethyl methacrylate (b3) include tetrahydrofurfuryl acrylate (e.g., Biscoat V#150, manufactured by Osaka Organic Chemicals Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

As a single-component formulation (b), single-component formulation (b1) is preferred in terms of further improving the reliability of the obtained color filter, such as its heat resistance and chemical resistance. Furthermore, single-component formulations (b1-2) are even more preferred in terms of excellent storage stability of the coloring composition.

Examples of monomeric forms (c) include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, tributyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 2,6]decane-8-yl methacrylate (commonly known as "dicyclopentyl methacrylate" in this field; it is also sometimes called "tricyclodecyl methacrylate"), tricyclo[5.2.1.0 ^2,6 ]decane- ⁸ -yl methacrylate. [5.2.1.0 ^2,6 ]decen-8-yl ester, tricyclo[5.2.1.0 2,6]decen-8-yl ester (commonly referred to as "dicyclopentenyl(meth)acrylate" in this field), tricyclo[5.2.1.0 ^2,6 ]decen-9-yl ester, dicyclopentyloxyethyl(meth)acrylate, isoborneol(meth)acrylate, azuryl(meth)acrylate, allyl(meth)acrylate, propargyl(meth)acrylate, phenyl(meth)acrylate, naphthyl(meth)acrylate, and benzyl(meth)acrylate, etc. (meth)acrylates; hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl(meth)acrylate and 2-hydroxypropyl(meth)acrylate; 2,2,3,3,4,4,5,5-octafluoropentane(meth)acrylate. (Meth)acrylates containing halogen atoms, such as esters; dicarboxylic acid diesters such as diethyl butyrate, diethyl transbutyrate, and diethyl itaconic acid; bicyclic [2.2.1]hept-2-ene, 5-methylbicyclic [2.2.1]hept-2-ene, 5-ethylbicyclic [2.2.1]hept-2-ene, 5-hydroxybicyclic [2.2.1]hept-2-ene, 5-hydroxymethylbicyclic [2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclic [2.2.1]hept-2-ene, and 5-methoxybicyclic [2.2.1] Hept-2-ene, 5-ethoxybiscyclic [2.2.1]hept-2-ene, 5,6-dihydroxybiscyclic [2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)biscyclic [2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)biscyclic [2.2.1]hept-2-ene, 5,6-dimethoxybiscyclic [2.2.1]hept-2-ene, 5,6-diethoxybiscyclic [2.2.1]hept-2-ene, 5-hydroxy-5-methylbiscyclic [2.2.1]. 1] Hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyl)bicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds such as (2.2.1) hepta-2-ene; N-phenylcisyldiimidide, N-cyclohexylcisyldiimidide, N-benzylcisyldiimidide, N-succinimo-3-cisyldiimidide benzoate, N-succinimo-4-cisyldiimidide butyrate, N-succinimo-6-cisyldiimidide hexanoate, N-succinimo-3-cisyldiimidide propionate, and N-(9-acridyl) Dicarbonyl amide derivatives such as cis-butene diamide; aromatic compounds containing vinyl groups such as styrene, ortho-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, 9-vinylcarbazole, and p-methoxystyrene; vinyl nitriles such as (meth)acrylonitrile; halides such as vinyl chloride and vinylidene chloride; vinyl amides such as (meth)acrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene, etc.

Of these, styrene, vinyltoluene, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester, tricyclo[5.2.1.0 2,6]decane-9-yl ester, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl ester, and tricyclo[5.2.1.0 ^2,6 ]decene-8-yl ester are preferred in terms of copolymerization reactivity and heat resistance ^. [2.2.1] Dexeno-9-yl ester, N-phenylcis-butene diimide, N-cyclohexylcis-butene diimide, N-benzylcis-butene diimide, bicyclo[2.2.1]hept-2-ene, phenyl methacrylate, 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, 9-vinylcarbazole, benzyl methacrylate, 2-hydroxyethyl methacrylate, and 2-ethylhexyl methacrylate, etc.

As resins (B), specific examples include: 3,4-epoxycyclohexyl methyl methacrylate/(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl methacrylate/(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6]decyl methacrylate/(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6]decyl methacrylate/(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl methacrylate/9-vinylcarbazole .../9-vinylcarbazole/(meth)acrylate/9-vinylcarbazole/(meth)acrylate/9-vinylcarbazole/(meth)acrylate/9-vinylcarbazole/(meth)acrylate/9-vinylcarbazole/(meth)acrylate/9-vinylcarbazole/( ^meth )acrylate/9-vinylcarbazole/(meth)acrylate/ ^9- vinylcarbazole/(meth)acrylate/9-vinylcarbazole/(meth)acrylate/9-vinylcarbazole/ 3,4-Epoxy Tricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylate phenyl acrylate/(m-vinylbenzoic acid) copolymer, 3,4-Epoxy Tricyclo[5.2.1.0 2,6]decyl acrylate/(meth)acrylate phenyl acrylate/(m-vinylbenzoic acid) copolymer, 3,4-Epoxy Tricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylate phenyl acrylate/(meth)acrylate .../(m-vinylbenzoic acid) copolymer, 3,4-Epoxy Tricyclo[5.2.1.0 2,6]decyl acrylate/(meth)acrylate/(m-vinylbenzoic acid) copolymer, 3,4-Epoxy Tricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylate/(m-vinylbenzoic acid) copolymer, 3,4-Epoxy Tricyclo[5.2.1.0 ^2,6] decyl acrylate/(meth)acrylate/(m-vin 1,2,3,3,4,4,5,5-octafluoropentyl acrylate ^/ (meth)acrylic acid copolymer ^{, ...} 3,4-Epoxytricyclo(meth)acrylate [5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylate/(meth)acrylate 2-ethylhexyl acrylate copolymer, 3,4-Epoxytricyclo(meth)acrylate [5.2.1.0 2,6]decyl acrylate/(meth)acrylate tricyclo(meth)acrylate [5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylate tricyclo(meth)acrylate [5.2.1.0 ^2,6] Resins as described in Japanese Patent Application Publication Nos. 9-106071, 2004-29518, and 2004-361455.

Preferably, resin (B) is a copolymer comprising structural units derived from monomer (a) and structural units derived from monomer (b).

Resin (B) may be composed of two or more types. In this case, resin (B) is preferably a copolymer containing at least one structural unit derived from monomer (a) and a structural unit derived from monomer (b), more preferably a copolymer containing at least one structural unit derived from monomer (a) and a structural unit derived from monomer (b1), further preferably a copolymer containing at least one structural unit derived from monomer (a) and a structural unit derived from monomer (b1-2), and even more preferably a copolymer containing a copolymer selected from 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl methacrylate/(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl methacrylate, or a copolymer of meth)acrylate and meth)acrylate. The copolymer of decyl acrylate/(meth)acrylate/N-cyclohexylmaleimide/(meth)acrylate ² -hydroxyethyl acrylate, decyl acrylate/(meth)acrylate/vinyltoluene copolymer, and ^decyl acrylate/(meth)acrylate/vinyltoluene copolymer.

The polystyrene-converted weight-average molecular weight (Mw) of resin (B) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, further preferably 3,000 or more and 30,000 or less, and even more preferably 5,000 or more and 30,000 or less. If the weight-average molecular weight is within the aforementioned range, there is a tendency for high solubility of the unexposed portion in the developing solution, and also for high residual film rate or high hardness of the obtained pattern.

The dispersion of resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1 or higher and 6 or lower, more preferably 1 or higher and 5 or lower, and even more preferably 1 or higher and 4 or lower.

The acid value (converted from solid content) of resin (B) is preferably 10 mg-KOH/g or higher and 300 mg-KOH/g or lower, more preferably 20 mg-KOH/g or higher and 250 mg-KOH/g or lower, even more preferably 25 mg-KOH/g or higher and 200 mg-KOH/g or lower, even more preferably 30 mg-KOH/g or higher and 180 mg-KOH/g or lower, and particularly preferably 40 mg-KOH/g or higher and 150 mg-KOH/g or lower. Here, the acid value is a value determined as the amount (mg) of potassium hydroxide required to neutralize 1g of the resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of resin (B) relative to 100% by weight of the solid content of the color-curing resin composition is preferably 5% to 90% by weight, more preferably 10% to 80% by weight, further preferably 13% to 70% by weight, and even more preferably 15% to 60% by weight. If the content of resin (B) is within the aforementioned range, there is a tendency for the unexposed portion to have high solubility in the developing solution.

<Polymerizing Compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by active free radicals and/or acids generated from a self-polymerizing initiator (D). Examples of polymerizable compounds with ethylene-unsaturated bonds include (meth)acrylate compounds.

The average vinyl unsaturated group equivalent number of the polymerizable compound (C) is less than 96.0. The inventors determined through research that if the average vinyl unsaturated group equivalent number exceeds this range, the contrast of the color filter deteriorates.

The average vinyl unsaturated group equivalent number of the polymerizable compound (C) is preferably 95.5 or less, more preferably 95.0 or less, further preferably 94.5 or less, and even more preferably 94.0 or less. There is no particular limitation on the lower limit, but the average vinyl unsaturated group equivalent number of the polymerizable compound (C) is preferably 83.0 or more, more preferably 83.5 or more, further preferably 84.0 or more, even more preferably 84.5 or more, and particularly preferably 85.0 or more.

Furthermore, the average number of vinyl unsaturated base equivalents of the polymerizable compound (C) is calculated using equation (1).

<Average Ethylene Unsaturated Base Equivalent Number>

The average number of vinyl unsaturated groups equivalent in the polymerizable compound (C) is represented by equation (1).

The average number of vinyl unsaturated base equivalents of polymerizable compound (C) = ΣK_{_i}m_{_i} ...(1)

In formula (1), _Ki represents the value of component i (molecular weight / number of ethylene unsaturated bonds) in all polymeric compounds (C) contained in the tinted curing resin composition.

_mi : represents the molar fraction of component i.

The polymerizable compound (C) is preferably a polymerizable compound containing three or more (preferably five or fewer, more preferably four or fewer) ethylene unsaturated bonds.

As a polymerizable compound, any polymerizable compound can be used as long as the average vinyl unsaturated group equivalent number of the polymerizable compound (C) is less than 96.0. Examples of polymerizable compounds include: trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, di-trihydroxymethylpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and tetrapentaerythritol deca(meth)acrylate. Acrylic esters, pentaerythritol nona(meth)acrylate, tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate.

The polymerizable compound (C) preferably comprises at least one selected from pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and glycerol tri(meth)acrylate, and more preferably comprises at least one selected from pentaerythritol triacrylate, pentaerythritol tetraacrylate, and glycerol triacrylate.

The polymerizable compound (C) can combine two or more of the examples described, and can also combine pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate.

In the case of a combination of pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate, the ratio (x:y) of pentaerythritol tri(meth)acrylate (x) to pentaerythritol tetra(meth)acrylate (y) is preferably 1 mol%~99 mol%:99 mol%~1 mol%, more preferably 10 mol%~90 mol%:90 mol%~10 mol%, further preferably 20 mol%~80 mol%:80 mol%~20 mol%, and even more preferably 30 mol%~70 mol%:70 mol%~30 mol%.

The content of the polymeric compound (C) relative to the total solid content is preferably 1% to 65% by mass, more preferably 5% to 60% by mass, even more preferably 10% to 55% by mass, and even more preferably 15% or more, 20% or more, or 25% or more by mass. When the content of the polymeric compound (C) is within the above range, there is a tendency to improve the film residue rate during colored pattern formation and the chemical resistance of the color filter. Furthermore, as the content increases within the above range, there is a tendency to further improve contrast.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active free radicals, acids, etc., through the action of light or heat, thereby initiating polymerization; known polymerization initiators can be used. Examples of polymerization initiators that generate active free radicals include: O-acetylgoxime compounds, benzenealkyl ketone compounds, triazine compounds, acetylglucosinolate compounds, and biimidazole compounds.

Examples of the O-acetylated compounds include, for example, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine. Amines, N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, and other O-acetyloxime compounds with a diphenyl sulfide skeleton; N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-] {2-Methyl-4-(3,3-dimethyl-2,4-dioxanecyclopentylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N-acetyoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[ O-acetylated compounds with a carbazole skeleton, such as 9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine; O-acetylated compounds with a fluorene skeleton, such as 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluorene-2-yl]acetone O-acetylated oxime; etc. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF), PBG-327 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.), and DFI-091 (manufactured by Daito Chemix Co., Ltd.) can also be used. The O-acetylated compound is preferably selected from at least one of the following groups: N-benzoyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-acetylatedoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-acetylatedoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxanecyclopentylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]acetone O-acetylated oxime. If the compounds are O-acetylgoximes, there is a tendency to obtain color filters with high brightness.

Examples of such benzyl ketone compounds include: 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one. Oligomers of 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl one, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, benzodiazepine dimethyl acetone, etc. Commercially available products such as Irgacure (registered trademarks) 369, 907, and 379 (manufactured by BASF) can also be used.

Examples of such triazine compounds 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-bis(trichloromethyl)-6-piperyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

Examples of phosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

Examples of the biimidazole compounds mentioned above include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (e.g., see Japanese Patent Application Publication No. 6-75372, Japanese Patent Application Publication No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkyl) Biimidazole compounds with a phenyl group at the 4,4',5,5'-position substituted with an alkoxyphenyl group (e.g., see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), etc. Biimidazole compounds with a phenyl group at the 4,4',5,5'-position substituted with an alkoxycarbonyl group (e.g., see Japanese Patent Publication No. 7-10913, etc.).

Examples of onanium salts that can act as acid-producing polymerization initiators include: 4-hydroxyphenyldimethylspar-p-toluenesulfonate, 4-hydroxyphenyldimethylspar-hexafluoroantimonate, 4-acetoxyphenyldimethylspar-p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzylspar-hexafluoroantimonate, triphenylspar-p-toluenesulfonate, triphenylspar-hexafluoroantimonate, diphenylmethylene-p-toluenesulfonate, diphenylmethylene-hexafluoroantimonate, etc.; or nitrobenzyltoluenesulfonate salts, benzoin toluenesulfonate salts, etc.

Furthermore, examples of polymerization initiators (D) include: benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as methyl benzoyl peroxide, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthroquinone, 2-ethylanthraquinone, and camphorquinone; and compounds such as 10-butyl-2-chloroacridone, benzoin, methyl phenylglyoxylate, and titanium thiocenene compounds.

As a polymerization initiator (D), it is preferably a polymerization initiator comprising at least one selected from the group consisting of O-acetylgimime compounds, benzyl ketone compounds, triazine compounds, acetylglucosamine compounds, and biimidazole compounds, and more preferably a polymerization initiator comprising an O-acetylgimime compound.

The content of polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, relative to 100 parts by mass of the combined amount of resin (B) and polymeric compound (C). If the content of polymerization initiator (D) is within the aforementioned range, there is a tendency for increased sensitivity and shorter exposure time, thus improving the productivity of color filters.

The content of polymerization initiator (D) relative to 100 parts by weight of polymerizable compound (C) is preferably 1 to 70 parts by weight, more preferably 2 to 65 parts by weight, further preferably 3 to 60 parts by weight, and even more preferably 55 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less. If the content of polymerization initiator (D) is within the aforementioned range, there is a tendency for increased contrast; if it is reduced within the aforementioned range, there is a tendency for further increased contrast.

The content of polymerization initiator (D) relative to the total amount of solid components is preferably 0.1% to 30% by mass, more preferably 0.5% to 25% by mass, further preferably 1% to 20% by mass, and even more preferably 15% by mass or less, or 10% by mass or less. If the content of polymerization initiator (D) is within the aforementioned range, there is a tendency for increased contrast; if it is reduced within the aforementioned range, there is a tendency for further increased contrast.

<Polymerization Initiator (D1)>

A polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound that has begun to polymerize by means of a polymerization initiator. In cases where a polymerization initiator (D1) is included, it is usually used in combination with a polymerization initiator (D).

Examples of polymerization initiators (D1) include amine compounds, alkoxyanthracene compounds, thiatonone compounds, and carboxylic acid compounds.

Examples of amine compounds include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

Examples of such alkoxyanthracene compounds include: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

Examples of such thiatonone compounds include: 2-isopropylthiatonone, 4-isopropylthiatonone, 2,4-diethylthiatonone, 2,4-dichlorothiatonone, and 1-chloro-4-propoxythiatonone.

Examples of such carboxylic acid compounds include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

When using these polymerization initiators (D1), their content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the combined amount of resin (B) and polymerizable compound (C). If the amount of polymerization initiator (D1) is within this range, high-sensitivity coloring patterns can be formed, and there is a tendency to improve the productivity of color filters.

Solvent (E)

The solvent (E) is not particularly limited and can be any solvent commonly used in this field. Examples include: ester solvents (solvents containing -COO- but not -O-), ether solvents (solvents containing -O- but not -COO-), ether-ester solvents (solvents containing both -COO- and -O-), ketone solvents (solvents containing -CO- but not -COO-), alcohol solvents (solvents containing OH- but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

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

Examples of ether solvents 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-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 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 anisole, etc.

Examples of ether solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate, etc.

Examples of ketone solvents include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone, etc.

Examples of alcohol solvents include: methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

Examples of aromatic hydrocarbon solvents include: benzene, toluene, xylene, and mesitylene.

Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Of the solvents, those with regard to coatability and drying properties are preferably organic solvents with a boiling point of 120°C or higher and 180°C or lower at 1 atm. Preferred solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide; more preferably, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate, and ethyl 3-ethoxypropionate.

The solvent (E) content is preferably 70% to 95% by mass, more preferably 75% to 92% by mass, relative to the total amount of the color-curing resin composition of the present invention. In other words, the total solid content of the color-curing resin composition is preferably 5% to 30% by mass, more preferably 8% to 25% by mass. If the solvent (E) content is within the aforementioned range, the flatness during application is improved, and the color concentration is not insufficient when forming a color filter, thus tending to improve display properties.

<Balancing Agent (F)>

As leveling agents (F), examples include silicone-based surfactants, fluorinated surfactants, and silicone-based surfactants containing fluorine atoms. These may also have polymerizable groups on their side chains.

As silicone-based surfactants, examples include those with intramolecular siloxane bonds. Specifically, examples include: Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, and Toray silicone SH8400 (Toray Dow Corning). Products manufactured by Corning (stock), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (Momentive Performance Materials Japan Co., Ltd.), etc.

Examples of fluorinated surfactants include those with intramolecular fluorocarbon chains. Specifically, examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, and Megafac... RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics Chemicals, Inc.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by ACG), and E5844 (manufactured by Daikin Fine Chemicals Research Institute), etc.

As silicone-based surfactants containing fluorine atoms, examples include surfactants with intramolecular silicate bonds and fluorocarbon chains. Specifically, examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC).

The leveling agent (F) content, relative to the total amount of the color-curing resin composition, is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.2% by mass or less, and even more preferably 0.005% by mass or more and 0.2% by mass or less. Furthermore, this content does not include the content of the dispersant. If the leveling agent (F) content is within the aforementioned range, the flatness of the color filter can be good.

Other ingredients

The color-curing resin composition of this invention may, as needed, include polymerization initiators, fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and other additives known in the art.

Examples of adhesion promoters include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. Alkane, 3-aminopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane, etc.

<Method for manufacturing colored curing resin components>

Colored curing resin compositions can be prepared, for example, by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and, as needed, a solvent (E), a leveling agent (F), a polymerization initiation aid (D1), and other components.

The colorant (A) can be pre-included in the pigment dispersion. The desired color-curing resin composition can be prepared by mixing the remaining components in the pigment dispersion at a specified concentration.

When dyes are included, the dye can be pre-dissolved in part or all of the solvent (E) to prepare a solution. Preferably, the solution is filtered using a filter with a pore size of approximately 0.01 μm to 1 μm.

Preferably, the mixed colored curing resin composition is filtered using a filter with a pore size of approximately 0.01 μm to 10 μm.

Color filters

Methods for manufacturing colored patterns for color filters from the color-curing resin composition of the present invention include photolithography, inkjet printing, and printing. Photolithography is preferred. Photolithography involves coating the color-curing resin composition onto a substrate, drying it to form a composition layer, and then exposing and developing the composition layer using a photomask. In photolithography, by not using a photomask during exposure and/or by not performing development, a colored coating film, which is the cured composition layer, can be formed.

The thickness of the color filter (hardened membrane) is, for example, 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, even more preferably 3 μm or less, even more preferably 1.5 μm or less, particularly preferably 0.5 μm or less, and more preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

As a substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and sodium-calcium glass with a silica-coated surface can be used; or resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and aluminum, silver, or silver/copper/palladium alloy thin films formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc., can also be formed on these substrates. Additionally, substrates made by treating silicon substrates with hexamethyldisilazane (HMDS) can also be used.

The formation of individual color pixels using photolithography can be performed under known or conventional apparatus or conditions. For example, it can be done as follows: First, a color-curing resin composition is coated onto a substrate. The substrate is then dried by heat drying (pre-baking) and/or depressurization drying to remove volatile components such as solvents, resulting in a smooth composition layer. Coating methods include: spin coating, slit coating, and a combination of slit and spin coating. The preferred temperature for heat drying is 30°C to 120°C, more preferably 50°C to 110°C. The preferred heating time is 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When performing depressurization drying, it is preferable to conduct the process under a pressure of 50 Pa to 150 Pa and a temperature range of 20°C to 25°C. The film thickness of the constituent layers is not particularly limited; it should be appropriately selected based on the target color filter film thickness.

Next, the photomask used to form the target coloring pattern is exposed to the substrate. The pattern on the photomask is not particularly limited; a pattern appropriate to the intended use is used. The light source used for exposure is preferably a light source that produces light with a wavelength range of 250 nm to 450 nm. For example, a filter that cuts off the wavelength range can be used to cut off light less than 350 nm, or a bandpass filter that selectively extracts light near 436 nm, 408 nm, and 365 nm. Specifically, mercury lamps, light-emitting diodes, metal halogen lamps, and halogen lamps are examples. To ensure uniform illumination of the exposure surface with parallel light, or to achieve accurate alignment of the photomask and substrate, it is preferable to use miniaturized projection exposure devices or proximity exposure devices such as mask aligners and steppers.

Development is performed by bringing the exposed composition layer into contact with a developing solution, thereby forming a colored pattern on the substrate. During development, the unexposed portions of the composition layer dissolve and are removed in the developing solution. The developing solution is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% to 10% by mass, more preferably 0.03% to 5% by mass. Furthermore, the developing solution may also contain a surfactant. The developing method can be any of the following: immersion, dipping, or spraying. The substrate can also be tilted at any angle during development.

After development, it is best to wash with water.

Furthermore, it is preferable to bake the obtained colored pattern afterward. The preferred baking temperature is 80℃~250℃, more preferably 100℃~245℃. The preferred baking time is 1 minute~120 minutes, more preferably 2 minutes~30 minutes.

The resulting colored pattern and colored coating are useful as color filters, which are used in display devices (e.g., liquid crystal displays, organic electroluminescence (EL) devices), electronic paper, solid-state imaging elements, etc.

[Implementation Example]

The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified, the percentages and parts representing the content or amount used are quality standards.

[Synthesis example 1]

According to Example 8 disclosed in Japanese Patent Application Publication No. 2020-055956, the compound represented by formula (II-135) was obtained.

[Synthesis example 2]

According to Example 2 disclosed in Japanese Patent Application Publication No. 2019-163233, the compound represented by formula (III-3) was obtained.

[Chemistry 20]

[Resin synthesis example 1]

To create a nitrogen atmosphere, a suitable amount of nitrogen gas was passed through a flask containing a reflux cooler, a dropping funnel, and a stirrer. 280 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 80°C while stirring. Then, over a period of 5 hours, a mixed solution of 38 parts acrylic acid, 289 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (mixing ratio 1:1), and 125 parts of propylene glycol monomethyl ether acetate was added dropwise. Simultaneously, over a period of 6 hours, a mixed solution prepared by dissolving 33 parts of 2,2-azobis(2,4-dimethylpentanones) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise. After the addition was complete, the solution was kept in a flask at 80°C for 4 hours, then cooled to room temperature to obtain a copolymer (resin (B-1)) solution with a type B viscosity (23°C) of 125 mPa·s and a solid content of 35.1%. The weight average molecular weight (Mw) of the resulting copolymer was 9200, the dispersion was 2.08, and the acid value of the solid content was 77 mg-KOH/g. Resin (B-1) has the following structural units.

[Chemistry 21]

The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polystyrene resin were determined by gel permeation chromatography (GPC) under the following conditions.

Device: HLC-8120GPC (Manufactured by Tosoh Corporation)

String: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: THF (tetrahydrofuran, tetrahydrofuran)

Flow rate: 1.0 mL/min

Solid concentration of the tested liquid: 0.001% by mass ~ 0.01% by mass

Injection volume: 50 μL

Detector: Refractive index (RI)

Calibration standard material: TSK Standard Polystyrene

F-40, F-4, F-288, A-2500, A-500

(Manufactured by Tosoh Corporation)

The ratio of the weight-average molecular weight to the number-average molecular weight (Mw/Mn) of the obtained polystyrene is defined as the dispersity.

[Examples 1-24, Comparative Example 1]

[Preparation of Colored Curing Resin Components]

The components were mixed in the manner shown in Tables 16 and 17 to obtain a colored, curable resin composition.

In Tables 16 and 17, each component represents one of the following compounds.

Colorant (A-1): The compound represented by formula (II-135)

Colorant (A-2): The compound represented by formula (III-3)

Resin (B-1): Resin (B-1) (converted to solids content)

Polymerizable compound (C-1): Pentaerythritol tetraacrylate (Average vinyl unsaturated group equivalent number 88.1; A-TMMT; Shin-Nakamura Chemical Co., Ltd.)

Polymerizable compound (C-2): Pentaerythritol triacrylate and pentaerythritol tetraacrylate (average vinyl unsaturated group equivalent number 94.6; A-TMM-3LM-N; trifunctional approximately 57 mol%, tetrafunctional approximately 43 mol; manufactured by Shin-Nakamura Chemical Co., Ltd.)

Polymerizable compound (C-3): Glyceryl triacrylate (Average vinyl unsaturated group equivalent number 84.7; ARONIX (registered trademark) M-930; Toa Synthetic Manufacturing Co., Ltd.)

Polymerizable compound (C-4): Dipentaerythritol hexaacrylate (average vinyl unsaturated group equivalent number 96.4; Kayarad (registered trademark) DPHA; Nippon Kayaku Co., Ltd.)

Polymerization initiator (D-1): N-acetylooxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine (PBG-327; oxime compound; manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

Polymerization initiator (D-2): 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]acetone O-acetylated oxime (DFI-091; oxime compound; manufactured by Daito Chemix)

Polymerization initiator (D-3): N-acetylated-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-oxacyclopentylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine (N-1919; oxime compound; manufactured by ADEKA)

Solvent (E-1): 4-Hydroxyl-4-methyl-2-pentanone

Solvent (E-2): Propylene glycol monomethyl ether acetate

Leveling agent (F-1): Polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning (stock))

[Making of Colored Coatings]

A colored, curable resin composition was spin-coated onto a 5cm square glass substrate (Eagle 2000; manufactured by Corning) to a thickness of 2.0μm after baking. The substrate was then pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, the colored composition layer was irradiated with light at an atmospheric exposure of 100mJ/ ^cm² (365nm reference) using an exposure machine (TME-150RSK; manufactured by Topcon). Subsequently, the layer was baked in an oven at 230°C for 30 minutes to obtain the colored coating.

[Contrast Rating]

The obtained colored coatings were analyzed using a contrast meter (CT-1; manufactured by Tussaka Electric Co., Ltd.), a colorimeter (BM-5A; manufactured by Topcon Co., Ltd.), with the blank value set to 30000. The results are shown in Tables 16 and 17.

According to the description, when using a specified amount of squaric acid innerium dye as a coloring agent and a specified polymerizable compound, the contrast is improved. Furthermore, when the amount of polymerizable compound increases and the amount of polymerization initiator decreases, the contrast is further improved.

Claims (9)

A color-curing resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) comprises a squaric acid inner-chain dye, wherein the squaric acid inner-chain dye comprises at least one of the group consisting of compounds represented by formula (I) and compounds represented by formula (III), wherein the polymerizable compound (C) has an average vinyl unsaturated base equivalent number represented by formula (1) of less than 96.0, and the content of the squaric acid inner-chain dye is 3 to 140 parts by weight relative to 100 parts by weight of the polymerization initiator (D), and the average vinyl unsaturated base equivalent number of polymerizable compound (C) is ΣK_{_i}m_{_i} … (1) where K_{_i} : Represents the value (molecular weight/number of ethylene unsaturated bonds) of component i in all polymeric compounds (C) contained in the color-curing resin composition; _mi : Represents the molar fraction of component i. In formula (I), ^R1 to ^R8 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon with 1 to 20 carbon atoms that may have substituents, or an alkoxy group with 1 to 20 carbon atoms that may have substituents; ^R9 and ^R10 independently represent a divalent aliphatic hydrocarbon with 1 to 20 carbon atoms that may have substituents, wherein the methylene group contained in the aliphatic hydrocarbon may be substituted to -O-; ^R11 and ^R12 independently represent a hydrocarbon with 6 to 20 carbon atoms having an aromatic hydrocarbon ring, wherein the hydrocarbon may have substituents, and the methylene group contained in the hydrocarbon may be substituted to -O-; ^R13 represents a hydrogen atom or a saturated hydrocarbon with 1 to 8 carbon atoms. In formula (III), R ³¹ to R ³⁸ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms that may have substituents, or an alkoxy group having 1 to 20 carbon atoms that may have substituents; R ³⁹ to R ⁴² each independently represent an hydrocarbon group having 1 to 20 carbon atoms that may have substituents; at least one of R ³⁹ to R ⁴² is an aliphatic hydrocarbon having 1 to 20 carbon atoms that has a carboxyl group as a substituent; and at least one of R ³⁹ to R ⁴² is an aromatic hydrocarbon having 6 to 20 carbon atoms that may have substituents; wherein the methylene group contained in the aliphatic hydrocarbon group may be substituted with -O-. The color-curing resin composition as claimed in claim 1, wherein the compound represented by formula (I) and the compound represented by formula (III) constitute 80% by mass or more of the total amount of colorant (A). The color-curing resin composition as described in claim 1 or claim 2, wherein the average vinyl unsaturated base equivalent number is 83.0 or more. The color-curing resin composition as described in claim 1 or claim 2, wherein the polymeric compound (C) comprises a polymeric compound having three or more but no more than five ethylene unsaturated bonds. The color-curing resin composition as described in claim 1 or claim 2, wherein the polymeric compound (C) comprises at least one selected from pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and glycerol tri(meth)acrylate. The color-curing resin composition as described in claim 1 or claim 2, wherein the polymerization initiator (D) comprises an O-acetylgimide compound. A color filter formed from a color-curing resin composition as described in any one of claims 1 to 6. A display device comprising a color filter as described in claim 7. A solid-state imaging element comprising a color filter as described in claim 7.