TWI889671B - Red colored curable resin composition, color filter and solid state imaging element - Google Patents

Abstract

The present invention aims to obtain a coloring curable resin composition capable of forming a thin-film color filter having strong absorption at a wavelength of 525 nm and a dense color. The coloring curable resin composition comprises a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The coloring agent (A) comprises a perylene compound (1) and an isoindoline pigment (A1). The perylene compound (1) has a maximum absorption at 400 nm to 560 nm and no maximum absorption at wavelengths exceeding 560 nm to 780 nm.

Description

Red colored curable resin composition, color filter, and solid-state imaging element

The present invention relates to a colored curable resin composition. In particular, it relates to a colored curable resin composition suitable for red applications.

Color filters used in display devices such as liquid crystal displays, electroluminescence displays, and plasma displays, as well as solid-state imaging devices such as charge-coupled devices (CCDs) and complementary metal-oxide-semiconductor transistors (CMOS) sensors, are made from a colored curable resin composition. The colored curable resin composition used to form these color filters is required to be capable of forming a thick, thin film, particularly one suitable for red applications. As a coloring curable resin composition for red applications, one containing C.I. Pigment Red 242 as a colorant is known (Patent Document 1). However, C.I. Pigment Red 242 has low absorption at a wavelength of 525 nm, the wavelength characteristic of red, resulting in weak coloring power. To achieve a rich color filter and expand the color reproduction range, the colorant concentration in the color filter must be increased. Increasing the colorant concentration in the color filter deteriorates the performance of the coloring curable resin composition, such as deteriorating the pattern shape, making this undesirable. Furthermore, if the coloring power is weak, the color filter needs to be thick in order to achieve the target color characteristics. However, when used in liquid crystal displays or solid-state imaging devices, thicker films are not ideal because they can cause color mixing with light from adjacent pixels.

Patent Document 2 describes a photosensitive coloring composition for a color filter substrate comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D). The composition discloses that the red photosensitive coloring composition contains C.I. Pigment Red 179 and an isoindoline-based pigment.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2010-24436

[Patent Document 2] Japanese Patent Publication No. 2017-116767

However, the color filters containing the red photosensitive coloring compositions disclosed in Patent Documents 1 and 2 have weak absorption at a wavelength of 525 nm, which is a characteristic required of red color filters, and cannot fully satisfy coloring power.

The purpose of the present invention is to obtain a colored curable resin composition capable of forming a thin-film color filter having strong absorption at a wavelength of 525 nm and a deep color.

That is, the gist of the present invention is as follows.

[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant comprises a perylene compound and an isoindoline pigment, wherein the perylene compound has a maximum absorption at 400 nm to 560 nm and does not have a maximum absorption at more than 560 nm to 780 nm.

[2] The colored curable resin composition according to [1], wherein the colorant further comprises a pigment other than the perylene compound and the isoindoline pigment.

[3] The colored curable resin composition as described in [1] or [2], further comprising a solvent.

[4] A color filter comprising the colored curable resin composition described in any one of [1] to [3].

[5] A solid-state imaging element comprising the color filter described in [4].

The present invention provides a colored curable resin composition useful for producing dark-colored, thin-film color filters. The colored curable resin composition of the present invention is particularly suitable as a colored curable resin composition for red applications.

The colored curable resin composition of the present invention comprises a colorant (hereinafter sometimes referred to as colorant (A)), a resin (hereinafter sometimes referred to as resin (B)), a polymerizable compound (hereinafter sometimes referred to as polymerizable compound (C)), and a polymerization initiator (hereinafter sometimes referred to as polymerization initiator (D)).

The colorant (A) comprises a perylene compound (hereinafter sometimes referred to as the perylene compound (1)) and an isoindoline pigment (hereinafter sometimes referred to as the isoindoline pigment (A1)). The perylene compound has a maximum absorption at 400 nm to 560 nm and does not have a maximum absorption at a wavelength exceeding 560 nm to 780 nm.

The colorant (A) may contain a colorant other than the perylene compound (1) and the isoindoline pigment (A1) (hereinafter sometimes referred to as the colorant (A2)).

The colorant (A) preferably further comprises a perylene compound (1) and a pigment other than the isoindoline pigment (A1) (hereinafter sometimes referred to as pigment (A2-2)).

The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter sometimes referred to as solvent (E)).

The colored curable resin composition of the present invention may further contain a polymerization initiation aid (hereinafter sometimes referred to as polymerization initiation aid (D1)).

The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter sometimes referred to as a leveling agent (F)).

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

<Colorant (A)>

The colorant (A) comprises a perylene compound (1) and an isoindoline pigment (A1).

<<Perylene compounds (1)>>

The perylene compound (1) has a maximum absorption at 400 nm to 560 nm and no maximum absorption at wavelengths exceeding 560 nm to 780 nm. Examples thereof include the compound represented by the following formula (1-A). Furthermore, the perylene compound (1) may be a dye or a pigment. Furthermore, the perylene compound (1) may have maximum absorption in multiple wavelength regions between 400 nm and 560 nm. For example, it may have one maximum absorption at 400 nm to 470 nm, one maximum absorption at wavelengths exceeding 470 nm to 510 nm, and one maximum absorption at wavelengths exceeding 510 nm to 570 nm.

[In formula (1-A), ^R1 and ^R2 each independently represent a methyl group having a substituent or a alkyl group having 2 to 30 carbon atoms which may have a substituent, and ^R3 to ^R10 each independently represent a hydrogen atom, a hydroxyl group, or a alkyl group having 1 to 10 carbon atoms which may have a substituent].

The alkyl group having 2 to 30 carbon atoms represented by R ¹ and R ² may be an aliphatic alkyl group or an aromatic alkyl group. The aliphatic alkyl group may be saturated or unsaturated and may be a chain or alicyclic.

Examples of the saturated or unsaturated chain alkyl groups represented by ^R1 and ^R2 include straight-chain alkyl groups such as ethyl, propyl, butyl, and pentyl; branched-chain alkyl groups such as isopropyl, (2-methyl)propyl, isobutyl, sec-butyl, tert-butyl, (2-ethyl)butyl, isopentyl, neopentyl, tert-pentyl, (1-methyl)pentyl, (1-ethyl)pentyl, and (1-hexyl)heptyl; and alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, (1-methyl)vinyl, 2-butenyl, 3-butenyl, and 1,3-butadienyl.

Examples of the saturated or unsaturated alicyclic alkyl group represented by R ¹ and R ² include cycloalkyl groups such as cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 1,2-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, and 2,2,6,6-tetramethylcyclohexyl; cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-2-ene and cyclohex-3-ene), cycloheptenyl, and cyclooctenyl; and norbornyl and adamantyl groups.

The saturated or unsaturated alkyl group represented by ^R1 and ^R2 may be a group formed by combining a chain alkyl group and an alicyclic alkyl group, for example, an alkyl group bonded to one or more alicyclic alkyl groups such as cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, and cyclobutylethyl.

Examples of the aromatic hydrocarbon group represented by ^R1 and ^R2 include phenyl, o-tolyl, m-tolyl, p-tolyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, 2,3-dimethylphenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 1-naphthyl, 2-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl, fluorenyl, phenanthrenyl, and anthracenyl.

The aromatic alkyl group represented by ^R1 and ^R2 is not particularly limited as long as it is a alkyl group having an aromatic alkyl ring. It may be a group formed by combining at least one of a chain alkyl group, an alicyclic alkyl group, and an aromatic alkyl group with an aromatic alkyl group. Examples thereof include aralkyl groups such as benzyl, 2-methylbenzyl, 3,4-methylbenzyl, phenylethyl, and phenylpropyl; arylalkenyl groups such as phenylethenyl (phenylvinyl); arylalkynyl groups such as phenylethynyl; phenyl groups having one or more phenyl groups bonded thereto, such as biphenyl and terphenyl; cyclohexylmethylphenyl, benzylphenyl, and (dimethyl(phenyl)methyl)phenyl.

Examples of the substituents that the methyl group represented by ^R1 and ^R2 and the alkyl group having 2 to 30 carbon atoms may have include halogen atoms such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; a nitro group; a cyano group; an amino group; a hydroxyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a thio group; an alkylthio group having 1 to 6 carbon atoms such as a methylthio group and an ethylthio group; a carboxyl group; an aminoformyl group; an alkoxycarbonyl group having 2 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; a sulfo group; an amine sulfonyl group; and an alkoxysulfonyl group having 1 to 6 carbon atoms such as a methoxysulfonyl group and an ethoxysulfonyl group.

R ¹ and R ² are each independently preferably a methyl group having a substituent, or an optionally substituted alkyl group having 8 to 20 carbon atoms, more preferably a methyl group having a substituent, or an optionally substituted alkyl group having 10 to 15 carbon atoms, further preferably a methyl group having a substituent, an optionally substituted chain alkyl group having 10 to 15 carbon atoms, or an optionally substituted aromatic alkyl group having 10 to 15 carbon atoms, further preferably a methyl group having a substituent, a saturated chain alkyl group having 10 to 15 carbon atoms, or an aromatic alkyl group having 10 to 15 carbon atoms, and particularly preferably a methyl group having a carboxyl group as a substituent, a branched chain alkyl group having 10 to 15 carbon atoms, or a monocyclic aromatic alkyl group having 10 to 15 carbon atoms.

Furthermore, R ¹ and R ² are preferably the same group.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ³ to R ¹⁰ include the same alkyl groups as those represented by R ¹ and R ² , except that they include a methyl group and do not include a group having 11 or more carbon atoms.

Examples of the substituent that the alkyl groups represented by R ³ to R ¹⁰ may have include the same substituents as those that the alkyl groups represented by R ¹ and R ² may have.

R ³ to R ¹⁰ are preferably each independently a hydrogen atom or a alkyl group having 1 to 10 carbon atoms which may have a substituent, more preferably a hydrogen atom or a alkyl group having 1 to 5 carbon atoms which may have a substituent, further preferably a hydrogen atom or a alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom.

Furthermore, R ³ to R ¹⁰ are preferably the same group.

The maximum absorption of a perylene compound can be measured as follows: a chloroform solution containing 0.001 mass % of the perylene compound is prepared, and the solution is placed in a measurement container (e.g., a cuvette) with an optical path length of 1 cm, for example, and spectroscopic measurement is performed.

The content of the perylene compound (1) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass, further preferably 1 to 35 parts by mass, further preferably 5 to 30 parts by mass, relative to 100 parts by mass of the resin (B).

The content of the perylene compound (1) in the total amount of the coloring agent (A) is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, further preferably 20% by mass to 70% by mass, and particularly preferably 25% by mass to 65% by mass. When the content of the perylene compound (1) is within the above range, a colored curable resin composition capable of forming a color filter having excellent red color properties can be obtained.

<<Isoindoline Pigment (A1)>>

The isoindoline pigment (A1) is not particularly limited as long as it is an isoindoline pigment, and a known isoindoline pigment can be used.

Examples of isoindoline pigments (A1) include those classified as pigments in the Color Index (published by the Society of Dyers and Colourists). Specifically, they include C.I. Pigment Yellow 109, 110, 137, 139, 173, 177, 179, and 185, and C.I. Pigment Orange 61 and 69.

The isoindoline pigment (A1) may be an isoindoline pigment not classified as a pigment in the Color Index (published by the Society of Dyers and Colourists). Examples thereof include the compound represented by the following formula (Y).

[In formula (Y), R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a alkyl group having 1 to 20 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.]

M represents a hydrogen atom or an alkali metal atom.

R ¹⁶ and R ¹⁷ represent a alkyl group having 1 to 20 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

L ¹¹ and L ¹² represent -CO- or -SO ₂ -].

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹¹ to R ¹⁷ include the same alkyl groups as those represented by R ¹ and R ² , except that they include a methyl group and do not include a group having 21 or more carbon atoms.

The heterocyclic group represented by R ¹¹ to R ¹⁷ may be monocyclic or polycyclic.

Examples of the substituent that the alkyl group or heterocyclic group represented by R ¹¹ to R ¹⁷ may have include the same substituents as those that the alkyl group represented by R ¹ and R ² may have.

R ¹¹ to R ¹⁵ are preferably a hydrogen atom.

R ¹⁶ and R ¹⁷ are preferably aromatic alkyl groups having 6 to 20 carbon atoms and having a substituent, more preferably aromatic alkyl groups having 6 to 10 carbon atoms and having a substituent, and still more preferably aromatic alkyl groups having 6 to 10 carbon atoms and having a carboxyl group as a substituent.

As ^L1 and ^L2 , -CO- is preferred.

From the perspective of obtaining a coloring curable resin composition capable of forming a color filter having excellent red color properties, the isoindoline pigment (A1) is preferably a yellow isoindoline pigment, more preferably C.I. Pigment Yellow 139, C.I. Pigment Yellow 185, or a compound represented by formula (Y), further preferably C.I. Pigment Yellow 139 or C.I. Pigment Yellow 185, and even more preferably C.I. Pigment Yellow 139.

These isoindoline pigments (A1) may be used alone or in combination of two or more.

The content of the isoindoline pigment (A1) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the resin (B).

The content of the isoindoline pigment (A1) in the total amount of the colorant (A) is preferably 10% to 80% by mass, more preferably 20% to 75% by mass, further preferably 30% to 70% by mass, and particularly preferably 35% to 65% by mass. When the content of the isoindoline pigment (A1) is within this range, a colored curable resin composition capable of forming a color filter having excellent red color properties can be obtained.

<<Colorant (A2)>>

The colored curable resin composition of the present invention may contain, as the colorant (A2), a dye other than the perylene compound (1) and the isoindoline pigment (A1) (hereinafter sometimes referred to as the dye (A2-1)) and/or the pigment (A2-2), preferably containing the pigment (A2-2).

The dye (A2-1) is not particularly limited as long as it does not contain the perylene compound (1), and known dyes can be used. For example, solvent dyes, acid dyes, direct dyes, mordant dyes, etc. can be listed. Examples of dyes include compounds classified as non-pigments and having a hue in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in the Dyeing Notes (published by Shikisensha Co., Ltd.). In addition, based on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, oxyanthracene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, perylene dyes (excluding the perylene compound (1)), and nitro dyes can be listed. Among these, organic solvent-soluble dyes are preferred.

The pigment (A2-2) is not particularly limited as long as it does not contain the perylene compound (1) and the isoindoline pigment (A1). Known pigments can be used, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

Examples of pigments classified as pigments include: C.I. Yellow Pigment 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 117, 125, 128, 147, 148, 150, 153, 154, 166, 194, 214, etc.; C.I. Orange Pigment 13, 31, 36, 38, 40, 43, 51, 55, 59, 64, 65, 71, 73, etc.; C.I. Red Pigment C.I. pigments include red pigments such as 9, 97, 105, 122, 123, 144, 166, 168, 176, 177, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 269, and 291; C.I. pigment blue pigments such as 15, 15:3, 15:4, 15:6, 16, and 60; C.I. pigment violet pigments such as 1, 19, 23, 32, 36, and 38; C.I. pigment green pigments such as 7, 36, and 58; C.I. pigment brown pigments such as 23 and 25; and C.I. pigment black pigments such as 1 and 7.

From the perspective of obtaining a coloring curable resin composition capable of forming a color filter having excellent red color properties, the pigment (A2-2) is preferably a red pigment, and more preferably C.I. Pigment Red 254.

When the colored curable resin composition of the present invention contains a colorant (A2), the content of the colorant (A2) (dye (A2-1) and/or pigment (A2-2)) is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 10% by mass or more, further preferably 20% by mass or more, and preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, based on the total amount of the colorant (A). When the content of the colorant (A2) is within this range, a colored curable resin composition capable of forming a color filter having excellent red color characteristics can be obtained. In particular, the content of the pigment (A2-2) in the total amount of the colorant (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 55% by mass or less.

The perylene compound (1), isoindoline pigment (A1), and the pigment (A2-2) used as required preferably have uniform particle sizes. By containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of pigment dispersants include surfactants, which can be cationic, anionic, nonionic, or amphoteric. Specifically, polyester-based, polyamine-based, and acrylic-based dispersants can be used alone or in combination. Examples of dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (registered trademark) (manufactured by BYK-Chemie). The resin (B) described below can be used as a dispersant.

When using a pigment dispersant, the amount used is preferably 1 part by mass to 200 parts by mass, and more preferably 10 parts by mass to 150 parts by mass, per 100 parts by mass of pigment. When the amount of pigment dispersant used is within this range, a uniformly dispersed pigment dispersion tends to be obtained.

When using two or more pigments, they can be mixed when used as separate dispersions.

The content of the colorant (A) relative to the total solid content of the colored curable resin composition is preferably 0.1% to 50% by mass, more preferably 0.5% to 40% by mass, and even more preferably 1% to 30% by mass. A colorant (A) content within this range is preferred because it provides sufficient color density for the color filter and allows the composition to contain the necessary amount of resin (B), thereby enabling the formation of a pattern with sufficient mechanical strength.

The term "total solid content" in this specification refers to the amount obtained by subtracting the solvent from the total amount of the colored curable resin composition. The total solid content and the content of each component relative to the total solid content can be measured using known analytical methods such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, more preferably a resin having a structural unit derived from at least one type (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "(a)"). The resin (B) further preferably has at least one structural unit selected from the group consisting of a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter referred to as "(b)"), a structural unit derived from a monomer (c) copolymerizable with (a) (which is different from (a) and (b)) (hereinafter referred to as "(c)"), and a structural unit having an ethylenically unsaturated bond in a side chain.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and mono[2-(methyl)acryloyloxyethyl] succinate. Preferred are acrylic acid, methacrylic acid, and maleic anhydride.

(b) Preferably, it is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxycyclopropane ring, an oxycyclobutane ring, and a tetrahydrofuran ring) and a (meth)acryloyloxy group.

Furthermore, in this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acryl" and "(meth)acrylate" have the same meaning.

Examples of (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxycyclobutane, and tetrahydrofurfuryl (meth)acrylate. Preferred are glycidyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, and 3-ethyl-3-(meth)acryloyloxymethyloxycyclobutane.

Examples of (c) include methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, and vinyltoluene. Preferred examples include styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide.

A resin having structural units with ethylenically unsaturated bonds in the side chains can be produced by adding (b) to a copolymer of (a) and (c), or by adding (a) to a copolymer of (b) and (c). Alternatively, the resin may be produced by adding (a) to a copolymer of (b) and (c) and then reacting the mixture with a carboxylic anhydride.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000.

The molecular weight dispersion of the resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value of resin (B), calculated on a solids basis, is preferably 30 mg-KOH/g to 160 mg-KOH/g, more preferably 40 mg-KOH/g to 140 mg-KOH/g, and even more preferably 50 mg-KOH/g to 130 mg-KOH/g. The acid value is the value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

The content of resin (B) relative to the total solid content of the colored curable resin composition is preferably 5% to 65% by mass, more preferably 8% to 60% by mass, and even more preferably 10% to 57% by mass.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by active free radicals and/or acids generated from the polymerization initiator (D). Examples thereof include polymerizable compounds having ethylenically unsaturated bonds, and preferably (meth)acrylate compounds.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

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

The content of the polymerizable compound (C) relative to the total solid content of the colored curable resin composition is preferably 10% to 50% by mass, more preferably 15% to 45% by mass, and even more preferably 20% to 40% by mass.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates active radicals include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one- 2-Imine, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4'5,5'-tetraphenylbiimidazole, etc.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass combined of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within this range, sensitivity tends to be increased and exposure time shortened, thereby improving the productivity of the color filter.

<Polymerization initiation aid (D1)>

The polymerization initiator (D1) is a compound or sensitizer used to accelerate the polymerization of the polymerizable compound that initiates polymerization with the polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

Examples of polymerization initiation aids (D1) include: 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthrone, and N-phenylglycine.

When the polymerization initiator (D1) is used, its 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 total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

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

Specific examples of solvents include: ester solvents (containing -COO- but not -O- in the molecule) such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetylacetate, cyclohexanol acetate, and γ-butyrolactone; ether solvents (containing -O- but not -COO- in the molecule) such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, Ether ester solvents such as propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate (solvents containing -COO- and -O- in the molecule); ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (hereinafter sometimes referred to as diacetone alcohol), heptanone, 4-methyl-2-pentanone, and cyclohexanone (solvents containing -CO- and not -COO- in the molecule); alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvents containing OH and not -O-, -CO-, and -COO- in the molecule); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, etc.

More preferred solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and cyclohexanone.

When a solvent (E) is included, the content of the solvent (E) relative to the total weight of the colored curable resin composition of the present invention is preferably 70% to 95% by mass, more preferably 75% to 92% by mass. In other words, the content of the total solid content of the colored curable resin composition relative to the total weight of the colored curable resin composition of the present invention is preferably 5% to 30% by mass, more preferably 8% to 25% by mass. When the content of the solvent (E) is within this range, flatness during coating is improved, and when forming a color filter, color density is not insufficient, resulting in improved display properties.

<Leveling Agent (F)>

Examples of leveling agents (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants containing fluorine atoms. These surfactants may also have polymerizable groups in their side chains.

Examples of silicone-based surfactants include surfactants with siloxane bonds in their molecules. Specifically, they include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Toray Dow Corning) Corning (manufactured by); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

Examples of the fluorine-based surfactants include those containing a fluorine-carbon chain within the molecule. Specifically, they include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac R31, Megafac R32, Megafac R33, Megafac R34, Megafac R35, Megafac R36, Megafac R37, Megafac R38, Megafac R39, Megafac R30, Megafac R31, Megafac R31, Megafac R32, Megafac R33, Megafac R35, Megafac R36, Megafac R37, Megafac R38, Megafac R39, Megafac R30 ... c) RS-718-K (manufactured by DIC Corporation); Eftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.); Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.); and E5844 (manufactured by Daikin Fine Chemical Laboratories Co., Ltd.).

Examples of silicone-based surfactants containing fluorine atoms include those containing siloxane bonds and fluorocarbon chains within their molecules. Specifically, they include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation).

When a leveling agent (F) is included, the content of the leveling agent (F) relative to the total amount of the colored curable resin composition is preferably 0.001% to 0.2% by mass, and more preferably 0.02% to 0.1% by mass. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within this range, the flatness of the color filter sheet is improved.

<Other ingredients>

The colored curable resin composition of the present invention may also contain fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other additives known in the art, as needed.

<Method for producing a colored curable resin composition>

The colored curable resin composition of the present invention can be prepared by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally a solvent (E), a leveling agent (F), and other ingredients.

The perylene compound (1), isoindoline pigment (A1), and the pigment (A2-2) used as needed are preferably pre-mixed with a portion or all of the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is approximately 0.2 μm or less. At this time, a portion or all of the above-mentioned pigment dispersant and resin (B) may also be prepared as needed. The remaining components are mixed with the thus-obtained pigment dispersion to a predetermined concentration to prepare a colored curable resin composition.

<Method for Manufacturing Color Filters>

Methods for producing colored patterns from the colored curable resin composition of the present invention include photolithography, inkjet printing, and printing. Among these, photolithography is preferred. Photolithography involves applying the colored curable resin composition onto a substrate, drying it to form a colored composition layer, and then exposing and developing the colored composition layer through a photomask. In photolithography, by not using a photomask during exposure and/or not performing development, a colored coating film can be formed as a cured product of the colored composition layer. The colored pattern or colored coating film thus formed constitutes the color filter of the present invention.

Substrates can be made from glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, or sodium calcium glass coated with silicon dioxide; or resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; or substrates with thin films of aluminum, silver, or silver/copper/palladium alloys formed on these substrates. Other color filter layers, resin layers, transistors, and circuits can also be formed on these substrates. Alternatively, silicon substrates treated with HMDS (hexamethyldisilazane) can be used.

The use of photolithography to form pixels of various colors can be performed using known or conventional equipment or conditions. For example, it can be produced as follows.

First, the coloring composition is applied to the substrate and then dried by heat drying (pre-baking) and/or reduced pressure drying to remove volatile components such as solvents, resulting in a smooth coloring composition layer.

Coating methods include rotary coating, slit coating, and slit and rotary coating.

The ideal temperature for heat drying is 30°C to 120°C, more preferably 50°C to 110°C. The ideal heating time is 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.

When performing pressure reduction drying, it is best to perform the drying at a pressure of 50Pa to 150Pa and a temperature of 20℃ to 25℃.

There is no specific restriction on the thickness of the coloring component layer; it can be appropriately selected based on the target color filter thickness.

Next, the coloring composition layer is exposed through a photomask that forms the target coloring pattern. The pattern on the photomask is not particularly limited; a pattern appropriate to the target application is used.

The light source used for exposure is preferably one that generates light with a wavelength between 250nm and 450nm. For example, a filter that cuts off wavelengths below 250nm can be used to cut off light within this wavelength range, or bandpass filters that selectively filter out light near 436nm, 408nm, or 365nm can be used to selectively filter out light within these wavelength ranges. Specific light sources include mercury lamps, LEDs, metal halide lamps, and halogen lamps.

To uniformly illuminate the entire exposure surface with parallel light and accurately align the photomask with the substrate on which the colored composition layer is formed, it is preferable to use an exposure device. Preferred exposure devices include steppers (reduced projection exposure devices) and proximity exposure devices with mask aligners.

The exposed coloring composition layer is exposed to a developer solution for development, forming a colored pattern on the substrate. During development, the unexposed portions of the coloring composition layer dissolve in the developer solution and are removed. Preferred developer solutions include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and 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 developer solution may also contain a surfactant.

The development method can be any of the following: a coating method, an immersion method, a spray method, etc. Furthermore, the substrate can be tilted at any angle during development.

After development, it is best to wash with water.

Furthermore, the obtained colored pattern is preferably post-baked. The post-baking temperature is preferably 80°C or higher, more preferably 100°C or higher, more preferably 150°C or higher, more preferably 160°C or higher, preferably 250°C or lower, and even more preferably 235°C or lower. The post-baking time is preferably 1 minute or longer, more preferably 2 minutes or longer, more preferably 10 minutes or longer, preferably 120 minutes or lower, more preferably 60 minutes or lower, and even more preferably 30 minutes or lower.

The thickness of the coating after post-baking is preferably 3 μm or less, more preferably 2.5 μm or less. The lower limit of the coating thickness is not particularly limited, but is generally 0.1 μm, may be 0.5 μm or more, and may be 1.0 μm or more.

The color filter comprising the colored curable resin composition of the present invention is a dark-colored, thin film. In particular, the absorption at a wavelength of 525 nm, a characteristic required for a red color filter, is stronger than that of a color filter comprising a colored curable resin composition containing C.I. Pigment Red 242 as a colorant. Furthermore, the absorption intensity, i.e., absorbance, of the color filter comprising the colored curable resin composition of the present invention at a wavelength of 525 nm is preferably 1.1 times or more, more preferably 1.2 times or more, the absorbance at 525 nm of a color filter comprising a colored curable resin composition containing C.I. Pigment Red 242 as a colorant (particularly the filter of Comparative Example 1 described below). The upper limit is not particularly limited, and may be, for example, 5.0 times or less, 4.0 times or less, or even 3.0 times or less. Furthermore, the colored curable resin composition preferably exhibits strong absorption at a wavelength of 525 nm and also suppresses absorption at wavelengths exceeding 560 nm to 780 nm, particularly at a wavelength of 565 nm. By suppressing absorption at wavelengths exceeding 560nm to 780nm, excellent color reproduction can be achieved.

Specifically, the absorbance of the color filter comprising the colored curable resin composition at 525 nm is preferably 0.65 or greater, more preferably 0.70 or greater, and even more preferably 0.75 or greater. Furthermore, the absorbance of the color filter comprising the colored curable resin composition at 565 nm is preferably 1.0 or less, more preferably 0.8 or less, and even more preferably 0.7 or less.

Due to its strong absorption at a wavelength of 525 nm and suppressed absorption at wavelengths exceeding 560 nm to 780 nm, the colored curable resin composition of the present invention enables the production of a rich color filter, particularly when forming a red color filter, without increasing the colorant concentration or increasing the film thickness. This color filter is useful as a color filter for use in display devices (e.g., liquid crystal displays, organic EL devices, electronic paper, etc.) and solid-state imaging devices, and is particularly effective in solid-state imaging devices.

[Example]

The present invention is described in more detail below with reference to the following examples. However, the present invention is not limited to the following examples. In the examples, unless otherwise specified, "parts" refers to "parts by mass" and "%" refers to "% by mass."

In the following synthetic examples, compounds were identified by mass spectrometry (LC; Agilent 1200 model, MASS; Agilent LC/MSD model) or elemental analysis (VARIO-EL; Elementar Co., Ltd.).

(Synthesis example 1)

8.0 parts of 3,4,9,10-perylenetetracarboxylic dianhydride (Tokyo Chemical Industry Co., Ltd.), 10 parts of 7-aminotridecane (Tokyo Chemical Industry Co., Ltd.), 1.3 parts of zinc acetate (Kanto Chemical Industry Co., Ltd.), and 314 parts of imidazole (Tokyo Chemical Industry Co., Ltd.) were added and stirred at 150°C for 3 hours. While the resulting mixture was maintained below 20°C, 267 parts of pre-prepared 37% hydrochloric acid (Kanto Chemical Industry Co., Ltd.) and 1300 parts of water were added, resulting in an orange-red precipitate. The mixture containing this orange-red precipitate was filtered, and the filtered residue was washed with 400 parts of water and 200 parts of methanol. The obtained residue was dried under reduced pressure at 60°C to obtain 12 parts of the compound represented by formula (1-1) (hereinafter also referred to as compound (1-1)) (yield 79%).

<Identification of Compound (1-1)>

(Mass analysis) Ionization mode = ESI+: m/z = [M+H] ⁺ 755

Exact Mass: 754

(Synthesis example 2)

8.0 parts of 3,4,9,10-perylenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.8 parts of glycine (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.3 parts of zinc acetate (manufactured by Kanto Chemical Industry Co., Ltd.), and 314 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 150°C for 7 hours. While the resulting mixture was maintained below 20°C, 267 parts of pre-prepared 37% hydrochloric acid (manufactured by Kanto Chemical Industry Co., Ltd.) and 1300 parts of water were added, resulting in an orange-red precipitate. The mixture containing this orange-red precipitate was filtered, and the filtered residue was washed with 400 parts of water and 200 parts of methanol. The obtained residue was dried under reduced pressure at 60°C to obtain 9.1 parts of the compound represented by formula (1-2) (also referred to as compound (1-2)) (yield 88%).

[Chemistry 4]

<Identification of Compound (1-2)>

(Mass analysis) Ionization mode = ESI-: m/z = [MH] ^- 505

Exact Mass: 506

(Synthesis example 3)

A nitrogen atmosphere was created by flowing an appropriate amount of nitrogen through a flask equipped with a reflux cooler, a dropping funnel, and a stirrer. 280 parts of propylene glycol monomethyl ether acetate was placed in the flask and heated to 80°C while stirring. Subsequently, a solution prepared by dissolving 38 parts of 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 (at a 1:1 ratio) in 125 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over approximately 5 hours using a dropping pump. Separately, a solution of 33 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask using a separate dropping pump over approximately 6 hours. After the addition was complete, the mixture was maintained at the same temperature for 4 hours before being cooled to room temperature. This yielded a solution of a copolymer (Resin (B-2)) with a solids content of 35.1%. The resulting copolymer had a weight-average molecular weight (Mw) of 9200, a dispersity of 2.08, and an acid value (based on solids content) of 77 mg-KOH/g. Resin (B-2) had the following structural units.

[Chemistry 5]

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

Device: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40°C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL/min

Detector: RI

Calibration standards: TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

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

[Preparation of Dispersion 1]

2.5 parts of Lumogen F Orange 240 (manufactured by BASF), 2.5 parts of compound (1-2), 5 parts of a dispersant (BYK LPN-6919, manufactured by BYK), 4 parts of resin (B-2) (based on solid content), and propylene glycol monomethyl ether acetate were mixed. 600 parts of 0.4 μm zirconium oxide beads were added and the mixture was shaken for one hour using a paint conditioner (manufactured by LAU). The zirconium oxide beads were then removed by filtration to obtain Dispersion 1. The amount of propylene glycol monomethyl ether acetate in Dispersion 1 was 186 parts, representing the amount of propylene glycol monomethyl ether acetate derived from Resin (B-2).

[Preparation of Dispersion 2]

12 parts of C.I. Pigment Red 242, 4.3 parts of dispersant (BYK LPN-6919, manufactured by BYK), 2.7 parts of resin (B-2) (based on solid content), and propylene glycol monomethyl ether acetate were mixed. 300 parts of 0.4 μm zirconium oxide beads were added and shaken for one hour using a paint conditioner (manufactured by LAU). The zirconium oxide beads were then removed by filtration to obtain Dispersion 2. The propylene glycol monomethyl ether acetate content in Dispersion 2 was 81 parts, representing the amount derived from Resin (B-2).

[Preparation of Dispersion 3]

15 parts of C.I. Pigment Red 179, 3.8 parts of dispersant (BYK LPN-6919, manufactured by BYK), 3.0 parts of resin (B-2) (based on solid content), and propylene glycol monomethyl ether acetate were mixed. 300 parts of 0.4 μm zirconium oxide beads were added and shaken for one hour using a paint conditioner (manufactured by LAU). The zirconium oxide beads were then removed by filtration to obtain Dispersion 3. The propylene glycol monomethyl ether acetate content in Dispersion 3 was 78.2 parts, representing the amount derived from Resin (B-2).

[Preparation of Dispersion 4]

12 parts of C.I. Pigment Yellow 139, 4.2 parts of dispersant (BYK LPN-6919, manufactured by BYK), 4.2 parts of resin (B-2) (based on solid content), and propylene glycol monomethyl ether acetate were mixed. 300 parts of 0.4 μm zirconium oxide beads were added and shaken for one hour using a paint conditioner (manufactured by LAU). The zirconium oxide beads were then removed by filtration to obtain Dispersion 4. The propylene glycol monomethyl ether acetate content in Dispersion 4 was 79.6 parts, representing the amount derived from Resin (B-2).

[Preparation of Dispersion 5]

14.1 parts of C.I. Pigment Red 254, 4.2 parts of dispersant (BYK LPN-6919, manufactured by BYK), 4.9 parts of resin (B-2) (based on solid content), and propylene glycol monomethyl ether acetate were mixed. 300 parts of 0.4 μm zirconium oxide beads were added and shaken for one hour using a paint conditioner (manufactured by LAU). The zirconium oxide beads were then removed by filtration to obtain Dispersion 5. The propylene glycol monomethyl ether acetate content in Dispersion 5 was 76.8 parts, representing the amount derived from Resin (B-2).

[Preparation of Dispersion 6]

10.3 parts of C.I. Pigment Yellow 185, 4.1 parts of dispersant (BYK LPN-6919, manufactured by BYK), 4.6 parts of resin (B-2) (based on solid content), and propylene glycol monomethyl ether acetate were mixed. 300 parts of 0.4 μm zirconium oxide beads were added and shaken for one hour using a paint conditioner (manufactured by LAU). The zirconium oxide beads were then removed by filtration to obtain Dispersion 6. The propylene glycol monomethyl ether acetate content in Dispersion 6 was 81.0 parts, representing the amount derived from Resin (B-2).

Each compound was dissolved in chloroform to a concentration of 0.001% by mass to obtain a solution. This solution was measured using a V-650 UV-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation). The measurement results of the wavelength at the maximum absorption point (maximum absorption wavelength) of each compound are shown in Table 1.

[Examples 1-4, Comparative Examples 1-2]

<Preparation of Colored Curing Resin Composition>

The components shown in Table 2 were mixed to obtain various colored curable resin compositions.

Resin (B): Resin (B-2) (solid content conversion)

Polymerizable compound (C): Dipentaerythritol polyacrylate ("A9550" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; solid content conversion)

Polymerization initiator (D): N-Benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF)

Solvent (E-1): Propylene glycol monomethyl ether acetate

Solvent (E-2): Cyclohexanone

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.; solid content conversion)

<Preparation of Colored Coating>

A colored curable resin composition was spin-coated onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) and then pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, the colored composition layer was exposed to light using an exposure system (TME-150RSK; manufactured by Topcon) in an atmospheric environment at an exposure dose of 60 mJ/ ^cm² (at 365 nm). Following exposure, the layer was post-baked in an oven at 230°C for 20 minutes to obtain a colored coating film.

<Film thickness measurement>

The film thickness of the obtained colored coating was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 3.

<Color Evaluation>

The obtained colored coating on the glass substrate was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) to measure the spectra and compare the absorbance at a wavelength of 525 nm and a wavelength of 565 nm. The results are shown in Table 3. In Table 3, abs(525) indicates the absorbance at a wavelength of 525 nm, and abs(565) indicates the absorbance at a wavelength of 565 nm.

As shown in Table 3, the colored curable resin compositions of Examples 1 and 2 yielded colored coatings with strong absorption at a wavelength of 525 nm and significantly suppressed absorption at a wavelength of 565 nm. Furthermore, the colored curable resin compositions of Examples 3 and 4 yielded colored coatings with very strong absorption at a wavelength of 525 nm, while suppressing absorption at a wavelength of 565 nm caused by C.I. Pigment Red 254.

Claims (5)

A red colored curable resin composition comprises a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant comprises a perylene compound (1) and an isoindoline pigment (A1), wherein the perylene compound (1) has a maximum absorption at 400 nm to 560 nm and does not have a maximum absorption at more than 560 nm to 780 nm, wherein the content of the colorant (A) is 30% by mass or less relative to the total solid content of the colored curable resin composition, and wherein the perylene compound (1) is a compound represented by formula (1-A). In formula (1-A), ^R1 and ^R2 each independently represent a methyl group having a carboxyl group as a substituent, a branched alkyl group having 10 to 15 carbon atoms, or a monocyclic aromatic alkyl group having 10 to 15 carbon atoms, ^{and R3} to ^R10 each independently represent a hydrogen atom, a hydroxyl group, or a alkyl group having 1 to 10 carbon atoms which may have a substituent. The red colored curable resin composition according to claim 1, wherein the colorant (A) further contains a pigment (A2-2) other than the perylene compound (1) and the isoindoline pigment (A1). The red colored curable resin composition according to claim 1 or 2, further comprising a solvent (E). A color filter comprising the red colored curable resin composition according to any one of claims 1 to 3. A solid-state imaging element comprises the color filter as described in claim 4.