TWI719961B - Colored curable resin composition, color filter and display device - Google Patents

Abstract

The subject of the present invention is to provide a colored curable resin composition, a color filter, and a display device, which can obtain a coating film with improved heat resistance. The colored curable resin composition is characterized by containing a compound (Aa) represented by a predetermined formula, a dye (Ab), a resin (B), a polymerizable compound (C), and a polymerization initiator (D) (wherein, It does not include a composition mixed with the remaining components after preparing a colored dispersion using the compound (Aa) and a solvent).

Description

Colored curable resin composition, color filter and display device Technical field

The present invention relates to a coloring curable resin composition, a color filter, and a display device in which a salt-forming colorant and a dye are used in combination.

Background technique

The use of the following compounds is disclosed in the coloring curable resin composition used in color filters and display devices (Patent Documents 1 and 2).

Patent Document 1 discloses a technique of dispersing the above-mentioned compound and pigment in a predetermined organic solvent in terms of improving storage stability. Patent Document 2 discloses a technique of dispersing the above-mentioned compound in a dispersant having a predetermined amine value in terms of improving the brightness of the color filter. However, none of the patent documents teaches a colored curable resin composition capable of improving heat resistance when dyes such as the above-mentioned compounds and salt-forming colorants are used.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2013-234319

Patent Document 2: JP 2013-235257 A

Summary of the invention

As described above, the conventionally known colored curable resin composition cannot sufficiently satisfy the requirements in terms of heat resistance.

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

[1] A colored curable resin composition characterized by containing a compound (Aa) represented by formula (AI), a dye (Ab), a resin (B), a polymerizable compound (C), and a polymerization initiator (D) ), which does not include a composition mixed with the remaining components after preparing a colored dispersion using the compound (Aa) and a solvent.

[式(A-I)中， R⁴¹~R⁴⁴分別獨立地表示可以具有取代基的碳數1~20的烷基、為碳數2~20的烷基且在構成該烷基的亞甲基間插入 有氧原子的基團、可以具有取代基的芳香族烴基、可以具有取代基的芳烷基或氫原子。R⁴¹和R⁴²可以鍵合併與它們鍵合的氮原子一起形成環，R⁴³和R⁴⁴可以鍵合併與它們鍵合的氮原子一起形成環。

[In formula (AI), R ⁴¹ to R ⁴⁴ each independently represent an optionally substituted alkyl group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons, and between the methylene groups constituting the alkyl group. An oxygen atom-inserted group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aralkyl group, or a hydrogen atom. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms. An oxygen atom is inserted between the methylene groups. R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -.

Ring T ¹ represents an aromatic heterocyclic ring which may have a substituent.

[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements.

m represents any natural number.

In addition, when a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

[式中，環T¹、R⁴¹~R⁴⁴及R⁴⁷~R⁵⁴分別與上述的意義相同。]]

[In the formula, rings T ¹ , R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ have the same meanings as above. ]]

[2] The colored curable resin composition according to [1], wherein [Y] ^m- in the formula (AI) is an anion of a heteropoly acid or a homopoly acid containing tungsten as an essential element.

[3] The colored curable resin composition according to [2], wherein [Y] ^m- in the formula (AI) is an anion of phosphotungstic acid, an anion of silicotungstic acid, or a tungsten-based homopolyacid Anion.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the dye (Ab) is selected from xanthene dyes, triarylmethane dyes, anthraquinone dyes, and tetrazolium dyes. One of the group consisting of heteroporphyrin dyes.

[5] The colored curable resin composition according to any one of [1] to [4], wherein the dye (Ab) is a xanthene dye.

[6] The coloring curable resin composition according to [4] or [5], wherein the xanthene dye is represented by the following formula (a1-1).

[式(a1-1)中，R¹~R⁴互相獨立地表示氫原子、可以具有取代基的碳數1~20的1價的飽和烴基、或可以具有取代基的碳數6~10的1價的芳香族烴基，該飽和烴基中所含的亞甲基(-CH₂-)可以被-O-、-CO-或-NR¹¹-替代。R¹及R²可以一起形成含有氮原子的環，R³及R⁴可以一起形成含有氮原子的環。

[In the formula (a1-1), R ¹ to R ⁴ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbons which may have a substituent, or a carbon 6-10 which may have a substituent A monovalent aromatic hydrocarbon group, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, or -NR ¹¹ -. R ¹ and R ² may form a ring containing a nitrogen atom together, and R ³ and R ⁴ may form a ring containing a nitrogen atom together.

R ⁵ represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ⁵ may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ¹¹ may be the same or different.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ⁹ and R ¹⁰ independently represent a hydrogen atom or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbon atoms. The -CH ₂ -contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, Instead of -NH- or -NR ⁸ -, R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

[7] The coloring curable resin composition according to any one of [1] to [6], wherein the weight average molecular weight of the resin (B) is 9000 or more.

[8] The colored curable resin composition according to any one of [1] to [7], wherein the acid value of the resin (B) is 60 mg-KOH/g or more.

[9] The colored curable resin composition according to any one of [1] to [8], wherein the content of the dye (Ab) is 0.01 to 100% by mass of the solid content of the colored curable resin composition 5 quality%.

[10] The colored curable resin composition according to any one of [1] to [9], wherein the mass ratio of dye (Ab)/compound (Aa) is 0.001 to 0.5.

[11] A color filter formed of the coloring curable resin composition according to any one of [1] to [10].

[12] A display device including the color filter described in [11].

According to the present invention, a colored curable resin composition, a color filter, and a display device can be provided, and the colored curable resin composition can provide a coating film with improved heat resistance.

detailed description

<Colored curable resin composition>

The colored curable resin composition of the present invention contains a compound represented by formula (AI) (hereinafter, sometimes referred to as a salt-forming colorant or compound (Aa).), dye (Ab), resin (B), and polymerizable compound (C), and polymerization initiator (D). However, it does not include a composition mixed with the remaining components after preparing a colored dispersion using the compound (Aa) and a solvent.

Compound (Aa)

[In formula (AI), R ⁴¹ to R ⁴⁴ each independently represent an optionally substituted alkyl group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons, and between the methylene groups constituting the alkyl group. An oxygen atom-inserted group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aralkyl group, or a hydrogen atom. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms. An oxygen atom is inserted between the methylene groups. R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -.

Ring T ¹ represents an aromatic heterocyclic ring which may have a substituent.

[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements.

m represents any natural number.

In addition, when a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

[In the formula, rings T ¹ , R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ have the same meanings as above. ]]

The aromatic heterocyclic ring of ring T ¹ may be a monocyclic ring or a condensed ring. In addition, the aromatic heterocyclic ring is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring.

Examples of monocyclic aromatic heterocyclic rings include: 5-membered rings containing nitrogen atoms such as pyrrole ring, oxazole ring, pyrazole ring, imidazole ring, and thiazole ring; Rings; 6-membered rings containing nitrogen atoms such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc. As the condensed aromatic heterocyclic ring, indole ring, benzimidazole ring, benzo Condensed rings containing nitrogen atoms such as thiazole ring and quinoline ring; rings containing no nitrogen atoms such as benzofuran ring.

Examples of substituents that the aromatic heterocyclic ring of ring T ¹ may have include halogen atoms, cyano groups, alkyl groups with 1 to 20 carbons which may be substituted by halogen atoms, and 6 to 6 carbons which may be substituted by halogen atoms. 20 aromatic hydrocarbon groups, optionally substituted amine groups, etc.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the optionally substituted amine group include: amine group; N-methylamino group, N-ethylamino group, N-phenylamino group, and other amines which may be substituted with a hydrocarbon group having 1 to 10 carbon atoms Group: N,N-dimethylamino, N,N-diethylamino and other amino groups that can be substituted with two hydrocarbon groups with 1 to 10 carbon atoms.

Among them, the aromatic heterocyclic ring of ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a 5-membered aromatic heterocyclic ring containing a nitrogen atom.

In addition, the ring T ^{1 is} more preferably a ring represented by the formula (Ab2-x1), and particularly preferably a ring represented by the formula (Ab2-y1).

[環T²表示芳香族雜環。

[Ring T ² represents an aromatic heterocyclic ring.

R ⁴⁵ and R ⁴⁶ each independently represent an optionally substituted alkyl group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms, and a group having an oxygen atom inserted between the methylene groups constituting the alkyl group , An optionally substituted aromatic hydrocarbon group, an optionally substituted aralkyl group or a hydrogen atom. R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.

R ⁵⁵ represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group.

k1 represents 0 or 1.

* Indicates the bonding end with the carbocation. ]

[R⁵⁶表示氫原子、碳數1~20的烷基、或可以具有取代基的芳香族烴基。

[R ⁵⁶ represents a hydrogen atom, a C 1-20 alkyl group, or an optionally substituted aromatic hydrocarbon group.

X2 represents an oxygen atom, -NR ⁵⁷ -or a sulfur atom.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ have the same meaning as above.

* Indicates the bonding end with the carbocation. ]

The aromatic heterocyclic ring of ring T ² may be the same as the aromatic heterocyclic ring exemplified in ring T ¹ .

[環T³表示具有氮原子的芳香族雜環。 In addition, the ring T ^{1 is} also preferably a ring represented by the formula (Ab2-x2), [Chemical formula 12]

[Ring T ³ represents an aromatic heterocyclic ring having a nitrogen atom.

R ⁵⁸ represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group.

R ⁵⁹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group or an optionally substituted aralkyl group.

k2 represents 0 or 1.

* Indicates the bonding end with the carbocation. ]

The ring T ^{1 is} also more preferably a ring represented by the formula (Ab2-y2).

[R⁶⁰表示氫、碳數1~20的烷基、或可被取代的芳香族烴基。

[R ⁶⁰ represents hydrogen, a C 1-20 alkyl group, or an optionally substituted aromatic hydrocarbon group.

R ⁵⁹ has the same meaning as above.

* Indicates the bonding end with the carbocation. ]

As R ⁴¹ and R ⁴² are bonded and form a ring with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ are bonded and form a ring with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ^{46 are} bonded and bond with them Examples of the ring formed by the combined nitrogen atoms include the following rings.

Examples of the alkyl group having 1 to 20 carbons represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ include methyl, ethyl, propyl, butyl, pentyl, and hexyl. , Heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl and other linear alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, Branched chain alkyl groups such as 2-ethylhexyl; cyclic alkyl groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

The carbon number of the linear or branched alkyl group is preferably from 1 to 8, more preferably from 1 to 6, and even more preferably from 1 to 4. In addition, the carbon number of the cyclic alkyl group is preferably 3-10, and more preferably 6-10. In addition, in ^{the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group of R 41} to R ⁴⁶ , the number of carbon atoms between the oxygen atoms is preferably 1 to 4, and more preferably 2 to 3.

Examples of the substituents that the alkyl group represented by R ⁴¹ to R ⁴⁶ may have include: amino; N-methylamino, N-ethylamino, N-phenylamino, N,N-di Amino groups that may be substituted such as methylamino groups and N,N-diethylamino groups; halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms.

^Examples of the substituent that the alkyl group of R 59 may have include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; and a cyano group.

In addition, ^{examples of the aromatic hydrocarbon groups represented by R 41} to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ , and R ⁵⁸ to R ⁶⁰ include phenyl, tolyl, xylyl, naphthyl, anthryl, phenanthryl, The aromatic hydrocarbon group having 6 to 20 carbon atoms such as biphenyl and terphenyl is preferably an aromatic hydrocarbon group having 6 to 15 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms.

The aromatic hydrocarbon group may also have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; and alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups. Group; Hydroxyl; Sulfamyl; M Alkylsulfonyl groups having 1 to 6 carbon atoms, such as sulfonyl groups; alkoxycarbonyl groups having 1 to 6 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl groups.

Examples of the optionally substituted aralkyl groups represented by R ⁴¹ to R ⁴⁶ and R ⁵⁹ include groups such as methylene, ethylene, propylene, etc. bonded to the groups described as the above-mentioned aromatic hydrocarbon groups. Groups such as alkanediyl groups (benzyl and phenethyl) having 1 to 5 carbon atoms.

The alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ may be linear, branched, and cyclic, and is preferably chain. Examples include linear, branched, and cyclic alkyl groups having 1 to 8 carbon atoms in R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ^60.

R ⁴¹ to R ⁴⁴ , R ⁵⁵ , R ⁵⁸ and R ⁵⁹ are each independently preferably an alkyl group having 1 to 20 carbons, an aromatic hydrocarbon group that may have a substituent, and more preferably an alkyl group having 1 to 6 carbons, which may be substituted The phenyl group.

R ⁴⁵ and R ⁴⁶ are each independently preferably a substituted alkyl group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms and an oxygen atom is inserted between the methylene groups constituting the alkyl group. , Aromatic hydrocarbon groups that may have substituents, more preferably methyl, ethyl, propyl, butyl, pentyl, methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl , Propoxymethyl, propoxyethyl, propoxypropyl, phenyl, o-tolyl, m-tolyl, p-tolyl.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, or a C 1-8 alkyl group, and each independently is particularly preferably a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

R ⁵⁶ is preferably an alkyl group having 1 to 10 carbons, or an aromatic hydrocarbon group that may have a substituent, and more preferably an alkyl group having 1 to 8 carbons, or a halogenated alkyl group having 1 to 4 carbon atoms, and carbon atoms. An alkoxy group having 1 to 4, a hydroxyl group, an alkyl group having 1 to 4 carbons, or an aromatic hydrocarbon group substituted with a methylsulfonyl group, more preferably phenyl, o-tolyl, m-tolyl, p-tolyl, A phenyl group in which a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group, or a methanesulfonyl group is bonded to at least any one of the ortho position, the para position, and the meta position with respect to the bonding end.

As R ⁵⁷ , a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferable.

As the cation part of the formula (Ab2), as shown in Table 1 below, cation 1 to cation 12 represented by the formula (Ab2-1) and the like can be given. In the table, * indicates the bonding end.

In Table 1, Ph1 to Ph9 refer to groups represented by the following formulas. In the formula, * represents the bonding end.

In addition, as the cation part of the formula (Ab2), as shown in Table 2 below, cation 13 to cation 16 represented by the formula (Ab2-2) and the like can also be cited. In the table, * indicates the bonding end.

[Table 2]

In Table 2, Ph1, Ph10, and Ph11 refer to groups represented by the following formulas. In the formula, * represents the bonding end.

Among them, as the cation portion of the formula (Ab2), cation 1 to cation 6, cation 11, or cation 12 are preferred, cation 1, cation 2, or cation 12 is particularly preferred, and cation 12 is most preferred.

<Anion part>

^{As [Y] m-} corresponding to the anion, an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements is used. Such anions can improve heat resistance and solvent resistance.

The anion [Y] ^m- is preferably an anion of heteropolyacid or homopolyacid containing tungsten as an essential element, and particularly preferably anions of phosphotungstic acid, silicotungstic acid and tungsten homopolyacid.

As the anion of the heteropoly acid or isopoly acid containing tungsten as an essential element, there can be mentioned: Keggin type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson type phosphotungstic acid ion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin tungstic acid ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [ W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and their mixtures.

[Y] ^{m- is} also preferably an anion composed of at least one element selected from the group consisting of silicon and phosphorus and oxygen.

Examples of the anion composed of at least one element selected from the group consisting of silicon and phosphorus and oxygen include SiO ₃ ^2- and PO ₄ ^3- .

Easiness in view of synthesis and post-processing, phosphotungstic acid anion preferably Keggin phosphotungstic acid ion, Dawson-type phosphotungstic acid ion; Keggin type silicon tungstate ion Silicotungstic acid anion, [W ₁₀ O _32] ^{4 -} such as tungsten with acid anion. Among them, phosphotungstic acid anions and tungsten-based homopolyacid anions are particularly preferred.

The compound represented by formula (A-I) can be synthesized according to the synthesis method described in JP 2015-28121 A.

As the compound (Aa), a compound represented by the following formula can be given.

The compound represented by formula (A-I) may be a combination of two or more kinds. Among them, the compound (Aa) is preferably a compound represented by formula (Aa2-53).

The content of the compound (Aa) relative to the total solid content is usually 1% by mass or more and 70% by mass or less, preferably 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 60% by mass. Hereinafter, it is particularly preferably 30% by mass or more and 50% by mass or less. If the content of the above-mentioned compound (Aa) is within the above-mentioned range, it is easier to obtain the desired spectral and color density. degree. In addition, in this specification, the "total amount of solid content" refers to the total amount of the components from the colored curable resin composition of the present invention except for the solvent. The total amount of solid content and the content of each component relative to it can be measured by a known analysis device such as liquid chromatography and gas chromatography, for example.

<Dye (Ab)>

The dye (Ab) is preferably one selected from the group consisting of xanthene dyes, triarylmethane dyes, anthraquinone dyes, and porphyrazine dyes, and more preferably xanthene dyes.

<Xanthene Dye>

The xanthene dye is more preferably a compound represented by the following formula (a1-1) (hereinafter, also referred to as compound (a1-1)). Compound (a1-1) may also be a tautomer.

[式(a1-1)中，R¹~R⁴互相獨立地表示氫原子、可以具有取代基的碳數1~20的1價的飽和烴基、或可以具有取代基的碳數6~10的1價的芳香族烴基，該飽和烴基中所含的亞甲基(-CH₂-)可以被-O-、-CO-或-NR¹¹-取代。R¹及R²可以一起形成含有氮原子的環，R³及R⁴可以一起形成含有氮原子的環。

[In the formula (a1-1), R ¹ to R ⁴ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbons which may have a substituent, or a carbon 6-10 which may have a substituent A monovalent aromatic hydrocarbon group, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be substituted with -O-, -CO-, or -NR ¹¹ -. R ¹ and R ² may form a ring containing a nitrogen atom together, and R ³ and R ⁴ may form a ring containing a nitrogen atom together.

R ⁵ represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ⁵ may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ¹¹ may be the same or different.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ⁹ and R ¹⁰ independently represent a hydrogen atom or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbon atoms. The -CH ₂ -contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, Instead of -NH- or -NR ⁸ -, R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

In formula (a1-1), when -SO ₃ ^- is present, its number is one.

Examples of monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms in R ¹ to R ⁴ include phenyl, tolyl, xylyl, mesityl, propylphenyl, and butylphenyl. Wait. Among them, R ¹ and R ^{4 are} preferably phenyl, tolyl, or xylyl.

Examples of the aromatic hydrocarbon group may have a substituent group, include: halogen ^{atoms, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H , -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ , these substituents preferably replace the hydrogen atoms contained in the aromatic hydrocarbon group. Among these, as a substituent group, preferably _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ⁹ R ^10, more preferably -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ^10. As -SO ₃ ^- Z ^{+ in this case} , -SO _3- ⁺ N(R ¹¹ ) ₄ is preferable. When R ¹ to R ⁴ are these groups, the coloring curable resin composition of the present invention containing the compound (a1-1) can form a color filter that generates less foreign matter and is excellent in heat resistance.

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ⁸ to R ¹¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl. , Octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl and other linear alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethyl Branched chain alkyl such as hexyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms. Among them, R ² and R ^{3 are} preferably methyl, ethyl, isopropyl, or propyl.

The hydrogen atom contained in the saturated hydrocarbon group in R ¹ to R ⁴ may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. As the number of carbon atoms which may be substituted saturated hydrocarbon group R ¹ ~ R ⁴ are hydrogen atoms, aromatic hydrocarbon group having 6 to 10, may include an aromatic hydrocarbon group with carbon number of R ¹ is Example of R & lt ~ ~ ⁴ 6 10 shown The same group.

The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted by, for example, a hydroxyl group or a halogen atom as a substituent.

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ^{4 together include the following rings.}

Examples of -OR ⁸ include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and Alkoxy groups such as eicosyloxy and the like.

Examples of -CO ₂ R ⁸ include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl, etc. .

Examples of -SR ⁸ include alkyl sulfides such as methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylsulfanyl, and eicosylsulfanyl. Alkyl and so on.

Examples of -SO ₂ R ⁸ include alkanes such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl. Sulfonyl and so on.

As -SO ₃ R ⁸ , for example, methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl, and 20 Alkoxysulfonyl and the like are alkoxysulfonyl and the like.

Examples of -SO ₂ NR ⁹ R ¹⁰ include: sulfasulfonyl; N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, N-isopropyl N-butylsulfamate, N-butylsulfamate, N-isobutylsulfamate, N-sec-butylsulfamate, N-tert-butylsulfamate, N-pentylamine Sulfonyl, N-(1-ethylpropyl)sulfasulfonyl, N-(1,1-dimethylpropyl)sulfasulfonyl, N-(1,2-dimethylpropyl) Sulfamoyl, N-(2,2-dimethylpropyl)sulfasulfonyl, N-(1-methylbutyl)sulfasulfonyl, N-(2-methylbutyl)sulfasulfon Acetyl, N-(3-methylbutyl)sulfasulfonyl, N-cyclopentylsulfasulfonyl, N-hexylsulfasulfonyl, N-(1,3-dimethylbutyl)amine Sulfonyl, N-(3,3-dimethylbutyl)sulfasulfonyl, N-heptylsulfasulfonyl, N-(1-methylhexyl)sulfasulfonyl, N-(1, 4-Dimethylpentyl)sulfasulfonyl, N-octylsulfasulfonyl, N-(2-ethylhexyl)sulfasulfonyl, N-(1,5-dimethylhexyl)sulfonyl N-1 substituted sulfasulfonyl groups such as N, N-(1,1,2,2-tetramethylbutyl)sulfasulfonyl; N,N-dimethylsulfasulfonyl, N,N- Ethyl methylsulfamate, N,N-diethylsulfamate, N,N-propyl methylsulfamate, N,N-isopropyl methylsulfamate, N, N-tert-Butylmethylsulfasulfonyl, N,N-butylethylsulfasulfonyl, N,N-bis(1-methylpropyl)sulfasulfonyl, N,N-heptylmethylamine Sulfonyl and other N, N-2 substituted sulfamyl and so on.

As R ^5, preferably ^{_{-CO 2 H, -CO 2 - Z}} +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or -SO ₂ NHR ^9, and more preferably -SO _{^{3 -, -SO 3 - Z +}} , -SO 3 H or -SO ₂ NHR ^9, more preferably -SO ₃ ^-.

m is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include alkyl groups having 1 to 6 carbon atoms among the alkyl groups mentioned above. Among them, as R ⁶ and R ⁷ , a hydrogen atom is preferred.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^{11 include benzyl, phenylethyl, and phenylbutyl.}

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ .

As the above-mentioned ⁺ N(R ¹¹ ) ₄ , it is preferable ^{that at least two of the four R 11} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, ^{the total carbon number of the four R 11} is preferably 20 to 80, and more preferably 20 to 60. ^{When +} N(R ¹¹ ) ₄ is present in the compound (a1-1), if R ¹¹ is these groups, a foreign substance can be formed from the coloring curable resin composition of the present invention containing the compound (a1-1) Fewer color filters.

In addition, as the xanthene dye, a compound represented by formula (a1-2) (hereinafter may be referred to as "compound (a1-2)") is also preferable. Compound (a1-2) may also be a tautomer.

[式(a1-2)中，R²¹及R²²互相獨立地表示碳數1~10的1價的飽和烴基，該R²¹、R²²的飽和烴基中所含的氫原子可以被碳數6~10的芳香族烴基或鹵素原子取代，該芳香族烴基中所含的氫原子可以被碳數1~3的烷氧基取代，上述R²¹、R²²的飽和烴基中所含的-CH₂-可以被-O-、-CO-或-NR¹¹-替代。

[In formula (a1-2), R ²¹ and R ²² independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbons, and the hydrogen atom contained in the saturated hydrocarbon group of ^{R 21} and R ^{22 may be replaced by a carbon 6} ~10 aromatic hydrocarbon group or halogen atom substitution, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a C 1 to 3 alkoxy group, the above-mentioned R ²¹ , R ²² saturated hydrocarbon group contains -CH ₂ -Can be replaced by -O-, -CO- or -NR ¹¹ -.

R ²³ and R ²⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

R ²¹ and R ²³ may form a ring containing a nitrogen atom together, and R ²² and R ²⁴ may form a ring containing a nitrogen atom together.

p and q represent an integer from 0 to 5 independently of each other. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different.

R ¹¹ has the same meaning as ^{R 11 described above.} ]

^Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbons in R ²¹ and R 22 include groups having 1 to 10 carbons among the groups in ^{R 8.}

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that the substituent may have include the same groups as those in ^{R 1.}

As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

R ²¹ and R ^{22 are} preferably a monovalent saturated hydrocarbon group having 1 to 3 carbons independently of each other.

Examples of the alkyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ²³ and R ^{24 include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, and isopropylsulfanyl.} Sulfanyl and so on.

Examples of the alkylsulfonyl groups having 1 to 4 carbon atoms in R ²³ and R ^{24 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropyl} Sulfonyl and so on.

R ²³ and R ^{24 are} preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and still more preferably a methyl group.

p and q are preferably an integer of 0-2, and 1 or 2 is preferable.

Examples of xanthene dyes include compounds represented by formula (1-1) to formula (1-43). In addition, in the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.

Among the above-mentioned compounds, the compound represented by any one of formula (1-24) to formula (1-36) corresponds to compound (a1-2).

Among these, the sulfonamide of C.I. Acid Red 289, the quaternary ammonium salt of C.I. Acid Red 289, the sulfonamide of C.I. Acid Violet 102, or the quaternary ammonium salt of C.I. Acid Violet 102 are preferable. Examples of such compounds include compounds represented by formula (1-1) to formula (1-8), formula (1-11), or formula (1-12), and the like.

In addition, from the viewpoint of excellent solubility in organic solvents, compounds represented by any one of formula (1-24) to formula (1-33) are also preferred, and compounds represented by formula (1-32) are particularly preferred. compound of.

As the xanthene dye, commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Chemical Co., Ltd., and "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) can be used. In addition, a commercially available xanthene dye can also be used as a starting material for synthesis with reference to Japanese Patent Application Laid-Open No. 2010-32999.

<Triarylmethane dye>

The triarylmethane dye preferably contains three aromatic hydrocarbon groups bonded Dyes based on compounds with a carbon atom structure. Examples of triarylmethane dyes include: CI Solvent Blue 2, 4, 5, 43, 124; CI Basic Violet 3, 14, 25; CI Basic Blue 1, 5, 7, 11, 26, and Japanese Patent Triarylmethane dyes and the like described in No. 4492760.

<Anthraquinone Dyes>

Examples of anthraquinone dyes include: CI Solvent Violet 11 (Hereinafter, the description of CI Solvent Violet is omitted and only numbers are used.), 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51 , 59, 60, CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, CI Solvent Green 3, 28, 29, 32, 33, CI Acid Green 25, 27, 28, 41, CI Acid Violet 34, CI Acid Blue 25, 27, 40, 45, 78, 80, 112 C.I. Disperse Violet 26, 27, CI Disperse Blue 1, 14, 56, 60, CI Direct Blue 40, CI Mordant Blue 8, etc.

<Porphyrazine Dyes>

The porphyrazine dye is a compound having a porphyrazine skeleton in the molecule. In addition, when the porphyrazine dye is an acid dye or a basic dye, it may form a salt with any cation or anion.

As other dyes, azo dyes and oxazine dyes can be used Materials, phthalocyanine dyes, etc., well-known dyes can be used, respectively.

Examples of azo dyes include: CI Direct Blue 51 (hereinafter, the description of CI Direct Blue is omitted, and only the number is described.), 57, 71, 81, 84, 85, 90, 93, 94, 95, 98, 100 , 101, 113, 149, 150, 153, 160, 162, 163, 164, 166, 167, 170, 172, 188, 192, 193, 194, 196, 198, 200, 207, 209, 210, 212, 213 , 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275; CI Direct Green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82, etc.; CI Acid Violet 11, 56, 58; CI Acid Blue 92, 102, 113, 117, etc.; CI Basic Blue 41, 54, 64, 66, 67, 129, etc.

Examples of oxazine dyes include: C.I. Direct Blue 97, 99, 106, 107, 108, 109, 190, 293 and the like.

Examples of phthalocyanine dyes include: C.I. Direct Blue 86, 87, 189, 199, C.I. Acid Blue 249, C.I. Basic Blue 3, and the like.

The content of the dye (Ab) in 100% by mass of the solid content of the colored curable resin composition is, for example, 0.01 to 5% by mass, preferably 0.05 to 4% by mass, more preferably 0.1 to 3% by mass, and particularly preferably 0.2~2% by mass.

The dye preferably contains 50% by mass or more of the xanthene dye (preferably a compound represented by formula (1-32)), more preferably 60% by mass or more, still more preferably 70% by mass or more, and still more preferably 80% by mass or more ,especially The content is preferably 90% by mass or more, and most preferably 100% by mass.

Among the dyes, in addition to xanthene dyes, one or more other dyes may be used in combination.

The mass ratio of dye (Ab) (in terms of solid content)/compound (Aa) (in terms of solid content) is preferably 0.001 to 0.5, more preferably 0.005 to 0.4, still more preferably 0.007 to 0.3, and still more preferably 0.009 to 0.2. When the above numerical range is not satisfied, the effect of improving heat resistance may not be obtained.

<Resin (B)>

The resin (B) contained in the colored curable resin composition of the present invention is preferably an alkali-soluble resin, and more preferably has a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride Addition polymer. Examples of such resins include the following resins [K1] to [K6].

Resin [K1]: At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)") and a cyclic ether structure having 2 to 4 carbon atoms Copolymer with ethylenically unsaturated bond monomer (b) (hereinafter sometimes referred to as "(b)")

Resin [K2]: (a), (b) and (a) copolymerizable monomer (c) (wherein, it is different from (a) and (b).) (hereinafter sometimes referred to as "(c)" ) Copolymer

Resin [K3]: Copolymer of (a) and (c)

Resin [K4]: A resin obtained by reacting a copolymer of (a) and (c) with (b)

Resin [K5]: A resin obtained by reacting the copolymer of (b) and (c) with (a)

Resin [K6]: A resin obtained by reacting the copolymer of (b) and (c) with (a), and then reacting carboxylic anhydride.

Examples of (a) include: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic 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, etc. containing carboxyl Bicyclic unsaturated compounds; unsaturated dicarboxylic acid anhydrides such as maleic anhydride; unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule such as α-(hydroxymeth)acrylic acid.

Among them, acrylic acid, methacrylic acid, and maleic anhydride are preferred from the viewpoints of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.

(b) means a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond The polymerizable compound. (b) It is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloxy group. In addition, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid, and "(meth)acrylic acid ester" and "(meth)acrylic acid ester" The description also has the same meaning.

Examples of (b) include: monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group and an ethylenically unsaturated bond The bond monomer (b2) (hereinafter may be referred to as "(b2)") and the monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter may be referred to as "(b3)").

Examples of (b1) include monomers (b1-1) having a structure in which linear or branched aliphatic unsaturated hydrocarbons are epoxidized (hereinafter sometimes referred to as "(b1-1)") And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter may be referred to as "(b1-2)").

As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of (b1-1) include: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, Glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl Ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2, 4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3, 4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene and 2,4,6-tris(glycidoxymethyl)styrene.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Diacel Co., Ltd.) , 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Diacel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (For example, Cyclomer M100; manufactured by Diacel Co., Ltd.), the compound represented by formula (1), and the compound represented by formula (2).

(In the formula, R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. X ^a and X ^b each independently represent a single bond ^{, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-.R ^c represents alkanediyl group having a carbon number 1 to 6 and O * represents. Bonded end.)

Examples of the compound represented by formula (1) include: compounds represented by formula (1-1) to formula (1-15). Among them, formula (1-1), formula (1-3), and formula (1-3) are preferred. (1-5), formula (1-7), formula (1-9), and formula (1-11) ~ formula (1-15), more preferably formula (1-1), formula (1) -7), the compound represented by the formula (1-9) and the formula (1-15).

Examples of the compound represented by formula (2) include: compounds represented by formula (2-1) to formula (2-15), and among them, formula (2-1), formula (2-3), and formula (2-5), formula (2-7), formula (2-9) and formula (2-11) ~ formula (2-15) represented by the compound, more preferably formula (2-1), formula (2 -7), the compound represented by the formula (2-9) and the formula (2-15).

The compound represented by the formula (1) and the compound represented by the formula (2) may be used alone, respectively, or the compound represented by the formula (1) and the compound represented by the formula (2) may be used in combination. When these are used in combination, the ratio of the compound represented by the formula (1) and the compound represented by the formula (2) (the compound represented by the formula (1): the compound represented by the formula (2)) is preferably on a molar basis It is 5:95 to 95:5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth)acryloxy group is more preferable.

As (b3), it is more preferable to have a tetrahydrofuran group and (meth)propene Monomers of acetoxy groups.

(B) is preferably (b1) from the viewpoint of further improving the reliability of the obtained color filter such as heat resistance and chemical resistance, and from the viewpoint of excellent storage stability of the colored curable resin composition, ( b1) is preferably (b1-2).

Examples of (c) include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate Ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate , Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technical field Among them, it is called "dicyclopentyl (meth)acrylate" as a common name. In addition, it is sometimes called "tricyclodecyl (meth)acrylate".), tricyclic [5.2.1.0 ^2,6 ] Decene-8-yl (meth)acrylate (in this technical field, as a common name, it is called "dicyclopentenyl (meth)acrylate".), dicyclopentyloxy (meth)acrylate Ethyl, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylate (Meth)acrylates such as naphthyl acrylate and benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. containing hydroxyl (meth)acrylic acid Esters; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1 ]Hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept -2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo [2.2.1]Hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene , 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6- Diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-ring Hexyloxycarbonylbicyclo[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, 5,6-bis(cyclohexoxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-ring Hexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide Imine benzoate, N-succinimidyl-4-maleimidin butyrate, N-succinimidyl-6-maleimidin caproate, N-succinimidyl Dicarbonyl amide compounds such as amino-3-maleimide propionate, N-(9-acridinyl) maleimide; styrene, α-methylstyrene, m-toluene Vinyl-containing aromatic compounds such as ethylene, p-methylstyrene, vinyl toluene, and p-methoxystyrene; vinyl nitrile such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride ; Vinylamide, methacrylamide, etc.; vinyl acetate and other esters; 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene Diene and so on.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, vinyl-containing aromatic compounds, dicarbonylimine compounds, and bicyclic unsaturated compounds are preferred. Specifically, styrene, vinyl toluene, benzyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ] decane-8-yl (meth)acrylate, and N-phenyl maleate are preferred. Imine, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2.1]hept-2-ene.

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydro Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene Acid anhydride. It is preferable that the usage-amount of carboxylic anhydride is 0.5-1 mol with respect to 1 mol of usage-amounts of (a).

Examples of the resin (B) include: 3,4-epoxycyclohexyl methyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy tricyclic [5.2.1.0 ^2,6 ] Resins such as decyl (meth)acrylate/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth) )Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/N- Cyclohexyl maleimide copolymer, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ] decyl (meth)acrylate/(meth)acrylic acid/vinyl toluene copolymer, 3-methyl Benzyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer and other resins [K2]; (meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer Resins such as styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl(meth)acrylate/(meth)acrylic acid copolymer [K3]; make (meth)acrylic acid Glycidyl ester and benzyl (meth)acrylate/(meth)acrylic acid copolymer addition resin, make glycidyl (meth)acrylate and tricyclodecyl (meth)acrylate/styrene/( Resin made by addition of meth)acrylic acid copolymer, adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer Resin such as resin [K4]; a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, making (meth)acrylic acid Resins such as resins that react with copolymers of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate [K5]; make (meth)acrylic acid and (meth)acrylic acid tricyclic Resin such as a resin obtained by reacting a copolymer of decyl ester/glycidyl (meth)acrylate and then reacting tetrahydrophthalic anhydride with the obtained resin [K6].

The weight average molecular weight in terms of polystyrene of the resin (B) is usually 3,000 to 100,000, preferably 5,000 to 50,000, more preferably 5,000 to 35,000, still more preferably 5,000 to 30,000, particularly preferably 6,000 to 30,000, most preferably 9,000 ~30,000. If the molecular weight is in the above-mentioned range, the hardness of the coating film increases, the residual film rate is also high, the solubility of the unexposed part with respect to the developer is good, and the resolution of the colored pattern tends to increase.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4, and still more preferably 1.3 to 3.

The acid value (in terms of solid content) of the resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 30 to 170 mg-KOH/g, and among them, preferably 40 to 170 mg-KOH/g, and among them, preferably 50 to 170 mg -KOH/g, more preferably 60 mg-KOH/g or more, 150 mg-KOH/g or less, still more preferably 135 mg-KOH/g or less.

Here, the acid value is the amount of potassium hydroxide required to neutralize 1 g of resin (B) (mg) The measured value can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass relative to the total solid content, among them, preferably 10 to 60% by mass, among them, preferably 13 to 60% by mass, and among them, preferably 17 to 55% by mass . When the content of the resin (B) is within the above-mentioned range, the coloring pattern is easily formed, and the resolution of the coloring pattern and the residual film rate tend to increase.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized using living radicals and/or acid generated by a polymerization initiator. For example, a compound having an ethylenically unsaturated bond can be mentioned, and one having a (meth)acrylate structure is preferred. Compound. The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds.

Examples of polymerizable compounds having one ethylenically unsaturated bond include: nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate Ester, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, (a), (b) and (c) above. Examples of polymerizable compounds having two ethylenically unsaturated bonds include: 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di( Meth) acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate. Examples of polymerizable compounds having three or more ethylenically unsaturated bonds include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol Tetraol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, Pentaerythritol deca(meth)acrylate, pentaerythritol nine(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate Base) 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 and caprolactone modified dipentaerythritol hexa(meth)acrylate.

Among these, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

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) in the colored curable resin composition of the present invention is usually 1-60% by mass, preferably 5-50% by mass, and more preferably 10-40% with respect to the total amount of solids. % By mass, more preferably 12 to 30% by mass. The content ratio of the resin (B) and the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20 on a mass basis, preferably 35:65 to 80:20 . When the content of the polymerizable compound (C) is within the above-mentioned range, the residual film rate during the formation of a colored pattern and the chemical resistance of the color filter tend to improve.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. by the action of light and heat. A known polymerization initiator is used.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, an phosphine oxide compound, an O-oxime compound, and a biimidazole compound, More preferably, it is a polymerization initiator containing an O-acetoxime compound.

Examples of O-acetoxime compounds include: N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3 -Yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxolanylmethoxy) benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzyloxy-1-[9-ethyl-6- (2-Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (the above are made by BASF), and N-1919 (made by ADEKA) can also be used. Among them, it is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy-1-(4 -Phenylsulfanylphenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane- At least one of the group consisting of 1-keto-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-ylidene amine.

啉代-1-(4-甲基硫烷基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-

啉 代苯基)-2-苄基丁烷-1-酮及2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]丁烷-1-酮。也可以使用Irgacure 369、907、379(以上為BASF公司製造)等市售品。 Examples of alkyl phenyl ketone compounds include: 2-methyl-2-

Lino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-

(Pholinophenyl)-2-benzylbutane-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

(Hydroxy)phenyl]butan-1-one. Commercial products such as Irgacure 369, 907, and 379 (the above are made by BASF Corporation) can also be used.

The alkyl phenyl ketone compound can also be 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) Phenyl) propane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy acetophenone and benzyl dimethyl ketal.

Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-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 and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine .

As an acylphosphine oxide compound, 2,4,6-trimethylbenzyldiphenylphosphine oxide can be mentioned. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

Specific examples of the biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis( 2,3-Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2-chlorobenzene Group)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) ) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl) (Phenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.) And an imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 07-010913 etc.). Among them, the compounds represented by the following formulae and their mixtures are preferred.

As other polymerization initiators, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzoin, Methyl phthalate, 4-phenylbenzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert (Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds ; 10-Butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiation aid (particularly, an amine-based polymerization initiation aid) described later.

The content of the polymerization initiator (D) is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass, and more preferably 1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and polymerizable compound (C) Part by mass is particularly preferably 1 to 20 parts by mass.

<Polymerization Initiator>

The polymerization initiation assistant is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound (C) that is polymerized by the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiation assistant, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid include amine-based polymerization initiation aids, alkoxyanthracene-based polymerization initiation aids, thioxanthone-based polymerization initiation aids, and carboxylic acid-based polymerization initiation aids.

Examples of amine-based polymerization initiators include: alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, 4-dimethylamino Ethyl benzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, etc. Ester; 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, of which alkylamino groups such as 4,4'-bis(diethylamino)benzophenone are preferred Benzophenone. Among them, alkylaminobenzophenone is preferred, and 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of alkoxyanthracene-based polymerization initiation aids 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 the thioxanthone-based polymerization initiation aid include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichloro Thioxanthone and 1-chloro-4-propoxythioxanthone.

Examples of the carboxylic acid-based polymerization initiation aid include: phenylsulfanyl acetic acid, methyl phenylsulfanyl acetic acid, ethyl phenyl sulfanyl acetic acid, methyl ethyl phenyl sulfanyl acetic acid, two Methylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-benzene Glycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthyloxyacetic acid.

When a polymerization initiation aid is used, its content is preferably 0.1 to 30 parts by mass, and 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). If the content of the polymerization initiation assistant is within this range, there is a tendency that 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 limited, and can be used alone or in combination of two or more solvents generally used in this field. Specifically, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether ester solvents ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH in the molecule and no -O-, -CO- And -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfide.

Examples of ester solvents include: methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl Propyl Ketoate, Methyl Acetate, Ethyl Acetate, Cyclohexanol Acetate and γ-butyrolactone.

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, and diethylene glycol monomethyl ether. Alcohol 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.

Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropane Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ester, 2-methoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-methoxy-2-methylpropionate, 2 -Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 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 , Diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

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

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

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

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

These solvents can also combine two or more types.

Among the above-mentioned solvents, organic solvents having a boiling point at 1 atm of 120° C. or more and 210° C. or less are preferable from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether are preferred. Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide and N-methylpyrrolidone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate , Ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N,N-dimethylformamide and N- Methylpyrrolidone.

The content of the solvent (E) relative to the total amount of the colored curable resin composition is usually 70 to 95% by mass, preferably 75 to 92% by mass, and more preferably 75 to 90% by mass. If the content of the solvent (E) is in the above-mentioned range, the flatness at the time of coating becomes good, and the color density is not insufficient when forming the color filter, and therefore, the display characteristics tend to become good.

<Leveling agent>

Examples of the leveling agent include organosilicon-based surfactants, fluorine-based surfactants, and organosilicon-based surfactants having fluorine atoms. These surfactants may have a polymerizable group in the side chain.

Examples of the organosilicon-based surfactant include surfactants having siloxane bonds in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Contract Company) .

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, 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 RS-718-K (manufactured by DIC Co., Ltd.), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381 , Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute).

As organosilicon surfactants with fluorine atoms, you can cite A surfactant with siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Co., Ltd.) can be cited.

Relative to the total amount of the colored curable resin composition, the content of the leveling agent is usually 0.0005 mass% or more and 0.6 mass% or less, preferably 0.001 mass% or more and 0.5 mass% or less, more preferably 0.001 mass% or more and 0.2 Mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, particularly preferably 0.005 mass% or more and 0.07 mass% or less. If the content of the leveling agent is within the above range, the flatness of the color filter can be improved.

Relative to the total solid content of the colored curable resin composition, the content of the leveling agent is usually 0.001% by mass or more and 2.0% by mass or less, preferably 0.002% by mass or more and 1.5% by mass or less, more preferably 0.004% by mass or more And 1.0% by mass or less, more preferably 0.008% by mass or more and 0.5% by mass or less, and particularly preferably 0.01% by mass or more and 0.3% by mass or less.

<Other ingredients>

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

<Production method of colored curable resin composition>

The colored curable resin composition of the present invention can be mixed, for example, by mixing compound (Aa), dye (Ab), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and if necessary Leveling agent, polymerization initiator and its Its ingredients are used to prepare. In addition to the compound (Aa), a colorant such as a pigment may be further mixed. The pigment is preferably used in a state where it is mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, a part or all of the above-mentioned pigment dispersant and resin (B) may be blended as necessary.

It is preferable to filter the mixed colored curable resin composition with a filter with a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

As a method of manufacturing a colored pattern from the colored curable resin composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferred. The photolithography method is a method of applying a colored curable resin composition to a substrate, drying it to form a colored composition layer, exposing the colored composition layer through a photomask, and performing development. In the photolithography method, by not using a photomask and/or not developing at the time of exposure, a colored coating film as a cured product of the colored composition layer can be formed. The colored pattern and colored coating film formed as above are the color filter of the present invention.

The film thickness of the produced color filter can be adjusted appropriately according to the purpose, application, etc., and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate, a resin plate, silicon, and a substrate on which aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed can be used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The formation of pixels of each color using photolithography can be done by well-known or customary methods. Use the equipment and conditions to carry out. For example, it can be produced as follows.

First, the colored curable resin composition is coated on a substrate, and heated and dried (pre-baked) and/or dried under reduced pressure, thereby removing volatile components such as the solvent and drying, thereby obtaining a smooth colored composition layer. Examples of the coating method include spin coating, slit coating, and slit and spin coating.

Next, the colored composition layer is exposed to light through a photomask for forming a target colored pattern. In order to be able to uniformly irradiate the entire exposure surface with parallel light or to enable accurate alignment of the photomask and the substrate on which the coloring composition layer is formed, it is preferable to use an exposure device such as a mask aligner and a stepper. Development is performed by contacting the exposed coloring composition layer with a developing solution to form a coloring pattern on the substrate. By development, the unexposed part of the coloring composition layer is dissolved in the developer and removed. As the developer, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The development method may be any of a puddle method, a dipping method, and a spray method. Furthermore, during development, the substrate can be tilted at any angle. After development, it is preferable to perform water washing.

Preferably, the obtained colored pattern is further post-baked. In order to impart various characteristics to the color filter having the colored pattern and colored coating film obtained as described above, it may be further subjected to surface coating treatment.

The color filter formed from the coloring curable resin composition of the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

[Example]

Hereinafter, examples are given to illustrate the present invention more specifically. However, the present invention is of course not limited by the following embodiments, and of course it can also be adapted before it can be adapted. The scope of the spirit described later is appropriately changed and implemented, and they are all included in the technical scope of the present invention. In addition, in the following, unless otherwise specified, "parts" means "parts by mass", and "%" means "% by mass".

The following reactions were carried out in a nitrogen atmosphere. After putting 8 parts of the compound represented by Formula (A-II-18) and 396 parts of methanol into a flask equipped with a cooling pipe and a stirring device, it stirred at room temperature for 30 minutes, and prepared the blue solution. Then, after adding 396 parts of water to the blue solution, it was further stirred at room temperature for 30 minutes to obtain a reaction solution.

53 parts of water was put into the beaker, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water and mixed at room temperature under an air atmosphere to prepare a phosphotungstic acid solution.

The obtained phosphotungstic acid solution was added dropwise to the previously prepared reaction solution over 1 hour. After stirring at room temperature for another 30 minutes, filtration was performed to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol, and after dispersing for 1 hour, the operation of filtering was repeated twice. The blue solid obtained by this operation was put into 200 parts of water, and after dispersing for 1 hour, the operation of filtering was repeated twice. The blue solid obtained by this operation was dried at 60°C under reduced pressure After drying, 17.1 parts of the compound (Aa2-53) represented by the formula (A-I-18) was obtained.

Resin synthesis example 1

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen is passed through at 0.02L/min to form a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 3-methoxybutyl ethyl are put in 105 parts of acid esters were heated to 70°C while stirring. Next, 60 parts of methacrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by formula (1-1) and the compound represented by formula (2-1) A mixture with a molar ratio of 50:50.) 240 parts were dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise to a flask kept at 70°C using a dropping funnel over 4 hours Inside. On the other hand, using another dropping funnel, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise to the flask over 4 hours. A solution of 225 parts of acetate. After the dropwise addition of the polymerization initiator solution was completed, it was kept at 70°C for 4 hours and then cooled to room temperature to obtain a resin B-1b solution with a solid content of 32.6% and an acid value of 110 mg-KOH/g (in terms of solid content) . The weight average molecular weight Mw of the obtained resin B-1b was 13,400, and the molecular weight distribution was 2.50.

Example 1: <Colored curable resin composition>

Coloring agent (A): 41.6 parts of the compound represented by formula (A-I-18); 0.4 parts of compound represented by formula (*)

Alkali-soluble resin (B): 29 parts of resin B-1b (in terms of solid content); polymerizable compound (C): 11 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); Polymerization initiator (D): N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Manufactured by the company; O-acetoxime compound) 4 parts; solvent (E): 413 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether modified silicone oil (Toray Silicone SH8400; Toray Dow Corning (Produced by Co., Ltd.) 0.15 parts were mixed to obtain a colored curable resin composition.

Comparative example 1: <Colored curable resin composition>

Coloring agent (A): 26 parts of compound represented by formula (AI-18); alkali-soluble resin (B): resin B-1b (in terms of solid content) 44 parts; polymerizable compound (C): dipentaerythritol hexaacrylic acid Esters (KAYARAD (registered trademark) DPHA: manufactured by Nippon Kayaku Co., Ltd.) 11 parts; polymerization initiator (D): N-benzyloxy-1-(4-phenylsulfanylphenyl)octane -1-keto-2-imine (Irgacure (registered trademark) OXE-01; BASF company Manufacturing; 4 parts of O-acetoxime compound); solvent (E): 68 parts of propylene glycol monomethyl ether acetate; solvent (E): 561 parts of 4-hydroxy-4-methyl-2-pentanone; and Leveling agent (F): 0.15 parts of polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored curable resin composition.

<Making of Color Filter>

The colored curable resin composition obtained in Example 1 and Comparative Example 1 was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then prebaked at 100°C for 3 minutes. Coloring composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), exposure was performed at an exposure amount (365 nm standard) of ^{150 mJ/cm 2 in an air atmosphere.} In addition, no photomask is used. The coloring composition layer after exposure was post-baked in an oven at 180°C for 20 minutes to produce a color filter (film thickness 2.0 μm).

<Evaluation of heat resistance>

The obtained color filter was heated at 230°C for 20 minutes, and the color difference (ΔEab*) before and after heating was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). The color difference (ΔEab*) of the color filter made from the colored curable resin composition obtained in Example 1 was 3.8, and the color difference (ΔEab*) of the color filter made from the colored curable resin composition obtained in Comparative Example 1 Eab*) is 8.5.

Industrial availability

The color filter formed from the colored curable resin composition of the present invention is used as a display device (for example, a liquid crystal display device, an organic EL device, an electronic Paper, etc.) and color filters used in solid-state imaging devices are useful.

Claims (9)

A colored curable resin composition characterized by containing a compound (Aa) represented by formula (AI), a dye (Ab), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), Among them, it does not include a composition mixed with the remaining components after preparing a colored dispersion using the compound (Aa) and a solvent, wherein the dye (Ab) is a compound represented by formula (*),

In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent an optionally substituted alkyl group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons, and the methylene group constituting the alkyl group is inserted between A group having an oxygen atom, an aromatic hydrocarbon group that may have a substituent, an aralkyl group that may have a substituent or a hydrogen atom, R ⁴¹ and R ⁴² may bond and form a ring together with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ can be bonded and form a ring with the nitrogen atom to which they are bonded. R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or An alkyl group having 1 to 8 carbon atoms may have an oxygen atom inserted between the methylene groups constituting the alkyl group, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -, ring T ¹ represents an aromatic heterocyclic ring which may have a substituent, [Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, m represents an arbitrary natural number. In addition, when a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

In the formula, ring T ¹ , R ⁴¹ ~R ⁴⁴ and R ⁴⁷ ~R ⁵⁴ have the same meaning as above

The colored curable resin composition according to claim 1, wherein [Y] ^m- is an anion of a heteropoly acid or a homopoly acid containing tungsten as an essential element. The colored curable resin composition according to claim 2, wherein [Y] ^m- is an anion of phosphotungstic acid, an anion of silicotungstic acid, or an anion of tungsten-based homopolyacid. The colored curable resin composition according to claim 1, wherein the resin The weight average molecular weight of (B) is 9000 or more. The colored curable resin composition according to claim 1, wherein the acid value of the resin (B) is 60 mg-KOH/g or more. The colored curable resin composition according to claim 1, wherein the content of the dye (Ab) is 0.01 to 5% by mass in 100% by mass of the solid content of the colored curable resin composition. The colored curable resin composition according to claim 1, wherein the mass ratio of dye (Ab)/compound (Aa) is 0.001 to 0.5. A color filter formed of the coloring curable resin composition according to claim 1. A display device including the color filter according to claim 8.