TW201714974A - Colored curable resin composition - Google Patents

Abstract

The present invention relates to a colored curable resin composition. Previously known colored curable resin composition has not satisfied the level that the conformation of color filters, such as colored patterns, was not favorable enough. However, the colored curable resin composition of the present invention contains a dye, a resin, a polymeric compound, and a polymerization initiator. The dye is at least one selected from the group composed of a xanthene dye, a triarylmethane dye, a compound represented by equation Ab2, and a coumarin dye, whereas the polymerization initiator includes a biimidazole compound and an O-acyl oxime compound.

Description

Colored curable resin composition Field of invention

The present invention relates to a colored curable resin composition.

Background of the invention

The colored curable resin composition is used for producing a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, or a plasma display. As such a colored curable resin composition, coloring containing N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine as an initiator is known Curable resin composition (Patent Document 1).

Prior art literature Patent literature

Patent Document 1: JP-A-2010-32999

Summary of invention

In the above-described colored curable resin composition known to date, the obtained colored pattern, that is, the shape of the color filter has not been sufficiently satisfied.

The present invention includes the following inventions.

[1] A colored curable resin composition containing a dye, a resin, a polymerizable compound, and a polymerization initiator, wherein the dye is selected from the group consisting of a xanthene dye, a triarylmethane dye, a compound represented by the formula (Ab2), and a coumarin dye The dye of at least one of the above, the polymerization initiator is a polymerization initiator comprising a biimidazole compound and an O-indenyl ruthenium compound.

[In the formula (Ab2), R ⁴¹ to R ⁴⁴ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with an unsubstituted or unsubstituted amino group or a halogen atom, and an alkyl group having 2 to 20 carbon atoms; A group in which an oxygen atom is interposed between methylene groups constituting the alkyl group, an aromatic hydrocarbon group which may be substituted, or an aralkyl group or a hydrogen atom which may be substituted. R ⁴¹ and R ⁴² may bond and form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond and form a ring together with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be interposed between the methylene groups constituting the alkyl group. 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 an arbitrary m-valent anion.

m represents an arbitrary natural number.

In the formula (Ab2), when a plurality of cations represented by the following chemical formulas are contained in one molecule, they may have the same structure or different structures: [wherein, ring T ¹ , and R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ are respectively synonymous with the above. ]]

[2] The colored curable resin composition according to [1], wherein the content ratio of the biimidazole compound to the O-mercaptopurine compound contained in the polymerization initiator is 1:9 on a mass basis. 9:1.

[3] A color filter formed of the colored curable resin composition described in [1] or [2].

[4] A display device comprising the color filter described in [3].

According to the colored curable resin composition of the present invention, a color filter excellent in shape can be formed.

Fig. 1 is a schematic view showing a cross-sectional shape of a colored pattern.

detailed description

The color-curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) contains a dye.

In the present specification, the compounds exemplified as the respective components can be used singly or in combination of plural kinds unless otherwise specified.

<Colorant (A)>

The colorant (A) is a dye selected from at least one of a xanthene dye (Aa), a triarylmethane dye (Ab), a compound represented by the formula (Ab2), and a coumarin dye (Ac) (hereinafter sometimes referred to as "Dye (A1)").

In the present specification, the term "dye" means a dye which is soluble in a solvent.

The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. As the xanthene dye (Aa), for example, C. I. Acid red 51 (hereinafter, the description of C.I. acid red is omitted, only the number is shown. Others are the same), 52, 87, 92, 94, 289, 388, etc. C. I. Acid red dye; C. I. Acid violet 9, 30, 102, etc. C. I. Acid violet dye; C. I. Alkaline red 1 (Rhodamine 6G), 2, 3, 4, 8, 10 (Rhodamine B), 11 etc. C. I. Basic red dye; C. I·Basic Violet 10, 11, 25, etc. C. I. Basic violet dye; C. I. Solvent red 218, etc. C. I. Solvent red dye; C. I. Mordant red 27, etc. C. I. Mordant red dye; C. I. Reactive Red 36 (Rose Red B), etc. C. I. Reactive red dye; sulfo rhodamine G; the xanthene dye described in JP-A-2010-32999; and the patent described in Japanese Patent No. 4492760 Xenon dyes; etc. As the xanthene dye (Aa), a dye which is dissolved in an organic solvent is preferable.

Among these, as the xanthene dye (Aa), a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as "compound (1a)") is preferable. Compound (1a) may be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In particular, as the xanthene dye (Aa), it is preferred to use only the compound (1a).

In the formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number of 6 to 10 which may have a substituent. The valent aromatic hydrocarbon group, 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 together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.

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 of each other 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 's} 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 four R ^{11 's} may be the same or different.

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

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated aliphatic hydrocarbon group may be -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 ring heterocyclic ring containing a nitrogen atom.

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

In the case of the formula (1a), when -SO ₃ ^{- is} present, the number thereof is preferably one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.

Examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom, -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 , preferably these substituents are substituted with a hydrogen atom 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 colored curable resin composition of the present invention containing the compound (1a) can form a color filter having less generation of foreign matter and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and a octyl group. a linear alkyl group such as a thiol group, a decyl group, a decyl group, a dodecyl group, a hexadecyl group or an eicosyl group; an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; A branched chain alkyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

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 can be substituted saturated hydrocarbon group R ¹ ~ R ⁴ are hydrogen atoms, aromatic hydrocarbon group having 6 to 10 include the same groups as R ¹ ~ R ⁴ carbon atoms in the aromatic hydrocarbon group having 6 to 10 illustrate Examples of Group.

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

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

Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and An alkoxy group such as an alkoxy group.

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

Examples of -SR ⁸ include alkylsulfanyl groups such as methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylsulfanyl and eicosylsulfanyl groups. Wait.

Examples of the -SO ₂ R ⁸ include alkylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosylsulfonyl alkylsulfonates.醯基等.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an eicosyloxy group. An alkoxysulfonyl group such as a sulfonyl group.

As -SO ₂ NR ⁹ R ¹⁰ , for example, an amine sulfonyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N-isopropylamine can be cited. Sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-sec-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine Sulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl) Aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonate Mercapto, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine Sulfosyl, N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1, 4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethylhexyl)amine sulfonate N-1 substituted amine sulfonyl group such as fluorenyl group, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine sulfonyl group, N,N -ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N-propyl Methylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N,N- An N,N-2 substituted amine sulfonyl group such as bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

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 , more preferably -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or -SO ₂ NHR ⁹ .

m is preferably from 1 to 4, more preferably 1 or 2.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include an alkyl group having 1 to 6 carbon atoms in the above-exemplified alkyl group. 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 a benzyl group, a phenylethyl group, and a phenylbutyl group.

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

As the above ⁺ N(R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably 20 to 80, and more preferably 20 to 60. In the case where ⁺ N(R ¹¹ ) _{4 is} present in the compound (1a), when R ¹¹ is such a group, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter having less foreign matter. Device.

The compound (1a) is preferably a compound represented by the formula (2a) (hereinafter sometimes referred to as "compound (2a)"). Compound (2a) can It is a tautomer.

In the formula (2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ²¹ and R ²² may together form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may together form a ring containing a nitrogen atom.

R ²⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ .

M1 represents an integer from 0 to 5. When m1 is 2 or more, a plurality of R ^{25 's} may be the same or different.

A1 represents an integer of 0 or 1.

X1 represents a halogen atom.

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Z1 ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and four R ^{27 's} may be the same or different.

R ²⁷ represents a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group of the above R ¹ to R ⁴ . The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

As the combination of R ²¹ - R ^24, preferably R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is a C divalent aromatic hydrocarbon group having 6 to 10, the hydrogen atoms contained in the aromatic hydrocarbon group are - SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ^{26 are} substituted. More preferably, R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group is -SO ₃ ^- Z1 ⁺ Or -SO ₂ NHR ^{26 is} substituted. When R ²¹ to R ²⁴ are these groups, the colored curable resin composition of the present invention containing the compound (2a) can form a color filter excellent in heat resistance.

The ring containing a nitrogen atom formed by R ²¹ and R ²² together with the ring containing a nitrogen atom formed by R ²³ and R ²⁴ may be the same ring as the ring formed by R ¹ and R ² . Among them, an aliphatic heterocyclic ring is preferred. Examples of the aliphatic heterocyclic ring include the following aliphatic heterocyclic rings.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ .

In the case where R ²¹ to R ²⁴ are -R ²⁶ , -R ²⁶ is preferably each independently a methyl group or an ethyl group. Further, -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ in R ^26, preferably branched chain alkyl group having a carbon number of 3 to 20 carbon atoms, more preferably branched chain alkyl group having 6 to 12, more preferably 2 Ethylhexyl. When R ²⁶ is such a group, the colored curable resin composition of the present invention containing the compound (2a) can form a color filter having less generation of foreign matter.

Z1 ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ .

As the above ⁺ N(R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ²⁷ is preferably 20 to 80, and more preferably 20 to 60. In the case where ⁺ N(R ²⁷ ) _{4 is} present in the compound (2a), when R ²⁷ is such a group, the colored curable resin composition of the present invention containing the compound (2a) can form less foreign matter. Color filter.

M1 is preferably from 1 to 4, more preferably 1 or 2.

Further, the compound (1a) is preferably a compound represented by the formula (3a) (hereinafter sometimes referred to as "compound (3a)"). Compound (3a) may be a tautomer thereof.

In the formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group of R ³¹ and R ³² may be a carbon number of 6 to 10 The aromatic hydrocarbon group or the halogen atom is substituted, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms, and the -CH ₂ - contained in the saturated hydrocarbon group of the above R ³¹ and R ³² may be Replaced by -O-, -CO- or -NR ¹¹ -.

R ³³ and R ³⁴ each 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 ³¹ and R ³³ may together form a ring containing a nitrogen atom, and R ³² and R ³⁴ may together form a ring containing a nitrogen atom.

p and q independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of R ³⁴ may be the same or different.

R ¹¹ represents the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³² include a group having 1 to 10 carbon atoms in the group in R ⁸ .

The aromatic hydrocarbon group having 6 to 10 carbon atoms which the substituent may have may be the same group as the group in R ¹ .

Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

R ³¹ and R ^{32 are} preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropyl sulfide. Alkyl and the like.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonate.醯基等.

R ³³ and R ^{34 are} preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

p and q are preferably integers from 0 to 2, preferably 0 or 1.

The compound (1a) is, for example, a compound represented by the formula (1-1) to the formula (1-43). In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably 2-ethylhexyl group.

Among the above compounds, the compound represented by the formula (1-1) to the formula (1-23) or the formula (1-37) to the formula (1-43) corresponds to the compound (2a), and the formula (1-24). The compound shown in any one of (1-36) corresponds to the compound (3a).

Further, in the formula (Ab2) to be described later, a compound in which R ⁴⁸ and R ⁵² are bonded to each other to form -R ⁴⁸ -OR ⁵² - is also listed as a xanthene dye (Aa).

Among these, C. is preferred. I. Sulfonamide of Acid Red 289, C. I. Quaternary ammonium salt of acid red 289, C. I. Sulfonamide or acid C of acid violet 102 I. Quaternary ammonium salt of Acid Violet 102. Examples of such a compound include a compound represented by the formula (1-1) to the formula (1-8), the formula (1-11) or the formula (1-12).

In addition, a compound represented by any one of Formula (1-24) to Formula (1-33) is also preferable in terms of excellent solubility in an organic solvent.

For the xanthene dye (Aa), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Nakagata Kasei Co., Ltd., "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.) can be used. another Further, a commercially available xanthene dye can also be used as a starting material, and it can be synthesized by referring to JP-A-2010-32999.

The triarylmethane dye (Ab) is a dye containing a compound having a structure in which three aromatic hydrocarbon groups are bonded to one carbon atom. As the triarylmethane dye (Ab), for example, C. I. Solvent blue 2, 4, 5, 43, 124; C. I. Basic purple 3, 14, 25; C. I. Basic blue 1, 5, 7, 11, 26 and the triarylmethane dyes described in Japanese Patent No. 4492760. A dye which is dissolved in an organic solvent is preferred.

Among these, as the triarylmethane dye (Ab), a dye containing a compound represented by the formula (Ab1) (hereinafter sometimes referred to as "compound (Ab1)") is preferable.

In the formula (Ab1), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group.

R ^9A to R ^12A each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with an unsubstituted or unsubstituted amino group or a halogen atom, an alkyl group having 2 to 20 carbon atoms, and an oxygen atom inserted to constitute the alkyl group. a group between methylene groups, an aromatic hydrocarbon group which may be substituted, an aralkyl group which may be substituted, or a hydrogen atom. R ^9A and R ^10A may bond and form a ring together with the nitrogen atom to which they are bonded, and R ^11A and R ^12A may bond and form a ring together with the nitrogen atom to which they are bonded.

A represents an aromatic hydrocarbon group which may be substituted.

[G] ^g- represents an arbitrary g-valent counter anion. g represents 0 or an arbitrary natural number. ]

In the formula (Ab1), when a plurality of cations represented by the following formula are contained in the molecule of Formula 1, these may have the same structure or different structures.

[wherein A and R ^1A to R ^12A are each synonymous with the above. ]

Examples of the alkyl group having 1 to 20 carbon atoms of R ^1A to R ^8A include the same groups as those exemplified as the linear or branched chain alkyl group of R ¹ , and more preferably 1 to 10 carbon atoms. More preferably, it has a carbon number of 1-8.

The oxygen atom of R ^1A to R ^12A has a group interposed between methylene groups constituting the alkyl group, and a group having 1 to 10 carbon atoms is preferable, and a group having 1 to 6 carbon atoms is more preferable. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group. When a plurality of oxygen atoms are inserted, the number of carbon atoms between the oxygen atoms is preferably 1 to 4, and more preferably 2 to 3.

Examples of the saturated hydrocarbon group of R ^9A to R ^12A include the same groups as those exemplified as R ¹ , and more preferably a carbon number of 1 to 10, and still more preferably a carbon number of 1 to 8. As the saturated hydrocarbon group, a linear or branched alkyl group is preferred.

The substituted or unsubstituted amino group which the saturated hydrocarbon group of R ^9A to R ^12A may have may be an amine group; N-methylamino group, N-ethylamino group, N-phenylamino group, N, N- Dimethylamino group, N,N-diethylamino group and the like.

Further, the aromatic hydrocarbon group of R ^9A to R ^12A is preferably a carbon number of 6 to 20, more preferably a carbon number of 6 to 15, and still more preferably a carbon number of 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a terphenyl group. In addition, the aromatic hydrocarbon group may have one or two or more substituents, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; and a carbon number such as a methoxy group or an ethoxy group; ~6 alkoxy group; hydroxyl group; amine sulfonyl group; alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group; alkoxy group having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group Alkylcarbonyl; etc.

Further, examples of the aralkyl group of R ^9A to R ^12A include a carbon number of 1 to 5 in which a methylene group, an ethyl group, and a propyl group are bonded to a group described as an aromatic hydrocarbon group of R ^9A to R ^12A . The group of the alkanediyl group and the like.

Among them, R ^1A to R ^{8A are} preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom.

Further, as R ^9A to R ^12A , a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted and an aralkyl group which may be substituted are preferable.

Examples of the aromatic hydrocarbon group in A include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group or a terphenyl group.

Examples of the substituent which the aromatic hydrocarbon group of A may have include a halogen atom, an amine group which may be substituted, a hydroxyl group, a sulfo group, -SO ₃ ^- or -SO ₃ J. Examples of the substituent which may be substituted for the above amine group include an alkyl group having 1 to 20 carbon atoms which may be substituted by an amine group or a halogen atom, a phenyl group which may be substituted with an alkoxy group having 1 to 10 carbon atoms, and the like.

Among them, as A, an aromatic hydrocarbon group which may be substituted is preferable.

As J, an inorganic cation or an organic cation can be mentioned. Specifically, a cation similar to Z ⁺ in the above compound (1a), a cation of the following formula, and the like can be given.

Examples of [G] ^g- include an anion represented by the formula (y1), the formula (y2) or the formula (y3).

[wherein, R ^B1 represents a monovalent organic group.

R ^B2 and R ^B3 represent a halogen atom or a halogenated hydrocarbon group, and R ^B2 and R ^B3 may be bonded to each other to form a ring containing -SO ₂ -N ^- -SO ₂ -. The above halogenated hydrocarbon group is preferably a fluorohydrocarbon group, and more preferably a perfluoroalkyl group.

R ^B4 and R ^B5 represent a divalent organic group. The organic group is preferably a divalent aromatic group.

M represents an aluminum atom or a boron atom. ]

Examples of the anion represented by the formula (y1) include a methanesulfonate anion, a toluenesulfonic acid anion, a naphthalenesulfonic acid, a dodecylbenzenesulfonate anion, a trifluoromethanesulfonate anion, a perfluorobutanesulfonate anion, and the like. .

Examples of the anion represented by the formula (y2) include an anion represented by the following formula.

Examples of the anion represented by the formula (y3) include an anion represented by the following formula.

Further, examples of [G] ^g- include a halide ion, a resin having a sulfonic acid anion, and a triperfluoroalkylsulfonyl methide acid anion.

The compound represented by the formula (Ab1) is, for example, a compound represented by the following formula. In the following formula, J is synonymous with the above.

The compound represented by the formula (Ab1) is, for example, a compound represented by the following formula.

The compound represented by the formula (Ab2) (hereinafter sometimes referred to as "compound (Ab2)")) also includes the tautomer thereof.

[In the formula (Ab2), R ⁴¹ to R ⁴⁴ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with an unsubstituted or unsubstituted amino group or a halogen atom, an alkyl group having 2 to 20 carbon atoms and oxygen. The atom is inserted into a group between the methylene groups constituting the alkyl group, an aromatic hydrocarbon group which may be substituted, an aralkyl group which may be substituted, 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, and R ⁴³ and R ⁴⁴ may bond and form a ring together with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be interposed between methylene groups constituting the alkyl group. 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 an arbitrary m-valent anion.

m represents an arbitrary natural number.

In the formula (Ab2), when a plurality of cations represented by the following formula are contained in the molecule of Formula 1, these may have the same structure or different structures.

[wherein, the rings T ¹ , R ⁴¹ to R ⁴⁴ and R ⁴ 7 to R ⁵⁴ are respectively synonymous with the above. ]]

The aromatic heterocyclic ring of the above ring T ¹ may be a single ring or a fused ring. Further, the aromatic heterocyclic ring is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocyclic ring include a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; and a 5-membered nitrogen atom such as a furan ring or a thiophene ring. a ring; a 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring; and the aromatic heterocyclic ring as a condensed ring, examples thereof include an anthracene ring, a benzimidazole ring, and a benzothiazole. a fused ring containing a nitrogen atom such as a ring or a quinoline ring; a ring containing no nitrogen atom such as a benzofuran ring;

Examples of the substituent which the aromatic heterocyclic ring of the ring T ¹ may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted. An amine group or the like which may be substituted.

Among them, the aromatic heterocyclic ring of the 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.

Further, the ring T ^{1 is} more preferably a ring represented by the formula (Ab2-x1), [Ring T ² represents an aromatic heterocyclic ring.

R ⁴⁵ and R ⁴⁶ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with an unsubstituted or unsubstituted amino group or a halogen atom, an alkyl group having 2 to 20 carbon atoms, and an oxygen atom inserted to constitute the alkyl group. A group between methylene groups, an aromatic hydrocarbon group which may be substituted, an aralkyl group which may be substituted, or a hydrogen atom. R ⁴⁵ and R ⁴⁶ may bond together with the nitrogen atom to which they are bound to form a ring.

R ⁵⁵ represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may be substituted.

K1 represents 0 or 1.

* indicates the bonding end with a carbocation. ]

A ring represented by the formula (Ab2-y1) is particularly preferred.

[R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may be substituted.

X 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 are} synonymous with the above.

* indicates the bonding end with a carbocation. ]

In the above formula, the aromatic heterocyclic ring of the ring T ² may be the same ring as the aromatic hetero ring exemplified in the ring T ¹ .

Further, the ring T ^{1 is} also preferably a ring represented by the formula (Ab2-x2). [Ring T ³ represents an aromatic heterocyclic ring having a nitrogen atom.

R ⁵⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may be substituted.

R ⁵⁹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an aromatic hydrocarbon group which may be substituted or an aralkyl group which may be substituted.

K2 represents 0 or 1.

* indicates the bonding end with a carbocation. ]

More preferably, it is a ring represented by the formula (Ab2-y2).

[R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may be substituted.

R ⁵⁹ is synonymous with the above.

* indicates the bonding end with a carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be the same as those exemplified as the saturated hydrocarbon group of R ¹ . Further, the saturated hydrocarbon group of R ⁴¹ to R ⁴⁶ , R ⁵⁵ and R ⁵⁸ to R ⁶⁰ preferably has a carbon number of 1 to 12.

The substituted or unsubstituted amine group which may substitute the saturated hydrocarbon group of R ⁴¹ to R ^{46 is} the same as the amine group which may substitute for R ^9A .

Examples of the substituent which the saturated hydrocarbon group of R ⁵⁹ may have include a halogen atom, a cyano group and the like.

Further, examples of the aromatic hydrocarbon group which may be substituted by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ include the same groups as the optionally substituted aromatic hydrocarbon group represented by R ^9A . .

Examples of the aralkyl group which may be substituted by R ⁴¹ to R ⁴⁶ and R ⁵⁹ include the same groups as the aralkyl group which may be substituted by R ^9A .

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include a group having 1 to 8 carbon atoms in the linear or branched chain alkyl group exemplified in R ¹ .

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ include a group having 1 to 10 carbon atoms in the linear or branched chain alkyl group exemplified in R ¹ .

Among them, R ⁴¹ to R ⁴⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁸ and R ^{59 are} preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may be substituted.

Further, R ⁴⁷ to R ^{54 are} preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and particularly preferably a hydrogen atom.

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

The cation portion of the formula (Ab2), as shown in the following Table 1, may be cation 1 to cation 12 represented by the formula (Ab2-1). In the table, * indicates the bonding end.

In Table 1, Ph1 to Ph9 mean a group represented by the following formula. Where * represents the bond end.

In addition, as the cation part of the formula (Ab2), as shown in the following Table 2, the cation 13 to the cation 16 represented by the formula (Ab2-2) may be mentioned. In the table, * indicates the bonding end.

In Table 2, Ph1, Ph10, and Ph11 are represented by the following formulas. Group. Where * represents the bond end.

Among them, as the cationic moiety of the formula (Ab2), a cation 1 to a cation 6, a cation 11, or a cation 12 is preferable, and a cation 1, a cation 2, or a cation 12 is particularly preferable.

Examples of the [Y] ^m- include the above-mentioned known anions, and further examples include an anion represented by the formula (y4), the formula (y5), and the formula (y6).

[wherein, R ^B6 represents a divalent organic group. R ^B7 represents a trivalent aromatic hydrocarbon group. n represents a natural number. ]

Examples of the anion represented by the formula (y4) include a methane disulfonic acid anion, a propane disulfonate anion, a toluene disulfonate anion, a naphthalene disulfonate anion, and an anion represented by the following formula.

Examples of the anion represented by the formula (y6) include an anion represented by the following formula. Where n is a natural number.

Among them, a preferred anion is a boron-containing anion, an aluminum-containing anion, and a fluorine-containing anion from the viewpoint of heat resistance.

The compound (Ab2) is, for example, a compound represented by the following formula.

The coumarin dye (Ac) is a dye containing a compound having a coumarin skeleton in the molecule. As the coumarin dye (Ac), for example, C. I. Acid yellow 227, 250; C. I. Disperse yellow 82, 184; C. I. Solvent Orange 112; C. I. Solvent yellow 160, 172; coumarin dyes described in Patent No. 1299948; and the like. A dye which is dissolved in an organic solvent is preferred.

Among these, as the coumarin dye, for example, a compound represented by the formula (Ac1) (hereinafter sometimes referred to as "compound (Ac1)")) is preferable.

In the formula (Ac1), X ^C represents an oxygen atom or a sulfur atom.

R ^1C each independently represents an alkyl group having 1 to 20 carbon atoms, and an oxygen atom can be inserted between methylene groups constituting the alkyl group.

R ^2C to R ^13C each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an aminomethyl fluorenyl group, an amine sulfonyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a decyl group, an amine group. a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a methylene group constituting the hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, -N(R ^14C )-, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group It may be substituted by a halogen atom, a cyano group, a nitro group, an aminomethyl fluorenyl group, an amine sulfonyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a decyl group or an amine group.

R ^14C represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^14C are present, they may be the same or different.

M represents a hydrogen atom or an alkali metal atom.

L ^C represents a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms. ]

Examples of the alkyl group having 1 to 20 carbon atoms of R ^1C include the same groups as those exemplified as the linear or branched chain alkyl group having 1 to 20 carbon atoms as R ¹ .

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ^2C to R ^14C include a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, a monovalent unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a carbon number of 6 a monovalent aromatic hydrocarbon group of ~10 or the like. The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is the same as the group exemplified as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ . Further, examples of the monovalent unsaturated hydrocarbon group having 1 to 20 carbon atoms include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a fluorene group. a linear alkenyl group such as an alkenyl group, an undecylene group, a dodecenyl group, a hexadecenyl group, an octadecyl group or an eicosyl group; a cyclopentenyl group, a cyclohexenyl group, and a ring a cycloalkenyl group such as heptyl group; In addition, the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is the same as the group exemplified as the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ .

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms of L ^C include a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, a divalent unsaturated hydrocarbon group having 1 to 20 carbon atoms, and a divalent carbon number of 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a group in which one hydrogen atom contained in a monovalent hydrocarbon group having 1 to 20 carbon atoms in R ^2C is a bonding terminal.

Further, a plurality of R ^1C to R ^{13C are} preferably the same groups as each other.

Among them, R ^1C is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

R ^2C to R ^{6C are} preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

R ^7C to R ^{13C are} preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom.

As L ^C , a saturated hydrocarbon group having 1 to 20 carbon atoms such as a sulfonyl group, a methylene group or a propylene group is preferable. Further, the divalent hydrocarbon group of L ^C preferably has a carbon number of 1 to 10, and more preferably has a carbon number of 1 to 5.

Further, as X ^C , an oxygen atom is particularly preferable.

The compound (Ac1) is, for example, a compound represented by the following formula.

The colorant (A) may further contain a dye other than the dye (A1) and/or a pigment (A2).

Examples of the dye other than the dye (A1) which may be further contained in the colorant (A) include a color index (published by The Society of Dyers and Colourists), a compound classified as a substance having a hue other than the pigment, and a dyeing note ( A well-known dye described in the color dyeing company. Further, examples of the chemical structure include azo dyes, cyanine dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, and squaric acid ( ) Dyes, acridine dyes, styryl dyes, quinoline dyes, and nitro dyes. Among these, a dye which is dissolved in an organic solvent is preferred.

Specifically, C. I. Solvent yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; I. Solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99; C. I. Solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C. I. 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; C. I. Solvent green 1, 3, 5, 28, 29, 32, 33; etc. C. I. Solvent dye, C. I. Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C. I. Acidic oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; I. Acid red 73, 80, 91, 97, 138, 151, 211, 274; C. I. Acidic green 3, 5, 9, 25, 27, 28, 41; C. I. Acid violet 34, 120; C. I. Acid blue 25, 27, 40, 45, 78, 80, 112; etc. C. I. Acid Dyestuff, C. I. Alkaline green 1; etc. C. I. Basic dye, C. I. Reactive yellow 2, 76, 116; C. I. Reactive Orange 16; etc. C. I. Reactive dye, C. I. Direct yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; C. I. Direct oranges 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; I. Direct blue 40; etc. C. I. Direct dye, C. I. Disperse yellow 51, 54, 76; C. I. Disperse violet 26, 27; C. I. Disperse blue 1, 14, 56, 60; etc. C. I. Disperse dyes, as C. I. Mordant dye, C. I. The mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C. I. Medicinal oranges 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; I. Mordant dye, C. I. Restore green 1 and so on C. I. Reducing dyes, etc.

In the dye, the content of the dye (A1) is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and still more preferably 85% by mass or more, based on the total amount of the dye. 100% by mass or less.

The pigment (A2) which can be further contained in the coloring agent (A) is not particularly limited, and a known pigment can be used. For example, a pigment classified as a pigment in the color index (published by The Society of Dyers and Colourists) can be cited. These may be used alone or in combination of two or more.

As the pigment, for example, C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigment; C. I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; . I. Pigment blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C. I. Pigment purple 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C. I. Pigment green 7,36,58 and other green pigments; C. I. Pigment brown 23, 25 and other brown pigments; C. I. Pigment black 1, 7 and other black pigments.

As the pigment, C. is preferred. I. Pigment red 122, 177, 242, 254 and other red pigments; C. I. Pigment yellow 138, 139, 150 and other yellow pigments; C. I. Pigment green 7,36,58 and other green pigments; C. I. Pigment blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C. I. Pigment violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments. By including the above-described pigment, the optimization of the transmission spectrum is easy, and the light resistance and chemical resistance of the color filter become good.

The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative or a basic group-introduced pigment derivative, a graft treatment on a pigment surface using a polymer compound or the like, or a sulfuric acid micronization method. The micronization treatment, the organic solvent for removing impurities, the washing treatment of water or the like, the removal treatment by an ion exchange method using ionic impurities, or the like.

The pigment preferably has a uniform particle size. By dispersing the pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

The pigment dispersing agent may, for example, be a surfactant, and may be a cationic, anionic, nonionic or amphoteric surfactant. Specifically, a surfactant such as a polyester-based, polyamine-based or acrylic-based surfactant can be mentioned. These pigment dispersants may be used singly or in combination of two or more. The pigment dispersing agent is represented by a brand name, and KP (manufactured by Shin-Etsu Chemical Co., Ltd.), (Kyoeisha Chemical Co., Ltd.), (Trademark)( (manufactured by BASF), EFKA (made by BASF) (registered trademark) (Ajinomoto (manufactured by the company), Disperbyk (registered trademark) ( Social system) and so on.

In the case of using a pigment dispersant, the amount thereof to be used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less based on the total amount of the pigment (A2). When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state is obtained.

In the case where the pigment (A2) is contained, the content ratio of the dye (A1) to the pigment (A2) is usually from 1:99 to 99:1, preferably from 1:99 to 70:30, more preferably 1 on a mass basis. :99~50:50.

As a combination in the case of preparing the colored curable resin composition of the present invention as a red colored curable resin composition, a coumarin dye (Ac), a red pigment, or the like can be given.

As a combination in the case of preparing the colored curable resin composition of the present invention as a green colored curable resin composition, a coumarin dye (Ac) and a green pigment, a coumarin dye (Ac), and a triarylmethane dye are exemplified. (Ab) and a green pigment, a coumarin dye (Ac), a compound represented by the formula (Ab2), a green pigment, and the like.

As a combination in the case of preparing the colored curable resin composition of the present invention as a blue colored curable resin composition, a xanthene dye (Aa), a triarylmethane dye (Ab), a xanthene dye (Aa), and a compound represented by the formula (Ab2), a xanthene dye (Aa) and a blue pigment, a xanthene dye (Aa) and a blue pigment and a violet pigment, a triarylmethane dye (Ab) and a violet pigment, from the formula (Ab2) The compound represented, the purple pigment, and the like. This In other cases, it preferably contains at least one selected from the group consisting of a triarylmethane dye (Ab) and a compound represented by the formula (Ab2), and more preferably contains a dye selected from the group consisting of a triarylmethane dye (Ab) and represented by the formula (Ab2). At least one of the compounds and a xanthene dye (Aa). The content of at least one selected from the group consisting of a triarylmethane dye (Ab) and a compound represented by the formula (Ab2) is preferably 40% by mass or more, and more preferably 50% by mass or more in the dye (A1).

The content of the coloring agent (A) is preferably 5% by mass or more and 60% by mass or less, more preferably 8% by mass or more and 55% by mass or less, and still more preferably 10% by mass or more, and 50% based on the total amount of the solid content. Below mass%. When the content of the coloring agent (A) is within the above range, the color density at the time of forming a color filter is sufficient, and a necessary amount of a resin or a polymerizable compound can be contained in the composition, so that a coloring pattern having sufficient mechanical strength can be formed. . Here, the "total amount of solid content" in the present specification means an amount by which the content of the solvent is removed from the total amount of the colored curable resin composition. The total amount of the solid components and the content of each component with respect to the solid components can be measured by, for example, a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, and is preferably an alkali-soluble resin, and preferably has at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "( a)") of the polymer of the structural unit.

The resin (B) is preferably a structural unit having a monomer (b) derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"), and other structural units. Copolymer.

Examples of the other structural unit include a monomer (c) copolymerizable with the monomer (a) (however, it is different from the monomer (a) and the monomer (b). Hereinafter, it is sometimes referred to as "(c)" a structural unit, a structural unit having an ethylenically unsaturated bond, or the like.

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, and zhongkang; Acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydroortene Unsaturated dicarboxylic acid such as phthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5- Carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxymethylbicyclo[2.2.1]hept-2-ene, 5- a carboxy-containing bicyclic unsaturated compound such as carboxyethylbicyclo[2.2.1]hept-2-ene; a carboxylic acid anhydride such as an acid anhydride of the above-mentioned unsaturated dicarboxylic acid of fumaric acid or mesaconic acid;

Examples thereof include a monovalent or higher polycarboxylic acid such as succinic acid mono [2-(methyl) propylene methoxyethyl] ester or phthalic acid mono [2-(methyl) propylene methoxyethyl] ester. Unsaturated mono[(meth)acryloxyalkyl]ester; unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid.

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

(b) means a polymerization of a cyclic ether structure having a carbon number of 2 to 4 (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. Sex compounds. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group is preferred.

(b), for example, a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxetanyl group and an ethylenically unsaturated bond The monomer (b2) (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)")).

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)")), A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferred. Specific examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and shrinkage. Glyceryl vinyl ether, vinylbenzyl glycidyl ether, α-methylvinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-dual ( Glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tri Glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4, 5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)benzene Alkene and the like.

Examples of (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, (registered trademark) 2000; Manufacture), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, (registered trademark) A400; Manufacture), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, (registered trademark) M100; Manufactured, a compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

In the formula (BI) and the formula (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a and X ^b represents a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates the bonding end with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms of R ^a and R ^b include a methyl group and an ethyl group.

Examples of the alkyl group in which the hydrogen atom of R ^a and R ^b is substituted by a hydroxyl group include a hydroxymethyl group and a hydroxyethyl group.

R ^a and R ^{b are} preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably Examples thereof include a hydrogen atom and a methyl group.

The alkanediyl group of R ^c may, for example, be a linear or branched alkanediyl group, and specific examples thereof include a methylene group and an exoethyl group.

X ^a and X ^{b are} preferably a single bond, *-R ^c -, or *-R ^c -O-, more preferably a single bond or *-R ^c -O-, and more preferably a single bond, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, particularly preferably a single bond, *-CH ₂ CH ₂ -O- (* represents a bonding end with O).

The compound represented by the formula (BI) may, for example, be a compound represented by any one of the formulae (BI-1) to (BI-15). Among them, it is preferred that the formula (BI-1), the formula (BI-3), the formula (BI-5), the formula (BI-7), the formula (BI-9) or the formula (BI-11)~(BI- The compound represented by 15) is more preferably a compound represented by the formula (BI-1), the formula (BI-7), the formula (BI-9) or the formula (BI-15).

The compound represented by the formula (BII) includes a compound represented by any one of the formulae (BII-1) to (BII-15). Among them, it is preferred from the formula (BII-1), the formula (BII-3), the formula (BII-5), the formula (BII-7), the formula (BII-9) or the formula (BII-11) to the formula (BII- The compound represented by 15) is more preferably a compound represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) or the formula (BII-15).

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

As the above (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-(methyl)propenyloxymethyloxetane and 3-ethyl-3-(methyl)propenyloxymethyloxane. Butane, 3-methyl-3-(methyl)propenyloxyethyloxetane, 3-ethyl-3-(methyl)propenyloxyethyloxetane, and the like.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate. , 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, Tricyclo [5.1.02 ^2,6 ]decane-8-yl (meth)acrylate (in the technical field, as a conventional name, it is called "dicyclopentyl (meth)acrylate". In addition, sometimes It is called "tricyclodecyl (meth) acrylate".), tricyclo[methyl]acrylic acid [5.2.1.0 ^2,6 ]decane-9-yl ester, trimethyl (meth)acrylate [5.2.1.0 ^2,6 ]nonene-8-yl ester (in the technical field, as a conventional name, it is called "dicyclopentenyl (meth) acrylate"), trimethyl (meth) acrylate [5.2.1.0 ^{2, 6} ] terpene-9-yl ester, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, ( Methyl) propyl acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (methyl) (meth) acrylate such as benzyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; (meth) acrylate having hydroxyl group; diethyl maleate, a dicarboxylic acid diester such as diethyl fumarate or 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- Alkene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(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-hydroxyl Methyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2. 1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-double (t- a bicyclic unsaturated compound such as butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl Maleidin, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-amber Imino-4-maleimine butyrate, N-succinimide-6-maleimide caprate, N-succinimide-3-maleimide a dicarbonylimine derivative such as an acid salt or N-(9-acridinyl)maleimide; a vinyl group such as styrene, α-methylstyrene, vinyltoluene or p-methoxystyrene Aromatic compound; nitrile containing vinyl such as (meth)acrylonitrile; halogenated hydrocarbon such as vinyl chloride or vinylidene chloride; decylamine containing vinyl group such as (meth) acrylamide; ester such as vinyl acetate; a diene such as 3-butadiene, isoprene or 2,3-dimethyl-1,3-butadiene; and the like.

Among these, from the aspects of copolymerization reactivity and heat resistance, it is preferable styrene, vinyl toluene, (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl ester, (meth) acrylic acid Tricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester, trimethyl [meth)acrylate [5.2.1.0 ^2,6 ]nonene-8-yl ester, trimethyl (meth)acrylate [5.2 .1.0 ^2,6 ]decene-9-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] Hept-2-ene, benzyl (meth)acrylate, and the like.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryl fluorenyl group. A resin having such a structural unit can be obtained by allowing a polymer having structural units derived from (a) and (b) It is obtained by addition of a monomer having an ethylenically unsaturated bond in a group reactive with a group having (a) or (b).

Examples of such a structural unit include a structural unit in which glycidyl (meth)acrylate is added to a (meth)acrylic acid unit, and a structure in which 2-hydroxyethyl (meth)acrylate is added to a maleic anhydride unit. A unit or a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit. Further, when these structural units have a hydroxyl group, a structural unit to which a carboxylic anhydride is further added may be exemplified as a structural unit having an ethylenically unsaturated bond.

The polymer having the structural unit derived from (a) can be produced, for example, by polymerizing a monomer constituting a structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, the solvent and the like are not particularly limited, and those generally used in the art can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), and organic peroxidation. The solvent (such as benzamidine peroxide) may be a solvent (E) to be described later as a solvent (E) of the colored curable resin composition of the present invention.

Incidentally, the obtained polymer may be used as it is, and a concentrated or diluted solution may be used, and a product obtained by reprecipitation or the like as a solid (powder) may be used. In particular, in the polymerization, the solvent contained in the colored curable resin composition of the present invention can be used as a solvent, and the solution after the reaction can be directly used in the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing procedure of the colored curable resin composition of the present invention can be simplified.

If necessary, a reaction catalyst of a carboxylic acid or a carboxylic acid anhydride and a cyclic ether (for example, tris(dimethylaminomethyl)phenol), a polymerization inhibitor (for example, hydroquinone, etc.), or the like can be used.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydroortylene. Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. .

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and (meth)acrylic acid 3,4-epoxytricyclo[5.2. .1.0 ^2.6 ]decyl ester/(meth)acrylic acid copolymer; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/benzene Ethylene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylic acid/N-cyclohexylmaleimide copolymer, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl ester / (meth)acrylic acid / vinyl toluene copolymer, (meth)acrylic acid 3,4-epoxytricyclo[5.2. 1.0 ^2,6 ] decyl ester / trimethyl [meth) acrylate [5.2.1.0 ^2,6 ] decene ester / (meth) acrylate / N-cyclohexyl maleimide copolymer, 3-methyl - 3-(Methyl)propenyloxymethyloxetane/(meth)acrylic acid/styrene copolymer; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(A) The acryl-based copolymer is described in JP-A-H09-106071, JP-A-2004-29518, and JP-A-2004-361455. Resin.

Among them, the resin (B) preferably contains a copolymer derived from the structural unit of (a) and the structural unit derived from (b).

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, still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is increased, the residual film ratio is high, the solubility of the unexposed portion to the developer is good, and the resolution of the colored pattern tends to be improved.

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

The solid content acid value of the resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, still more preferably 70 to 135 mg-KOH/g. Here, the solid content acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration using a potassium hydroxide aqueous solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, even more preferably 17 to 55% by mass, based on the total amount of the solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio tend to increase.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, etc., and preferably (methyl group). ) acrylate compound.

Examples of the polymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl card. a compound having one ethylenically unsaturated bond, such as a compound exemplified as (Ba), (Bb) and (Bc), a phenolic acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, or the like; 1,6 - hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A a compound having two ethylenically unsaturated bonds such as bis(acryloxyethyl)ether and 3-methylpentanediol di(meth)acrylate; trimethylolpropane tri(meth)acrylate, a compound having three ethylenically unsaturated bonds such as pentaerythritol tri(meth)acrylate or tris(2-(meth)acryloxyethyl)isocyanurate; pentaerythritol tetra(meth)acrylate, a compound having four ethylenically unsaturated bonds, such as ethylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate a compound having five ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa(meth) acrylate, ethylene glycol a compound having six ethylenically unsaturated bonds, such as dipentaerythritol hexa(meth) acrylate, propylene glycol-modified dipentaerythritol hexa(meth) acrylate, and caprolactone-modified dipentaerythritol hexa(meth) acrylate; Tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol 九 (meth) acrylate, tetrakis pentaerythritol deca (meth) acrylate, etc. having 7 or more ethylenically unsaturated bonds Compound;

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having five to six ethylenically unsaturated bonds. Dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferred.

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) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid component. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of formation of the colored pattern and the chemical resistance of the color filter tend to be improved.

Further, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably 35:65 by mass. ~80:20.

<Polymerization initiator (D)>

The polymerization initiator (D) is a compound capable of generating an active radical by the action of light or heat to initiate polymerization, and includes an O-mercaptopurine compound and a biimidazole compound. Further, the polymerization initiator (D) may further contain a polymerization initiator other than the O-indenyl ruthenium compound and the biimidazole compound. These are not particularly limited, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates the living radicals include an alkyl phenyl ketone compound, a triazine compound, and a fluorenyl phosphorus oxide compound.

The above O-indenyl hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine or N-benzidine. Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 -yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxearylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-( 2-methylbenzimidyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6- (2-Methylbenzylidene)-9H-oxazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. be usable (registered trademark) OXE01, OXE02 (above), manufactured by BASF Corporation, and N-1919 (made by ADEKA). Wherein the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzylformamide 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)-3 -cyclopentylpropan-1-one-2-imine and N-acetoxy-1-[4-{4-(2-hydroxyethoxy)phenyl}sulfanylphenyl]-propane- At least one of 1-keto-2-imine, more preferably selected from N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine And at least one of N-acetoxy-1-[4-{4-(2-hydroxyethoxy)phenyl}sulfanylphenyl]-propan-1-one-2-imine. If it is these O-fluorenyl hydrazine compounds, it tends to obtain a high-density color filter.

The biimidazole compound may, for example, be a compound represented by the formula (d2).

[wherein, R ^d1 to R ^d6 represent an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms of R ^d1 to R ^d6 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable.

Examples of the substituent which may be substituted with the aromatic hydrocarbon group of the above R ^d1 to R ^d6 include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferable.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis (2, 3-Dichlorophenyl)-4,4'5,5'-tetraphenylbiimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four (alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2' - bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204 An imidazole compound in which a phenyl group at the 4, 4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, refer to JP-A-7-10913) No. bulletin, etc.). Among them, a compound represented by the formula (d3) is preferred.

In the formula (d3), R ^d7 to R ^d10 each independently represent a hydrogen atom or an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group). R ^d11 and R ^d12 each independently represent a hydrogen atom or a halogen atom (preferably a chlorine atom). ]

Specific examples of the compound represented by the above formula (d3) include a compound represented by the following formula, and a mixture of these is preferable.

The above alkyl phenyl ketone compound is a compound having a partial structure represented by the formula (d4) or a partial structure represented by the formula (d5). In these partial structures, the benzene ring may have a substituent.

As the compound having a partial structure represented by the formula (d4), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)- ]]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. be usable Commercial products such as 369, 907, and 379 (above, manufactured by BASF Corporation).

Examples of the compound having a partial structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4- (2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Olefin of ketone, α,α-diethoxyacetophenone, benzoin dimethyl ketal, and the like.

In terms of sensitivity, the alkyl phenyl ketone compound is preferably a compound having a partial structure represented by the formula (d4).

The triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloro). Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. be usable Commercial product such as (registered trademark) 819 (manufactured by BASF Corporation).

Further, examples of the polymerization initiator (D) include benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; benzophenone, o-benzylbenzoic acid methyl ester , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)diphenyl a benzophenone compound such as ketone or 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine or camphorquinone; 10-butyl-2- Chloramphenicone, benzoin, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.

In the polymerization initiator (D), the content ratio of the O-mercapto fluorene compound to the biimidazole compound (biimidazole compound: O-indenyl hydrazine compound) is preferably from 1:9 to 9:1, more preferably on a mass basis. It is 4:6 to 9:1, further preferably 5:5 to 8:2, and particularly preferably 6:4 to 8:2.

The total content of the O-mercapto fluorene compound and the biimidazole compound is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 55% by mass or more, and usually preferably 5 parts by mass or more, based on the total amount of the polymerization initiator (D). It is 100% by mass or less.

The polymerization initiator (D) preferably further contains at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, and a fluorenyl phosphine oxide compound, and more preferably an O-mercapto fluorene compound and a biimidazole compound. A polymerization initiator of an alkyl phenyl ketone compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, the exposure time is shortened due to the high sensitivity. The tendency is that the productivity of the color filter is improved.

<Polymerization Initiator (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a polymerizable compound in which polymerization is initiated by a polymerization initiator. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxyfluorene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate and ethyl 4-dimethylaminobenzoate; Aminobenzoic acid esters such as isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate; N, N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone An alkylaminobenzophenone such as 4,4'-bis(ethylmethylamino)benzophenone; and the like; among them, an alkylaminobenzophenone, preferably 4,4'-bis (preferably) Diethylamino)benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Examples of the alkoxyfluorene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. 1-Chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylphenylsulfide. Alkyl acetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

As the polymerization initiation aid (D1), a thioxanthone compound is preferred.

In the case of using the polymerization initiation aid (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Share. In addition, when the polymerization initiation aid (D1) is used, the content thereof is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, more preferably 100 to 60 parts by mass, more preferably 100 parts by mass based on the total amount of the polymerization initiator (D). It is 15 to 55 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, the coloring pattern can be further formed with high sensitivity, and the productivity of the color filter tends to increase.

<thiol compound (T)>

The colored curable resin composition of the present invention preferably further contains a thiol compound (T).

The thiol compound (T) is a compound having a sulfanyl group (-SH) in the molecule.

Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyl oxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, and 2 -sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanylpyridinium Pyridine, 2-sulfanylpyridine-3-thiol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxyl -2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2 -thioalkylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-Dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2-sulfur Alkyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidin-2-thiol, 4,5-diphenylimidazole-2- Thiol, 2-sulfanyl imidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-indolyl-5-sulfanyl-1,2,4-triazole, 3-amine 5--5-sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4 - Triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole 5-Amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl)methanethiol 2-sulfanyl-5-thiazolidinone 2-sulfanylthiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfane 5-methylbenzimidazole, 2-sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole , 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthoxazole, 3 -sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo[2,4-d]pyridine, 2-amino-6-anthracenethiol, 6-sulfur Alkyl hydrazine, 4-sulfanyl-1H-pyrazolo[2,4-d]pyrimidine, and the like.

Examples of the compound having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, and dibutyl. Alcohol bis(3-sulfanyl propionate), butanediol bis(3-sulfanyl acetate), ethylene glycol bis(3-sulfanyl acetate), trimethylolpropane tri 3-sulfanyl acetate), butanediol bis(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanylpropionate), trimethylolpropane tris(3) -thioalkyl acetate), pentaerythritol tetrakis(3-sulfanylpropionate), pentaerythritol tetrakis(3-sulfanyl acetate), trishydroxyethyltris(3-sulfanylpropionate) Pentaerythritol tetrakis(3-sulfanylbutyrate), 1,4-bis(3-sulfanylbutoxy)butane, and the like.

As the thiol compound (T), a compound having one sulfanyl group in the molecule is preferable, and 2-sulfanyl benzothiazole is particularly preferable.

The content of the thiol compound (T) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within this range, the sensitivity tends to be improved and the developability tends to be good.

<Solvent (E)>

The colored curable resin composition of the present invention preferably further contains a solvent (E).

The solvent (E) is not particularly limited, and a solvent which is generally used in the field can be used. For example, an ester solvent (a solvent containing -COO- or a -O- in a molecule), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (in the molecule) a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule, a solvent not containing -COO-), an alcohol solvent (containing OH in the molecule, and containing no -O-, -CO) - and -COO-solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, and acetic acid. Isobutyl ester, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, B Methyl acetate, ethyl acetate, cyclohexanol acetate, and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol single. Ethyl 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-methyl Oxy-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 the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, two Glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

Examples of the ketone solvent include acetone, 2-butanone, 2-heptanone, and 3- Heptone, 4-heptanone, 4-methyl-2-pentanone, diacetone alcohol, cyclopentanone, cyclohexanone and isophorone.

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

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

Among the above-mentioned solvents, an organic solvent having a boiling point of from 120 ° C to 180 ° C at 1 atm is preferred from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and two are preferable. Glycol monoethyl ether, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl Ethyl ether, ethyl lactate, diacetone alcohol and ethyl 3-ethoxypropionate.

The content of the solvent (E) is preferably 65 to 95% by mass, and more preferably 70 to 92% by mass based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of the solid content of the colored curable resin composition is preferably 5 to 35% by mass, and more preferably 8 to 30% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and when the color filter is formed, the color density is not insufficient, and thus the display characteristics tend to be good.

<Leveling agent (F)>

The colored curable resin composition of the present invention may contain a leveling agent (F).

Examples of the leveling agent (F) include an organic lanthanoid surfactant, a fluorine-based surfactant, and an organic ruthenium-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the organic oxime-based surfactant include a surfactant having a decane bond in the molecule. Specifically, it can be enumerated DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH8400 (trade name: Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 ( Shin-Etsu Chemical Co., Ltd., TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 ( ‧ ‧ ‧ Contract company made) and so on.

The fluorine-based surfactant mentioned above may be a surfactant having a fluorocarbon chain in the molecule. Specifically, it can be enumerated (registered trademark) FC430, with FC431 (Sumitomo Manufactured by) (registered trademark) F142D, with F171, with F172, with F173, with F177, with F183, with F554, with R30, with RS-718-K (manufactured by DIC Corporation), (registered trademark) EF301, with EF303, with EF351, with EF352 (Mitsubishi Electronic Manufacturing Co., Ltd.), (registered trademark) S381, the same as S382, the same SC101, the same SC105 (made by Asahi Glass Co., Ltd.), and E5844 (manufactured by Research institute manufacturing).

Examples of the organic fluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specifically, it can be enumerated (registered trademark) R08, the same as BL20, the same F475, the same F477, and the same F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and further preferably 0.01% by mass or less based on the total amount of the colored curable resin composition. The above 0.05% by mass or less. In addition, the content of the above-mentioned pigment dispersant is not contained in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as is known in the art, as needed.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) and a stream which are used as needed. The flat agent (F), the polymerization initiation aid (D1), the thiol compound (T) and other components are prepared by mixing.

When the pigment (A2) is used, it is preferably mixed with a part or all of the solvent (E) in advance, and dispersed by using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. In this case, a part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. By mixing the remaining components in the pigment dispersion liquid thus obtained to have a predetermined concentration, the intended colored curable resin composition can be prepared.

For the dye (A1), a solution may be prepared by dissolving in part or all of the solvent (E) in advance. It is preferred to filter the solution with a filter having a pore diameter of about 0.01 to 1 μm.

The mixed colored curable resin composition is preferably filtered by a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

A method of forming a color filter from the colored curable resin composition of the present invention includes a photolithography method and a method using an inkjet device. In the photolithography method, for example, the colored curable resin composition of the present invention is applied onto a substrate, a volatile component such as a solvent is removed, and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask. The method of development. After development, a colored pattern can be formed by heating as needed. In the method of forming the colored pattern described above, a colored coating film which is a cured product of the colored composition layer can be formed by using a photomask and/or no development at the time of exposure. The coloring pattern and the colored coating film thus obtained can be made into a color filter.

As the substrate, a glass plate, a resin plate, a crucible, or a product such as an aluminum, silver, silver/copper/palladium alloy film or the like can be formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the intended use, etc., and is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 6 μm.

The formation of each color pixel by photolithography can be carried out under known or conventional devices and conditions. For example, it can be produced as follows.

First, the colored curable resin composition is coated on a substrate and passed through The mixture is heated and dried (prebaked) and/or dried under reduced pressure to remove volatile components such as a solvent and dried to obtain a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, a slit, and a spin coating method.

Next, the colored composition layer is exposed through a photomask for forming a colored pattern of the target.

Since the parallel light rays can be uniformly irradiated to the entire exposed surface, and the correct alignment of the photomask and the substrate on which the colored composition layer is formed is performed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

The colored composition layer after exposure is developed in contact with the developer to form a colored pattern on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferable. The development method can be immersed ( Any one of a method, a dipping method, and a spray method. Further, the substrate can be inclined at an arbitrary angle during development.

It is preferred to carry out water washing after development.

Further, it is preferred to post-bait the obtained colored pattern.

According to the colored curable resin composition of the present invention, a color filter having particularly excellent shape can be produced. This color filter can be used as a color filter for a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, or the like) and a solid-state image pickup element.

[Examples]

The color-curable resin group of the present invention is exemplified below by way of examples. The compounds are described in more detail. In the examples, "%" and "parts" are % by mass and parts by mass unless otherwise specified.

In the following synthesis examples, the compounds were subjected to mass analysis (LC; Agilent Model 1200, MASS; Agilent LC/MSD type) or elemental analysis (VARIO-EL; (manufactured by the company))) Identification.

[Synthesis Example 1]

In a flask equipped with a cooling tube and a stirring device, 15 parts of a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (trade name: Chugai Aminol Fast Pink R; manufactured by the company) 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide were maintained at 20 ° C or lower with stirring, and 10.9 parts of sulfite chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, maintained at this temperature for 5 hours, allowed to react, and then cooled to 20 ° C. The cooled reaction solution was maintained at 20 ° C or lower while stirring, and a mixed liquid of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, the mixture was stirred at this temperature for 5 hours to cause a reaction. Next, after the obtained reaction mixture was subjected to solvent distillation using a rotary evaporator, a small amount of methanol was added thereto, and the mixture was vigorously stirred. The mixture was added to a mixture of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a xanthene dye Aa (expressed by the formula (Aa-1-1) to the formula (Aa-1-8). A mixture of the compounds) 11.3 parts.

[Synthesis Example 2]

40.5 parts of the compound represented by the formula (Ax) and 60.5 parts of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under light-shielding conditions, and stirred at 150 ° C in 200 parts of N-methylpyridone. 8 hours. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 1200 parts of water and 75 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour, and crystals were precipitated. The precipitated crystal was obtained as a residue obtained by suction filtration, washed with 100 parts of methanol, and then dried under reduced pressure at 60 ° C for one night to obtain 49 parts of the compound represented by the formula (Ay). The yield was 85%.

Next, 28.8 parts of the compound represented by the formula (Ay), 21.6 parts of 1-bromopropane and 24.2 parts of potassium carbonate were added to 144 parts of N-methylpyridone, and the mixture was stirred at 90 ° C for 4 hours. The obtained reaction liquid was cooled to room temperature, concentrated, added to 560 parts of water, and stirred at 10 to 15 ° C for 1 hour, and crystallized. The obtained crystal was obtained as a residue obtained by suction filtration, dried, washed with 1000 parts of ion-exchanged water, and then dried under reduced pressure at 60 ° C for one night to obtain 30 parts of the compound represented by formula (1-32). The yield was 91%.

Identification of compounds represented by formula (1-32)

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 659.3

Exact quality: 658.3

[Synthesis Example 3]

The following reaction was carried out under a nitrogen atmosphere. After adding 33 parts of potassium thiocyanate and 160 parts of acetone to a flask equipped with a cooling tube and a stirring device, it was stirred at room temperature. Mix for 30 minutes. Next, 50 parts of 2-methylbenzhydryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and then 41.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Next, after the reaction mixture was ice-cooled, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Next, 32.1 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred under heating and reflux for 7 hours. Next, after cooling the reaction mixture to room temperature, the reaction solution was poured into 120 parts of tap water, and then 200 parts of toluene was added, followed by stirring for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and as a result, it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, and then washed with 200 parts of tap water, and finally washed with 200 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, and after stirring for 30 minutes, a filtered and dried organic layer was obtained. The obtained organic layer was subjected to solvent distillation using an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 40.5 parts of the compound represented by formula (B-I-9). (Yield 41%)

The following reaction was carried out under a nitrogen atmosphere. 9.7 parts and 4 of the compound represented by the formula (B-I-9) were placed in a flask equipped with a cooling tube and a stirring device. After 10 parts of 4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added, at 95 to 100 ° C. Stir for 3 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 170.0 parts of isopropyl alcohol. Next, the diluted reaction solution was poured into 300 parts of saturated brine, and 100 parts of toluene was added thereto, followed by stirring for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and as a result, it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, and after stirring for 30 minutes, a filtered and dried organic layer was obtained. The obtained organic layer was subjected to solvent distillation using an evaporator to obtain a blue-purple solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60 ° C to obtain 15.1 parts of the compound represented by formula (A-II-9). (yield 75%)

Identification of compounds represented by formula (A-II-9)

(mass analysis) ionization mode = ESI+: m/z = 615.4 [M-Cl] ⁺

Exact quality: 650.3

The following reaction was carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10 parts of the compound represented by the formula (A-II-9) and 5.7 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed. After 30 parts of N,N-dimethylformamide, it was stirred at 40 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and then added dropwise to 500.0 parts of tap water while stirring for one hour, and a dark blue suspension was obtained. The resulting suspension was filtered to give a blue-green solid. Further, the blue-green solid was dried under reduced pressure at 60 ° C to obtain 13.2 parts of a compound represented by the formula (Ab2-9). (yield 96%)

0.35g of the compound represented by formula (Ab2-9) was dissolved in chloroform, so that the volume becomes 250cm ^3, in which the dilution water 2cm ³ with ion exchange, so that the volume becomes 100cm ³ (concentration: 0.028g / L), spectrophotometric The absorption spectrum was measured (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2.7 (arbitrary units) at λ max = 627 nm.

[Synthesis Example 4]

4.98 parts of 2,2-bis(3-amino-4-hydroxyphenyl)phosphonium and 28.1 parts of methanol were mixed. To the obtained mixture, 8.18 parts of ethyl 3-ethoxy-3-iminopropionate hydrochloride was slowly added under stirring at 10 ° C or lower. The obtained mixture was stirred at 10 ° C or lower for 7 hours, at room temperature for 24 hours, and at 60 ° C for 24 hours. After cooling the obtained reaction mixture to room temperature, the precipitated crystals were taken out by filtration. The crystals taken out were washed with methanol, and dried under reduced pressure at 60 ° C to obtain 6.77 parts of a compound represented by formula (pt1).

<Identification of a compound represented by the formula (pt1)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 473.1

Exact quality: 472.1

42.4 parts of 2,4-dimethylaniline, 35.4 parts of triethylamine, and 132 parts of N,N-dimethylformamide were mixed, and stirred at 50 °C. While maintaining the temperature of the mixture at 50 to 60 ° C, 70.2 parts of 1-bromo-2-ethylhexane was added, followed by stirring at 60 ° C for 65 hours. After the mixture was allowed to cool to room temperature, 1000 parts of water and 433 parts of toluene were added, and the toluene layer was separated. The toluene layer was washed three times with 1000 parts of a saturated aqueous sodium chloride solution, and then subjected to solvent distillation using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 50.6 parts of a compound represented by formula (pt2-1).

<Identification of a compound represented by the formula (pt2-1)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 234.2

Exact quality: 233.2

46.7 parts of the compound represented by the formula (pt2-1), 37.4 parts of 3-bromoanisole, 1.35 parts of palladium acetate (II), 33.7 parts of potassium t-butoxide, 2,8,9-triisopropyl group under a nitrogen atmosphere. -2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (1.0 M in toluene solution) 3.42 parts and 520 parts of toluene were mixed, and stirred at 100 ° C for 6 hours. The resulting mixture was allowed to cool to room temperature and then added to 1000 parts of water. After the resulting mixture was filtered, the toluene layer was separated. The toluene layer was washed with a saturated aqueous sodium hydrogencarbonate solution, dried over magnesium sulfate and filtered. will The filtrate was subjected to solvent distillation using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 30.9 parts of the compound represented by formula (pt3-1).

<Identification of a compound represented by the formula (pt3-1)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 340.3

Exact quality: 339.3

17.0 parts of the compound represented by the formula (pt3-1) and 199 parts of dichloromethane were mixed under a nitrogen atmosphere. While maintaining the mixture at 15 to 23 ° C, boron tribromide (1.0 M dichloromethane solution) was added in an amount equivalent to the compound represented by the formula (pt3-1). Then, the mixture was stirred at room temperature for 8 hours. The obtained mixture was added to 250 parts of ice water, and the dichloromethane layer was separated. The dichloromethane layer was washed with 250 parts of water, dried over magnesium sulfate and filtered. The obtained filtrate was subjected to solvent distillation using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 13.9 parts of a compound represented by formula (pt4-1).

<Identification of a compound represented by the formula (pt4-1)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 326.3

Exact quality: 325.2

13.9 parts of the compound represented by the formula (pt4-1) and 26.4 parts of N,N-dimethylformamide were mixed. While maintaining the mixture at 23 to 55 ° C, 13.1 parts of phosphonium chloride was added. Then, the mixture was stirred at 60 ° C for 6 hours. After the mixture was cooled to room temperature, it was added to 150 parts of ice water and neutralized with a 48% aqueous sodium hydroxide solution. 300 parts of ethyl acetate was added to the mixture, and the mixture was filtered, and the ethyl acetate layer was separated from the obtained filtrate. The ethyl acetate solution was washed with 300 parts of water, dried over magnesium sulfate and filtered. The obtained filtrate was subjected to solvent distillation using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 11.6 parts of a compound represented by formula (pt5-1).

<Identification of a compound represented by the formula (pt5-1)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 354.2

Exact quality: 353.2

9.65 parts of the compound represented by the formula (pt5-1), 6.14 parts of the compound represented by the formula (pt1), 0.553 parts of piperidine and 51.1 parts of toluene were mixed under a nitrogen atmosphere. The mixture was stirred at 100 ° C for 19 hours. The mixture was added to 231 parts of methanol. By sinking the supernatant, the resulting sink The precipitate was taken out. 231 parts of methanol was added to the precipitate, and after stirring, the mixture was suction filtered. The obtained residue was washed with 20 parts of methanol to obtain a residue obtained by suction filtration. This residue was purified by column chromatography to give 9.10 parts of the compound represented by formula (Ac1-3).

<Identification of a compound represented by the formula (Ac1-3)>

¹ H-NMR (CDCl ₃ , 270 MHz) δ 0.82-0.92 (12H, m), 1.26-1.52 (16H, br m), 1.77 (2H, br s), 2.05 (6H, s), 2.38 (6H, s ), 3.32-3.42 (2H, m), 3.71-3.78 (2H, m), 6.42-6.45 (4H, m), 7.02 (2H, d), 7.11 (2H, d), 7.15 (2H, s), 7.33(2H,d), 7.66(2H,d), 7.96(2H,dd),8.39(2H,d),8.62(2H,s)

[Synthesis Example 5]

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to be replaced with a nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 85 ° C with stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]癸225 parts of a mixture of alkane-9-yl acrylate (containing 50:50 by molar ratio), 81 parts of vinyl toluene (mixture of isomers) dissolved in 80 parts of propylene glycol monomethyl ether acetate, The prepared mixed solution was dropped into the flask over 4 hours.

On the other hand, a solution in which 30 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate was added dropwise thereto over 5 hours. After completion of the dropwise addition of the initiator solution, the mixture was kept at 85 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Ba) solution. The solid content of the resin Ba solution was 37%, and the viscosity measured by a B-type viscometer (23 ° C) was 246 mPa·s. The weight average molecular weight of the resin Ba was 1.06 × 10 ⁴ , the acid value in terms of solid content was 115 mg-KOH/g, and the molecular weight distribution was 2.01. The resin Ba has the following structural unit.

[Synthesis Example 6]

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to be replaced with a nitrogen atmosphere, and 235 parts of ethyl lactate was charged, and the mixture was heated to 70 ° C with stirring. Next, 38 parts of acrylic acid, 50 parts of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]癸-8 or / and 9-based acrylate, and 138 parts of cyclohexylmaleimide were used for 3 hours. A mixed solution of tricyclo [5.2.1.0 ^2,6 ]non-3-ene-8 or/and 9-yl acrylate 25 parts and 425 parts of ethyl lactate was dropped into the flask. On the other hand, a mixed solution of 3 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 86 parts of ethyl lactate was dropped into the flask over 5.5 hours. After completion of the dropwise addition, the mixture was kept at this temperature for 4 hours, and then cooled to room temperature to obtain a B-type viscosity (23 ° C) of 27 mPa·s, a solid content of 26.9%, and a copolymer (resin Bb) solution. The resulting copolymer (resin Bb) had a weight average molecular weight Mw of 7.0 × 10 ³ , a solid content acid value of 112 mg-KOH/g, and a molecular weight distribution of 2.3. The resin Bb has the following structural unit.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was carried out under the following conditions using a GPC method.

Device: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Detector: RI

Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution.

Examples 1 to 7, Comparative Example 1

<Preparation of Colored Curable Resin Composition>

Each component of Table 3 was mixed to obtain a colored curable resin composition. In addition, the pigment is mixed with a part of the dispersing agent and the solvent Ea in advance, and the pigment is sufficiently dispersed by using a bead mill to prepare a pigment dispersion liquid, which is used for mixing.

In Table 3, the fraction of the resin indicates a value converted into a solid content.

Dye (A1); Aa1; xanthene dye Aa

Dye (A1); Aa2; a compound represented by formula (1-32)

Dye (A1); Ab1; C.I. Acid Blue 1

Dye (A1); Ab2; a compound represented by the formula (Ab2-9)

Dye (A1); Ac1; a compound represented by formula (Ac1-3)

Pigment (A2); A2a; C.I. Pigment Blue 15:6

Pigment (A2); A2b; C.I. Pigment Green 58

Resin (B); Ba; resin Ba

Resin (B); Bb; Resin Bb

Resin (B); Bc; methacrylic acid / benzyl methacrylate copolymer (copolymerization ratio (mass ratio); 30/70, Mw; 1.2 × 10 ⁴ )

Polymerizable compound (C); Ca; dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerizable compound (C); Cb; pentaerythritol triacrylate (A-TMM-3LM-N; manufactured by Shin-Nakamura Chemical Co., Ltd.)

Polymerization initiator (D); Da; N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine ( (registered trademark) OXE-01; manufactured by BASF; O-mercaptopurine compound)

a polymerization initiator (D); Db; a compound represented by the following formula (SOA-009; Manufactured by the company; O-mercaptopurine compound)

a polymerization initiator (D); Dc; a mixture of compounds represented by the following formula (CHEMCURE-TCDM; Manufactured by the company; biimidazole compound)

Polymerization initiator (D); Dd; 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one ( (registered trademark) 907; manufactured by BASF; alkyl phenyl ketone compound)

Polymerization initiation aid (D1); D1a; 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.; thioxanthone compound)

Thiol compound (T); 2-sulfanylbenzothiazole ( (registered trademark) M; Sanshin Chemical Industry Co., Ltd.)

Solvent (E); Ea; propylene glycol monomethyl ether acetate

Solvent (E); Eb; ethyl lactate

Solvent (E); Ec; diacetone alcohol

Leveling agent (F); polyether modified eucalyptus SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<sensitivity evaluation>

On a glass substrate of 5 cm square (Eagle 2000; manufactured by Corning Incorporated), the film thickness after baking was set to the value shown in the film thickness of Table 3, and the colored curable resin composition was applied by spin coating. Prebaking at 100 ° C for 3 minutes formed a colored composition layer. After cooling, the interval between the substrate on which the colored composition layer was formed and the quartz glass photomask was 100 μm, and an exposure machine (TME-150RSK; (manufactured by the company), light irradiation was performed under an air atmosphere at an exposure amount of 80 mJ/cm ² (365 nm basis). As the photomask, a gray scale mask having a transmittance of the light transmitting portion of 1 to 100% was used. The colored composition layer after light irradiation was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide and water at 24 ° C for 60 seconds, and after washing with water, in an oven at 230 ° C. After baking for 30 minutes, a colored pattern was obtained.

The film thickness of the obtained coloring pattern was measured, and the value corresponding to the minimum exposure amount in which the residual film ratio shown by the following formula was 90% or more was used as the sensitivity.

Residual film rate = [film thickness in each light transmitting portion] / [film thickness in 100% transmittance portion]

<Measurement of film thickness>

The film thickness of the obtained coloring pattern was measured using the film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Evaluation of shape of colored pattern>

On a glass substrate of 5 cm square (Eagle 2000; manufactured by Corning Incorporated), the film thickness after baking was set to the value shown in the film thickness of Table 3, and the colored curable resin composition was applied by spin coating. Prebaking at 100 ° C for 3 minutes formed a colored composition layer. After cooling, the interval between the substrate on which the colored composition layer was formed and the quartz glass photomask was 100 μm, and an exposure machine (TME-150RSK; (manufactured by the company), light irradiation was performed under an air atmosphere at an exposure amount (365 nm basis) shown in the sensitivity column of Table 4. As a photomask, a photomask in which a line and a gap pattern of 100 μm were formed was used. The colored composition layer after light irradiation was immersed and developed at 24 ° C for 60 seconds in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and then dried in an oven at 230 ° C. After 30 minutes of baking, a colored pattern was obtained.

For the obtained coloring pattern, a scanning electron microscope (S-4000; Hitachi Co., Ltd.) was used. Manufacture), observe the shape. In Fig. 1, if it is a shape indicated by (p1) (so-called forward tapered shape), it is denoted by ○, and if it is a shape represented by (p2), it is denoted by Δ, and if it is represented by (p3) The shape is marked as ×. In the case of the shape represented by (p1), when the inorganic film is laminated on the colored pattern, the inorganic film tends to be less likely to be cracked or peeled off, which is preferable. The results are shown in Table 4.

<Color Evaluation>

For the obtained color pattern, a color measuring machine (OSP-SP-200; The product was measured for spectroscopic analysis, and the xy chromaticity coordinates (x, y) and the tristimulus value Y in the XYZ color system of CIE were measured using the characteristic function of the C light source. The color filters of Examples 1 to 6 and Comparative Example 1 were blue, and the color filter of Example 7 was green. The larger the value of Y, the higher the brightness. The results are shown in Table 4.

Industrial utilization possibility

According to the colored curable resin composition of the present invention, a color filter having an excellent shape can be produced.

Claims (4)

A colored curable resin composition containing a dye, a resin, a polymerizable compound, and a polymerization initiator, wherein the dye is selected from the group consisting of a xanthene dye, a triarylmethane dye, a compound represented by the formula (Ab2), and a coumarin dye At least one dye, the polymerization initiator is a polymerization initiator comprising a biimidazole compound and an O-indenyl ruthenium compound, In the formula (Ab2), R ⁴¹ to R ⁴⁴ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with an unsubstituted or unsubstituted amino group or a halogen atom, and an alkyl group having 2 to 20 carbon atoms. a group in which an methylene group of the alkyl group is inserted with an oxygen atom, an aromatic hydrocarbon group which may be substituted, or an aralkyl group or a hydrogen atom which may be substituted, and a nitrogen atom to which R ⁴¹ and R ⁴² may bond and bind thereto Forming a ring together, R ⁴³ and R ⁴⁴ may bond and form a ring together with the nitrogen atom to which they are bonded, and R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and an alkyl group having 1 to 8 carbon atoms. An oxygen atom may be interposed between 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 -, and ring T ¹ represents a fragrance which may have a substituent a heterocyclic ring, [Y] ^m- represents an arbitrary m-valent anion, and m represents an arbitrary natural number. In the formula (Ab2), when a plurality of cations represented by the following chemical formula are contained in one molecule, they may be For the same structure, it can also be a different structure, In the formula, ring T ¹ , and R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ are respectively synonymous with the above. The colored curable resin composition of claim 1, wherein the content ratio of the biimidazole compound to the O-mercaptopurine compound contained in the polymerization initiator is from 1:9 to 9:1 on a mass basis. A color filter formed of the colored curable resin composition of claim 1 or 2. A display device comprising the color filter of claim 3.