KR102299144B1 - The blue curable resin composition, color filter and display device - Google Patents

Abstract

The color filter formed from the conventional colored curable resin composition had room for improvement in the point of brightness.
The blue curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and as the colorant (A), the maximum absorption wavelength in chloroform is It is 500 nm to 600 nm and contains a dye having a silicon atom (A1) and a blue colorant.
In addition, the present invention relates to a color filter formed of the blue curable resin composition and a display device including the same.

Description

Blue curable resin composition, color filter, and display device TECHNICAL FIELD

The present invention relates to a blue curable resin composition.

Colored curable resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, and a plasma display. As such a colored curable resin composition, the colored curable resin composition containing the mixture of the compound represented by Formula (A1-1) - Formula (A1-8), and C.I. Pigment Blue 15:6 is known (patent document 1).

[Formula 1]

(Patent Document 1) Japanese Patent Application Laid-Open No. 2011-118369

The color filter formed from said colored curable resin composition had room for improvement in the point of brightness.

The present invention includes the following inventions.

[1] A colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D) are included, and as the colorant (A), the maximum absorption wavelength in chloroform is 500 nm to 600 nm, and a silicon atom The blue curable resin composition containing the dye (A1) which has and a blue coloring agent.

[2] The blue curable resin composition according to [1], wherein the polymerization initiator (D) contains a polymerization initiator represented by the following formula (d1).

[Formula 2]

[in formula (d1),

R ^d1 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, a saturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, or even if it has a substituent A preferred aralkyl group having 7 to 33 carbon atoms is represented, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group or aralkyl group is -O-, -CO-, -S-, -SO ₂ - or -NR It may be substituted by ^{d5 -.}

R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or a saturated hydrocarbon group having 1 to 10 carbon atoms.

R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.

R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, and the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group is, -O-, -CO-, or -S- may be substituted, and the methine group (-CH<) _{contained in the said aliphatic hydrocarbon group may be substituted by -PO 3} <, The hydrogen atom contained in the said aliphatic hydrocarbon group may be substituted with an OH group.

R ^d5 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the methylene group (-CH2-) contained in the saturated hydrocarbon group may be substituted with -O- or -CO-.]

[3] The blue curable resin composition as described in [1] or [2] whose content rate of the said coloring agent (A) is 3 mass % or more and 60 mass % or less with respect to the total amount of solid content of blue curable resin composition.

[4] The blue curable resin composition according to any one of [1] to [3], wherein the blue coloring agent is a pigment having a phthalocyanine skeleton.

[5] The blue curable resin according to any one of [1] to [4], wherein the mass ratio of the content of the dye (A1) to the content of the blue colorant (dye (A1)/blue colorant) is 0.01 or more and 2 or less. composition.

[6] A color filter formed from the blue curable resin composition according to any one of [1] to [5].

[7] A display device comprising the color filter according to [6].

The color filter formed from the blue curable resin composition of this invention is excellent in brightness.

The blue curable resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D).

In addition, unless otherwise indicated, the compound and functional group illustrated in this specification can be used individually or in combination of multiple types.

The blue curable resin composition of the present invention is a colorant (A) with a dye (A1) having a maximum absorption wavelength in chloroform of 500 nm to 600 nm and having a silicon atom (hereinafter also referred to as “dye (A1)”) and blue a colorant (A2). As dye (A1), the dye whose maximum absorption wavelength in chloroform is 500 nm - 580 nm is preferable, and the dye which is 500 nm - 560 nm is especially preferable.

The dye (A1) is preferably a dye having a silicon atom and having an imidazole skeleton, triarylmethane skeleton, cyanine skeleton, or xanthene skeleton. As dye which has a silicon atom and has imidazole skeleton, the compound represented by Formula (IA) disclosed by Unexamined-Japanese-Patent No. 2010-526897 is contained, for example.

[Formula 3]

[In formula (IA), R ¹ is a group represented by the following formula (ia), and X is a halogen atom.

[Formula 4]

[n represents an integer of 1 to 8, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom.]

As a compound represented by Formula (IA), Preferably the compound represented by a following formula is mentioned.

[Formula 5]

Among the dyes (A1), dyes having a silicon atom and at least one skeleton selected from the group consisting of a triarylmethane skeleton, a cyanine skeleton and a xanthene skeleton are preferable, have a silicon atom, and have a xanthene skeleton The dye which has is more preferable. As a dye which has a silicon atom and has a xanthene skeleton, the dye which has a xanthene skeleton which has an organosilicon group in a substituent is preferable. Here, the organosilicon group represents a group having a carbon-silicon bond. Among the dyes having a xanthene skeleton having an organosilicon group as a substituent, a dye having a xanthene skeleton having a silylalkyl group such as a trimethylsilylalkyl group, a triethylsilylalkyl group, a trimethoxysilylalkyl group, and a triethoxysilylalkyl group in the substituent is preferred, The compound represented by Formula (IB) (it may also describe as "compound (IB)" below) is more preferable. Compound (IB) also includes its tautomer.

[Formula 6]

[In formula (IB), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or a group represented by the formula (ib). Provided that at least one of R ²¹ ~ R ²⁴ is a group represented by the formula (ib).

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ib)

[R ²⁹ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. A plurality of R ²⁹ may be the same or different, respectively.

R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, -CH ₂ - constituting the alkanediyl group is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH -, -CONH-, or -NHCO- may be substituted. However, in the said alkanediyl group, adjacent -CH ₂ - is not substituted at the same time, and -CH ₂ - at the terminal is not substituted]

In R ²¹ to R ²⁴ , a hydrogen atom included in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom, and —CH ₂ — included in the saturated hydrocarbon group is —O—, —CO—, -NR ¹¹ It may be substituted by -, -OCO-, -COO-, -OCONH-, -CONH-, or -NHCO-. However, in the said saturated hydrocarbon group, adjacent -CH ₂ - is not substituted at the same time, and -CH ₂ - at the terminal is not substituted.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ²⁷ and R ²⁸ are, each ^{_{independently, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO ₂ R ¹⁰ , -SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ¹² is represented.

R ¹⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

Z ⁺ represents ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ .

R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ¹³ each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

p represents the integer of 0-4.]

The compound represented by the formula (IB) includes a compound represented by the following formula (IC) (hereinafter, also referred to as "compound (IC)") and its tautomer.

[Formula 7]

[In formula (IC), R ³¹ to R ³⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or a group represented by the formula (ic). Provided that at least one of R ³¹ ~ R ³⁴ dogs, a group represented by the formula (ic).

[Formula 8]

[n represents an integer of 1 to 8, R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom.]

In R ³¹ to R ³⁴ , a hydrogen atom included in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom, and —CH ₂ — included in the saturated hydrocarbon group is —O—, —CO— or -NR ¹¹ - may be substituted. However, in the said saturated hydrocarbon group, adjacent -CH ₂ - is not substituted at the same time, and -CH ₂ - at the terminal is not substituted.

R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ³⁷ and R ³⁸ are, each ^{_{independently, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO ₂ R ¹⁰ , -SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ¹² is represented.

R ¹⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

Z ⁺ represents ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ .

R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ¹³ each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

m represents the integer of 0-4.]

^{Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R 21} to R ²⁴ and R ³¹ to R ³⁴ in the formulas (IB) and (IC) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, decyl group, 1-methylbutyl group, 1,1,3, 3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, 1,1,5,5-tetramethylhexyl group, etc. are mentioned.

As the ^{monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R 21} to R ²⁴ and R ³¹ to R ³⁴ , a methyl group, an ethyl group, a propyl group and a butyl group are preferable.

A hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ^{34 may be substituted with a halogen atom.} Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group and a chlorobutyl group.

_{-CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ may be substituted with -O-, -CO- or -NR ^{11 -.} However, in the said saturated hydrocarbon group, adjacent -CH ₂ - is not substituted at the same time, and -CH ₂ - at the terminal is not substituted.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ¹¹ include a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, A linear alkyl group having 1 to 20 carbon atoms, such as n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and n-icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert - a branched chain alkyl group having 3 to 20 carbon atoms, such as a butyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group; a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclo A C3-C20 alicyclic saturated hydrocarbon group, such as a decyl group, is mentioned.

_{Examples of the group in which -CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms are substituted with -O- include groups represented by the following formula (* represents a bond).

[Formula 9]

_{As the group in which -CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with -CO-, for example, a group represented by the following formula (* represents a bond) is exemplified.

[Formula 10]

_{Examples of the group in which -CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms and ^{is substituted with -NR 11} - include groups represented by the following formula (* represents a bond).

[Formula 11]

_{-CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ is -OCO-, -COO-, -OCONH-, -CONH- and -NHCO- It may be substituted with at least 1 group selected from the group which consists of. However, in the said saturated hydrocarbon group, adjacent -CH ₂ - is not substituted at the same time, and -CH ₂ - at the terminal is not substituted.

_{As the group in which -CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with -OCO-, for example, a group represented by the following formula (* represents a bond) is exemplified.

[Formula 12]

_{As the group in which -CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with -COO-, for example, a group represented by the following formula (* represents a bond) is exemplified.

[Formula 13]

_{Examples of the group in which -CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms are substituted with -OCONH- include groups represented by the following formula (* represents a bond).

[Formula 14]

_{Examples of the group in which -CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms are substituted with -CONH- include groups represented by the following formula (* represents a bond).

[Formula 15]

_{Examples of the group in which -CH 2} - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms are substituted with -NHCO- include groups represented by the following formula (* represents a bond).

[Formula 16]

The ^{phenyl group represented by R 21} to R ²⁴ and R ³¹ to R ³⁴ may have a substituent. As the substituent, a halogen ^{atom, -R 10, -OH, -OR 10} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 10, -SR 10, -SO 2 R 10 , -SO ₃ R ¹⁰ and -SO ₂ NR ¹¹ R ¹² .

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ to R ¹³ include a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- A linear alkyl group having 1 to 20 carbon atoms, such as an octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and n-icosyl group; isopropyl group, isobutyl group, sec-butyl group branched chain alkyl groups having 3 to 20 carbon atoms, such as group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and C3-C20 alicyclic saturated hydrocarbon groups, such as a tricyclodecyl group.

-OR ^{10 includes} , for example, 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 icosyloxy group. can

Examples of _{^{Z +, -SO 3 - - -SO}} 3 is N ⁺ (R ¹³⁾ ₄ are preferred.

Examples of -CO ₂ R ¹⁰ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of -SR ¹⁰ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

Examples of -SO ₂ R ^10, for example, there may be mentioned methyl sulfonyl group, ethyl sulfonyl, butyl sulfonyl group, sulfonyl group, hexyl, decyl and the sulfonyl group and the sulfonyl group Ikoma silsul.

-SO ₃ R ^{10 includes} , for example, a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

-SO ₂ NR ¹¹ R ^{12 is} , for example, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N -isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1) -Dimethylpropyl)sulfamoyl group, N-(1,2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N- (2-methylbutyl)sulfamoyl group, N-(3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group , N-(3,3-dimethylbutyl)sulfamoyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N- Octylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group, N-(1,5-dimethyl)hexylsulfamoyl group, N-(1,1,2,2-tetramethylbutyl)sulfamoyl group, etc. N-1 substituted sulfamoyl group of;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group, and an N-2-substituted sulfamoyl group.

Examples of R ²¹ ~ R is a phenyl group having a substituent represented by ²⁴ and R ³¹ ~ R ^34, -R ¹⁰ are preferred, more preferably a univalent saturated hydrocarbon group having 1 to 10 carbon atoms.

At least one of R ²¹ to R ²⁴ is a group represented by a formula (ib).

In group represented by Formula (ib), R ²⁹ represents a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, or a C1-C4 alkoxy group.

A methyl group, an ethyl group, a propyl group, and a butyl group are mentioned as a C1-C4 alkyl group represented by R<^29>.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ²⁹ include a methoxy group, an ethoxy group, a propoxy group, and a tert-butoxy group.

^{As R 29 in} group represented by formula (ib), a methyl group, an ethyl group, a methoxy group, and an ethoxy group are preferable, and a methoxy group or an ethoxy group is more preferable.

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ⁵⁰ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, an isobutylene group, and a 2-methyltrimethylene group. , isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group, etc. are mentioned, among these, a C1-C6 alkanediyl group is preferable, and a C1-C4 alkanediyl group is more desirable.

As group represented by a formula (ib), group represented by a following formula is mentioned, for example.

[Formula 17]

[Formula 18]

In formula (ib), as a group in which -CH ₂ ^{- constituting R 50} was substituted with -O-, for example, a group represented by the following is exemplified (* represents a bond).

[Formula 19]

[Formula 20]

In formula (ib), as a group in which -CH ₂ ^{- constituting R 50} is substituted with -CO-, for example, a group represented by the following is exemplified (* represents a bond).

[Formula 21]

[Formula 22]

In formula (ib), as a group in which -CH ₂ - ^{constituting R 50 is substituted with -NR 11} -, for example, a group represented by the following is exemplified (* represents a bond).

[Formula 23]

[Formula 24]

In formula (ib), as a group in which -CH ₂ ^{- constituting R 50} is substituted with -OCO-, for example, a group represented by the following is exemplified (* represents a bond).

[Formula 25]

[Formula 26]

In formula (ib), as a group in which -CH ₂ ^{- constituting R 50} is substituted with -COO-, the group represented by the following is mentioned, for example (* represents a bond).

[Formula 27]

[Formula 28]

In formula (ib), as a group in which -CH ₂ ^{- constituting R 50} was substituted with -OCONH-, for example, a group represented by the following is exemplified (* represents a bond).

[Formula 29]

[Formula 30]

In formula (ib), as a group in which -CH ₂ ^{- constituting R 50} was substituted with -CONH-, for example, a group represented by the following is exemplified (* represents a bond).

[Formula 31]

[Formula 32]

In formula (ib), as group in which -CH ₂ ^{- constituting R 50} was substituted with -NHCO-, the group represented by the following is mentioned, for example (* represents a bond).

[Formula 33]

[Formula 34]

As a formula (ib), group represented by a following formula is preferable.

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

At least one of R ³¹ to R ³⁴ is a group represented by formula (ic).

In formula (ic), a methyl group, an ethyl group, a propyl group, and a butyl group are mentioned as a C1-C4 alkyl group represented by ^R<39>.

As R ³⁹ , a hydrogen atom, a methyl group, an ethyl group, and a propyl group are preferable, and a hydrogen atom, a methyl group, and an ethyl group are more preferable.

As group represented by Formula (ic), group represented by following formula (i-1) - Formula (i-12) is mentioned, for example. As group represented by a formula (ic), group represented by a formula (i-2), a formula (i-3), a formula (i-5), and a formula (i-6) is preferable.

[Formula 41]

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ²⁵ , R ²⁶ , R ³⁵ and R ³⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, tert-butyl group, isopentyl group and neopentyl group are mentioned.

R ^27, R ^28, -SO ₃ represented by R ³⁷ and R ^{38 -} Examples of Z ^+, a -SO ₃ Na or -SO ₃ K is preferred.

^{R 27, R 28, R -CO} 2 indicated by ^37, and R ^{38 -} Examples of Z ^+, is -CO ₂ Na, or -CO ₂ K are preferred.

_{-CO 2} R ¹⁰ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ is, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, or a hexyloxycarbonyl group. and an icosyloxycarbonyl group.

_{-SO 3} R ¹⁰ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ is, for example, a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, and a hexyloxysulfonyl group. A phonyl group and an icosyloxysulfonyl group are mentioned.

As _{-SO 2} NR ¹¹ R ¹² represented by ^{R 27} , R ²⁸ , R ³⁷ and R ³⁸ , for example, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-iso Propylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-(1-) Ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1,2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N -(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-(3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamoyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-( 1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group, N-(1,5-dimethyl)hexylsulfamoyl group, N-(1,1) , an N-1 substituted sulfamoyl group such as a 2,2-tetramethylbutyl)sulfamoyl group;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group, An N-2 substituted sulfamoyl group is mentioned.

As the ^{monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 10} , a methyl group, an ethyl group, a propyl group and a butyl group are preferable.

A hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{10 may be substituted with a halogen atom.}

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

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group and a chlorobutyl group.

As Z ^{+, +} N(R ¹³ ) ₄ is preferable.

It is preferable that all four R ^{13 in +} N(R ¹³ ) _{4 are the same.} Moreover, 20-80 are preferable and, as for total carbon number of four R<^{13>, 20-60 are more preferable.}

As the ^{monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 11} and R ¹² , a methyl group, an ethyl group, a propyl group, a butyl group or a 2-ethylhexyl group is preferable.

As a C1-C20 monovalent saturated hydrocarbon group represented by R<^13> , a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group, an ethyl group, and a propyl group are more preferable.

At least one of R ²¹ to R ²⁴ is a group represented by the formula (ib), and as other R ²¹ to R ²⁴ , a methyl group, an ethyl group, a propyl group, and the following groups are preferable (* is a group with a nitrogen atom represents a bonding hand),

[Formula 42]

A methyl group, an ethyl group, a propyl group, and the following groups are more preferable (* represents a bond with a nitrogen atom).

[Formula 43]

At least one of R ³¹ to R ³⁴ is a group represented by the formula (ic), and as other R ³¹ to R ³⁴ , a methyl group, an ethyl group, a propyl group, and the following groups are preferable;

[Formula 44]

A methyl group, an ethyl group, a propyl group, and the following groups are more preferable (* represents a bond with a nitrogen atom).

[Formula 45]

R ²⁵ , R ²⁶ , R ³⁵ and R ³⁶ are preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.

R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ are preferably -CO ₂ ^- , -CO ₂ H, -SO ₃ H, -SO ₃ ^- , more preferably -SO ₃ H, -SO ₃ - am.

R ¹⁰ is preferably a methyl group, an ethyl group, a propyl group or a butyl group.

R ¹¹ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or a 2-ethylhexyl group.

R ¹² is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or a 2-ethylhexyl group.

R ¹³ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group.

The integer of 0-2 is preferable, as for p and m, it is more preferable that it is 0 or 1, It is more preferable that it is 0.

As a specific example of a compound (IB), what is shown below is mentioned, for example. As compound (IB), (I-1)-(I-4), (I-13)-(I-16), (I-25)-(I-28), (I-37)-(I) -40), (I-49) to (I-54), (I-55) to (I-62), (I-87) to (I-94), (I-117) to (I-123) ) is preferable, (I-1) to (I-4), (I-13) to (I-16), (I-25) to (I-28), (I-55) to (I- 62), (I-87) to (I-94), (I-117), (I-119) to (I-123) are more preferable.

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

[Formula 50]

[Formula 51]

[Formula 52]

[Formula 53]

[Formula 54]

[Formula 55]

[Formula 56]

[Formula 57]

[Formula 58]

[Formula 59]

Specific examples of the compound (IC) include, for example, those represented by the formulas (I-1) to (I-54), those represented by the formulas (I-117) to (I-119), and the formulas (I-). 121) and those represented by Formula (I-123). As compound (IC), (I-1)-(I-4), (I-13)-(I-16), (I-25)-(I-28), (I-37)-(I) -40), (I-49) to (I-54), (I-117) to (I-119) are preferable, and (I-1) to (I-4), (I-13) to ( I-16), (I-25) to (I-28), (I-117), and (I-119) are more preferable.

Compound (IB) is a formula (IV)

[Formula 60]

[wherein, R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁸ , R ²⁷ and p each have the same meaning as above. X ² represents a halogen atom or a trifluoromethylsulfonyloxy group.]

A compound represented by (hereinafter sometimes referred to as "compound (IV)") and formula (V)

[Formula 61]

[In the formula, R ²³ and R ²⁴ each have the same meaning as above.]

It can manufacture by mixing and reacting the compound represented by (Hereinafter, it may describe as "compound (V)") in an organic solvent.

Examples ^{of the halogen atom represented by X 2} include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom.

X ² is preferably a halogen atom, more preferably chlorine atom.

It is preferable that R ²⁷ is -SO ₃ ^-.

The usage-amount of compound (V) is 1 mol or more and 10 mol or less normally with respect to 1 mol of compound (IV), Preferably they are 1 mol or more and 3 mol or less, More preferably, they are 1 mol or more and 2 mol or less.

Compound (IB) in which R ²⁷ is -SO ₃ ^- or -CO ₂ ^- (hereinafter, may be referred to as compound (II-1)) is represented by formula (VI)

[Formula 62]

[In the formula, R ²⁵ , R ²⁶ , R ²⁸ and p have the same meanings as above.

X ¹ and X ² each independently represent a halogen atom or a trifluoromethylsulfonyloxy group.

R ⁴⁰ represents -SO ₂ - or -CO-.]

A compound represented by (hereinafter, sometimes referred to as "compound (VI)") and formula (III)

[Formula 63]

[In the formula, R ²¹ and R ²² have the same meaning as above.]

A compound represented by (hereinafter, sometimes referred to as "compound (III)") is mixed and reacted in an organic solvent, and then, the formula (V)

[Formula 64]

[In the formula, R ²³ and R ²⁴ each have the same meaning as above.]

It can manufacture by mixing and reacting the compound represented by (Hereinafter, it may describe as "compound (V)") in an organic solvent.

A fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom represented by X<^{1>, Preferably it is a chlorine atom.}

It is preferable that X ¹ and X ^{2 are the same.}

It is preferable that it is a halogen atom each independently, and, as for X<^1> and X<^{2>, it is more preferable that it is a chlorine atom.}

It is preferable that R ⁴⁰ is -SO _{2 -.}

The usage-amount of compound (III) is 1 mol or more and 30 mol or less normally with respect to 1 mol of compound (VI), Preferably it is 1 mol or more and 20 mol or less, More preferably, it is 1 mol or more and 10 mol or less, further Preferably they are 1 mol or more and 3 mol or less, Especially preferably, they are 1 mol or more and 2 mol or less.

The usage-amount of compound (V) is 1 mol or more and 30 mol or less normally with respect to 1 mol of compound (VI), Preferably it is 1 mol or more and 20 mol or less, More preferably, it is 1 mol or more and 10 mol or less, further Preferably they are 1 mol or more and 3 mol or less, Especially preferably, they are 1 mol or more and 2 mol or less.

The usage-amount of compound (V) is 1 mol or more and 50 mol or less normally with respect to 1 mol of compound (III), Preferably they are 1 mol or more and 30 mol or less, More preferably, they are 1 mol or more and 20 mol or less.

Compound (IB) is useful as a dye. It is useful as a coloring agent of the coloring curable resin composition used especially for the color filter of display apparatuses, such as a liquid crystal display, at the point with high solubility to an organic solvent.

The content of the dye (A1) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, in 100% by mass of the total amount of solid content of the blue curable resin composition, preferably is 40 mass% or less, more preferably 30 mass% or less, still more preferably 20 mass% or less.

Here, the "total amount of solid content" in this specification means the quantity which removed content of the solvent from the total amount of blue curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

The content of the dye (A1) is preferably 0.01% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably in 100% by mass of the total amount of the colorant (A). It is 5 mass % or more, Preferably it is 90 mass % or less, More preferably, it is 80 mass % or less, More preferably, it is 60 mass % or less, More preferably, it is 50 mass % or less.

Moreover, it is preferable that the content rate of a compound (IB) is 80 mass % or more in 100 mass % of dye (A1), More preferably, it is 90 mass % or more, More preferably, it is 95 mass % or more.

Moreover, it is preferable that the content rate of dye (A1) is 50 mass % or more in a total of 100 mass % of dyes, More preferably, it is 70 mass % or more, More preferably, it is 80 mass % or more, It is also preferable that it is 100 mass %. and 100 mass % or less may be sufficient, and 90 mass % or less may be sufficient as it.

<Blue coloring agent (A2)>

The blue curable resin composition of this invention contains a blue coloring agent (A2) as a coloring agent (A) other than the said dye (A1).

As a blue colorant, a blue compound among compounds classified as dyes in the color index (blue dye (A2-1)), or a blue compound among compounds classified as pigments in the color index (published by The Society of Dyers and Colorists) (blue pigment (A2-2)) is mentioned.

Examples of the blue dye (A2-1) include C.I. Solvent Blue 4, 5, 37, 67, 70, 90;

CI Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103 , 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234 , 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;

CI Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99 , 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164 , 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210 , 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259 , 260, 268, 274, 275, 293;

C.I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

CI Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, and 84 are mentioned.

Specifically, as a blue pigment (A2-2), CI pigment blue (Hereinafter, description of CI pigment blue is abbreviate|omitted, and it is set as description only of numbers.) 15, 15:3, 15:4, 15: 6, 16, 60, 75, 80 are mentioned, CI pigment blue 15, 15:3, 15:4, 15:6, 16, 75 are preferable, CI pigment blue 15, 15:3, 15 :4, 15:6 are more preferable, and CI pigment blue 15:6 is especially preferable.

Especially, a blue pigment (A2-2) is preferable and the blue pigment (blue phthalocyanine pigment) which consists of a compound which has phthalocyanine skeleton is more preferable. Examples of the blue pigment composed of a compound having a phthalocyanine skeleton include C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 16, and 75.

It is preferable that content rate of a blue pigment (A2-2) is 80 mass % or more in 100 mass % of blue coloring agents (A2), More preferably, it is 90 mass % or more, More preferably, it is 95 mass % or more.

The content rate of the blue colorant (A2) is preferably 0.1 mass% or more, more preferably 1 mass% or more, still more preferably 3 mass% or more, still more preferably 5 in 100 mass% of the colorant (A). It is mass % or more, Preferably it is 99 mass % or less, More preferably, it is 95 mass % or less, More preferably, it is 90 mass % or less.

Further, the total content of the dye (A1) and the blue colorant (A2) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably, in 100% by mass of the total amount of the colorant (A). is 95% by mass or more.

In addition, the mass ratio of the content of the dye (A1) to the content of the blue colorant (dye (A1)/blue colorant (A2)) is preferably 0.01 or more, more preferably 0.05 or more, and preferably 10 or less. , More preferably 2 or less, particularly preferably 1.8 or less, and 0.7 or less may be sufficient.

<Other color materials (A3)>

The blue curable resin composition of this invention may also contain the color material (A3) different from dye (A1) or a blue coloring agent (A2) as a coloring agent (A). As another color material (A3), dye (A3-1) (however, it is different from dye (A1) or blue coloring agent (A2)) and pigment (A3-2) (however, it is different from blue coloring agent (A2)) can be heard

Examples of the dye (A3-1) (however, different from the dye (A1) or the blue colorant (A2)) include oil-soluble dyes, acid dyes, alkaline dyes, direct dyes, mordant dyes, amine salts of acid dyes, and acid dyes. and dyes such as sulfonamide derivatives, for example, compounds classified as dyes in the Color Index (published by The Society of Dyers and Colorists), and known dyes described in the dyeing notes (color dyes). can In addition, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dyes other than dye (A1), phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, scrylium dye , an acridine dye, a styryl dye, a coumarin dye, a quinoline dye, and a nitro dye. Among these, organic solvent-soluble dyes are preferable.

Specifically, C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Solvent Red 45, 49, 125, 130, 218;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56;

C.I. Solvent Green 1, 4, 5, 7, 34, 35, etc. C.I. solvent dyes,

CI 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;

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91 , 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Violet 6 B, 7, 9, 17, 19, 30, 102;

C.I. acid dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109;

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C.I. direct dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

C.I. Disperse dyes such as C.I. Disperse Yellow 54 and 76;

C.I. Basic Red 1, 10;

C.I. basic green 1; C.I. basic dye such as;

C.I. reactive yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. reactive red 36; C.I. reactive dyes such as;

C.I. modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modern Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. modern dyes such as C.I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53;

C.I. vat dye such as C.I. vat green 1,

and the like.

Among them, violet dye and red dye are preferable.

What is necessary is just to select these dyes suitably according to the spectral spectrum of a desired color filter.

The total content of the dye (A3-1) is, in 100% by mass of the total amount of the colorant (A), preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, Preferably it is 50 mass % or less, More preferably, it is 40 mass % or less, More preferably, it is 30 mass % or less.

It does not specifically limit as said pigment (A3-2) (however, it is different from a blue coloring agent (A2)), A well-known pigment can be used, For example, it is pigment by Color Index (published by The Society of Dyers and Colorists). compounds classified as

As the pigment (A3-2), for example, C.I. Pigment Yellow 1 (Hereinafter, description of CI Pigment Yellow is omitted, and description is made only of numbers.), 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, yellow pigments such as 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

C.I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 red pigment;

C.I. Violet pigments, such as pigment violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments, such as pigment green 7, 36, 58;

C.I. Brown pigments, such as Pigment Brown 23 and 25;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

These pigments may be used individually or in mixture of 2 or more types.

As a pigment, C.I. Yellow pigments such as Pigment Yellow 138, 139, and 150, C.I. Red pigments such as Pigment Red 177, 242, 254, and C.I. Violet pigments, such as pigment violet 1, 19, 23, 29, 32, 36, 38, are preferable. By including said pigment, optimization of the transmission spectrum of the color filter using the blue curable resin composition of this invention is easy, and the light resistance and chemical-resistance of a color filter become favorable.

The total content of the pigment is preferably 1% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more in 100% by mass of the total amount of the colorant (A). It is mass % or more, Preferably it is 99 mass % or less, More preferably, it is 95 mass % or less, More preferably, it is 90 mass % or less.

The content rate of the coloring agent (A) is preferably 1 mass % or more and 70 mass % or less, more preferably 3 mass % or more and 60 mass % or less, further preferably 3 mass % or more and 50 mass % or less with respect to the total amount of solid content. It is mass % or less, Especially preferably, it is 5 mass % or more and 35 mass % or less. If the content rate of a coloring agent (A) is in said range, desired spectroscopy and color density can be obtained.

<Resin (B)>

Although resin (B) is not specifically limited, It is preferable that it is alkali-soluble resin, At least 1 type of monomer (a) (hereinafter referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acids. A copolymer having a structural unit derived from ) is more preferable.

The copolymer having a structural unit derived from (a) has a structure derived from a monomer (b) (hereinafter sometimes referred to as “(b)”) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. It is preferable that it is a copolymer which has at least 1 sort(s) selected from the group which consists of a unit and the structural unit which has an ethylenically unsaturated bond. The copolymer may further have other structural units.

As the other structural unit, a structural unit derived from the monomer (c) copolymerizable with (a) (however, (a) and (b) are different.) (hereinafter sometimes referred to as “(c)”) can be heard

Specific 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, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetra unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [ 2.2.1] Bicyclo unsaturated compounds containing a carboxy group, such as hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride;

Unsaturated mono [(meth)acryloyloxyalkyl] of polyvalent carbonic acid having a divalent or higher value, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] esters;

Unsaturated acrylates containing a hydroxyl group and a carboxy group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid, etc. are mentioned.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity and the solubility point to the aqueous alkali solution of resin obtained.

When a copolymer contains the structural unit derived from (a), it is preferable that the ratio is 1-50 mass % in 100 mass % of copolymers, More preferably, it is 5-30 mass %.

(b) has, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond polymerizable compound.

As for (b), the monomer which has a C2-C4 cyclic ether and a (meth)acryloyloxy group is preferable.

In addition, in this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations, such as "(meth)acryloyl" and "(meth)acrylate", also have the same meaning.

Examples of (b) include a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, and a monomer having a tetrahydropril group and an ethylenically unsaturated bond.

As (b), for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate , 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane, and tetrahydrofurpril (meth)acrylate are mentioned. .

As (b), it is preferable that it is a monomer which has an oxiranyl group and ethylenically unsaturated bond at the point which can make higher reliability, such as heat resistance and chemical-resistance of the color filter obtained.

When a copolymer contains the structural unit derived from (b), it is preferable that the ratio is 50-99 mass % in 100 mass % of copolymers, More preferably, it is 60-95 mass %.

As (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, as a common name, "dicyclopentanyl (meth) acrylate" It is also called "tricyclodecyl (meth)acrylate" in some cases.), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (common name in the technical field) as "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) (meth)acrylic acid esters such as acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

Hydroxyl group-containing (meth)acrylic acid esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo[2.2.1]hepto-2-ene, 5-hydroxymethylbicyclo[2.2.1]hepto-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hepto-2 -ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hepto-2-ene,5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hepto- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Bicyclo unsaturated compounds, such as hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the point of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth)acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo[2.2.1]hepto-2-ene are preferable.

When a copolymer contains the structural unit derived from (c), it is preferable that the ratio is 1-99 mass % in 100 mass % of copolymers.

The structural unit which has an ethylenically unsaturated bond, Preferably it is a structural unit which has a (meth)acryloyl group in a side chain. A resin having such a structural unit is obtained by adding a monomer having a group capable of reacting with the group of (a) or (b) and an ethylenically unsaturated bond to a polymer having a structural unit derived from (a) or (b). lose

As such a structural unit, the structural unit which added glycidyl (meth)acrylate to the (meth)acrylic acid unit, the structural unit which added 2-hydroxyethyl (meth)acrylate to the maleic anhydride unit, glycidyl (meth) ) a structural unit obtained by adding (meth)acrylic acid to an acrylate unit; and the like. Moreover, when these structural units have a hydroxyl group, the structural unit which further added carbonic anhydride is also mentioned as a structural unit which has an ethylenically unsaturated bond.

Specifically as resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/ Copolymers having structural units derived from (a) and (b) such as (meth)acrylic acid copolymers; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl dil (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer; 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyltoluene copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth) Copolymers having structural units derived from (a), (b) and (c) such as acrylic acid/styrene copolymer; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer , Benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; Resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer , Tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer with glycidyl (meth) acrylate added, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) ) A copolymer having a structural unit derived from (a) and (c), such as a resin obtained by adding glycidyl (meth) acrylate to an acrylic acid copolymer; tricyclodecyl (meth) acrylate/glycidyl (meth) ) Resin in which (meth)acrylic acid is reacted with a copolymer of acrylate, resin in which (meth)acrylic acid is reacted with a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate ( A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from b); a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate In addition to the resin in which (meth)acrylic acid was reacted with A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from (b), such as a resin reacted with lahydrophthalic anhydride, and further adding carbonic anhydride, etc. can be heard

The above-mentioned resin is, for example, the method described in the document "Experimental method of polymer synthesis" (Otsutakayuki Publishing House, Chemical Dongin Co., Ltd. 1st edition, 1st edition published March 1, 1972) and the cited literature described in the document. It can be prepared as a reference.

The resin (B) is preferably a copolymer having a structural unit derived from (a) and (b); a copolymer having a structural unit derived from (a), (b) and (c); and ( It is 1 type selected from the group which consists of a copolymer which has the structural unit derived from a) and (c), More preferably, the copolymer which has the structural unit derived from (a) and (b); And (a) ), a copolymer having a structural unit derived from (b) and (c); It is one selected from the group consisting of, and particularly preferably a copolymer having a structural unit derived from (a) and (b). .

The weight average molecular weight of resin (B) in terms of polystyrene becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When molecular weight exists in said range, when forming a coloring pattern, the residual film rate before and behind image development is high, the solubility with respect to the developing solution of an unexposed part is favorable, and there exists a tendency for the resolution of a coloring pattern to improve.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value (in terms of solid content) of resin (B) becomes like this. Preferably it is 40-170 mg-KOH/g, More preferably, it is 50-150 mg-KOH/g, More preferably, it is 60-135 mg-KOH/g. Here, an acid value is a value measured as the quantity (mg) of potassium hydroxide required to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

To [ content of resin (B) ] with respect to the total amount of solid content, Preferably it is 7-75 mass %, More preferably, it is 13-70 mass %, More preferably, it is 17-70 mass %, More preferably, it is 17 -65 mass %. When content of resin (B) exists in said range, a coloring pattern can be formed and there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, preferably Preferably, it is a (meth)acrylic acid ester compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxy Ethyl acrylate, N-vinylpyrrolidone, etc., and the above-mentioned (a), (b), and (c) are mentioned.

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tri Ethylene glycol di(meth)acrylate, the bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned.

Especially, it is preferable that a polymeric compound is a polymeric compound which has three or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate , propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa ( meth)acrylate etc. are mentioned, Especially, dipentaerythritol penta (meth)acrylate and dipentaerythritol hexa (meth)acrylate are preferable.

The weight average molecular weight of a polymeric compound (C) becomes like this. Preferably it is 150 or more and 2,900 or less, More preferably, they are 250 or more and 1,500 or less.

It is preferable that content of a polymeric compound (C) is 4-65 mass % with respect to the total amount of solid content, More preferably, it is 7-60 mass %, More preferably, it is 10-55 mass %.

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

When content of a polymeric compound (C) exists in said range, there exists a tendency for the residual-film rate at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

<Polymerization Initiator (D)>

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

As a polymerization initiator (D), an O-acyl oxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, an acylphosphine oxide compound, etc. are mentioned.

As the O-acyloxime compound, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) ) octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-a2-methyl-4-(3) ,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl｝-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2) -Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-3-cyclopentylpropan-1-one-2-imine, [11-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-11H-benzo[a]car bazol-8-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone oxime O-acetate etc. are mentioned. You may use commercial items, such as Irgacure (trademark) OXE01, OXE02 (above, BASF company make), and N-1919 (made by ADEKA company). Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl). Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine and [11-(2-ethylhexyl)- 5-(2,4,6-trimethylbenzoyl)-11H-benzo[a]carbazol-8-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone oxime At least one selected from the group consisting of O-acetate is preferable, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and [11-(2-ethylhexyl)- 5-(2,4,6-trimethylbenzoyl)-11H-benzo[a]carbazol-8-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone oxime At least 1 sort(s) chosen from the group which consists of O-acetate is more preferable.

As the O-acyl oxime compound, a compound represented by the following formula (d1) (hereinafter, sometimes referred to as “compound (d1)”) is preferable.

[Formula 65]

[In formula (d1),

R ^d1 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, a saturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, or even if it has a substituent A preferred aralkyl group having 7 to 33 carbon atoms is represented, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group or aralkyl group is -O-, -CO-, -S-, -SO ₂ - or -NR It may be substituted by ^{d5 -.}

In addition, in this specification, "aromatic hydrocarbon group" means the group which consists only of an aromatic ring moiety.

R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or a saturated hydrocarbon group having 1 to 10 carbon atoms.

R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.

R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, and the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group is, -O-, -CO-, or -S- may be substituted, and the methine group (-CH<) _{contained in the said aliphatic hydrocarbon group may be substituted by -PO 3} <, The hydrogen atom contained in the said aliphatic hydrocarbon group may be substituted with an OH group.

R ^d5 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be substituted with -O- or -CO-.]

It is preferable that carbon number of the aromatic hydrocarbon group represented by R ^d1 is 6-15, More preferably, it is 6-12, More preferably, it is 6-10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

Moreover ^{, the aromatic hydrocarbon group represented by R d1} may have 1 or 2 or more substituents. The substituent is preferably substituted at the α-position or the γ-position of the aromatic hydrocarbon group, and more preferably at the γ-position. Examples of the substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a butadecyl group, a pentadecyl group, and the like. A saturated hydrocarbon group having 1 to 15 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; and the like.

It is preferable that it is 1-10, and, as for carbon number of the saturated hydrocarbon group as said substituent, it is more preferable that it is 1-7. The saturated hydrocarbon group as the substituent may be any one of linear, branched, and cyclic, or may be a group in which a chain group and a cyclic group are combined. _{The methylene group (-CH 2} -) contained in the saturated hydrocarbon group as the substituent may be substituted with -O- or -S-. In addition, the hydrogen atom contained in the said saturated hydrocarbon group may be substituted with halogen atoms, such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and it is preferable that it is substituted with the fluorine atom. However, in the saturated hydrocarbon group as the substituent, adjacent methylene groups are not substituted at the same time, and a terminal methylene group is not substituted.

Examples of the substituent of the aromatic hydrocarbon group represented by R ^{d1 include groups represented by the following formula.} In the formula, * represents a bond.

[Formula 66]

[Formula 67]

^Examples of the aromatic hydrocarbon group which may have a substituent represented by R d1 include groups represented by the following formula. In the formula, * represents a bond.

[Formula 68]

[Formula 69]

As the ^{aromatic hydrocarbon group which may have a substituent represented by R d1} , a group represented by the following formula is preferable.

[Formula 70]

[In the formula, R ^d6 represents a saturated hydrocarbon group having 1 or more and 10 or less carbon atoms which may be substituted with a halogen atom, and the hydrogen atom contained in ^{R d6 may be substituted with a halogen atom.} m2 represents an integer of 1 to 5.]

Examples of the saturated hydrocarbon group represented by R ^d6 include the same groups as the saturated hydrocarbon group exemplified as a substituent of the aromatic hydrocarbon group represented by ^{R d1 .} It is preferable that it is 2 or more and 7 or less, and, as for carbon number of the saturated hydrocarbon group represented by R ^{d6, it is more preferable that it is 2 or more and 5 or less.} In addition, the saturated hydrocarbon group R ^d6, straight-chain, branched-chain, and may be any of the annular would, preferably a chain.

As good a halogen atom, and substituting the hydrogen atoms contained in R ^d6, there may be mentioned a fluorine atom, a chlorine atom, an iodine atom, a bromine atom, a fluorine atom is particularly preferred. Moreover, ^{it is preferable that 2 or more and 10 or less of the hydrogen atoms contained in R d6} are substituted with halogen atoms, and it is preferable that 3 or more and 6 or less are substituted with halogen atoms. The substitution position of the R ^d6 O- group is preferably an ortho position or a para position, and particularly preferably a para position.

Moreover, it is preferable that it is 1-2, and, as for m2, it is especially preferable that it is 1.

It is preferable that carbon number of the heterocyclic group represented by R ^d1 is 3-20, More preferably, it is 3-10, More preferably, it is 3-5. Examples of the heterocyclic group include a pyrrolyl group, a prill group, a thienyl group, an indolyl group, a benzopril group, and a carbazolyl group.

Moreover, ^{the heterocyclic group of R d1} may have 1 or 2 or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent which the aromatic hydrocarbon group of R ^{d1 may have.}

It is preferable that carbon number of the saturated hydrocarbon group represented by R ^{d1 is 1-12. Examples} of the saturated hydrocarbon group represented by R d1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a butadecyl group. , a pentadecyl group, and the like. These saturated hydrocarbon groups may be linear, branched, or cyclic, or may be a group in which a chain group and a cyclic group are combined. In addition, in ^{the saturated hydrocarbon group of R d1} , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 -, and the hydrogen atom is , OH group, or SH group may be substituted. However, in the said saturated hydrocarbon group, adjacent methylene groups are not substituted at the same time, and the methylene group of the terminal is not substituted.

R ^d5 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. The saturated hydrocarbon group may be linear (linear or branched) or cyclic, and may be linear, branched or cyclic, or may be a group in which a chain group and a cyclic group are combined. In addition, in ^{the saturated hydrocarbon group of R d5} , the methylene group (-CH ₂ -) may be substituted with -O- or -CO-. However, in the said saturated hydrocarbon group, adjacent methylene groups are not substituted at the same time, and the methylene group of the terminal is not substituted.

Specific examples of the saturated hydrocarbon group which may have a substituent represented by R ^{d1 include a group represented by the following formula.} * indicates a bond.

[Formula 71]

In addition, good aralkyl group which may have a substituent represented by R ^d1 is an aromatic hydrocarbon group that the group R ^d1 combining the alkanediyl group derived from a saturated hydrocarbon group represented by represented by R ^d1 is preferred. It is preferable that carbon number of the said aralkyl group is 7-33, More preferably, it is 7-18, More preferably, it is 7-12. Art are alkyl groups, may have a substituent at least one or two, there may be mentioned the art as the substituents, an aromatic hydrocarbon group represented by the R ^d1, and R ^d1, saturated hydrocarbon groups, even if the same group a group exemplified as the substituents have shown by. The group combining a divalent group derived from an aromatic hydrocarbon group, saturated hydrocarbon group represented by wherein R ^d1 is induced in the art R ^d1, and specifically there may be mentioned groups represented by the following formula. In the formula, * represents a bond. The methylene group (-CH ₂ -) contained in the aralkyl group may be substituted with -O-, -CO-, -S-, -SO ₂ - or -N(R ^{d5 )-.} However, in the said aralkyl group, adjacent methylene groups are not substituted at the same time, and the methylene group of the terminal is not substituted.

[Formula 72]

Among these, as R ^d1 , an aromatic hydrocarbon group which may have a substituent or a saturated hydrocarbon group which may have a substituent is preferable, and an aromatic hydrocarbon group which may have a substituent is more preferable.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d2 is, 6 to 15, it is preferable, and more preferably from 6-12, more preferably 6-10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

The number of carbon atoms of the heterocyclic group represented by R ^d2, is 3 to 20 and is, more preferably from 3-10, more preferably 3-5. Examples of the heterocyclic group include a pyrrolyl group, a prill group, a thienyl group, an indolyl group, a benzopril group, and a carbazolyl group.

It is preferable that carbon number of the saturated hydrocarbon group represented by R ^d2 is 1-7, More preferably, it is 1-5, Especially preferably, it is 1-3. Examples of the saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The saturated hydrocarbon group may be linear, branched, or cyclic, or may be a group in which a chain group and a cyclic group are combined.

Among them, R ^d2 is preferably a chain saturated hydrocarbon group, more preferably a chain saturated hydrocarbon group having 1 to 5 carbon atoms, still more preferably a chain saturated hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a methyl group. .

It is preferable that carbon number of the aromatic hydrocarbon group represented by R ^d3 is 6-15, More preferably, it is 6-12, More preferably, it is 6-10. As said aromatic hydrocarbon group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group etc. are mentioned, for example, A phenyl group and a naphthyl group are more preferable.

In addition, ^{the aromatic hydrocarbon group represented by R d3} may have 1 or 2 or more substituents. The substituent is preferably substituted at the α-position or the γ-position of the aromatic hydrocarbon group. As the substituent, an aliphatic hydrocarbon group having 1 to 15 carbon atoms is preferable, and specifically, a C1 group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. to 15 alkyl groups; alkenyl groups having 1 to 15 carbon atoms such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl and decenyl; and the like.

As for carbon number of the aliphatic hydrocarbon group as said substituent, it is more preferable that it is 1-7. The aliphatic hydrocarbon group as the substituent may be any of linear, branched, and cyclic, or may be a group in which a chain group and a cyclic group are combined. In addition, in the aliphatic hydrocarbon group as the substituent, the methylene group (-CH ₂ -) may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) is -N< It may be substituted. However, in the aliphatic hydrocarbon group as the substituent, adjacent methylene groups are not substituted at the same time, and methylene groups at the terminals are not substituted.

As ^{an aliphatic hydrocarbon group as a substituent of the aromatic hydrocarbon group represented by Rd3} , the group etc. which are represented by a following formula are mentioned, for example. In the formula, * represents a bond.

[Formula 73]

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^{d3 include groups represented by the following formula.} In the formula, * represents a bond.

[Formula 74]

It is preferable that carbon number of the heterocyclic group represented by R ^d3 is 3-20, More preferably, it is 3-10, More preferably, it is 3-5. Examples of the heterocyclic group include a pyrrolyl group, a prill group, a thienyl group, an indolyl group, a benzopril group, and a carbazole group.

The ^{heterocyclic group represented by R d3} may have one or two or more substituents, and examples of the substituent include the same groups as the substituents that the aromatic hydrocarbon group represented by ^{R d1 may have.}

Among them, R ^d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), the number of substituents is 2 or more, It is preferable that there are 5 or less.

It is preferable that carbon number of the aromatic hydrocarbon group represented by R ^d4 is 6-15, More preferably, it is 6-12, More preferably, it is 6-10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

Moreover ^{, the aromatic hydrocarbon group represented by R d4} may have 1 or 2 or more substituents. Examples of the substituent include the same groups as the substituents that the aromatic hydrocarbon group of ^{R d1 may have.}

It is preferable that carbon number of the aliphatic hydrocarbon group represented by R ^d4 is 1-13, More preferably, it is 2-10, More preferably, it is 4-9. ^Examples of the aliphatic hydrocarbon group for R d4 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a butadecyl group, Alkyl groups such as pentadecyl group; ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetra Alkenyl groups, such as a decenyl group and a pentadecenyl group; etc. are mentioned. These aliphatic hydrocarbon groups may be linear (linear or branched), cyclic, or a combination of a chain group and a cyclic group. In addition, in the aliphatic hydrocarbon group represented by ^{R d4} _{, the methylene group (-CH 2} -) may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) is -PO3< may be substituted for The hydrogen atom contained in the said aliphatic hydrocarbon group may be substituted by the OH group. However, in the said aliphatic hydrocarbon group, adjacent methylene groups are not substituted at the same time, and the methylene group of the terminal is not substituted.

Examples of the aliphatic hydrocarbon group which may have a substituent represented by R ^{d4 include groups represented by the following formula.} In the formula, * represents a bond.

[Formula 75]

R ^d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and still more preferably a branched chain alkyl group having no substituent.

As a compound (d1), as shown to following Tables 1-7, the compounds (d1-1) - (d1-67) represented by a formula (d1) are mentioned. In the table, * represents a bond.

[Formula 76]

Among them, compounds (d1-3) to (d1-6), (d1-18) to (d1-52), (d1-55), (d1-56), (d1-60), (d1-61) ) is preferred, more preferably compounds (d1-3) to (d1-6), (d1-18) to (d1-41), and still more preferably compounds (d1-24) and (d1-36). ) to (d1-40), and particularly preferably a compound (d1-24).

It is preferable that the content rate of the polymerization initiator represented by Formula (d1) is 50 mass % or more in 100 mass % of polymerization initiators (D), More preferably, it is 70 mass % or more, More preferably, it is 90 mass % or more, Especially preferably Preferably, it is 95 mass % or more.

As the alkylphenone compound, for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2 -Benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy -2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, an oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. You may use commercial items, such as Irgacure (trademark) 369, 907, 379 (above, BASF Corporation make).

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4'5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open Nos. 6-75372 and 6-75373, etc.), 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra (alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (For example, see Japanese Patent Application Laid-Open No. 48-38403, Japanese Unexamined Patent Publication No. 62-174204, etc.). ), an imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2) -yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin. Benzoin compounds such as isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4, Benzophenone compounds such as 4'-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; Quinones such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone Compound; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, a titanocene compound, etc. are mentioned.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound. , More preferably, it is a polymerization initiator containing an O-acyl oxime compound.

To [ content of a polymerization initiator (D) / 100 mass parts of total amounts of resin (B) and a polymeric compound (C)), Preferably it is 0.1-40 mass parts, More preferably, it is 1-30 mass parts.

The blue curable resin composition of this invention may also contain a solvent (E), a leveling agent (F), etc. further.

<Solvent (E)>

The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvent (solvent containing -COO- in a molecule|numerator and not containing -O-), ether solvent (solvent containing -O- in a molecule|numerator and not containing -COO-), ether ester Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (containing OH in the molecule, - solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl lactate, ethyl lactate, butyl lactate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methylanisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and methyl 3-ethoxypropionate. , 3-ethyl ethoxypropionate, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate propyl, 2-ethoxypropionate methyl, 2-ethoxypropionate ethyl, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono and propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo Pentanone, cyclohexanone, isophorone, etc. are mentioned.

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

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned.

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

These solvents may be used independently or may use 2 or more types together.

Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methyl Pyrrolidone etc. are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1 -Butanol, ethyl 3-ethoxypropionate, and N-methylpyrrolidone are more preferable.

To [ content of a solvent (E) / total amount of blue curable resin composition ], Preferably it is 50-95 mass %, More preferably, it is 55-92 mass %. In other words, solid content of blue curable resin composition becomes like this. Preferably it is 5-50 mass %, More preferably, it is 8-45 mass %. When content of a solvent (E) exists in the said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

<Leveling agent (F)>

The blue curable resin composition of this invention may also contain a leveling agent (F). As a leveling agent (F), a silicone type surfactant, the silicone type surfactant etc. which have a silicone type surfactant, a fluorine type surfactant, and a fluorine atom are mentioned. These may have a polymerizable group in a side chain. As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326 , KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Joint Stock Company). .

As a fluorochemical surfactant, the surfactant etc. which have a fluorocarbon chain|strand in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, East FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafax (registered trademark) F142D, Dong F171, Dong F172, Dong F173, Dong F177, Dong F183, Dong F554, Dong R30, RS-718-K (manufactured by DIC Co., Ltd.), FTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electric Chemical Co., Ltd.), SURFRON (registered trademark) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Refining Chemical Research Institute), and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megafax (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

When containing a leveling agent (F), the content becomes like this with respect to the total amount of blue curable resin composition. Preferably they are 0.001 mass % or more and 0.7 mass % or less, More preferably, they are 0.002 mass % or more and 0.5 mass % or less, further Preferably it is 0.005 mass % or more and 0.3 mass % or less. When content of a leveling agent (F) exists in the said range, the flatness of a color filter can be made favorable.

<Other ingredients>

The blue curable resin composition of the present invention may contain additives known in the art, such as polymerization initiation aids, fillers, other high molecular compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.

<The manufacturing method of blue curable resin composition>

The blue curable resin composition of this invention is, for example, a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D), and the solvent (E) used as needed, a leveling agent ( It can prepare by mixing F) and other components.

The blue pigment (A2-2) and the pigment (A3-2) used as needed are mixed with a part or all of a solvent (E) beforehand, and the average particle diameter of a pigment becomes about 0.2 micrometer or less, It is preferable to disperse|distribute using a mill etc. At this time, you may mix|blend a part or all of a pigment dispersant and resin (B) as needed.

The target blue curable resin composition can be prepared by mixing the remaining component with the pigment dispersion liquid obtained in this way so that it may become predetermined density|concentration.

The compound (IB) is preferably dissolved in a part or all of the solvent (E) in advance to prepare a solution. It is preferable to filter the said solution with a filter with a pore diameter of about 0.01-1 micrometer.

It is preferable to filter the blue curable resin composition after mixing with the filter of about 0.01-10 micrometers in pore diameter.

<The manufacturing method of a color filter>

As a method of manufacturing a colored pattern from the blue curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithography method is a method of apply|coating the said blue curable resin composition to a board|substrate, drying it, forming a coloring composition layer, exposing the said coloring composition layer through a photomask, and developing. The photolithographic method WHEREIN: The colored coating film which is hardened|cured material of the said coloring composition layer can be formed by not using a photomask at the time of exposure and/or not developing. The colored pattern and colored coating film thus formed can be used as the color filter of the present invention.

The film thickness of the color filter to produce is not specifically limited, According to the objective, a use, etc., it can adjust suitably, For example, 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

Examples of the substrate include a glass plate such as quartz glass, boric acid glass, alumina silicate glass, and soda lime glass coated with silica, a resin plate such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and aluminum on the substrate. , silver, silver/copper/palladium alloy thin films, etc. are used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

Formation of each color pixel by the photolithographic method can be performed with a well-known or customary apparatus and conditions. For example, it can be produced as follows.

First, a blue curable resin composition is apply|coated on a board|substrate, volatile components, such as a solvent, are removed and dried by heat-drying (pre-baking) and/or drying under reduced pressure, and a smooth coloring composition layer is obtained.

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

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that they are 10 second - 60 minutes, and it is more preferable that they are 30 second - 30 minutes.

When drying under reduced pressure, it is preferable to carry out under a pressure of 50 to 150 Pa at a temperature range of 20 to 25°C.

The film thickness of a coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the color filter made into the objective.

Next, the coloring composition layer is exposed through the photomask for forming the objective coloring pattern. The pattern on the said photomask is not specifically limited, The pattern according to the intended use is used.

As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250-450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, or 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges, good to do Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, since parallel light rays can be uniformly irradiated to the whole exposure surface or precise alignment of a photomask and the board|substrate with a coloring composition layer can be performed.

A coloring pattern is formed on a board|substrate by making a developing solution contact and developing the coloring composition layer after exposure. By image development, the unexposed part of a coloring composition layer melt|dissolves in a developing solution, and is removed. As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Furthermore, the developing solution may contain surfactant.

The developing method may be any of a paddle method, a dipping method, and a spray method. In addition, you may incline a board|substrate at an arbitrary angle at the time of development. After image development, it is preferable to wash with water.

Moreover, it is preferable to post-baking to the obtained coloring pattern. 150-250 degreeC is preferable and, as for post-baking temperature, 160-235 degreeC is more preferable. 1 to 120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

ADVANTAGE OF THE INVENTION According to the blue curable resin composition of this invention, the color filter excellent in brightness can be formed. The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not inherently limited by the following examples, and is carried out with appropriate changes within the range that can be suitable for the gist of the preceding and latter period. It is of course also possible, and they are all included in the technical scope of the present invention. In the examples, % and parts indicating the content or the amount used are based on mass unless otherwise specified.

In the following examples, the structure of the compound was confirmed by mass spectrometry (LC; 1200 manufactured by Agilent, MASS; LC/MSD manufactured by Agilent).

[Synthesis Example 1]

40.6 parts of compound (VI) and 8 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as compound (III) are mixed in the presence of 50 parts of 1-methyl-2-pyrrolidone under light-shielding conditions, at 30°C It stirred for 3 hours. The resulting reaction solution was cooled to room temperature, added to a mixed solution of 400 parts of water and 20 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were obtained as a residue of suction filtration and then dried to obtain 44 parts of a compound represented by the formula (I-1-A).

[Formula 77]

Next, 44 parts of a compound represented by formula (I-1-A) and 21.4 parts of trimethoxy[3-(methylamino)propyl]silane (manufactured by Tokyo Chemical Industry Co., Ltd.) 1-methyl-2-pyrrolidone In the presence of 50 parts, it heated at 100 degreeC for 5 hours. After cooling the obtained reaction liquid to room temperature, it filtered, wash|cleaned with 100 parts of water, the obtained crystal|crystallization was dried, and 52 parts of compounds represented by Formula (I-1) were obtained.

[Formula 78]

Identification of the compound represented by formula (I-1)

(Mass spectrometry) Ionization mode = ESI + : m/z = [M + H] ⁺ 599.2

Exact　Mass：　598.1

0.35 g of the compound represented by formula (I-1) was dissolved in chloroform to make a volume of 250 cm 3 , 2 cm 3 of which was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g/L), and spectroscopy The absorption spectrum was measured using a photometer (quartz cell, optical path length; 1 cm). The maximum absorption wavelength λ _max of this compound was 546 nm.

[Synthesis of resin]

An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, replaced with a nitrogen atmosphere, 280 parts by weight of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 80° C. while stirring. Next, 38 parts by weight of ^{acrylic acid, 289 parts by weight of a mixture of 3,4-epoxytricyclo[5.2.1.0 2,6} ]decane-8 or/and 9-yl acrylate, and 125 parts by weight of propylene glycol monomethyl ether acetate are mixed. The solution was dripped over 5 hours. On the other hand, the mixed solution which melt|dissolved 33 weight part of 2, 2- azobis (2, 4- dimethylvaleronitrile) in 235 weight part of propylene glycol monomethyl ether acetate was dripped over 6 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin B-1) having a B-type viscosity (23) of 125 mPas, a solid content of 37.0 wt%, and a solution acid value of 27 mg-KOH/g. The weight average molecular weight Mw of the produced|generated copolymer was 9200, and the dispersion degree was 2.08.

[Formula 79]

About the measurement of the polystyrene conversion weight average molecular weight Mw and number average molecular weight Mn of resin obtained by said synthesis example, it performed on condition of the following using GPC method.

Apparatus 　　　　　　; HLC-8120 GPC (manufactured by Toso Co., Ltd.)

Column　　　　　；TSK-GELG2000HXL

Column temperature　　　; 40℃

Solvent　　　　　　；THF

Flow rate　　　　　　; 1.0mL/min

Test solution solid content concentration; 0.001 to 0.01 mass%

Injection volume　　　　　; 50μL

Detector　　　　　；RI

Standard material for calibration　；TSK　STANDARD　POLYSTYRENE

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

(manufactured by Toso Co., Ltd.)

Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution.

[Preparation of blue curable resin composition]

Each component was mixed so that it might become a composition shown in Table 8, and the blue curable resin composition was obtained.

In Table 8, each component shows the following.

(A) Colorant: A-1: C.I. Pigment Blue 15: 6 (pigment) 12.0 parts, acrylic pigment dispersant 2.0 parts, and propylene glycol monomethyl ether acetate 80.5 parts were mixed and dispersed in advance.

(A) Colorant: A-2: The solution which mixed 5.0 parts of compound represented by Formula (I-1), and 89.9 parts of propylene glycol monomethyl ether acetate

[Formula 80]

(A) Colorant: A-3: The solution which mixed 7.2 parts of dye (A-3) (mixture of the compound represented by Formula (A3-1) - Formula (A3-8)) and 92.7 parts of propylene glycol monomethyl ether acetate

[Formula 81]

(B) Resin: B-1: Resin B-1 solution

(C) Polymerizable compound: C-1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.; KAYARAD (registered trademark) DPHA)

(D) Polymerization initiator: D-1: following formula

[Formula 82]

compound represented by

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

(F) Leveling agent: F-1: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Formation of 50 μm square hole pattern]

After apply|coating blue curable resin composition by the spin coating method on the glass substrate (Eagle XG; Corning company make) of 2 inches edge, it prebaked at 100 degreeC for 3 minute(s). After cooling, with respect to the board|substrate to which this blue curable resin composition was apply|coated, through the mask pattern in which the 5 micrometers square hole was arranged, using the exposure machine (TME-150RSK; Topcon Co., Ltd. product), in atmospheric atmosphere, 80 mJ/cm<2> It was irradiated with light at an exposure dose (based on 365 nm). After exposure, development was performed for 23 to 60 seconds using a developer, followed by rinsing with running water for 20 seconds, followed by spray drying. Then, it post-baked at 230 degreeC for 30 minute(s), and formed the 50 micrometers square hole pattern on the glass substrate.

[Film thickness measurement]

About the obtained pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). A result is shown in Table 9.

[Chromaticity evaluation]

About the pattern on the obtained glass substrate, the spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd. product), and the xy chromaticity coordinate (x) in the XYZ color system of CIE using the chromaticity function of the C light source. , y) were measured. A result is shown in Table 9. From the chromaticity coordinates, it was confirmed that the color of the pattern on the obtained glass substrate was blue.

When the chromaticity was matched, the pattern formed from the colored curable resin composition containing the colorants (A-1) and (A-2) had a large Y and excellent brightness compared to the pattern formed from the colored curable resin composition of the comparative example. .

[Industrial Applicability]

ADVANTAGE OF THE INVENTION According to the blue curable resin composition of this invention, the color filter excellent in brightness can be formed. The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Claims (7)

A dye containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) has a maximum absorption wavelength in chloroform of 500 nm to 600 nm and has a silicon atom ( A1) and a blue colorant,
The blue curable resin composition whose mass ratio (dye (A1)/blue coloring agent) of content of the said dye (A1) with respect to content of the said blue coloring agent is 0.01 or more and 2 or less. According to claim 1,
Blue curable resin composition in which the said polymerization initiator (D) contains the polymerization initiator represented by following formula (d1).
[Formula 1]

[in formula (d1),
R ^d1 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, a saturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, or even if it has a substituent A preferred aralkyl group having 7 to 33 carbon atoms is represented, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group or aralkyl group is -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 - may be substituted.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or a saturated hydrocarbon group having 1 to 10 carbon atoms.
R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.
R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, and the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group is, -O-, -CO- or -S- may be substituted, the methine group (-CH<) _{contained in the said aliphatic hydrocarbon group may be substituted by -PO 3} <, and the hydrogen atom contained in the said aliphatic hydrocarbon group is It may be substituted with OH group.
R ^d5 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be substituted with -O- or -CO-.] According to claim 1,
Blue curable resin composition whose content rate of the said coloring agent (A) is 3 mass % or more and 60 mass % or less with respect to the total amount of solid content of blue curable resin composition. According to claim 1,
The blue curable resin composition in which the said blue coloring agent is a blue phthalocyanine pigment. delete The color filter formed from the blue curable resin composition in any one of Claims 1-4. A display device comprising the color filter according to claim 6 .