KR102173711B1 - The compound, colored curable resin composition - Google Patents

Abstract

According to the colored curable resin composition containing the compound of the present invention, a color filter and a display device having good heat resistance can be provided.

Description

Compound and colored curable resin composition {THE COMPOUND, COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a compound and a colored curable resin composition.

Dyes are used for color display using reflected light or transmitted light, for example, in fields such as fiber materials, liquid crystal displays, and ink jets. As such a dye, for example, rhodamine B represented by the following formula (Rb) as a compound having a xanthene skeleton is widely known (Non-Patent Document 1).

[Formula 1]

(Non-Patent Document 1) 「New Dye Chemistry」 by Yutaka Hosoda, Kibodang Co., Ltd., 1st edition, May 1973, p.274

The conventionally known colored curable resin composition containing the above compound has not been sufficiently satisfactory in terms of heat resistance.

Accordingly, an object of the present invention is to provide a colored curable resin composition containing the above compound and excellent in heat resistance.

To achieve the above object,

The present invention provides a compound represented by formula (I).

[Formula 2]

[In formula (I),

R ¹ is an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent 3-20 alicyclic saturated hydrocarbon groups are shown, and -CH ₂ -contained in the said alkyl group may be substituted with -O-, -CO-, or -NR ¹¹ -. However, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O-, -CO-, or -NR ¹¹ -.

R ³ and R ⁴ are each independently a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a 2 to 20 carbon number which may have a substituent. Represents an unsaturated hydrocarbon group or an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and -CH ₂ -contained in the alkyl group may be substituted with -O-, -CO-, or -NR ¹¹ -. . However, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O-, -CO-, or -NR ¹¹ -.

R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ⁷ is a hydrogen ^{_{atom, -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 ^{8 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10, -SO 3 It represents R ¹⁰ or -SO ₂ NR ¹¹ R ¹² .

m represents an integer of 0 to 4, and when m is 2 or more, a plurality of R ⁸ may be the same or different, respectively.

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

R ¹⁰ represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom.

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

R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms. A plurality of R ¹³ may be the same or different, respectively.

X represents a halogen atom.

a represents the integer of 0 or 1.]

Further, the present invention provides a colored curable resin composition comprising the compound of the present invention, a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

In addition, the present invention provides a color filter formed of the colored curable resin composition of the present invention.

In addition, the present invention provides a display device including the color filter of the present invention.

The color filter formed from the colored curable resin composition containing the compound of the present invention has good heat resistance.

The compound of the present invention is a compound represented by formula (I) (hereinafter also referred to as "compound (I)"). The tautomer is also contained in the compound of this invention.

Each component and group illustrated below can be used alone or in combination.

<Compound (I)>

[Formula 3]

[In formula (I), R ¹ is an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an unsaturated hydrocarbon having 2 to 20 carbon atoms which may have a substituent A group or a saturated alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent is represented, and -CH ₂ -contained in the alkyl group may be substituted with -O-, -CO-, or -NR ¹¹ -. However, adjacent -CH ₂ -is not simultaneously substituted with -O-, -CO- or -NR ¹¹ -, and the terminal -CH ₂ -is substituted with -O-, -CO- or -NR ¹¹ -. No work.

R ³ and R ⁴ are each independently a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a 2 to 20 carbon number which may have a substituent. An unsaturated hydrocarbon group or an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms which may have a substituent is represented, and -CH ₂ -contained in the alkyl group may be substituted with -O-, -CO-, or -NR ¹¹ -. However, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O-, -CO-, or -NR ¹¹ -.

R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ⁷ is a hydrogen ^{_{atom, -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 ^{8 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10, -SO 3 It represents R ¹⁰ or -SO ₂ NR ¹¹ R ¹² .

m represents an integer of 0 to 4, and when m is 2 or more, a plurality of R ⁸ may be the same or different, respectively.

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

R ¹⁰ represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom.

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

R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms. A plurality of R ¹³ may be the same or different, respectively.

X represents a halogen atom.

a represents the integer of 0 or 1.]

In Formula (I), when -SO ₃ ^- is present, the number is 1.

Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R ¹ , R ³ and R ⁴ include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group, isopropylphenyl group, tert-butylphenyl group, sec-butyl group, pentylphenyl group , Hexylphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, benzopyrenyl group, and the like, and a phenyl group, a toluyl group, and a xylyl group are preferable. It is preferable that it is 6-20, and, as for the carbon number of the aromatic hydrocarbon group represented by R ³ and R ⁴ , it is more preferable that it is 6-10.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ³ and R ⁴ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-oxy group. Linear alkyl groups such as a yl group, n-nonyl group, and n-decyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group, etc. And a branched chain alkyl group, and a linear alkyl group is preferable. It is preferable that it is 1-10, and, as for the carbon number of the alkyl group represented by R ¹ , R ³ and R ⁴ , it is more preferable that it is 1-8.

Examples of the unsaturated hydrocarbon group having 2 to 20 carbon atoms represented by R ¹ , R ³ and R ⁴ include vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 2-methyl-1-propenyl group, 1- Butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 1-hexenyl group, linear or branched alkenyl group having 2 to 20 carbon atoms; ethynyl group, propargyl group, 2-butynyl group, 3 C2-C20 linear or branched alkynyl groups, such as -butynyl group, 1-pentynyl group, and 1-hexynyl group, are mentioned. The number of carbon atoms of the unsaturated hydrocarbon group represented by R ¹ , R ³ and R ⁴ is preferably 2 to 10, and more preferably 2 to 8.

-CH ₂ -contained in the C1-C20 alkyl group represented by R ¹ , R ³ and R ⁴ may be substituted with -O-, -CO-, or -NR ¹¹ -, preferably -O- It may be substituted. However, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O-, -CO-, or -NR ¹¹ -. In addition, when -CH ₂ -contained in the alkyl group is substituted with -O-, -CO-, or -NR ¹¹ -, it is preferable that the hydrogen atom contained in the alkyl group is substituted with a hydroxy group as a substituent. Do. The preferable number of carbon atoms of the alkyl group in which the methylene group may be substituted with -O-, -CO- or -NR ¹¹ -is 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6. As the alkyl group in which the methylene group may be substituted with -O-, -CO-, or -NR ¹¹ -, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.

In addition, the methylene groups -O-, -CO- or -NR ¹¹ - when it is substituted by, an end with -O-, -CO- or -NR ¹¹ - between, or -O-, -CO- or -NR ¹¹ - As for the number of carbon atoms between and oxygen atom or -CO-, 1-4 are preferable, and 2-3 are more preferable.

As an alkyl group which -CH ₂ -may be substituted with -O-, -CO-, or -NR ¹¹ -, a group represented by the following formula is mentioned. In the formula, * represents a bond hand.

[Formula 4]

Examples of the saturated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ¹ , R ³ and R ⁴ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group. have.

Examples of the substituent which may be substituted for the aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R ¹ include halogen atoms such as fluorine atom, chlorine atom and bromine atom; fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloro A halogenated alkyl group having 1 to 12 carbon atoms such as a methyl group; a mercapto group: a hydroxy group; a cyano group; a nitro group; and a group containing a silicon atom.

In addition, examples of the substituent which may be substituted with a C1-C20 alkyl group, a C2-C20 unsaturated hydrocarbon group, or a C3-C20 alicyclic saturated hydrocarbon group represented by R ¹ include halogens such as fluorine atom, chlorine atom and bromine atom Atom; mercapto group: hydroxyl group; cyano group; nitro group; aromatic hydrocarbon group having 6 to 10 carbon atoms, and groups containing silicon atoms; halogen atom, hydroxy group, and aromatic having 6 to 10 carbon atoms A hydrocarbon group is preferred, and a hydroxy group is particularly preferred.

As the aromatic hydrocarbon group having 6 to 10 carbon atoms, among the groups exemplified as the aromatic hydrocarbon group represented by R ¹ , a group having 6 to 10 carbon atoms is exemplified.

The group containing a silicon atom means a group containing a silicon atom as a constituent element of the group. The number of carbon atoms of the group containing a silicon atom is usually 1 to 30, and preferably 1 to 20. As a group containing a silicon atom, a group represented by formula (Z1) is preferable.

[Formula 5]

[In the formula, R ^21A represents a single bond or an alkanediyl group having 1 to 14 carbon atoms, and -CH ₂ -contained in the alkanediyl group is -O-, -CO-, -NR ²² -, -OCO -, -COO-, -OCONH-, -CONH-, or -NHCO- may be substituted, and the hydrogen atom contained in the said alkanediyl group may be substituted with a hydroxy group.

R ²² represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ^22A , R ^23A, and R ^24A each independently represent a hydrogen atom, a hydroxy group, a saturated hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

* Represents a bonding hand.]

Examples of the alkanediyl group having 1 to 14 carbon atoms represented by R ^21A include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonan-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-di Diary, linear alkanediyl group such as dodecane-1,12-diyl group; ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2, 2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methyl And branched alkanediyl groups such as butane-1,4-diyl groups, and a linear alkanediyl group is preferable.

The number of carbon atoms of the alkanediyl group represented by R ^21A is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4.

-CH ₂ -contained in the alkanediyl group represented by R ^21A is substituted with -O-, -CO-, -NR ²² -, -OCO-, -COO-, -OCONH-, -CONH-, or -NHCO- It may be substituted, preferably -OCO-, -COO-, or -OCONH-. However, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is -O-, -CO-, -NR ²² -, -OCO-, -COO-, -OCONH- , -CONH- or -NHCO- is not substituted.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ²² include a linear or branched alkyl group exemplified as an alkyl group represented by R ¹ and a group exemplified as an alicyclic saturated hydrocarbon group represented by R ¹ . A chain alkyl group is preferred.

The number of carbon atoms in the saturated hydrocarbon group represented by R ²² is preferably 1 to 12, more preferably 1 to 8, and still more preferably 1 to 6.

Examples of the saturated hydrocarbon group having 1 to 4 carbon atoms represented by R ^22A , R ^23A and R ^24A include linear alkyl groups such as methyl group, ethyl group, n-propyl group and n-butyl group; isopropyl group, sec-butyl group, tert- Branched chain alkyl groups, such as a butyl group; Alicyclic saturated hydrocarbon groups, such as a cyclopropyl group and a cyclobutyl group, etc. are mentioned.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^22A , R ^23A and R ^24A include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and tert-butoxy group. I can.

It is preferable that all of R ^22A , R ^23A, and R ^24A are the same group.

It is preferable that R ^22A , R ^23A and R ^24A are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

As a group containing a silicon atom, the group shown below is mentioned.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

As a group in which -CH ₂ contained in the alkanediyl group represented by R ^21A is substituted with -O-, the groups shown below are exemplified (* indicates a bond).

[Formula 11]

As a group in which -CH ₂ -contained in the alkanediyl group represented by R ^21A is substituted with -CO-, the groups shown below are exemplified (* indicates a bond).

[Formula 12]

[Formula 13]

As a group in which -CH ₂ -contained in the alkanediyl group represented by R ^21A is substituted with -NR ¹² -, groups represented below are exemplified (* indicates a bond).

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

As a group in which -CH ₂ -contained in the alkanediyl group represented by R ^21A is substituted with -OCO-, the groups shown below are exemplified (* indicates a bond).

[Formula 18]

[Formula 19]

As a group in which -CH ₂ -contained in the alkanediyl group represented by R ^21A is substituted with -COO-, the groups shown below are exemplified (* indicates a bond).

[Formula 20]

[Formula 21]

As a group in which -CH ₂ -contained in the alkanediyl group represented by R ^21A is substituted with -OCONH-, the groups shown below are exemplified (* indicates a bond).

[Formula 22]

[Formula 23]

As a group in which -CH ₂ -contained in the alkanediyl group represented by R ^21A is substituted with -CONH-, the groups shown below are exemplified (* indicates a bond).

[Formula 24]

[Formula 25]

As a group in which -CH ₂ -contained in the alkanediyl group represented by R ^21A is substituted with -NHCO-, the groups shown below are exemplified (* indicates a bond).

[Formula 26]

[Formula 27]

As a group in which the alkanediyl group represented by R ^21A may be substituted with a hydroxy group, the groups represented below are exemplified (* indicates a bond).

[Formula 28]

As a group containing a silicon atom, a group represented by the following formula is preferable.

[Chemical Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

Among them, R ¹ is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the substituent which may be substituted with the C6-C30 aromatic hydrocarbon group represented by R ³ and R ⁴ include a halogen atom, a halogenated alkyl group having 1 to 12 carbon atoms, -OH, -OR ¹⁰ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ¹⁰ , -SH, -SR ¹⁰ , -SO ₂ R ¹⁰ , -SO ₃ R ¹⁰ , -SO ₂ NR ¹¹ R ¹² , -CN, -NO ₂ and a group containing a silicon atom, and a halogen atom, a halogenated alkyl group, -SH, -OH, -CN, -NO ₂ and a group containing a silicon atom are preferable.

As a substituent which may substitute a C1-C20 alkyl group, a C2-C20 unsaturated hydrocarbon group, or a C3-C20 alicyclic saturated hydrocarbon group represented by R ³ and R ⁴ , a halogen atom, -OH, -OR ¹⁰ , _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z +, -CO 2 H, -CO 2 R 10, -SH, -SR 10, -SO 2 R 10, -SO 3 R 10, -SO 2 NR ¹¹ R ¹² , -CN, -NO ₂ and a group containing a silicon atom are mentioned, and a group containing a halogen atom, -SH, -OH, -CN, -NO ₂ and a silicon atom is preferable.

Further, as _{^{-SO 2 NR 11 R 12, -SO}} 2 NHR 10 are preferred.

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

Examples of the halogenated alkyl group having 1 to 12 carbon atoms include the same groups as those illustrated as the halogenated alkyl group which may be substituted with the aromatic hydrocarbon group represented by R ¹ . As the group containing the silicon atom, the same group as the group exemplified as the group containing a silicon atom which may be substituted for the aromatic hydrocarbon group represented by R ¹ is mentioned.

As R ³ and R ⁴ , a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent is preferable, and a hydrogen atom, an ethyl group, a propyl group or the following formula It is preferable that the group appears,

[Formula 34]

It is more preferable that it is a methyl group, an ethyl group, a propyl group, or a group represented by the following formula.

[Formula 35]

One of R ³ and R ⁴ is an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, and the other is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent, or both of R ³ and R ⁴ It is preferable that it is a C1-C20 alkyl group which may have a substituent.

In the compound represented by formula (I), at least one of R ¹ , R ³ and R ⁴ may be a group containing a silicon atom. In addition, when either one of R ³ and R ⁴ is a group containing a silicon atom, the other is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁵ and R ⁶ include a group having 1 to 6 carbon atoms among linear or branched chain alkyl groups exemplified as the alkyl group represented by R ¹ . Especially, as R ⁵ and R ⁶ , a hydrogen atom is preferable.

R ⁷ is a hydrogen ^{_{atom, -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, and it is preferably a hydrogen atom, -SO ₃ ^- or -SO ₃ H, and more preferably -SO ₃ ^- or -SO ₃ H.

R ^{8 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10, -SO 3 It represents R ¹⁰ or -SO ₂ NR ¹¹ R ¹² , and is preferably -SO ₃ ^- or -SO ₃ H.

The R ^10, R ^11, R ^12, and as the saturated hydrocarbon group represented by R ^13, R ¹ a linear or branched chain alkyl group exemplified as the alkyl group represented by, and the same groups exemplified groups as alicyclic saturated hydrocarbon groups represented by R ¹ May be used, and it is preferably a linear or branched alkyl group. Further, the number of carbon atoms in the saturated hydrocarbon group represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is preferably 1 to 12, more preferably 1 to 8, and still more preferably 1 to 6.

The hydrogen atom contained in the saturated hydrocarbon group for R ¹¹ and R ¹² may be substituted with, for example, a hydroxy group or a halogen atom as a substituent.

Examples of -OR ¹⁰ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group, etc. Can be mentioned.

Examples of -CO ₂ R ¹⁰ include alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group. .

-SR ¹⁰ as there may be mentioned an alkylsulfonyl group, such as methyl sulfanyl group, ethyl sulfanyl group, a butyl sulfanyl group, hexyl sulfanyl group, decyl sulfanyl group and sulfanyl group Ikoma chamber.

Examples of -SO ₂ R ¹⁰ include alkyloxysulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group and icosylsulfonyl group.

As -SO ₃ R ¹⁰ , alkyloxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group, and icosyloxysulfonyl group, etc. Can be lifted. Examples of R ¹⁰ -SO ₃ R ^10, a branched alkyl group having 3 to 20 carbon atoms, and more preferably is a branched chain alkyl group having a carbon number of 6 to 12 more preferred, and 2-ethylhexyl group.

As -SO ₂ NR ¹¹ R ¹² , a sulfamoyl group; 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, N-2 substituted sulfamoyl group, etc. are mentioned. In the N-1 substituted sulfamoyl group, as R ⁸ , a branched chain alkyl group having 3 to 20 carbon atoms is preferable, a branched chain alkyl group having 6 to 12 carbon atoms is more preferable, and a 2-ethylhexyl group is still more preferable.

Z ⁺ is ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ , and preferably ⁺ N (R ¹³ ) ₄ .

^{In +} N(R ¹³ ) ₄ , it is preferable that all of the four R ¹³ are the same. In addition, the total number of carbon atoms of the four R ¹³ is more preferably from 20 to 80 is preferable, and 20 to 60.

-SO ₃ ^- Z ⁺ is, -SO ₃ ^- is preferably N (R ¹³⁾ _4.

-CO ₂ ^- Examples of Z ^+, for example, may be mentioned -CO ₂ Na, -CO ₂ K.

^{Examples of +} N(R ¹³ ) ₄ include NH ₄ ⁺ and a cation represented by the following formula.

[Formula 36]

m is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

As a specific example of the compound represented by formula (I), a compound represented by the following formula is mentioned. Among them, a compound represented by formula (I-1)-a compound represented by formula (I-4), a compound represented by formula (I-25)-a compound represented by formula (I-30), and formula (I-35) The compound represented-the compound represented by the formula (I-40), the compound represented by the formula (I-75)-the compound represented by the formula (I-114) are preferable, The compound that appears is more preferable.

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

[Chemical Formula 46]

[Chemical Formula 47]

[Formula 48]

Compound (I) is, for example, in the presence of an alkali metal carbonate, formula (II)

[Chemical Formula 49]

[In the formula, X ¹¹¹ and X ¹¹² each independently represent a halogen atom.]

The compound represented by (hereinafter sometimes referred to as "compound (II)") and formula (III)

[Formula 50]

[In formula (III), R ³ and R ⁴ each represent the same meaning as described above.]

The compound represented by (hereinafter sometimes referred to as "compound (III)") is reacted in an organic solvent, and the formula (IV)

[Formula 51]

After obtaining the formula (Ⅳ) of, X ^112, R ³ and R ⁴ are, each represents the same meanings.] (There is a case that the substrate referred to as "compound (Ⅳ)"), compounds represented by the compound (Ⅳ) and equation (Ⅴ)

[Formula 52]

[In formula (V), R ¹ represents the same meaning as above.]

The compound represented by (hereinafter sometimes referred to as "compound (V)") can be produced by reacting in an organic solvent in the presence of an alkali metal carbonate.

Examples of the organic solvent in the reaction of compound (II) and compound (III) include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, and butanol; Nitrated hydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone; and the like.

The reaction temperature in the reaction of compound (II) and compound (III) is preferably 0 to 100°C, and more preferably 20 to 80°C. The reaction time is preferably 1 hour to 12 hours, and more preferably 1 hour to 8 hours.

The amount of compound (III) used is preferably 1 mol or more and 30 mol or less, and more preferably 1 mol or more and 20 mol or less per 1 mol of compound (II).

Examples of the organic solvent in the reaction of compound (IV) and compound (V) include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, and butanol; Nitrated hydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone; and the like.

The reaction temperature in the reaction of compound (IV) and compound (V) is preferably 0 to 180°C, more preferably 10 to 130°C. The reaction time is preferably from 1 hour to 48 hours, and more preferably from 1 hour to 24 hours.

The amount of compound (V) to be used is preferably 1 mol or more and 30 mol or less, and more preferably 1 mol and 20 mol or less, based on 1 mol of compound (III).

The method of obtaining the compound (I) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, a method of obtaining a precipitate that precipitates after completion of the reaction by filtration is mentioned. It is preferable that the crystal obtained by filtration is washed with water or the like, and then dried. Further, if necessary, further purification may be performed by a known method such as recrystallization.

The compound (I) of the present invention can be used as a dye.

<Colored curable resin composition>

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and contains a compound (I) as the colorant (A). . Two or more types of compounds (I) may be included.

The colorant (A) may further contain at least one selected from the group consisting of a pigment (A1) and a dye (A2) (but different from the compound (I)).

The colored photosensitive resin composition of the present invention may further contain a solvent (E), a leveling agent (F), and the like.

The content rate of the compound (I) contained in the colored photosensitive resin composition is preferably 0.025 mass% or more and 48 mass% or less, more preferably 0.08 mass% or more and 42 mass% or less, and 0.1 mass% or more and 30 The mass% or less is more preferable.

Here, the "total amount of solid content" in this specification means the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component thereto can be measured by known analysis means such as liquid chromatography or gas chromatography.

In addition, the content rate of compound (I) is preferably 10% by mass or more, more preferably 20% by mass or more, 100% by mass or less, and 90% by mass or less in the total amount of the coloring agent (A). do.

<Pigment (A1)>

The pigment (A1) is not particularly limited, and a known pigment can be used, and examples thereof include compounds classified as pigments by the color index (published by The Society of Dyers and Colorists).

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

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, etc. Red pigment;

C.I. Blue pigments, such as Pigment Blue 15, 15:3, 15:4, 15:6, 60, 80;

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, and 58; etc. are mentioned.

As a pigment, C.I. Yellow pigments such as Pigment Yellow 138, 139, 150, C.I. Red pigments such as Pigment Red 177, 242, 254, C.I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60, and C.I. Pigment violet 1, 19, 23, 29, 32, 36, 38, etc. violet pigments are preferable. Among them, yellow pigments and red pigments are particularly preferred.

The content of the pigment (A1) is usually 10 to 500 parts by mass, preferably 30 to 500 parts by mass, and more preferably 30 to 400 parts by mass, based on 100 parts by mass of the compound (I).

<Dye (A2)>

Examples of the dye (A2) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes and sulfonamide derivatives of acid dyes. For example, the color index (The Society of Dyers and Colorists (published by Dyers and Colorists), and known dyes described in dye notes (color dyes). In addition, according to the chemical structure, azo dye, coumarin dye, xanthene dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acry Dean dyes, styryl dyes, quinoline dyes, merocyanine dyes, and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

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 Blue 4, 5, 37, 67, 70, 90;

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

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 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 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;

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

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

C.I. Direct Red 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 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; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. Direct dye,

C.I. Disperse Yellow 54, 76, et al., C.I. Disperse dye,

C.I. Basic Red 1 and 10;

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;

C.I. Basic Green 1; C.I. Basic dyes,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. Reactive Red 36; C.I. Reactive dyes,

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

C.I. 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 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, 84;

C.I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. Modern dye,

C.I. Bat Green No. 1 C.I. Bat dye, etc. are mentioned.

The dye (A2) is preferably at least one selected from the group consisting of a yellow dye (A3) and a red dye (A4).

The yellow dye represents a dye having a maximum absorption wavelength of 400 to 470 nm in chloroform, and a dye having a maximum absorption wavelength of 430 to 470 nm is preferable.

The red dye represents a dye having a maximum absorption wavelength of 490 to 550 nm in chloroform, and a dye having a maximum absorption wavelength of 490 to 540 nm is preferable.

As the red dye (A4), a dye having a xanthene skeleton different from that of compound (I) is preferable, and a dye having a xanthene skeleton in which the carbon atoms at the 3rd and 6th positions of the xanthene are bonded to the nitrogen atom is more preferable.

As the dye having a xanthene skeleton, a compound represented by formula (1b) (hereinafter, referred to as "compound (1b)" in some cases) is preferable. Compound (1b) may be the tautomer.

[Formula 53]

[In formula (1b), R ^51a to R ^54a are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 1 having 6 to 10 carbon atoms which may have a substituent. A valence aromatic hydrocarbon group is shown, and the methylene group (-CH ₂ -) contained in the said saturated hydrocarbon group may be substituted with -O-, -CO-, or -NR ^61a- . R ^51a and R ^52a may be taken together to form a ring containing a nitrogen atom, and R ^3a and R ^4a may be taken together to form a ring containing a nitrogen atom.

R ^55a _{is, -OH, -SO 3 -, -SO} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 -Z +, -CO 2 R 58a, -SO 3 R 58a or -SO ₂ NR ^59a R ^60a .

R ^56a and R ^57a each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents the integer of 0-5. When m is 2 or more, a plurality of R ^55a may be the same or different.

a represents the integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ^61a ) ₄ , Na ⁺ or K ⁺ , and four R ^61a may be the same or different.

R ^58a represents a C 1 to C 20 monovalent saturated hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ^59a and R ^60a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO- , -NH- or -NR ^58a- may be substituted, and R ^59a and R ^60a may be bonded to each other to form a 3-10 membered heterocycle containing a nitrogen atom.

R ^61a represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

When -SO ₃ -is included in equation (1a), the number is 1.

Examples of the saturated hydrocarbon group represented by R ^51a to R ^54a include the same groups as those exemplified as a linear or branched alkyl group or an alicyclic saturated hydrocarbon group exemplified as an alkyl group represented by R ³ , and aromatic represented by R ^51a to R ^54a As the hydrocarbon group, among the groups exemplified as the aromatic hydrocarbon group represented by R ³ , the same group as the group having 6 to 10 carbon atoms can be mentioned.

Among them, R ^51a and R ^52a Either one of and any one of R ^53a and R ^54a is an aromatic hydrocarbon group which may have a substituent, the other is a hydrogen atom or a saturated hydrocarbon group which may have a substituent, or all of R ^51a to R ^54a have a substituent It is preferable that it is an optionally saturated hydrocarbon group.

Examples of the alkyl group represented by R ^56a and R ^57a include the same groups as the alkyl group illustrated as R ⁵ . As R ^56a and R ^57a , a hydrogen atom is preferable.

Examples of the saturated hydrocarbon group represented by R ^58a , R ^59a , R ^60a and R ^61a include the same groups as those exemplified as the saturated hydrocarbon group represented by R ¹⁰ .

Examples of the aralkyl group represented by R ^61a include the same group as the group having 7 to 10 carbon atoms among the groups exemplified as the aralkyl group represented by R ¹ .

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

As red dye (A4), a compound represented by the following formula is mentioned, for example. R ⁴⁰ in the following formula represents a 2-ethylhexyl group.

[Chemical Formula 54]

[Chemical Formula 55]

[Formula 56]

The content of the dye (A2) is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass based on 100 parts by mass of compound (I). .

<Resin (B)>

The resin (B) is not particularly limited, but it is preferably an alkali-soluble resin, and at least one kind of monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "(a)" A copolymer having a structural unit derived from) is more preferable.

The copolymer having the structural unit derived from (a) is a structure derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as ``(b)'') It is preferably a copolymer having at least one type selected from the group consisting of a unit and a structural unit having an ethylenically unsaturated bond. The copolymer may further have other structural units.

Other structural units include structural units derived from (a) and copolymerizable monomers (c) (however, (a) and (b) are different) (hereinafter sometimes referred to as ``(c)''). I can.

As (a), specifically, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, for example;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetra 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 carboxyl groups, such as hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic acids anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride;

Unsaturated mono [(meth)acryloyloxyalkyl] of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2-(meth)acryloyloxyethyl] and phthalic acid mono [2-(meth)acryloyloxyethyl] Esters;

Unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid, and the like are mentioned.

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

When the copolymer contains the structural unit derived from (a), the ratio is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, in 100% by mass of the copolymer.

(b) is a polymerization having, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxyron ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Refers to the sex compound.

(b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

In addition, in this specification, "(meth)acrylic acid" represents at least 1 type selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" 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 ] decyl acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane, and tetrahydrofurfuryl (meth) acrylate. .

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

When the copolymer contains the structural unit derived from (b), the ratio is preferably 50 to 99% by mass, more preferably 70 to 95% by mass, in 100% by mass of the copolymer.

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 ] decane-8-yl (meth)acrylate (in this technical field, it is referred to as "dicyclopentanyl (meth)acrylate" as a common name. In addition, it may be referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ] decene-8-yl (meth)acrylate (in this technical field, a common name It is referred to 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;

Hydroxy 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-hydroxy ratio 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, etc. are mentioned.

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

When the copolymer contains the structural unit derived from (c), the ratio is preferably 1 to 99% by mass in 100% by mass of the copolymer.

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

As such a structural unit, a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, a structural unit obtained by adding 2-hydroxyethyl (meth)acrylate to a maleic anhydride unit, and glycidyl (meth)acrylate ) A structural unit in which (meth)acrylic acid was added to an acrylate unit, etc. are mentioned. In addition, when these structural units have a hydroxy group, a structural unit to which a carboxylic anhydride is further added is also mentioned as a structural unit which has an ethylenic 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, glycy Diyl (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 copolymers; benzyl (meth)acrylate/(meth)acrylic acid copolymers, styrene/(meth)acrylic acid copolymers , Benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate added , Tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer with glycidyl (meth)acrylate added thereto, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth) ) Copolymer having structural units derived from (a) and (c), such as a resin in which glycidyl (meth)acrylate is added to an acrylic acid copolymer; tricyclodecyl (meth)acrylate/glycidyl (meth )A resin in which (meth)acrylic acid is reacted with an acrylate copolymer, a resin in which (meth)acrylic acid is reacted with a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate, etc. A copolymer having a structural unit obtained by adding (a) to the structural unit derived from b) and a structural unit derived from (c); a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate In addition to the resin reacted with (meth)acrylic acid, (A) is added to the structural unit derived from (b), such as a resin in which lahydrophthalic anhydride is reacted, and a copolymer having a structural unit derived from (c) and a structural unit obtained by further adding a carboxylic anhydride Can be mentioned.

Resin (B) is, for example, a method described in the document ``Experimental method for polymer synthesis'' (Otsu Takayuki, Ltd., first edition, first edition 　 published on March 1, 1972) and citations described in the document. It can be prepared with reference to the literature.

The resin (B) is preferably a copolymer having structural units derived from (a) and (b); a copolymer having structural units derived from (a), (b) and (c); and ( It is a type selected from the group consisting of a copolymer having a structural unit derived from a) and (c), more preferably, a copolymer having a structural unit derived from (a) and (b); And (a) , (b) and (c) is a type selected from the group consisting of a copolymer having structural units derived from, and particularly preferably a copolymer having structural units derived from (a) and (b).

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is also high, the solubility in the developer of the unexposed portion is good, and the resolution of the colored pattern tends to be improved.

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

The acid value of the resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 30 to 150 mg-KOH/g, and still more preferably 40 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

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

<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 a compound having a polymerizable ethylenically unsaturated bond, and the like, preferably It is a (meth)acrylic acid ester compound.

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

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and , 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, and the like, and among them, dipentaerythritol penta (meth)acrylate and dipentaerythritol hexa (meth)acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass in the total amount of the solid content.

In addition, the content ratio [resin (B): polymerizable compound (C)] of the resin (B) and the polymerizable compound (C) is on a mass basis, preferably 20:80 to 80:20, more preferably It is 35:65~80:20.

When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film rate at the time of forming the colored pattern and the chemical resistance of the color filter are improved.

<Polymerization initiator (D)>

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

Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds and acylphosphine oxide compounds.

As the O-acyloxime compound, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) )Octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-6-2-methyl-4-(3 ,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl｝-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2) -Methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-day] -3 -cyclopentylpropane -1 -one -2 -immigration and the like. Commercial items such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) may be used. Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl) At least one member selected from the group consisting of octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine is preferable, and , N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine is more preferable.

As an alkylphenone compound, for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-morphonophenyl)- 2-Benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one, 2-hydride Roxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl] propane-1-one, 1-hydroxycyclo Oligomers of hexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α, α-diethoxyacetophenone, and benzyldimethylketal. Commercially available products such as Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF) may be used.

As a 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 (for example, see Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. 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-chloro) Phenyl)-4,4', 5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Laid-Open No. 48-38403, Japanese Patent Laid-Open No. 62-174204, etc.) , Imidazole compounds in which the phenyl group at the 4,4', 5,5'-position is substituted by a carboalkoxy group (see, for example, Japanese Patent Laid-Open No. 7-10913, etc.), and the like.

As a triazine compound, for example, 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.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4- Phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. Benzophenone compounds of; 9,10-phenanthrenequinone, 2-ethylanthraquinone, and quinone compounds such as camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, etc. Can be lifted.

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-acyloxime compound.

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

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. For example, ester solvents (solvents that contain -COO- in the molecule and do not contain -O-), ether solvents (solvents that contain -O- in the molecule and do not contain -COO-), ether esters Solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule,- Solvents which do not contain 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, 2-hydroxyisobutanoate methyl, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As an 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, phenethyl, methylanisole And the like.

As the ether ester solvent, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethyl ethoxypropionate, 2-methyl methoxypropionate, 2-ethyl methoxypropionate, propyl 2-methoxypropionate, 2-methyl ethoxypropionate, 2-ethylethoxypropionate, 2-methoxy-2- Methyl methylpropionate, 2-ethoxy-2-ethylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.

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 (1-methyl-2-pyrrolidone).

These solvents may be used alone or in combination of two or more.

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, 3-ethoxy ethylpropionate, 4-hydroxy-4-methyl-2-pentanone, N, N- Dimethylformamide, N-methylpyrrolidone (1-methyl-2-pyrrolidone), etc. are preferable, and 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, 3-ethoxy ethylpropionate, and N-methylpyrrolidone (1-methyl-2-pyrrolidone) are more preferable.

The content of the solvent (E) is preferably 70 to 95 mass%, and more preferably 75 to 92 mass% with respect to the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30 mass%, more preferably 8 to 25 mass%. When the content of the solvent (E) is in the above range, the flatness at the time of application is improved, and the color density is not insufficient when the color filter is formed, so that display characteristics tend to be improved.

<Leveling agent (F)>

As the leveling agent (F), a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom may be mentioned. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. 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 Industries, Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (made by Momentive Performance Materials Japan joint company), etc. .

Examples of the above fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapak (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, copper R30, copper RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Corporation), Surfron (registered trademark) S381 , Copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Research Institute, Ltd.), and the like.

Examples of the silicone-based surfactants having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in a molecule. Specifically, Megapak (registered trademark) R08, copper BL20, copper F475, copper F477, and copper F443 (manufactured by DIC Corporation), and the like can be mentioned.

When the leveling agent (F) is contained, its content is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, furthermore, with respect to the total amount of the colored curable resin composition. Preferably it is 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

If necessary, the colored curable resin composition of the present invention may contain additives known in the art such as a polymerization initiator, filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, chain transfer agent, and the like.

<Production method of colored curable resin composition>

The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and a solvent (E) and a leveling agent used as necessary. It can be prepared by mixing (F) and other components.

In the case of containing the pigment (A1), the pigment is preferably mixed with a part or all of the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Do. In this case, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. The target colored curable resin composition can be prepared by mixing the remaining components to a predetermined concentration in the pigment dispersion liquid thus obtained.

It is preferable to prepare a solution by dissolving compound (I) in some or all of the solvent (E) in advance. It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 μm.

It is preferable to filter the colored curable resin composition after mixing with a filter of about 0.01-10 micrometers of pore diameters.

<Production method of color filter>

As a method for producing a colored pattern from the colored curable resin composition of the present invention, a photolithography method, an ink jet method, a printing method, and the like can be mentioned. Among them, the photolithography method is preferred. The photolithography method is a method of applying the colored curable resin composition to a substrate, drying it to form a colored composition layer, exposing the colored composition layer to light through a photomask, and developing. In the photolithography method, by not using a photomask during exposure and/or not developing, a colored coating film that is a cured product of the colored composition layer can be formed. The colored pattern or colored coating film thus formed can be used as the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted according to the purpose or application, and is, for example, 0.1 to 30 µm, preferably 0.1 to 20 µm, and more preferably 0.5 to 6 µm. .

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with a silica coating on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicone, and the like What formed aluminum, silver, silver/copper/palladium alloy thin film, etc. is used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The formation of each color pixel by the photolithography method can be performed under known or commonly used devices and conditions. For example, it can be produced as follows.

First, a colored curable resin composition is applied on a substrate, followed by drying by heating (pre-baking) and/or drying under reduced pressure to remove and dry volatile components such as a solvent to obtain a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.

The temperature in the case of heating and drying is preferably 30 to 120, and more preferably 50 to 110. Moreover, as a heating time, it is preferable that it is 10 seconds-60 minutes, and it is more preferable that it is 30 seconds-30 minutes. When drying under reduced pressure, it is preferable to perform under a pressure of 50 to 150 Pa and in a temperature range of 20 to 25.

The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.

As a light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm can be cut with a filter that cuts this wavelength range, or light in the vicinity of 436 nm, 408 nm, and 365 nm is selectively extracted using a band pass filter that extracts these wavelength ranges. You can do it. Specifically, 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 an exposure apparatus such as a mask aligner and a stepper, since it is possible to uniformly irradiate parallel light rays over the entire exposure surface or to accurately align the photomask and the substrate on which the colored composition layer is formed.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By development, the unexposed part of the colored composition layer is dissolved in a developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration of such an alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant.

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

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

According to the colored curable resin composition containing the compound of the present invention, a color filter having good heat resistance can be provided. The color filter is useful as a color filter used in a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples from the beginning, but is carried out with appropriate changes within the range that may be suitable for the purpose of the previous and the latter days. It is also possible, of course, and they are all included in the technical scope of the present invention. In the examples,% and parts indicating the content to 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; Agilent 1200 type, MASS; Agilent LC/MSD type).

Example 1

40.6 parts of a compound represented by the following formula (VIH-1) as compound (II), 8.0 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 14 parts of potassium carbonate as compound (III) 1-methyl-2- In the presence of 50 parts of pyrrolidone, the obtained solution was stirred at 30 for 3 hours. After cooling the obtained reaction solution to room temperature, it was 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, whereby crystals precipitated. The precipitated crystal was obtained as a residue of suction filtration and then dried to obtain 44.0 parts of a compound represented by formula (I-4-A).

[Chemical Formula 57]

Then, 44.2 parts of the compound represented by the formula (I-4-A), 22.5 parts of 3-mercapto-1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 14 parts of potassium carbonate, in the presence of 500 parts of methanol, under reflux, 5 Heated for hours. After cooling the obtained reaction liquid to room temperature, methanol was distilled off under reduced pressure, and 100 parts of water was added to the residue, filtered, and washed with 100 parts of water. The obtained crystal was dried under reduced pressure at 60 for 24 hours to obtain 39 parts of a compound represented by formula (I-76).

[Chemical Formula 58]

Identification of the compound represented by formula (I-76)

(Mass Spectrometry) Ionization Mode = ESI+: m/z = [M+H] ⁺ 498.1

Exact　Mass：　497.1

Example 2

In Example 1, instead of 3-mercapto-1-propanol, except for using 2-(2-mercaptoethoxy)ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), it was synthesized in the same manner as in Example 1. And 51 parts of compounds represented by formula (I-77) were obtained.

[Chemical Formula 59]

Identification of the compound represented by formula (I-77)

(Mass Spectrometry) Ionization Mode = ESI+: m/z = [M+H] ⁺ 528.1

Exact　Mass：　527.1

Synthesis Example 1. Synthesis of resin

In a flask equipped with a reflux condenser, a dropping lot, and a stirrer, an appropriate amount of nitrogen was flowed to form a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added, followed by heating to 85 while stirring. Next, in the flask, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] A mixture of decane-9-ylacrylate (the content ratio is 50:50 by molar ratio) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) 171 parts of a solution dissolved in 40 parts of propylene glycol monomethyl ether acetate using a dropping pump It was dripped over about 5 hours. On the other hand, a solution in which 26 parts of polymerization initiators 2, 2'-azobis (2,4-dimethylvaleronitrile) were dissolved in 120 parts of propylene glycol monomethyl ether acetate was dripped into the flask over about 5 hours using another dropping pump. . After the dropwise addition of the polymerization initiator was completed, it was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH/g.

[Chemical Formula 60]

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene of the resin was performed under the following conditions by the GPC method.

Equipment　　　　　; HLC-8120 GPC (manufactured by Tosoh Corporation)

Column　　　　　；TSK-GELG2000HXL

Column temperature　　；40

Solvent　　　　　; Tetrahydrofuran (THF)

Flow velocity　　　　　; 1.0mL/min

Test liquid 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 Tosoh Corporation)

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

Example 3, 4 and Comparative example 1. Preparation of colored curable resin composition

Each component was mixed so that it might become the composition shown in Table 1, and the colored curable resin composition was obtained.

In Table 1, each component is as follows.

Coloring agent (A-1): Compound represented by formula (I-76)

Coloring agent (A-2): Compound represented by formula (I-77)

Coloring agent (A-3): Rhodamine B

Resin (B): Resin B1 (solid content conversion)

Polymerizable compound (C): dipentaerythritol hexaacrylate

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Corporation; O-acyloxime compound) )

Solvent (E-1): 1-methyl-2-pyrrolidone

Solvent (E-2): ethyl lactate

Solvent (E-3): Dimethylformamide

Leveling agent (F): Polyether modified silicone oil (Toray silicone SH8400; Toray Dow Corning Co., Ltd. product)

Was mixed to obtain a colored curable resin composition.

Experimental Example 1. Formation of colored pattern and evaluation of heat resistance

A colored photosensitive composition was applied on a glass substrate (Eagle XG; manufactured by Corning) having a 2-inch edge by spin coating, and then prebaked at 100 for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure amount of 150 mJ/cm 2 (365 nm) was used in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). Standard). As a photomask, a 100 µm line and space pattern was used. After light irradiation, the coating film was immersed for 23 to 80 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and then subjected to post-baking at 220 for 20 minutes for coloring. Got the pattern.

In the formation of the colored pattern, a coating film was obtained in the same manner as above except that a photomask was not interposed at the time of irradiation with light. The chromaticity of the obtained coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). Next, after heating the same coating film at 230 for 20 minutes, the chromaticity was measured again using a colorimeter (OSP-SP-200; manufactured by OLYMPUS), and the color difference (ΔEab*) of the coating film before and after heating was determined. The color differences (ΔEab*) of the coating films formed from the colored curable resin compositions of Examples 3 and 4 were 9.4 and 10.2, respectively. In addition, the color difference (ΔEab*) of the coating film formed of the colored curable resin composition of Comparative Example 1 was 50.3. From this, it was found that the colored coating film and the colored pattern formed from the colored curable resin composition containing the compound of the present invention were excellent in heat resistance.

According to the colored curable resin composition containing the compound of the present invention, a color filter having good heat resistance can be provided. The color filter is useful as a color filter used in a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Claims (4)

A compound represented by formula (I).
[Formula 1]

[In formula (I),
R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -contained in the alkyl group is -O-, -CO- Alternatively, it may be substituted with -NR ¹¹ -. However, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O-, -CO-, or -NR ¹¹ -.
R ³ and R ⁴ each independently represent a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and -CH contained in the alkyl group ₂ -may be substituted with -O-, -CO-, or -NR ¹¹ -. However, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O-, -CO-, or -NR ¹¹ -.
R ⁵ and R ⁶ each independently represent a hydrogen atom.
R ⁷ represents a hydrogen atom, -SO ₃ ^- , or -SO ₃ H.
R ⁸ represents -SO ₃ ^- or -SO ₃ H.
m represents an integer of 0 to 4, and when m is 2 or more, a plurality of R ⁸ may be the same or different, respectively.
R ¹¹ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms.
X represents a halogen atom.
a represents the integer of 0 or 1.]
A colored curable resin composition comprising the compound according to claim 1, a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
A color filter formed from the colored curable resin composition according to claim 2.
A display device comprising the color filter according to claim 3.