KR101948954B1 - Compound and colored curable resin composition - Google Patents

Abstract

[상기 화학식 (I)에서, R¹은 치환기를 갖고 있어도 좋은 탄소수 6∼30의 방향족 탄화수소기를 나타낸다.
R³ 및 R⁴는 각각 독립적으로 수소 원자, 치환기를 갖고 있어도 좋은 페닐기 또는 치환기를 갖고 있어도 좋은 탄소수 1∼10의 1가의 포화 탄화수소기 등으로 나타낸다.
R⁵ 및 R⁶은 각각 독립적으로 수소 원자 또는 탄소수 1∼6의 알킬기를 나타낸다.
R⁷ 및 R⁸은 각각 독립적으로 -SO₃ ^--CO₂ ^- 등을 나타낸다.
m은 0∼4의 정수를 나타낸다.
Z⁺는 ⁺N(R¹³)₄, Na⁺ 또는 K⁺를 나타낸다.
R¹⁰은 탄소수 1∼20의 1가의 포화 탄화수소기 등을 나타낸다.
R¹¹ 및 R¹²는 각각 독립적으로 수소 원자 또는 탄소수 1∼20의 1가의 포화 탄화수소기를 나타낸다.
R¹³은 수소 원자 또는 탄소수 1∼20의 1가의 포화 탄화수소기를 나타낸다.]The present invention aims to provide a compound represented by the formula (I).

[In the above formula (I), R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent.
R ³ and R ⁴ each independently represent a hydrogen atom, a phenyl group which may have a substituent, or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁷ and R ⁸ each independently represent -SO ₃ ^- -CO ₂ ^- or the like.
m represents an integer of 0 to 4;
Z ⁺ represents a N ⁺ (R ¹³⁾ _4, Na ⁺ or K ^+.
R ¹⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
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 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Description

COMPOUND AND COLORED CURABLE RESIN COMPOSITION [0001]

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

BACKGROUND ART Dyes are used for color display by using reflected light or transmitted light in the fields of textile materials, liquid crystal displays, inkjets, and the like. As such a dye, rhodamine B having a xanthene skeleton and represented by the following chemical formula (Rb) is widely known (Hosoda Yutaka, New Dye Chemistry, Page 274].

The present invention includes the following inventions.

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

[In the above formula (I), R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent.

R ³ and R ⁴ each independently represent a hydrogen atom, a phenyl group which may have a substituent or a monovalent saturated hydrocarbon group of 1 to 10 carbon atoms which may have a substituent. -CH ₂ - included in the saturated hydrocarbon group may be 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 and R ⁸ are each independently selected from _{^{-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 .

m represents an integer of 0 to 4; When m is 2 or more, plural R ^{8 s} may be the same or different.

Z ⁺ represents a N ⁺ (R ¹³⁾ _4, Na ⁺ or K ^+.

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.

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 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The plurality of R < ¹³ > may be the same or different.]

[2] The compound according to [1], wherein R ¹ is a group represented by the formula (i).

[In the above formula (i), R ² represents a halogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. -CH ₂ - included in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -.

n represents an integer of 0 to 5; When n is 2 or more, plural R ² may be the same or different.

* Represents the number of bonds (bonds) with oxygen atoms.]

[3] At least one of R ³ and R ⁴ is a phenyl group having a substituent or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms and having a substituent,

The substituent in the phenyl group and the saturated hydrocarbon group is a group containing a silicon atom,

The compound according to [2], wherein -CH ₂ - included in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ - (R ¹¹ is defined as in [1]).

[4] The compound according to [3], wherein the group containing a silicon atom is a group represented by the formula (iia).

[In the above formula (iia), L ¹ represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH ₂ - included in the alkanediyl group is -O-, -CO- or -NR ¹¹¹ - Or may be substituted.

R ¹¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms.

R ¹⁴⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. The plural R ¹⁴⁴ may be the same or different.

* Represents the number of bonds with a nitrogen atom or a carbon atom.]

[5] The compound according to [3] or [4], wherein the group containing a silicon atom is a group represented by the formula (ii).

[Wherein p represents an integer of 1 to 8, R ¹⁴ 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, * represents a nitrogen atom or a carbon atom, ≪ / RTI > The plurality of R < ¹⁴ > may be the same or different.]

[6] R ¹ is an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent,

R ³ and R ⁴ are each independently a hydrogen atom, a phenyl group which may have a substituent, or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, The compound according to [1], wherein -CH ₂ - included in the hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -.

[7] The compound according to [6], wherein R ¹ is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent.

[8] R ¹ is an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent,

R ³ and R ⁴ are each independently a hydrogen atom, a phenyl group which may have a substituent, or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a halogen atom And -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, -CO-, or -NR ¹¹ -, wherein R ¹¹ is defined as in [1], [1] 7].

[9] A colorant comprising the compound according to any one of [1] to [8].

[10] A colored curable resin composition comprising a compound according to any one of [1] to [8], a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

[11] The colored curable resin composition according to [10], further comprising at least one selected from the group consisting of a yellow dye and a red dye.

[12] A coated film formed by using the colored curable resin composition according to [10] or [11].

[13] A color filter formed using the colored curable resin composition according to [10] or [11].

[14] A display device including the color filter according to [13].

The compounds of the present invention are excellent in solubility in an organic solvent.

The compound of the present invention is a compound represented by the formula (I) (hereinafter sometimes referred to as " compound (I) "). The compound of the present invention also includes tautomers thereof.

≪ Compound (I) >

[In the above formula (I), R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent.

R ³ and R ⁴ each independently represent a hydrogen atom, a phenyl group which may have a substituent or a monovalent hydrocarbon group of 1 to 10 carbon atoms which may have a substituent. -CH ₂ - included in the saturated hydrocarbon group may be 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 and R ⁸ are each independently selected from _{^{-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 .

m represents an integer of 0 to 4; When m is 2 or more, plural R ^{8 s} may be the same or different.

Z ⁺ represents a N ⁺ (R ¹³⁾ _4, Na ⁺ or K ^+.

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.

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 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The plurality of R < ¹³ > may be the same or different.]

As the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ³ and R ⁴ ,

A straight chain alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl groups;

Branched alkyl groups having 3 to 10 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl;

And an alkyl group having 1 to 6 carbon atoms is preferable, and among these, a methyl group, an ethyl group, a propyl group and a butyl group are more preferable.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁵ and R ⁶ 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, , Isopentyl group and neopentyl group, and methyl group and ethyl group are preferable.

As the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ to R ¹³ ,

A linear alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl;

Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl;

An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group

.

The saturated hydrocarbon group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, Branched alkyl group.

Examples of the aromatic hydrocarbon group represented by R ¹ include a phenyl group, a naphthyl group, an anthryl ring, a phenanthryl group, a pyrenyl group and a benzopyranyl group, and an aromatic hydrocarbon group having 6 to 14 carbon atoms is preferable, Of an aromatic hydrocarbon group is more preferable.

As the substituent in the monovalent saturated hydrocarbon group of 1 to 10 carbon atoms represented by R ³ and R ⁴ ,

Halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom;

A saturated hydrocarbon group containing 1 to 10 carbon atoms including a halogen atom;

Thiol group; A hydroxy group; Cyano; A nitro group; A group containing a silicon atom;

And the like.

As the substituent in the aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R ¹ ,

Saturated hydrocarbon groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl;

Halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom;

A saturated hydrocarbon group having 1 to 12 carbon atoms containing a halogen atom;

Thiol group; A hydroxy group; Cyano; A nitro group; A group containing a silicon atom;

And the like.

The group containing a silicon atom means a group containing a silicon atom as a constituent of the group. The group containing a silicon atom is preferably a group represented by the formula (iia), more preferably a group represented by the formula (ii).

[In the above formula (iia), L ¹ represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH ₂ - included in the alkadiyl group is -O-, -CO- or -NR ¹¹¹ - Or may be substituted.

R ¹¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms.

R ¹⁴⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. The plural R ¹⁴⁴ may be the same or different.

* Represents the number of bonds with a nitrogen atom or a carbon atom.]

Examples of the alkanediyl group having 1 to 12 carbon atoms represented by L ¹ include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane- -1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane- Diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecan-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane- A diethyl group, a heptadecane-1,17-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane- Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4 - Diary and so on.

L ¹ is preferably an alkanediyl group having 1 to 8 carbon atoms.

As the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R < ¹¹¹ &

A linear alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl;

Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl;

An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group;

.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹⁴⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, N-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl. Alkyl groups are preferred.

Examples of the alkoxy group having 1 to 12 carbon atoms represented by R ¹⁴ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec- N-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, And an alkoxy group having 1 to 4 carbon atoms is preferable.

[Wherein p represents an integer of 1 to 8, R ¹⁴ 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, * represents a nitrogen atom or a carbon atom, &Quot;

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

R ¹⁴ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group, and more preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group.

The three R < ¹⁴ > s are preferably the same.

p is preferably an integer of 1 to 6, more preferably an integer of 1 to 4.

Examples of the group containing a silicon atom include those shown below. * Represents the number of bonds with a nitrogen atom or a carbon atom. Among them, those represented by the formulas (ii-2), (ii-3), (ii-5) and (ii-6) are preferable.

Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent represented by R ¹ include the following groups. * Represents the number of bonds with oxygen atoms.

R ¹ is preferably a group represented by the formula (i).

[In the above formula (i), R ² represents a halogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. -CH ₂ - included in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ - (R ¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms).

n represents an integer of 0 to 5; When n is 2 or more, plural R ² may be the same or different.

* Represents the number of bonds with oxygen atoms.]

As the monovalent saturated hydrocarbon group of 1 to 10 carbon atoms represented by R ² ,

An n-butyl group, an isobutyl group, an n-pentyl group, a n-hexyl group, an n-heptyl group, an n-octyl group, etc. An alkyl group having 1 to 10 carbon atoms;

Branched alkyl groups having 3 to 10 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl;

Alicyclic saturated hydrocarbon groups of 3 to 10 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;

Lt; / RTI >

Is preferably an alkyl group having 1 to 8 carbon atoms,

A methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group are more preferable.

Examples of the substituent of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ² include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; And a group containing a silicon atom.

Examples of the saturated hydrocarbon group containing a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a chlorobutyl group, a chloromethyl group, a dichloromethyl group , A trichloromethyl group, a tetrachloroethyl group, a bromomethyl group and a dibromomethyl group, and a saturated hydrocarbon group containing a fluorine atom is preferable, and a perfluoroalkyl group is more preferable.

The group containing a silicon atom is preferably a group represented by the above-mentioned formula (iia), more preferably a group represented by the above-described formula (ii).

Examples of the halogen atom represented by R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom.

R ² is preferably a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms and a halogen atom containing a halogen atom, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms and a halogen atom, more preferably a fluoro And a trifluoromethyl group.

n is preferably an integer of 0 to 3, more preferably 1 or 2.

When R ² in the formula (i) is a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms and a group containing a silicon atom as the substituent, specifically, the following groups may be mentioned.

Among them, a group represented by the following formula is preferable.

The group represented by the formula (i) is preferably the following group (* represents the number of bonds with an oxygen atom).

The phenyl group represented by R ³ and R ⁴ may have a substituent.

As the substituent, a halogen ^{atom, -R 10, -OH, -OR 10} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -SR 10, -SO 2 R 10, -SO 3 R ¹⁰ and -SO may be mentioned ₂ NR ¹¹ R ^12.

Among these substituents, -R ¹⁰ is preferable, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable.

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

Examples of -OR ¹⁰ include a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and eicosyloxy group .

Z ⁺ is N ⁺ (R ¹³⁾ _4, Na ⁺ or K ^+, and, preferably, ⁺ N (R ¹³⁾ _4.

In _{^{+ N (R 13) 4,}} 4 of R ¹³ it is preferably all the same. The total number of carbon atoms of the four R < ¹³ > s is preferably from 20 to 80, more preferably from 20 to 60. [

-SO ₃ ^- Z ⁺ is preferably -SO ₃ ^{- +} N (R ¹³ ) ₄ .

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 include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group.

Examples of -SO ₃ R ¹⁰ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

Examples of -SO ₂ NR ¹¹ R ¹² include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, Butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) (2-methylpropyl) sulfamoyl group, N- (2-methylpropyl) sulfamoyl group, N- Butylsulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N- N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group , N-1 (e.g., N-1, 2-dioxolyl) such as N- (2-ethylhexyl) sulfamoyl, N- Substituted sulfamoyl groups;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

R ³ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group having -R ¹⁰ , more preferably a hydrogen atom, an ethyl group, a propyl group or a group represented by the following formula (* Lt; / RTI >

R ⁴ is preferably a phenyl group which may have a substituent, more preferably a phenyl group having -R ¹⁰ , more preferably a group represented by the following formula (* represents the number of bonds with a nitrogen atom).

Wherein R &

Is preferably the following group (* represents the number of bonds with carbon atoms).

R ⁵ and R ⁶ are each independently preferably a hydrogen atom, a methyl group and an ethyl group, more preferably a hydrogen atom.

-SO ₃ R ^7, and R ⁸ is represented by ^- Z ⁺ is preferably -SO ₃ ^- is N ⁺ (R ¹³⁾ _4.

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

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

Examples of -SO ₃ R ¹⁰ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.

Examples of -SO ₂ NR ¹¹ R ¹² include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, Butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) (2-methylpropyl) sulfamoyl group, N- (2-methylpropyl) sulfamoyl group, N- Butylsulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N- N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group , N-1 (e.g., N-1, 2-dioxolyl) such as N- (2-ethylhexyl) sulfamoyl, N- Substituted sulfamoyl groups;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

R ⁷ and R ⁸ are each independently preferably -SO ₃ H or -SO ₃ ^- .

R ¹⁰ is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec- Practical skill.

R ¹¹ is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more 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 or an alkyl group having 1 to 8 carbon atoms, more 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 or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group.

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

In the compound represented by the formula (I), at least one of R ³ and R ⁴ is a phenyl group having a substituent or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms and a substituent, and in the phenyl group and the saturated hydrocarbon group The substituent is preferably a group containing a silicon atom. -CH ₂ - included in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -.

Specific examples of the compound represented by the formula (I) include those shown below.

Among them, preferred are the formulas (I-1) to (I-4), the formulas (I-25) to (I-30), and the formulas (I-35) to (I-40).

The compound (I) wherein R ⁷ = -SO ₃ ^- or -CO ₂ ^-

(Wherein X ¹¹¹ and X ¹¹² each independently represents a halogen atom, and R ¹¹⁷ represents -SO ₂ - or -CO-.)

(Hereinafter sometimes referred to as " compound (II) "), a compound represented by the formula (III)

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

(Hereinafter sometimes referred to as " compound (III) ") is reacted in an organic solvent to obtain a compound represented by the formula (IV)

[Wherein X ¹¹² , R ⁷ , R ³ and R ⁴ each have the same meaning as defined above].

The compound (IV) and the compound represented by the formula (V) are obtained after obtaining the compound represented by the formula (IV)

[In the above formula (V), R ² and n are each as defined above.]

(Hereinafter sometimes referred to as " compound (V) ") in an organic solvent.

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

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

Examples of the organic solvent in the reaction between the compound (IV) and the 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 the compound (IV) with the compound (V) is preferably 30 ° C to 180 ° C, more preferably 20 ° C to 130 ° C. The reaction time is preferably 1 hour to 24 hours, more preferably 1 hour to 8 hours.

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

The method for obtaining the desired compound (I) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, there is a method in which the precipitate precipitated after the reaction is removed by filtration. The crystals obtained by filtration are preferably washed with water or the like, and then dried successively. Further, if necessary, it may be further purified by a known technique such as recrystallization.

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

The colorant (A) comprising the compound (I) of the present invention also falls within the scope of the present invention.

The compound (I) of the present invention has high solubility in an organic solvent, and the color filter of a display device such as a liquid crystal display formed from a colored photosensitive resin composition containing the compound (I) has high brightness.

≪ Colored photosensitive resin composition &

The colored photosensitive resin composition of the present invention comprises a compound (I), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

In the colored photosensitive resin composition of the present invention, the compound (I) is used as the colorant (A). The colored photosensitive resin composition may contain two or more compounds (I).

The colored photosensitive resin composition may further include at least one selected from the group consisting of the pigment (A1) and the dye (A2) other than the compound (I).

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

The content 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 more preferably 0.1 mass% or more More preferably 30 mass% or less. Here, the "total amount of solid content" in the present specification means the amount excluding the content of the solvent in the total amount of the colored curable resin composition. The total amount of the solid content and the content of each component in the total amount can be measured by known analytical means such as liquid chromatography or gas chromatography.

≪ Pigment (A1) >

The pigment (A1) is not particularly limited and known pigments can be used. For example, the pigment is classified into pigments in the Color Index (The Society of Dyers and Colourists).

As the pigment, for example, C.I. 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93 (hereinafter abbreviated as "Pigment Yellow 1" Yellow pigments such as 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194 and 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, Red pigment;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and 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;

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

C.I. Pigment black 1, pigment black 7, and the like.

These pigments may be used alone, or two or more pigments may be mixed and used.

As the 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. Pigment Blue 15, 15: 3, 15: 4, 15: 6 and 60, and C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, and 38 are preferred. By including the above-mentioned pigment, the transmission spectrum of the color filter using the colored curable resin composition of the present invention can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

≪ 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. The Society of Dyers and Colourists), and known dyes described in Dyeing Note (Shika Sensha).

According to the chemical structure, azo dyes, coumarin dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, Dyes, styryl dyes, quinoline dyes, and nitro dyes. Of 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. C.I. 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, 112, 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, 215, 198, 206, 211, 215, 216, 217, 218, 219, 288, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 276, 268, 270, 274, 277, 280, 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 6B, 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, 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., such as Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, Acid dyes,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 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, 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, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 198, 199, 200, 201, 202, 203, 207, 209, 210, 202, 203, 207, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, Direct dyes,

C.I. Disperse Yellow 54, C.I. Disperse dyes,

C.I. Basic Red 1, 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. 43, 38, 39, 41, 43, 43, 43, 43, 42, 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. 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. CI. 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, Modern dyes,

C.I. C.I. Bat dyes,

And the like.

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 is preferably a dye which exhibits a maximum absorption wavelength in chloroform of 400 to 470 nm and a maximum absorption wavelength of 430 to 470 nm in chloroform.

The red dye is preferably a dye which exhibits a maximum absorption wavelength in chloroform of 490 to 550 nm and a maximum absorption wavelength of 490 to 540 nm in chloroform.

The yellow dye (A3) is preferably a dye having a coumarin skeleton. The dye having a coumarin skeleton includes the compounds described in JP-A-2013-231165 and the compounds described below.

The red dye (A4) is preferably a dye having a xanthene skeleton different from the compound (I), and more preferably a dye having a xanthene skeleton in which carbon atoms at the 3-position and the 6-position are bonded to nitrogen atoms.

Examples of the red dye (A4) include a dye having a xanthene skeleton and having a phenylamino group, a diphenylamino group, a phenylalkylamino group and the like as a substituent of the xanthene skeleton, specifically the compounds described below.

R ⁴⁰ in the following formula represents a 2-ethylhexyl group.

The content of the yellow dye is usually 1 part by mass or more and 30 parts by mass or less, preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the compound (I) Or less.

The content of the red dye is usually 1 part by mass or more and 30 parts by mass or less, preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the compound (I) Parts by mass or less.

≪ Resin (B) >

The resin (B) is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) [hereinafter sometimes referred to as " resin (B) ") is a resin derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride Units. ≪ / RTI >

Examples of such a resin (B) include the following resins [K1] to [K6].

At least one monomer (a) [hereinafter sometimes referred to as "(a)") selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether having 2 to 4 carbon atoms And a monomer (b) having an ethylenically unsaturated bond (hereinafter occasionally referred to as "(b)");

(A) and (b), and a monomer (c) copolymerizable with (a), which is different from (a) and (b) ≪ / RTI >

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

Resin [K4] Resin (b) is reacted with a copolymer of (a) and (c);

Resin [K5] Resin (a) is reacted with a copolymer of (b) and (c);

Resin [K6] Resin (a) is reacted with a copolymer of (b) and (c) and the carboxylic acid anhydride is further reacted.

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

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, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-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 acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride;

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate, mono [2- ] Esters;

unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as? - (hydroxymethyl) acrylic acid; And the like.

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

(b) can be obtained, for example, by reacting a polymerizable compound having an ethylenic unsaturated bond with a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one member selected from the group consisting of oxiran ring, oxetane ring and tetrahydrofuran ring) .

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

In the present specification, "(meth) acrylic acid" represents at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Quot ;, " (meth) acryloyl ", and " (meth) acrylate "

(b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as " b2) "), monomers having a tetrahydrofuryl group and an ethylenic unsaturated bond, and the like.

Examples of the monomer (b1) include a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

(b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl- Methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryl Dioctyloxetane, and the like.

(b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate [for example, Viscot V # 150, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.] and tetrahydrofurfuryl methacrylate.

(b) is preferably (b1) in that the reliability of heat resistance, chemical resistance, etc. of the resulting color filter can be further enhanced.

(meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate [referred to in the art as "dicyclopentanyl (meth) acrylate" . (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (Meth) acrylate], dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (Meth) acrylate esters such as pargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

(Meth) acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclo-unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N-phenylmaleimide, N -Cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene are preferred.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Ohtsu Takayuki, First Edition, First Edition, issued March 1, 1972, Can be prepared by reference to the literature.

Specifically, a method of placing a predetermined amount of (a) and (b), a polymerization initiator and a solvent in a reaction vessel and replacing oxygen with nitrogen, for example, . The polymerization initiator, solvent and the like to be used herein are not particularly limited and those generally used in the field can be used. Examples of the polymerization initiator include azo compounds (such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (such as benzoyl peroxide) , And the solvent may be any one that dissolves the respective monomers, and examples of the solvent (E) of the colored curable resin composition of the present invention include solvents described later.

As the obtained copolymer, the solution after the reaction may be used as it is, or a solution obtained by concentration or dilution may be used, and it may be extracted as a solid (powder) by re-precipitation or the like.

Particularly, when a solvent contained in the colored curable resin composition of the present invention is used as a solvent in the polymerization, the solution after the reaction can be used as it is for preparing the colored curable resin composition of the present invention. Therefore, The manufacturing process of the resin composition can be simplified.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) A resin [K1] such as a (meth) acrylic acid copolymer; (Meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / Vinyltoluene copolymer, and a resin [K2] such as 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; A resin such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) K3]; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (meth) ) Resin, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting a (meth) acrylic acid with a copolymer; A resin such as a resin obtained by further reacting a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride, and the like .

The resin (B) is preferably one kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], more preferably a resin [K2] It is one kind selected from the group. If these resins are used, the colored curable resin composition is excellent in developing property. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K2] is more preferable.

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 and the residual film ratio is also high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the coloring pattern tends to be improved.

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

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g.

The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

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

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound which can be polymerized by 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, (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, 2-hydroxyethyl Acrylate, N-vinylpyrrolidone, and the above-mentioned (a), (b) and (c).

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) Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acrylate, tetrapentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, - (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra Propylene glycol-modified dipentaerythritol hexa (meth) acrylate, Caprolactone-modified tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like. Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa Acrylate is 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 from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total solid content.

The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is preferably 20:80 to 80:20, more preferably 35: : 65 to 80:20.

When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a color pattern and the chemical resistance of the color filter tend to be 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 or an acid by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used.

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

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3- cyclopentylpropan- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3- Dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ ) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- Yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxime compound is preferably an N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan- 1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- , And N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine are more preferable.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy- 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one,?,? - diethoxyacetophenone and benzyldimethyl ketal. IRGACURE (registered trademark) 369, 907, 379 (manufactured by BASF), or the like may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372, JP-A 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) ) Diimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) 4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, Imidazole compounds in which the phenyl group at the 4 ', 5,5'-position is substituted by a carboalkoxy group (for example, see JP-A 7-10913).

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- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like.

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

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

The polymerization initiator (D) is preferably a polymerization initiator comprising at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and imidazole compounds , And more preferably 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, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester solvent ( A solvent containing -COO- and -O- in a molecule), a ketone solvent (a solvent containing -CO- in the molecule and not including -COO-), an alcohol solvent (containing OH in the molecule, -O- , -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, 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, and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydrofuran , 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, A brush, 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, Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate.

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

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

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

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

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 Methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone, , 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 propionate, and N-methyl pyrrolidone are more preferred.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on 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% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color characteristic is not insufficient when the color filter is formed, and the display characteristics tend to be good.

≪ Leveling agent (F) >

Examples of the leveling agent (F) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specific examples thereof include TORAY silicone DC3PA, TORAY silicone SH7PA, TORAY silicone DC11PA, TORAY silicone SH21PA, TORAY silicone SH28PA, TORAY silicone SH29PA, TORAY silicone SH30PA, TORAY silicone SH8400 (trade name: Toray Dow Corning) KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan Manufactured by KODO CHEMICAL CO., LTD.).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples of the polymer include Flared (registered trademark) FC430, Florad FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, (Trade name) manufactured by Mitsubishi Chemical Corporation, Mfg. Co., Ltd., Mfg. Co., Ltd., Mfg. F183, Mfg. (Manufactured by Asahi Chemical Industry Co., Ltd.), Surflon (registered trademark) S381, Surfron S382, Surfron SC101, Surfron SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Co., Ltd.) .

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

When the leveling agent (F) is contained, the content thereof is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, relative to the total amount of the colored curable resin composition, Preferably 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 components >

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

≪ Process for producing colored curable resin composition >

The colored curable resin composition of the present invention can be obtained, for example, by mixing the compound (I), the resin (B), the polymerizable compound (C) and the polymerization initiator (D) A solvent (E), a leveling agent (F), a polymerization initiator (D1), and other components.

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

The compound (I) is preferably dissolved in a part or all of the solvent (E) in advance to prepare a solution. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 mu m.

The colored curable resin composition after mixing is preferably filtered with a filter having a pore diameter of about 0.01 to 10 mu m.

<Manufacturing Method of Color Filter>

A coated film formed using the colored curable resin composition of the present invention and a color filter formed using the colored curable resin composition also fall within the scope of the present invention.

The coating film of the present invention can be obtained by a conventionally known method and can be obtained, for example, by applying the above-mentioned colored curable resin composition to a substrate and drying to form a colored composition layer, and further curing the colored curable resin composition layer have.

The curing can be performed by heating or exposing the colored curable resin composition layer by a conventionally known method.

The color filter of the present invention can be formed by the same process as the coating film of the present invention. The color filter of the present invention may include a coloring pattern.

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, a printing method and the like.

Among them, a photolithographic method is preferable.

The photolithographic method is a method in which the above-mentioned colored curable resin composition is applied to a substrate, followed by drying to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithographic method, a colored coating film which is a cured product of the colored composition layer can be formed by not using and / or not developing a photomask at the time of exposure. The coloring pattern or colored coating film thus formed is the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited and may be appropriately adjusted depending on the purpose and application, and is, for example, from 0.1 to 30 탆, preferably from 0.1 to 20 탆, more preferably from 0.5 to 6 탆.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass and soda lime glass whose surface is coated with silica, resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate, silicon, Aluminum, silver, silver / copper / palladium alloy thin film, or the like is formed. A separate color filter layer, a resin layer, a transistor, a circuit, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus or condition. For example, it can be produced as follows.

First, a colored curable resin composition is coated on a substrate and heated and dried (pre-baked) and / or reduced-pressure drying to remove volatile components such as a solvent and dried to obtain a smooth colored composition layer.

Examples of the application method include a spin coat method, a slit coat method, and a slit and spin coat method.

The temperature for heating and drying is preferably 30 to 120 占 폚, more preferably 50 to 110 占 폚. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

In the case of performing the reduced-pressure drying, it is preferably carried out at a temperature of 20 ° C to 25 ° C under a pressure of 50 to 150 Pa.

The film thickness of the coloring composition layer is not particularly limited and may be suitably selected in accordance with the intended thickness of the color filter.

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring 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 having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm is cut using a filter that cuts the wavelength region, or light having wavelengths around 436 nm, 408 nm, and 365 nm is extracted using a bandpass filter Or may be selectively extracted. 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 because it is possible to uniformly irradiate the entire exposure surface with a parallel light beam or accurately align the photomask with the substrate on which the coloring composition layer is formed.

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

The developing method may be any of a puddle method, a dipping method and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. After development, it is preferable to wash with water.

Further, post-baking is preferably performed on the obtained coloring pattern. The post bake temperature is preferably 150 ° C to 250 ° C, more preferably 160 ° C to 235 ° C. The post baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

Example

Hereinafter, the present invention will be described more specifically by way of examples. In the examples,% and parts representing the content or amount 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; manufactured by Agilent LC / MSD type).

Example 1

In the following examples, as the compound (II), a compound of the formula (II) wherein X ¹¹¹ and X ¹¹² are chlorine atoms and R ¹¹⁷ is -SO ₂ was used.

40.6 parts of the compound (II) and 8.0 parts of diethylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as the compound (III) were mixed under the light shielding conditions in the presence of 50 parts of 1-methyl-2-pyrrolidone, And the mixture was stirred at 30 ° C for 3 hours.

The obtained 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 collected as a residue of suction filtration and dried to obtain 44.0 parts of a compound represented by the formula (I-4-A).

Subsequently, 44.0 parts of the compound represented by the formula (I-1-A) and 22.5 parts of 2,6-di-t-butyl-p-cresol (manufactured by Tokyo Kasei Kogyo Co., Was heated in the presence of 50 parts of money at 100 DEG C for 5 hours. The obtained reaction solution was cooled to room temperature, filtered, washed with 100 parts of water, and the obtained crystals were dried to obtain 52 parts of a compound represented by the formula (I-4).

Identification (identification) of the compound represented by the formula (I-4)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 626.3

                        Exact Mass: 625.3

Example 2

40.6 parts of the compound (II) and 30.0 parts of the compound of the formula (III-1) as the compound (III)

Under the light-shielding conditions in the presence of 21.3 parts of [Tokyo Kasei Kogyo Co., Ltd.] and 50 parts of 1-methyl-2-pyrrolidone, and the resulting solution was stirred at 30 ° C for 3 hours. The obtained 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 collected as a residue of suction filtration and dried to obtain 48.6 parts of a compound represented by the formula (I-28-A).

Subsequently, 54.8 parts of the compound represented by the formula (I-28-A) and 22.5 parts of 2,6-di-t-butyl-p-cresol (manufactured by Tokyo Kasei Kogyo Co., Was heated in the presence of 50 parts of money at 100 DEG C for 5 hours. The obtained reaction solution was cooled to room temperature, filtered, washed with 100 parts of water, and the obtained crystals were dried to obtain 60 parts of a compound represented by the formula (I-28).

Example 3

40.6 parts of the compound (II) and 40.0 parts of the compound of the formula (III-2) as the compound (III)

(Manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed in the presence of 50 parts of 1-methyl-2-pyrrolidone under light-shielding conditions, and the resulting solution was stirred at 30 ° C for 3 hours. The obtained 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 collected as a residue of suction filtration and dried to obtain 56.3 parts of a compound represented by the formula (I-40-A).

Subsequently, 58.9 parts of the compound represented by the formula (I-40-A) and 22.5 parts of 2,6-di-t-butyl-p-cresol (manufactured by Tokyo Kasei Kogyo Co., Was heated in the presence of 50 parts of money at 100 DEG C for 5 hours. The obtained reaction solution was cooled to room temperature, filtered, washed with 100 parts of water, and the obtained crystals were dried to obtain 66 parts of a compound represented by the formula (I-40).

&Lt; Measurement of solubility &

Propylene glycol monomethyl ether (hereinafter abbreviated as PGME), ethyl lactate (abbreviated as EL hereinafter), propylene glycol monomethyl ether (hereinafter abbreviated as &quot; PGMA &quot;) of rhodamine B (manufactured by Tokyo Kasei Kogyo Co., The solubility in glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) was determined as follows.

In a 50 ml sample tube, the compound was mixed in the following proportions with respect to 100 parts by mass of the solvent, and then the cap of the sample tube was sealed and vibrated with an ultrasonic vibrator at 30 占 폚 for 3 minutes. Then, the mixture was allowed to stand at room temperature for 30 minutes, suction filtrated, and the residue was visually observed. When insoluble matter was not identified, it was determined that the solubility was good, and when insoluble matter was confirmed, it was determined that the solubility was poor, and the results are shown in Table 1 as x.

3 parts by mass 0.03 g of the compound, 1 g of the solvent (EL)

1 part by mass Compound (0.01 g), 1 g of solvent (PGME)

0.5 parts by mass 0.005 g of the compound, 1 g of the solvent (PGMEA)

The compound (Rb) may be rhodamine B; Manufactured by Tokyo Kasei High School.

[Synthesis of resin]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was appropriately flowed to make a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 DEG C with stirring. Subsequently, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Decane-9-yl acrylate (content ratio: 50:50 in molar ratio) (trade name "E-DCPA", manufactured by Daicel Chemical Industries, Ltd.) in 40 parts of propylene glycol monomethyl ether acetate, Was added dropwise over about 5 hours. On the other hand, a solution prepared by dissolving 26 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was dropped into a flask over about 5 hours using another dropping pump Respectively. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a copolymer and resin (B-1) solution having a solid content of 43.5%. The obtained resin (B-1) had a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mg-KOH / g.

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

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

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; Tetrahydrofuran [THF]

Flow rate; 1.0 ml / min

Solid concentration of the test solution; 0.001 to 0.01 mass%

Dose; 50 μl

Detector; RI

Calibration standards; TSK standard polystyrene

F-40, F-4, F-288, A-2500 and A-500 (manufactured by Tosoh Corporation)

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

[Preparation of colored curable resin composition]

The components shown in Table 2 were mixed to obtain a colored curable resin composition. In Table 2, the number of resins shows the numerical value in terms of solid content.

In Table 2, the respective components are expressed as follows.

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD (R) DPHA; Manufactured by Nippon Kayaku Co., Ltd.]

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure (registered trademark) OXE-01; Manufactured by BASF; O-acyloxime compound]

Solvent (E1): Propylene glycol monomethyl ether acetate

Solvent (E2): Propylene glycol monomethyl ether

Leveling agent (F): Megapack (registered trademark) F554 (manufactured by DIC Corporation)

Yellow dye (Ad1-2): A dye represented by the formula (Ad1-2)

Yellow dye (Ad2-10): A dye represented by the formula (Ad2-10)

Red dye (III-1): a dye represented by the formula (III-1) wherein R ⁴⁰ represents a 2-ethylhexyl group,

Red dye (III-15): The dye represented by the formula (III-15)

[Formation of pattern]

The colored photosensitive composition was coated on a square glass substrate (Eagle XG; Corning) having one side of 2 inches by a spin coating method, and then prebaked at 100 캜 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 mu m, and exposure equipment (TME-150RSK; (Manufactured by Topcon Co., Ltd.) at an exposure amount of 150 mJ / cm &lt; 2 &gt; (based on 365 nm) in an air atmosphere. As the photomask, a photomask having a 100 占 퐉 line and space pattern is used. After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 80 seconds, rinsed with water, and postbaked in an oven at 220 DEG C for 20 minutes And a pattern was obtained.

Coloring patterns were obtained from the colored curable resin compositions of Examples 4 to 8 and Comparative Example 2.

&Lt; Measurement of film thickness &

For the obtained coloring pattern, the film thickness was measured using a film thickness measuring device [DEKTAK3; (Manufactured by Nippon Shinkuigetsu Co., Ltd.).

&Lt; Evaluation of color &

The obtained coloring pattern was measured with a colorimeter [OSP-SP-200; (X, y) and a tristimulus value (Y) in an XYZ colorimetric system of CIE were measured using a characteristic function of a C light source. The larger the value of Y, the higher the brightness. The results are shown in Table 3.

Industrial availability

The compounds of the present invention are excellent in solubility in an organic solvent. The color filter formed from the colored photosensitive resin composition containing the compound of the present invention has high brightness.

Claims (14)

A compound represented by the formula (I).

[In the above formula (I), R ¹ represents a group represented by the formula (i).
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group of 1 to 10 carbon atoms which may have a substituent, and the substituent in the saturated hydrocarbon group represents a group represented by the formula (ii).
R ⁵ and R ⁶ represent a hydrogen atom.
R ⁷ and R ⁸ are each independently a -SO ₃ ^- shows a Z ^+, -SO ₃ R ¹⁰ or _{^{-SO 2 NR 11 R 12 -,}} -SO 3 H, -SO 3.
m represents an integer of 0 to 4; When m is 2 or more, plural R ^{8 s} may be the same or different.
Z ⁺ represents a N ⁺ (R ¹³⁾ _4, Na ⁺ or K ^+.
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.
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 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The plurality of R &lt; ¹³ &gt; may be the same or different.]

[In the above formula (i), R ² represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms.
n represents an integer of 0 to 5; When n is 2 or more, plural R ² may be the same or different.
* Represents the number of bonds (bonds) with oxygen atoms.]

In the above formula (ii), p represents an integer of 1 to 8, R ¹⁴ represents an alkoxy group having 1 to 4 carbon atoms, and * represents the number of bonds with a nitrogen atom or a carbon atom. The plurality of R &lt; ¹⁴ &gt; may be the same or different.] delete delete delete delete delete delete delete A colorant comprising the compound of claim 1. A colored curable resin composition comprising the compound of claim 1, a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colored curable resin composition according to claim 10, further comprising at least one selected from the group consisting of a yellow dye and a red dye. A coating film formed using the colored curable resin composition according to claim 10. A color filter formed using the colored curable resin composition according to claim 10. A display device comprising the color filter according to claim 13.