CN101930176A

CN101930176A - Colored photosensitive composition

Info

Publication number: CN101930176A
Application number: CN2010102178867A
Authority: CN
Inventors: 城内由子; 赤坂哲郎
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2009-06-24
Filing date: 2010-06-22
Publication date: 2010-12-29
Anticipated expiration: 2030-06-22
Also published as: JP2011028236A; TW201106102A; TWI512397B; CN101930176B; KR20100138779A; JP5621337B2; KR101721996B1

Abstract

A colored photosensitive composition containing a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant is a colorant containing a compound represented by formula (2).

[In the formula (2), G ¹ represents an alkylene group with 2 to 12 carbon atoms, and the hydrogen atom contained in the alkylene group can be substituted by an alkyl group with 1 to 4 carbon atoms, and the alkylene group contained in the alkylene group -CH ₂ - may be substituted by -O-, J ¹ represents a hydrogen atom, -NR ^a R ^b or -NR ^a R ^b H ⁺ Q ^- , R ^a and R ^b each independently represent a hydrogen atom or a carbon atom number of 1 to 1 8 alkyl group, Q ^- represents a halide ion, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , X-CO ₂ ^- or Y-SO ₃ ^- , X and Y each independently represent a monovalent organic group, n ^a represents an integer of 1 to 4].

Description

Coloring photosensitive combination

Technical field

The color filter that the present invention relates to coloring photosensitive combination and use this coloring photosensitive combination.

Background technology

The color filter that is used for display device such as display panels, electroluminescence (element), Plasmia indicating panel is to use coloring photosensitive combination to make.The contained colorant of coloring photosensitive combination uses dyestuff or pigment.

Known such coloring photosensitive combination is the composition (patent documentation 1) that contains xanthene dye, pigment, adhesive resin, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent.

A non-patent literature 1: " これ Ga デイスプレイ overall picture だ! (display overall picture) " p.114 (spring Gu She etc. are outstanding; かん I is published distribution on April 18th, 2005)

Patent documentation 2: the Jap.P. spy opens the 2010-32999 communique

Summary of the invention

Further, in order to reach the high-contrastization of color filter, wish a kind of new coloring photosensitive combination of exploitation.

The inventor discusses in order to solve above-mentioned problem, and the result has finished the present invention.

Promptly the invention provides following [1]～[10].

[1]. a kind of coloring photosensitive combination, it contains colorant, adhesive resin, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent, and colorant is the colorant that comprises the compound of formula (2) expression,

[in the formula (2), G ¹The alkylidene of expression carbon number 2～12, the contained hydrogen atom of this alkylidene can be replaced by the alkyl of carbon number 1～4, and this alkylidene is contained-CH ₂-can be replaced by-O-,

J ¹The expression hydrogen atom ,-NR ^aR ^bPerhaps-NR ^aR ^bH ⁺Q ^-,

R ^aAnd R ^bThe alkyl of representing hydrogen atom or carbon number 1～8 independently of one another,

Q ^-Expression halide ion, BF ₄ ^-, PF ₆ ^-, ClO ₄ ^-, X-CO ₂ ^-Perhaps Y-SO ₃ ^-,

X and Y represent the organic group of 1 valency independently of one another,

n ^aThe integer of expression 1～4.]

[2]. as [1] described coloring photosensitive combination, wherein, J ¹Be-NR ^aR ^bPerhaps-NR ^aR ^bH ⁺Q ^-

[3]. as [1] or [2] each described coloring photosensitive combination, wherein, colorant is the colorant that also contains the compound of formula (1) expression,

[in the formula (1), R ¹～R ⁴Represent independently of one another hydrogen atom ,-R ⁶The perhaps aromatic hydrocarbyl of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can by halogen atom ,-R ⁶,-OH ,-OR ⁶,-SO ₃ ^-,-SO ₃H ,-SO ₃M ,-CO ₂H ,-CO ₂R ⁶,-SO ₃R ⁶,-SO ₂NHR ⁸Perhaps-SO ₂NR ⁸R ⁹Replace,

R ⁵Expression-SO ₃ ^-,-SO ₃H ,-SO ₃M ,-CO ₂H ,-CO ₂R ⁶,-SO ₃R ⁶,-SO ₂NHR ⁸Perhaps-SO ₂NR ⁸R ⁹,

M represents 0～5 integer.When m is a integer more than 2, a plurality of R ⁵Can be the same or different,

X represents halogen atom, and a represents 0 or 1 integer,

R ⁶The saturated hydrocarbyl of expression carbon number 1～10, the contained hydrogen atom of the saturated hydrocarbyl of this carbon number 1～10 can be replaced by halogen atom, and this saturated hydrocarbyl is contained-CH ₂-can by-O-,-CO-or-NR ¹⁰-replace,

R ¹⁰The saturated hydrocarbyl of expression hydrogen atom or carbon number 1～10, the contained hydrogen atom of this saturated hydrocarbyl can be replaced by halogen atom, and this saturated hydrocarbyl is contained-CH ₂-quilt-O-or-CO-replaces,

R ⁸And R ⁹Represent independently of one another carbon number 1～10 alkyl, carbon number 3～30 naphthenic base or-Q ¹, the contained hydrogen atom of this alkyl and this naphthenic base can by hydroxyl, halogen atom ,-Q ¹,-CH=CH ₂Perhaps-CH=CHR ⁶Replacing, this alkyl and this naphthenic base be contained-CH ₂-can by-O-,-CO-or-NR ¹⁰-replace R ⁸And R ⁹Bonding and form the heterocycle of carbon number 1～10 mutually, the contained hydrogen atom of this heterocycle can be by R ⁶,-OH or-Q ¹Replace,

Q ¹The expression aromatic hydrocarbyl of carbon number 6～10 or the aromatic heterocycle of carbon number 3～10, the contained hydrogen atom of this aromatic hydrocarbyl and aromatic heterocycle can by-OH ,-R ⁶,-OR ⁶,-NO ₂,-CH=CH ₂,-CH=CHR ⁶Perhaps halogen atom replaces,

M represents sodium atom or potassium atom,

Wherein, the compound of formula (1) expression+charge number with-charge number is identical.]

[4]. as each described coloring photosensitive combination in [1]～[3], wherein, colorant is the colorant that also contains organic pigment.

[5]. as [4] described coloring photosensitive combination, wherein, organic pigment is to contain the C.I. pigment blue 15: 6 organic pigment.

[6]. as each described coloring photosensitive combination in [1]～[5], wherein, the content of the compound of formula (2) expression is 1～50 quality % with respect to colorant.

[7]. as each described coloring photosensitive combination in [1]～[6], wherein, Photoepolymerizationinitiater initiater is the compound with oxime structure.

[8]. a kind of filming, each described coloring photosensitive combination forms in its use [1]～[7].

[9]. a kind of color filter, each described photosensitive composition forms in its use [1]～[7].

[10]. as [9] described color filter, it forms by photo-engraving process.

Description of drawings

Fig. 1 is the skeleton diagram of explanation manufacturing method of color filter of the present invention;

Fig. 2 is the skeleton diagram of explanation manufacturing method of color filter of the present invention;

Fig. 3 is the skeleton diagram of explanation manufacturing method of color filter of the present invention;

Fig. 4 is the skeleton diagram of explanation manufacturing method of color filter of the present invention.

Embodiment

Coloring photosensitive combination of the present invention contains colorant (below, be called " colorant (A) " sometimes), and colorant (A) contains the compound of formula (2) expression,

J ¹The expression hydrogen atom ,-NR ^aR ^bPerhaps-NR ^aR ^bH ⁺Q ^-,

X and Y represent the organic group of 1 valency independently of one another,

n ^aThe integer of expression 1～4.]

The alkylidene of carbon number 2～12 has methylene, ethylidene, glyceryl (propylidene), Ding Erji (butylidene) etc. for example.

-CH ₂The alkylidene of-the carbon number 2～12 that can be replaced by-O-has the group of formula (G-1) expression and the group of formula (G-2) expression for example.

[in formula (G-1) and the formula (G-2), G ²～G ⁵The alkylidene of representing carbon number 1～8 independently of one another.

n ¹The integer of expression 1～3.

n ²The integer of expression 0～3.

Wherein, the carbon atom that the group of formula (G-1) expression is contained and the total number of oxygen atom are 3～12, and the carbon atom that the group of formula (G-2) expression is contained and the total number of oxygen atom are respectively 2～12.

* the bonding position of expression and-NH-.]

The alkyl of carbon number 1～4 is exemplified as methyl, ethyl, propyl group, butyl etc.

-SO ₂-NH-G ¹-J ¹Be exemplified as the group that for example following formula is represented.

G ¹During for the group of formula (G-1) expression ,-SO ₂-NH-G ¹-J ¹Be exemplified as the group that for example following formula is represented.

G ¹During for the group of formula (G-2) expression ,-SO ₂-NH-G ¹-J ¹Be exemplified as the group that for example following formula is represented.。

J ¹For-NR ^aR ^bThe time ,-SO ₂-NH-G ¹-J ¹Be exemplified as the group that following formula is represented.

J ¹For-NR ^aR ^bH ⁺Q ^-The time ,-SO ₂-NH-G ¹-NR ^aR ^bH ⁺Be exemplified as the group that following formula is represented.

Q ^-Expression halide ion, BF ₄ ^-, PF ₆ ^-, ClO ₄ ^-, X-CO ₂ ^-Perhaps Y-SO ₃ ^-

X and Y represent the organic group of 1 valency.The organic group of 1 valency has the alkyl of carbon number 1～20, the naphthenic base of carbon number 3～20, the aryl of carbon number 6～20 and the group that they combine for example.

The alkyl of carbon number 1～20 has methyl, ethyl, propyl group, butyl, hexyl, decyl etc. for example.

The naphthenic base of carbon number 3～20 has cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ring decyl etc. for example.

The aryl of carbon number 6～20 has phenyl, naphthyl, phenanthryl for example.

X-CO ₂ ^-Be to contain CO ₂ ^-The organism negative ion of base, Y-SO ₃ ^-Be to contain SO ₃ ^-The organism negative ion of base for example, has the negative ion of formula (Q-1)～formula (Q-4) expression for example.

[R ^yThe alkyl of expression carbon number 1～20.

M represents 0～5 integer.]

Q ^-Preferred X-CO ₂ ^-And Y-SO ₃ ^-, the more preferably negative ion of formula (Q-4) expression.The tendency that these negative ion have the dissolubility of compound in solvent of formula of making (2) expression to uprise.

The compound of formula (2) expression has for example compound of formula (2-1)～formula (2-92) expression for example.

For example, the example more specifically of the compound of formula (2-24) expression has the compound of formula (2-24-1) and formula (2-24-2) expression for example.

The content of colorant (A) is preferably 10～70 quality % with respect to the solid state component in the coloring photosensitive combination, more preferably 15～55 quality %, more preferably 20～50 quality %.Here, solid state component is meant the total of the composition outside the desolventizing in the coloring photosensitive combination.

The content of colorant (A) is when above-mentioned scope, and colour saturation is abundant when making color filter, and can make the adhesive resin that contains necessary amount in the composition, can form the sufficient pattern of physical strength, thereby desirable.

Preferred 1～50 quality % of content of the compound of formula (2) expression in the colorant (A), more preferably 1～40 quality %, further preferred 2～30 quality %.

The content of the compound of formula (2) expression in the colorant (A) reaches the optimization that penetrates spectrum easily, and can obtain the color filter of high-contrast and high brightness when above-mentioned scope.

Colorant (A) is selected according to the color of purpose color filter, also can contain multiple dyestuff or pigment.

Colorant (A) preferably except the compound that contains formula (2) expression, also contains the colorant of xanthene dye.

Xanthene dye for example specifically have for example rhodamine B, sulfo group rhodamine 101, sulfo group rhodamine B, rhodamine 6G,

C.I. acid red 51,91,92,289

C.I. acid violet 102

C.I. solvent red 49,72

C.I. alkali red 1:1 etc.

Xanthene dye is the represented compound of formula (1) preferably.

(in the formula (1), R ¹～R ⁴Represent independently of one another hydrogen atom ,-R ⁶The perhaps aromatic hydrocarbyl of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can by halogen atom ,-R ⁶,-OH ,-OR ⁶,-SO ₃ ^-,-SO ₃H ,-SO ₃M ,-CO ₂H ,-CO ₂R ⁶,-SO ₃R ⁶,-SO ₂NHR ⁸Perhaps-SO ₂NR ⁸R ⁹Replace,

X represents halogen atom.A represents 0 or 1 integer,

R ⁶The saturated hydrocarbyl of expression carbon number 1～10, the contained hydrogen atom of the saturated hydrocarbyl of this carbon number 1～10 can be replaced by halogen atom, and this saturated hydrocarbyl is contained-CH ₂-can by-O-,-CO-or-NR ¹⁰-replace.

R ¹⁰The saturated hydrocarbyl of expression hydrogen atom or carbon number 1～10, the contained hydrogen atom of this saturated hydrocarbyl can be replaced by halogen atom, and this saturated hydrocarbyl is contained-CH ₂-can by-O-,-CO-replaces.

R ⁸And R ⁹Represent independently of one another carbon number 1～10 alkyl, carbon number 3～30 naphthenic base or-Q ¹, the contained hydrogen atom of this alkyl and this naphthenic base can by hydroxyl, halogen atom ,-Q ¹,-CH=CH ₂Perhaps-CH=CHR ⁶Replacing, this alkyl and naphthenic base be contained-CH ₂-can by-O-,-CO-or-NR ¹⁰-replace.Perhaps R ⁸And R ⁹Bonding and form the heterocycle of carbon number 1～10 mutually, the contained hydrogen atom of this heterocycle can be by R ⁶,-OH or-Q ¹Replace.

Q ¹The expression aromatic hydrocarbyl of carbon number 6～10 or the aromatic heterocycle of carbon number 5～10, the contained hydrogen atom of above-mentioned aromatic hydrocarbyl and aromatic heterocycle can by-OH ,-R ⁶,-OR ⁶,-NO ₂,-CH=CH ₂,-CH=CHR ⁶Perhaps halogen atom replaces,

M represents sodium atom or potassium atom.

Wherein, the compound of formula (1) expression+charge number with-charge number is identical.)

R ⁶Methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, amyl group, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, suberyl, octyl group, 2-ethylhexyl, ring octyl group, nonyl, decyl (decanyl), three ring decyls, methoxy-propyl, ethoxycarbonyl propyl, own oxygen base propyl group, 2-ethyl hexyl oxy propyl group, methoxyl hexyl, ethoxycarbonyl propyl etc. are arranged for example.

The aromatic hydrocarbyl of carbon number 6～10 has phenyl, naphthyl etc. for example.

As the substituting group of the aromatic hydrocarbyl of this carbon number 6～10 for the halogen atom of example, fluorine, chlorine, bromine etc. are arranged for example.

-SO ₃R ⁶Methoxyl sulfonyl, ethoxy sulfonyl, own oxygen base sulfonyl, last of the ten Heavenly stems oxygen base sulfonyl etc. is arranged for example.

-CO ₂R ⁶Methoxycarbonyl is arranged for example, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, butoxy carbonyl, isobutoxy carbonyl, pentyloxy carbonyl, the isoamoxy carbonyl, the neopentyl oxygen carbonyl, the cyclopentyloxy carbonyl, hexyloxy carbonyl, cyclohexyloxy carbonyl, heptan oxygen base carbonyl, ring oxygen base carbonyl in heptan, carbonyl octyloxy, 2-ethylhexyl oxygen base carbonyl, ring octyl group oxygen base carbonyl, nonyl oxygen base carbonyl, decyl (decanyl) oxygen base carbonyl, three ring decyl (decanyl) oxygen base carbonyls, the methoxy propoxy carbonyl, the ethoxy propoxycarbonyl, own oxygen base propoxycarbonyl, 2-ethyl hexyl oxy propoxycarbonyl, methoxyl hexyloxy carbonyl etc.

-SO ₂NHR ⁸Sulfamoyl is arranged for example; N-(methyl) sulfamoyl; N-(ethyl) sulfamoyl; N-(propyl group) sulfamoyl; N-(isopropyl) sulfamoyl; N-(butyl) sulfamoyl; N-(isobutyl) sulfamoyl; N-(amyl group) sulfamoyl; N-(isopentyl) sulfamoyl; N-(neopentyl) sulfamoyl; N-(cyclopentyl) sulfamoyl; N-(hexyl) sulfamoyl; N-(cyclohexyl) sulfamoyl; N-(heptyl) sulfamoyl; N-(suberyl) sulfamoyl; N-(octyl group) sulfamoyl; N-(2-ethylhexyl) sulfamoyl; N-(1,5-dimethyl hexyl) sulfamoyl; N-(ring octyl group) sulfamoyl; N-(nonyl) sulfamoyl; N-(decyl) sulfamoyl; N-(three ring decyls) sulfamoyl; N-(methoxy-propyl) sulfamoyl; N-(ethoxycarbonyl propyl) sulfamoyl; N-(propoxyl group propyl group) sulfamoyl; N-(isopropoxide propyl) sulfamoyl; N-(own oxygen base propyl group) sulfamoyl; N-(2-ethyl hexyl oxy propyl group) sulfamoyl; N-(methoxyl hexyl) sulfamoyl; N-(3-phenyl-1-methyl-propyl) sulfamoyl etc.

-SO ₂NHR ⁸And-SO ₂NR ⁸R ⁹The group that also has following formula to represent for example.

In the above-mentioned formula, X ¹The expression halogen atom.X ¹In halogen atom fluorine atom, chlorine atom and bromine atoms are arranged for example.

In the above-mentioned formula, X ³The alkyl of expression carbon number 1～3 or the alkoxy of carbon number 1～3, the hydrogen atom of this alkyl and alkoxy can be replaced by halogen atom.

The alkyl of the carbon number 1～3 that can be replaced by halogen atom has methyl, ethyl, propyl group, isopropyl, trifluoromethyl etc. for example.

The alkoxy of the carbon number 1～3 that can be replaced by halogen atom has methoxyl, ethoxy, propoxyl group, fluoro methoxyl etc. for example.

In the above-mentioned formula, X ²The alkyl of expression carbon number 1～3, alkoxy, halogen atom or the nitro of carbon number 1～3, the hydrogen atom of this alkyl and alkoxy can be replaced by halogen atom.

X ²In halogen atom fluorine atom, chlorine atom and bromine atoms are arranged for example.

In the above-mentioned formula, X ²The meaning of expression is same as described above.

In the above-mentioned formula, X ³The meaning of expression is same as described above.

-SO ₂NR ⁸R ⁹Contained R ⁸And R ⁹The branch-like alkyl of preferred carbon number 6～8, naphthenic base, allyl, phenyl, the aralkyl of carbon number 8～10, the hydroxyl alkyl of carbon number 2～8 and the alkyl or aryl that contains alkoxy of aryl and carbon number 2～8 of carbon number 5～7, especially preferred 2-ethylhexyl.

The preferred ethyl of the substituting group of the aromatic hydrocarbyl of carbon number 6～10, propyl group, phenyl, 3,5-dimethylphenyl ,-SO ₃R ⁶Perhaps-SO ₂NHR ⁸

Aromatic hydrocarbyl with substituent carbon number 6～10 has aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, ethylphenyl, hexyl phenyl, decyl phenyl, fluorophenyl, chlorphenyl, bromophenyl, hydroxy phenyl, methoxyphenyl, Dimethoxyphenyl, ethoxyl phenenyl, own oxygen base phenyl, last of the ten Heavenly stems oxygen base phenyl, trifluoromethyl etc. for example.

R ¹And R ²In one of at least or R ³And R ⁴In the alkyl of one of at least preferred carbon number 1～4 or aromatic hydrocarbyl that can substituted carbon number 6～10.

R ¹And R ²In one of at least and R ³And R ⁴In the alkyl of one of at least preferred carbon number 1～4 or aromatic hydrocarbyl that can substituted carbon number 6～10.

R ¹And R ²In one of at least and R ³And R ⁴In one of at least more preferably can substituted carbon number 6～10 aromatic hydrocarbyl.

R ⁵Be preferably carboxyl, ethoxy carbonyl, sulfo group, N-(2-ethyl hexyl oxy propyl group) sulfamoyl, N-(1,5-dimethyl hexyl) sulfamoyl, N-(3-phenyl-1-methyl-propyl) sulfamoyl, N-(isopropoxide propyl) sulfamoyl.

The compound of compound preferred formula (1-1) expression of formula (1) expression,

[in the formula (1-1), R ¹¹～R ¹⁴Represent independently of one another hydrogen atom ,-R ⁶The perhaps aromatic hydrocarbyl of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can by halogen atom ,-R ⁶,-OH ,-OR ⁶,-SO ₃ ^-,-SO ₃H ,-SO ₃Na ,-CO ₂H ,-CO ₂R ⁶,-SO ₃R ⁶,-SO ₂NHR ⁸Perhaps-SO ₂NR ⁸R ⁹Replace,

R ¹⁵The expression hydrogen atom ,-SO ₃ ^-,-SO ₃H ,-SO ₂NHR ⁸Perhaps-SO ₂NR ⁸R ⁹,

R ¹⁶Expression-SO ₃ ^-,-SO ₃H ,-SO ₂NHR ⁸Perhaps-SO ₂NR ⁸R ⁹,

R ⁶, R ⁸, R ⁹, the meaning represented of m, X and a is same as described above.

Wherein, the compound of formula (1-1) expression+charge number with-charge number is identical.]

The compound of compound preferred formula (1-2) expression of formula (1) expression,

[(in the formula (1-2), R ²¹～R ²⁴Represent independently of one another hydrogen atom ,-R ²⁶The perhaps aromatic hydrocarbyl of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can by halogen atom ,-R ²⁶,-OH ,-OR ²⁶,-SO ₃ ^-,-SO ₃Na ,-CO ₂H ,-CO ₂R ²⁶,-SO ₃H ,-SO ₃R ²⁶Perhaps-SO ₂NHR ²⁸Replace,

R ²⁵Expression-SO ₃ ^-,-SO ₃Na ,-CO ₂H ,-CO ₂R ²⁶,-SO ₃H or-SO ₂NHR ²⁸,

R ²⁶The saturated hydrocarbyl of expression carbon number 1～10, the contained hydrogen atom of this saturated hydrocarbyl can be by-OR ²⁷Perhaps halogen atom replaces,

R ²⁷The saturated hydrocarbyl of expression carbon number 1～10.

R ²⁸The expression hydrogen atom ,-R ²⁶,-CO ₂R ²⁶The perhaps aromatic hydrocarbyl of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can be by-R ²⁶Perhaps-OR ²⁶Replace,

The meaning that m, X and a represent is same as described above.

Wherein, the compound of formula (1-2) expression+charge number with-charge number is identical.]

The compound of compound preferred formula (1-3) expression of formula (1) expression,

[in the formula (1-3), R ³¹And R ³²Represent phenyl independently of one another, the contained hydrogen atom of this phenyl can by halogen atom ,-R ²⁶,-OR ²⁶,-CO ₂R ²⁶,-SO ₃R ²⁶Perhaps-SO ₂NHR ²⁸Replace,

R ³³Expression-SO ₃ ^-Perhaps-SO ₂NHR ²⁸,

R ³⁴The expression hydrogen atom ,-SO ₃ ^-Perhaps-SO ₂NHR ²⁸,

R ²⁶, R ²⁸, the meaning represented of X and a is same as described above.

Wherein, the compound of formula (1-3) expression+charge number with-charge number is identical.]

The compound of compound preferred formula (1-4) expression of formula (1) expression,

[in the formula (1-4), R ⁴¹And R ⁴²Represent phenyl independently of one another, the contained hydrogen atom of this phenyl can be by-R ²⁶Perhaps-SO ₂NHR ²⁸Replace,

R ⁴³Expression-SO ₃ ^-Perhaps-SO ₂NHR ²⁸,

R ²⁶, R ²⁸, X and a represent meaning same as described above.

Wherein, the compound of formula (1-4) expression+charge number with-charge number is identical.]

The compound of formula (1) expression has for example compound of formula (1a)～formula (1f) expression for example.

[in the formula (1a), R ^bAnd R ^cRepresent independently respectively hydrogen atom ,-SO ₃ ^-,-CO ₂H or-SO ₂NHR ^aR ^aExpression 2-ethylhexyl.The meaning that X and a represent is same as described above.]

[in the formula (1b), R ^bThe meaning of expression is same as described above.]

The compound of formula (1b) expression is the dynamic isomer of the compound of formula (1b-1) expression.

[in the formula (1b-1), R ^b, the meaning represented of X and a is same as described above.]

[in formula (1c) and the formula (1d), R ^d, R ^cAnd R ^fDifference is expression-SO independently ₃ ^-,-SO ₃Na or-SO ₂NHR ^aR ^aExpression 2-ethylhexyl.]

[in formula (1e) and the formula (1f), R ^g, R ^hAnd R ⁱRepresent independently respectively hydrogen atom ,-SO ₃ ^-,-SO ₃H or-SO ₂NHR ^aR ^aExpression 2-ethylhexyl.]

Having-SO in the compound of formula (1) expression ₂NHR ⁸Compound can obtain by the following method, for example by conventional method to having-SO ₃The pigment of H or pigment intermediate carry out chlorination, make having-SO of obtaining again ₂The pigment of Cl or pigment intermediate and R ⁸-NH ₂The amine reaction of expression.Also can obtain, make a kind of pigment,, make it then to react with amine with this pigment and above-mentioned the same ground chlorination by the method that the upper right hurdle～hurdle, lower-left of the 3rd page in Japanese patent laid-open 3-78702 communique is put down in writing by such method.

Colorant (A) preferably also contains the colorant of organic pigment.

As organic pigment, for example have for example particularly: C.I. pigment blue 15,15:3,15:4,15:6, blue pigments such as 60; C.I.

pigment violet

1,19,23,29,32,36, violet pigment of 38 etc. etc.Wherein, preferred C.I. pigment purple 23, C.I. pigment blue 15: 3 or 15:6, especially preferably contain the C.I. pigment blue 15: 6.These pigment may be used alone, can also be two or more kinds in combination.

As required, can handle or utilize the cleaning treatment of removing organic solvent that impurity uses or water etc. to the micronize that the organic pigment in the above-mentioned pigment carry out that the surface treatment that imports pigment derivative that acidic groups or basic group are arranged etc. is handled, used to rosin, sulfuric acid micronize method is handled, utilized in the grafting that utilizes macromolecular compound that surface of pigments is carried out etc. and carries out, utilize ion exchange process etc. remove ionic impurity remove processing etc.

Preferably, the uniform particle diameter of organic pigment.Carry out dispersion treatment by making it to contain pigment dispersing agent, can obtain the dispersible pigment dispersion that pigment is dispersed in state such in the solution equably.

Surfactants such as kation system, negative ion system, nonionic system, both sexes, polyester system, polyamine system, acrylic acid series etc. are arranged for example as above-mentioned pigment dispersing agent.Can only use a kind, also can be used in combination more than 2 kinds.

When using pigment dispersing agent, in the pigment of per 1 mass parts, below preferred 1 mass parts of its use amount, more preferably 0.05 mass parts above, below 0.5 mass parts.The use amount of pigment dispersing agent has the tendency of the dispersible pigment dispersion that can obtain the homogeneous disperse state when above-mentioned scope.

Especially, preferred C.I. pigment blue 15: 6 with the mass ratio of the compound of formula (1) expression be 97: 3～50: 50.

When the content of the organic pigment in the colorant (A) during, penetrate the easy optimization of spectrum, and owing to obtain high-contrast, high brightness, thereby good, and thermotolerance, drug resistance are good, therefore more satisfactory in above-mentioned scope.

Coloring photosensitive combination of the present invention contains adhesive resin (B).Adhesive resin can use known.

Adhesive resin is the resin with alkali dissolution, is the multipolymer that contains the formation unit that is derived from compound (B0) (below be sometimes referred to as " (B0) ") and be derived from the formation unit of compound (B2) (below be sometimes referred to as " (B2) ").Above-claimed cpd (B0) possesses carbon-to-carbon unsaturated double-bond and cyclic ether structure, and compound (B2) is selected from least a kind in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides.

As the cyclic ether structure of (B0), for example can enumerate epoxy construction, oxetanes structure and tetrahydrofuran structure.

The structure that epoxy construction can enumerate structure that the chain alkene epoxidation is obtained, obtain monocycle cycloolefin epoxidation and will encircle the structure that the cycloolefin epoxidation obtains preferably will be encircled the structure that the cycloolefin epoxidation obtains more more.

(B0) preferably contain the compound of carbon-to-carbon unsaturated double-bond and epoxy construction, the compound that more preferably has the carbon-to-carbon unsaturated double-bond and will encircle the structure that the cycloolefin epoxidation obtains more.When (B0) being these compounds, resulting filming and solvent resistance, the excellent heat resistance of color filter.

The compound of the structure that contains the carbon-to-carbon unsaturated double-bond and the chain alkene epoxidation is obtained specifically can be enumerated, the compound of following formula (IV) expression of diglycidyl (methyl) acrylate, Beta-methyl diglycidyl (methyl) acrylate, β-ethyl diglycidyl (methyl) acrylate, glycidyl vinyl ether, the record of Japanese patent laid-open 7-248625 communique etc.

[in the formula (IV), R ⁶¹～R ⁶³The alkyl of representing hydrogen atom or carbon number 1～10 independently of one another, m1 are 1～5 integer.]

The compound of following formula (IV) expression for example can be enumerated, adjacent vinyl benzyl glycidol ether, between the vinyl benzyl glycidol ether, to the vinyl benzyl glycidol ether, the adjacent vinyl benzyl glycidol ether of Alpha-Methyl, vinyl benzyl glycidol ether between Alpha-Methyl, Alpha-Methyl is to the vinyl benzyl glycidol ether, 2,3-diepoxy propoxyl group methyl styrene, 2,4-diepoxy propoxyl group methyl styrene, 2,5-diepoxy propoxyl group methyl styrene, 2,6-diepoxy propoxyl group methyl styrene, 2,3,4-three glycidoxy methyl styrenes, 2,3,5-three glycidoxy methyl styrenes, 2,3,6-three glycidoxy methyl styrenes, 3,4,5-three glycidoxy methyl styrenes and 2,4,6-three glycidoxy methyl styrenes.

The compound of the structure that contains the carbon-to-carbon unsaturated double-bond and monocycle cycloolefin epoxidation is obtained preferably has (methyl) acryloxy and the compound of structure that monocycle cycloolefin epoxidation is obtained.Above-mentioned monocycle cycloolefin has cyclopentene, cyclohexene, cycloheptene, cyclooctene etc. for example.

The compound of the structure that contains the carbon-to-carbon unsaturated double-bond and monocycle cycloolefin epoxidation is obtained, for example can enumerate, the single oxidation 1 of vinyl cyclohexene, the 2-epoxy-the 4-vinyl cyclohexane (for example, セロキサイ De 2000, ダイセ Le chemical industry (strain) manufacturing), acrylic acid-3,4-epoxycyclohexyl methyl ester (for example, サイ Network ロマ one A400, ダイセ Le chemical industry (strain) manufacturing), methacrylic acid-3,4-epoxycyclohexyl methyl ester (for example, サイ Network ロマ one M100, ダイセ Le chemical industry (strain) is made) etc.

Here, expression acryloxy of " (methyl) acryloxy " in this instructions and methacryloxy is at least a.Statement such as " (methyl) acrylic acid ... ester " and " (methyl) acrylic acid " also has same meaning.

The compound (B1) (below be sometimes referred to as " (B1) ") that contains the carbon-to-carbon unsaturated double-bond and will encircle the structure that the cycloolefin epoxidation obtains more preferably has (methyl) acryloxy and will encircle the compound of the structure that the cycloolefin epoxidation obtains more.Above-mentioned many ring cycloolefins can be enumerated two cyclopentene, tricyclo decene, norbornane, different norborene, bicyclooctene, bicyclononene, two ring undecylenes, three ring undecylenes, two ring dodecylenes, three ring dodecylenes etc.

(B1) for example can enumerate, acrylic acid-3,4-epoxy norborneol ester, methacrylic acid-3, the compound of the compound of 4-epoxy norborneol ester, formula (B1-1) expression and formula (B1-2) expression, preferably at least a kind of compound from the compound that the compound and the formula (B1-2) of formula (B1-1) expression are represented, selecting.

[in formula (B1-1) and the formula (B1-2), R ⁷¹And R ⁷²The alkyl of representing the carbon number 1～4 that hydrogen atom or its hydrogen atom can be replaced by hydroxyl independently of one another.

X ¹And X ²The alkylidene or the expression *-(CH that represent singly-bound or carbon number 1～6 independently of one another ₂) _s-X ³-(CH ₂) _t-.

X ³Expression-S-,-O-or-NH-.

S represents 1～6 integer, and t represents 0～6 integer.S+t≤6 wherein.

* represent bonding position with O.]

Alkyl as the carbon number 1～4 that can be replaced by hydroxyl, specifically can enumerate hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc., preferable methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably methyl.

R ⁷¹And R ⁷²Preferred hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably hydrogen atom, methyl.

The heteroatoms that can contain the alkylidene of heteroatomic carbon number 1～6 can be enumerated, oxygen atom, sulphur atom and nitrogen-atoms.In addition, the heteroatoms number is not contained in the carbon number.

The alkylidene of carbon number 1～6 can be enumerated, methylene, ethylidene, propane-1,2-two bases (promptly 1,2-propylidene), propane-1,3-two bases (promptly 1, the 3-propylidene), butane-1,4-two bases (promptly 1,4-butylidene), pentane-1,5-two bases (promptly 1, the 5-pentylidene), hexane-1,6-two bases (promptly 1,6-hexylidene),

X ¹And X ²Preferred singly-bound, methylene, ethylidene ,-O-CH ₂-or-O-(CH ₂) ₂-, more preferably singly-bound or-O-(CH ₂) ₂-.

The compound of formula (B1-1) expression can be enumerated the compound of formula (B1-1-1)～formula (B1-1-15) expression etc., the compound of preferred formula (B1-1-1), formula (B1-1-3), formula (B1-1-5), formula (B1-1-7), formula (B1-1-9), formula (B1-1-11)～formula (B1-1-15) expression, the more preferably compound of formula (B1-1-1), formula (B1-1-7), formula (B1-1-9) or formula (B1-1-15) expression.

Compound as formula (B1-2) expression, can enumerate, the compound of formula (B1-2-1)～formula (B1-2-15) expression etc., the compound of preferred formula (B1-2-1), formula (B1-2-3), formula (B1-2-5), formula (B1-2-7), formula (B1-2-9), formula (B1-2-11)～formula (B1-2-15) expression, the more preferably compound of formula (B1-2-1), formula (B1-2-7), formula (B1-2-9) or formula (B1-2-15) expression.

Be selected from least a kind of compound in the compound of the compound of formula (B1-1) expression and formula (B1-2) expression, can use separately separately.In addition, they also can mix with arbitrary ratio.During mixing, its mixture ratio is formula (B1-1): the mol ratio of formula (B1-2), preferred 5: 95～95: 5, more preferably 10: 90～90: 10, preferred especially 20: 80～80: 20.

Compound with above-mentioned carbon-to-carbon unsaturated double-bond and oxetanes structure preferably has the compound of oxa-cyclobutyl and (methyl) acryloxy.

Compound with carbon-to-carbon unsaturated double-bond and oxetanes structure specifically has 3-methyl-3-methacryloxy methyl oxetanes for example, 3-methyl-3-acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-methacryloxy methyl oxetanes, 3-ethyl-3-acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloxy ethyl oxetanes, 3-ethyl-3-methacryloxyethyl oxetanes or 3-ethyl-3-acryloxy ethyl oxetanes.

Compound with above-mentioned carbon-to-carbon unsaturated double-bond and tetrahydrofuran structure preferably has the monomer of tetrahydrofuran base and (methyl) acryloxy.

Compound with carbon-to-carbon unsaturated double-bond and tetrahydrofuran structure specifically has acrylic acid tetrahydro furfuryl ester (for example, PVC スコ one ト V#150, Osaka organic chemistry industry (strain) manufacturing), methacrylic acid tetrahydro furfuryl ester etc. for example.

(B2) for example can enumerate the unsaturated monocarboxylic class of acrylic acid, methacrylic acid, butenoic acid etc.;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1, unsaturated dicarboxylic classes such as 4-cyclohexene dicarboxylic acid;

Methyl-5-norborene-2,3-dicarboxylic acid, 5-carboxyl two ring [2.2.1]-2-heptene, 5,6-dicarboxyl two ring [2.2.1]-2-heptene, 5-carboxyl-5-methyl bicyclic [2.2.1]-2-heptene, 5-carboxyl-5-ethyl two ring [2.2.1]-2-heptene, 5-carboxyl-6-methyl bicyclic [2.2.1]-2-heptene, 5-carboxyl-6-ethyl two ring [2.2.1]-2-heptene etc. contain two ring unsaturated compound classes of carboxyl;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5, the acid anhydrides of 6-dicarboxyl two ring [2.2.1]-2-heptene acid anhydrides unsaturated dicarboxylic classes such as (carbic anhydrides);

Unsaturated list [(methyl) acryloxyalkyl] the ester class of the polybasic carboxylic acids more than 2 yuan such as succinic acid list [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester;

Contain unsaturated esters of acrylic acid of hydroxyl and carboxyl etc. in the such same a part of acrylic acid-α-(hydroxymethyl) ester.

Wherein, based on copolyreaction, dissolubility in aqueous alkali, preferred acrylic acid, methacrylic acid, maleic anhydride.They can be used alone or in combination.

Adhesive resin (B) is to contain from the formation unit of (B0) with from the multipolymer of the formation unit of (B2), from the formation unit of (B0) with from the ratio of the formation unit of (B2) the words that are aggregated in following scope with respect to the formation unit that constitutes above-mentioned multipolymer, since possess the good tendency of storage stability, thermotolerance and physical strength, therefore comparatively desirable.

Formation unit from (B0): 2～98 moles of %

Formation unit from (B2): 2～98 moles of %

In addition, the ratio of above-mentioned formation unit is in following scope, and is based on the angle of development and solvent resistance, desirable more.

Formation unit from (B0): 40～85 moles of %

Formation unit from (B2): 15～60 moles of %

Above-mentioned adhesive resin (B) but the manufacturing reference example as, document " experimental method of Polymer Synthesizing " (the big grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people) method of record and the citing document of document record.

Concrete, by with a certain amount of (B0) and (B2), polymerization initiator and solvent pack in the reaction vessel, nitrogen replacement oxygen under the situation that does not have oxygen, stirs, heats, is incubated, and obtains multipolymer.In addition,, can directly use reacted solution, also can use the solution that concentrates or dilute, also can pass through again method taking-up solid (powder) uses such as precipitation for the multipolymer that obtains.

In addition, adhesive resin (B) is except containing the formation unit and the formation unit from (B2) from (B0), also contain from can with (B0) and (B2) (B3) the formation unit of (below be sometimes referred to as " (B3) ") of the compound of copolymerization (still, (B1) and (B2) except).

Above-mentioned (B3) can enumerate, (methyl) alkyl-acrylates of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate etc.;

The alkyl-acrylates of methyl acrylate, isopropyl acrylate etc.;

(methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-methyl cyclohexane ester, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] (methyl) acrylic acid cyclic alkyl ester classes such as decane-8-base ester (in this technical field, trivial name is called (methyl) acrylic acid two cyclopentyl esters (ジシ Network ロペ Application タニ Le (メタ) ア Network リレ one ト)), (methyl) acrylic acid two cyclopentyloxy ethyl esters (ジシ Network ロペ Application タニ Le オキシエチ Le (メタ) ア Network リレ one ト), (methyl) isobornyl acrylate;

(methyl) acrylic acid aryl ester class of (methyl) phenyl acrylate etc.;

(methyl) acrylic acid aralkyl ester class of (methyl) benzyl acrylate etc.;

The dicarboxylic diester of diethyl maleate, DEF, diethyl itaconate etc.;

The hydroxyalkyl acrylate class of (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-2-hydroxy propyl ester etc.;

Two ring [2.2.1]-2-heptene, 5-methyl bicyclic [2.2.1]-2-heptene, 5-ethyl two ring [2.2.1]-2-heptene, 5-hydroxyl two ring [2.2.1]-2-heptene, 5-hydroxymethyl two ring [2.2.1]-2-heptene, 5-(2 '-hydroxyethyl) two ring [2.2.1]-2-heptene, 5-methoxyl two ring [2.2.1]-2-heptene, 5-ethoxy two ring [2.2.1]-2-heptene, 5,6-dihydroxy two ring [2.2.1]-2-heptene, two 5.6-(hydroxymethyl) two ring [2.2.1]-2-heptene, 5,6-two (2 '-hydroxyethyl) two ring [2.2.1]-2-heptene, 5,6-dimethoxy two ring [2.2.1]-2-heptene, 5,6-diethoxy two ring [2.2.1]-2-heptene, 5-hydroxy-5-methyl base two ring [2.2.1]-2-heptene, 5-hydroxyl-5-ethyl two ring [2.2.1]-2-heptene, 5-hydroxymethyl-5-methyl bicyclic [2.2.1]-2-heptene, 5-tert-butoxycarbonyl two ring [2.2.1]-2-heptene, 5-cyclohexyl oxygen carbonyl two ring [2.2.1]-2-heptene, 5-phenyloxycarbonyl two ring [2.2.1]-2-heptene, 5,6-two (tert-butoxycarbonyl) two ring [2.2.1]-2-heptene, two ring unsaturated compound classes of 5-6-two (cyclohexyl oxygen carbonyl) two ring [2.2.1]-2-heptene etc.;

N-phenyl maleic anhydride imines, N-cyclohexyl maleic anhydride imines, N-benzyl maleic anhydride imines, N-succinimido-3-maleic anhydride imines benzoic ether, N-succinimido-4-maleic anhydride imines butyric ester, N-succinimide-6-maleic anhydride imines capronate, N-succinimide-3-maleic anhydride the contract dicarbapentaborane imide derivative class of imines etc. of imines propionic ester and N-(9-acridinyl) maleic anhydride that contracts that contracts that contracts that contracts that contracts that contracts that contracts;

Styrene, α-Jia Jibenyixi, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.

Wherein, contract imines, N-cyclohexyl maleic anhydride contract imines, N-benzyl maleic anhydride contract imines, two ring [2.2.1]-2-heptene etc. of preferred benzyl acrylate, styrene, N-phenyl maleic anhydride.

Above-mentioned (B3) can be used alone or in combination.

When containing (B3), from the ratio of the formation unit of (B0)～(B3) preferably for the total molal quantity of the formation unit of above-mentioned formation multipolymer in following scope.

Formation unit from (B0): 2～97 moles of % (more preferably 10～48 moles of %)

Formation unit from (B2): 2～97 moles of % (more preferably 10～48 moles of %)

Formation unit from (B3): 1～96 mole of % (more preferably 4～80 moles of %)

The adhesive resin (B) that contains above-mentioned (B0)～(B3) can as above be made.

In addition; as the formation unit in the above-mentioned adhesive resin (B); contain macromonomer class, the formation unit of formula (II) expression and the formation unit of formula (III) expression etc. that end contains acryloyl group or monomethyl acryloyl group, from pattern tack, solvent resistance excellence.

(in formula (II) and the formula (III), R ⁵³And R ⁵⁶The alkyl of representing hydrogen atom or carbon number 1～6 independently of one another.)

Adhesive resin (B) with formation unit of formula (II) expression, can followingly obtain: make (B2), (B3) copolymerization obtain multipolymer, with the compound of the multipolymer that obtains and formula (III-1) expression, reaction in carboxyl that (B2) contains or acid anhydrides and obtaining.

(in formula (II-1) and the formula (III-1), R ⁵⁴And R ⁵⁶The same).

Adhesive resin with constituent of formula (III) expression, can followingly obtain: make (B2) and (B3) copolymerization obtain multipolymer, the compound of the multipolymer that obtains and formula (III-1) expression reacted in the same manner by the method for for example opening the record of 2005-189574 communique with the Jap.P. spy obtain.

The weight-average molecular weight of the polystyrene conversion of adhesive resin (B) is preferred 3,000～100,000, and more preferably 5,000～50,000.The weight-average molecular weight of adhesive resin (B) has the good tendency of coating in above-mentioned scope, is not prone to film during development and reduces, and the good tendency of removal of non-pixel portion is arranged when developing.

The molecular weight distribution of adhesive resin (B) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferred 1.1～6.0, and more preferably 1.2～4.0.Molecular weight distribution has the tendency of development excellence in above-mentioned scope.

The content of adhesive resin (B) is with respect to preferred 10～35 quality % of the solid constituent in the coloring photosensitive combination, more preferably 15～30 quality %.The content of adhesive resin (B) is in the words of above-mentioned scope, following tendency is arranged: its dissolubility in developer solution is abundant, be not prone to the development residue on the substrate of non-pixel portion, and be not prone to the film minimizing of the pixel portion of exposure part when developing, the removal of non-pixel portion is good.

Coloring photosensitive combination of the present invention contains optical polymerism compound (C).Optical polymerism compound (C) is the living radical that utilizes Photoepolymerizationinitiater initiater (D) to be produced by rayed, acid etc. and can polymeric compounds, and the compound of the carbon-to-carbon unsaturated bond with polymerism etc. is for example arranged for example.

Above-mentioned optical polymerism compound (C) preferably has the multi-functional optical polymerism compound of the functional group more than 3.As multi-functional optical polymerism compound tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate etc. are arranged for example with the functional group more than 3.Above-mentioned optical polymerism compound (C) can use separately, also can make up more than 2 kinds and to use, and its content is with respect to preferred 7～65 quality % of the solid constituent in the coloring photosensitive combination, more preferably 13～60 quality %, further preferred 17～55 quality %.The content of above-mentioned optical polymerism compound (C) is in above-mentioned scope, has film thickness ratios before and after solidifying fully, developing to improve, undercutting (undercut) is difficult to enter pattern and adaptation becomes good tendency.

Photosensitive composition of the present invention contains Photoepolymerizationinitiater initiater (D).Photoepolymerizationinitiater initiater is produced living radical, acid etc., can make polymerizable compound (C) polymeric compounds by rayed, preferably produce the compound of free radical with ultraviolet ray.Above-mentioned Photoepolymerizationinitiater initiater (D) has living radical to produce agent, acid producing agent etc. for example.

Living radical produces agent and produces living radical by rayed.Above-mentioned living radical produces agent acetophenone based compound, benzoin based compound, benzophenone based compound, thioxanthones based compound, triazine based compound, oxime compound etc. for example.

Consider the compound that Photoepolymerizationinitiater initiater (D) preferably has the oxime structure from the sensitivity aspect.

Above-mentioned oxime compound has for example O-acyl group oxime compound for example; its object lesson has N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-butanone-2-imines for example; N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone-2-imines; N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethane-1-imines; N-acetoxyl group-1-[9-ethyl-6-(2-methyl-4-(3; 3-dimethyl-2; 4-dioxo cyclopentyl (ペ Application タニ Le) methoxyl) benzoyl)-9H-carbazole-3-yl] ethane-1-imines etc., preferred N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone-2-imines.Oxime compound is N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone-2-imines, can obtain the color filter of high brightness.

Oxime compound also can use イ Le ガキユア OXE01, イ Le ガキユア OXE02 (more than be チバジヤパ Application society make), N-1919 commercially available products such as (manufacturings of ADEKA society).

Above-mentioned acetophenone based compound has for example diethoxy acetophenone for example, 2-methyl-2-morpholino base-1-(4-methyl sulphur aminoacyl phenyl)-1-acetone, 2-dimethylamino-1-(4-morpholino base phenyl)-2-benzyl-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl]-oligomer of 1-acetone etc., preferred 2-methyl-2-morpholino base-1-(4-methyl sulphur aminoacyl phenyl)-1-acetone.

Above-mentioned acyloin based compound has benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether etc. for example.

Above-mentioned benzophenone based compound has for example benzophenone, o-benzoyl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulphur, 3 for example; 3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone etc.

Above-mentioned thioxanthones based compound has for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2 for example, 4-diethyl thioxanthone, 2,4-dichloro-thioxanthones, 1-chloro-4-propoxyl group thioxanthones etc.

Above-mentioned triazine based compound has 2 for example, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1,3 of 4-, the 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1,3,5-triazines, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl of 4-]-1,3,5-triazine etc.

Living radical beyond the above-mentioned illustration produces agent and also can use as 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, 2,2 '-two (adjacent chlorophenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-two imidazoles, 10-butyl-2-chloro acridone, 2-EAQ, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.

As above-mentioned acid producing agent, salt or toluenesulfonic acid nitrobenzyl salt (or ester) class, toluenesulfonic acid benzoin salt (or ester) class etc. of 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro stibate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro stibate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro stibate, diphenyl iodine tosilate, diphenyl iodine hexafluoro stibate etc. are arranged for example.

In addition, in the compound that produces agent as above-mentioned living radical, the living radical of generation is arranged also in also acidic compound.For example, triazine is that Photoepolymerizationinitiater initiater also uses as acid producing agent.

The content of Photoepolymerizationinitiater initiater (D) is with respect to preferred 0.1～30 quality % of the total amount of adhesive resin (B) and optical polymerism compound (C), more preferably 1～20 quality %.The content of Photoepolymerizationinitiater initiater is in above-mentioned scope, and high sensitivityization, time shutter shorten, and throughput rate improves.

Can further contain photopolymerization in the coloring photosensitive combination of the present invention and cause auxiliary agent (F).Photopolymerization causes auxiliary agent (F) makes up with Photoepolymerizationinitiater initiater (D) usually and uses, and is polymeric compounds or the sensitizer that is used to promote by the optical polymerism compound of Photoepolymerizationinitiater initiater initiated polymerization.

Cause auxiliary agent (F) as photopolymerization amine compound, alkoxy anthracene based compound, thioxanthones based compound etc. are arranged for example.

As above-mentioned amine compound, for example triethanolamine is arranged for example, methyldiethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl esters, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, benzoic acid-2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid-2-Octyl Nitrite, N, the N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone (common name Michler's keton), 4,4 '-two (diethylamino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., wherein, preferred 4,4 '-two (diethylamino) benzophenone.

As above-mentioned alkoxy anthracene based compound, for example have 9 for example, 10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.

As above-mentioned thioxanthones based compound, for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2 are arranged for example, 4-diethyl thioxanthone, 2,4-dichloro-thioxanthones, 1-chloro-4-propoxyl group thioxanthones etc.

Photopolymerization causes auxiliary agent (F) can be used separately, also can make up more than 2 kinds and use.In addition, cause auxiliary agent (F) as photopolymerization and also can use commercially available product, commercially available photopolymerization causes auxiliary agent (F) for example trade name " EAB-F " (hodogaya chemical industry (strain) manufacturing) etc. for example.

Combination as Photoepolymerizationinitiater initiater in the coloring photosensitive combination of the present invention (D) and photopolymerization initiation auxiliary agent (F), diethoxy acetophenone/4 are arranged for example, 4 '-two (diethylamino) benzophenone, 2-methyl-2-morpholino-1-(4-methyl sulphur aminoacyl phenyl)-1-acetone/4,4 '-two (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone/4,4 '-two (diethylamino) benzophenone, benzyl dimethyl ketal/4,4 '-two (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone/4,4 '-two (diethylamino) benzophenone, 1-hydroxy-cyclohexyl phenyl ketone/4,4 '-two (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl]-oligomer/4 of 1-acetone, 4 '-two (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone/4,4 '-two (diethylamino) benzophenone etc., preferable examples has 2-methyl-2-morpholino-1-(4-methyl sulphur aminoacyl phenyl)-1-acetone/4,4 '-two (diethylamino) benzophenone.

When using these photopolymerization to cause auxiliary agent (F), with respect to per 1 mole of Photoepolymerizationinitiater initiater (D), preferred 0.01～10 mole of its use amount, more preferably 0.01～5 mole.

Coloring photosensitive combination of the present invention contains solvent (E).As solvent (E), ethers, the ketone outside aromatic hydrocarbon based, above-mentioned, alcohols, ester class, amide-type, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) etc. are arranged for example.

As above-mentioned ethers, tetrahydrofuran is arranged for example, oxinane, 1, the 4-dioxane, the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, the diethylene glycol single-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, the diethylene glycol dipropyl ether, the diethylene glycol dibutyl ethers, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, propylene glycol monomethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, the ethyl carbitol acetic acid esters, acetate of butyl carbitol, anisole (methyl phenyl ethers anisole), phenetol, methyl anisole etc.

As above-mentioned aromatic hydrocarbon based, for example benzene,toluene,xylene, mesitylene etc. are arranged for example.

As above-mentioned ketone, for example acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, 4-hydroxy-4-methyl-2 pentanone, cyclopentanone, cyclohexanone etc. are arranged for example.

As above-mentioned alcohols, for example methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc. are arranged for example.

As above-mentioned ester class, for example ethyl acetate is arranged for example, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, acetate-3-methoxyl butyl ester, acetate-3-methyl-3-methoxyl butyl ester, gamma-butyrolacton etc.

As above-mentioned amide-type, for example N is arranged for example, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone etc.

Wherein, preferred ethers, ketone and ester class.More preferably propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 4-hydroxy-4-methyl-2 pentanone are also used these then better.

Again, above-mentioned solvent can use separately, use more than 2 kinds also capable of being combined.

The content of the solvent in the coloring photosensitive combination (E) is with respect to preferred 70～95 quality % of coloring photosensitive combination, more preferably 75～90 quality %.The content of solvent (E) is in above-mentioned scope, and the flatness when coating is arranged is good and colour saturation can be enough and display characteristic is good tendency when forming color filter.

Photosensitive composition of the present invention also can further contain surfactant (G).As surfactant (G) have for example be selected from the polysiloxane series surfactant, fluorine is surfactant and the polysiloxane series surfactant with fluorine atom.

As above-mentioned polysiloxane series surfactant, surfactant with siloxane bond etc. is arranged for example.Particularly, ト one レシリコ one Application DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, polyether modified silicon oil SH8400 (trade name: ト one レシリコ one Application are arranged for example; East レダウコ one ニ Application ゲ (strain) manufacturing), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufacturing of モメ Application テイ Block パ Off オ one マ Application スマテリア Le ズジヤパ Application contract commercial firm) etc.

As above-mentioned fluorine is surfactant, and surfactant with fluorocarbon chain etc. is arranged for example.Off ロラ one De (trade name) FC430 is arranged particularly for example, same FC431 (manufacturing of Sumitomo スリ one エ system (strain)), メガ Off ア Star Network (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same R30 (DIC (strain) manufacturing), エ Off ト Star プ (trade name) EF301, same EF303, EF351, EF352 (the マテリア of Mitsubishi Le electronics changes into (strain) and makes), サ one Off ロ Application (trade name) S381, same S382, same SC101, same SC105 (Asahi Glass (strain) manufacturing), E5844 (manufacturing of (strain) ダイキ Application Off アイ Application ケミカ Le research institute), BM-1000, BM-1100 (all be trade name: BM Chemie society makes) etc.

As above-mentioned polysiloxane series surfactant, surfactant with siloxane bond and fluorocarbon chain etc. is arranged for example with fluorine atom.Particularly, メガ Off ア Star Network (registered trademark) R08, same BL20, same F475, same F477, same F443 (DIC (strain) manufacturing) etc.

These surfactants can use separately, use more than 2 kinds also capable of being combined.

The content of surfactant (G) is with respect to preferred 0.00001～0.1 quality % of coloring photosensitive combination, more preferably 0.00005～0.01 quality %.The content of surfactant (G) has the good tendency of flatness in above-mentioned scope.

As using coloring photosensitive combination of the present invention to form the method for patterning of color filter, following method is arranged for example and use the method etc. of the ink-jet machine need not photo-engraving process, said method is, coloring photosensitive combination of the present invention (for example is coated on substrate or another resin bed, earlier at another coloring photosensitive combination layer that forms on the substrate etc.) on, remove the volatile ingredient desolvate and to wait, form dyed layer, be situated between by photomask expose this dyed layer and development.

By known methods such as optical lithographies, on glass substrate 21, form several TFT22 (referring to Fig. 1) for every pixel.TFT22 by grid (gate) electrode 22a, grid (gate) dielectric film 22b, be formed on this gate insulating film 22b polysilicon film 22c and by for example oxide film (SiO ₂) and nitride film (SiN _x) the film formed diaphragm 22d of lamination constitute, this gate electrode 22a for example is formed on the glass substrate 21 by molybdenum (Mo), constitutes the part of grid (gate) line simultaneously; This gate insulating film 22b is formed on the gate electrode 22a, for example by nitride film (SiN _x) and oxide film (SiO ₂) laminated film constitute.The zone relative with gate electrode 22a of polysilicon film 22c is raceway groove (channel) zone of TFT22, and the two side areas of this channel region is zone, source (source) or leaks (drain) zone.Going up the connecting hole (contact hole) that is provided with by diaphragm 22d is electrically connected the source region of polysilicon film 22c with the signal wire 27 that is for example formed by aluminium.In addition, by connecting hole described later (contact hole) 201 drain region of polysilicon film 22c is electrically connected with pixel electrode 24.

For each pixel, when on glass substrate 21, forming several TFT22, on glass substrate 21, form calibration symbol (figure does not show) in the formation TFT22.This calibration symbol is as the positioning reference in the formation operation of colour filter 23 described later.In addition, these calibration symbols can dual-purpose be the symbol of the applying benchmark of driving substrate and counter substrate also.Calibration symbol forms in the time of can forming metal levels such as distribution or polysilicon layer in the manufacturing process of TFT22, utilizes its one deck to form in same operation at least.

Then, by spin-coating method or additive method at TFT22 and be formed with and form thickness 0.5～5.0 μ m, the coloring photosensitive combination layer 23A of 1.0 μ m for example on the glass substrate 21 of calibration symbol.This coloring photosensitive combination layer 23A is corresponding to color filter of the present invention.

Then, by under under the temperature of 30 ℃～120 ℃ of scopes preferred 60～110 ℃, heat-treating, make coloring photosensitive combination layer 23A drying.For dry coloring photosensitive combination layer 23A, can make up drying under reduced pressure and heat drying and carry out.Then, Jie by photomask (figure do not show) to coloring phototonus composition layer 23A irradiation ultraviolet radiation, optionally do not remove not portion's (be non-exposure portion) by developer solution again, form the connecting hole (contacthole) 201 of the drain region that arrives polysilicon film 22c, washing then.Then, flow again (reflow), and the contained curable composition of coloring photosensitive combination layer 23A is solidified, heating under 100 ℃～300 ℃ the range temperature, under preferred 150～230 ℃ in order to make coloring photosensitive combination layer 23A.

Thus, coloring photosensitive combination layer 23A becomes the colour filter 23 (referring to Fig. 2) that contains Red lightscreening plate 23a, green color filter 23b, blue color filter 23c corresponding to each pixel column.Zone between each optical filter of colour filter 23 is the Mixed Zone in abutting connection with look, but these zones are lightproof areas relative with signal wire 27, so especially no problem on quality.In addition, the zone between these each optical filters can be not painted.

Then, for example form by for example spin-coating method that thickness is the diaphragm photosensitive resin film 29 of 0.3～2.0 μ m, cover colour filter 23 (referring to Fig. 3).Then, Jie by photomask (figure do not show) to photosensitive resin film 29 irradiation ultraviolet radiations, optionally remove corresponding to the zone of connecting hole 201 and portion not by developer solution again, form the connecting hole (contact hole) 202 of the drain region that arrives polysilicon film 22c, washing then.Then, flow again (reflow), for example heating under 200 ℃ under 100 ℃～300 ℃ the range temperature in order to make photosensitive resin film 29.Then,, carry out etching, in order to remove the oxide film that forms owing to oxygen plasma, for example carry out etching again with rare fluoric acid with oxygen plasma in order to remove residue and the organism of piling up in the connecting hole 202.

Then, on photosensitive resin film 29, form transparent conductive material such as ITO (Indium-TinOxide: the oxide hybrid films of indium and tin) by for example splash method, by optical lithography and etching method, this ITO film is carried out design producing, form transparent pixel electrode 24 (referring to Fig. 4).This pixel electrode 24 can be formed by aluminium (Al) or silver metals such as (Ag) according to method for making.Then, after known method formation oriented film, bonding this driving substrate and counter substrate are made liquid crystal indicator.

Can obtain high the filming of contrast according to coloring photosensitive combination of the present invention.

Embodiment

Below, illustrate in greater detail the present invention according to embodiment.The short of special record of " % " in the example and " part " is exactly quality % and mass parts.

Synthesis example 1

[synthesis example of the compound of formula (2) expression]

Synthesizing of the compound of＜formula (2-24-1a) expression 〉

In flask, drop into 75 parts of 4-nitrobenzene dimethoxy nitriles, 375 parts of N,N-dimethylacetamide with cooling tube and stirring apparatus, Yi Bian under agitation maintain below 20 ℃, Yi Bian slowly add 68.9 parts of sodium carbonate.Under agitation maintain below 20 ℃ on one side again, Yi Bian the 68.9 parts of 3-mercapto-propionates that drip.Dropping liquid at room temperature stirred 3.5 hours after finishing, and reaction solution is filtered, filtrate is injected into 2250 parts 1 equivalent hydrochloric acid, and the isolated by filtration precipitation is carefully cleaned with ion exchange water, at 50 ℃ of following drying under reduced pressure, obtain the compound of 104.4 parts of formulas (2-24-1a) expression.

Synthesizing of the compound of＜formula (2-24-1b) expression 〉

In flask, drop into 52.0 parts of compounds (2-24-1a), 104.0 parts of N with cooling tube and stirring apparatus, dinethylformamide, under agitation maintain below 20 ℃ on one side, Yi Bian drip 40.2 part 1,8-diazabicyclo [5.4.0]-7-undecylene (DBU).Dropping liquid at room temperature stirred 2.5 hours after finishing.Reaction solution is injected into 208.0 parts water, add again concentrated hydrochloric acid to pH below 2.Filter out precipitation, carefully clean,, obtain 33.6 parts of compounds (2-24-1b) at 50 ℃ of following drying under reduced pressure with ion exchange water.

Synthesizing of the compound of＜formula (2-24-1c) expression 〉

In flask, drop into 33.0 parts of compounds (2-24-1b), 396 parts of acetate with cooling tube and stirring apparatus, Yi Bian at room temperature stir, Yi Bian add 4.2 parts of sodium tungstates.Under agitation maintain below 30 ℃ on one side again, Yi Bian splash into 87.5 part of 30% hydrogen peroxide.Dropping liquid is warming up to 50 ℃ after finishing, and stirs 2 hours.With the reaction solution cool to room temperature, be dissolved in the solution that obtains in 396 parts of methyl alcohol 60.7 parts of potassium acetates and inject reaction solution, stirred 1 hour.Filter out precipitation, use washed with methanol,, obtain the compound of 35.0 parts of formulas (2-24-1c) expression at 50 ℃ of following drying under reduced pressure.

Synthesizing of the compound of＜formula (2-24-1d) expression 〉

In flask, drop into 5.0 parts of compounds (2-24-1c), 0.82 part of cupric chloride, 0.40 part of ammonium molybdate, 19.1 parts of quinoline with cooling tube and stirring apparatus.Flask is placed on is redefined in 100 ℃ of oil baths, be warming up to 160 ℃ while stir.Continue again to stir 3 hours, be cooled to 100 ℃, add 66.5 parts of methyl alcohol.Filter out precipitation, use washed with methanol,, obtain the compound of 2.0 parts of formulas (2-24-1d) expression at 50 ℃ of following drying under reduced pressure.

Synthesizing of the compound of＜formula (2-24-1) expression 〉

In flask, drop into 57.6 parts of anhydrous N,N-dimethylacetamide, 1.5 parts of anhydrous N, dinethylformamide with cooling tube and stirring apparatus.Be cooled to 0 ℃, drip 2.3 parts of thionyl chlorides, continue down to stir 1 hour at 0 ℃.Add 1.8 parts of compounds (2-24-1d) again, at room temperature stirred 30 minutes, stirred 1.5 hours down, stirred 4 hours down at 80 ℃ at 50 ℃.Be cooled to 0 ℃, drip 2.8 parts of N, N-dimethyl-1, the mixed solution of 3-propane diamine and 4.2 parts of triethylamines.At room temperature stirred 15 minutes, and stirred 4 hours down, add 506.9 parts of methyl alcohol at 80 ℃.Filter out precipitation, carefully clean,, obtain the compound of 1.6 parts of formulas (2-24-1) expression at 50 ℃ of following drying under reduced pressure with methyl alcohol.

Synthesis example 2

The synthesis example of the compound of＜formula (1) expression 〉

In flask, drop into potpourri (China and foreign countries change into manufacturing), 150 parts of chloroforms and 8.9 parts of N of the compound of compound shown in 15 parts of formulas (A0-1) and formula (A0-2) expression with cooling tube and stirring apparatus, dinethylformamide, under agitation maintain below 20 ℃ on one side, Yi Bian drip 10.9 parts of thionyl chlorides.Dropping liquid is warming up to 50 ℃ after finishing, and keeps this temperature and makes it reaction in 5 hours, is cooled to 20 ℃ then.On one side cooled reaction solution is under agitation maintained below 20 ℃, Yi Bian drip the mixed liquor of 12.5 parts of 2 ethyl hexylamines and 22.1 parts of triethylamines.Then, made it reaction in 5 hours synthermal the stirring down.Then, distill the solvent of removing in the resulting reaction mixture, add small amount of methanol then, carry out high degree of agitation with rotary evaporator.While stirring this potpourri is added in the mixed liquor of 375 parts of ion exchange waters, crystallization is separated out.Filter out the crystallization of separating out, carefully clean with ion exchange water, at 60 ℃ of following drying under reduced pressure, obtain the compound of 11.3 parts of formulas (A1-a) expression and the potpourri of the compound that formula (A2-b) is represented (potpourri of the compound of formula (A1-1)～formula (A1-8) expression; Dyestuff A1)

[in formula (A1-a) and the formula (A1-b), R ^g, R ^hAnd R ⁱRepresent independently of one another hydrogen atom ,-SO ₃ ^-,-SO ₃H or N-(2-ethylhexyl) sulphur aminoacyl].

[in the above-mentioned formula, * represents the bonding position with-NH-.]

Synthesis example 3

In having the 1L flask of backflow cooling tube, tap funnel and stirring machine, divide feeding nitrogen, become nitrogen atmosphere, add 200 mass parts 3-methoxyl-1-butanols and 105 mass parts 3-methoxyl butylacetic acid esters, be heated to 70 ℃ while stirring with 0.02L/.Then, dissolve 60 mass parts methacrylic acids, 240 mass parts 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl acrylate (compound of the compound of formula (B1-1-1) expression and formula (B1-2-1) expression mixes with mol ratio at 50: 50) and 140 mass parts 3-methoxyl butylacetic acid esters, spend 4 hours this lysate being added drop-wise to insulation with tap funnel is in 70 ℃ the flask.On the other hand, with 30 mass parts polymerization initiators 2,2-azo two (2, the 4-methyl pentane nitrile) is dissolved in the 225 mass parts 3-methoxyl butylacetic acid esters, spends be added drop-wise in the flask in 4 hours with another tap funnel this solution.After polymerization initiator drip to finish, keep 70 ℃ 4 hours, cool to room temperature then, obtaining weight-average molecular weight Mw is 1.3 * 10 ⁴, molecular weight distribution (Mw/Mn) is 2.5, solid constituent is that 33 quality %, acid number are the resin solution B1 of 34mg-KOH/g (acid number of solution).

The mensuration of＜molecular weight 〉

The mensuration of weight-average molecular weight of resulting resin B 1 (Mw) and number-average molecular weight (Mn) is used the GPC method, carries out under the following conditions.

Device: HLC-8120GPC (eastern ソ one (strain) manufacturing)

(chromatogram) post: TSK-GELG2000HXL

(chromatogram) column temperature: 40 ℃

Solvent: THF

Flow velocity: 1.0mL/ branch

Detected liquid-solid body constituent concentration: 0.001～0.01 quality %

Injection rate IR: 50 μ L

Detecting device: RI

The calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500,

A-500 (eastern ソ one (strain) manufacturing)

Embodiment 1

Mix following material, use porose beaded glass grinding machine (PVC one ズミ Le) that pigment is disperseed fully,

(A) colorant C.I. pigment blue 15: 6 27 parts

9.1 parts of acrylic acid series pigment dispersing agents

196 parts of propylene glycol monomethyl ether

Then, mix following material, obtain coloring photosensitive combination.

(A) colorant: 27 parts of the compounds of formula (2-24-1) expression

(A) colorant: the compound of formula (1) expression: 6.0 parts of dyestuff A1

(B) resin: 152 parts of resin solution B1

(C) optical polymerism compound: 50 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulphur aminoacyl phenyl)-1-octanone

15 parts of ketone-2-imines

(manufacturing of イ Le ガキユア OXE01 チバジヤパ Application society)

(E) solvent: 376 parts of 4-hydroxy-4-methyl-2 pentanones

Embodiment 2

Mix following material, use porose beaded glass grinding machine that pigment is disperseed fully,

(A) colorant C.I. pigment blue 15: 6 27 parts

9.1 parts of acrylic acid series pigment dispersing agents

196 parts of propylene glycol monomethyl ether

Then, mix following material, obtain coloring photosensitive combination.

27 parts of the salt of (A) colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid

(オリヱ Application ト chemical industry (strain) manufacturing)

(A) colorant: the compound of formula (1) expression: 6.0 parts of dyestuff A1

(B) resin: 152 parts of resin solution B1

(C) optical polymerism compound: 50 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

15 parts of-2-imines

(イ Le ガキユア OXE01; チバジヤパ Application society makes)

(E) solvent: 376 parts of 4-hydroxy-4-methyl-2 pentanones

Embodiment 3

(A) colorant C.I. pigment blue 15: 6 31 parts

11 parts of acrylic acid series pigment dispersing agents

226 parts of propylene glycol monomethyl ether

Then, mix following material, obtain coloring photosensitive combination.

13 parts of the salt of (A) colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid

(オリヱ Application ト chemical industry (strain) manufacturing)

(A) colorant: the compound of formula (1) expression: 5.0 parts of dyestuff A1

(B) resin: 152 parts of resin solution B1

(C) optical polymerism compound: 50 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

15 parts of-2-imines

(イ Le ガキユア OXE01; チバジヤパ Application society makes)

(E) solvent: 312 parts of 4-hydroxy-4-methyl-2 pentanones

Embodiment 4

Mix following material, obtain coloring photosensitive combination.

57 parts of the salt of (A) colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid

(オリヱ Application ト chemical industry (strain) manufacturing)

(A) colorant: the compound of formula (1) expression: 5.0 parts of dyestuff A1

(B) resin: 152 parts of resin solution B1

(C) optical polymerism compound: 50 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

15 parts of-2-imines

(イ Le ガキユア OXE01; チバジヤパ Application society makes)

(E) solvent: 526 parts of 4-hydroxy-4-methyl-2 pentanones

Reference example 1

(A) colorant C.I. pigment blue 15: 6 18 parts

(A) colorant C.I. pigment Violet 23 is 5.7 parts

6.1 parts of acrylic acid series pigment dispersing agents

154 parts of propylene glycol monomethyl ether

Then, mix following material, obtain coloring photosensitive combination.

(B) resin: 136 parts of resin solution B1

(C) optical polymerism compound: 55 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

15 parts of-2-imines

(イ Le ガキユア OXE01; チバジヤパ Application society makes)

(E) solvent: 319 parts of propylene glycol monomethyl ether

[formation of pattern]

Glass substrate (イ one ゲ Le 2000 2 inches of the length of sides; コ one ニ Application ゲ society makes] go up with after the spin-coating method coating coloring photosensitive combination 100 ℃ of following preliminary dryings 3 minutes.After the cooling, the substrate that is coated with this coloring photosensitive combination is set at 100 μ m with the interval with quartz glass system photomask of pattern, uses exposure machine (TME-150RSK; トプコ Application (strain) is made), under air atmosphere, with 150mJ/cm ²Exposure (365nm benchmark) carry out rayed.After the rayed, film containing in the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04% dipping 80 seconds under 23 ℃, develop, after the washing, in baking oven, carry out back under 220 ℃ and dried by the fire 20 minutes above-mentioned.Put cold after, use determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) manufacturing) thickness of the resulting pattern of mensuration, the result is 2.0 μ m.

[chromaticity evaluation]

For the pattern on the glass substrate that obtains, use colour examining machine (OSP-SP-200; Olympus (strain) is made) measure beam split, use the isochrome function of illuminant-C, measure xy chromaticity coordinate in the XYZ color specification system of CIE (Bx, By) and brightness.The result is presented in the table 1.

[contrast evaluation]

Except not using photomask exposes, the formation of other and pattern is similarly operated, and for filming on the resulting glass substrate, uses contrast colour examining machine (CT-1; Kettle Ban Dianjishe makes, detecting device, BM-5A, light source; F-10), blank value is set at 10000, measures contrast.With light polarizing film (POLAX-38S; Le ケオ society makes) clamp filming on the glass substrate, with it as sample.The result is presented in the table 1.

Table 1

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Reference example 1
						Bx	0.141	0.141	0.141	0.143	0.143
By	0.085	0.085	0.085	0.085	0.085
						Brightness	9.4	9.2	9.4	8.8	8.8
Contrast	6900	6740	6960	7020	5150

Embodiment 5

(A) colorant C.I. pigment blue 15: 6 17 parts

5.7 parts of acrylic acid series pigment dispersing agents

122 parts of propylene glycol monomethyl ether

Then, mix following material, obtain coloring photosensitive combination.

3.6 parts of the salt of (A) colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid

(オリヱ Application ト chemical industry (strain) manufacturing)

(A) colorant: the compound of formula (1) expression: 3.6 parts of dyestuff A1

(B) resin: 152 parts of resin solution B1

(C) optical polymerism compound: 50 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

15 parts of-2-imines

(イ Le ガキユア OXE01; チバジヤパ Application society makes)

(E) solvent: 320 parts of 4-hydroxy-4-methyl-2 pentanones

Embodiment 6

(A) colorant C.I. pigment blue 15: 6 15 parts

5.2 parts of acrylic acid series pigment dispersing agents

111 parts of propylene glycol monomethyl ether

Then, mix following material, obtain coloring photosensitive combination.

6.4 parts of the salt of (A) colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid

(オリヱ Application ト chemical industry (strain) manufacturing)

(A) colorant: the compound of formula (1) expression: 3.8 parts of dyestuff A1

(B) resin: 152 parts of resin solution B1

(C) optical polymerism compound: 50 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

15 parts of-2-imines

(イ Le ガキユア OXE01; チバジヤパ Application society makes)

(E) solvent: 320 parts of 4-hydroxy-4-methyl-2 pentanones

[formation of pattern]

Carry out operation similarly to Example 1, make pattern.Use the determining film thickness device to measure the thickness of resulting pattern, the result is 3.0 μ m.

[chromaticity evaluation]

Carry out operation similarly to Example 1, measure the xy chromaticity coordinate (Bx, By) and brightness.The result is presented in the table 2.

[contrast evaluation]

Carry out operation similarly to Example 1, measure the contrast of filming on the resulting glass substrate.The result is presented in the table 2.

Table 2

	Embodiment 5	Embodiment 6
			Bx	?0.144	?0.145
By	?0.085	?0.085
			Brightness	?9.6	?9.6
Contrast	?6200	?6450

Synthesis example 4

Has stirring machine, thermometer, the backflow cooling tube, in the flask of tap funnel and nitrogen ingress pipe, import the 182g propylene glycol monomethyl ether, atmosphere is become after the nitrogen by air, be warming up to 100 ℃, then, splash into a kind of solution, continue down to stir at 100 ℃ again, this solution is by 70.5g (0.40 mole) benzyl methacrylate, (43.0g 0.5 mole) methacrylic acid, 22.0g added 3.6g 2 in the potpourri that monomethacrylates of (0.10 mole) tricyclodecane skeleton (Hitachi changes into (strain) system FA-513M) and 136g propylene glycol monomethyl ether constitute, 2 '-azobis isobutyronitrile forms.Then, atmosphere in the flask is become air by nitrogen, in flask, drop into 35.5g[0.25 mole, (carboxyl with respect to the methacrylic acid that is used for this reaction is 50 moles of %)] glycidyl methacrylate, 0.9g three (dimethylaminomethyl) phenol and 0.145g quinhydrones, continue down reaction at 110 ℃, obtain solid constituent 32%, the solid constituent acid number is the resin solution B2 of 79mgKOH/g.The weight-average molecular weight of the polystyrene conversion of being measured by GPC is 30,000.

Embodiment 7

(A) colorant C.I. pigment blue 15: 6 27 parts

9.1 parts of acrylic acid series pigment dispersing agents

196 parts of propylene glycol monomethyl ether

Then, mix following material, obtain coloring photosensitive combination.

1.1 parts of the salt of (A) colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid

(オリヱ Application ト chemical industry (strain) manufacturing)

(A) colorant: the compound of formula (1) expression: 4.8 parts of dyestuff A1

(B) resin: 152 parts of resin solution B1

(C) optical polymerism compound: 50 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

15 parts of-2-imines

(イ Le ガキユア OXE01; チバジヤパ Application society makes)

(E) solvent: 280 parts of ethyl lactates

Embodiment 8

(A) colorant C.I. pigment blue 15: 6 25 parts

8.4 parts of acrylic acid series pigment dispersing agents

181 parts of propylene glycol monomethyl ether

Then, mix following material, obtain coloring photosensitive combination.

2.3 parts of the salt of (A) colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid

(オリヱ Application ト chemical industry (strain) manufacturing)

(A) colorant: the compound of formula (1) expression: 4.8 parts of dyestuff A1

(B) resin: 152 parts of resin solution B1

(C) optical polymerism compound: 50 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

15 parts of-2-imines

(イ Le ガキユア OXE01; チバジヤパ Application society makes)

(E) solvent: 308 parts of ethyl lactates

Comparative example 1

(A) colorant C.I. pigment blue 15: 6 20 parts

5 parts of acrylic acid series pigment dispersing agents

137 parts of propylene glycol monomethyl ether

Then, mix following material, obtain coloring photosensitive combination.

(A) colorant: the compound of formula (1) expression: 3.5 parts of dyestuff A1

(B) resin: 157 parts of resin solution B1

(C) optical polymerism compound: 50 parts of dipentaerythritol acrylates

(KAYARAD DPHA; Japan's chemical drug (strain) is made)

15 parts of-2-imines

(イ Le ガキユア 0XE01; チバジヤパ Application society makes)

(E) solvent: 289 parts of 4-hydroxy-4-methyl-2 pentanones

[formation of pattern]

Carry out operation similarly to Example 1, make pattern.Use the determining film thickness device to measure the thickness of resulting pattern, the result is 2.2 μ m.

[chromaticity evaluation]

Carry out operation similarly to Example 1, measure the xy chromaticity coordinate (Bx, By) and brightness.The result is presented in the table 3.

[contrast evaluation]

Carry out operation similarly to Example 1, measure the contrast of filming on the resulting glass substrate.The result is presented in the table 3.

Table 3

	Embodiment 7	Embodiment 8	Comparative example 1
				Bx	?0.141	?0.141	?0.141
By	?0.085	?0.085	?0.085
				Brightness	?9.7	?9.7	?9.7
Contrast	?6360	?6420	?5750

What form at the coloring photosensitive combination that uses embodiment films, and confirms high-contrast.

Utilizability on the industry

According to the present invention, can make the colour filter of high-contrast, this colour filter is applicable to the formation that consists of the color-patch map picture of employed colour filter in liquid crystal display element or the solid-state imager.

Symbol description

21 glass substrates

22TFT (switch element)

The 22a gate electrode

The 22b gate insulating film

The 22c polysilicon film

22d diaphragm 23 colour filters

23A coloring photosensitive combination layer (color filter)

The 23a Red lightscreening plate

The 23b green color filter

The 23c blue color filter

24 pixel electrodes

27 signal wires

29 photosensitive resin films (diaphragm)

201,202 connecting holes

Claims

1. coloring photosensitive combination, it contains colorant, adhesive resin, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent, and colorant is the colorant that contains the compound of formula (2) expression,

In the formula (2), G ¹The alkylidene of expression carbon number 2～12, the contained hydrogen atom of this alkylidene can be replaced by the alkyl of carbon number 1～4, and this alkylidene is contained-CH ₂-can be replaced by-O-,

J ¹The expression hydrogen atom ,-NR ^aR ^bPerhaps-NR ^aR ^bH ⁺Q ^-,

X and Y represent the organic group of 1 valency independently of one another,

n ^aThe integer of expression 1～4.

2. coloring photosensitive combination as claimed in claim 1, wherein, J ¹Be-NR ^aR ^bPerhaps-NR ^aR ^bH ⁺Q ^-

3. coloring photosensitive combination as claimed in claim 1, wherein, colorant is the colorant that also contains the compound of formula (1) expression,

In the formula (1), R ¹～R ⁴Represent independently of one another hydrogen atom ,-R ⁶The perhaps aromatic hydrocarbyl of carbon number 6～10, the contained hydrogen atom of this aromatic hydrocarbyl can by halogen atom ,-R ⁶,-OH ,-OR ⁶,-SO ₃ ^-,-SO ₃H ,-SO ₃M ,-CO ₂H ,-CO ₂R ⁶,-SO ₃R ⁶,-SO ₂NHR ⁸Perhaps-SO ₂NR ⁸R ⁹Replace,

M represents 0～5 integer, when m is a integer more than 2, and a plurality of R ⁵Can be the same or different,

X represents halogen atom, and a represents 0 or 1 integer,

R ¹⁰The saturated hydrocarbyl of expression hydrogen atom or carbon number 1～10, the contained hydrogen atom of this saturated hydrocarbyl can be replaced by halogen atom, and this saturated hydrocarbyl is contained-CH ₂-can by-O-or-CO-replaces,

M represents sodium atom or potassium atom,

Wherein, the compound of formula (1) expression+charge number with-charge number is identical.

4. coloring photosensitive combination as claimed in claim 1, wherein, colorant is the colorant that also contains organic pigment.

5. coloring photosensitive combination as claimed in claim 4, wherein, organic pigment is to contain the C.I. pigment blue 15: 6 organic pigment.

6. coloring photosensitive combination as claimed in claim 1, wherein, the content of the compound of formula (2) expression is 1～50 quality % with respect to colorant.

7. coloring photosensitive combination as claimed in claim 1, wherein, Photoepolymerizationinitiater initiater is the compound with oxime structure.

8. film for one kind, it uses the described coloring photosensitive combination of claim 1 to form.

9. color filter, it uses the described photosensitive composition of claim 1 to form.

10. color filter as claimed in claim 9, it forms by photo-engraving process.