CN102914942A

CN102914942A - Colored curable resin composition

Info

Publication number: CN102914942A
Application number: CN2012102722516A
Authority: CN
Inventors: 市冈贤二; 朴昭妍
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Corp; Sumitomo Chemical Co Ltd
Priority date: 2011-08-05
Filing date: 2012-08-01
Publication date: 2013-02-06
Anticipated expiration: 2032-08-01
Also published as: CN102914942B; CN107037689B; KR20130016089A; KR101632461B1; CN107037689A

Abstract

The present invention provides a colored curable resin composition, comprising a colorant, resin, a polymerizable compound and a polymerization initiator, wherein the colorant contains xanthene dye and anthraquinone dye.

Description

Colored curable resin composition

Technical field

The present invention relates to a kind of colored curable resin composition.

Background technology

Colored curable resin composition is used to be manufactured on the color filter that uses in the display device such as display panels, electroluminescence panel and plasm display panel.As such colored curable resin composition, known xanthene dye and the C.I. alizarol saphirol of only comprising is as the colored curable resin composition (JP2010-32999-A) of colorant.

With regard to known above-mentioned colored curable resin composition all the time, the contrast of the color filter that is obtained by this colored curable resin composition may not necessarily be of great satisfaction.

Summary of the invention

The present invention comprises following invention.

[1] a kind of colored curable resin composition, it comprises colorant, resin, polymerizable compound and polymerization initiator,

Colorant comprises xanthene dye and anthraquinone dye.

[2] according to [1] described colored curable resin composition, wherein, the content of anthraquinone dye is more than the 0.1 quality % and below the 70 quality % with respect to the total amount of colorant.

[3] according to [1] or [2] described colored curable resin composition, wherein, colorant also comprises pigment.

[4] a kind of color filter, it is formed by each described colored curable resin composition in [1]～[3].

[5] a kind of display device, it comprises [4] described color filter.

According to colored curable resin composition of the present invention, can form the color filter of high-contrast.

Description of drawings

Fig. 1 is the skeleton diagram that the manufacture method to color filter of the present invention describes.

Fig. 2 is the skeleton diagram that the manufacture method to color filter of the present invention describes.

Fig. 3 is the skeleton diagram that the manufacture method to color filter of the present invention describes.

Symbol description

21 glass substrates

22TFT (on-off element)

The 22a gate electrode

The 22b gate insulating film

The 22c polysilicon film

The 22d diaphragm

23 color-filter layers

23A colored curable resin composition layer (color filter)

The 23a red color filter

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

Embodiment

Colored curable resin composition of the present invention is the colored curable resin composition that comprises colorant (A), resin (B), polymerizable compound (C) and polymerization initiator (D), and colorant (A) comprises xanthene dye (Aa) and anthraquinone dye (Ab).This colored curable resin composition preferably further comprises solvent (E) and/or levelling agent (F).

Colored curable resin composition of the present invention is by comprising xanthene dye (Aa) and anthraquinone dye (Ab) as colorant (A), thereby can make the color filter of high-contrast.

＜colorant (A) 〉

Colorant (A) comprises xanthene dye (Aa) and anthraquinone dye (Ab).Preferably further comprise pigment (Ad).In addition, also can comprise the dyestuff different from xanthene dye (Aa) and anthraquinone dye (Ab) (below, sometimes be called " dyestuff (Ac) ".)。

Xanthene dye (Aa) is the dyestuff that comprises the compound that has the xanthene skeleton in the molecule.As xanthene dye (Aa), for example can list the C.I. CI 45430 (below, the record of omitting the C.I. acid red, only record numbering.Other dyestuffs too.), 52,87,92,94,289,388, C.I. acid violet 9,30,102, C.I. alkali red 1:1 (rhodamine 6G), 2,3,4,8, C.I. alkali red 1:1 0 (rhodamine B), 11, C.I. alkaline purple 10,11,25, C.I. solvent red 218, C.I. medium red 27, C.I. reactive red 36 (rose red b), sulfo group Rhodamine G, the xanthene dye of putting down in writing among the xanthene dye of putting down in writing among the JP2010-32999-A and the JP4492760-B etc.The xanthene dye that preferably in organic solvent, dissolves.

Wherein, as xanthene dye (Aa), preferably comprise the compound shown in the formula (1a) (below, sometimes be called " compound (1a) ".) dyestuff.Compound (1a) also can be its dynamic isomer.In the situation that use compound (1a), the content of the compound (1a) in the xanthene dye (Aa) is preferably more than the 50 quality %, more preferably more than the 70 quality %, more preferably more than the 90 quality %.Particularly preferably only use compound (1a) as xanthene dye (Aa).

[in the formula (1a), R ¹～R ⁴Represent that independently of one another hydrogen atom, carbon number are that maybe can to have substituent carbon number be 6～10 1 valency aromatic hydrocarbyl for 1～20 1 valency saturated hydrocarbyl, the hydrogen atom that contains in this saturated hydrocarbyl can be 6～10 aromatic hydrocarbyl or halogen atom replacement by carbon number, the hydrogen atom that contains in this aromatic hydrocarbyl can be 1～3 alkoxy replacement by carbon number, contain in the above-mentioned saturated hydrocarbyl-CH ₂-can by-O-,-CO-or-NR ¹¹-displacement.R ₁And R ²Can form with nitrogen-atoms the ring of nitrogen atom, R ³And R ⁴Can form with nitrogen-atoms the ring of nitrogen atom.

R ⁵Expression-OH ,-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z ⁺,-CO ₂H ,-CO ₂ ^-Z ⁺,-CO ₂R ⁸,-SO ₃R ⁸Or-SO ₂NR ⁹R ¹⁰

R ⁶And R ⁷Represent that independently of one another hydrogen atom or carbon number are 1～6 alkyl.

M represents 0～5 integer.Be in the situation of the integer more than 2 at m, a plurality of R ⁵Can be identical or different.But, at R ⁵For-SO ₃ ^-Situation under, m is 1.

A represents 0 or 1 integer.

X represents halogen atom.

R ⁸The expression carbon number is 1～20 1 valency saturated hydrocarbyl, and the hydrogen atom that contains in this saturated hydrocarbyl can be replaced by halogen atom.

Z ⁺Expression ⁺N (R ¹¹) ₄, Na ⁺Or K ⁺

R ⁹And R ¹⁰Represent that independently of one another it is 1～20 1 valency saturated hydrocarbyl that hydrogen atom maybe can have substituent carbon number, contain in this representative examples of saturated aliphatic alkyl-CH ₂-can by-O-,-CO-,-NH-or-NR ⁸-displacement, R ⁹And R ¹⁰Can be bonded to each other and form 3～10 member heterocyclic ring containing nitrogens with nitrogen-atoms.

R ¹¹Represent that independently of one another hydrogen atom, carbon number are that 1～20 1 valency saturated hydrocarbyl or carbon number are 7～10 aralkyl.]

As expression R ¹～R ⁴Carbon number be 6～10 1 valency aromatic hydrocarbyl, for example can list phenyl, tolyl, xylyl, sym-trimethyl benzene base, propyl group phenyl and butyl phenyl.

As the substituting group that this aromatic hydrocarbyl can have, can list halogen atom ,-R ⁸,-OH ,-OR ⁸,-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z ⁺,-CO ₂H ,-CO ₂R ⁸,-SR ⁸,-SO ₂R ⁸,-SO ₃R ⁸,-SO ₂NR ⁹R ¹⁰Deng.Wherein, as substituting group, preferred-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z ⁺And-SO ₂NR ⁹R ¹⁰, more preferably-SO ₃ ^-Z ⁺And-SO ₂NR ⁹R ¹⁰As in this situation-SO ₃ ^-Z ⁺, preferred-SO ₃ ^-+N (R ¹¹) ₄R ¹～R ⁴During for these groups, can be formed by the colored curable resin composition of the present invention of inclusion compound (1a) foreign matter and occur less and the color filter of excellent heat resistance.

As R ¹And R ²Ring and the R of the nitrogen atom that forms with nitrogen-atoms ³And R ⁴The ring of the nitrogen atom that forms with nitrogen-atoms for example can list the ring of following nitrogen atom.

As expression R ⁸～R ¹¹Carbon number be 1～20 1 valency saturated hydrocarbyl, can list the carbon numbers such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl and be 1～20 straight chain shape alkyl; The carbon numbers such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl are 3～20 branched-chain alkyl; The carbon numbers such as cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, three ring decyls are 3～20 ester ring type saturated hydrocarbyl.

As-OR ⁸, for example can list methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy and eicosane oxygen base.

As-CO ₂R ⁸, for example can list methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxy carbonyl and eicosane oxygen base carbonyl.

As-SR ⁸, for example can list methyl mercapto, ethylmercapto group, butylthio, own sulfenyl, last of the ten Heavenly stems sulfenyl and eicosane sulfenyl.

As-SO ₂R ⁸, for example can list mesyl, ethylsulfonyl, fourth sulfonyl, own sulfonyl, last of the ten Heavenly stems sulfonyl and eicosane sulfonyl.

As-SO ₃R ⁸, for example can list methoxyl sulfonyl, ethoxy sulfonyl, propoxyl group sulfonyl, tert-butoxy sulfonyl, own oxygen base sulfonyl and eicosane oxygen base sulfonyl.

As-SO ₂NR ⁹R ¹⁰, for example can list:

Sulfamoyl;

N-methyl sulfamoyl, N-ethyl sulfamoyl, N-propyl group sulfamoyl, N-isopropyl sulfamoyl, N-butyl sulfamoyl, N-isobutyl sulfamoyl, N-sec-butyl sulfamoyl, N-tert-butyl group sulfamoyl, N-amyl group sulfamoyl, N-(1-ethyl propyl) sulfamoyl, N-(1, the 1-dimethyl propyl) sulfamoyl, N-(1, the 2-dimethyl propyl) sulfamoyl, N-(2, the 2-dimethyl propyl) sulfamoyl, N-(1-methyl butyl) sulfamoyl, N-(2-methyl butyl) sulfamoyl, N-(3-methyl butyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-hexyl sulfamoyl, N-(1, the 3-dimethylbutyl) sulfamoyl, N-(3, the 3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methyl hexyl) sulfamoyl, N-(1,4-dimethyl amyl group) sulfamoyl, N-octyl group sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1, the 5-dimethyl) hexyl sulfamoyl, N-(1,1,2,2-tetramethyl butyl) N-such as sulfamoyl one replaces sulfamoyl;

N; N-dimethylamino sulfonyl, N; N-ethyl-methyl sulfamoyl, N, N-diethyl amino sulfonyl, N, N-propyl group methyl sulfamoyl, N; N-isopropyl methyl sulfamoyl, N; N-tert-butyl group methyl sulfamoyl, N, N-butyl ethyl sulfamoyl, N, two (1-methyl-propyl) sulfamoyls of N-, N; the N such as N-heptyl methyl sulfamoyl, N-two replaces sulfamoyl etc.

In addition, as expression R ⁹, R ¹⁰Carbon number be the substituting group that 1～20 1 valency saturated hydrocarbyl can have, can list hydroxyl and halogen atom.

R ⁵Preferably-CO ₂H ,-CO ₂ ^-Z ⁺,-CO ₂R ⁸,-SO ₃ ^-,-SO ₃ ^-Z ⁺,-SO ₃H or SO ₂NHR ⁹, more preferably SO ₃ ^-,-SO ₃ ^-Z ⁺,-SO ₃H or SO ₂NHR ⁹

M is preferred 1～4, and more preferably 1 or 2.

As expression R ⁶And R ⁷Carbon number be 1～6 alkyl, can list in the above-mentioned alkyl of enumerating carbon number and be 1～6 alkyl.

As expression R ¹¹Carbon number be 7～10 aralkyl, can list benzyl, phenethyl, benzene butyl etc.

Z ⁺For ⁺N (R ¹¹) ₄, Na ⁺Or K ⁺, be preferably ⁺N (R ¹¹) ₄

As above-mentioned+N (R ¹¹) ₄, preferred four R ¹¹In at least two be 5～20 1 valency saturated hydrocarbyl for carbon number.In addition, four R ¹¹Total carbon atom number be preferably 20～80, more preferably 20～60.Exist in the compound (1a) ⁺N (R ¹¹) ₄Situation under, R ¹¹During for these groups, can be formed by the colored curable resin composition of the present invention of inclusion compound (1a) color filter of few foreign.

As compound (1a), more preferably the compound shown in the formula (2a) (below, sometimes be called " compound (2a) ".)。Compound (2a) can be its dynamic isomer.

In the situation that use compound (2a), the content of the compound (2a) in the xanthene dye (Aa) is preferably more than the 50 quality %, more preferably more than the 70 quality %, more preferably more than the 90 quality %.

[in the formula (2a), R ²¹～R ²⁴Represent independently respectively hydrogen atom ,-R ²⁶Maybe can have substituent carbon number and be 6～10 1 valency aromatic hydrocarbyl.

R ²¹And R ²²Can form with nitrogen-atoms the ring of nitrogen atom, R ²³And R ²⁴Can form with nitrogen-atoms the ring of nitrogen atom.

R ²⁵Expression-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z1 ⁺Or-SO ₂NHR ²⁶

M1 represents 0～5 integer.Be in the situation of the integer more than 2 at m1, a plurality of R ²⁵For identical or different.But, at R ²⁵For-SO ₃ ^-Situation under, m1 is 1.

A1 represents 0 or 1 integer.

X1 represents halogen atom.

R ²⁶The expression carbon number is 1～20 1 valency saturated hydrocarbyl.

Z1 ⁺Expression ⁺N (R ²⁷) ₄, Na ⁺Or K ⁺

R ²⁷Represent independently that respectively carbon number is 1～20 1 valency saturated hydrocarbyl or benzyl.]

As expression R ²¹～R ²⁴Carbon number be 6～10 1 valency aromatic hydrocarbyl, can list and above-mentioned R ¹～R ⁴The middle same group of group of enumerating as aromatic hydrocarbyl.The hydrogen atom that contains in this aromatic hydrocarbyl can be by-SO ₃ ^-,-SO ₃H ,-SO ₃ ^-Z1 ⁺,-SO ₃R ²⁶Or-SO ₂NHR ²⁶Replace.

As R ²¹～R ²⁴Combination, preferred following combination: R ²¹And R ²³Be hydrogen atom; R ²²And R ²⁴Be 6～10 1 valency aromatic hydrocarbyl for carbon number, the hydrogen atom quilt-SO that contains in this aromatic hydrocarbyl ₃ ^-,-SO ₃H ,-SO ₃ ^-Z1 ⁺,-SO ₃R ²⁶Or-SO ₂NHR ²⁶Replace.Further preferably be combined as: R ²¹And R ²³Be hydrogen atom, R ²²And R ²⁴Be 6～10 1 valency aromatic hydrocarbyl for carbon number, the hydrogen atom quilt-SO that contains in this aromatic hydrocarbyl ₃ ^-Z1 ⁺Or-SO ₂NHR ²⁶Replace.

At R ²¹～R ²⁴During for these groups, can be formed by the colored curable resin composition of the present invention of inclusion compound (2a) color filter of excellent heat resistance.

As R ²¹And R ²²Ring and the R of the nitrogen atom that forms with nitrogen-atoms ²³And R ²⁴The ring of the nitrogen atom that forms with nitrogen-atoms can list and R ¹And R ²The ring of the nitrogen atom that the ring that forms with nitrogen-atoms is same.Wherein, preferred aliphat heterocycle.As this aliphatics heterocycle, for example can list following aliphatics heterocycle.

As expression R ²⁶And R ²⁷Carbon number be 1～20 1 valency saturated hydrocarbyl, can list and R ⁸～R ¹¹The middle same group of group of enumerating as saturated hydrocarbyl.

At R ²¹～R ²⁴For-R ²⁶Situation under ,-R ²⁶Be preferably independently respectively methyl or ethyl.In addition, as-SO ₃R ²⁶And-SO ₂NHR ²⁶In R ²⁶, preferred carbon number is 3～20 branched-chain alkyl, more preferably carbon number is 6～12 branched-chain alkyl, further preferred 2-ethylhexyl.At R ²⁶During for these groups, can be formed by the colored curable resin composition of the present invention of inclusion compound (2a) foreign matter few color filter occurs.

Z1 ⁺For ⁺N (R ²⁷) ₄, Na ⁺Or K ⁺, be preferably ⁺N (R ²⁷) ₄

As above-mentioned ⁺N (R ²⁷) ₄, preferred four R ²⁷In at least two be 5～20 1 valency saturated hydrocarbyl for carbon number.In addition, four R ²⁷Total carbon atom number be preferably 20～80, more preferably 20～60.Exist in the compound (2a) ⁺N (R ²⁷) ₄Situation under, can be by comprising R ²⁷Few color filter occurs for the colored curable resin composition of the present invention of the compound (2a) of these groups forms foreign matter.

M1 is preferred 1～4, and more preferably 1 or 2.

As compound (1a), comprise the compound shown in the formula (3a) (below, sometimes be called " compound (3a) ".) dyestuff also be preferred.Compound (3a) can be its dynamic isomer.In the situation that use compound (3a), the content of the compound (3a) in the xanthene dye (Aa) is preferably more than the 50 quality %, more preferably more than the 70 quality %, more preferably more than the 90 quality %.

[in the formula (3a), R ³¹And R ³²Represent that independently of one another carbon number is 1～10 1 valency saturated hydrocarbyl, the hydrogen atom that contains in this saturated hydrocarbyl can be 6～10 aromatic hydrocarbyl or halogen atom replacement by carbon number, the hydrogen atom that contains in this aromatic hydrocarbyl can be 1～3 alkoxy replacement by carbon number, contain in the above-mentioned saturated hydrocarbyl-CH ₂-can by-O-,-CO-or-NR ¹¹-displacement.

R ³³And R ³⁴Represent that independently of one another carbon number is that 1～4 alkyl, carbon number are that 1～4 alkylthio group or carbon number are 1～4 alkyl sulphonyl.

R ³¹And R ³³Can form with nitrogen-atoms the ring of nitrogen atom, R ³²And R ³⁴Can form with nitrogen-atoms the ring of nitrogen atom.

P and q represent 0～5 integer independently of one another.In the situation that p is more than 2, a plurality of R ³³Can be identical or different, in the situation that q is more than 2, a plurality of R ³⁴Can be identical or different.

R ¹¹Expression and above-mentioned synonym.]

As R ³¹And R ³²In carbon number be 1～10 1 valency saturated hydrocarbyl, can list R ⁸1 valency saturated hydrocarbyl in carbon number be 1～10 group.

The carbon number that can be used as substituting group and have is 6～10 aromatic hydrocarbyl, can list and R ¹In used identical group.

Be 1～3 alkoxy as carbon number, such as listing methoxyl, ethoxy, propoxyl group etc.

R ³¹And R ³²Be preferably independently of one another carbon number and be 1～3 1 valency saturated hydrocarbyl.

As expression R ³³And R ³⁴Carbon number be 1～4 alkyl, can list methyl, ethyl, propyl group, butyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group etc.

As R ³³And R ³⁴In carbon number be 1～4 alkylthio group, can list methyl mercapto, ethylmercapto group, rosickyite base, butylthio, isopropyl sulfenyl etc.

As R ³³And R ³⁴In carbon number be 1～4 alkyl sulphonyl, can list mesyl, ethylsulfonyl, the third sulfonyl, fourth sulfonyl, isopropyl sulfonyl etc.

R ³³And R ³⁴Preferred carbon number is 1～4 alkyl, more preferably methyl.

The integer of p and q preferred 0～2 is preferably 0 or 1.

As compound (1a), for example can list the compound that is represented by formula (1-1)～formula (1-42) respectively.Be explained, in the formula, R ²⁶The expression carbon number is 1～20 1 valency saturated hydrocarbyl, is preferably carbon number and is 6～12 branched-chain alkyl, more preferably the 2-ethylhexyl.Compound shown in formula (1-1)～formula (1-29) is equivalent to compound (2a), and the compound shown in formula (1-30)～formula (1-42) is equivalent to compound (3a).

Wherein, sulfonamide compound, the quaternary ammonium salt of C.I. acid red 289, the sulfonamide compound of C.I. acid violet 102 or the quaternary ammonium salt of C.I. acid violet 102 of preferred C.I. acid red 289.As such compound, such as listing the compound shown in formula (1-1)～formula (1-8), formula (1-11) and the formula (1-12) etc.

In addition, from the aspect of the dissolubility excellence organic solvent, the compound shown in preferred formula (1-30)～formula (1-39).

Xanthene dye (Aa) can use by commercially available xanthene dye (for example, China and foreign countries change into " the Chugai Aminol Fast Pink R-H/C " that (strain) makes, " the Rhodamin 6G " that ridge, field chemical industry (strain) is made).In addition, also can be to be synthesized as initiation material and with reference to TOHKEMY 2010-32999 communique by commercially available xanthene dye.

Anthraquinone dye (Ab) is the dyestuff that comprises the compound that has the anthraquinone skeleton in the molecule.As anthraquinone dye (Ab), for example can list:

C.I. solvent yellow 117,163,167,189,

C.I. solvent orange 77,86,

C.I. solvent red 111,143,145,146,150,151,155,168,169,172,175,181,207,222,227,230,245,247,

C.I. solvent violet 11,13,14,26,31,36,37,38,45,47,48,51,59,60,

C.I. solvent blue 19 4,18,35,36,45,58,59,59:1,63,68,69,78,79,83,94,97,98,100,101,102,104,105,111,112,122,128,132,136,139,

C.I. solvent green 3,28,29,32,33,

C.I. acid red 80,

C.I. ACID GREEN 25,27,28,41,

C.I. acid violet 34,

C.I. acid blue 25,27,40,45,78,80,112,

C.I. disperse yellow 51,

C.I. disperse violet 26,27,

C.I. disperse blue 1,14,56,60,

It is C.I. directly blue 40,

C.I. medium red 3,11,

C.I. medium indigo plant 8 etc.

The anthraquinone dye that anthraquinone dye (Ab) preferably dissolves in organic solvent, more preferably blueness, purple or red anthraquinone dye.

Wherein, as anthraquinone dye (Ab), preferably comprise the compound shown in the formula (1b) (below, sometimes be called " compound (1b) ".) dyestuff.In the situation that use compound (1b), the content of the compound (1b) in the anthraquinone dye (Ab) is preferably more than the 50 quality %, more preferably more than the 70 quality %, more preferably more than the 90 quality %.Particularly preferably only use compound (1b) as anthraquinone dye (Ab).

[in the formula (1b), A represent hydroxyl or-NH-R ⁵²

R ⁵¹And R ⁵²Representing independently respectively hydrogen atom, can have substituent carbon number to be 1～10 aliphatic alkyl, can having substituent carbon number is the group shown in 3～10 ester ring type alkyl or the formula (1b ')

(formula (1b ') in, R ⁵³The expression carbon number be 1～6 alkyl, halogen atom ,-SO ₃H ,-CO ₂H ,-CO ₂R ⁵⁴,-NHCOR ⁵⁴,-SO ₃R ⁵⁴Or-SO ₂NR ⁵⁴R ⁵⁵

R ⁵⁴The expression carbon number is 1～10 saturated hydrocarbyl, and the hydrogen atom that contains in this saturated hydrocarbyl can be by halogen atom, hydroxyl or amino the replacement.

R ⁵⁵Expression hydrogen atom, carbon number are 1～10 saturated hydrocarbyl.

R represents 0～5 integer.In the situation that r is more than 2, a plurality of R ⁵³Can be identical or different.

X ⁵¹Expression singly-bound or carbon number are 1～6 alkylidene.)。]

(1b) has-SO at compound ₃H and/or-CO ₂In the situation of H, these groups can form salt (for example, Na salt, K salt).

As expression R ⁵¹And R ⁵²Carbon number be 1～10 aliphatic alkyl, such as listing methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl, neopentyl, 2-ethylhexyl etc.

Substituting group as these aliphatic alkyls can have can list hydroxyl, halogen atom etc.

As expression R ⁵¹And R ⁵²Carbon number be 3～10 ester ring type alkyl, such as listing cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, three ring decyls etc.

Substituting group as these ester ring type alkyl can have can list hydroxyl, halogen atom etc.

As expression R ⁵³Carbon number be 6～10 alkyl, such as listing methyl, ethyl, propyl group, butyl, amyl group, hexyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl, neopentyl etc.

As expression R ⁵⁴And R ⁵⁵Carbon number be 1～10 saturated hydrocarbyl, such as listing the straight chain shape alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl; The branched-chain alkyls such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl; The saturated fat ring type alkyl such as cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, three ring decyls.

As-CO ₂R ⁵⁴, for example can list methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxy carbonyl and eicosane oxygen base carbonyl.

As-NHCOR ⁵⁴, for example can list N-acetylamino, N-propionamido, N-butyrylamino, N-isobutyryl amino and N-pivaloyl amino.

As-SO ₃R ⁵⁴, for example can list methoxyl sulfonyl, ethoxy sulfonyl, propoxyl group sulfonyl, tert-butoxy sulfonyl, own oxygen base sulfonyl and eicosane oxygen base sulfonyl.

As-SO ₂NR ⁵⁴R ⁵⁵For example can list N-methyl sulfamoyl, N-ethyl sulfamoyl, N-propyl group sulfamoyl, N-isopropyl sulfamoyl, N-butyl sulfamoyl, N-isobutyl sulfamoyl, N-sec-butyl sulfamoyl, N-tert-butyl group sulfamoyl, N-amyl group sulfamoyl, N-(1-ethyl propyl) sulfamoyl, N-(1, the 1-dimethyl propyl) sulfamoyl, N-(1, the 2-dimethyl propyl) sulfamoyl, N-(2, the 2-dimethyl propyl) sulfamoyl, N-(1-methyl butyl) sulfamoyl, N-(2-methyl butyl) sulfamoyl, N-(3-methyl butyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-cyclohexyl sulfamoyl, N-hexyl sulfamoyl, N-(1, the 3-dimethylbutyl) sulfamoyl, N-(3, the 3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methyl hexyl) sulfamoyl, N-(1,4-dimethyl amyl group) sulfamoyl, N-octyl group sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1, the 5-dimethyl) hexyl sulfamoyl, N-(1,1,2,2-tetramethyl butyl) sulfamoyl, the N-one such as N-(the amino amyl group of 5-) sulfamoyl replace sulfamoyl;

As expression X ⁵¹Carbon number be 1～6 alkylidene, for example can list methylene, ethylidene, 1,3-propylidene, 1,2-propylidene, 1,4-butylidene, 1,5-pentylidene, 1,6-hexylidene, 1,1-ethylidene, 1,3-butylidene, 2-methyl isophthalic acid, 3-propylidene, 2-methyl isophthalic acid, 2-propylidene, 1,4-pentylidene, 2-methyl isophthalic acid, 4-butylidene etc.

As compound (1b), for example can list the compound shown in formula (2-1)～formula (2-13).

As anthraquinone dye (Ab), preferred C.I. solvent blue 35 (compound shown in the formula (2-4)), C.I. solvent blue 45, C.I. acid blue 80 (compound shown in the formula (2-11)), C.I. solvent blue 19 04 (compound shown in the formula (2-12)) and C.I. solvent blue 19 22 (compound shown in the formula (2-13)).During for these anthraquinone dyes, can form the filming of high-contrast, pattern, and foreign matter occurs also few.

As dyestuff (Ac), so long as the dyestuff different from xanthene dye (Aa) and anthraquinone dye (Ab), then have no particular limits, can list oil-soluble dyes, acid dyes, basic-dyeable fibre, direct dyes, mordant dye, the amine salt of acid dyes, the dyestuffs such as the sulfamide derivative of acid dyes, for example can list and be categorized as dyestuff among " color index " (カラ one イ Application デ Star Network ス) (The Society of Dyers and Colourists publication) is pigment compound in addition, the known dyestuff of record in " dyeing ノ one ト " (look dyes society).In addition, according to chemical constitution, can list azo dyes, cyanine dye, triphenhlmethane dye, phthalocyanine dye, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azomethine dyes (azomethine dye), squarylium cyanine dyes, acridine dye, styryl dye, coumarine dye, quinoline dye and nitro dye.Wherein, preferred organic solvent-soluble dye.

Particularly, can list 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;

C.I. solvent orange 2,7,11,15,26,56;

C.I. solvent blue 4,5,37,67,70,90;

C.I. the C.I. solvent dye such as solvent green 1,4,5,7,34,35;

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

C.I. azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,57,66,73,80,88,91,97,103,111,114,129,133,134,138,143,145,150,151,158,176,182,183,195,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,308,312,315,316,339,341,345,346,349,382,383,394,401,412,417,418,422,426;

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, 7,17,19;

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

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

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

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

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

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

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

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

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

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

C.I. medium red 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95;

C.I.

medium 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. medium purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58;

C.I.

medium indigo plant

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. C.I. mordant dyes such as medium green 1,3,4,5,10,15,26,29,33,34,35,41,43,53 etc.

As pigment (Ad), have no particular limits, can use known pigment, for example can list the compound that is categorized as pigment among " color index " (カラ one イ Application デ Star Network ス) (The Society of Dyers and Colourists publication).

As pigment, such as listing: C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194, the yellow uitramarines such as 214;

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

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

C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60; C.I.

pigment violet

1,19,23,29,32,36, the violet pigments such as 38;

C.I. pigment Green 7,36, the viridine greens such as 58;

C.I. pigment brown 23, the browns such as 25;

C.I. pigment black 1, the black pigments such as 7 etc.

As pigment, preferred C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60 and C.I.

pigment violet

1,19,23,29,32,36, the violet pigments such as 38, more preferably C.I. pigment blue 15: 3,15:6 and C.I. pigment Violet 23, further preferred C.I. pigment blue 15: 6.In the situation that colored curable resin composition of the present invention is prepared into blue-colored hardening resin composition, by containing above-mentioned pigment, easily realize the optimization of transmitted spectrum, make the photostability of color filter and chemical reagent resistance good.

These pigment can use separately, also can two or more mixing use.

Pigment can implement as required rosin process, use the surface treatment that imports pigment derivative that acidic-group or basic group are arranged etc., utilize the grafting to surface of pigments of macromolecular compound etc. to process, based on the micronize of sulfuric acid micronize method etc. process or utilize cleaning treatment that the organic solvent that is used for removing impurity or water etc. carry out, utilize ionic impurity that ion exchange process etc. carries out remove processing etc.

Pigment preferably makes particle diameter even.Carry out dispersion treatment by containing pigment dispersing agent, can obtain the dispersible pigment dispersion of the state that pigment disperses equably in solution.

As above-mentioned pigment dispersing agent, such as surfactant that can list kation system, negative ion system, nonionic system, both sexes, polyester system, polyamine system, acrylic acid series etc. etc.These pigment dispersing agents may be used alone, can also be used in combination two or more.As pigment dispersing agent, can list trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), Floren (common prosperity society chemistry (strain) is made), Solsperse (Zeneca (strain) manufacturing), EFKA (manufacturing of CIBA company), AJISPER (Ajinomoto Fine-Techno Co.Int. manufacturing), Disperbyk (manufacturing of BYK company) etc.

In the situation that use pigment dispersing agent, its use amount is preferably more than the 1 quality % and below the 100 quality % with respect to the total amount of pigment (Ad), more preferably more than the 5 quality % and below the 50 quality %.When the use amount of pigment dispersing agent is above-mentioned scope, there is the tendency of the dispersible pigment dispersion that obtains homogeneously dispersed state.

The content of xanthene dye (Aa) is preferably more than the 0.1 quality % and below the 70 quality % with respect to the total amount of colorant (A), more preferably more than the 0.5 quality % and below the 50 quality %.

The content of anthraquinone dye (Ab) is preferably more than the 0.1 quality % and below the 70 quality % with respect to the total amount of colorant (A), more preferably more than the 0.5 quality % and below the 50 quality %.

In the situation that colorant (A) comprises pigment (Ad), the content of pigment (Ad) is preferably more than the 10 quality % and below the 99.8 quality % with respect to the total amount of colorant (A), more preferably more than the 30 quality % and below the 99 quality %.

In the situation that colorant (A) comprises dyestuff (Ac), the content of dyestuff (Ac) is preferably more than the 0.1 quality % and below the 50 quality % with respect to the total amount of colorant (A), more preferably more than the 0.5 quality % and below the 30 quality %.

Colorant (A) for the situation of colorant that comprises xanthene dye (Aa), anthraquinone dye (Ab) and pigment (Ad) under, the containing than being preferably respectively xanthene dye (Aa) of these dyestuffs: 0.1 quality % is above and below the 70 quality %; Anthraquinone dye (Ab): more than the 0.1 quality % and below the 70 quality %; Pigment (Ad): more than the 29.9 quality % and below the 99.8 quality %.

Xanthene dye (Aa) more preferably: 0.5 quality % is above and below the 50 quality %; Anthraquinone dye (Ab): more than the 0.5 quality % and below the 50 quality %; Pigment (Ad): more than the 49.5 quality % and below the 99 quality %.

The content of colorant (A) is preferably 5～60 quality % with respect to the total amount of solid constituent, more preferably 8～55 quality %, more preferably 10～50 quality %.When the content of colorant (A) is above-mentioned scope, can make the colour saturation when making color filter abundant, and make resin (B), the polymerizable compound (C) that contains aequum in the composition, therefore can form the sufficient pattern of physical strength.At this, " total amount of solid constituent " in this instructions refers to from the amount of the total amount desolventizing content of colored curable resin composition.The total amount of solid constituent and with respect to its content of each composition such as measuring with known analysis means such as liquid chromatography or gas chromatographies.

＜resin (B) 〉

Resin (B) has no particular limits, and is preferably alkali soluble resin.As resin (B), can list following resin [K1]～[K6] etc.

Resin [K1]: be selected from least a (a) in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides (below, sometimes be called " (a) ") and have the multipolymer of the monomer (b) that carbon number is 2～4 cyclic ether structure and ethylenic unsaturated link (below, sometimes be called " (b) ");

Resin [K2]: (a), (b) and can with the monomer (c) of (a) copolymerization (still, from (a) and (b) different.) multipolymer of (below, sometimes be called " (c) ");

Resin [K3]: multipolymer (a) and (c);

Resin [K4]: the resin that (b) obtained with (a) and (c) copolymer reaction;

Resin [K5]: the resin that (a) obtained with (b) and (c) copolymer reaction;

Resin [K6]: make (a) and copolymer reaction (b) and (c), the resin that obtains with the carboxylic acid anhydrides reaction again.

As (a), particularly, such as listing: unsaturated monocarboxylic classes such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, p-vinyl benzoic acids;

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, the Isosorbide-5-Nitrae-unsaturated dicarboxylic classes such as cyclohexene dicarboxylic acid;

Methyl-5-norborene-2,3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", the 5-carboxyl-carboxylic dicyclo unsaturated compound classes such as 6-ethyl dicyclo [2.2.1] hept-2-ene";

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5, the unsaturated dicarboxylic class acid anhydrides such as 6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydride;

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

Such as unsaturated esters of acrylic acid that in a part, contains hydroxyl and carboxyl of α-(methylol) acrylic acid and so on etc.

Wherein, from aspect, the deliquescent aspect of gained resin aqueous alkali of copolyreaction, preferred acrylic acid, methacrylic acid, maleic anhydride etc.

(b) refer to for example to have the polymerizable compound that carbon number is 2～4 cyclic ether structure (for example, be selected from oxirane ring, oxetanes ring and the tetrahydrofuran ring at least a) and ethylenic unsaturated link.(b) preferably has the monomer that carbon number is 2～4 cyclic ether and (methyl) acryloxy.

Be explained, in this instructions, " (methyl) acrylic acid " expression is selected from least a kind in the group that is comprised of acrylic acid and methacrylic acid.The statement that " (methyl) acryloyl group " reaches " (methyl) acrylate " etc. also has same implication.

As (b), for example can list monomer (a1) with Oxyranyle and ethylenic unsaturated link (below, sometimes be called " (b1) "), have oxetanyl and ethylenic unsaturated link monomer (b2) (below, sometimes be called " (b2) "), have monomer (b3) (below, sometimes be called " (b3) ") of tetrahydrofuran base and ethylenic unsaturated link etc.

(b1) for example can list have that the unsaturated fatty hydrocarbons that makes straight chain shape or chain carries out epoxidation and the monomer (b1-1) of the structure that obtains (below, sometimes be called " (b1-1) "), monomer (b1-2) (below, sometimes be called " (b1-2) ") with the structure that makes unsaturated lipid ring type hydrocarbon carry out epoxidation and obtain.

As (b1-1), can list (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid Beta-methyl glycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl esters, the glycidyl vinyl ether, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to the vinyl benzyl glycidyl ether, Alpha-Methyl-adjacent vinyl benzyl glycidyl ether, an Alpha-Methyl-vinyl benzyl glycidyl ether, Alpha-Methyl-to the vinyl benzyl glycidyl ether, 2, two (the glycidyl oxygen ylmethyl) styrene of 3-, 2, two (the glycidyl oxygen ylmethyl) styrene of 4-, 2, two (the glycidyl oxygen ylmethyl) styrene of 5-, 2, two (the glycidyl oxygen ylmethyl) styrene of 6-, 2,3,4-three (glycidyl oxygen ylmethyl) styrene, 2,3,5-three (glycidyl oxygen ylmethyl) styrene, 2,3,6-three (glycidyl oxygen ylmethyl) styrene, 3,4,5-three (glycidyl oxygen ylmethyl) styrene, 2,4,6-three (glycidyl oxygen ylmethyl) styrene etc.

As (b1-2), can list the single oxide of vinyl cyclohexene, 1,2-epoxy radicals-4-vinyl cyclohexane (for example CELLOXIDE 2000: Daicel chemical industry (strain) is made), (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl methyl esters (for example CYCLOMER A400: Daicel chemical industry (strain) make), (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl methyl esters (for example CYCLOMER M100: Daicel chemical industry (strain) make), compound shown in the formula (I), compound shown in the formula (II) etc.

[in formula (I) and the formula (II), R ^aAnd R ^bExpression hydrogen atom or carbon number are 1～4 alkyl, and the hydrogen atom that contains in this alkyl can be replaced by hydroxyl.

X ^aAnd X ^bThe expression singly-bound ,-R ^c-, *-R ^c-O-, *-R ^c-S-or *-R ^c-NH-.

R ^cThe expression carbon number is 1～6 alkylidene.

* represent the bonding position with O.]

Be 1～4 alkyl as carbon number, can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.

As the alkyl that hydrogen atom is replaced by hydroxyl, can list 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.

As R ^aAnd R ^b, preferably can list hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably can list hydrogen atom, methyl.

As alkylidene, can list methylene, ethylidene, 1,2-propylidene, 1,3-propylidene, Isosorbide-5-Nitrae-butylidene, 1,5-pentylidene, 1,6-hexylidene etc.

As X ^aAnd X ^b, preferably can list singly-bound, methylene, ethylidene, *-CH ₂-O-and *-CH ₂CH ₂-O-more preferably can list singly-bound, *-CH ₂CH ₂-O-(* represents the bonding position with O).

As the compound shown in the formula (I), can list the compound shown in formula (I-1)～formula (I-15) etc.Preferably can list the compound shown in formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)～formula (I-15).More preferably can list the compound shown in formula (I-1), formula (I-7), formula (I-9) or the formula (I-15).

As the compound shown in the formula (II), can list the compound shown in formula (II-1)～formula (II-15) etc.Preferably can list the compound shown in formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)～formula (II-15).More preferably can list the compound shown in formula (II-1), formula (II-7), formula (II-9) or the formula (II-15).

Compound shown in compound shown in the formula (I) and the formula (II) can be distinguished separately and use.In addition, these compounds can mix with arbitrary ratio.In the situation that mix, its mixture ratio is take molar ratio computing preferred formula (I): formula (II) is as 5: 95～95: 5, more preferably 10: 90～90: 10, and more preferably 20: 80～80: 20.

As the monomer (b2) with oxetanyl and ethylenic unsaturated link, more preferably has the monomer of oxetanyl and (methyl) acryloxy.As (b2), can list 3-methyl-3-methacryloxy methyl oxetanes, 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 Ethyloxetane, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloxy Ethyloxetane etc.

As the monomer (b3) with tetrahydrofuran base and ethylenic unsaturated link, more preferably has the monomer of tetrahydrofuran base and (methyl) acryloxy.

As (b3), particularly, can list acrylic acid tetrahydro furfuryl ester (VISCOATV#150 for example, Osaka organic chemistry industry (strain) is made), methacrylic acid tetrahydro furfuryl ester etc.

As (b), the viewpoint from the reliability of the thermotolerance that can further improve the color filter of gained, chemical reagent resistance etc. is preferably (b1).And then, from the viewpoint of the excellent storage stability that makes colored curable resin composition, more preferably (b1-2).

As (c), for example can list: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid cyclopentyl ester, (methyl) acrylic acid cyclohexyl ester, (methyl) acrylic acid 2-methylcyclohexyl ester, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester (in the art, is called as " (methyl) acrylic acid two cyclopentyl esters " as trivial name.In addition, sometimes be called " (methyl) acrylic acid three ring decyl ester ".), (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decene-8-base ester (in the art, is called as " (methyl) acrylic acid dicyclopentenyl ester " as trivial name.), (methyl) esters of acrylic acid such as (methyl) acrylic acid two cyclopentyloxy ethyl esters, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid allyl ester, (methyl) acrylic acid propargyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) acrylic acid benzyl ester;

(methyl) esters of acrylic acid of the hydroxyls such as (methyl) acrylic acid 2-hydroxyethyl ester, (methyl) acrylic acid 2-hydroxy-propyl ester;

The dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate;

Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl dicyclo [2.2.1] hept-2-ene", 5-ethoxy dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5,6-two (methylol) dicyclo [2.2.1] hept-2-ene", 5,6-two (2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5, two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene"s of 6-, the dicyclo unsaturated compound classes such as two (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-;

The dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridinyl) maleimide;

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

Wherein, from copolyreaction and stable on heating viewpoint, optimization styrene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc.

In the resin [K1], from the ratio of the structural unit of each composition, in the entire infrastructure unit that consists of resin [K1], be preferably following scope.

Structural unit from (a): 2～60 % by mole

Structural unit from (b): 40～98 % by mole

Following scope more preferably.

Structural unit from (a): 10～50 % by mole

Structural unit from (b): 50～90 % by mole

There is storage stability, the development when forming colored pattern, and the tendency of the solvent resistance excellence of the color filter of gained of colored curable resin composition in the ratio of the structural unit of resin [K1] when above-mentioned scope.

Resin [K1] can be made as a reference with the citing document of putting down in writing in for example document " experimental method of Polymer Synthesizing " (" the real test method of Polymer Synthesizing ") (grand outstanding sale room (strain) chemistry of going in large Tianjin is with the 1st edition the 1st printing distribution on March 1st, 1972 of people) the middle method of putting down in writing and the document.

Particularly, can list following methods: with (a) of ormal weight and (b), polymerization initiator and solvent etc. drop in the reaction vessel, for example utilize nitrogen replacement oxygen, become deoxidation atmosphere, when stirring, heat and be incubated.Be explained, polymerization initiator used herein and solvent etc. have no particular limits, and can use material usually used in this field.For example, as polymerization initiator, can list azo-compound (2,2 '-azoisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitriles) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, so long as the material of each monomer dissolving is got final product, can list solvent described later etc. as the solvent (E) of colored curable resin composition of the present invention.

Be explained, the multipolymer that obtains can directly use reacted solution, also can use the solution after concentrated or the dilution, can also use with the material of the methods such as precipitation again as solid (powder) taking-up.Especially when its polymerization, solvent contained in the photosensitive composition of the application of the invention is as solvent, thereby reacted solution directly can be used in the preparation of photosensitive composition of the present invention, and can simplify the manufacturing process of photosensitive composition of the present invention.

In the resin [K2], from the ratio of the structural unit of each composition, in the entire infrastructure unit that consists of resin [K2], be preferably following scope:

Structural unit from (a): 2～45 % by mole

Structural unit from (b): 2～95 % by mole

Structural unit from (c): 1～65 % by mole;

Following scope more preferably:

Structural unit from (a): 5～40 % by mole

Structural unit from (b): 5～80 % by mole

Structural unit from (c): 5～60 % by mole.

There is the tendency of solvent resistance, thermotolerance and physical strength excellence of color filter of storage stability, the development when forming colored pattern and the gained of colored curable resin composition in the ratio of the structural unit of resin [K2] when above-mentioned scope.

Resin [K2] for example can similarly be made with the method for putting down in writing as the manufacture method of resin [K1].

In the resin [K3], from the ratio of the structural unit of each composition, in the entire infrastructure unit that consists of resin [K3], be preferably following scope:

Structural unit from (a): 2～60 % by mole

Structural unit from (c): 40～98 % by mole;

Following scope more preferably:

Structural unit from (a): 10～50 % by mole

Structural unit from (c): 50～90 % by mole.

Resin [K3] for example can similarly be made with the method for putting down in writing as the manufacture method of resin [K1].

Resin [K4] can be that 2～4 cyclic ether is made with the carboxylic acid and/or the carboxylic acid anhydrides addition that (a) have by the carbon number that obtains (a) and multipolymer (c) and (b) had.

At first, similarly make (a) and multipolymer (c) with the method for putting down in writing as the manufacture method of resin [K1].In this situation, be preferably the ratio identical with the cited ratio of resin [K3] from the ratio of the structural unit of each composition.

The carbon number that (b) had is reacting from the carboxylic acid of (a) and/or the part of carboxylic acid anhydrides in 2～4 cyclic ether and the above-mentioned multipolymer.

After the manufacturing of (a) and multipolymer (c), be air with the atmosphere in the flask from nitrogen replacement, the catalysts (such as three (dimethylaminomethyl) phenol etc.) of (b), carboxylic acid or carboxylic acid anhydrides and cyclic ether and polymerization inhibitor (such as quinhydrones etc.) etc. are put into flask, for example reacted 1～10 hour at 60～130 ℃, thereby can make resin [K4].

(b) use amount is preferably 5～80 moles with respect to (a) 100 moles, more preferably 10～75 moles.Use amount by making (b) exists the balance of solvent resistance, thermotolerance, physical strength and the sensitivity of the storage stability, the development when forming pattern and the gained pattern that make colored curable resin composition to become good tendency in this scope.Because cyclic ether is reactive high, and is difficult to remaining unreacted (b), therefore, as (b) that use in the resin [K4], preferred (b1), further preferred (b1-1).

The use amount of above-mentioned catalysts is preferably 0.001～5 mass parts with respect to (a), (b) and total amount 100 mass parts (c).The use amount of above-mentioned polymerization inhibitor is preferably 0.001～5 mass parts with respect to (a), (b) and total amount 100 mass parts (c).

The reaction conditionss such as feeding method, temperature of reaction and time can be considered thermal discharge due to manufacturing equipment, the polymerization etc. and suitably adjust.Be explained, same with polymerizing condition, can consider thermal discharge due to manufacturing equipment, the polymerization etc., suitably adjust feeding method, temperature of reaction.

About resin [K5], as the phase one, similarly obtain (b) and multipolymer (c) with the manufacture method of above-mentioned resin [K1].With above-mentioned same, the multipolymer that obtains can directly use reacted solution, also can use the solution after concentrated or the dilution, can also use with the material of the methods such as precipitation again as solid (powder) taking-up.

From the ratio of (b) and structural unit (c), the total mole number with respect to the entire infrastructure unit that consists of above-mentioned multipolymer preferably is respectively following scope:

Structural unit from (b): 5～95 % by mole

Structural unit from (c): 5～95 % by mole;

Following scope more preferably:

Structural unit from (b): 10～90 % by mole

Structural unit from (c): 10～90 % by mole.

And then, with the same condition of the manufacture method of resin [K4] under, make carboxylic acid that (a) have or carboxylic acid anhydrides and (b) and the cyclic ether from (b) that has of multipolymer (c) react, thereby can obtain resin [K5].

The use amount of (a) that reacts with above-mentioned multipolymer is preferably 5～80 moles with respect to (b) 100 moles.Because cyclic ether is reactive high, and is difficult to remaining unreacted (b), therefore, as (b) that use in the resin [K5], preferred (b1), further preferred (b1-1).

Resin [K6] is the resin that carboxylic acid anhydrides is further obtained with resin [K5] reaction.

Carboxylic acid anhydrides and the hydroxyl that is produced by the reaction of cyclic ether and carboxylic acid or carboxylic acid anhydrides are reacted.

As carboxylic acid anhydrides, can list maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides (carbic anhydride (Himic anhydride)) etc.The use amount of carboxylic acid anhydrides is preferably 0.5～1 mole with respect to 1 mole of the use amount of (a).

As resin (B), particularly, can list (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl methyl ester/(methyl) acrylic copolymer, acrylic acid 3,4-epoxy radicals three ring [5.2.1.0 ^2.6] decyl ester/resins [K1] such as (methyl) acrylic copolymer; (methyl) acrylic acid glycidyl esters/(methyl) acrylic acid benzyl ester/(methyl) acrylic copolymer, (methyl) acrylic acid glycidyl esters/styrene/(methyl) acrylic copolymer, acrylic acid 3,4-epoxy radicals three ring [5.2.1.0 ^2.6] decyl ester/(methyl) acrylic acid/N-N-cyclohexylmaleimide multipolymer, 3-methyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes/resins [K2] such as (methyl) acrylic acid/styrol copolymer; (methyl) acrylic acid benzyl ester/(methyl) acrylic copolymer, the styrene/resins [K3] such as (methyl) acrylic copolymer; The resin that (methyl) acrylic acid glycidyl esters is obtained with (methyl) acrylic acid benzyl ester/(methyl) acrylic copolymer addition, the resin that (methyl) acrylic acid glycidyl esters is obtained with three ring decyl ester/styrene/(methyl) the acrylic copolymer additions of (methyl) acrylic acid, the resins such as resin [K4] that (methyl) acrylic acid glycidyl esters is obtained with three ring decyl ester/(methyl) acrylic acid benzyl ester/(methyl) the acrylic copolymer additions of (methyl) acrylic acid; The resin that makes (methyl) acrylic acid and (methyl) acrylic acid three encircle the copolymer reaction of decyl ester/(methyl) acrylic acid glycidyl esters and obtain, the resins such as resin [K5] that (methyl) acrylic acid is obtained with the copolymer reaction of (methyl) acrylic acid three ring decyl ester/styrene/(methyl) acrylic acid glycidyl esters; Make the copolymer reaction of (methyl) acrylic acid and (methyl) acrylic acid three ring decyl ester/(methyl) acrylic acid glycidyl esters, resulting resin and tetrabydrophthalic anhydride are reacted and the resins such as resin [K6] that obtain etc.

These resins can use separately, and also two or more kinds may be used.

Wherein, as resin (B), preferred resin [K1] and resin [K2].

The weight-average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000～100, and 000, more preferably 5,000～50,000, more preferably 5,000～30,000.Molecular weight is when above-mentioned scope, and hardness of film improves, and residual film ratio is also high, and unexposed the favorable solubility to developer solution exists the tendency that the resolution of colored pattern improves.

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

The acid number of resin (B) is preferably 50～170mg-KOH/g, and more preferably 60～150,70～135mg-KOH/g more preferably.At this, acid number be as in and the amount (mg) of the required potassium hydroxide of 1g resin (B) and the value measured for example can be obtained by using potassium hydroxide aqueous solution carry out titration.

The content of resin (B) is preferably 7～65 quality % with respect to the total amount of solid constituent, more preferably 13～60 quality %, more preferably 17～55 quality %.The content of resin (B) can form colored pattern when above-mentioned scope, and exists resolution and the residual film ratio raising tendency of colored pattern.

＜polymerizable compound (C) 〉

Polymerizable compound (C) is can be by the living radical that produced by polymerization initiator (D) and/or acid and the compound of polymerization, such as compound that can list the ethylenic unsaturated link with polymerism etc., be preferably (methyl) acrylate compounds.

Wherein, polymerizable compound (C) is preferably the polymerizable compound with 3 above ethylenic unsaturated links.As such polymerizable compound, for example can list trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, the four seasons penta tetrol ten (methyl) acrylate, the four seasons penta tetrol nine (methyl) acrylate, three (2-(methyl) acryloxy ethyl) isocyanuric acid ester, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, propylene glycol modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc.Polymerizable compound may be used singly or in combination of two or more.

Wherein, preferred dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate.

The weight-average molecular weight of polymerizable compound (C) is preferably more than 150 and below 2,900, and more preferably 250～1, below 500.

The content of polymerizable compound (C) is preferably 7～65 quality % with respect to the total amount of solid constituent, more preferably 13～60 quality %, more preferably 17～55 quality %.The content of polymerizable compound (C) is in above-mentioned scope the time, the tendency that the residual film ratio when existing colored pattern and forming and the chemical reagent resistance of color filter improve.

＜polymerization initiator (D) 〉

The compound of beginning polymerization then has no particular limits polymerization initiator (D) so long as can utilize the effect of light, heat to produce living radical, acid etc., can use known polymerization initiator.

As polymerization initiator (D); preferably comprise at least a kind the polymerization initiator that is selected from alkyl phenones compound, triaizine compounds, acylphosphine oxide compound, O-acyl group oxime compound and the united imidazole, more preferably comprise the polymerization initiator of O-acyl group oxime compound.

O-acyl group oxime compound is for having the compound of the part-structure shown in the formula (d1).

Below, * represents bonding position.

As O-acyl group oxime compound; for example can list N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) butane-1-ketone-2-imines; N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) octane-1-ketone-2-imines; N-benzoyloxy-1-(4-phenyl sulfenyl phenyl)-3-cyclopentyl propane-1-ketone-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-dioxa cyclopentyl-methyl oxygen base) benzoyl }-9H-carbazole-3-yl] ethane-1-imines; N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-imines; N-benzoyloxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-ketone-2-imines etc.Can use the commercially available products such as IRGACURE (registered trademark) OXE01, OXE02 (more than, BASF AG make), N-1919 (manufacturing of ADEKA company).

Wherein, O-acyl group oxime compound is preferably at least a kind that is selected from N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) octane-1-ketone-2-imines and N-benzoyloxy-1-(4-phenyl sulfenyl the phenyl)-3-cyclopentyl propane-1-ketone-2-imines, more preferably N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) octane-1-ketone-2-imines.During for these O-acyl group oxime compounds, there is the tendency of the color filter that obtains high brightness.

The alkyl phenones compound is the compound with the part-structure shown in the part-structure shown in the formula (d2) or the formula (d3).In these part-structures, phenyl ring can have substituting group.

As the compound with part-structure shown in the formula (d2), such as listing 2-methyl-2-morpholino-1-(4-methyl sulfenyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl] butane-1-ketone etc.Can use the commercially available products such as IRGACURE (registered trademark) 369,907,379 (more than, BASF AG make).

As the compound with part-structure shown in the formula (d3), for example can list 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl) propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(the 4-isopropenyl phenyl) propane-oligomer of 1-ketone, α, α-ethoxybenzene ethyl ketone, benzyl dimethyl ketal etc.

From the aspect of sensitivity, as the alkyl phenones compound, preferably has the compound of part-structure shown in the formula (d2).

As triaizine compounds, for example can list 2, two (the trichloromethyl)-6-(4-methoxyphenyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3,5-triazine, two (the trichloromethyl)-6-piperonyls-1 of 2,4-, 3, the 5-triazine, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1,3 of 2,4-, the 5-triazine, 2, two (the trichloromethyl)-6-(2-(5-methylfuran-2-yl) vinyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-(2-(furans-2-yl) vinyl)-1 of 4-, 3,5-triazine, two (the trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1 of 2,4-, 3, the 5-triazine, two (the trichloromethyl)-6-(2-(3,4-Dimethoxyphenyl) vinyl)-1 of 2,4-, 3,5-triazine etc.

As the acylphosphine oxide compound, can list 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.Can use the commercially available products such as IRGACURE (registered trademark) 819 (BASF AG's manufacturing).

As united imidazole, for example can list 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,3-dichlorophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline (such as reference JPH06-75372-A, JPH06-75373-A etc.), 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline (such as reference JPS48-38403-B, JPS62-174204-A etc.), the imidazolium compounds that replaced by alkoxy carbonyl group of phenyl of 4,4 ' 5,5 '-position (such as reference JPH07-10913-A etc.) etc.

And then, as polymerization initiator (D), can list the benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, o-benzoyl base benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzil, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.These polymerization initiators preferably cause auxiliary agent (D1) (particularly amine) with polymerization described later and are used in combination.

As acid agent, such as listing the salts such as 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate, nitrobenzyl toluenesulfonic acid salt, benzoin toluenesulfonic acid salt etc.

The content of polymerization initiator (D) is preferably 0.1～30 mass parts with respect to total amount 100 mass parts of resin (B) and polymerizable compound (C), more preferably 1～20 mass parts.There is the tendency of time shutter shortening in the content of polymerization initiator (D) owing to high-sensitivity when above-mentioned scope, so the throughput rate of color filter improves.

When containing polymerization initiator (D), can also contain polymerization and cause auxiliary agent (D1).It is for compound or the sensitizer of promotion by the polymerization of the polymerizable compound of polymerization initiator initiated polymerization that polymerization causes auxiliary agent (D1).

Cause auxiliary agent (D1) as polymerization, can list amines, alkoxy anthracene compound, thioxanthones compound and carboxylic acid compound etc., be preferably the thioxanthones compound.

As amines, can list triethanolamine, 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.Can use the commercially available products such as EAB-F (hodogaya chemical industry (strain) is made).

As the alkoxy anthracene compound, can list 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.

As the thioxanthones compound, can list ITX, ITX, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.

As carboxylic acid compound, can list phenyl sulfenyl acetic acid, aminomethyl phenyl sulfenyl acetic acid, ethylphenyl sulfenyl acetic acid, Methylethyl phenyl sulfenyl acetic acid, 3,5-dimethylphenyl sulfenyl acetic acid, methoxyphenyl sulfenyl acetic acid, Dimethoxyphenyl sulfenyl acetic acid, chlorphenyl sulfenyl acetic acid, dichlorophenyl sulfenyl acetic acid, N-phenylglycine, phenoxyethanoic acid, naphthyl sulfenyl acetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.

Polymerization causes auxiliary agent and may be used singly or in combination of two or more.

In the situation that use these polymerizations to cause auxiliary agent (D1), its use amount is preferably 0.1～30 mass parts with respect to total amount 100 mass parts of resin (B) and polymerizable compound (C), more preferably 1～20 mass parts.Polymerization causes the amount of auxiliary agent (D1) when this scope, can form colored pattern with high sensitivity more, the tendency that exists the throughput rate of color filter to improve.

＜solvent (E) 〉

Solvent (E) has no particular limits, and can use solvent usually used in this field.For example, can from ester solvent (molecule contains-COO-and not containing-O-solvent), ether solvents (molecule contains-O-and not containing-COO-solvent), ether-ether solvent (molecule contains-COO-and-solvent of O-), ketone solvent (molecule contains-CO-and not containing-COO-solvent), alcoholic solvent (molecule contains OH and do not contain-O-,-CO-and-solvent of COO-), choice for use the aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc.

As ester solvent, can list methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate and gamma-butyrolacton etc.

As ether solvents, can list 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, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, the propylene glycol single-butyl ether, 3-methoxyl-n-butyl alcohol, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, Isosorbide-5-Nitrae-dioxs, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, the diethylene glycol dipropyl ether, the diethylene glycol dibutyl ethers, methyl phenyl ethers anisole, phenetol, methylanisole etc.

As the ether-ether solvent, can list Methoxy Methyl Acetate, the Methoxy acetic acid ethyl ester, the Methoxy acetic acid butyl ester, the ethoxy methyl acetate, the ethoxy ethyl acetate, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2-methoxy methyl propionate, 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, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, the ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, the TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters etc.

As ketone solvent, can list 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc.

As alcoholic solvent, can list methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine etc.

As aromatic hydrocarbon solvents, can list benzene,toluene,xylene, sym-trimethyl benzene etc.

As amide solvent, can list DMF, DMA, 1-METHYLPYRROLIDONE etc.

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

In above-mentioned solvent, from the viewpoint of coating, drying property, the boiling point among the preferred 1atm is more than 120 ℃ and the organic solvent below 180 ℃.As solvent, preferred propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, glycol monomethyl methyl ether, diethylene glycol monomethyl ether, TC, 4-hydroxy-4-methyl-2-pentanone and N, dinethylformamide, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl lactate and 3-ethoxyl ethyl propionate.

The content of solvent (E) is preferably 70～95 quality % with respect to the total amount of colored curable resin composition of the present invention, more preferably 75～92 quality %.In other words, the total amount of the solid constituent of colored curable resin composition is preferably 5～30 quality %, more preferably 8～25 quality %.When the content of solvent (E) was above-mentioned scope, it is good that the flatness during coating becomes, and when forming color filter, because colour saturation is sufficient, therefore, exist display characteristic to become good tendency.

＜levelling agent (F) 〉

As levelling agent (F), can list the silicone-based surfactant, fluorine is surfactant and the silicone-based surfactant with fluorine atom etc.They can have polymerizable group at side chain.

As the silicone-based surfactant, can list surfactant that has siloxane bond in the molecule etc.Particularly, can list 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; The beautiful DOW CORNING in east (strain) is made), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufacturing of Momentive Performance Materials Japan contract commercial firm) etc.

Be surfactant as above-mentioned fluorine, can list surfactant that has fluorocarbon chain in the molecule etc.Particularly, can list Fluorad (registered trademark) FC430, Fluorad FC431 (Sumitomo 3M (strain) manufacturing), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (DIC (strain) manufacturing), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (the Mitsubishi Materials electronics changes into (strain) and makes), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) manufacturing) and E5844 (manufacturing of (strain) Daikin Fine Chemical research institute) etc.

As the above-mentioned silicone-based surfactant with fluorine atom, can list surfactant that has siloxane bond and fluorocarbon chain in the molecule etc.Particularly, can list Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477 and Megafac F443 (DIC (strain) manufacturing) etc.

These surfactants may be used singly or in combination of two or more.

The content of levelling agent (F) is preferably more than the 0.001 quality % with respect to the total amount of colored curable resin composition and below the 0.2 quality %, be preferably more than the 0.002 quality % and below the 0.1 quality %, more preferably more than the 0.01 quality % and below the 0.05 quality %.The content of levelling agent (F) can make the flatness of color filter good when above-mentioned scope.

＜other compositions 〉

Colored curable resin composition of the present invention can contain the various adjuvants such as filling agent, other macromolecular compounds, driving fit promoter, antioxidant, light stabilizer, chain-transferring agent as required.

The manufacture method of＜colored curable resin composition 〉

Colored curable resin composition of the present invention for example can prepare by mixed colorant (A), resin (B), polymerizable compound (C) and polymerization initiator (D) and the solvent (E) that uses as required, levelling agent (F), polymerization initiation auxiliary agent (D1) and other compositions.

Xanthene dye (Aa), anthraquinone dye (Ab) and the dyestuff (Ac) that uses as required can be dissolved in advance respectively and be prepared into solution in part or all of solvent (E).

Preferably with the filtrator about 0.01～1 μ m of aperture this solution is filtered.

In the situation that contain pigment (Ad), preferably, in advance part or all with solvent (E) of pigment (Ad) mixed, use ball mill etc. make its mean grain size that is dispersed to pigment be 0.2 μ m following about till.At this moment, can cooperate as required part or all of above-mentioned pigment dispersing agent, resin (B).In the dispersible pigment dispersion of gained, mix remaining colorant (A), remaining resin (B), polymerizable compound (C), polymerization initiator (D) and remaining solvent (E) and the levelling agent (F) that uses as required, polymerization initiation auxiliary agent (D1) and other compositions etc. in the mode that becomes normal concentration, thereby can prepare the target colored curable resin composition.

Preferably with the filtrator about 0.01～10 μ m of aperture mixed colored curable resin composition is filtered.

The manufacture method of＜color filter and liquid crystal indicator 〉

As the method that is formed color filter by colored curable resin composition of the present invention, can list the method for photoetching process and use ink-jet machine etc.Photoetching process, evaporates into the mode of grading by desolventizing etc. and makes its drying at substrate coating colored curable resin composition of the present invention for for example, forms the coloured composition layer, and the method for this coloured composition layer being exposed, developing across photomask.After development, can form colored pattern by heating as required.In the formation method of above-mentioned colored pattern, can when exposure, not use photomask yet, and/or do not develop, form thus as the painted of solidfied material of above-mentioned coloured composition layer and film.The colored pattern that so obtains and painted filming can be used as color filter.

As substrate, can be use quartz glass, pyrex, alumina silicate glass, apply the surperficial glass plates such as soda-lime glass with monox, the resin plate of polycarbonate, polymethylmethacrylate, polyethylene terephthalate etc., silicon has formed the substrate of aluminium, silver, silver/copper/palldium alloy film etc. at aforesaid substrate.On these substrates, can also form other color-filter layer (color-filter layer that for example, is formed at substrate by colored curable resin composition etc.), resin bed, transistor, circuit etc.

The thickness of the color filter of made has no particular limits, can suitably adjust according to target purposes etc., and for example be 0.1～30 μ m, be preferably 1～20 μ m, more preferably 1～6 μ m.

Then, to be formed with thin film transistor (TFT) (below, be called " TFT ".) glass substrate on form pattern method describe.

Particularly, by known methods such as photoetching techniques, on glass substrate 21, according to pixels form a plurality of TFT22 (with reference to Fig. 1).TFT22 is made of gate electrode 22a, gate insulating film 22b, polysilicon film 22c and diaphragm 22d, and wherein, gate electrode 22a is positioned on the glass substrate 21, is formed and consisted of the part of gate line by for example molybdenum (Mo); Gate insulating film 22b is formed on this gate electrode 22a, by for example nitride film (SiN _x) and oxide film (SiO ₂) stacked film consist of; Polysilicon film 22c is formed on this gate insulating film 22b; Diaphragm 22d is by for example oxide film (SiO ₂) and nitride film (SiN _x) stacked film form.The zone facing to gate electrode 22a of polysilicon film 22c is passage (channel) zone of TFT22, and in addition, the zone of the both sides of this passage area is source region or drain region.The source region of polysilicon film 22c is electrically connected with the signal wire 27 that is for example formed by aluminium (Al) by the connecting hole (contact hole) that is arranged on the diaphragm 22d.Be explained, as described later, the drain region of polysilicon film 22c is electrically connected with pixel electrode 24 by connecting hole (contact hole) 201.

When on glass substrate 21, according to pixels forming a plurality of TFT22, on glass substrate 21, form simultaneously alignment mark (not shown) with TFT22.As described later, this alignment mark becomes the benchmark of the contraposition in the formation operation of color-filter layer 23.Be explained, these alignment marks also can double as the mark of the benchmark that becomes the applying that drives substrate and counter substrate.When forming metal level, the polysilicon layer of wiring etc. in the manufacturing process of TFT22, utilize at least its one deck forms alignment mark in same operation.

Then, the glass substrate 21 coatings photosensitive composition of the present invention that is being formed with TFT22 and alignment mark, utilize the volatile ingredients such as heat drying (prebake) and/or drying under reduced pressure desolventizing and make its drying, form thickness 0.5～5.0 μ m, for example the coloured composition layer of 1.0 μ m.

As coating process, can list spin-coating method, slot coated method, slit and spin-coating method etc.

Preferred 30～120 ℃ of temperature when carrying out heat drying, more preferably 60～110 ℃.In addition, as heat time heating time, be preferably 10 second～60 minute, more preferably 30 second～30 minute.

When carrying out drying under reduced pressure, preferably under the pressure of 50～150Pa, carry out under 20～25 ℃ the temperature range.

Then, face toward colour cell compound layer irradiation ultraviolet radiation across photomask (not shown), optionally remove unwanted part by developer solution again, obtain thus being configured as the coloured composition layer of the pixel of the connecting hole (contact hole) 201 that is formed with the drain region that arrives polysilicon film 22c, then wash.

By developing, the unexposed section of coloured composition layer is dissolved in the developer solution and is removed.As developer solution, the aqueous solution of the alkali compounds such as preference such as potassium hydroxide, sodium bicarbonate, sodium carbonate, Tetramethylammonium hydroxide.Concentration in the aqueous solution of these alkali compounds is preferably 0.01～10 quality %, more preferably 0.03～5 quality %.And then developer solution can contain surfactant.

Developing method can be any in stirring (paddle) method, infusion process, the spray process etc.And then when developing, can make substrate tilt to arbitrarily angle.

Afterwards, for the coloured composition layer that is formed with connecting hole (contact hole) 201 being flowed (reflow) again and/or making the curing such as polymerizable compound (C) that contain in this coloured composition layer, under 100～300 ℃ of preferred temperature of 150～230 ℃ for example, heating for example 1～120 minute preferred 10～60 minutes.Can form thus the colored curable resin composition layer 23A as colored pattern.This colored curable resin composition layer 23A is corresponding to color filter of the present invention.

Repeat this operation, form colored curable resin composition layer 23A by red colored hardening resin composition, green coloring hardening resin composition and blue-colored hardening resin composition respectively, thereby can form corresponding each pixel column and comprise the color-filter layer 23 (with reference to Fig. 2) of red color filter 23a, green color filter 23b and blue color filter 23c.Although the zone between each color filter of color-filter layer 23 becomes the Mixed Zone of the color of adjacency, this zone is the lightproof area facing to signal wire 27, therefore nothing impact on quality.Be explained, the zone between this each color filter is not colored.

Then, for example form photosensitive resin film 29 as the diaphragm of thickness 0.3～2.0 μ m by spin-coating method for example in the mode that covers color-filter layer 23.Then, across photomask (not shown) to photosensitive resin film 29 irradiation ultraviolet radiations, optionally remove zone and the unwanted part corresponding with connecting hole 201 by developer solution again, thus, form the connecting hole (contact hole) 202 of the drain region that arrives polysilicon film 22c, then wash.Afterwards, flow again (reflow) in order to make photosensitive resin film 29, the temperature of 100～300 ℃ scopes for example 200 ℃ heat.Then, in order to remove residue and the organism such as dyestuff that is deposited in the contact hole 202, and utilize oxygen plasma to carry out etching, and then in order to remove the oxide film that is formed by oxygen plasma, diluted hydrofluoric acid carry out etching and for example utilize.

Then, for example utilizing at photosensitive resin film 29, sputtering method forms for example ITO (Indium-Tin Oxide: the oxide hybrid films of indium and tin) of transparent conductive material, to form pattern to the ITO film by photoetching technique and etching, form transparent pixel electrode 24 (with reference to Fig. 3).Be explained, this pixel electrode 24 also can be formed by aluminium (Al), silver metals such as (Ag) according to the device of making.Afterwards, form alignment films by known method, then carry out the applying of this driving substrate and counter substrate, thereby can make liquid crystal indicator.

According to colored curable resin composition of the present invention, can make the excellent especially color filter of contrast.This color filter is useful as the color filter in display device (such as liquid crystal indicator, organic El device, Electronic Paper etc.) and solid-state imager.

Embodiment

Below, by embodiment colored curable resin composition of the present invention is illustrated in greater detail.

" % " in the example reaches " part ", as long as without specifying, be quality % and mass parts.

In the following synthesis example, compound utilizes ultimate analysis (VARIO-EL:(Alementar (strain) manufacturing)) identify.

(synthesis example 1)

In the flask with condenser pipe and stirring apparatus, the potpourri of the compound shown in the compound shown in the throw-in type (A0-1) and the formula (A0-2) (trade name ChugaiAminol Fast Pink R; China and foreign countries change into manufacturings) 8.9 parts of 15 parts, 150 parts of chloroforms and DMFs, under agitation keep below 20 ℃ on the limit, 10.9 parts of limit dropping thionyl chlorides.After dripping end, be warmed up to 50 ℃, under this temperature, keep making its reaction in 5 hours, afterwards, be cooled to 20 ℃.Cooled reaction solution is under agitation maintained below 20 ℃ on the limit mixed liquor that limit 12.5 parts of 2 ethyl hexylamines of dropping and triethylamine are 22.1 parts.Afterwards, stirring made its reaction in 5 hours under this temperature.Then, with the reaction mixture distillation desolventizing of Rotary Evaporators to obtaining, then, add a small amount of methyl alcohol, vigorous stirring.This potpourri is joined while stirring in the mixed liquor of 375 parts of ion exchange waters, make crystallization.Filter the crystallization of separating out, fully clean with ion exchange water, at 60 ℃ of drying under reduced pressure, obtain 11.3 parts of dyestuffs (Aa-1) (potpourri of the compound shown in formula (A1-1)～formula (A1-8)).

(synthesis example 2)

200 parts of 20 parts of compounds shown in hybrid under the shading condition (1x) and N-ethyl ortho-aminotoluenes (making with the pure pharmaceutical worker's industry of light (strain)) stir the solution of gained 6 hours at 110 ℃.The reactant liquor of cooling gained adds in the mixed liquor of 800 parts in water, 50 parts of 35% hydrochloric acid to room temperature, at room temperature stirs 1 hour, and the result has separated out crystallization.Form with the residue of suction filtration obtains the crystallization of being separated out, and then carries out drying, obtains 24 parts of the compounds shown in the formula (1-30).Yield is 80%.

The structure of the compound shown in the formula (1-30) is utilized mass spectrophotometry (LC; 1200 types that Agilent makes, the LC/MSD type that MASS:Agilent makes) confirm.

(mass spectrophotometry) ionization pattern=ESI+; M/z=[M+H] ⁺603.4

Accurate mass (Exact Mass): 602.2

(synthesis example 3)

Except using N-propyl group-2, the 6-xylidin replaces similarly obtaining the compound shown in the formula (1-38) with synthesis example 1 beyond the N-ethyl ortho-aminotoluene.

The evaluation of the compound shown in the formula (1-38)

(mass spectrophotometry) ionization pattern=ESI+:m/z=[M+H] ⁺659.9

Accurate mass (Exact Mass): 658.9

(synthesis example 4)

12.6 parts of 12 parts of compounds shown in hybrid (1x), 60 parts of METHYLPYRROLIDONEs and piperidines (Tokyo change into industry (strain) make) stir the potpourri of gained 5 hours at 60 ℃.After making above-mentioned reactant liquor cooling room temperature, add in the mixed liquor of 600 parts in water, 100 parts of 35% hydrochloric acid, stirring at room 1 hour.Form with the residue of suction filtration is taken out the crystallization of being separated out, and then carries out drying, obtains 12.4 parts of the compounds shown in the formula (1-27).Yield is 83%.

The evaluation of the compound shown in the formula (1-27)

(mass spectrophotometry) ionization pattern=ESI+:m/z=[M+H] ⁺503.4

Accurate mass (Exact Mass): 502.2

(synthesis example 5)

25.8 parts of 15 parts of compounds shown in hybrid (1x), 75 parts of METHYLPYRROLIDONEs and decahydroquinolines (Tokyo change into industry (strain) make) stir the potpourri of gained 24 hours at 110 ℃.After making above-mentioned reactant liquor be cooled to room temperature, add in the mixed liquor of 600 parts in water, 100 parts of 35% hydrochloric acid, stirring at room 1 hour.Form with the residue of suction filtration is taken out the crystallization of being separated out, and then carries out drying, obtains 19.5 parts of the compounds shown in the formula (1-29).Yield is 86%.

The evaluation of the compound shown in the formula (1-29)

(mass spectrophotometry) ionization pattern=ESI+:m/z=[M+H] ⁺611.4

Accurate mass (Exact Mass): 610.3

(synthesis example 6)

Speed with 0.02L/ minute in the flask with reflux condenser, tap funnel and stirring machine flows into nitrogen and becomes nitrogen atmosphere, adds ethyl lactate 305 mass parts, is heated to while stirring 70 ℃.

Then, at acrylic acid 46 mass parts, acrylic acid 3,4-epoxy radicals three ring [5.2.1.0 ^2.6] decyl ester is (with the compound shown in the mol ratio 50: 50 hybrid (I-1) and the compound shown in the formula (II-1).) dissolve in 240 mass parts and ethyl lactate 185 mass parts, preparation solution dripped this lysate to being incubated in 70 ℃ flask with tap funnel with 4 hours.

On the other hand, dissolved polymerization initiator 2 with dropping in 4 hours with other tap funnel in ethyl lactate 225 mass parts, the solution that two (2,4-methyl pentane nitrile) 30 mass parts of 2 '-azo form is in flask.After the dropping of the solution of polymerization initiator finishes, kept 4 hours at 70 ℃, cool to room temperature then, obtaining weight-average molecular weight Mw is 9.1 * 10 ³, molecular weight distribution is 2.1, solid constituent is that 26 quality %, solid constituent acid number are resin B 1 solution of 120mg-KOH/g.Resin B 1 has the structural unit shown in following.

(synthesis example 7)

Has stirring machine, thermometer, reflux condensing tube, in the flask of tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether 182g, after making the interior atmosphere of flask become nitrogen from air, be warmed up to 100 ℃, then, by methacrylic acid benzyl ester 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), drip in the potpourri that the monomethacrylates of tricyclodecane skeleton (Hitachi changes into the FA-513M that (strain) makes) 22.0g (0.10 mole) and propylene glycol monomethyl ether 136g form and be added with 2, the solution of 2 '-azoisobutyronitrile 3.6g continues to stir at 100 ℃ again.

Then, make the interior atmosphere of flask become air from nitrogen, in flask, drop into methyl propenoic acid glycidyl base ester 35.5g[0.25 mole, (carboxyl with respect to the methacrylic acid that uses in this reaction is 50 % by mole)], three (dimethylaminomethyl) phenol 0.9g and quinhydrones 0.145g, continue reaction at 110 ℃, obtain solid constituent and be 29%, the solid constituent acid number is resin B 2 solution of 79mgKOH/g.The weight-average molecular weight that the styrene that utilizes GPC to record converts is 30,000.

(synthesis example 8)

In the flask with stirring machine, thermometer, reflux condenser and tap funnel, flow into nitrogen with 0.02L/ minute and become nitrogen atmosphere, add 305 parts of propylene glycol monomethyl ether, be heated to while stirring 70 ℃.Then, at 60 parts in acrylic acid, acrylic acid 3,4-epoxy radicals three ring [5.2.1.0 ^2.6] decyl ester is (with the compound shown in the mol ratio 50: 50 hybrid (I-1) and the compound shown in the formula (II-1).) dissolving in 140 parts of 440 parts and the propylene glycol monomethyl ether, preparation solution dripped this lysate to being incubated in 70 ℃ flask with tap funnel with 4 hours.

On the other hand, dissolved polymerization initiator 2 with other tap funnel to drip in 4 hours in 225 parts of propylene glycol monomethyl ether, two (2,4-methyl pentane nitrile) the 30 parts of solution that form of 2 '-azo are in flask.After the dropping of the solution of polymerization initiator finishes, kept 4 hours at 70 ℃, cool to room temperature then, obtaining weight-average molecular weight Mw is 9.1 * 10 ³, molecular weight distribution is 2.16, solid constituent is 34.8%, solid constituent converts acid number is resin B 3 solution of 81mgKOH/g.Resin B 3 has the structural unit shown in following.

Recording of the weight-average molecular weight of the resin that obtains in the synthesis example (Mw) and number-average molecular weight (Mn) uses the GPC method to carry out under following condition.

Device: K2479 (manufacturing of (strain) Shimadzu Seisakusho Ltd.)

Post: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow velocity: 1.0mL/min

Detecting device: RI

Proofread and correct and use standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (eastern Cao (strain) manufacturing)

The ratio (Mw/Mn) of the weight-average molecular weight of polystyrene conversion obtained above and number-average molecular weight is set as molecular weight distribution.

(embodiment 1)

(preparation of colored curable resin composition)

Mix following composition,

(A) colorant: C.I. pigment blue 15: 24 parts of 6 (pigment),

6.1 parts of acrylic acid series pigment dispersing agents, and

163 parts of propylene glycol monomethyl ether;

Use ball mill that pigment is disperseed fully, then, mix following composition, obtain colored curable resin composition:

(A) colorant: 1.8 parts of dyestuffs (A1-a) (xanthene dye)

(A) colorant: (the Sudan blue II:Aldrich company makes C.I. solvent blue 35; Anthraquinone dye) 1.8 part

(B) resin: 60 parts of resin B 1 (solid constituent conversion)

(C) polymerizable compound: dipentaerythritol acrylate

(KAYARAD (registered trademark) DPHA: Japanese chemical drug (strain) is made) 40 parts

(D) polymerization initiator: 5 parts of N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) octanes-1-ketone-2-imines (manufacturing of IRGACURE (registered trademark) OXE01:BASF company)

(F) levelling agent: 0.08 part of polyether modified silicon oil (Toray Silicone SH8400: eastern beautiful DOW CORNING Co., Ltd. makes)

(E) solvent: 682 parts of ethyl lactates

(E) solvent: 8 parts of propylene glycol monomethyl ether.

The making of＜colored pattern 〉

Utilize spin-coating method at the square glass substrate of 5cm (manufacturing of Eagle 2000:CORNING company) coating colored curable resin composition, afterwards, 100 ℃ of prebake 3 minutes, obtain the coloured composition layer.After letting cool, will be formed with the substrate of coloured composition layer and the interval of quartz glass photomask processed and be made as 100 μ m, use exposure machine (TME-150RSK:TOPCON (strain) manufacturing), under air atmosphere, with 150mJ/cm ²Exposure (365nm benchmark) carried out irradiation.As photomask, use the photomask that is formed with 100 μ m live widths and line-spacing (line and space) pattern.In containing the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04% at 24 ℃ to 60 seconds of coloured composition layer immersion development behind the irradiation, after the washing, in baking oven, 230 ℃ of rear curing of carrying out 30 minutes, obtain colored pattern.

＜determining film thickness 〉

To the colored pattern of gained, use determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) manufacturing)) measured thickness.

＜chromaticity evaluation 〉

To the colored pattern of gained, use colorimeter (OSP-SP-200; Olympus (strain) is made) measured spectrum, use the characteristic function of illuminant-C to measure xy chromaticity coordinate (x, y) and tristimulus values Y in the XYZ primary colours system of CIE.The value of Y is larger, and expression brightness is higher.The results are shown in table 3 and table 4.

＜contrast evaluation 〉

Except when exposing, not using the photomask, carry out same operation with the making of colored pattern, made painted filming.The painted of gained filmed, and (CT-1: kettle slope motor company makes, and color colour difference meter BM-5A:TOPCON company makes to use the contrast meter, light source: F-10, polarizing coating: kettle slope motor (strain) is made), blank value is made as 30000, measured contrast.If painted contrast of filming is high, then can say in colored pattern, to be similarly high-contrast.The results are shown in table 3 and table 4.

(comparative example 1)

Mix following composition:

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

5 parts of acrylic acid series pigment dispersing agents, and

137 parts of propylene glycol monomethyl ether,

Use ball mill that pigment is fully disperseed, then, mix following composition, obtain colored curable resin composition:

(A) colorant: 3.5 parts of dyestuffs (Aa-1) (xanthene dye)

(B) resin: 157 parts of resin B 2 solution

(C) polymerizable compound: dipentaerythritol acrylate

(Japanese chemical drug (strain) manufacturing) 50 parts

(D) 15 parts of polymerization initiator: OXE01 (BASF AG's manufacturing)

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

Embodiment 2～15

According to the composition shown in table 1 and the table 2, carry out same operation with embodiment 1, obtain thus colored curable resin composition.

[table 1]

[table 2]

Be explained, in table 1 and the table 2, " Ad-1 ¹⁾" reach " E-1 with the acrylic acid series pigment dispersing agent ³⁾" propylene glycol monomethyl ether of amount of hurdle record mixes, and it carried out pre-dispersed.

" E-1 ²⁾" hurdle represents the total content of propylene glycol monomethyl ether.

In table 1 and the table 2, each composition represents following material.In addition, the mass parts of resin (B) expression solid constituent conversion.

Xanthene dye (Aa): Aa-1: dyestuff (Aa-1)

Xanthene dye (Aa): Aa-2: the compound shown in the formula (1-30)

Xanthene dye (Aa): Aa-3: the compound shown in the formula (1-38)

Xanthene dye (Aa): Aa-4:C.I. acid red 52 (Tokyo changes into industry (strain) manufacturing)

Xanthene dye (Aa): Aa-5: the compound shown in the formula (1-27)

Xanthene dye (Aa): Aa-6: the compound shown in the formula (1-29)

Anthraquinone dye (Ab): Ab-1:C.I. solvent blue 35 (the blue II:Aldrich of the Sudan makes)

Anthraquinone dye (Ab): Ab-2:C.I. solvent blue 45 (manufacturing of SavinylBlueRS:Clariant company)

Anthraquinone dye (Ab): Ab-3:C.I. acid blue 80 (manufacturing of Coomassie (registered trademark) BlueB150:ICI company)

Anthraquinone dye (Ab): Ab-4:C.I. solvent blue 19 04 (manufacturing of Polysynthren Blue RBL P:Clariant company)

Anthraquinone dye (Ab): Ab-5:C.I. solvent blue 19 22 (manufacturing of Polysynthren Blue R:Clariant company)

Pigment (Ad): Ad-1:C.I. pigment blue 15: 6

Resin (B): B-1: resin B 1

Resin (B): B-2: resin B 2

Resin (B): B-3: resin B 3

Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA: Japanese chemical drug (strain) is made)

Polymerization initiator (D): (IRGACURE (registered trademark) OXE01:BASF company makes D-1:N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) octane-1-ketone-2-imines; O-acyl group oxime compound)

Polymerization initiator (D): (IRGACURE (registered trademark) 907:BASF company makes D-2:2-methyl-2-morpholino-1-(4-methyl sulfenyl phenyl) propane-1-ketone; The alkyl phenones compound)

Polymerization causes auxiliary agent (D1): 2,4-diethyl thioxanthone (KAYACURE (registered trademark) DETX-S: make by Japanese chemical drug (strain); The thioxanthones compound)

Solvent (E): E-1: propylene glycol monomethyl ether

Solvent (E): E-2: ethyl lactate

Solvent (E): E-3: propylene glycol monomethyl ether

Solvent (E): E-4:4-hydroxy-4-methyl-2-pentanone

Levelling agent (F): polyether modified silicon oil (Toray Silicone SH8400; The beautiful DOW CORNING in east (strain) is made)

To the colored curable resin composition such as embodiment 2～15 obtained above and comparative example 1, estimate similarly to Example 1.The results are shown in table 3 and table 4.

[table 3]

[table 4]

According to the colored curable resin composition of embodiment, confirm the demonstration high-contrast of filming of gained.This shows, be useful by paintedly filming of obtaining of colored curable resin composition of the present invention, colored pattern as the color filter of high-contrast, and the display characteristic of liquid crystal indicator that comprises this color filter is excellent.

Claims

1. colored curable resin composition, it comprises colorant, resin, polymerizable compound and polymerization initiator,

Colorant comprises xanthene dye and anthraquinone dye.

2. colored curable resin composition according to claim 1, wherein, the content of anthraquinone dye is more than the 0.1 quality % and below the 70 quality % with respect to the total amount of colorant.

3. colored curable resin composition according to claim 1 and 2, wherein, colorant also comprises pigment.

4. color filter, it is formed by each described colored curable resin composition in the claim 1～3.

5. display device, it comprises color filter claimed in claim 4.