CN102914942B

CN102914942B - Colored curable resin composition

Info

Publication number: CN102914942B
Application number: CN201210272251.6A
Authority: CN
Inventors: 市冈贤二; 朴昭妍
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2011-08-05
Filing date: 2012-08-01
Publication date: 2017-03-01
Anticipated expiration: 2032-08-01
Also published as: CN102914942A; KR20130016089A; CN107037689B; KR101632461B1; CN107037689A

Abstract

The present invention provides a kind of colored curable resin composition, which contain toner, resin, polymerizable compound and polymerization initiator, coloring agent comprises ton dyestuff 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 for manufacturing in display panels, electroluminescence panel and plasma display Show color filter used in the display devices such as device panel.As such colored curable resin composition it is known that only comprising Ton dyestuff and C.I. alizarol saphirol as coloring agent colored curable resin composition (JP2010-32999-A).

For all the time known above-mentioned colored curable resin composition, by this colored curable resin composition The contrast of the color filter obtaining may not necessarily be of great satisfaction.

Content of the invention

The present invention comprises invention below.

[1] a kind of colored curable resin composition, which contain toner, resin, polymerizable compound and polymerization and causes Agent,

Coloring agent comprises ton dyestuff and anthraquinone dye.

[2] colored curable resin composition according to [1], wherein, the content of anthraquinone dye is with respect to coloring agent Total amount be 0.1 mass % more than and 70 mass % below.

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

[4] a kind of color filter, its colored curable resin composition any one of [1]～[3] is formed.

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

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

Brief description

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

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

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

Symbol description

21 glass substrates

22TFT (switch element)

22a gate electrode

22b gate insulating film

22c polysilicon film

22d protecting film

23 color-filter layers

23A colored curable resin composition layer (color filter)

23a red color filter

23b green color filter

23c blue color filter

24 pixel electrodes

27 holding wires

29 photosensitive resin films (protecting film)

201st, 202 connecting hole

Specific embodiment

The colored curable resin composition of the present invention be comprise coloring agent (A), resin (B), polymerizable compound (C) and The colored curable resin composition of polymerization initiator (D), coloring agent (A) comprises a ton dyestuff (Aa) and anthraquinone dye (Ab). This colored curable resin composition preferably further comprises solvent (E) and/or levelling agent (F).

The colored curable resin composition of the present invention is used as by comprising a ton dyestuff (Aa) and anthraquinone dye (Ab) Toner (A) is such that it is able to manufacture the color filter of high-contrast.

Coloring agent (A) comprises a ton dyestuff (Aa) and anthraquinone dye (Ab).Preferably further comprise pigment (Ad).Additionally, The dyestuffs different from ton dyestuff (Aa) and anthraquinone dye (Ab) can also be comprised (below, sometimes referred to as " dyestuff (Ac) ".).

Ton dyestuff (Aa) is the dyestuff comprising the compound that intramolecular has ton skeleton.As ton dyestuff (Aa), C.I. CI 45430 for example can be included (below, omit the record of C.I. Xylene Red, only record numbering.Other dyestuffs are also same Sample.), 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. lives Red 36 (rose red bs) of property, described in the ton dyestuff described in Sulforhodamine G, JP2010-32999-A and JP4492760-B Ton dyestuff etc..The ton dyestuff preferably dissolving in organic solvent.

Wherein, as ton dyestuff (Aa), preferably comprise compound shown in formula (1a) (below, sometimes referred to as " compound (1a)”.) dyestuff.Compound (1a) can also be its tautomer.In the case of using compound (1a), ton contaminates The content of the compound (1a) in material (Aa) is preferably more than 50 mass %, more than more preferably 70 mass %, further preferably More than 90 mass %.Particularly preferably compound (1a) is only used as ton dyestuff (Aa).

[in formula (1a), R¹～R⁴Represent 1 valency saturated hydrocarbyl that hydrogen atom, carbon number are 1～20 or can independently of one another The carbon number with substituent group is 6～10 1 valency aromatic hydrocarbyl, and the hydrogen atom containing in this saturated hydrocarbyl can be former by carbon Subnumber is 6～10 aromatic hydrocarbyl or halogen atom replacement, and the hydrogen atom containing in this aromatic hydrocarbyl can be by carbon atom The alkoxyl for 1～3 for the number replaces ,-the CH containing in above-mentioned saturated hydrocarbyl₂- can be by-O- ,-CO- or-NR¹¹- displacement.R₁And R² The ring of nitrogen atom, R can be formed together with nitrogen-atoms³And R⁴The ring of nitrogen atom can be formed together with nitrogen-atoms.

R⁵Represent-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰.

R⁶And R⁷Represent hydrogen atom or alkyl that carbon number is 1～6 independently of one another.

M represents 0～5 integer.M be more than 2 integer in the case of, multiple R⁵Can be identical or different.But, R⁵For-SO₃ ^-In the case of, m is 1.

A represents 0 or 1 integer.

X represents halogen atom.

R⁸Represent the 1 valency saturated hydrocarbyl that carbon number is 1～20, the hydrogen atom containing in this saturated hydrocarbyl can be by halogen Atom replaces.

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺.

R⁹And R¹⁰The carbon number representing hydrogen atom independently of one another or can having substituent group is 1～20 1 valency saturated hydrocarbons Base ,-the CH containing in this representative examples of saturated aliphatic alkyl₂- can be by-O- ,-CO- ,-NH- or-NR⁸- displacement, R⁹And R¹⁰Can be each other In conjunction with and form 3～10 member heterocyclic ring containing nitrogens together with nitrogen-atoms.

R¹¹Represent that 1 valency saturated hydrocarbyl that hydrogen atom, carbon number are 1～20 or carbon number are 7～10 independently of one another Aralkyl.]

As expression R¹～R⁴Carbon number be 6～10 1 valency aromatic hydrocarbyl, for example can include phenyl, toluene Base, xylyl, sym-trimethylbenzene. base, propyl group phenyl and butyl phenyl.

The substituent group can having as this aromatic hydrocarbyl, can include halogen atom ,-R⁸、-OH、-OR⁸、-SO₃ ^-、- SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂R⁸、-SR⁸、-SO₂R⁸、-SO₃R⁸、-SO₂NR⁹R¹⁰Deng.Wherein, as substituent group, preferably- SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺And-SO₂NR⁹R¹⁰, more preferably-SO₃ ^-Z⁺And-SO₂NR⁹R¹⁰.As-the SO in the case of this₃ ^-Z⁺, preferably- SO₃ ^-+N(R¹¹)₄.R¹～R⁴During for these groups, can be by the colored curable resin combination of the present invention of inclusion compound (1a) Thing formed foreign body occur less and excellent heat resistance color filter.

As R¹And R²The ring of the nitrogen atom being formed together with nitrogen-atoms and R³And R⁴Formed together with nitrogen-atoms is contained The ring of nitrogen-atoms, for example, can include the ring of following nitrogen atom.

As expression R⁸～R¹¹Carbon number be 1～20 1 valency saturated hydrocarbyl, can include methyl, ethyl, propyl group, The carbon numbers such as butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl be 1～ 20 straight-chain alkyl；The carbon numbers such as isopropyl, isobutyl group, isopentyl, neopentyl, 2- ethylhexyl are 3～20 side chain Shape alkyl；The carbon numbers such as cyclopropyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, tricyclodecyl be 3～20 ester ring type satisfy And alkyl.

As-OR⁸, for example, can include methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan Base, octyloxy, 2- ethyl hexyl oxy and eicosane epoxide.

As-CO₂R⁸, for example can include methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, Hexyloxy carbonyl and eicosane epoxide carbonyl.

As-SR⁸, for example, can include methyl mercapto, ethylmercapto group, butylthio, own sulfenyl, last of the ten Heavenly stems sulfenyl and eicosane sulfenyl.

As-SO₂R⁸, for example can include mesyl, ethylsulfonyl, fourth sulfonyl, own sulfonyl, last of the ten Heavenly stems sulfonyl and Eicosane sulfonyl.

As-SO₃R⁸, for example, can include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxy Sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl.

As-SO₂NR⁹R¹⁰, for example, can include：

Sulfamoyl；

N- Methylsulfamoyl, N- ethylsulfamovl, N- propylsulfamov, N- isopropylsulfamoyl base, N- butyl Sulfamoyl, N- isobutyl group sulfamoyl, N- sec-butyl sulfamoyl, N- tert-butyl group sulfamoyl, N- amyl group sulfamoyl, N- (1- ethyl propyl) sulfamoyl, N- (1,1- dimethyl propyl) sulfamoyl, N- (1,2- dimethyl propyl) sulfamoyl, N- (2,2- dimethyl propyl) sulfamoyl, N- (1- methyl butyl) sulfamoyl, N- (2- methyl butyl) sulfamoyl, N- (3- Methyl butyl) sulfamoyl, N- Cyclopentylsulfamoyl base, N- hexyl sulfamoyl, N- (1,3- dimethylbutyl) sulfamoyl, N- (3,3- dimethylbutyl) sulfamoyl, N- heptyl sulfamoyl, N- (1- methylhexyl) sulfamoyl, N- (Isosorbide-5-Nitrae-diformazan Base amyl group) sulfamoyl, N- octyl group sulfamoyl, N- (2- ethylhexyl) sulfamoyl, N- (1,5- dimethyl) hexyl ammonia sulphur The N- mono- replacement sulfamoyls such as acyl group, N- (1,1,2,2- tetramethyl butyl) sulfamoyl；

N, N- DimethylsuIfamoyl, N, N- ethyl-methyl sulfamoyl, N, N- diethyl amino sulfonyl, N, N- propyl group first Base sulfamoyl, N, N- isopropyl methyl sulfamoyl, N, N- tertbutyl methyl sulfamoyl, N, N- butyl ethyl sulfonamides Base, N, N- double (1- methyl-propyl) sulfamoyl, N, the N such as N- hept-ylmethyl sulfamoyl, N- bis- replacement sulfamoyl etc..

Additionally, as expression R⁹、R¹⁰Carbon number be 1～20 the substituent group that can have of 1 valency saturated hydrocarbyl, can enumerate Go out hydroxyl and halogen atom.

R⁵Preferably-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃ ^-、-SO₃ ^-Z⁺、-SO₃H or SO₂NHR⁹, more preferably SO₃ ^-、-SO₃ ^-Z⁺、- SO₃H or SO₂NHR⁹.

M preferably 1～4, more preferably 1 or 2.

As expression R⁶And R⁷Carbon number be 1～6 alkyl, carbon atom in the above-mentioned alkyl enumerated can be included The alkyl for 1～6 for the number.

As expression R¹¹Carbon number be 7～10 aralkyl, benzyl, phenethyl, benzene butyl etc. can be included.

Z⁺For⁺N(R¹¹)₄、Na⁺Or K⁺, preferably⁺N(R¹¹)₄.

As above-mentioned+N (R¹¹)₄, preferably four R¹¹In at least two be 5～20 for carbon number 1 valency saturated hydrocarbyl. Additionally, four R¹¹Total carbon atom number be preferably 20～80, more preferably 20～60.Exist in compound (1a)⁺N(R¹¹)₄'s In the case of, R¹¹During for these groups, can be formed by the colored curable resin composition of the present invention of inclusion compound (1a) The color filter of few foreign.

As compound (1a), the compound more preferably shown in formula (2a) is (below, sometimes referred to as " compound (2a) ".). Compound (2a) can be its tautomer.

In the case of using compound (2a), the content of the compound (2a) in ton dyestuff (Aa) is preferably 50 matter Amount more than %, more than more preferably 70 mass %, more than more preferably 90 mass %.

[in formula (2a), R²¹～R²⁴Separately represent hydrogen atom ,-R²⁶Or can have substituent group carbon number be 6 ～10 1 valency aromatic hydrocarbyl.

R²¹And R²²The ring of nitrogen atom, R can be formed together with nitrogen-atoms²³And R²⁴Can be formed together with nitrogen-atoms and contain The ring of nitrogen-atoms.

R²⁵Expression-SO₃ ^-、-SO₃H、-SO₃ ^-Z1⁺Or-SO₂NHR²⁶.

M1 represents 0～5 integer.M1 be more than 2 integer in the case of, multiple R²⁵For identical or different.But, R²⁵For-SO₃ ^-In the case of, m1 is 1.

A1 represents 0 or 1 integer.

X1 represents halogen atom.

R²⁶Represent the 1 valency saturated hydrocarbyl that carbon number is 1～20.

Z1⁺Represent⁺N(R²⁷)₄、Na⁺Or K⁺.

R²⁷Separately represent 1 valency saturated hydrocarbyl or benzyl that carbon number is 1～20.]

As expression R²¹～R²⁴Carbon number be 6～10 1 valency aromatic hydrocarbyl, can include and above-mentioned R¹～R⁴In The same group of the group enumerated as aromatic hydrocarbyl.The hydrogen atom containing in this aromatic hydrocarbyl can be by-SO₃ ^-、- SO₃H、-SO₃ ^-Z1⁺、-SO₃R²⁶Or-SO₂NHR²⁶Replace.

As R²¹～R²⁴Combination, preferably following combine：R²¹And R²³For hydrogen atom；R²²And R²⁴For carbon number be 6～ 10 1 valency aromatic hydrocarbyl, the hydrogen atom containing in this aromatic hydrocarbyl is by-SO₃ ^-、-SO₃H、-SO₃ ^-Z1⁺、-SO₃R²⁶Or- SO₂NHR²⁶Replace.Further preferred is combined as：R²¹And R²³For hydrogen atom, R²²And R²⁴The 1 valency virtue being 6～10 for carbon number Fragrant race alkyl, the hydrogen atom containing in this aromatic hydrocarbyl is by-SO₃ ^-Z1⁺Or-SO₂NHR²⁶Replace.

In R²¹～R²⁴During for these groups, can be by the colored curable resin group of the present invention of inclusion compound (2a) Compound forms the color filter of excellent heat resistance.

As R²¹And R²²The ring of the nitrogen atom being formed together with nitrogen-atoms and R²³And R²⁴Formed together with nitrogen-atoms Nitrogen atom ring, can include and R¹And R²The ring of the same nitrogen atom of the ring that formed together with nitrogen-atoms.Wherein, Preferred aliphat heterocycle.As this aliphatic heterocycle, for example, can include following aliphatic heterocycle.

As expression R²⁶And R²⁷Carbon number be 1～20 1 valency saturated hydrocarbyl, can include and R⁸～R¹¹Middle conduct The same group of group that saturated hydrocarbyl is enumerated.

In R²¹～R²⁴For-R²⁶In the case of ,-R²⁶Separately it is preferably methyl or ethyl.Additionally, conduct-SO₃R²⁶ And-SO₂NHR²⁶In R²⁶, preferably carbon number is 3～20 branched-chain alkyl, and more preferably carbon number is 6～12 side chain Shape alkyl, further preferred 2- ethylhexyl.In R²⁶During for these groups, can by the present invention of inclusion compound (2a) Color hardening resin composition forms foreign body and few color filter occurs.

Z1⁺For⁺N(R²⁷)₄、Na⁺Or K⁺, preferably⁺N(R²⁷)₄.

As above-mentioned⁺N(R²⁷)₄, preferably four R²⁷In at least two be 5～20 for carbon number 1 valency saturated hydrocarbyl. Additionally, four R²⁷Total carbon atom number be preferably 20～80, more preferably 20～60.Exist in compound (2a)⁺N(R²⁷)₄'s In the case of, can be by comprising R²⁷The colored curable resin composition of the present invention of compound (2a) for these groups forms different There is few color filter in thing.

M1 preferably 1～4, more preferably 1 or 2.

As compound (1a), the compound shown in contained (3a) is (below, sometimes referred to as " compound (3a) ".) dye Material is also preferred.Compound (3a) can be its tautomer.In the case of using compound (3a), ton dyestuff (Aa) content of the compound (3a) in is preferably more than 50 mass %, more than more preferably 70 mass %, more preferably More than 90 mass %.

[in formula (3a), R³¹And R³²Represent the 1 valency saturated hydrocarbyl that carbon number is 1～10, this saturated hydrocarbons independently of one another The hydrogen atom containing in base can be replaced by the aromatic hydrocarbyl that carbon number is 6～10 or halogen atom, this aromatic hydrocarbyl In the hydrogen atom that contains can be replaced by the alkoxyl that carbon number is 1～3 ,-the CH containing in above-mentioned saturated hydrocarbyl₂- permissible By-O- ,-CO- or-NR¹¹- displacement.

R³³And R³⁴Represent alkylthio group or carbon that the alkyl, carbon number that carbon number is 1～4 is 1～4 independently of one another Atomic number is 1～4 alkyl sulphonyl.

R³¹And R³³The ring of nitrogen atom, R can be formed together with nitrogen-atoms³²And R³⁴Can be formed together with nitrogen-atoms and contain The ring of nitrogen-atoms.

P and q represents 0～5 integer independently of one another.In the case that p is more than 2, multiple R³³Can be identical or different, In the case that q is more than 2, multiple R³⁴Can be identical or different.

R¹¹Represent synonymous with above-mentioned.]

As R³¹And R³²In carbon number be 1～10 1 valency saturated hydrocarbyl, R can be included⁸1 valency saturated hydrocarbyl in Carbon number is 1～10 group.

The carbon number can having as substituent group is 6～10 aromatic hydrocarbyl, can include and R¹In used Identical group.

The alkoxyl being 1～3 as carbon number, for example, can include methoxyl group, ethyoxyl, propoxyl group etc..

R³¹And R³²It is preferably the 1 valency saturated hydrocarbyl that carbon number is 1～3 independently of one another.

As expression R³³And R³⁴Carbon number be 1～4 alkyl, methyl, ethyl, propyl group, butyl, different can be included Propyl group, isobutyl group, sec-butyl, tert-butyl group etc..

As R³³And R³⁴In carbon number be 1～4 alkylthio group, methyl mercapto, ethylmercapto group, rosickyite base, fourth can be included Sulfenyl, isopropyisulfanyl etc..

As R³³And R³⁴In carbon number be 1～4 alkyl sulphonyl, can include mesyl, ethylsulfonyl, Third sulfonyl, fourth sulfonyl, isopropylsulfonyl etc..

R³³And R³⁴Preferably carbon number is 1～4 alkyl, more preferably methyl.

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

As compound (1a), for example, can include the compound being represented respectively by formula (1-1)～formula (1-42).Said Bright, in formula, R²⁶Represent the 1 valency saturated hydrocarbyl that carbon number is 1～20, preferably carbon number is 6～12 branched-chain alkyl, More preferably 2- ethylhexyl.Compound shown in formula (1-1)～formula (1-29) is equivalent to compound (2a), formula (1-30) Compound shown in～formula (1-42) is equivalent to compound (3a).

Wherein, preferably the sulfonamide compound of C.I. Xylene Red 289, the quaternary ammonium salt of C.I. Xylene Red 289, C.I. acid violet 102 sulfonamide compound or the quaternary ammonium salt of C.I. acid violet 102.As such compound, for example can include formula (1-1)～ Formula (1-8), formula (1-11) and the compound shown in formula (1-12) etc..

Additionally, from the excellent aspect of dissolubility in organic solvent, shown in preferred formula (1-30)～formula (1-39) Compound.

Ton dyestuff (Aa) can be using ton the dyestuff (" Chugai that for example, middle tank formation (strain) manufactures being commercially available Aminol Fast Pink R-H/C ", " Rhodamin 6G " that field ridge chemical industry (strain) manufactures).In addition it is also possible to quilt Commercially available ton dyestuff is synthesized as initiation material and with reference to Japanese Unexamined Patent Publication 2010-32999 publication.

Anthraquinone dye (Ab) is the dyestuff comprising the compound that intramolecular has anthraquinone skeleton.As anthraquinone dye (Ab), For example can include：

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, 227th, 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、 101st, 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,

C.I. sun 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, the anthracene of more preferably blue, purple or redness Quinone dyestuff.

Wherein, as anthraquinone dye (Ab), preferably comprise compound shown in formula (1b) (below, sometimes referred to as " compound (1b)”.) dyestuff.In the case of using compound (1b), the content of the compound (1b) in anthraquinone dye (Ab) is preferably More than 50 mass %, more than more preferably 70 mass %, more than more preferably 90 mass %.Particularly preferably only using chemical combination Thing (1b) is as anthraquinone dye (Ab).

[in formula (1b), A represents hydroxyl or-NH-R⁵².

R⁵¹And R⁵²Separately represent hydrogen atom, can have substituent group carbon number be 1～10 aliphatic hydrocarbon Base, can have substituent group carbon number be 3～10 ester ring type alkyl or formula (1b ') shown in group

(in formula (1b '), R⁵³Represent alkyl, halogen atom ,-SO that carbon number is 1～6₃H、-CO₂H、-CO₂R⁵⁴、- NHCOR⁵⁴、-SO₃R⁵⁴Or-SO₂NR⁵⁴R⁵⁵.

R⁵⁴Represent the saturated hydrocarbyl that carbon number is 1～10, the hydrogen atom containing in this saturated hydrocarbyl can be former by halogen Son, hydroxyl or amino replace.

R⁵⁵Represent the saturated hydrocarbyl that hydrogen atom, carbon number are 1～10.

R represents 0～5 integer.In the case that r is more than 2, multiple R⁵³Can be identical or different.

X⁵¹Expression singly-bound or the alkylidene that carbon number is 1～6.).]

In compound (1b), there is-SO₃H and/or-CO₂In the case of H, these groups can be with forming salt (for example, Na salt, K Salt).

As expression R⁵¹And R⁵²Carbon number be 1～10 aliphatic alkyl, for example can include methyl, ethyl, third Base, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, new penta Base, 2- ethylhexyl etc..

The substituent group can having as these aliphatic alkyls, can include hydroxyl, halogen atom etc..

As expression R⁵¹And R⁵²Carbon number be 3～10 ester ring type alkyl, for example can include cyclopropyl, ring penta Base, cyclohexyl, suberyl, cyclooctyl, tricyclodecyl etc..

The substituent group can having as these ester ring type alkyl, can include hydroxyl, halogen atom etc..

As expression R⁵³Carbon number be 6～10 alkyl, for example can include methyl, ethyl, propyl group, butyl, penta Base, hexyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl etc..

As expression R⁵⁴And R⁵⁵Carbon number be 1～10 saturated hydrocarbyl, for example can include methyl, ethyl, third The straight-chain alkyls such as base, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl；Isopropyl, isobutyl group, isopentyl, new penta The branched-chain alkyls such as base, 2- ethylhexyl；The saturated fats such as cyclopropyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, tricyclodecyl Ring type alkyl.

As-CO₂R⁵⁴, for example can include methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, Hexyloxy carbonyl and eicosane epoxide carbonyl.

As-NHCOR⁵⁴, for example, can include N- acetylamino, N- propionamido, N- butyrylamino, N- isobutyryl amino And N- pivaloyl amino.

As-SO₃R⁵⁴, for example, can include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary fourth oxygen Base sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl.

As-SO₂NR⁵⁴R⁵⁵, for example, can include N- Methylsulfamoyl, N- ethylsulfamovl, N- propyl group sulfonamides Base, N- isopropylsulfamoyl base, N- Butylsulfamoyl base, N- isobutyl group sulfamoyl, N- sec-butyl sulfamoyl, the N- tert-butyl group Sulfamoyl, N- amyl group sulfamoyl, N- (1- ethyl propyl) sulfamoyl, N- (1,1- dimethyl propyl) sulfamoyl, N- (1,2- dimethyl propyl) sulfamoyl, N- (2,2- dimethyl propyl) sulfamoyl, N- (1- methyl butyl) sulfamoyl, N- (2- methyl butyl) sulfamoyl, N- (3- methyl butyl) sulfamoyl, N- Cyclopentylsulfamoyl base, N- Cyclohexylsulfamoyl Base, N- hexyl sulfamoyl, N- (1,3- dimethylbutyl) sulfamoyl, N- (3,3- dimethylbutyl) sulfamoyl, N- heptan Base sulfamoyl, N- (1- methylhexyl) sulfamoyl, N- (Isosorbide-5-Nitrae-dimethyl amyl group) sulfamoyl, N- octyl group sulfamoyl, N- (2- ethylhexyl) sulfamoyl, N- (1,5- dimethyl) hexyl sulfamoyl, N- (1,1,2,2- tetramethyl butyl) ammonia sulphur The N- mono- replacement sulfamoyls such as acyl group, N- (5- Aminopentyl) sulfamoyl；

As expression X⁵¹Carbon number be 1～6 alkylidene, for example can include methylene, ethylidene, 1,3- Asia third Base, propylene, tetramethylene, pentamethylene, hexamethylene, 1,1- ethylidene, 1,3- butylidene, 2- methyl- Trimethylene, 2- methyl isophthalic acid, 2- propylidene, Isosorbide-5-Nitrae-pentylidene, 2- methyl isophthalic acid, 4- butylidene etc..

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

As anthraquinone dye (Ab), preferably C.I. solvent blue 35 (compound shown in formula (2-4)), C.I. solvent blue 45, C.I. acid blue 80 (compound shown in formula (2-11)), C.I. solvent blue 19 04 (compound shown in formula (2-12)) and C.I. Solvent blue 19 22 (compound shown in formula (2-13)).Film, the pattern of high-contrast during for these anthraquinone dyes, can be formed, And foreign body occurs also few.

As dyestuff (Ac), as long as the dyestuff different from ton dyestuff (Aa) and anthraquinone dye (Ab), then not especially Restriction, can include oil-soluble dyes, acid stain, basic stain, direct dyess, mordant dye, the amine salt of acid stain, The dyestuffs such as the sulfamide derivative of acid stain, for example, can include《Color index》(カラ mono- イ Application デ Star Network ス) (The Society of Dyers and Colourists publishes) in be categorized as compound beyond dyestuff is pigment,《Dyeing ノ mono- ト》Known dyestuff described in (Se Ran society).Additionally, according to chemical constitution, azo dye, cyanine dye, triphen can be included Methylmethane dyestuff, 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, preferably Organic solvent-soluble dyestuff.

Specifically, C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99,162 can be included；

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

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

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, it is possible to use known pigment, for example, can include《Color index》 It is categorized as the change of pigment in (カラ mono- イ Application デ Star Network ス) (The Society of Dyers and Colourists publication) Compound.

As pigment, for example, can include：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、214 Deng yellow uitramarine；

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

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

C.I. pigment blue 15,15:3、15:4、15:6th, the blue pigment such as 60；C.I. pigment violet 1,19,23,29,32,36, 38 grade violet pigments；

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

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

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

As pigment, preferably C.I. pigment blue 15,15:3、15:4、15:6th, the blue pigments such as 60 and C.I. pigment violet 1, 19th, the violet pigment such as 23,29,32,36,38, more preferably C.I. pigment blue 15:3、15:6 and C.I. pigment Violet 23s, excellent further Select C.I. pigment blue 15:6.The colored curable resin composition of the present invention is being prepared into blue-colored curable resin combination In the case of thing, by containing above-mentioned pigment, easily realizing the optimization of transmitted spectrum, make light resistance and resistance toization of color filter Learn agents good.

These pigment can be used alone it is also possible to two or more be used in mixed way.

Pigment can be implemented Colophonium as needed and process, using the pigment derivative being imported with acidic-group or basic group Deng surface treatment, using macromolecular compound etc. the grafting to surface of pigments process, micro- based on sulfuric acid particles method etc. Granulated processed or utilize the cleaning treatment that organic solvent or water for removing impurity etc. carries out, entered using ion exchange etc. Removing process of the ionic impurity of row etc..

Pigment preferably makes uniform particle sizes.By carrying out decentralized processing containing pigment dispersing agent, pigment can be obtained in solution In the dispersible pigment dispersion of state that is uniformly dispersed.

As above-mentioned pigment dispersing agent, for example, can include cation system, anion system, nonionic system, both sexes, polyester Surfactant of system, polyamine system, acrylic acid seriess etc. etc..These pigment dispersing agents may be used alone, can also be used in combination Two or more.As pigment dispersing agent, trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), Floren (common prosperity society can be included Chemical (strain) manufactures), Solsperse (Zeneca (strain) manufacture), EFKA (manufacture of CIBA company), AJISPER (Ajinomoto Fine-Techno Co.Int. manufactures), Disperbyk (manufacture of BYK company) etc..

In the case of using pigment dispersing agent, its usage amount with respect to pigment (Ad) total amount be preferably 1 mass % with Above and below 100 mass %, more than more preferably 5 mass % and below 50 mass %.The usage amount of pigment dispersing agent is above-mentioned Scope when, there is the tendency of the dispersible pigment dispersion obtaining homogeneously dispersed state.

The content of ton dyestuff (Aa) is preferably more than 0.1 mass % and 70 mass % with respect to the total amount of coloring agent (A) Hereinafter, more than more preferably 0.5 mass % and below 50 mass %.

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

In the case that coloring agent (A) comprises pigment (Ad), the content of pigment (Ad) is excellent with respect to the total amount of coloring agent (A) Elect below more than 10 mass % and 99.8 mass % as, more than more preferably 30 mass % and below 99 mass %.

In the case that coloring agent (A) comprises dyestuff (Ac), the content of dyestuff (Ac) is excellent with respect to the total amount of coloring agent (A) Elect below more than 0.1 mass % and 50 mass % as, more than more preferably 0.5 mass % and below 30 mass %.

In the case that coloring agent (A) is the coloring agent comprising a ton dyestuff (Aa), anthraquinone dye (Ab) and pigment (Ad), These dyestuffs be respectively preferably a ton dyestuff (Aa) containing ratio：More than 0.1 mass % and below 70 mass %；Anthraquinone dye (Ab)：More than 0.1 mass % and below 70 mass %；Pigment (Ad)：More than 29.9 mass % and below 99.8 mass %.

More preferably ton dyestuff (Aa)：More than 0.5 mass % and below 50 mass %；Anthraquinone dye (Ab)：0.5 matter Below amount more than % and 50 mass %；Pigment (Ad)：More than 49.5 mass % and below 99 mass %.

The content of coloring agent (A) is preferably 5～60 mass %, more preferably 8～55 matter with respect to the total amount of solid constituent Amount %, more preferably 10～50 mass %.When the content of coloring agent (A) is above range, can make to make color filter When colour saturation fully, and make to contain the desired amount of resin (B), polymerizable compound (C) in compositionss, therefore, it is possible to form machine The sufficient pattern of tool intensity.Here, " total amount of solid constituent " in this specification refers to from colored curable resin composition Total amount remove solvent amount.The total amount of solid constituent and for example can use liquid phase color with respect to the content of its each composition The known analysis means such as spectrum or gas chromatogram are measured.

Resin (B) has no particular limits, preferably alkali soluble resin.As resin (B), following tree can be included Fat [K1]～[K6] etc..

Resin [K1]：At least one (a) in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides is (below, sometimes referred to as " (a) ") and there is the monomer (b) of the ring-type ether structure that carbon number is 2～4 and ethylenic unsaturated bond (below, sometimes referred to as " (b) ") copolymer；

Resin [K2]：(a), (b) and can with the monomer (c) of (a) copolymerization (but, different from (a) and (b).) (below, Copolymer sometimes referred to as " (c) ")；

Resin [K3]：The copolymer of (a) and (c)；

Resin [K4]：Make the resin obtained from copolymer reaction of (b) and (a) and (c)；

Resin [K5]：Make the resin obtained from copolymer reaction of (a) and (b) and (c)；

Resin [K6]：Make (a) and (b) and (c) copolymer reaction, again with resin obtained from carboxylic acid anhydride reactant.

As (a), specifically, for example, can include：Acrylic acid, methacrylic acid .beta.-methylacrylic acid, o-, m-, p- second The unsaturated monocarboxylic class such as thiazolinyl benzoic acid；

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acid, 4- vinyl neighbour's benzene two Formic acid, 3,4,5,6- tetrahydrophthalic acid, 1,2,3,6- tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae- The unsaturated dicarboxylic class such as cyclohexene dicarboxylic acid；

Methyl -5- norborene -2,3- dicarboxylic acids, 5- carboxyl bicyclic [2.2.1] hept-2-ene", 5,6- dicarboxyl are bicyclic [2.2.1] hept-2-ene", 5- carboxyl -5- methyl bicycle [2.2.1] hept-2-ene", 5- carboxyl -5- ethyl bicyclic [2.2.1] hept- 2- Alkene, 5- carboxyl -6- methyl bicycle [2.2.1] hept-2-ene", 5- carboxyl -6- ethyl bicyclic [2.2.1] hept-2-ene" etc. are carboxylic Bicyclic unsaturated compound class；

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

Mono succinate (2- (methyl) acryloyl-oxyethyl) ester, phthalic acid list (2- (methyl) acryloxy second Base) more than 2 yuan of the polybasic carboxylic acid such as ester unsaturated single ((methyl) acryloxyalkyl) esters；

The unsaturated esters of acrylic acid containing hydroxyl and carboxyl in same molecule as α-(methylol) acrylic acid etc Deng.

Wherein, in terms of copolyreaction, deliquescent aspect in aqueous alkali for the gained resin, preferably third Olefin(e) acid, methacrylic acid, maleic anhydride etc..

B () refers to for example there is the ring-type ether structure that carbon number is 2～4 (for example, selected from oxirane ring, oxa- ring At least one in butane ring and oxolane ring) and ethylenic unsaturated bond polymerizable compound.B () preferably has carbon former Subnumber is 2～4 cyclic ether and the monomer of (methyl) acryloxy.

It is explained, in this specification, " (methyl) acrylic acid " expression forms selected from acrylic acid and methacrylic acid At least one in group.The statement of " (methyl) acryloyl group " and " (methyl) acrylate " etc. also has same implication.

As (b), for example, can include and there is the monomer (a1) of Oxyranyle and ethylenic unsaturated bond (below, have When be referred to as " (b1) "), there is the monomer (b2) of oxetanyl and ethylenic unsaturated bond (below, sometimes referred to as " (b2) "), there is monomer (b3) (below, sometimes referred to as " (b3) ") of tetrahydrofuran base and ethylenic unsaturated bond etc..

(b1) for example can include to have makes the unsaturated fatty hydrocarbons of straight-chain or branched carry out epoxidation and obtain The monomer (b1-1) (below, sometimes referred to as " (b1-1) ") of structure, have and so that unsaturated ester ring type hydrocarbon is carried out epoxidation and obtain The monomer (b1-2) (below, sometimes referred to as " (b1-2) ") of the structure arriving.

As (b1-1), (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl can be included sweet Oil base ester, (methyl) propenoic acid beta-ethyl glycidyl base ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl Base ether, a vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, the contracting of Alpha-Methyl-neighbour's vinyl benzyl A water glyceryl ether, Alpha-Methyl-vinylbenzyl glycidyl base ether, Alpha-Methyl-to vinylbenzyl glycidyl base ether, 2, Double (glycidyl oxy methyl) styrene of 3-, double (glycidyl oxy methyl) styrene of 2,4-, 2,5- are double, and (shrink is sweet Oil base epoxide methyl) styrene, 2,6- double (glycidyl oxy methyl) styrene, 2,3,4- tri- (glycidyl epoxides Methyl) styrene, 2,3,5- tri- (glycidyl oxy methyl) styrene, 2,3,6- tri- (glycidyl oxy methyl) benzene Ethylene, 3,4,5- tri- (glycidyl oxy methyl) styrene, 2,4,6- tri- (glycidyl oxy methyl) styrene etc..

As (b1-2), VCH list oxide, 1,2- epoxy radicals -4- vinyl cyclohexane (example can be included As CELLOXIDE 2000：Daicel chemical industry (strain) manufacture), (methyl) acrylic acid 3,4- expoxycyclohexyl methyl ester (example As CYCLOMER A400：Daicel chemical industry (strain) manufacture), (methyl) acrylic acid 3,4- expoxycyclohexyl methyl ester is (for example CYCLOMER M100：Daicel chemical industry (strain) manufactures), the compound shown in formula (I), the compound shown in formula (II) etc..

[in formula (I) and formula (II), R^aAnd R^bExpression hydrogen atom or the alkyl that carbon number is 1～4, contain in this alkyl Hydrogen atom can be optionally substituted by a hydroxyl group.

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

R^cRepresent the alkylidene that carbon number is 1～6.

* represent the bonding position with O.]

The alkyl being 1～4 as carbon number, can include methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, Zhong Ding Base, tert-butyl group etc..

The alkyl being optionally substituted by a hydroxyl group as hydrogen atom, can include hydroxymethyl, 1- hydroxyethyl, 2- hydroxyethyl, 1- Hydroxypropyl, 2- hydroxypropyl, 3- hydroxypropyl, 1- hydroxyl -1- Methylethyl, 2- hydroxyl -1- Methylethyl, 1- hydroxyl fourth Base, 2- hydroxybutyl, 3- hydroxybutyl, 4- hydroxybutyl etc..

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

As alkylidene, can include methylene, ethylidene, propylene, trimethylene, tetramethylene, 1, 5- pentylidene, hexamethylene etc..

As X^aAnd X^b, preferably can include singly-bound, methylene, ethylidene, *-CH₂- O- and *-CH₂CH₂- O-, more excellent Choosing can include singly-bound, *-CH₂CH₂- O- (* represents the bonding position with O).

As the compound shown in formula (I), compound shown in formula (I-1)～formula (I-15) etc. can be included.Preferably may be used Include formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or the chemical combination shown in formula (I-11)～formula (I-15) Thing.Formula (I-1), formula (I-7), formula (I-9) or the compound shown in formula (I-15) more preferably can be included.

As the compound shown in formula (II), compound shown in formula (II-1)～formula (II-15) etc. can be included.Preferably Formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)～formula (II-15) institute can be included The compound showing.Formula (II-1), formula (II-7), formula (II-9) or the compound shown in formula (II-15) more preferably can be included.

Compound shown in formula (I) and the compound shown in formula (II), can individually use.Additionally, these chemical combination Thing can be mixed with arbitrary ratio.In the case of mixing, its blending ratio is with the preferred formula (I) of molar ratio computing：Formula (II) For 5: 95～95: 5, more preferably 10: 90～90: 10, more preferably 20: 80～80: 20.

As the monomer (b2) with oxetanyl and ethylenic unsaturated bond, more preferably there is oxetanyl The monomer of (methyl) acryloxy.As (b2), 3- methyl -3- methacryloxymethyl oxa- ring fourth can be included Alkane, 3- methyl -3- acryloyloxymethyl oxetanes, 3- ethyl -3- methacryloxymethyl oxetanes, 3- Ethyl -3- acryloyloxymethyl oxetanes, 3- methyl -3- methacryloxyethyl oxetanes, 3- methyl - 3- acryloyl-oxyethyl oxetanes, 3- ethyl -3- methacryloxyethyl oxetanes, 3- ethyl -3- third Alkene trimethylammonium oxetanes etc..

As the monomer (b3) with tetrahydrofuran base and ethylenic unsaturated bond, more preferably have tetrahydrofuran base and The monomer of (methyl) acryloxy.

As (b3), specifically, (such as VISCOATV#150, Osaka is organic can to include acrylic acid tetrahydro furfuryl ester Chemical industry (strain) manufactures), methacrylic acid tetrahydro furfuryl ester etc..

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

As (c), for example, can include：(methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) acrylic acid are just Butyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) third Olefin(e) acid dodecyl ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid cyclopentyl ester, (first Base) cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexane base ester, (methyl) acrylic acid three ring [5.2.1.0^2,6] decane- 8- base ester (in the art, is referred to as " (methyl) acrylic acid bicyclopentyl ester " as trivial name.Additionally, sometimes referred to as " (methyl) acrylic acid tricyclodecyl ester ".), (methyl) acrylic acid three ring [5.2.1.0^2,6] decene -8- base ester (and this technology neck In domain, it is referred to as " (methyl) acrylic acid dicyclopentenyl base ester " as trivial name.), (methyl) acrylic acid bicyclopentyl epoxide second Base ester, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) allyl acrylate, (first Base) (the first such as acrylic acid propargyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate Base) esters of acrylic acid；

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

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

Bicyclic [2.2.1] hept-2-ene", 5- methyl bicycle [2.2.1] hept-2-ene", 5- ethyl bicyclic [2.2.1] hept-2-ene", 5- hydroxyl bicyclic [2.2.1] hept-2-ene", 5- hydroxymethyl bicyclic [2.2.1] hept-2-ene", 5- (2 '-hydroxyethyl) are bicyclic [2.2.1] hept-2-ene", 5- methoxyl group bicyclic [2.2.1] hept-2-ene", 5- ethyoxyl bicyclic [2.2.1] hept-2-ene", 5,6- dihydroxy Base bicyclic [2.2.1] hept-2-ene", 5,6- bis- (methylol) bicyclic [2.2.1] hept-2-ene", 5,6- bis- (2 '-hydroxyethyl) are bicyclic [2.2.1] hept-2-ene", 5,6- dimethoxy bicyclic [2.2.1] hept-2-ene", 5,6- diethoxy bicyclic [2.2.1] hept-2-ene", 5- hydroxy-5-methyl base bicyclic [2.2.1] hept-2-ene", 5- hydroxyl -5- ethyl bicyclic [2.2.1] hept-2-ene", 5- hydroxymethyl -5- Methyl bicycle [2.2.1] hept-2-ene", 5- tert-butoxycarbonyl bicyclic [2.2.1] hept-2-ene", 5- cyclohexyloxy carbonyl are bicyclic [2.2.1] hept-2-ene", 5- phenyloxycarbonyl bicyclic [2.2.1] hept-2-ene", 5,6- are double (tert-butoxycarbonyl) bicyclic [2.2.1] The bicyclic unsaturated compound classes such as double (cyclohexyloxy carbonyl) bicyclic [2.2.1] hept-2-ene" of hept-2-ene", 5,6-；

N-phenylmaleimide, N- N-cyclohexylmaleimide, N- benzyl maleimide, N- succinimido- 3- maleimidobenzoyl ester, N- succinimido -4- malimidobutanoate, N- succinimido -6- Malaysia The dicarbapentaborane such as acid imide alkyl caproate, N- succinimido -3- maleimidopropionic acid ester, N- (9- acridinyl) maleimide Imide derivative class；

Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second Alkene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3- fourth Diene, isoprene, 2,3- dimethyl -1,3-butadiene etc..

Wherein, from the viewpoint of copolyreaction and thermostability, optimization styrene, N-phenylmaleimide, N- ring Hexyl maleimide, N- benzyl maleimide, bicyclic [2.2.1] hept-2-ene" etc..

In resin [K1], from the ratio of the construction unit of each composition, in the entire infrastructure unit constituting resin [K1] In, preferably following scope.

Construction unit from (a)：2～60 moles of %

Construction unit from (b)：40～98 moles of %

More preferably following scope.

Construction unit from (a)：10～50 moles of %

Construction unit from (b)：50～90 moles of %

, in above range, the preservation that there is colored curable resin composition is steady for the ratio of the construction unit of resin [K1] Qualitative, formed colored pattern when developability and gained the excellent solvent resistance of color filter tendency.

Resin [K1] can be with such as document《The laboratory method of Polymer Synthesizing》(" the real method of Polymer Synthesizing ") (big Tianjin Grand row writes sale room (strain) chemistry with the 1st edition the 1st printing on March 1st, 1972 distribution of people) described in method and the document in The citation recorded is as a reference to manufacture.

Specifically, following methods can be included：(a) and (b) of ormal weight, polymerization initiator and solvent etc. are put into In reaction vessel, for example, utilize nitrogen displacement oxygen, become deoxidizing atmosphere, while stirring, heated and be incubated.Give Illustrate, polymerization initiator used herein and solvent etc. have no particular limits, it is possible to use usually used in this field Material.For example, as polymerization initiator, can include azo-compound (2,2 '-azodiisobutyronitrile, 2,2 '-azo double (2, 4- methyl pentane nitrile) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, as long as making the thing of each monomer dissolving Matter, can include solvent described later etc. as the solvent (E) of the colored curable resin composition of the present invention.

It is explained, the copolymer obtaining can be directly using reacted solution, it is possible to use after concentrating or diluting Solution, the material that using methods such as reprecipitations as solid (powder body) take out can also be used.Especially when it is polymerized, pass through It is used contained solvent in the photosensitive composition of the present invention as solvent such that it is able to will be straight for reacted solution Connect and use in the preparation of the photosensitive composition of the present invention, and the coloring phototonus tree of the present invention can be simplified The manufacturing process of oil/fat composition.

In resin [K2], from the ratio of the construction unit of each composition, in the entire infrastructure unit constituting resin [K2] In, preferably following scope：

Construction unit from (a)：2～45 moles of %

Construction unit from (b)：2～95 moles of %

Construction unit from (c)：1～65 mole of %；

More preferably following scope：

Construction unit from (a)：5～40 moles of %

Construction unit from (b)：5～80 moles of %

Construction unit from (c)：5～60 moles of %.

, in above range, the preservation that there is colored curable resin composition is steady for the ratio of the construction unit of resin [K2] Qualitative, form developability during colored pattern and the solvent resistance of color filter of gained, thermostability and mechanical strength Tendency.

Manufactured in the same manner as the method that resin [K2] for example can be recorded with the manufacture method as resin [K1].

In resin [K3], from the ratio of the construction unit of each composition, in the entire infrastructure unit constituting resin [K3] In, preferably following scope：

Construction unit from (a)：2～60 moles of %

Construction unit from (c)：40～98 moles of %；

More preferably following scope：

Construction unit from (a)：10～50 moles of %

Construction unit from (c)：50～90 moles of %.

Manufactured in the same manner as the method that resin [K3] for example can be recorded with the manufacture method as resin [K1].

Resin [K4] by obtaining the copolymer of (a) and (c) and can make the ring that the carbon number that (b) has is 2～4 Carboxylic acid that shape ether and (a) have and/or carboxylic acid anhydrides addition are manufacturing.

First, manufacture the copolymer of (a) and (c) with the manufacture method as resin [K1] in the same manner as the method recorded.Should In the case of, the ratio from the construction unit of each composition is preferably and the ratio identical ratio cited by resin [K3].

Then, make the carboxylic acid from (a) in the cyclic ether and above-mentioned copolymer that the carbon number that (b) has is 2～4 And/or a part for carboxylic acid anhydrides reacts.

After manufacture of (a) and the copolymer of (c), by the atmosphere in flask from nitrogen displacement be air, by (b), carboxylic The catalysts (such as three (dimethylaminomethyl) phenol etc.) of acid or carboxylic acid anhydrides and cyclic ether and polymerization inhibitor (such as hydroquinone Deng) etc. put in flask, for example 60～130 DEG C react 1～10 hour, such that it is able to manufacture resin [K4].

B the usage amount of () is preferably 5～80 moles with respect to 100 moles of (a), more preferably 10～75 moles.By making In this scope, there is development when making the storage stability of colored curable resin composition, formation pattern in the usage amount of (b) Property and the balance of the solvent resistance of gained pattern, thermostability, mechanical strength and sensitivity become good tendency.Due to ring-type The reactivity of ether is high, and is difficult to remaining unreacted (b), accordingly, as used in resin [K4] (b), preferably (b1), enter one Step is preferably (b1-1).

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

The reaction conditions such as feeding method, reaction temperature and time can consider caused thermal discharge of manufacturing equipment, polymerization etc. And suitably adjusted.Be explained, with polymerizing condition as such, it is contemplated that manufacturing equipment, be polymerized caused by thermal discharge etc., fit When adjustment feeding method, reaction temperature.

With regard to resin [K5], as the first stage, obtain in the same manner as the manufacture method of above-mentioned resin [K1] (b) and The copolymer of (c).As described above, the copolymer obtaining can be directly using reacted solution, it is possible to use concentrate or Solution after dilution, can also be used the material taking out using methods such as reprecipitations as solid (powder body).

From the ratio of the construction unit of (b) and (c), total with respect to the entire infrastructure unit constituting above-mentioned copolymer Molal quantity, preferably respectively following scope：

Construction unit from (b)：5～95 moles of %

Construction unit from (c)：5～95 moles of %；

More preferably following scope：

Construction unit from (b)：10～90 moles of %

Construction unit from (c)：10～90 moles of %.

And then, under conditions of same with the manufacture method of resin [K4], make carboxylic acid that (a) have or carboxylic acid anhydrides with The b cyclic ether from (b) that the copolymer of () and (c) has reacts, such that it is able to obtain resin [K5].

The usage amount of (a) that reacted with above-mentioned copolymer is preferably 5～80 moles with respect to 100 moles of (b).By High in the reactivity of cyclic ether, and be difficult to remaining unreacted (b), accordingly, as used in resin [K5] (b), preferably (b1), further preferably (b1-1).

Resin [K6] be make carboxylic acid anhydrides react with resin [K5] further obtained from resin.

The hydroxyl that carboxylic acid anhydrides are produced with the reaction by cyclic ether and carboxylic acid or carboxylic acid anhydrides is made to react.

As carboxylic acid anhydrides, maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acid acid anhydride, 4- can be included Vinylphthalic acid acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl four Hydrogen phthalic anhydride, 5,6- dicarboxyl bicyclic [2.2.1] hept-2-ene" anhydride (carbic anhydride (Himic anhydride)) Deng.The usage amount of carboxylic acid anhydrides is preferably 0.5～1 mole with respect to 1 mole of the usage amount of (a).

As resin (B), specifically, (methyl) acrylic acid 3,4- epoxycyclohexylmethyl ester/(first can be included Base) acrylic copolymer, acrylic acid 3,4- epoxy radicals three ring [5.2.1.0^2.6] tree such as decyl ester/(methyl) acrylic copolymer Fat [K1]；(methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) Glycidyl acrylate/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 copolymer, 3- methyl -3- (methyl) acryloyloxymethyl oxygen The resins [K2] such as azetidine/(methyl) acrylic/styrene copolymer；(methyl) benzyl acrylate/(methyl) acrylic acid The resins [K3] such as copolymer, styrene/(methyl) acrylic copolymer；Make (methyl) glycidyl acrylate and (methyl) The resin of benzyl acrylate/obtained from (methyl) acrylic copolymer addition, make (methyl) glycidyl acrylate with The resin of (methyl) acrylic acid tricyclodecyl ester/styrene/obtained from (methyl) acrylic copolymer addition, make (methyl) propylene Acid glycidyl base ester and (methyl) acrylic acid tricyclodecyl ester/(methyl) benzyl acrylate/(methyl) acrylic copolymer The resins such as resin obtained from addition [K4]；Make (methyl) acrylic acid and (methyl) acrylic acid tricyclodecyl ester/(methyl) propylene Resin obtained from the copolymer reaction of acid glycidyl base ester, make (methyl) acrylic acid and (methyl) acrylic acid tricyclodecyl The resin such as resin [K5] obtained from copolymer reaction of ester/styrene/(methyl) glycidyl acrylate；Make (methyl) Acrylic acid and the copolymer reaction of (methyl) acrylic acid tricyclodecyl ester/(methyl) glycidyl acrylate, then make gained The resin arriving and tetrabydrophthalic anhydride react obtained from the resin [K6] such as resin etc..

These resins can be used alone it is also possible to and use two or more.

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

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000～100,000, more preferably 5,000～ 50,000, more preferably 5,000～30,000.In above range, hardness of film improves molecular weight, and residual film ratio is also high, , there is the tendency that the resolution of colored pattern improves in the favorable solubility to developer solution for the unexposed portion.

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

The acid number of resin (B) preferably 50～170mg-KOH/g, more preferably 60～150, more preferably 70～ 135mg-KOH/g.Here, acid number is the value measuring as the amount (mg) of the potassium hydroxide needed for neutralization 1g resin (B), such as Can be titrated by using potassium hydroxide aqueous solution and be obtained.

The content of resin (B) is preferably 7～65 mass %, more preferably 13～60 matter with respect to the total amount of solid constituent Amount %, more preferably 17～55 mass %.The content of resin (B), in above range, can form colored pattern, and There is the resolution of colored pattern and residual film ratio improves tendency.

Polymerizable compound (C) is can be polymerized by the living radical and/or the acid that are produced by polymerization initiator (D) Compound, for example can include and there is compound of ethylenic unsaturated bond of polymerism etc., preferably (methyl) acrylic acid Ester compounds.

Wherein, polymerizable compound (C) preferably has the polymerizable compound of more than 3 ethylenic unsaturated bonds.Make For such polymerizable compound, for example, can include trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (first Base) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, the four seasons penta 4 Alcohol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) isocyanide Urea acid esters, glycol-modified tetramethylolmethane four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylic acid Ester, propylene glycol modified tetramethylolmethane four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, oneself Lactone-modified tetramethylolmethane four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc..Polymerization Property compound may be used singly or in combination of two or more.

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

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

The content of polymerizable compound (C) with respect to solid constituent total amount be preferably 7～65 mass %, more preferably 13 ～60 mass %, more preferably 17～55 mass %.The content of polymerizable compound (C) within the above range when, exist The tendency that the chemical reagent resistance of residual film ratio when colored pattern is formed and color filter improves.

Polymerization initiator (D) is as long as can be produced living radical, acid etc. and be started polymerization using the effect of light, heat Compound, then have no particular limits, it is possible to use known polymerization initiator.

As polymerization initiator (D), preferably comprise selected from alkyl phenones compound, triaizine compounds, acylphosphine oxide The polymerization initiator of at least one in compound, O- acyl group oxime compound and united imidazole, more preferably comprises O- acyl group oxime The polymerization initiator of compound.

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

Hereinafter, * represents bonding position.

As O- acyl group oxime compound, for example, can include N- benzoyloxy -1- (4- phenylsulfartyl phenyl) butane -1- Ketone -2- imines, N- benzoyloxy -1- (4- phenylsulfartyl phenyl) octane -1- ketone -2- imines, N- benzoyloxy -1- (4- Phenylsulfartyl phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetoxyl group -1- [9- ethyl -6- (2- toluyl Base) -9H- carbazole -3- base] ethane -1- imines, N- acetoxyl group -1- [9- ethyl -6- 2- methyl -4- (3,3- dimethyl -2, 4- dioxolyl methyl epoxide) benzoyl -9H- carbazole -3- base] ethane -1- imines, N- acetoxyl group -1- [9- second Base -6- (2- methyl benzoyl) -9H- carbazole -3- base] -3- cyclopenta propane -1- imines, N- benzoyloxy -1- [9- second Base -6- (2- methyl benzoyl) -9H- carbazole -3- base] -3- cyclopenta propane -1- ketone -2- imines etc..Can use IRGACURE (registered trade mark) OXE01, OXE02 (more than, BASF AG manufacture), N-1919 (manufacture of ADEKA company) etc. are commercially available Product.

Wherein, O- acyl group oxime compound is preferably selected from N- benzoyloxy -1- (4- phenylsulfartyl phenyl) butane -1- Ketone -2- imines, N- benzoyloxy -1- (4- phenylsulfartyl phenyl) octane -1- ketone -2- imines and N- benzoyloxy -1- (4- Phenylsulfartyl phenyl) at least one in -3- cyclopenta propane -1- ketone -2- imines, more preferably N- benzoyloxy -1- (4- Phenylsulfartyl phenyl) octane -1- ketone -2- imines.During for these O- acyl group oxime compounds, there is the color filter obtaining high brightness Tendency.

Alkyl phenones compound is the chemical combination with the part-structure shown in formula (d2) or the part-structure shown in formula (d3) Thing.In these part-structures, phenyl ring can have substituent group.

As the compound with part-structure shown in formula (d2), for example, can include 2- methyl -2- morpholino -1- (4- Methylsulfanylphenyl) propane -1- ketone, 2- dimethylamino -1- (4- morphlinophenyl) -2- benzyl butane -1- ketone, 2- (diformazan Base amino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] butane -1- ketone etc..IRGACURE can be used Commercially available products such as (registered trade mark) 369,907,379 (more than, BASF AG manufactures).

As the compound with part-structure shown in formula (d3), for example, can include 2- hydroxy-2-methyl -1- phenyl third Alkane -1- ketone, 2- hydroxy-2-methyl -1- (4- (2- hydroxyl-oxethyl) phenyl propane -1- ketone, 1- hydroxycyclohexylphenylketone, 2- The oligomer of hydroxy-2-methyl -1- (4- isopropenyl phenyl) propane -1- ketone, α, a α-acetophenone, benzyl dimethyl Ketal etc..

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

As triaizine compounds, for example, can include double (the trichloromethyl) -6- (4- methoxyphenyl) -1,3,5- tri- of 2,4- Double (trichloromethyl) -6- (4- methoxyl group the naphthyl) -1,3,5-triazines of piperazine, 2,4-, double (trichloromethyl) -6- piperonyl -1 of 2,4-, Double (trichloromethyl) -6- (4- the methoxyl-styrene) -1,3,5-triazines of 3,5- triazines, 2,4-, double (the trichloromethyl) -6- of 2,4- Double (trichloromethyl) -6- (2- (furan -2- base) ethylene of (2- (5- methylfuran -2- base) vinyl) -1,3,5-triazines, 2,4- Base) -1,3,5-triazines, double (the trichloromethyl) -6- (2- (4- diethylamino -2- aminomethyl phenyl) vinyl) -1,3,5- of 2,4- Double (trichloromethyl) -6- (2- (3,4- Dimethoxyphenyl) vinyl) -1,3,5-triazines of triazine, 2,4- etc..

As acylphosphine oxide compound, 2,4,6- trimethylbenzoyldiphenyl oxides etc. can be included. The commercially available products such as IRGACURE (registered trade mark) 819 (BASF AG's manufacture) can be used.

As united imidazole, for example, can include 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl joins miaow Azoles, 2,2 '-bis- (2,3- Dichlorobenzene base) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (referring for example to JPH06-75372-A, JPH06- 75373-A etc..), 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines (referring for example to JPS48-38403-B, JPS62-174204-A etc..), 4,4 ' 5, the imidazolium compoundss that the phenyl of 5 '-position is replaced by alkoxy carbonyl group are (referring for example to JPH07- 10913-A etc.) etc..

And then, as polymerization initiator (D), benzoin, benzoin methyl ether, benzoin ethyl ether, benzene can be included occasionally The benzoin compound such as relation by marriage isopropyl ether, benzoin isobutyl ether；Benzophenone, o-benzoyl base benzoic acid methyl ester, 4- benzene Base benzophenone, 4- benzoyl -4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, The benzophenone cpds such as 2,4,6- tri-methyl benzophenones；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2-ethyl-anthraquinone, camphorquinone； 10- butyl -2- chloro-acridine ketone, benzil, phenylglyoxalates methyl ester, titanocenes compound etc..These polymerization initiators preferably with Polymerization described later causes auxiliary agent (D1) (particularly amine) to be applied in combination.

As acid agent, for example, can include 4- hydroxy phenyl dimethyl sulfonium tosilate, 4- hydroxy phenyl diformazan Base 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, The salts such as diphenyl iodine hexafluoro antimonate, nitrobenzyl tosylate class, benzoin toluenesulfonic acid salt etc..

The content of polymerization initiator (D) is preferred with respect to total amount 100 mass parts of resin (B) and polymerizable compound (C) For 0.1～30 mass parts, more preferably 1～20 mass parts.The content of polymerization initiator (D) in above range, due to Gao Ling Sensitivity and exist time of exposure shortening tendency, therefore color filter productivity ratio improve.

While containing polymerization initiator (D), polymerization can also be contained and cause auxiliary agent (D1).Polymerization causes auxiliary agent (D1) It is the compound of polymerization or the sensitizer for promoting the polymerizable compound being caused polymerization by polymerization initiator.

Cause auxiliary agent (D1) as polymerization, amines, alkoxy anthracene compound, thioxanthone compounds and carboxylic can be included Acid compound etc., preferably thioxanthone compounds.

As amines, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylamino peace can be included Breath fragrant acid methyl ester, 4- dimethylamino ethyl benzoate, 4- dimethylamino benzoic acid isopentyl ester, benzoic acid 2- diformazan Base amino ethyl ester, 4- dimethylamino benzoic acid 2- Octyl Nitrite, N, N- dimethyl-p-toluidine, 4,4 '-bis- (dimethylaminos Base) benzophenone (common name Michler's keton), 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (ethylmethylamino) hexichol Ketone etc., wherein, preferably 4,4 '-bis- (diethylamino) benzophenone.Can be using EAB-F (hodogaya chemical industry (strain) Manufacture) etc. commercially available product.

As alkoxy anthracene compound, can include 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 Deng.

As thioxanthone compounds, ITX, ITX, 2,4- diethyl thioxanthene can be included Ketone, 2,4- bis- clopenthixal ketone, 1- chloro- 4- propoxythioxanthone etc..

As carboxylic acid compound, phenylsulfartyl acetic acid, aminomethyl phenyl sulfenyl acetic acid, ethylphenyl sulfenyl vinegar can be included Acid, Methylethyl phenyl sulfenyl acetic acid, 3,5-dimethylphenyl sulfenyl acetic acid, methoxyphenyl sulfenyl acetic acid, Dimethoxyphenyl sulfur Base acetic acid, chlorophenyl sulfanyl acetic acid, Dichlorobenzene base sulfenyl acetic acid, N-phenylglycine, phenoxyethanoic acid, naphthylthio acetic acid, N- naphthyl glycine, naphthoxy acetic acid etc..

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

In the case of causing auxiliary agent (D1) using these polymerizations, its usage amount is with respect to resin (B) and polymerism chemical combination Total amount 100 mass parts of thing (C) are preferably 0.1～30 mass parts, more preferably 1～20 mass parts.Polymerization causes auxiliary agent (D1) Amount in this scope, can with more high sensitivity formed colored pattern, exist color filter productivity ratio improve tendency.

Solvent (E) has no particular limits, it is possible to use solvent usually used in this field.For example, it is possible to it is molten from ester Agent (intramolecular contains-COO- and do not contain the solvent of-O-), (intramolecular contains-O- and does not contain the molten of-COO- ether solvents Agent), ether-ether solvent (solvent that intramolecular contains-COO- and-O-), (intramolecular contains-CO- and does not contain-COO-'s ketone solvent Solvent), alcoholic solvent (intramolecular contains OH and do not contain the solvent of-O- ,-CO- and-COO-), aromatic hydrocarbon solvents, amide molten Select in agent, dimethyl sulfoxide etc. to use.

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acid, acetic acid second can be included Ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl n-butyrate., fourth Acid butyl ester, methyl pyruvate, ethyl pyruvate, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, Hexacyclonic Acid Ester and gamma-butyrolacton etc..

As ether solvents, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, second two can be included Alcohol single-butyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, 3- methoxyl group-n-butyl alcohol, 3- methoxyl group -3- methyl Butanol, oxolane, Pentamethylene oxide., Isosorbide-5-Nitrae-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl phenyl ethers anisole, ethyl phenyl ether, methylanisole etc..

As ether-ether solvent, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, second can be included Epoxide methyl acetate, ethyoxyl ethyl acetate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxy-propionic acid first Ester, 3- ethoxyl ethyl propionate, 2- methoxy methyl propionate, 2- methoxypropionate, 2- methoxy propyl propyl propionate, 2- ethoxy Base methyl propionate, 2- ethoxyl ethyl propionate, 2- methoxyl group -2 Methylpropionic acid methyl ester, 2- ethyoxyl -2 Methylpropionic acid ethyl ester, 3- methoxybutyl acetass, 3- methyl -3- methoxybutyl acetass, propylene glycol monomethyl ether, propylene glycol list second Base ether acetic acid ester, propylene glycol monopropyl ether acetass, ethylene glycol single methyl ether acetass, ethylene glycol monomethyl ether acetate, two Ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetass etc..

As ketone solvent, 4- hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3- heptanone, 4- can be included Heptanone, 4-methyl-2 pentanone, Ketocyclopentane, Ketohexamethylene, isophorone etc..

As alcoholic solvent, methanol, ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol, glycerol can be included Deng.

As aromatic hydrocarbon solvents, benzene,toluene,xylene, sym-trimethylbenzene. etc. can be included.

As amide solvent, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone can be included Deng.

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

In above-mentioned solvent, from the viewpoint of coating, drying property, boiling point in preferably 1atm be more than 120 DEG C and Less than 180 DEG C of organic solvent.As solvent, preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl Ether, 3- ethoxyl ethyl propionate, ethylene glycol single methyl ether, diethylene glycol monomethyl ether, TC, 4- hydroxyl- 4-methyl-2 pentanone and DMF, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, breast Acetoacetic ester and 3- ethoxyl ethyl propionate.

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

As levelling agent (F), silicone-based surfactant, fluorine system surfactant and the silicon with fluorine atom can be included Ketone system surfactant etc..They can have polymerizable group in side chain.

As silicone-based surfactant, intramolecular can be included there is surfactant of siloxanes key etc..Concrete and Speech, can include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA, Toray Silicone SH8400 (trade name；The beautiful DOW CORNING (strain) in east manufactures), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan contract commercial firm manufactures) etc..

As above-mentioned fluorine system surfactant, intramolecular can be included there is surfactant of fluorocarbon chain etc..Specifically For, Fluorad (registered trade mark) FC430, Fluorad FC431 (Sumitomo 3M (strain) manufacture), Megafac (note can be included Volume trade mark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (DIC (strain) manufacture), EFTOP (registered trade mark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (Mitsubishi Materials electronics chemical conversion (strain) manufactures), Surflon (registered trade mark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) manufacture) and E5844 ((strain) Daikin Fine Chemical research is manufactured) etc..

As the above-mentioned silicone-based surfactant with fluorine atom, intramolecular can be included there is siloxanes key and fluorine Surfactant of carbochain etc..Specifically, Megafac (registered trade mark) R08, Megafac BL20, Megafac can be included F475, Megafac F477 and Megafac F443 (DIC (strain) manufacture) etc..

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

The content of levelling agent (F) is preferably more than 0.001 mass % with respect to the total amount of colored curable resin composition And 0.2 below mass %, more than preferably 0.002 mass % and below 0.1 mass %, more than more preferably 0.01 mass % and Below 0.05 mass %.The content of levelling agent (F), in above range, can make the flatness of color filter good.

The colored curable resin composition of the present invention can contain as needed filler, other macromolecular compounds, The various additives such as closely sealed accelerator, antioxidant, light stabilizer, chain-transferring agent.

The colored curable resin composition of the present invention, for example, can pass through mixed colorant (A), resin (B), polymerism Compound (C) and polymerization initiator (D) and the solvent (E) using as needed, levelling agent (F), polymerization initiation auxiliary agent (D1) And other compositions are preparing.

Ton dyestuff (Aa), anthraquinone dye (Ab) and the dyestuff (Ac) using as needed can be first dissolved in molten respectively in advance It is prepared into solution in part or all of agent (E).

Preferably with the filter in 0.01～1 μm about of aperture, this solution is filtered.

In the case of containing pigment (Ad) it is preferred that in advance by pigment (Ad) and solvent (E) part or all Mixing, makes it be dispersed to the mean diameter of pigment for till less than 0.2 μm about using ball mill etc..At this point it is possible to according to need Coordinate above-mentioned pigment dispersing agent, resin (B) part or all.To become normal concentration in the dispersible pigment dispersion of gained Mode mix remaining coloring agent (A), remaining resin (B), polymerizable compound (C), polymerization initiator (D) and remaining Solvent (E) and the levelling agent (F) using as needed, polymerization cause auxiliary agent (D1) and other compositions etc. such that it is able to prepare Target coloration hardening resin composition.

Preferably with the filter in 0.01～10 μm about of aperture, mixed colored curable resin composition was carried out Filter.

Method as forming color filter by the colored curable resin composition of the present invention, can include photoetching process and make Method with ink jet technique etc..Photoetching process is to be coated with the colored curable resin composition of the present invention for example on substrate, passes through Removing solvent etc. evaporates into grading mode makes it be dried, and forms coloring compositions nitride layer, and across photomask to this coloured composition The method that layer is exposed, develops.After development, colored pattern can be formed as desired by heating.Above-mentioned color-patch map It is also possible to not use photomask in exposure in the forming method of case, and/or do not developed, be consequently formed as above-mentioned The coloring film of the solidfied material of colour cell compound layer.So obtained colored pattern and coloring film can be used as color filters.

As substrate, can be using quartz glass, pyrex, alumina silicate glass, be coated with table with silicon oxide The glass plates such as the soda-lime glass in face, the resin of Merlon, polymethyl methacrylate, polyethylene terephthalate etc. Plate, silicon, the substrate of aluminum, silver, silver/copper/palldium alloy thin film etc. is defined on aforesaid substrate.These substrates can also be formed Other color-filter layers (color-filter layer for example, being formed on substrate by colored curable resin composition etc.), resin bed, crystalline substance Body pipe, circuit etc..

The thickness of made color filter has no particular limits, and suitably can be adjusted according to intended applications etc., example As for 0.1～30 μm, preferably 1～20 μm, more preferably 1～6 μm.

Then, to being formed with thin film transistor (TFT) (hereinafter referred to as " TFT ".) glass substrate on formed pattern method Illustrate.

Specifically, by the known method such as photoetching technique, multiple TFT22 are according to pixels formed on glass substrate 21 (with reference to Fig. 1).TFT22 is made up of gate electrode 22a, gate insulating film 22b, polysilicon film 22c and protecting film 22d, wherein, gate electrode 22a, on glass substrate 21, is formed by such as molybdenum (Mo) and constitutes a part for gate line；Gate insulating film 22b, is formed at On this gate electrode 22a, by such as nitride film (SiN_x) and oxide-film (SiO₂) stacked film constitute；Polysilicon film 22c, is formed at On this gate insulating film 22b；Protecting film 22d, by such as oxide-film (SiO₂) and nitride film (SiN_x) stacked film formed.Polysilicon The region against gate electrode 22a of film 22c is passage (channel) region of TFT22, additionally, the both sides of this passage area Region is source region or drain region.The source region of polysilicon film 22c is by the connecting hole being arranged on protecting film 22d (contact hole) is electrically connected by the holding wire 27 that aluminum (Al) is formed with for example.It is explained, as described later, polysilicon film 22c Drain region be electrically connected by connecting hole (contact hole) 201 and pixel electrode 24.

When glass substrate 21 according to pixels forms multiple TFT22, glass substrate 21 is formed with TFT22 simultaneously and is aligned Labelling (not shown).As described later, this alignment mark becomes the benchmark of the para-position in the formation process of color-filter layer 23.Said Bright, these alignment marks can also be as the labelling becoming driving substrate and the benchmark fitted of counter substrate.System in TFT22 When making the metal level of formation wiring etc., polysilicon layer in technique, form alignment mark in same operation using at least one layer.

Then, the coloring phototonus resin of the present invention is coated with the glass substrate 21 being formed with TFT22 and alignment mark Compositionss, are removed the volatile ingredients such as solvent and so that it is dried using heat drying (prebake) and/or drying under reduced pressure, form thickness 0.5～5.0 μm, such as 1.0 μm of coloring compositions nitride layer.

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

Preferably 30～120 DEG C of temperature when being thermally dried, more preferably 60～110 DEG C.Additionally, as during heating Between, preferably 10 seconds～60 minutes, more preferably 30 seconds～30 minutes.

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

Then, across photomask (not shown) against colour cell compound layer irradiation ultraviolet radiation, then by developer solution optionally Remove unwanted part, thus obtain the formable connecting hole (contact for being formed with the drain region reaching polysilicon film 22c Hole) 201 pixel coloring compositions nitride layer, then washed.

By development, the unexposed portion of coloring compositions nitride layer is dissolved in developer solution and is removed.As developer solution, preferably The aqueous solution of the such as alkali compoundss such as potassium hydroxide, sodium bicarbonate, sodium carbonate, Tetramethylammonium hydroxide.These alkaline chemical combination Concentration in the aqueous solution of thing is preferably 0.01～10 mass %, more preferably 0.03～5 mass %.And then, developer solution is permissible Containing surfactant.

Developing method can be any one in stirring (paddle) method, infusion process, spray process etc..And then can in development So that substrate tilts to arbitrary angle.

Afterwards, in order that the coloring compositions nitride layer being formed with connecting hole (contact hole) 201 flows again (reflow) and/or Polymerizable compound (C) containing in this coloring compositions nitride layer etc. is made to solidify, at such as 100～300 DEG C preferably 150～230 DEG C At a temperature of, heat such as 1～120 minute preferably 10～60 minutes.The color solidification as colored pattern thus can be formed Property resin composition layer 23A.This colored curable resin composition layer 23A corresponds to the color filter of the present invention.

Repeat this operation, respectively by red colored hardening resin composition, green coloring hardening resin composition and Blue-colored hardening resin composition forms colored curable resin composition layer 23A such that it is able to form each picture corresponding The color-filter layer 23 (with reference to Fig. 2) that element arranges and comprises red color filter 23a, green color filter 23b and blue color filter 23c.Though So the region between each color filter of color-filter layer 23 becomes the Mixed Zone of adjacent color, but this region is against holding wire 27 Lightproof area, therefore no affect in quality.It is explained, the region between this each color filter can be made to be not tinted.

Then, formed using by way of cover color-filter layer 23 for example as 0.3～2.0 μm of thickness by such as spin-coating method The photosensitive resin film 29 of protecting film.Then, across photomask (not shown) to photosensitive resin film 29 irradiation ultraviolet radiation, then lead to Cross developer solution and optionally remove region corresponding with connecting hole 201 and unwanted part, thus, formed and reach polysilicon film The connecting hole (contact hole) 202 of the drain region of 22c, is then washed.Afterwards, in order that photosensitive resin film 29 flows again (reflow), such as 200 DEG C of the temperature in 100～300 DEG C of scope is heated.Then, it is deposited in contact hole to remove The residues such as the dyestuff in 202 and Organic substance, and be etched using oxygen plasma, and then, in order to remove by oxygen plasma The oxide-film being formed, and be etched using such as diluted hydrofluoric acid.

Then, photosensitive resin film 29 forms transparent conductive material such as ITO (Indium- using such as sputtering method Tin Oxide：The oxide hybrid films of indium and stannum), pattern will be formed by photoetching technique and etching to ito film, formed transparent Pixel electrode 24 (with reference to Fig. 3).It is explained, this pixel electrode 24 can also be according to the device making by aluminum (Al), silver Etc. (Ag) metal is formed.Afterwards, alignment films are formed by known method, then carry out the patch of this driving substrate and counter substrate Close, such that it is able to manufacture liquid crystal indicator.

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

Embodiment

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

" % " and " part " in example, as long as no special instructions, is quality % and mass parts.

In following synthesis example, compound utilizes elementary analysiss (VARIO-EL：(Alementar (strain) manufacture)) reflected Fixed.

(synthesis example 1)

In the flask with condensing tube and agitating device, shown in the compound shown in throw-in type (A0-1) and formula (A0-2) Compound mixture (trade name ChugaiAminol Fast Pink R；Middle tank formation manufacture) 15 parts, 150 parts of chloroform and 8.9 parts of DMF, less than 20 DEG C of side maintenance under agitation, 10.9 parts of side Deca thionyl chloride.After completion of dropwise addition, It is warmed up to 50 DEG C, maintaining at such a temperature makes it react in 5 hours, afterwards, is cooled to 20 DEG C.Reaction solution after cooling is being stirred Mix and maintain less than 20 DEG C below, the mixed liquor of 12.5 parts of side Deca 2 ethyl hexylamine and 22.1 parts of triethylamine.Afterwards, in this temperature The lower stirring of degree makes it react in 5 hours.Then, with Rotary Evaporators, solvent is distilled off to the reactant mixture obtaining, then, plus Enter a small amount of methanol, be stirred vigorously.This mixture is added in the mixed liquor of 375 parts of ion exchange water while stirring, makes crystallization Separate out.Filter separated out crystallization, fully cleaned with ion exchange water, in 60 DEG C of drying under reduced pressure, obtain dyestuff (Aa-1) (formula (A1-1) mixture of the compound shown in～formula (A1-8)) 11.3 parts.

(synthesis example 2)

Under dark conditions hybrid (1x) shown in 20 parts of compound and N- ethyl-ortho-toluidine (and Wako Pure Chemical Industries (strain) manufactures) 200 parts, the solution of gained is stirred 6 hours at 110 DEG C.The reactant liquor of cooling gained, to room temperature, is added to water 800 parts, in the mixed liquor of 50 parts of 35% hydrochloric acid, be stirred at room temperature 1 hour, result has separated out crystallization.With the residue of sucking filtration Form obtains separated out crystallization, is then dried, obtains 24 parts of the compound shown in formula (1-30).Yield is 80%.

The structure of the compound shown in formula (1-30) utilizes mass spectral analyses (LC；1200 types that Agilent manufactures, MASS： The LC/MSD type that Agilent manufactures) confirmed.

(mass spectral analyses) ionize pattern=ESI+；M/z=[M+H]⁺603.4

Accurate mass (Exact Mass)：602.2

(synthesis example 3)

Except using N- propyl group -2,6- dimethylaniline replaces beyond N- ethyl-ortho-toluidine, in the same manner as synthesis example 1 To the compound shown in formula (1-38).

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

(mass spectral analyses) ionize pattern=ESI+：M/z=[M+H]⁺659.9

Accurate mass (Exact Mass)：658.9

(synthesis example 4)

12 parts of compound shown in hybrid (1x), 60 parts of METHYLPYRROLIDONE and piperidines (Tokyo chemical conversion industry (strain) manufactures) 12.6 parts, the mixture of gained is stirred 5 hours at 60 DEG C.After making above-mentioned reactant liquor cool down room temperature, it is added to In 600 parts of water, the mixed liquor of 100 parts of 35% hydrochloric acid, it is stirred at room temperature 1 hour.Taken out in the form of the residue of sucking filtration and separated out Crystallization, be then dried, obtain 12.4 parts of the compound shown in formula (1-27).Yield is 83%.

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

(mass spectral analyses) ionize pattern=ESI+：M/z=[M+H]⁺503.4

Accurate mass (Exact Mass)：502.2

(synthesis example 5)

(Tokyo is melted into work for 15 parts of compound shown in hybrid (1x), 75 parts of METHYLPYRROLIDONE and decahydroquinoline Industry (strain) manufactures) 25.8 parts, the mixture of gained is stirred 24 hours at 110 DEG C.After making above-mentioned reactant liquor be cooled to room temperature, It is added to 600 parts of water, in the mixed liquor of 100 parts of 35% hydrochloric acid, be stirred at room temperature 1 hour.Taken out in the form of the residue of sucking filtration The crystallization being separated out, is then dried, and obtains 19.5 parts of the compound shown in formula (1-29).Yield is 86%.

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

(mass spectral analyses) ionize pattern=ESI+：M/z=[M+H]⁺611.4

Accurate mass (Exact Mass)：610.3

(synthesis example 6)

With the speed inflow nitrogen of 0.02L/ minute in the flask with reflux condenser, Dropping funnel and blender Become nitrogen atmosphere, add ethyl lactate 305 mass parts, be heated to 70 DEG C while stirring.

Then, in acrylic acid 46 mass parts, acrylic acid 3,4- epoxy radicals three ring [5.2.1.0^2.6] decyl ester is (with mol ratio Compound shown in 50: 50 hybrid (I-1) and the compound shown in formula (II-1).) 240 mass parts and ethyl lactate 185 matter Dissolve in amount part, prepare solution, arrived with 4 hours this lysates of Deca with Dropping funnel and be incubated in 70 DEG C of flask.

On the other hand, dissolved polymerization with other Dropping funnel in ethyl lactate 225 mass parts with 4 hours Deca to cause Agent 2, the solution of double (2,4- methyl pentane nitrile) 30 mass parts of 2 '-azo is in flask.The solution of polymerization initiator drip Plus after terminating, keep 4 hours at 70 DEG C, be then cooled to room temperature, obtaining weight average molecular weight Mw is 9.1 × 10³, molecular weight distribution For 2.1, solid constituent be 26 mass %, solid constituent acid number be 120mg-KOH/g resin B 1 solution.Resin B 1 has following Shown construction unit.

(synthesis example 7)

In the flask with blender, thermometer, reflux condensing tube, Dropping funnel and nitrogen ingress pipe, import the third two Alcohol monomethyl ether acetate 182g, makes atmosphere in flask after air is changed into nitrogen, be warmed up to 100 DEG C, then, by methyl-prop Olefin(e) acid benzyl ester 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), the monomethacrylate of tricyclodecane skeleton Ester (Hitachi chemical conversion (strain) FA-513M that manufactures) 22.0g (0.10 mole) and propylene glycol monomethyl ether 136g composition In mixture, Deca is added with 2, the solution of 2 '-azodiisobutyronitrile 3.6g, then continues stirring at 100 DEG C.

Then, make atmosphere in flask be changed into air from nitrogen, put into methyl propenoic acid glycidyl base ester in flask 35.5g [0.25 mole, (being 50 moles of % with respect to the carboxyl of methacrylic acid used in this reaction)], three (dimethylaminos Ylmethyl) phenol 0.9g and hydroquinone 0.145g, continues reaction at 110 DEG C, obtaining solid constituent is that 29%, solid constituent acid number is Resin B 2 solution of 79mgKOH/g.The weight average molecular weight of the styrene conversion being recorded using GPC is 30,000.

(synthesis example 8)

In the flask with blender, thermometer, reflux condenser and Dropping funnel, nitrogen is flowed into 0.02L/ minute And become nitrogen atmosphere, add 305 parts of propylene glycol monomethyl ether, be heated to 70 DEG C while stirring.Then, in acrylic acid 60 parts, acrylic acid 3,4- epoxy radicals three ring [5.2.1.0^2.6] decyl ester is (with the chemical combination shown in mol ratio 50: 50 hybrid (I-1) Compound shown in thing and formula (II-1).) dissolve in 440 parts and 140 parts of propylene glycol monomethyl ether, prepare solution, use Dropping funnel with 4 hours this lysates of Deca to insulation in 70 DEG C of flask.

On the other hand, dissolved in 225 parts of propylene glycol monomethyl ether with 4 hours Deca with other Dropping funnel Polymerization initiator 2, the solution of 30 parts of 2 '-azo double (2,4- methyl pentane nitrile) is in flask.The solution of polymerization initiator Completion of dropwise addition after, 70 DEG C keep 4 hours, be then cooled to room temperature, obtain weight average molecular weight Mw be 9.1 × 10³, molecular weight Be distributed as 2.16, solid constituent be 34.8%, solid constituent conversion acid number be 81mgKOH/g resin B 3 solution.Resin B 3 There are following shown construction units.

The weight average molecular weight (Mw) of the resin obtaining in synthesis example and number-average molecular weight (Mn) record using GPC method with Carry out under conditions of lower.

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

Post：SHIMADZU Shim-pack GPC-80M

Column temperature：40℃

Solvent：THF (oxolane)

Flow velocity：1.0mL/min

Detector：RI

Correction standard substance：TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500 (eastern Cao's (strain) manufactures)

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

(embodiment 1)

(preparation of colored curable resin composition)

Mixing following component,

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

6.1 parts of acrylic acid seriess pigment dispersing agent and

163 parts of propylene glycol monomethyl ether；

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

(A) coloring agent：1.8 parts of dyestuff (A1-a) (ton dyestuff)

(A) coloring agent：C.I. solvent blue 35 (the Sudan indigo plant II：Aldrich manufactures；Anthraquinone dye) 1.8 parts

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

(C) polymerizable compound：Dipentaerythritol acrylate

(KAYARAD (registered trade mark) DPHA：Japanese chemical medicine (strain) manufactures) 40 parts

(D) polymerization initiator：N- benzoyloxy -1- (4- phenylsulfartyl phenyl) octane -1- ketone -2- imines (IRGACURE (registered trade mark) OXE01：BASF AG manufactures) 5 parts

(F) levelling agent：Polyether modified silicon oil (Toray Silicone SH8400：Dong Li DOW CORNING Co., Ltd. manufactures) 0.08 part

(E) solvent：682 parts of ethyl lactate

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

Using spin-coating method 5cm square glass substrate (Eagle 2000：CORNING company manufactures) upper coating coloring is admittedly The property changed resin combination, afterwards, in 100 DEG C of prebake 3 minutes, obtains coloring compositions nitride layer.After letting cool, colour cell will be formed with The substrate of compound layer is set to 100 μm, using exposure machine (TME-150RSK with the interval of quartz glass photomask：TOPCON (strain) manufactures), under air atmosphere, with 150mJ/cm²Light exposure (365nm benchmark) carried out light irradiation.As photomask, Using the photomask being formed with 100 μm of live widths and line-spacing (line and space) pattern.Containing nonionic system surface activity In the water system developer solution of agent 0.12% and potassium hydroxide 0.04% 24 DEG C to light irradiation after coloring compositions nitride layer immersion development 60 seconds, after washing, in an oven, carry out the solidify afterwards of 30 minutes at 230 DEG C, obtain colored pattern.

Colored pattern to gained, using film thickness measuring device (DEKTAK3；Japanese vacuum technique (strain) manufactures)) measure Thickness.

Colored pattern to gained, using colorimeter (OSP-SP-200；Olympus (strain) manufacture) determine spectrum, make Determine xy chromaticity coordinate (x, y) in the XYZ primary colours system of CIE and tristimulus values Y with the characterisitic function of illuminant-C.The value of Y is got over Greatly, represent that brightness is higher.Result is shown in table 3 and table 4.

In addition to not using photomask when in exposure, the making with colored pattern carries out same operation, has made coloring Film.Coloring film to gained, using contrast meter (CT-1：Hu Ban Motor Corporation manufactures, color evaluating BM-5A： TOPCON company manufactures, light source：F-10, polarizing coating：Kettle slope motor (strain) manufactures), blank value is set to 30000, it is right to determine Degree of ratio.If the contrast of coloring film is high, it may be said that being similarly high-contrast in colored pattern.Result is shown in table 3 And table 4.

(comparative example 1)

Mix following composition：

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

5 parts of acrylic acid seriess pigment dispersing agent and

137 parts of propylene glycol monomethyl ether,

Make pigment fully dispersed using ball mill, then, mix following component, obtain colored curable resin composition：

(A) coloring agent：3.5 parts of dyestuff (Aa-1) (ton dyestuff)

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

(C) polymerizable compound：Dipentaerythritol acrylate

50 parts of (Japanese chemical medicine (strain) manufactures)

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

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

Embodiment 2～15

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

[table 1]

[table 2]

It is explained, in table 1 and table 2, " Ad-1¹⁾" and acrylic acid seriess pigment dispersing agent and " E-1³⁾" amount recorded of hurdle Propylene glycol monomethyl ether mixes so as to carry out pre-dispersed.

“E-1²⁾" hurdle represents the total content of propylene glycol monomethyl ether.

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

Ton dyestuff (Aa)：Aa-1：Dyestuff (Aa-1)

Ton dyestuff (Aa)：Aa-2：Compound shown in formula (1-30)

Ton dyestuff (Aa)：Aa-3：Compound shown in formula (1-38)

Ton dyestuff (Aa)：Aa-4：C.I. Xylene Red 52 (Tokyo chemical conversion industry (strain) manufacture)

Ton dyestuff (Aa)：Aa-5：Compound shown in formula (1-27)

Ton dyestuff (Aa)：Aa-6：Compound shown in formula (1-29)

Anthraquinone dye (Ab)：Ab-1：C.I. solvent blue 35 (the Sudan indigo plant II：Aldrich manufactures)

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

Anthraquinone dye (Ab)：Ab-3：C.I. acid blue 80 (Coomassie (registered trade mark) BlueB150：ICI company system Make)

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

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

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 trade mark) DPHA：Japanese chemical medicine (strain) manufactures)

Polymerization initiator (D)：D-1：N- benzoyloxy -1- (4- phenylsulfartyl phenyl) octane -1- ketone -2- imines (IRGACURE (registered trade mark) OXE01：BASF AG manufactures；O- acyl group oxime compound)

Polymerization initiator (D)：D-2：2- methyl -2- morpholino -1- (4- methylsulfanylphenyl) propane -1- ketone (IRGACURE (registered trade mark) 907：BASF AG manufactures；Alkyl phenones compound)

Polymerization causes auxiliary agent (D1)：2,4- diethyl thioxanthones (KAYACURE (registered trade mark) DETX-S：Japanese chemical medicine (strain) manufactures；Thioxanthone compounds)

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 (strain) in east manufactures)

Colored curable resin composition to embodiment 2～15 such as obtained above and comparative example 1, same with embodiment 1 Evaluated sample.Result is shown in table 3 and table 4.

[table 3]

[table 4]

According to the colored curable resin composition of embodiment, confirm the film display high-contrast of gained.Thus may be used See, by the colored curable resin composition of the present invention obtain coloring film, colored pattern as high-contrast color filter It is useful, the display characteristic comprising the liquid crystal indicator of this color filter is excellent.

Claims

1. a kind of colored curable resin composition, which contain toner, resin, has the ethylenic unsaturated bond of polymerism Polymerizable compound and the polymerization initiator producing living radical using the effect of light,

Coloring agent comprises ton dyestuff and anthraquinone dye,

Described ton dyestuff is the dyestuff of the compound shown in contained (1a),

In formula (1a), R¹～R⁴Represent hydrogen atom independently of one another, carbon number is 1～20 1 valency saturated hydrocarbyl, or optionally Have selected from halogen atom ,-R⁸、-OH、-OR⁸、-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂R⁸、-SR⁸、-SO₂R⁸And-SO₃R⁸ Substituent group carbon number be 6～10 1 valency aromatic hydrocarbyl,

The hydrogen atom containing in this saturated hydrocarbyl optionally by carbon number be 6～10 aromatic hydrocarbyl or halogen atom replace, The hydrogen atom containing in this aromatic hydrocarbyl is optionally replaced by the alkoxyl that carbon number is 1～3, contains in described saturated hydrocarbyl - CH₂- optionally by-O- ,-CO- or-NR¹¹- displacement,

R¹And R²Form the ring of nitrogen atom, R optionally together³And R⁴Form the ring of nitrogen atom optionally together,

R⁵Represent-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸Or-SO₃R⁸,

R⁶And R⁷Represent hydrogen atom or alkyl that carbon number is 1～6 independently of one another,

M represents 0～5 integer, m be more than 2 integer in the case of, multiple R⁵It is optionally identical or different,

A represents 0 or 1 integer,

X represents halogen atom,

R⁸Represent the 1 valency saturated hydrocarbyl that carbon number is 1～20, the hydrogen atom containing in this saturated hydrocarbyl is optionally by halogen atom Replace,

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺,

R¹¹Represent the 1 valency saturated hydrocarbyl that hydrogen atom, carbon number are 1～20 or the virtue that carbon number is 7～10 independently of one another Alkyl.

2. colored curable resin composition according to claim 1, wherein, the content of anthraquinone dye is with respect to coloring agent Total amount be 0.1 mass % more than and 70 mass % below.

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

4. a kind of color filter, its colored curable resin composition any one of claims 1 to 3 is formed.

5. a kind of display device, it comprises the color filter described in claim 4.