CN102636957B

CN102636957B - Photosensitive composition and compound

Info

Publication number: CN102636957B
Application number: CN201210038468.0A
Authority: CN
Inventors: 朴昭妍; 辰巳泰基; 井上雅人
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2011-02-14
Filing date: 2012-02-13
Publication date: 2016-06-22
Anticipated expiration: 2032-02-13
Also published as: CN102636957A; KR20120093096A; KR101766745B1; JP5807568B2; JP2012185483A; TW201237118A; TWI515268B

Abstract

A kind of photosensitive composition containing coloring agent, resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent, coloring agent is the coloring agent containing compound shown in formula (1)。Wherein, R¹～R¹⁸Represent hydrogen atom, 1 valency aliphatic alkyl of carbon number 1～8 or nitro etc.。R¹⁹And R²⁰Represent hydrogen atom, methyl, ethyl or amino。M¹Represent Cr or Co。R²¹～R²⁴Represent 1 valency aromatic hydrocarbyl of hydrogen atom, 1 valency aliphatic alkyl of carbon number 1～8 or carbon number 6～10。R²⁵And R²⁶Represent hydrogen atom or methyl。R²⁷Represent ethylidine, trimethylene or propylene。N represents the integer of 0～3。

Description

Photosensitive composition and compound

Technical field

The present invention relates to photosensitive composition and compound。

Background technology

The color filter used in liquid crystal display cells or solid-state imager has red pixel, among the photosensitive composition forming this red pixel, it is known to use dyestuff as coloring agent。Such as, in patent documentation 1, record containing the OrasolRedG photosensitive composition as orchil。

[patent documentation 1] Japanese Patent Laid-Open 2009-163226 publication

Summary of the invention

On this aspect of solvent resistance, there is the situation that can not make us fully being satisfied with in always known above-mentioned photosensitive composition。

The present invention provides following [1]～[10] item。

[1] a kind of photosensitive composition, containing coloring agent, resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent, coloring agent is the coloring agent containing compound shown in formula (1)。

[in formula (1), R¹～R¹⁸Represent hydrogen atom, halogen atom, 1 valency aliphatic alkyl of carbon number 1～8, nitro or-SO independently of one another₂R²⁹。

R²⁹Expression-R³²,-OH or-NHR³⁰。

R³⁰Represent hydrogen atom, 1 valency aliphatic alkyl of carbon number 1～8, the cyclohexyl that can be replaced by the alkyl of carbon number 1～4 ,-R³¹-O-R³²、-R³¹-CO-O-R³²、-R³¹-O-CO-R³²Or the aralkyl of carbon number 7～10。

R³¹Represent the divalent aliphatic alkyl of carbon number 1～8。

R³²Represent 1 valency aliphatic alkyl of carbon number 1～8。

R¹⁹And R²⁰Represent hydrogen atom, methyl, ethyl or amino independently of one another。

M¹Represent Cr or Co。

R²¹～R²⁴Representing 1 valency aromatic hydrocarbyl of hydrogen atom, 1 valency aliphatic alkyl of carbon number 1～8 or carbon number 6～10 independently of one another, the hydrogen atom that this aliphatic alkyl and this aromatic hydrocarbyl comprise can by hydroxyl ,-OR³², sulfonic group ,-SO₃Na、-SO₃K or halogen atom replace。

R²⁵And R²⁶Represent hydrogen atom or methyl independently of one another。

R²⁷Represent ethylidine, trimethylene or propylene。

N represents the integer of 0～3。When the integer that n is more than 2, multiple R²⁷May be the same or different each other。]

[2] photosensitive composition as described in [1], wherein R¹～R¹⁸It is each independently hydrogen atom, nitro or-SO₂R²⁹、

R²⁹For-R³²、

R³²For carbon number 1～8 1 valency aliphatic alkyl,

R¹⁹And R²⁰Be each independently methyl,

R²¹～R²⁴Be each independently carbon number 1～8 1 valency aliphatic alkyl,

R²⁵And R²⁶Be each independently hydrogen atom,

N is 0。

[3] photosensitive composition as described in [2], wherein R¹～R¹⁸Among at least one be hydrogen atom, at least one be nitro, and at least one is-SO₂R²⁹。

[4] photosensitive composition as described in [3], wherein R¹～R¹⁰It is each independently hydrogen atom。

[5] photosensitive composition as described in [4], wherein R¹～R¹⁸Among at least one be hydrogen atom,

R¹¹～R¹⁸Among at least one is nitro, and

R¹¹～R¹⁸Among at least one be-SO₂R²⁹。

[6] photosensitive composition as described in [1], wherein Photoepolymerizationinitiater initiater is containing at least one Photoepolymerizationinitiater initiater among benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime compound and double imidazole compound。

[7] photosensitive composition as described in [1], wherein M¹For Cr。

[8] photosensitive composition described in any one in [1]～[7] is formed and the color filter that obtains。

[9] display device containing [8] described color filter。

[10] compound shown in a kind of formula (1)。

R²⁹Expression-R³²,-OH or-NHR³⁰。

R³¹Represent the divalent aliphatic alkyl of carbon number 1～8。

R³²Represent 1 valency aliphatic alkyl of carbon number 1～8。

M¹Represent Cr or Co。

R²⁷Represent ethylidine, trimethylene or propylene。

Invention effect

Photosensitive composition according to the present invention, can form the high color solidification thing of solvent resistance (such as film, pattern)。

Detailed description of the invention

The photosensitive composition of the present invention contains coloring agent (A), resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E), and coloring agent (A) is the coloring agent containing compound shown in formula (1) (below also referred to as " compound (1) ")。

Compound (1) is that chromium complex anion or cobalt complex anion and origin are in the cationic salt of xanthene compounds。

R²⁹Expression-R³²,-OH or-NHR³⁰。

R³⁰Represent hydrogen atom, 1 valency aliphatic alkyl of carbon number 1～8, the cyclohexyl that can be replaced by the alkyl of carbon number 1～4 ,-R³¹-O-R³²、-R³¹-CO-O-R³²、-R³-O-CO-R³²Or the aralkyl of carbon number 7～10。

R³¹Represent the divalent aliphatic alkyl of carbon number 1～8。

R³²Represent 1 valency aliphatic alkyl of carbon number 1～8。

M¹Represent Cr or Co。

R²⁷Represent ethylidine, trimethylene or propylene。

1 valency aliphatic alkyl of carbon number 1～8 can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1-methyl butyl, 1,1,3,3-tetramethyl butyl, 1,5-dimethylhexanyl, 1,6-dimethyl heptyl, 2-ethylhexyl and 1,1,5,5-tetramethylhexyl etc.。

1 valency aliphatic alkyl of carbon number 1～4, i.e. alkyl can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.。

The divalent aliphatic alkyl of carbon number 1～8 can enumerate methylene, ethylidine, trimethylene, propylene, tetramethylene, 1,3-butylidene, pentamethylene, hexamethylene, 1,7-Asia heptyl, octamethylene etc.。

1 valency aromatic hydrocarbyl of carbon number 6～10 can enumerate the aryl such as phenyl, tolyl, 3,5-dimethylphenyl, trimethylphenyl, ethylbenzene, propyl phenyl, butylbenzene base, naphthyl；The aralkyl etc. such as benzyl, diphenyl methyl, phenylethyl, 3-phenyl propyl。

The cyclohexyl that can be replaced by the alkyl of carbon number 1～4 can enumerate 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-propylcyclohexyl, 2-isopropylcyclohexyl, 2-butylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl etc.。

As-R³¹-O-R³²Methoxy, ethoxyl methyl, propoxy methyl, methoxy ethyl, ethoxyethyl group, Among, methoxy-propyl, ethoxycarbonyl propyl, propoxypropyl, 2-oxygen-4-methoxybutyl, octyloxy propyl group, 3-ethoxycarbonyl propyl, 3-(2-ethyl hexyl oxy) propyl group etc. can be enumerated。

-R³¹-CO-O-R³²Methoxycarbonylmethyl, dion e, ethoxy carbonyl methyl, ethoxycarbonylethyl group, propoxycarbonyl methyl, propoxycarbonylethyl, butoxy carbonyl methyl, butoxy carbonyl ethyl etc. can be enumerated。

-R³¹-O-CO-R³²Acetoxy-methyl, Acetoxvethyl, ethylcarbonyl group oxygen ylmethyl, ethylcarbonyl group oxygen base ethyl, propyl group carbonyloxymethyl, propyl group ketonic oxygen base ethyl, butyl carbonyloxymethyl, butyl ketonic oxygen base ethyl etc. can be enumerated。

-SO₂R²⁹Sulfonic group can be enumerated；Sulfamoyl；

N-Methylsulfamoyl, N-ethylsulfamovl, N-propylsulfamov, N-isopropylsulfamoyl base, N-Butylsulfamoyl base, 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-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) sulfamoyl, the sulfamoyl that the aliphatic alkyls such as N-acrylic sulfamoyl replace；

N-(2-methoxy ethyl) sulfamoyl, N-(2-ethoxyethyl group) sulfamoyl, N-(1-methoxy-propyl) sulfamoyl, N-(3-methoxy-propyl) sulfamoyl, N-(3-ethoxycarbonyl propyl) sulfamoyl, N-(3-propoxypropyl) sulfamoyl, N-(3-isopropoxide propyl) sulfamoyl, N-(3-hexyloxy propyl group) sulfamoyl, N-(2-ethyl hexyl oxy propyl group) sulfamoyl, N-(3-tert-butoxy propyl group) sulfamoyl, N-(4-octyloxy butyl) sulfamoyls etc. are by-R³¹-O-R³²The sulfamoyl replaced；

N-(Methoxycarbonylmethyl) sulfamoyl, N-(dion e) sulfamoyl, N-(ethoxy carbonyl methyl) sulfamoyl, N-(ethoxycarbonylethyl group) sulfamoyl, N-(propoxycarbonyl methyl) sulfamoyl, N-(propoxycarbonylethyl) sulfamoyl, N-(butoxy carbonyl methyl) sulfamoyl, N-(butoxy carbonyl ethyl) sulfamoyl etc. are by-R³¹-CO-O-R³²The sulfamoyl replaced；

N-(acetoxy-methyl) sulfamoyl, N-(Acetoxvethyl) sulfamoyl, N-(ethylcarbonyl group oxygen ylmethyl) sulfamoyl, N-(ethylcarbonyl group oxygen base ethyl) sulfamoyl, N-(propyl group carbonyloxymethyl) sulfamoyl, N-(propyl group ketonic oxygen base ethyl) sulfamoyl, N-(butyl carbonyloxymethyl) sulfamoyl, N-(butyl ketonic oxygen base ethyl) sulfamoyl etc. are by-R³¹-O-CO-R³²The sulfamoyl replaced；

The sulfamoyl that cyclohexyl that N-cyclohexylsulfamoyl, N-(2-methylcyclohexyl) sulfamoyl, N-(3-methylcyclohexyl) sulfamoyl, N-(4-methylcyclohexyl) sulfamoyl, N-(4-butylcyclohexyl) sulfamoyl etc. are had substituent group is replaced；

The sulfamoyl etc. that N-benzyl sulfamoyl, N-(1-phenylethyl) sulfamoyl, N-(2-phenylethyl) sulfamoyl, N-(3-phenyl propyl) sulfamoyl, N-(4-phenyl butyl) sulfamoyl, N-[2-(2-naphthyl) ethyl] sulfamoyl, N-[2-(4-aminomethyl phenyl) ethyl] sulfamoyl, N-(3-phenyl-1-propyl group) sulfamoyl, N-(3-phenyl-1-methyl-propyl) sulfamoyl etc. are replaced by aralkyl。

-SO₂R²⁹For-SO₂R³²、-SO₂H or-SO₂NHR³⁰。Wherein preferred-SO₂R³²And-SO₂NHR³⁰。

-SO₂NHR³⁰In R³⁰It is preferably 1 valency aliphatic alkyl of hydrogen atom or carbon number 1～8, more preferably hydrogen atom or 2-ethylhexyl。

When the compound of the present invention has-SO₂R³²Time, it is preferable that R¹¹～R¹⁴In at least one and R¹⁵～R¹⁸In at least one be-SO₂R³²。When having multiple-SO₂R³²Time, multiple R³²May be the same or different each other。

-SO₂R³²In R³²It it is 1 valency aliphatic alkyl of carbon number 1～8, it is preferable that 1 valency aliphatic alkyl of carbon number 1～4。-SO₂R³²Can enumerate, methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropelsulfonyl, normal-butyl sulfonyl, sec-butylsulfonyl, tert. butylsulfonyl, pentylsulfonyl, hexyl sulfonyl, heptyl sulfonyl, octyl group sulfonyl, 1-methyl butyl sulfonyl, 1; 1; 3; 3-tetramethyl butyl sulfonyl, 1; 5-dimethylhexanyl sulfonyl, 1,6-dimethyl heptyl sulfonyl, 2-ethylhexyl sulfonyl and 1,1; 5,5-tetramethylhexyl sulfonyls etc.。Wherein, it is preferable that methyl sulphonyl and ethylsulfonyl, more preferably methyl sulphonyl。

R¹～R¹⁸Preferably it is each independently hydrogen atom, nitro or-SO₂R²⁹。

R¹～R¹⁸Among, it is preferable that at least one is hydrogen atom。Additionally, R¹～R¹⁰It is each independently hydrogen atom, R¹⁰～R¹⁸Among, it is hydrogen atom more preferably at one。Additionally, it is preferred that R¹¹～R¹⁴Among at least one and R¹⁵～R¹⁸Among at least one be hydrogen atom。

Based on the tendency with high-fire resistance, it is preferable that R¹～R¹⁸Among at least one be nitro, more preferably R¹¹～R¹⁸Among at least one be nitro。Additionally, it is preferred that R¹¹～R¹⁴Among at least one and R¹⁵～R¹⁸Among at least one is nitro。

Furthermore it is preferred that R¹～R¹⁸In at least one be-SO₂R²⁹, more preferably R¹¹～R¹⁸Among at least one be-SO₂R²⁹。Additionally, it is preferred that R¹¹～R¹⁴At least one and R¹⁵～R¹⁸Among at least one be-SO₂R²⁹。When having multiple-SO₂R²⁹Time, multiple R²⁹May be the same or different each other。

Additionally, R¹～R¹⁰It is each independently hydrogen atom, R¹¹～R¹⁴At least one and R¹⁵～R¹⁸Among at least one be hydrogen atom, R¹¹～R¹⁴At least one and R¹⁵～R¹⁸Among at least one be nitro, it is preferred that R¹¹～R¹⁴At least one and R¹⁵～R¹⁸Among at least one be-SO₂R²⁹。

R¹⁹And R²⁰It is each independently hydrogen atom, methyl, ethyl or amino, is more preferably each independently methyl or ethyl。

Based on the point improving colour saturation, R²¹～R²⁴Preferred hydrogen atom maybe can have 1 valency aliphatic alkyl of the carbon number 1～8 of substituent group, more preferably 1 valency aliphatic alkyl of hydrogen atom or carbon number 1～8, it is preferred that 1 valency aliphatic alkyl of the carbon numbers such as ethyl 1～4。

R²⁵And R²⁶It is each independently hydrogen atom or methyl, it is preferable that be each independently hydrogen atom。

R²⁷Preferred ethylidine and trimethylene, more preferably ethylidine。

N is the integer of 0～3, it is preferable that the integer of 0～2, more preferably 0。When n is these numerical value, the raw material of compound (1) is easier to start with。

Additionally, more preferably R¹～R¹⁰It is each independently hydrogen atom, R¹¹～R¹⁴At least one and R¹⁵～R¹⁸Among at least one be hydrogen atom, R¹¹～R¹⁴At least one and R¹⁵～R¹⁸Among at least one be nitro, R¹¹～R¹⁴At least one and R¹⁵～R¹⁸Among at least one be-SO₂R²⁹, R¹⁹And R²⁰It is each independently methyl, R²¹～R²⁴It is each independently 1 valency aliphatic alkyl of carbon number 1～4, R²⁵And R²⁶Being each independently hydrogen atom, n is 0, R²⁹It is-R³², R³²It it is 1 valency aliphatic alkyl of carbon number 1～4。

Among compound (1), it is preferred that pyrazoles azo-compound complex anion part can the compound etc. shown in enumerative (1-a1)～formula (1-a64)。

Among compound (1), the preference of complex anion can be enumerated, the anion etc. shown in formula (1-b1)～formula (1-b60)。

Among compound (1), it is preferred that origin can the cation etc. shown in enumerative (1-c1)～formula (1-c36) in the cation example of xanthene compounds。

Compound (1) can pass through following reaction and prepare: use the compound (below also referred to as " compound (1d) ") shown in formula (1d) and chromium compound to form chromium complex salt, then this chromium complex salt and xanthene compounds generation salt exchange reaction are made, or use compound (1d) and cobalt compound to form cobalt complex salt, then make this cobalt complex salt and xanthene compounds (b) that salt exchange reaction occurs。

[in formula (a4), R¹～R⁵、R¹¹～R¹⁴And R¹⁹Meaning ibid。]

[in formula (b), R²¹～R²⁷And the meaning of n is ibid。A^-Represent 1 valency anion。]

1 valency anion can enumerate Cl^-、Br^-、I^-、ClO₄ ^-、PF₆ ^-Or BF₄ ^-Deng。

Xanthene compounds (b) can prepare by making the compound shown in formula (b0) react in organic solvent with the compound shown in formula (b1)。

[formula (b0) and in formula (b1), R²¹～R²⁷, n and A^-Meaning ibid。]

In above-mentioned reaction, reaction temperature preferably 15 DEG C～60 DEG C, preferably 1 hour～12 hours response time。Additionally, based on shortening the response time or improving the point of productivity, it is preferred to use acid catalyst and/or dehydrant。

Acid catalyst can enumerate sulphuric acid, p-methyl benzenesulfonic acid etc.。

Dehydrant can be enumerated, the carbodiimide class such as dicyclohexylcarbodiimide, DIC, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride；1-alkyl-2-pyridinium halide salt；1,1 '-carbonyl dimidazoles；Two (2-oxygen-3-oxazolidinyl) secondary phosphoryl chloride phosphorus oxychloride；Two-2-pyridine radicals carbonate etc.。Wherein, as dehydrant, based on easily carrying out post processing and refining point, it is preferable that 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride。

Can enumerate as the organic solvent used in above-mentioned reaction, dichloromethane, chloroform, oxolane, toluene, acetonitrile etc.。

The compound (1d) becoming complex anion part of compound (1) can be prepared by the method known in dye field, diazol and pyrazole compound carry out diazo coupling。Such as, the compound shown in formula (1b) that the amine (below also referred to as " amine (1a) ") shown in formula (1a) is obtained by nitrous acid, nitrite or nitrites diazotising can be used as above-mentioned diazol。

[formula (1a) and in formula (1b), R¹¹～R¹⁴Meaning ibid。A^1-Represent inorganic or organic anion。]

Above-mentioned inorganic anion can be enumerated, for instance fluoride ion, chloride ion, bromide ion, iodide ion, high chloro acid ion, hypochlorite ion etc.。Above-mentioned organic anion can be enumerated, for instance CH₃COO^-、C₆H₅COO^-Deng。Preferred chloride ion, bromide ion, CH₃COO^-Deng。

By in aqueous solvent, the diazo coupling of compound shown in formula (1b) and compound shown in formula (1c) can manufacture the compound (below also referred to as " compound (1d) ") shown in formula (1d)。Reaction temperature preferably-5 DEG C～60 DEG C, more preferably 0 DEG C～30 DEG C。Preferably 1 hour～12 hours response time, more preferably 1 hour～4 hours。Above-mentioned aqueous solvent can be enumerated, for instance N-Methyl pyrrolidone etc.。

[in formula (1c), R¹～R⁵And R¹⁹Meaning ibid。]

When compound (1d) has-SO₂R²⁹,-SO₂R²⁹For-SO₂NHR³⁰Time, though can use, there is-SO₂NHR³⁰Amine (1a) manufacture, but have after sulfonic amine (1a) carries out coupling reaction preferably in use, then sulfonic group sulfuryl amine prepared。Such as, in compound (1d), first synthesis has sulfonic azo-compound (hereinafter referred to as " compound (1s) "), again through thionyl halide compound p-sulfonic acid base (-SO₃H) sulphonyl halogenation (-SO is carried out₂X；X is halogen atom) obtain sulfonyl halogen compound, then pass through and make sulfonyl halogen compound and amine (R³⁰NH₂) react, sulfuryl amine sulfonic group, manufacture compound (1d)。

The concrete example of compound (1s) can be enumerated, compound shown in formula (1-a1), formula (1-a2), formula (1-a5)～(1-a20), it is preferable that the compound shown in formula (1-a5), (1-a6), (1-a15) and (1-a16)。Thionyl halide compound can be enumerated, thionyl fluoride, thionyl chloride, thionyl bromide, sulfurous acyl iodides etc., it is preferable that thionyl chloride, thionyl bromide etc., it is particularly preferred to thionyl chloride。Thionyl halide make consumption relative to 1 mole compound (1s), it is preferable that 1～10 mole。Separately, when reaction system is mixed into water, it is preferable that be excessively used thionyl halide compound。

Sulphonyl halogenation carries out in a solvent。Solvent can use, for instance the ethers (particularly preferably cyclic ethers class) such as Isosorbide-5-Nitrae-dioxanes；The halogenated hydrocarbons etc. such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethanes, dichloroethylene, trichloro ethylene, perchloroethylene, dichloropropane, chloropentane, glycol dibromide。Solvent make consumption relative to 1 mass parts compound (1s), for instance be below more than 3 mass parts (preferably more than 5 mass parts), 10 mass parts (preferably below 8 mass parts)。

Additionally, for sulphonyl halogenation, it is preferable that and with N, N-dialkylformamide (such as, DMF, N, N-diethylformamide etc.)。When use N, N-dialkylformamide time, its make consumption relative to 1 mole of thionyl halide compound for such as, 0.05～1 mole。It is pre-mixed compound (1s) and N, N-dialkylformamide in a solvent, adds thionyl halide compound afterwards again, heating can be suppressed。

Reaction temperature during sulphonyl halogenation be such as, more than more than 0 DEG C, preferably 30 DEG C, below less than 70 DEG C, preferably 60 DEG C。Response time be such as, more than more than 0.5 hour, preferably 3 hour, below less than 8 hours, preferably 5 hour。

After can being isolated by the sulfonyl halogen compound of upper modulation again with amine (R³⁰NH₂) reaction, it is possible to do not carry out isolating and directly as reactant mixture and amine (R³⁰NH₂) reaction。Separately, when isolating, for instance can hybrid reaction mixture and water, leaching precipitate out crystallization。Obtain sulfonyl halogen compound crystallization with amine (R³⁰NH₂) before reaction, can carry out as required washing and drying。

Amine (R³⁰NH₂) comprise n-pro-pyl amine, n-butylamine, n-hexyl amine, dimethylhexylamine (1,5-dimethylhexylamine etc.), tetramethyl butyl amine (1,1,3,3-tetramethyl butyl amine etc.), DEHA (2-DEHA etc.), aminophenyl butane (3-amino-1-phenyl butane etc.), isopropoxide propyl amine etc.。Amine (R³⁰NH₂) make consumption relative to 1 mole of sulfonyl halogen compound, more than 2 moles, less than 10 moles, it is preferable that less than 7 moles。

Sulfonyl halogen compound and amine (R³⁰NH₂) order of addition be not particularly limited, but preferably in sulfonyl halogen compound add (dropping) amine (R³⁰NH₂)。Additionally, sulfonyl halogen compound and amine (R³⁰NH₂) reaction preferably carry out in a solvent。Solvent can use the solvent identical with when modulating sulfonyl halogen compound。

Additionally, sulfonyl halogen compound and amine (R³⁰NH₂) reaction carry out preferably under the existence of base catalyst。Base catalyst can be enumerated, for instance the tertiary amine (aliphatic tertiary amine such as triethylamine, triethanolamine；The aromatic nitrile bases such as pyridine), and the secondary amine (secondary aliphatic amine such as diethylamide；The annular aliphatic secondary amine such as piperidines) etc.。Wherein, it is preferable that the aliphatic tertiary amines such as tertiary amine, especially triethylamine。Base catalyst make consumption relative to amine (R³⁰NH₂), more than 1.1 moles, less than 6 moles, it is preferable that more than 1.1 moles, less than 5 moles。

Amine (R is added in sulfonyl halogen compound³⁰NH₂) and during base catalyst, the interpolation of base catalyst is not particularly limited opportunity, can at amine (R³⁰NH₂) before or after add, it is possible to amine (R³⁰NH₂) add simultaneously。In addition, it is possible to add again after mixing with reactive amine in advance, it is possible to amine (R³⁰NH₂) individually add。

Sulfonyl halogen compound and amine (R³⁰NH₂) reaction temperature be such as more than 0 DEG C, less than 50 DEG C, it is preferable that more than 0 DEG C, less than 30 DEG C。In addition the response time is 1～5 hour。

The method obtaining the compound (1d) as purpose compound from reactant mixture is not particularly limited, and can adopt known various method。For example, it is preferable to reactant mixture is mixed jointly with acid (such as acetic acid etc.) and water, then the crystallization that leaching precipitates out。Preferably in advance above-mentioned acid is modulated into aqueous acid, then added in above-mentioned aqueous solution by reactant mixture。Temperature preferably more than 10 DEG C less than 50 DEG C during interpolation reactant mixture, more preferably more than 20 DEG C less than 50 DEG C, it is preferred that more than 20 DEG C less than 30 DEG C。Furthermore it is preferred that after adding reactant mixture to aqueous acid, stir 0.5～2 hours at the temperature disclosed above further。The crystallization of leaching is preferably cleaned with water etc., then dries。Additionally, also can as required, be purified further by known methods such as recrystallization。

(the M in formula (1) when the anionicsite of compound (1) is chromium complex anion¹For Cr), can pass through to make compound (1d) and chromium compound react at 70～100 DEG C in aqueous solvent and manufacture。Compound (1d) and chromium compound preferably react with mol ratio 2: 1～4: 1。

Above-mentioned chromium compound can be enumerated, chromic formate, chromium acetate, Chlorizate chromium, charomic fluoride etc., it is preferable that chromic formate, chromium acetate, chromium ammonium suplhate (III) 12 water etc.。

Compound (1) can pass through to make chromium complex salt and xanthene compounds (b) occur salt exchange reaction to manufacture in a solvent。Chromium complex salt and xanthene compounds (b) is preferably made to react with mol ratio 1: 1～1: 4。

(the M in formula (1) when the anionicsite of compound (1) is cobalt complex anion¹For Co), can pass through to make compound (1d) and cobalt compound react at 70～100 DEG C in aqueous solvent and manufacture。Compound (1d) and cobalt compound is preferably made to react with mol ratio 2: 1～4: 1。

Above-mentioned cobalt compound can be enumerated, cobaltous chloride, cobalt acetate, cobaltous sulfate, acetylacetone cobalt (III) etc., it is preferable that acetylacetone cobalt (III) etc.。

Compound (1) can by making cobalt complex salt and xanthene compounds occur salt exchange reaction to manufacture in a solvent。Cobalt complex salt and xanthene compounds (b) is preferably made to react with mol ratio 1: 1～1: 4。

Compound (1) specifically can be enumerated, the compound etc. shown in formula (1-1)～formula (1-26)。

The content of compound (1) is in coloring agent (A), it is preferable that below more than 1 mass % 99 mass %, more preferably below more than 1 mass % 80 mass %, it is preferred that below more than 3 mass % 70 mass %。

Coloring agent (A) can contain compound (1) simultaneously and be different from the dyestuff of compound (1)。This dyestuff can be enumerated, the dyestuffs such as the sulfamide derivative of oil-soluble dyes, acid stain, the amine salt of acid stain or acid stain, include, for example, Colour Index (TheSocietyofDyersandColourists publication) is classified as the compound of dyestuff or the known dye recorded in dyeing handbook (Se Ran society)。

Specifically, (" C.I. solvent yellow " omitted below, only records numbering to C.I. solvent yellow 4。), 14,15,23,24,38,62,63,68,82,94,98,99,162,

C.I. solvent red 45,49,125,130,

C.I. solvent orange 2, the C.I. solvent dyes such as 7,11,15,26,56；

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, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 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, the C.I. acid staiies such as 7,9,17,19；

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

C.I. mordant dye can enumerate C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65,

C.I. mordant rouge 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. mordant dyeing 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. the C.I. mordant dye etc. such as mordant dyeing purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58。

Coloring agent (A) can contain pigment and compound (1) further simultaneously。

Pigment can be enumerated, organic pigment, such as, C.I. pigment violet 1, the violet pigments such as 19,23,29,32,36,38；C.I. the yellow uitramarine such as 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；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, the red pigments etc. such as 97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264,265。Wherein preferably at least contain selected from C.I. pigment yellow 13 8,139,150, one in C.I. paratonere 177,242,254。By containing above-mentioned pigment, it is possible to making the easy optimization of transmission spectrum, chemical-resistant improves。

These pigment can individually or two or more mixing use。

Organic pigment can implement following process as required: surface treatment that Colophonium processed, used the pigment derivative etc. having imported acidic groups or basic group, grafting surface of pigments carried out via macromolecular compound etc. process, the micronized that carries out via sulfuric acid particles method etc. processes, or for removing the clean process of organic solvent or the water etc. of impurity, for the removing process etc. of ion exchange etc. of deionizing impurity。

Organic pigment preferable particle size is homogeneous。By so as to carry out dispersion process containing pigment dispersing agent, the pigment dispersible pigment dispersion in the state being uniformly dispersed in solution can be obtained。

Above-mentioned pigment dispersing agent can be enumerated, for instance, cation system, anion system, nonionic system, both sexes, Polyester, polyamine system, the surfactant etc. such as acrylic acid series。These pigment dispersing agents can be used alone or in combination of two kinds or more。Pigment dispersing agent can be enumerated with trade name, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Off ロ mono-レ Application (common prosperity society chemistry (strain) system), ソ Le スパ mono-ス (ゼネカ (strain) system), EFKA (CIBA society system), アジスパ mono-(gourmet powder Off アイ Application テ Network ノ (strain) system), Disperbyk (PVC Star Network ケミ mono-society system) etc.。

When using pigment dispersing agent, it makes consumption relative to pigment (A2), it is preferable that 100 mass %, more preferably below more than 5 mass % 50 mass %。When making consumption in above-mentioned scope of pigment dispersing agent, there is the tendency of the dispersible pigment dispersion obtaining homogeneous dispersity。

When in coloring agent (A) containing pigment, the content of this pigment preferably 1～99 mass %, more preferably 10～97 mass %。

The content ratio (mass ratio) of compound (1) and pigment preferably 1: 99～99: 1, more preferably 3: 97～90: 10。By so as to be such ratio, it is possible to easily optimization transmission spectrum, it is thus achieved that good high-contrast, high brightness。Further, thermostability, chemical-resistant also improve。

Especially, the mass ratio of compound (1) and at least one in C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. paratonere 177, C.I. paratonere 242 and C.I. paratonere 254 preferably 3: 97～90: 10, more preferably 3: 97～70: 30。

The content of coloring agent (A) is relative to the solid constituent in photosensitive composition, it is preferable that 5～60 mass %, more preferably 8～55 mass %, it is preferred that 10～50 mass %。Herein, solid constituent refers to the total of the composition removing solvent in photosensitive composition。If the content of coloring agent (A) is in above-mentioned scope, then as color filter, there is enough colour saturations, and can make containing enough binder polymers in compositions, and then the sufficient pattern of mechanical strength can be formed。

The photosensitive composition of the present invention contains resin (B)。Resin (B) is not particularly limited, but preferred bases soluble resin。

Resin (B) can be enumerated, for instance following resin [K1]～[K4] etc.。

[K1] has the copolymer of the cyclic ether structure of carbon number 2～4 and the monomer (a) (below also referred to as " (a) ") of ethylene unsaturated bond and at least one (b) (below also referred to as " (b) ") among unsaturated carboxylic acid and unsaturated carboxylic acid anhydride。

[K2] (a) and (b) with can with the copolymer of the monomer (c) (wherein, (a) is different from (b)) (below also referred to as " (c) ") of (a) copolymerization

The copolymer of [K3] (b) and (c)

The resin that [K4] makes the copolymer of (b) and (c) react with (a) and obtain。

By making resin (B) containing origin in the construction unit of (a), can further improve the reliability of the thermostability of the multicolour pattern of acquisition, chemical-resistant etc.。

(a) refer to have such as, the polymerizable compound of the cyclic ether structure (such as, at least one among oxirane ring, epoxy butane ring and oxolane ring (butyl oxide link)) of carbon number 2～4 and ethylene unsaturated bond。A () is preferably has the cyclic ether of carbon number 2～4 and the monomer of (methyl) acryloxy。

Separately, in this manual, " (methyl) acrylic acid " represents at least one among acrylic acid and methacrylic acid。The narration of " (methyl) acryloyl group " and " (methyl) acrylate " etc. also has the identical meaning。

A () can enumerate, such as, the monomer (a1) (below also referred to as " (a1) ") with epoxy ethyl and ethylene unsaturated bond, the monomer (a2) (below also referred to as " (a2) ") with epoxybutyl and ethylene unsaturated bond, there is the monomer (a3) (below also referred to as " (a3) ") etc. of tetrahydrofuran base and ethylene unsaturated bond。

(a1) can enumerate, for instance, there is the monomer (a1-1) (below also referred to as " (a1-1) ") of chain type alkene epoxidation structure, there is the monomer (a1-2) (below also referred to as " (a1-2) ") of ring type alkene epoxidation structure。

(a1-1) can enumerate, (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl ester, vinyl glycidyl ether, adjacent ethylene benzyl glycidyl ether, between ethylene benzyl glycidyl ether, to ethylene benzyl glycidyl ether, Alpha-Methyl neighbour's ethylene benzyl glycidyl ether, an Alpha-Methyl-ethylene benzyl glycidyl ether, Alpha-Methyl-to ethylene benzyl glycidyl ether, 2,3-bis-(glycidoxypropyl methyl) styrene, 2,4-bis-(glycidoxypropyl methyl) styrene, 2,5-bis-(glycidoxypropyl methyl) styrene, 2,6-bis-(glycidoxypropyl methyl) styrene, 2,3,4-tri-(glycidoxypropyl methyl) styrene, 2,3,5-tri-(glycidoxypropyl methyl) styrene, 2,3,6-tri-(glycidoxypropyl methyl) styrene, 3,4,5-tri-(glycidoxypropyl methyl) styrene, 2,4,6-tri-(glycidoxypropyl methyl) styrene etc.。

(a1-2) can enumerate, a vinylcyclohexene oxide, 1,2-epoxy-4 vinyl cyclohexene (such as, セロキサイ De 2000；ダイセ Le chemical industry (strain) make), 3,4-epoxycyclohexyl-methyl (methyl) acrylate (such as, サイ Network ロマ mono-A400；ダイセ Le chemical industry (strain) make), 3,4-epoxycyclohexyl-methyl (methyl) acrylate (such as, サイ Network ロマ mono-M100；ダイセ Le chemical industry (strain) makes), the compound shown in formula (I) and the compound etc. shown in formula (II)。

[formula (I) and in formula (II), R^aAnd R^bRepresenting hydrogen atom or the alkyl of carbon number 1～4 independently of one another, the hydrogen atom that this alkyl comprises can be optionally substituted by a hydroxyl group。

X¹And X²Represent singly-bound ,-R independently of one another^c-、*-R^c-O-、*-R^c-S-、*-R^c-NH-。

R^cRepresent the alkylidene of carbon number 1～6。

* the bonding position with O is represented。]

The alkyl of carbon number 1～4 can be enumerated, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.。

The alkyl that hydrogen atom is optionally substituted by a hydroxyl group can be enumerated, methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc.。

R^aAnd R^bPreferably enumerate hydrogen atom, methyl, methylol, 1-hydroxyethyl, 2-hydroxyethyl, more preferably enumerate hydrogen atom, methyl。

Alkylidene can be enumerated, methylene, ethylidine, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene etc.。

X¹And X²Preferably enumerate singly-bound, methylene, ethylidine, *-CH₂-O-(* represents the bonding position with O) base, *-CH₂CH₂-O-base, more preferably enumerates singly-bound, *-CH₂CH₂-O-base。

Compound shown in formula (I) can be enumerated, the compound etc. shown in formula (I-1)～formula (I-15)。Preferred enumerative (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11)～formula (I-15)。More preferably enumerative (I-1), formula (I-7), formula (I-9), formula (I-15)。

Compound shown in formula (II) can the compound etc. shown in enumerative (II-1)～formula (II-15)。Preferred enumerative (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11)～formula (II-15)。More preferably enumerative (II-1), formula (II-7), formula (II-9), formula (II-15)。

Compound shown in formula (I) and the compound shown in formula (II) can individually use。In addition it is also possible to arbitrary ratio mixing。During mixing, its blending ratio is with molar ratio computing, it is preferable that formula (I): formula (II) is 5: 95～95: 5, more preferably 10: 90～90: 10, especially preferred 20: 80～80: 20。

The monomer (a2) with epoxybutyl and ethylene unsaturated bond more preferably has the monomer of epoxybutyl and (methyl) acryloxy。(a2) can enumerate, 3-methyl-3-isobutene. pivaloyloxymethyl oxetanes, 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-acryloyl group oxygen base Ethyloxetane etc.。

The monomer (a3) with tetrahydrofuran base and ethylene unsaturated bond more preferably has the monomer of tetrahydrofuran base and (methyl) acryloxy。

(a3) specifically can enumerate, acrylic acid tetrahydro furfuryl ester (such as, PVC ス U one ト V#150, Osaka Organic Chemical Industry (strain) are made), methacrylic acid tetrahydro furfuryl ester etc.。

Based on the point of the reliability that can improve the thermostability of multicolour pattern of acquisition, chemical-resistant etc. further, (a) is preferably (a1)。Further, based on the point of the storage stability of excellent photosensitive composition, more preferably (a1-2)。

B () specifically can enumerate, for instance acrylic acid, methacrylic acid (methacrylate), butenoic acid, neighbour, to unsaturated monocarboxylic acid classes such as vinylbenzoic acids；

The unsaturated dicarboxylic acid classes such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-ethylene phthalandione, 4-ethylene phthalandione, 3,4,5,6-tetrahydrochysene phthalandiones, 1,2,3,6-tetrahydrochysene phthalandione, dimethyl tetrahydro phthalandione, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid；

Methyl-5-norborene-2,3-dicarboxylic acids, 5-carboxyl dicyclo [2.2.1]-2-heptene, 5,6-dicarboxyl dicyclo [2.2.1]-2-heptene, 5-carboxyl-5-methyl bicycle [2.2.1]-2-heptene, 5-carboxyl-5-ethyl dicyclo [2.2.1]-2-heptene, 5-carboxyl-6-methyl bicycle [2.2.1]-2-heptene, 5-carboxyl-6-ethyl dicyclo [2.2.1]-2-heptene etc. have the dicyclo unsaturated compound class of carboxyl；

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-ethylene anhydride phthalic acid, 4-ethylene anhydride phthalic acid, 3,4,5,6-tetrahydrochysene anhydride phthalic acid, 1,2, the unsaturated dicarboxylic acid class anhydride such as 3,6-tetrahydrochysene anhydride phthalic acids, dimethyl tetrahydro anhydride phthalic acid, 5,6-dicarboxyl dicyclo [2.2.1]-2-heptene anhydride (carbic anhydride)；

The unsaturated list of polybasic carboxylic acid ((methyl) acryloyloxyalkyl) esters of mono succinate (2-(methyl) acrylyl oxy-ethyl), phthalandione list (2-(methyl) acrylyl oxy-ethyl) etc. more than 2 yuan；

Also can enumerate the unsaturated esters of acrylic acid etc. in same a part containing hydroxyl and carboxyl of α-(hydroxymethyl) acrylic compounds。

Wherein, based on the point of copolyreaction or the deliquescent point in aqueous alkali, it is preferable that acrylic acid, methacrylic acid (methacrylate), maleic anhydride etc.。

C () can enumerate, for instance (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecyl acrylate, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, three ring [5.2.1.0^2,6] ten-8-base (methyl) acrylate (in this technical field, are commonly referred to (methyl) acrylic acid dicyclo n-pentyl ester。), dicyclo n-pentyloxy ethyl (methyl) acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid diamantane (obsolete) ester, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) esters of acrylic acid such as (methyl) benzyl acrylate；

Hydroxyl (methyl) esters of acrylic acids such as 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate；

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

Dicyclo [2.2.1]-2-heptene, 5-methyl bicycle [2.2.1]-2-heptene, 5-ethyl dicyclo [2.2.1]-2-heptene, 5-hydroxyl dicyclo [2.2.1]-2-heptene, 5-hydroxymethyl dicyclo [2.2.1]-2-heptene, 5-(2 '-hydroxyethyl) dicyclo [2.2.1]-2-heptene, 5-methoxyl group dicyclo [2.2.1]-2-heptene, 5-ethyoxyl dicyclo [2.2.1]-2-heptene, 5,6-dihydroxy dicyclo [2.2.1]-2-heptene, 5,6-bis-(hydroxymethyl) dicyclo [2.2.1]-2-heptene, 5,6-bis-(2 '-hydroxyethyl) dicyclo [2.2.1]-2-heptene, 5,6-dimethoxy dicyclo [2.2.1]-2-heptene, 5,6-diethoxy dicyclo [2.2.1]-2-heptene, 5-hydroxy-5-methyl base dicyclo [2.2.1]-2-heptene, 5-hydroxyl-5-ethyl dicyclo [2.2.1]-2-heptene, 5-hydroxymethyl-5-methyl bicycle [2.2.1]-2-heptene, 5-tert-butoxycarbonyl dicyclo [2.2.1]-2-heptene, 5-cyclohexyloxy carbonyl dicyclo [2.2.1]-2-heptene, 5-phenyloxycarbonyl dicyclo [2.2.1]-2-heptene, 5,6-bis-(tert-butoxycarbonyl) dicyclo [2.2.1]-2-heptene, the dicyclo unsaturated compound classes such as 5,6-bis-(cyclohexyloxy carbonyl) dicyclo [2.2.1]-2-heptene；

The dicarbonyl imides derivatives class such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-butanimide-3-maleimidobenzoyl ester, N-butanimide-4-malimidobutanoate, N-butanimide-6-maleimide caproate, N-butanimide-3-maleimidopropionic acid ester, N-(9-acridinyl) maleimide；

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

Wherein, based on the point of copolyreaction and thermostability, it is preferable that styrene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1]-2-heptene etc.。

In resin [K1], the ratio of the construction unit of different origin is in the entire infrastructure unit constituting resin [K1], it is preferable that in following scope。

Origin is in the construction unit of (a): 60～98 moles of % (more preferably 65～95 moles of %)

Origin is in the construction unit of (b): 2～40 moles of % (more preferably 5～35 moles of %)

When the ratio of construction unit of resin [K1] is in above-mentioned scope, storage stability, developability, cured pattern solvent resistance have the tendency becoming good。

Resin [K1] is referred to such as, and the document of quoting recorded in the method recorded in document " Polymer Synthesizing laboratory method " (big Jin Longhangzhu publishing house (strain) chemistry is published on March 1st, 1972 with the 1st edition the 1st printing of people) and the document manufactures。

Specifically, can list and (a) and (b) of ormal weight, polymerization initiator and solvent etc. are loaded in reaction vessel, by replacing oxygen with nitrogen, the method stirring under deoxygenation conditions, heating, be incubated。Separately, polymerization initiator used herein and solvent etc. are not particularly limited, and can use normally used any compound in this field。Such as, polymerization initiator can be enumerated, azo-compound (2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.) or organic peroxide (benzoyl peroxide etc.), as long as solvent can dissolve each monomer, the aftermentioned solvent etc. of the solvent as photosensitive polymer combination can be used。

Separately, it is thus achieved that copolymer can directly use reacted solution, it is possible to use concentration or the solution after dilution, it is possible to use by the solid (powder) that the method such as precipitation again is taken out。Solvent during particularly as this polymerization, by using solvent described later (D), can directly use reacted solution, and then can simplify manufacturing process。

In resin [K2], the ratio of the construction unit of different origin is in the entire infrastructure unit constituting resin [K2], it is preferable that in following scope。

Origin is in the construction unit of (a): 2～95 moles of % (more preferably 5～80 moles of %)

Origin is in the construction unit of (c): 1～65 mole of % (more preferably 1～60 mole of %)

When the ratio of construction unit of resin [K2] is in above-mentioned scope, storage stability, developability, the solvent resistance of cured pattern, thermostability and mechanical strength have the tendency becoming good。

Resin [K2] can by with such as, manufacture as the method that the method described in the manufacture method of resin [K1] is identical。

Specifically, can enumerating (a), (b) and (c) of ormal weight, polymerization initiator and solvent etc. load in reaction vessel, by replacing oxygen with nitrogen, and the method stirring under deoxygenation conditions, heating, be incubated。The copolymer obtained can directly use reacted solution, it is possible to use concentration or the solution after dilution, it is possible to use by the solid (powder) that the methods such as precipitation again are taken out。

In resin [K3], the ratio of the construction unit of different origin is in the entire infrastructure unit constituting resin [K3], it is preferable that in following scope。

(b) 2～40 moles of %, more preferably 5～35 moles of %

(c) 60～98 moles of %, more preferably 65～95 moles of %

Resin [K3] can by with such as, manufacture as the method that the method described in the manufacture method of resin [K1] is identical。

Resin [K4] can pass through first to obtain the copolymer of (b) and (c), then makes to obtain on the cyclic ether of carbon number 2～4 that carboxyl addition that (c) have has in (a)。

First, the copolymer of (b) and (c) is manufactured according to the method identical with the method described in the manufacture method as [K1], now, the ratio of the construction unit of different origin is in constituting the entire infrastructure unit of copolymer of (b) and (c), it is preferable that in following scope。

(b) 5～50 moles of %, more preferably 10～45 moles of %

(c) 50～95 moles of %, more preferably 55～90 moles of %

Then, the part reaction of carboxyl that the cyclic ether of the carbon number 2～4 that (a) have and the origin in above-mentioned copolymer comprise in the construction unit of (c) and/or carboxylic acid anhydrides is made。

After the manufacture of the copolymer of (b) and (c), and then the atmosphere gas in flask is replaced as air by nitrogen, the total amount pressing the catalysts (such as three (dimethylaminomethyl) phenol etc.) of (a), carboxyl and cyclic ether relative to (a)～(c) is 0.001～5 mass %, and polymerization inhibitor (such as hydroquinone etc.) etc. is that 0.001～5 mass % joins in flask by the total amount relative to (a)～(c), such as, reaction 1～10 hour at 60～130 DEG C, be derived from resin [K4]。The reaction condition of loading method, reaction temperature and time etc. it is contemplated that manufacture equipment or polymerization caloric value etc. suitably adjust。Separately, same to polymerizing condition, it is contemplated that to manufacture equipment or polymerization caloric value etc., suitably adjust loading method or reaction temperature。

Now (a) make consumption relative to (b), it is preferable that 5～80 moles of %, more preferably 10～75 moles of %, more preferably 15～70 moles of %。When making it within the scope of this, there is the tendency that the balance of storage stability, developability, solvent resistance, thermostability, mechanical strength and sensitivity improves。

Resin (B) specifically can be enumerated, 3,4-epoxycyclohexyl-methyl (methyl) acrylate/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0^2.6] resin [K1] such as decyl acrylate/(methyl) acrylic copolymer；(methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/styrene/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0^2.6] resin [K2] such as decyl acrylate/(methyl) acrylic acid/N-N-cyclohexylmaleimide copolymer, 3-methyl-3-(methyl) acryloyloxymethyl oxetanes/(methyl) acrylic/styrene copolymer；The resins [K3] such as (methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) acrylic copolymer；On (methyl) benzyl acrylate/(methyl) acrylic copolymer, addition has the resin of (methyl) glycidyl acrylate, on tricyclodecyl (methyl) acrylate/styrene/(methyl) acrylic copolymer, addition has the resin of (methyl) glycidyl acrylate, on tricyclodecyl (methyl) acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, addition has the resins [K4] etc. such as the resin of (methyl) glycidyl acrylate。Wherein, it is preferable that resin [K1] and resin [K2], more preferably resin [K1], it is preferred that 3,4-epoxy three ring [5.2.1.0^2.6] decyl acrylate/(methyl) acrylic copolymer。

The weight average molecular weight of the polystyrene conversion of resin (B) preferably 3,000～100,000, more preferably 5,000～50,000, it is preferred that 5,000～35,000, it is particularly preferred to 6,000～30,000, it is particularly preferred that 7,000～28,000。When molecular weight is in above-mentioned scope, has and improve the tendency that hardness of film, residual film ratio be high, unexposed portion improves for the favorable solubility of developer solution, exploring degree。

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

The acid number of resin (B) preferably 50～150, more preferably 60～135, it is preferred that 70～135。Acid number refers to the measured value neutralizing the potassium hydroxide amount (mg) required for 1g resin (B) herein, for instance can by using potassium hydroxide aqueous solution titration to try to achieve。

The content of resin (B) is relative to the solid constituent of photosensitive composition, it is preferable that 7～65 mass %, more preferably 13～60 mass %, it is preferred that 17～55 mass %。When the content of resin (B) is in above-mentioned scope, pattern can be formed, there is tendency in addition that carry high-resolution and residual film ratio。

The photosensitive composition of the present invention contains photopolymerizable compound (C)。Photopolymerizable compound (C) refers to according to being irradiated the compound that the living radical making Photoepolymerizationinitiater initiater (D) produce and acid etc. carry out being polymerized by light, include, for example the compound etc. of the ethylene unsaturated bond with polymerism, it is preferable that (methyl) acrylate compounds。

Wherein, photopolymerizable compound (C) preferably has the photopolymerizable compound of more than 3 ethylene unsaturated bonds。Such photopolymerizable compound can be enumerated, for instance tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylates, dipentaerythritol acrylate, dipentaerythritol hexamethacrylate etc.。Photopolymerizable compound (C) can be used singly or two or more kinds in combination。

The content of photopolymerizable compound (C) is relative to the solid constituent of photosensitive composition, it is preferable that 7～65 mass %, more preferably 13～60 mass %, it is preferred that 17～55 mass %。When the content of above-mentioned photopolymerizable compound (C) is in above-mentioned scope, having solidification abundant, the film thickness ratio before and after development improves, and not easily forms undercutting (undercut), adhesion in pattern well, so preferably。

The photosensitive composition of the present invention contains Photoepolymerizationinitiater initiater (D)。

Above-mentioned Photoepolymerizationinitiater initiater (D) is as long as produce the rear compound starting polymerization such as living radical, acid by the effect of light and be namely not particularly limited, it is possible to use known polymerization initiator。Photoepolymerizationinitiater initiater (D) while containing by the compound of effect generation living radical, the acid etc. of light, can cause auxiliary agent (D1) possibly together with photopolymerization。Photopolymerization causes auxiliary agent (D1) to be the compound or sensitizer that use to promote the polymerization of the photopolymerizable compound by Photoepolymerizationinitiater initiater initiation polymerization。

Photoepolymerizationinitiater initiater (D) is preferably by the compound of the effect generation living radical of light; more preferably the Photoepolymerizationinitiater initiater of at least one among benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime compound and double imidazole compound is contained, it is preferred that the Photoepolymerizationinitiater initiater containing oxime compound。

Benzene alkyl ketone compound can be enumerated, diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methylsulfonyl phenyl)-1-acetone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl-1-butanone, 2-dimethylamino-1-(4-morphlinophenyl)-2-(4-methylphenylmethyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl)-1-acetone, 1-hydroxycyclohexylphenylketone, the oligomer etc. of 2-hydroxy-2-methyl-1-(4-(1-ethylene methacrylic) phenyl)-1-acetone, preferred 2-methyl-2-morpholino-1-(4-methylsulfonyl phenyl)-1-acetone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl-1-butanone etc.。It is used as the commercially available product of base ガキユア 369,907 (above for チバジヤパ Application society system) etc.。

Triaizine compounds can be enumerated, 2, 4-bis-(trichloromethyl)-6-(4-methoxyphenyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(4-methoxyl group naphthyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-piperonyl-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(4-methoxyl-styrene)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(2-(5-methylfuran-2-base) vinyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(2-(furan-2-base) vinyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(2-(3, 4-Dimethoxyphenyl) vinyl)-1, 3, 5-triazine etc.。

Acylphosphine oxide series initiators can be enumerated, TMDPO etc.。The commercially available products such as イ Le ガキユア 819 (チバジヤパ Application society manufacture) can also be used。

Oxime compound can enumerate N-benzoyloxy-1-(4-phenyl sulfonyl phenyl)-1-butanone-2-imines, N-benzoyloxy-1-(4-phenyl sulfonyl phenyl)-1-octanone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3; 3-dimethyl-2,4-dioxolyl methyl oxygen base) benzoyl }-9H-carbazole-3-base] ethane-1-imines etc.。The commercially available products such as イ Le ガキユア OXE-01, OXE-02 (be above チバジヤパ Application society manufacture), N-1919 (manufacture of ADEKA society) can also be used。

Double imidazole compound can be enumerated, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetraphenyl double imidazole, 2, 2 '-bis-(2, 3-Dichlorobenzene base)-4, 4 ', 5, 5 '-tetraphenyl double imidazole is (such as, consult Japanese Patent Laid-Open 6-75372 publication, Japanese Patent Laid-Open 6-75373 publication etc.), 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetraphenyl double imidazole, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-four (alkoxyl phenyl) double, two imidazoles, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-four (dialkoxy phenyl) double, two imidazoles, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-four (tri-alkoxy phenyl) double, two imidazoles is (such as, consult Japan Patent examined patent publication 48-38403 publication, Japanese Patent Laid-Open No. Sho 62-174204 publication etc.), 4, 4 ', 5, the imidazolinium compounds that 5 '-position phenyl alkoxy phosphinylidyne replaces is (such as, consult Japanese Patent Laid-Open 7-10913 publication etc.) etc.。Preferable examples has 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-bis-(2,3-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-bis-(2,4-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl double imidazole。

Further, Photoepolymerizationinitiater initiater (D) can be enumerated, the Benzoinum compound such as Benzoinum, Benzoinum methyl ether, Benzoinum ethylether, benzoin isobutyl propyl group ether, benzoin isobutyl butyl ether；Benzophenone, o-benzoyl yl benzoic acid methyl ester, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfur, 3; 3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2; the benzophenone cpd of 4,6-tri-methyl benzophenones etc.；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.。Auxiliary agent (D1) (especially amine) combination is caused to use more satisfactory these and photopolymerization described later。

The acid agent being produced acid by light can be enumerated, for instance salt or nitrobenzyl tosylate class, the Benzoinum toluenesulfonic acid salts etc. such as 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate。

Photoepolymerizationinitiater initiater (D) can also be produced living radical and the compound of acid as such as triaizine compounds by light simultaneously。

Photopolymerization causes auxiliary agent (D1) to enumerate, amines, alkoxy anthracene compound, thioxanthone compounds, carboxylic acid compound etc.。

Amine compound can enumerate triethanolamine, methyl diethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl ester, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, benzoic acid-2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid-2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein, preferably 4, 4 '-bis-(diethylamino) benzophenone。The commercially available products such as EAB-F (hodogaya chemical industry (strain) system) can also be used。

The content of Photoepolymerizationinitiater initiater (D) is relative to total amount 100 mass parts of resin (B) and photopolymerizable compound (C), it is preferable that 0.1～30 mass parts, more preferably 1～20 mass parts。When the content of Photoepolymerizationinitiater initiater is in above-mentioned scope, can so as to high-sensitivity, shortening time of exposure, improve productivity ratio。

The photosensitive composition of the present invention can contain photopolymerization further and cause auxiliary agent (D1)。Photopolymerization causes auxiliary agent (D1) generally and Photoepolymerizationinitiater initiater (D) combination uses, and is the compound or sensitizer that use to promote the polymerization of the photopolymerizable compound by Photoepolymerizationinitiater initiater initiation polymerization。

Amines can enumerate triethanolamine, methyl diethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl ester, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, benzoic acid-2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid-2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein, preferably 4, 4 '-bis-(diethylamino) benzophenone。The commercially available products such as EAB-F (hodogaya chemical industry (strain) system) can also be used。

Alkoxy anthracene compound can be enumerated, 9,10-dimethoxy anthracenes, EDMO, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracenes, 2-ethyl-9,10-dibutoxy anthracene etc.。

Thioxanthone compounds can be enumerated, ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc.。

Carboxylic acid compound can be enumerated, phenylSulphon guanidine-acetic acid, aminomethyl phenyl sulphonyl acetic acid, ethylphenyl sulfonyl acetic acid, Methylethyl phenyl sulfonyl acetic acid, 3,5-dimethylphenyl sulfonyl acetic acid, methoxy phenylsulfonyl acetic acid, Dimethoxyphenyl sulfonyl acetic acid, Chlorophenylsulfonyl acetic acid, Dichlorobenzene base sulfonyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N-naphthyl glycine, naphthoxy acetic acid etc.。

Photopolymerization cause auxiliary agent (D1) can individually or combine two or more use。

When using these photopolymerization to cause auxiliary agent (D1), it makes consumption total amount 100 mass parts relative to resin (B) and polymerizable compound (C), it is preferable that 0.01～50 mass parts, more preferably 0.1～40 mass parts。Additionally, relative to Photoepolymerizationinitiater initiater (D) 1 mole, it is preferable that 0.01～10 mole, more preferably 0.01～5 mole。When polymerization causes the amount of auxiliary agent (D1) within the scope of this, pattern can be formed further in high sensitivity, there is the tendency improving pattern productivity ratio。

The photosensitive composition of the present invention contains solvent (E)。

Solvent (E) is not particularly limited, and can use normally used solvent in this field。Use can be selected from the ketone solvent (solvent containing-CO-) beyond the ether solvents (solvent containing-O-) such as, beyond ester solvent (containing the solvent of-COO-), ester solvent, ether-ether solvent (solvent containing-COO-and-O-), ester solvent, alcoholic solvent, aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide etc.。

Ester solvent can be enumerated, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl n-butyrate., butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, ethyl cyclohexyl alcohol ester, gamma-butyrolacton etc.。

Ether solvents can be enumerated, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxyl group-n-butyl alcohol, 3-methoxyl group-3-methyl butanol, oxolane, Pentamethylene oxide., 1, 4-dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, methoxybenzene, ethyl phenyl ether, methyl anisole etc.。

Ether-ether solvent can be enumerated, methoxy menthyl acetate, ethyl methoxyacetate, 2-Methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 2-methoxyl group-2 Methylpropionic acid methyl ester, 2-ethyoxyl-2 Methylpropionic acid ethyl ester, 3-methoxybutyl acetas, 3-methyl-3-methoxybutyl acetas, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetas, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monoethyl ether acetas, butyl carbitol acetate etc.。

Ketone solvent can be enumerated, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, dipropyl ketone, 4-methyl-2 pentanone, Ketocyclopentane, Ketohexamethylene, isophorone etc.。

Alcoholic solvent can be enumerated, methanol, ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol, glycerol etc.。

Aromatic hydrocarbon solvents can enumerate benzene,toluene,xylene, mesitylene etc.。

Amide solvent can enumerate, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone etc.。

These solvents can be used singly or two or more kinds in combination。

Among above-mentioned solvent, based on the point of coating, drying property, it is preferable that the boiling point in 1atm more than 120 DEG C, the organic solvent of less than 180 DEG C。Wherein, preferred propylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N, dinethylformamide, N-Methyl pyrrolidone etc., more preferably propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl lactate, 3-ethoxyl ethyl propionate etc.。When containing these solvents, flatness during coating is excellent。

In photosensitive composition, the content of solvent (E) is relative to photosensitive composition, it is preferable that 70～95 mass %, more preferably 75～92 mass %。In other words, preferably 5～30 mass % of the solid constituent in photosensitive composition, more preferably 8～25 mass %。The content of solvent (E) is in above-mentioned scope, and flatness during coating becomes good, additionally, colour saturation will not be had when forming color filter not enough, therefore display characteristic has the trend improved。

The photosensitive composition of the present invention also can contain surfactant (F) further。Surfactant (F) can be enumerated silicone-based surfactant, fluorine system surfactant and have the silicone-based surfactant etc. of fluorine atom。They can have polymerizable group on side chain。

Can enumerate as silicone-based surfactant, there is the surfactant etc. of siloxane bond。Specifically, for example there are TORAYSILICONEDC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, polyether modified silicone oil SH8400 (trade name: レダウ U one ニ Application グ (strain) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (モメ Application テイ Block パ Off オ mono-マ Application スマテリア Le ズジヤパ Application contract commercial firm manufacture) etc.。

Above-mentioned fluorine system surfactant can enumerate the surfactant etc. with fluoro carbochain。Specifically can enumerate, Off ロラ mono-De (trade name) FC430, same FC431 (Sumitomo スリ mono-エ system (strain) manufacture), メガ Off ア Star Network (trade name) F142D, same F171, same F172, same F173, same F177, same F183, same R30, same RS-718-K (DIC (strain) manufacture), エ Off ト Star プ (trade name) EF301, same EF303, same EF351, same EF352 (Rhizoma Sparganii マテリア Le chemical conversion (strain) system), サ mono-Off ロ Application (trade name) S381, same S382, same SC101, same SC105 (Asahi Glass (strain) system), E5844 (research of (strain) ダイキ Application Off アイ Application ケミ Le is made) etc.。

As the above-mentioned silicone-based surfactant with fluorine atom, the surfactant etc. with siloxane bond and fluoro carbochain can be enumerated。Specifically, for example there are メガ Off ア Star Network (registered trade mark) R08, same to BL20, same to F475, same to F477, same to F443 (DIC (strain) manufacture) etc.。

These surfactants can use alone or in combination of two kinds or more。

The content of surfactant (F), relative to photosensitive composition preferably more than 0.001 mass %, below 0.2 mass %, more preferably more than 0.002 mass %, below 0.1 mass %, it is preferred that more than 0.01 mass %, below 0.05 mass %。The content of surfactant (F) is when above-mentioned scope, it is possible to make the flatness of film improve。

When the photosensitive composition of the present invention is the compositions being made up of coloring agent (A), alkali soluble resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D), solvent (E) and surfactant (F), its coating is excellent, it is possible to obtain solvent resistance and the multicolour pattern of light splitting all excellences。

In the photosensitive composition of the present invention, the content of preferred coloring agent (A) is 0.5～10 mass %, the content of resin (B) is 1～20 mass %, the content of photopolymerizable compound (C) is 1～15 mass %, the content of Photoepolymerizationinitiater initiater (D) is 0.5～10 mass %, and the content of solvent (E) is 45～97 mass %。In addition, more preferably the content of coloring agent (A) is 1～7 mass %, the content of resin (B) is 3～10 mass %, the content of photopolymerizable compound (C) is 3～12 mass %, the content of Photoepolymerizationinitiater initiater (D) is 1～5 mass %, the content of solvent (E) is 66～92 mass %, it is preferred that the content of coloring agent (A) is 2～5 mass %, the content of resin (B) is 4～8 mass %, the content of photopolymerizable compound (C) is 5～10 mass %, the content of Photoepolymerizationinitiater initiater (D) is 2～4 mass %, the content of solvent (E) is 73～87 mass %。

When the photosensitive composition of the present invention using photopolymerization cause auxiliary agent (D1), relative to solid constituent 100 weight portion in photosensitive composition, photopolymerization causes the content of auxiliary agent to be preferably 0.1～10 mass parts, more preferably 0.5～5 mass parts, it is preferred that 1～3 mass parts。

When the photosensitive composition of the present invention uses surfactant (F), relative to solid constituent 100 weight portion in photosensitive composition, the content of surfactant (F) is preferably 0.001～1 mass parts, more preferably 0.01～0.5 mass parts, more preferably 0.05～1 mass parts。

The photosensitive composition of the present invention can contain the various additives such as filler, other macromolecular compounds, adhesion promoter, antioxidant, UV absorbent, light stabilizer, chain-transferring agent as required。

As the method using the photosensitive composition of the present invention to form multicolour pattern, for example there are following method, such as, the photosensitive composition of the present invention is coated on substrate or other resin bed (such as, the other photosensitive composition layer etc. first formed on substrate) on, the volatile ingredients such as removing/dry solvent form dyed layer, expose, via photomask, the method that this dyed layer carries out developing, be used without the method etc. of the ink jet technique of photoetch method。

Now the thickness of film is not particularly limited, it is possible to suitably adjust according to the material used, purposes etc., for instance be 0.1～30 μm, preferably 1～20 μm it is preferred that 1～6 μm。

The coating process of photosensitive composition can be enumerated, for instance extrusion coating methods, direct heliogravure rubbing method, inverse type heliogravure rubbing method, CAP rubbing method, chill coating coating (diecoating) method etc.。In addition it is also possible to use the coating machines such as dip coaterd, scraping strip coating machine, spin coater, slit & spin coater, slit coater (also referred to as DieCoater, CurtainFlowCoater (showering curtain type plane coating machine), SpinlessCoater (non-rotating rubbing method)) to be coated。

The removing of solvent/dry and can enumerate such as natural drying, aeration-drying, drying under reduced pressure, heat drying etc.。Concrete baking temperature preferably 10 DEG C～120 DEG C, more preferably 25 DEG C～100 DEG C。Preferably 10 seconds～60 minutes drying time, more preferably 30 seconds～30 minutes。Drying under reduced pressure is preferably under the pressure of 50～150pa, carry out in the scope of 20～25 DEG C。

Dried film is exposed via the photomask being used for being formed target pattern。The pattern form on photomask now is not particularly limited, and uses pattern form according to intended applications。

The light source that exposure uses, it is preferable that send the light source of the light of the wavelength of 250～450nm。Specifically can enumerate, finsen lamp, light emitting diode, metal halide lamp, Halogen light etc., it is possible to use cut the color filter of particular wavelength region and cut and be exposed, it is possible to use select the band filter in specific wavelength territory and optionally take out and be exposed。

In order to plane of exposure entirety is irradiated parallel rays equably, make mask and the correct para-position of base material, it is preferred to use the device such as mask aligner, step-by-step exposure machine。

After exposure, it is possible to by contacting, make the dissolving of established part such as unexposed portion with developer solution, development obtains pattern。Developer solution can enumerate the aqueous solution etc. of alkali compounds (potassium hydroxide, sodium carbonate, Tetramethylammonium hydroxide etc.)。This developer solution can contain surfactant。

Developing method can use any one in paddling process, infusion process, nebulization etc.。Further, during development, substrate can with arbitrarily angled inclination。Washing it is preferably performed after development。

Further, according to necessity, it is also possible to carry out after bake。After bake is preferably in the scope of 150～230 DEG C, 10～240 minutes。

Can be obtained good film or the patterns such as colour saturation, brightness, contrast, sensitivity, exploring degree, thermostability by the photosensitive composition of the present invention, these are all useful as color filter。Further, it is also possible to using known form be applied to display device that these color filters are had as one part component parts such as, the various all machines relevant to coloured image such as known liquid crystal indicator, organic el device, solid-state imager。

[embodiment]

By the following examples the photosensitive composition of the present invention is illustrated in greater detail。

" % " and " part " in example, as long as being not particularly limited, is quality % and mass parts。

Synthesis example 1

30 portions of rhodamine Bs (Tokyo chemical conversion industry (strain) system) are dissolved in 288 parts of chloroforms, add 2.3 parts of N, N-dimethyl-4-aminopyridines, 1.75 parts of 10-camphorsulfonic acids, 16.24 parts of (+)-2,3-Epoxy-1-propanols, stirred below 1 hour in 20 DEG C。While stirring, drip the chloroformic solution having dissolved 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (Tokyo chemical conversion industry (strain) system) 17.41 parts in chloroform 72 parts and obtain。After reaction terminates, in this reactant liquor, add 1N aqueous hydrochloric acid solution carry out separatory, obtain organic layer。For this organic layer, repeat 2 these operations。Then, in this organic layer, add 10% saline solution carry out separatory, obtain organic layer。For this organic layer, repeat 2 these operations。After adding magnesium sulfate dehydration in the organic layer obtained, filtration obtains filtrate。From this filtrate, remove solvent by vaporizer, the red solid of acquisition is dried at lower 60 DEG C of decompression, is derived from the compound (productivity 89.5%) shown in 30 parts of formulas (d-1)。

The qualification of the compound shown in formula (d-1)

(quality analysis) ionization mode=ESI+:m/z=499.3 [M-Cl^-]⁺

Accurate mass: 534.2

Embodiment 1

After adding 65 parts of water to 7.5 parts of 2-amino-4-methyl sulphonyl-6-nitrophenol (CASNo.101861-04-5), add 1.3 parts of sodium hydroxide so as to dissolve。Add 6.1 part of 35% sodium nitrite (pharmaceutical worker industry (strain) system pure with light) aqueous solution under ice cooling, then add 19.4 part of 35% hydrochloric acid bit by bit so as to dissolve, stir 2 hours, it is thus achieved that containing the suspension of diazol。Then it is slowly added into and 5.6 parts of sulfamic acids (pharmaceutical worker industry (strain) system pure with light) are dissolved in the aqueous solution in 26 parts of water, it is suppressed that excessive sodium nitrite。

Then, making 5.6 parts of Edaravones (pharmaceutical worker industry (strain) system pure with light) be suspended in 70 parts of water, using sodium hydroxide to adjust pH is 8.0。Herein, the suspension containing above-mentioned diazol lasting 15 minutes, the sodium hydroxide solution of dropping 10% makes pH be stabilized to the scope of 7.5 from 7 aptly。After completion of dropwise addition, stirring obtains yellow suspension in 30 minutes further。Stir 1 hour。By being dried at the yellow solid of filtration gained under reduced pressure 60 DEG C, obtain the compound (productivity 87%) shown in 11.7 parts of formulas (p-2)。

The compound of 10 parts of formulas (p-2) is added in the dimethylformamide (Tokyo chemical conversion industry (strain) system) of 100 parts and dissolve, after adding 3.1 parts of chromium ammonium suplhate (III) 12 water (making with light pure pharmaceutical worker industry (strain)), 1.1 parts of sodium acetates (pharmaceutical worker's industry (strain) system pure with light), it is heated to reflux 4 hours half。After being cooled to room temperature, reaction solution is injected in 1500 part of 20% saline solution, the Chinese red solid obtained is dried at 60 DEG C, obtain the compound (productivity 63%) shown in 13.6 parts of formulas (z-2) after filtering。

The qualification of the compound shown in formula (z-2)

(quality analysis) ionization mode=ESI-:m/z=882.1 [M-Na⁺]^-

Accurate mass: 905.1

Make the compound dissolution shown in 5 parts of formulas (z-2) in 75 parts of METHYLPYRROLIDONEs。The solution adding the compound 2.63 parts shown in formula (d-1) to be dissolved in 35 parts of METHYLPYRROLIDONEs in this solution and to obtain, stirs 2 hours。After reaction terminates, 300 parts of water of dropping wherein, the red solid that leaching precipitates out, reduces pressure and is dried at lower 60 DEG C, obtain the compound (productivity 86.8%) shown in 6.4 parts of formulas (1-27) accordingly。

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

(quality analysis) ionization mode=ESI+:m/z=1382.4 [M-Cl^-]⁺

Accurate mass: 1381.3

Synthesis example 2

Becoming nitrogen atmosphere gas with the 0.02L/ speed divided to pouring nitrogen in the flask possess blender, thermometer, reflux condensing tube and Dropping funnel, add 305 mass parts ethyl lactates, while stirring, heating is to 70 DEG C。Then, it is modulated into and has dissolved 60 mass parts methacrylic acids, 240 mass parts 3,4-epoxy three ring [5.2.1.0^2.6] compound shown in following formula (I-1) and the compound shown in formula (II-1) (mix by decyl acrylate with mol ratio 50: 50。) and the solution of 140 mass parts ethyl lactates, this lysate Dropping funnel is lasted 4 hours, is added drop-wise to insulation in the flask of 70 DEG C。On the other hand, by 30 mass parts polymerization initiators 2,2 '-azo two (2,4-methyl pentane nitrile) is dissolved in another Dropping funnels of solution of 225 mass parts ethyl lactates and lasts 4 hours and be added drop-wise in flask。After the completion of dropwise addition of polymerization initiator solution, keeping 4 hours in 70 DEG C, be cooled to thereafter room temperature, obtaining weight average molecular weight Mw is 1.3 × 10⁴, solid constituent 33 mass %, solution acid number 34mg-KOH/g resin B 1 solution。The acid number that can be calculated the solid constituent of resin B 1 by above-mentioned solid constituent and solution acid number is 100mg-KOH/g。

Synthesis example 3

333g propylene glycol methyl ether acetate is imported in the flask possess blender, thermometer, reflux cooling pipe, Dropping funnel and gas introduction tube。Thereafter, importing in flask by gas introduction tube by nitrogen, making the atmosphere gas displacement in flask is nitrogen。Thereafter, after the solution warms in flask to 100 DEG C, use Dropping funnel to last 2 hours in flask, drip the mixture being made up of N-benzyl maleimide 18.7g, benzyl methacrylate 70.5g, methacrylic acid 51.7g, methyl methacrylate 90.0g, azodiisobutyronitrile 5.2g and propylene glycol methyl ether acetate 182g, continue at after completion of dropwise addition and stir 5 hours at 100 DEG C。

After stirring terminates, in flask, air is imported by gas introduction tube, making the atmosphere gas displacement in flask is after air, 28.5g glycidyl methacrylate, 1.3g tri-(dimethylamino methyl) phenol and 0.165g hydroquinone is put in flask, sustained response 6 hours at 110 DEG C, it is thus achieved that weight average molecular weight Mw is 16 × 10³, solid constituent 31%, acid number 80mg-KOH/g (being converted into solid constituent) resin B 2 solution。

For the mensuration of the polystyrene conversion weight average molecular weight of above-mentioned resin, GPC method is adopted to carry out under the following conditions。

Device: HLC-8120GPC (ソ mono-(strain) system)

Chromatographic column: TSK-GELG2000HXL

Column temperature: 40 DEG C

Solvent: THF

Flow velocity: 1.0mL/min

Fluid to be measured solid component concentration: 0.001～0.01%

Injection rate: 50 μ L

Detector: RI

Correction standard substance: TSKSTANDARDPOLYSTYRENEF-40, F-4, F-288, A-2500, A-500 (ソ mono-(strain) system)

Embodiment 2

(modulation of photosensitive composition)

(A) compound (1): the compound shown in formula (1-27) 30 parts

(B) resin: resin B 1 (being converted into solid constituent) 40 parts

(C) photopolymerizable compound: Dipentaerythritol Pentaacrylate and 60 parts of the mixture of dipentaerythritol acrylate (KAYARADDPHA: Japanese chemical medicine (strain) system)

(D) Photoepolymerizationinitiater initiater: N-benzoyloxy-1-(4-phenyl sulfonyl phenyl)-1-octanone-2-imines (イ Le ガキユア OXE01:BASF Japanese firm system) 12 parts

(D) Photoepolymerizationinitiater initiater: 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone (イ Le ガキユア 369:BASF Japanese firm system) 6 parts

(D1) photopolymerization causes auxiliary agent: 4,4 '-bis-(diethylamino) benzophenone (EAB-F: hodogaya chemical (strain) is made) 2 parts

(E) solvent: propylene glycol monomethyl ether 597 parts

(E) solvent: ethyl lactate 43 parts

(F) surfactant: polyether modified silicone oil (ト mono-レシリ U one Application SH8400: レダウ U one ニ Application グ (strain) system) 0.09 part

Mixing above-mentioned substance obtains photosensitive composition。

(formation of pattern)

On the glass substrate (イ mono-グ Le 2000: U one ニ Application グ society system) of 2 inch square, it is coated with photosensitive composition with spin-coating method, then, at 100 DEG C, gives baking 3 minutes。After cooling, make to be coated with and be spaced apart 100 μm between the substrate of this photosensitive composition and quartz glass photomask, use exposure machine (TME-150RSK: トプ U Application (strain) system), with 100mJ/cm under atmospheric atmosphere gas²Light exposure (365nm benchmark) carry out light irradiation。It addition, photomask uses the mask of the whole intermittent pattern of the pad (LineandSpacePattern) defining 100 μm。This substrate is immersed in the aqueous solution containing 0.12% nonionic system surfactant and 0.04% potassium hydroxide, impregnates and develop for 80 seconds at 23 DEG C after irradiating by light, after washing, in stove, and after bake 30 minutes at 230 DEG C。Letting cool after but, measure the thickness of obtained multicolour pattern with determining film thickness device (DEKTAK3: Japan's vacuum technique (strain) system), result is 2.0 μm。

(color performance evaluation)

The pattern obtained is used colour examining machine (OSP-SP-200: Olympus (strain) is made) mensuration light splitting, uses the XYZ that the isochrome function of illuminant-C records CIE to mark the xy chromaticity coordinate (x, y) (i.e. colourity) soaking front and back in colour system system and brightness Y。Result is in Table 1。

(solvent resistance evaluation)

Except not using photomask to be exposed when forming above-mentioned pattern, all the other are implemented same operation and make film。The film obtained is soaked 30 minutes in the METHYLPYRROLIDONE of 23 DEG C, colour examining machine (OSP-SP-200: Olympus (strain) is made) is used to measure light splitting, mark the xy chromaticity coordinate (Rx, Ry) (i.e. colourity) soaking front and back in colour system system and brightness RY with the XYZ of the isochrome function mensuration CIE of illuminant-C, calculate the aberration Δ Eab* before and after soaking。The more little solvent resistance of aberration Δ Eab* is more good。The result of aberration Δ Eab* is in Table 1。

In addition, use on cutter (カ Star タ mono-) and super cutter guide (ス mono-パ mono-カ Star タ mono-ガイ De) (Tai Youji material society system) film after steeping, cut with the interval of 1mm, produce the grid of 100 1mm × 1mm。This grid is pasted the wide adhesive tape (セロテ mono-プ) (registered trade mark) of 24mm (ニチバ Application (strain) society system), with erasing rubber in the upper wiping of adhesive tape (セロテ mono-プ) (registered trade mark), so that adhesive tape (セロテ mono-プ) (registered trade mark) attaches in cured coating film, after 2 minutes, hold one end of adhesive tape (セロテ mono-プ), on coated surface, keep right angle, peel off without a break。Afterwards, range estimation count on substrate the film of residual without departing from number of squares。This grid is namely as adhesion, and result is in Table 1。

Comparative example 1

(A) coloring agent: OrasolRedG (チバジヤパ Application (strain) system) 47.5 parts

(B) resin: resin B 2 solution 16 parts

(C) photopolymerizable compound: Dipentaerythritol Pentaacrylate and 23.9 parts of the mixture of dipentaerythritol acrylate (KAYARADDPHA: Japanese chemical medicine (strain) system)

(D) Photoepolymerizationinitiater initiater: 3.6 parts of 2-methyl-2-morpholino-1-(4-methylsulfonyl phenyl)-1-acetone (イ Le ガキユア 907:BASF ジヤパ Application (strain) system)

(D) Photoepolymerizationinitiater initiater: 2,4-bis-(trichloromethyl)-6-piperonyl-1,3,5-triazines (TAZ-PP: Japan シイベ Le ヘグ Na one (strain) system) 2.8 parts

(D1) photopolymerization causes auxiliary agent: 4,4 '-bis-(diethylamino) benzophenone (EAB-F: hodogaya chemical (strain) is made) 1.2 parts

(E) solvent: propylene glycol monomethyl ether 267 parts

(E) solvent: propylene glycol methyl ether acetate 138 parts

(F) surfactant: メガ Off ア Star Network F475 (DIC (strain) system) 0.1 part

Mixing above-mentioned substance obtains photosensitive composition。Photosensitive composition is implemented the evaluation identical with embodiment 1。Result is in Table 1。

[table 1]

*), time owing to soaking in METHYLPYRROLIDONE, color coating splits away off from glass substrate, thus cannot measure aberration Δ Eab* and adhesion。

The film that the photosensitive composition using the present invention is formed and obtains has good solvent resistance。It follows that the photosensitive composition according to the present invention, it is possible to obtain the color filter of the film of excellent solvent resistance, pattern and high-quality。

Industrial applicability

Photosensitive composition according to the present invention, it is possible to obtain the color filter of the good film of solvent resistance, pattern and high-quality。

Claims

1. a photosensitive composition, containing coloring agent, resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent, coloring agent is the coloring agent containing compound shown in formula (1)；

In formula (1), R¹～R¹⁸Represent hydrogen atom, nitro or-SO independently of one another₂R²⁹；

R¹～R¹⁰It is each independently hydrogen atom,

R¹¹～R¹⁸Among at least one be hydrogen atom,

R¹¹～R¹⁸Among at least one be nitro,

R¹¹～R¹⁸Among at least one be-SO₂R²⁹；

R²⁹Expression-R³²；

R³²Represent 1 valency aliphatic alkyl of carbon number 1～8；

R¹⁹And R²⁰Represent methyl independently of one another；

M¹Represent Cr or Co；

R²¹～R²⁴Represent 1 valency aliphatic alkyl of carbon number 1～8 independently of one another；

R²⁵And R²⁶Represent hydrogen atom independently of one another；

N represents 0。

2. photosensitive composition according to claim 1, wherein Photoepolymerizationinitiater initiater is containing at least one Photoepolymerizationinitiater initiater among benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime compound and double imidazole compound。

3. photosensitive composition according to claim 1, wherein M¹For Cr。

4. a color filter, the photosensitive composition described in any one of claims 1 to 3 is formed。

5. a display device, containing the color filter described in claim 4。

6. the compound shown in formula (1),

R¹～R¹⁰It is each independently hydrogen atom,

R¹¹～R¹⁸Among at least one be hydrogen atom,

R¹¹～R¹⁸Among at least one be nitro,

R¹¹～R¹⁸Among at least one be-SO₂R²⁹；

R²⁹Expression-R³²；

R³²Represent 1 valency aliphatic alkyl of carbon number 1～8；

R¹⁹And R²⁰Represent methyl independently of one another；

M¹Represent Cr or Co；

R²⁵And R²⁶Represent hydrogen atom independently of one another；

N represents 0。