CN102636957A

CN102636957A - Colored photosensitive resin composition and compound

Info

Publication number: CN102636957A
Application number: CN2012100384680A
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: 2012-08-15
Anticipated expiration: 2032-02-13
Also published as: KR20120093096A; KR101766745B1; JP5807568B2; JP2012185483A; TW201237118A; CN102636957B; TWI515268B

Abstract

The present invention provides a colored photosensitive resin composition which comprises colorant, resin, a photopolymerizable compound, a photopolymerization initiating agent and solvent. The colorant comprises the compound which is represented by a formula (I), wherein, R1-R8 represent hydrogen atom, univalent aliphatic alkyl with 1-8 carbon atoms, or nitryl, etc. R19 and R20 respresent hydrogen atom, methyl, ethyl or amino group. M1 represents Cr or Co. R21-R24 represent hydrogen atom, univalent aliphatic alkyl with 1-8 carbon atoms, or univalent aromatic alkyls with 6-10 carbon atoms. R25 and R26 respectively represent hydrogen atom or methyl. R27 represents ethenyl, 1,3-propylidene or 1,2-propylidene, and n represents an integer of 0-3.

Description

Photosensitive composition and compound

Technical field

The present invention relates to photosensitive composition and compound.

Background technology

Employed color filter has red pixel in liquid crystal display cells or the solid-state imager, and among the photosensitive composition that forms this red pixel, known have the dyestuff of use as colorant.For example, in the patent documentation 1, record and contain the photosensitive composition of Orasol Red G as orchil.

[patent documentation 1] Japanese Patent Laid is opened the 2009-163226 communique

Summary of the invention

Always known above-mentioned photosensitive composition is on this aspect of solvent resistance, and existence can not be made us fully satisfied situation.

The present invention provides following [1]～[10].

[1] a kind of photosensitive composition contains colorant, resin, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent, and colorant is the colorant that contains compound shown in the formula (1).

[in the formula (1), R ¹～R ¹⁸Represent independently of one another hydrogen atom, halogen atom, carbon number 1～8 1 valency aliphatic alkyl, nitro or-SO ₂R ²⁹

R ²⁹Expression-R ³²,-OH or-NHR ³⁰

R ³⁰1 valency aliphatic alkyl of expression hydrogen atom, carbon number 1～8, can by the substituted cyclohexyl of the alkyl of carbon number 1～4 ,-R ³¹-O-R ³²,-R ³¹-CO-O-R ³²,-R ³¹-O-CO-R ³²Or the aralkyl of carbon number 7～10.

R ³¹The divalent aliphatic alkyl of expression carbon number 1～8.

R ³²1 valency aliphatic alkyl of expression carbon number 1～8.

R ¹⁹And R ²⁰Represent hydrogen atom, methyl, ethyl or amino independently of one another.

M ¹Expression Cr or Co.

R ²¹～R ²⁴Represent 1 valency aliphatic alkyl of hydrogen atom, carbon number 1～8 or 1 valency aromatic hydrocarbyl of carbon number 6～10 independently of one another, the hydrogen atom that this aliphatic alkyl and this aromatic hydrocarbyl comprised can by hydroxyl ,-OR ³², sulfonic group ,-SO ₃Na ,-SO ₃K or halogen atom replace.

R ²⁵And R ²⁶Represent hydrogen atom or methyl independently of one another.

R ²⁷Expression ethylidine, 1,3-propylidene or 1,2-propylidene.

N representes 0～3 integer.When n is the integer more than 2, a plurality of R ²⁷Each other can be identical or different.]

[2] like [1] described photosensitive composition, wherein R ¹～R ¹⁸Be independently of one another hydrogen atom, nitro or-SO ₂R ²⁹,

R ²⁹For-R ³²,

R ³²For 1 valency aliphatic alkyl of carbon number 1～8,

R ¹⁹And R ²⁰Be independently of one another methyl,

R ²¹～R ²⁴Be independently of one another carbon number 1～8 1 valency aliphatic alkyl,

R ²⁵And R ²⁶Be independently of one another hydrogen atom,

N is 0.

[3] like [2] described photosensitive composition, wherein R ¹～R ¹⁸Among at least one be hydrogen atom, at least one is nitro, and at least one is-SO ₂R ²⁹

[4] like [3] described photosensitive composition, wherein R ¹～R ¹⁰Be hydrogen atom independently of one another.

[5] like [4] described photosensitive composition, wherein R ¹～R ¹⁸Among at least one be hydrogen atom,

R ¹¹～R ¹⁸Among at least one is a nitro, and

R ¹¹～R ¹⁸Among at least one is-SO ₂R ²⁹

[6] like [1] described photosensitive composition, wherein Photoepolymerizationinitiater initiater is to contain at least a Photoepolymerizationinitiater initiater that is selected among benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime compound and the double imidazole compound.

[7] like [1] described photosensitive composition, wherein M ¹Be Cr.

[8] form by each the described photosensitive composition in [1]～[7] and color filter.

[9] display device that contains [8] said color filter.

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

R ²⁹Expression-R ³²,-OH or-NHR ³⁰

R ³¹The divalent aliphatic alkyl of expression carbon number 1～8.

R ³²1 valency aliphatic alkyl of expression carbon number 1～8.

M ¹Expression Cr or Co.

R ²⁷Expression ethylidine, 1,3-propylidene or 1,2-propylidene.

The invention effect

According to photosensitive composition of the present invention, can form the high color solidification thing of solvent resistance (for example film, pattern).

Embodiment

Photosensitive composition of the present invention contains colorant (A), resin (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E), and colorant (A) is the colorant that contains compound shown in the formula (1) (following also claim " compound (1) ").

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

R ²⁹Expression-R ³²,-OH or-NHR ³⁰

R ³⁰1 valency aliphatic alkyl of expression hydrogen atom, carbon number 1～8, can by the substituted cyclohexyl of the alkyl of carbon number 1～4 ,-R ³¹-O-R ³²,-R ³¹-CO-O-R ³²,-R ³-O-CO-R ³²Or the aralkyl of carbon number 7～10.

R ³¹The divalent aliphatic alkyl of expression carbon number 1～8.

R ³²1 valency aliphatic alkyl of expression carbon number 1～8.

M ¹Expression Cr or Co.

R ²⁷Expression ethylidine, 1,3-propylidene or 1,2-propylidene.

1 valency aliphatic alkyl of carbon number 1～8 can be enumerated 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-dimethyl hexyl, 1,6-dimethyl heptyl, 2-ethylhexyl and 1,1; 5,5-tetramethyl hexyl etc.

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

[0019]

The divalent aliphatic alkyl of carbon number 1～8 can be enumerated methylene, ethylidine, 1,3-propylidene, 1,2-propylidene, 1,4-butylidene, 1,3-butylidene, 1,5-pentylidene, 1,6-hexylidene, 1, the inferior heptyl, 1 of 7-, the inferior octyl group of 8-etc.

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

Can be enumerated 2-methylcyclohexyl, 2-ethyl cyclohexyl, 2-propyl group cyclohexyl, 2-isopropylcyclohexyl-, 2-butyl cyclohexyl, 4-methylcyclohexyl, 4-ethyl cyclohexyl, 4-propyl group cyclohexyl, 4-isopropylcyclohexyl-, 4-butyl cyclohexyl etc. by the substituted cyclohexyl of the alkyl of carbon number 1～4.

As-R ³¹-O-R ³²Can enumerate methoxy, ethoxyl methyl, propoxyl group methyl, methoxy ethyl, ethoxyethyl group, propoxyl group ethyl, methoxy-propyl, ethoxycarbonyl propyl, propoxyl group propyl group, 2-oxygen-4-methoxyl butyl, octyloxy propyl group, 3-ethoxycarbonyl propyl, 3-(2-ethyl hexyl oxy) propyl group etc.

-R ³¹-CO-O-R ³²Can enumerate methoxycarbonyl methyl, methoxycarbonyl ethyl, ethoxy carbonyl methyl, ethoxy carbonyl ethyl, propoxycarbonyl methyl, propoxycarbonyl ethyl, butoxy carbonyl methyl, butoxy carbonyl ethyl etc.

-R ³¹-O-CO-R ³²Can enumerate acetoxy-methyl, acetoxyl group ethyl, ethyl ketonic oxygen ylmethyl, ethyl ketonic oxygen base ethyl, propyl group ketonic oxygen ylmethyl, propyl group ketonic oxygen base ethyl, butyl ketonic oxygen ylmethyl, butyl ketonic oxygen base ethyl etc.

-SO ₂R ²⁹Can enumerate sulfonic group; Sulfamoyl;

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

Quilt-R such as 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-propoxyl group propyl group) sulfamoyl, N-(3-isopropoxide propyl) sulfamoyl, N-(the own oxygen base of 3-propyl group) sulfamoyl, N-(2-ethyl hexyl oxy propyl group) sulfamoyl, N-(3-tert-butoxy propyl group) sulfamoyl, N-(4-octyloxy butyl) sulfamoyl ³¹-O-R ³²Substituted sulfamoyl;

Quilt-R such as N-(methoxycarbonyl methyl) sulfamoyl, N-(methoxycarbonyl ethyl) sulfamoyl, N-(ethoxy carbonyl methyl) sulfamoyl, N-(ethoxy carbonyl ethyl) sulfamoyl, N-(propoxycarbonyl methyl) sulfamoyl, N-(propoxycarbonyl ethyl) sulfamoyl, N-(butoxy carbonyl methyl) sulfamoyl, N-(butoxy carbonyl ethyl) sulfamoyl ³¹-CO-O-R ³²Substituted sulfamoyl;

Quilt-R such as N-(acetoxy-methyl) sulfamoyl, N-(acetoxyl group ethyl) sulfamoyl, N-(ethyl ketonic oxygen ylmethyl) sulfamoyl, N-(ethyl ketonic oxygen base ethyl) sulfamoyl, N-(propyl group ketonic oxygen ylmethyl) sulfamoyl, N-(propyl group ketonic oxygen base ethyl) sulfamoyl, N-(butyl ketonic oxygen ylmethyl) sulfamoyl, N-(butyl ketonic oxygen base ethyl) sulfamoyl ³¹-O-CO-R ³²Substituted sulfamoyl;

N-cyclohexyl sulfamoyl, N-(2-methylcyclohexyl) sulfamoyl, N-(3-methylcyclohexyl) sulfamoyl, N-(4-methylcyclohexyl) sulfamoyl, N-(4-butyl cyclohexyl) sulfamoyl etc. are had the substituted sulfamoyl of substituent cyclohexyl;

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 by substituted sulfamoyl of aralkyl etc.

-SO ₂R ²⁹For-SO ₂R ³²,-SO ₂H or-SO ₂NHR ³⁰Wherein preferably-SO ₂R ³²And-SO ₂NHR ³⁰

-SO ₂NHR ³⁰In R ³⁰Be preferably 1 valency aliphatic alkyl of hydrogen atom or carbon number 1～8, more preferably hydrogen atom or 2-ethylhexyl.

When compound of the present invention has-SO ₂R ³²The time, preferred R ¹¹～R ¹⁴In at least one and R ¹⁵～R ¹⁸In at least one be-SO ₂R ³²A plurality of when having-SO ₂R ³²The time, a plurality of R ³²Each other can be identical or different.

-SO ₂R ³²In R ³²Be 1 valency aliphatic alkyl of carbon number 1～8,1 valency aliphatic alkyl of preferred carbon number 1～4.-SO ₂R ³²Can enumerate, methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropyl sulfonyl, normal-butyl sulfonyl, sec-butyl sulfonyl, tert-butyl group sulfonyl, amyl group sulfonyl, hexyl sulfonyl, heptyl sulfonyl, octyl group sulfonyl, 1-methyl butyl sulfonyl, 1,1,3; 3-tetramethyl butyl sulfonyl, 1; 5-dimethyl hexyl sulfonyl, 1,6-dimethyl heptyl sulfonyl, 2-ethylhexyl sulfonyl and 1,1; 5,5-tetramethyl hexyl sulfonyl etc.Wherein, preferable methyl sulfonyl and ethylsulfonyl, more preferably methyl sulphonyl.

R ¹～R ¹⁸Preferably be independently of one another hydrogen atom, nitro or-SO ₂R ²⁹

R ¹～R ¹⁸Among, preferably at least one is a hydrogen atom.In addition, R ¹～R ¹⁰Be hydrogen atom independently of one another, R ¹⁰～R ¹⁸Among, more preferably at least one is a hydrogen atom.In addition, further preferred R ¹¹～R ¹⁴Among at least one and R ¹⁵～R ¹⁸Among at least one be hydrogen atom.

Based on tendency with high-fire resistance, preferred R ¹～R ¹⁸Among at least one be nitro, more preferably R ¹¹～R ¹⁸Among at least one be nitro.In addition, further preferred R ¹¹～R ¹⁴Among at least one and R ¹⁵～R ¹⁸Among at least one is a nitro.

In addition, preferred R ¹～R ¹⁸In at least one be-SO ₂R ²⁹, more preferably R ¹¹～R ¹⁸Among at least one be-SO ₂R ²⁹In addition, further preferred R ¹¹～R ¹⁴At least one and R ¹⁵～R ¹⁸Among at least one is-SO ₂R ²⁹A plurality of when having-SO ₂R ²⁹The time, a plurality of R ²⁹Each other can be identical or different.

In addition, R ¹～R ¹⁰Be hydrogen atom independently of one another, R ¹¹～R ¹⁴At least one and R ¹⁵～R ¹⁸Among at least one be hydrogen atom, R ¹¹～R ¹⁴At least one and R ¹⁵～R ¹⁸Among at least one be nitro, further preferred R ¹¹～R ¹⁴At least one and R ¹⁵～R ¹⁸Among at least one be-SO ₂R ²⁹

R ¹⁹And R ²⁰Being hydrogen atom, methyl, ethyl or amino independently of one another, more preferably is methyl or ethyl independently of one another.

Based on the point that improves colour saturation, R ²¹～R ²⁴Preferred hydrogen atom maybe can have 1 valency aliphatic alkyl of substituent carbon number 1～8, more preferably 1 valency aliphatic alkyl of hydrogen atom or carbon number 1～8,1 valency aliphatic alkyl of carbon numbers 1～4 such as further preferred ethyl.

R ²⁵And R ²⁶Being hydrogen atom or methyl independently of one another, preferably is hydrogen atom independently of one another.

R ²⁷Preferred ethylidine

3-propylidene, more preferably ethylidine.

N is 0～3 integer, preferred 0～2 integer, more preferably 0.When n was these numerical value, the raw material of compound (1) was started with more easily.

In addition, more preferably R ¹～R ¹⁰Be hydrogen atom independently of one another, R ¹¹～R ¹⁴At least one and R ¹⁵～R ¹⁸Among at least one be hydrogen atom, R ¹¹～R ¹⁴At least one and R ¹⁵～R ¹⁸Among at least one be nitro, R ¹¹～R ¹⁴At least one and R ¹⁵～R ¹⁸Among at least one be-SO ₂R ²⁹, R ¹⁹And R ²⁰Be methyl independently of one another, R ²¹～R ²⁴Be 1 valency aliphatic alkyl of carbon number 1～4 independently of one another, R ²⁵And R ²⁶Be hydrogen atom independently of one another, n is 0, R ²⁹Be-R ³², R ³²It is 1 valency aliphatic alkyl of carbon number 1～4.

Among the compound (1), but the compound shown in preferred pyrazoles azo-compound complex anion part enumerative (1-a1)～formula (1-a64) etc.

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

Among the compound (1), but preferred origin is in the kation shown in kation example enumerative (the 1-c1)～formula (1-c36) of xanthene compounds etc.

Compound (1) can make through following reaction: compound shown in the use formula (1d) (following also claim " compound (1d) ") and chromium compound form the chromium complex salt; Make this chromium complex salt and xanthene compounds generation salt exchange reaction then; Perhaps use compound (1d) and cobalt compound to form the cobalt complex salt, make this cobalt complex salt and xanthene compounds (b) that the salt exchange reaction takes place then.

[in the formula (a4), R ¹～R ⁵, R ¹¹～R ¹⁴And R ¹⁹Meaning the same.]

[in the formula (b), R ²¹～R ²⁷And the meaning of n is the same.A ^-Represent 1 valency negative ion.]

1 valency negative ion can be enumerated Cl ^-, Br ^-, I ^-, ClO ₄ ^-, PF ₆ ^-Or BF ₄ ^-Deng.

Xanthene compounds (b) can make through the compound shown in compound shown in the formula (b0) and the formula (b1) is reacted in organic solvent.

[in formula (b0) and the formula (b1), R ²¹～R ²⁷, n and A ^-Meaning the same.]

In above-mentioned reaction, preferred 15 ℃～60 ℃ of temperature of reaction, preferred 1 hour～12 hours of reaction time.In addition, the point based on shortening reaction time or raising productive rate preferably uses acid catalyst and/or dewatering agent.

Acid catalyst can be enumerated sulfuric acid, p-toluenesulfonic acid etc.

Dewatering agent can be enumerated, carbodiimide classes such as dicyclohexylcarbodiimide, DIC, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride; 1-alkyl-2-halogenation pyridine salt; 1,1 '-carbonyl dimidazoles; The inferior phosphoryl chloride phosphorus oxychloride of two (2-oxygen-3-oxazolidinyl); Two-2-pyridine radicals carbonate etc.Wherein, as dewatering agent, based on carrying out aftertreatment and refining point easily, preferred 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride.

Can enumerate methylene chloride, chloroform, tetrahydrofuran, toluene, acetonitrile etc. as the organic solvent that uses in the above-mentioned reaction.

The compound that becomes the complex anion part (1d) of compound (1) can make through method known in the dye field, that diazo salt and pyrazole compound are carried out diazo coupling.Compound shown in the formula (1b) that for example, can the amine shown in the formula (1a) (following also claim " amine (1a) ") be got through nitrous acid, nitrite or nitrites diazotising uses as above-mentioned diazo salt.

[in formula (1a) and the formula (1b), R ¹¹～R ¹⁴Meaning the same.A ^1-Represent inorganic or organic anion.]

Above-mentioned inorganic anion can be enumerated, for example fluoride ion, chloride ion, bromide ion, iodide ion, high chloro acid ion, hypochlorite ion etc.Above-mentioned organic anion can be enumerated, for example CH ₃COO ^-, C ₆H ₅COO ^-Deng.Preferred chloride ion, bromide ion, CH ₃COO ^-Deng.

Through in aqueous solvent, the diazo coupling of compound shown in compound shown in the formula (1b) and the formula (1c) can be made the compound shown in the formula (1d) (following also claim " compound (1d) ").Preferred-5 ℃～60 ℃ of temperature of reaction, more preferably 0 ℃～30 ℃.Preferred 1 hour～12 hours of reaction time, more preferably 1 hour～4 hours.Above-mentioned aqueous solvent can be enumerated, for example N-Methyl pyrrolidone etc.

[in the formula (1c), R ¹～R ⁵And R ¹⁹Meaning the same.]

(1d) has-SO when compound ₂R ²⁹,-SO ₂R ²⁹For-SO ₂NHR ³⁰The time, have-SO though can use ₂NHR ³⁰Amine (1a) make, but preferably have after sulfonic amine (1a) carries out coupling reaction in use, again the sulfonic group sulfuryl amine is made.For example, in compound (1d), earlier synthetic have a sulfonic azo-compound (below be called " compound (1s) "), again through thionyl halide compound p-sulfonic acid base (SO ₃H) carry out sulphonyl halogenation (SO ₂X; X is a halogen atom) obtain sulfonyl halogen compound, then through making sulfonyl halogen compound and amine (R ³⁰NH ₂) react, the sulfuryl amine sulfonic group, make compound (1d).

The concrete example of compound (1s) can be enumerated, the compound shown in formula (1-a1), formula (1-a2), the formula (1-a5)～(1-a20), the compound shown in preferred formula (1-a5), (1-a6), (1-a15) reach (1-a16).The thionyl halide compound can be enumerated, thionyl fluoride, thionyl chloride, thionyl bromide, sulfurous acyl iodides etc., preferred thionyl chloride, thionyl bromide etc., preferred especially thionyl chloride.The use amount of thionyl halide is with respect to 1 mole compound (1s), preferred 1～10 mole.In addition, when sneaking into water in the reaction system, preferred excessive use thionyl halide compound.

The sulphonyl halogenation is carried out in solvent.Solvent can use, and for example 1, ethers such as 4-dioxan (preferred especially cyclic ethers class); Chloroform, methylene chloride, phenixin, 1,2-ethylene dichloride, dichloroethylene, triclene, perchloro-ethylene, propylene dichloride, chloropentane, 1, halogenated hydrocarbons such as 2-ethylene dibromide etc.The use amount of solvent for example is 3 mass parts above (more than preferred 5 mass parts), 10 mass parts following (below preferred 8 mass parts) with respect to 1 mass parts compound (1s).

In addition, preferred and use N for the sulphonyl halogenation, N-dialkylformamide (for example, N, dinethylformamide, N, N-DEF etc.).When using N, during the N-dialkylformamide, its use amount with respect to 1 mole of thionyl halide compound for for example, 0.05～1 mole.In solvent, be pre-mixed compound (1s) and N, the N-dialkylformamide is added the thionyl halide compound afterwards again, can suppress heating.

Temperature of reaction during the sulphonyl halogenation be for example, more than 0 ℃, preferred more than 30 ℃, below 70 ℃, preferred below 60 ℃.Reaction time be for example, more than 0.5 hour, preferred more than 3 hours, below 8 hours, preferred below 5 hours.

After the sulfonyl halogen compound that is formed by last modulation can be emanated again with amine (R ³⁰NH ₂) reaction, also can not emanate and directly as reaction mixture and amine (R ³⁰NH ₂) reaction.In addition, when emanating, but for example hybrid reaction potpourri and water, the crystallization that leaching is separated out gets final product.The sulfonyl halogen compound crystallization that obtains with amine (R ³⁰NH ₂) before the reaction, can wash as required and dry.

Amine (R ³⁰NH ₂) comprise n-pro-pyl amine, n-butylamine, n-hexyl amine, dimethyl hexyl amine (1; 5-dimethyl hexyl amine 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 (R ³⁰NH ₂) use amount with respect to 1 mole of sulfonyl halogen compound, more than 2 moles, below 10 moles, preferred below 7 moles.

Sulfonyl halogen compound and amine (R ³⁰NH ₂) interpolation do not have special qualification in proper order, but preferably in sulfonyl halogen compound, add (dropping) amine (R ³⁰NH ₂).In addition, sulfonyl halogen compound and amine (R ³⁰NH ₂) reaction preferably in solvent, carry out.Solvent can use solvent identical when modulating sulfonyl halogen compound.

In addition, sulfonyl halogen compound and amine (R ³⁰NH ₂) reaction preferably in the presence of base catalyst, carry out.Base catalyst can be enumerated, for example tertiary amine (aliphatic tertiary amines such as triethylamine, triethanolamine; And secondary amine (secondary aliphatic amine such as diethylamide aromatic nitrile bases such as pyridine); Annular aliphatic secondary amine such as piperidines) etc.Wherein, aliphatic tertiary amines such as preferred tertiary amine, especially triethylamine.The use amount of base catalyst is with respect to amine (R ³⁰NH ₂), more than 1.1 moles, below 6 moles, preferred more than 1.1 moles, below 5 moles.

In sulfonyl halogen compound, add amine (R ³⁰NH ₂) and during base catalyst, the interpolation of base catalyst does not have special qualification opportunity, can be at amine (R ³⁰NH ₂) before or after add, also can with amine (R ³⁰NH ₂) add simultaneously.In addition, also can be in advance with add again after reactive amine mixes, also can with amine (R ³⁰NH ₂) add separately respectively.

Sulfonyl halogen compound and amine (R ³⁰NH ₂) temperature of reaction for for example more than 0 ℃, below 50 ℃, preferred more than 0 ℃, below 30 ℃.Reaction time is 1～5 hour in addition.

Do not have special qualification from the reaction mixture acquisition as the method for the compound (1d) of purpose compound, can adopt known the whole bag of tricks.For example, preferably with reaction mixture and acid (for example acetate etc.) and water mixed together, the leaching crystallization of separating out again.Preferably in advance above-mentioned acid is modulated into aqueous acid, again reaction mixture is added in the above-mentioned WS.Temperature when adding reaction mixture is preferred more than 10 ℃ below 50 ℃, and is more preferably more than 20 ℃ below 50 ℃, further preferred more than 20 ℃ below 30 ℃.In addition, preferably add reaction mixture to aqueous acid after, under said temperature, further stirred about 0.5～2 hour.The preferred waters of crystallization of leaching etc. are cleaned, and are dry again.In addition, also can further purify through known method such as recrystallizations as required.

(the M in the formula (1) when the anionicsite of compound (1) is the chromium complex anion ¹Be Cr), can make through compound (1d) and chromium compound are reacted under 70～100 ℃ in aqueous solvent.Compound (1d) preferably reacted with mol ratio with chromium compound in 2: 1～4: 1.

Above-mentioned chromium compound can be enumerated, chromic formate, chromium acetate, chromium chloride, charomic fluoride etc., preferable formic acid chromium, chromium acetate, chromium ammonium suplhate (III) 12 water etc.

Compound (1) can be made through making chromium complex salt and xanthene compounds (b) that the salt exchange reaction take place in solvent.Chromium complex salt and xanthene compounds (b) were reacted with mol ratio in 1: 1～1: 4.

(the M in the formula (1) when the anionicsite of compound (1) is the cobalt complex anion ¹Be Co), can make through compound (1d) and cobalt compound are reacted under 70～100 ℃ in aqueous solvent.Compound (1d) and cobalt compound were reacted with mol ratio in 2: 1～4: 1.

Above-mentioned cobalt compound can be enumerated, cobalt chloride, cobalt acetate, cobaltous sulphate, acetylacetone cobalt (III) etc., preferred acetylacetone cobalt (III) etc.

Compound (1) can be made through making cobalt complex salt and xanthene compounds that the salt exchange reaction take place in solvent.Cobalt complex salt and xanthene compounds (b) were reacted with mol ratio in 1: 1～1: 4.

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

The content of compound (1) is in colorant (A), below the above 99 quality % of preferred 1 quality %, more preferably below the above 80 quality % of 1 quality %, further below the above 70 quality % of preferred 3 quality %.

Can contain compound (1) in the colorant (A) simultaneously and be different from the dyestuff of compound (1).This dyestuff can be enumerated; The amine salt of oil-soluble dyes, acid dyes, acid dyes or the dyestuffs such as sulfamide derivative of acid dyes; For example can enumerate; Be classified as the compound of dyestuff in the Colour Index (The Society of Dyers and Colourists publication), or the known dye of record in the dyeing handbook (look dyes society).

Particularly, C.I. solvent yellow 4 (following omission " C.I. solvent yellow ", only record numbering.)、14、15、23、24、38、62、63、68、82、94、98、99、162，

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

C.I. solvent orange 2,7,11,15,26, C.I. solvent dyes such as 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, 7,9,17, C.I. acid dyess such as 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 be enumerated 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. the 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. C.I. mordant dye 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 etc.

Can further contain pigment and compound (1) simultaneously in the colorant (A).

Pigment can be enumerated, organic pigment, for example, C.I. pigment violet 1,19,23,29,32,36, violet pigments such as 38; C.I. 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 13,31,36,38,40,42,43,51,55,59,61,64,65,71, orange pigments such as 73;

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264, red pigments such as 265 etc.Wherein preferably contain at least and be selected from a kind of in C.I. pigment yellow 13 8,139,150, the C.I. paratonere 177,242,254.Through containing above-mentioned pigment, can make the easy optimization of transmission spectrum, chemical-resistant improves.

These pigment can separately or mix more than 2 kinds and use.

Organic pigment can be implemented following processing as required: the micronize that the grafting that rosin handles, use the surface treatment of the pigment derivative that imported acidic groups or basic group etc., carry out surface of pigments via macromolecular compound etc. handles, carry out via sulfuric acid micronize method etc. is handled, or be used to remove organic solvent or the water etc. of impurity clean processing, be used to remove ionic impurity ion exchange process etc. remove processing etc.

Organic pigment preferable particle size homogeneous.Carry out dispersion treatment through making it to contain pigment dispersing agent, can obtain pigment and be the dispersible pigment dispersion that homogeneous is scattered in the state in the solution.

Above-mentioned pigment dispersing agent can be enumerated, for example, surfactant such as kation system, negative ion system, nonionic system, both sexes, polyester system, polyamine system, acrylic acid series etc.These pigment dispersing agents can use more than 2 kinds alone or in combination.Pigment dispersing agent can be enumerated with trade name, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Off ロ one レ Application (common prosperity society chemistry (strain) system), ソ Le スパ one ス (ゼネカ (strain) system), EFKA (CIBA society system), アジスパ one (monosodium glutamate Off アイ Application テ Network ノ (strain) system), Disperbyk (PVC Star Network ケミ one society's system) etc.

When using pigment dispersing agent, its use amount is with respect to pigment (A2), and preferred 100 quality % are more preferably below the above 50 quality % of 5 quality %.When the use amount of pigment dispersing agent is in above-mentioned scope, has the tendency of the dispersible pigment dispersion that obtains the homogeneous disperse state.

When containing pigment in the colorant (A), preferred 1～99 quality % of the content of this pigment, more preferably 10～97 quality %.

Preferred 1: 99～99: 1 of the content ratio (mass ratio) of compound (1) and pigment, more preferably 3: 97～90: 10.Through making it to be such ratio, easily the optimization transmission spectrum obtains good high-contrast, high brightness.Further, thermotolerance, chemical-resistant also improve.

Especially; Compound (1) and preferred 3: 97～90: 10 of at least a kind the mass ratio that is selected from 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 the C.I. paratonere 254, more preferably 3: 97～70: 30.

The content of colorant (A) is with respect to the solid constituent in the photosensitive composition, preferred 5～60 quality %, more preferably 8～55 quality %, further preferred 10～50 quality %.Here, solid constituent is meant the total of removing the composition that desolvates in the photosensitive composition.If the content of colorant (A) in above-mentioned scope, then as color filter, has enough colour saturations, and can make and contain enough binder polymers in the composition, and then can form the sufficient pattern of physical strength.

Photosensitive composition of the present invention contains resin (B).Resin (B) does not have qualification especially, but the preferred bases soluble resin.

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

[K1] has the cyclic ether structure of carbon number 2～4 and the monomer (a) of ethene property unsaturated link (following also title " (a) ") and is selected from the multipolymer of at least a kind (b) (the following also title " (b) ") among unsaturated carboxylic acid and the unsaturated carboxylic acid acid anhydrides.

[K2] (a) with (b) with can with the multipolymer of the monomer (c) (wherein, (a) being different from (b)) of (a) copolymerization (following also claim " (c) ")

[K3] (b) with (c) multipolymer

The resin that [K4] makes (b) and multipolymer (c) get with (a) reacting.

Through making resin (B) contain the structural unit of origin, can further improve the reliability of the thermotolerance, chemical-resistant etc. of the multicolour pattern of acquisition in (a).

(a) be meant for example have, the polymerizable compound of the cyclic ether structure of carbon number 2～4 (for example, be selected among oxirane ring, epoxy butane ring and the tetrahydrofuran ring (butyl oxide link) at least a kind) and ethene property unsaturated link.(a) be preferably the monomer of cyclic ether with carbon number 2～4 and (methyl) acryloxy.

In addition, in this manual, " (methyl) acrylic acid " expression is selected from least a kind among acrylic acid and the methacrylic acid.The narration that " (methyl) acryloyl group " reaches " (methyl) acrylic ester " etc. also has the identical meaning.

(a) can enumerate; For example, have epoxy ethyl and ethene property unsaturated link monomer (a1) (following also claim " (a1) "), have epoxy butyl and ethene property unsaturated link monomer (a2) (following also claim " (a2) "), have the monomer (a3) (following also claim " (a3) ") of tetrahydrofuran base and ethene property unsaturated link etc.

(a1) can enumerate, for example, have the monomer (a1-1) (following also claim " (a1-1) ") of chain type alkene epoxidation structure, a monomer (a1-2) (following also claim " (a1-2) ") with ring type alkene epoxidation structure.

(a1-1) can enumerate (methyl) glycidyl acrylate, (methyl) acrylic acid Beta-methyl ethylene oxidic ester, (methyl) propenoic acid beta-ethyl ethylene oxidic ester, vinyl glycidyl ether, adjacent ethylene benzyl glycidol ether, an ethylene benzyl glycidol ether, to ethylene benzyl glycidol ether, the adjacent ethylene benzyl glycidol ether of Alpha-Methyl, an Alpha-Methyl-ethylene benzyl glycidol ether, Alpha-Methyl-to ethylene benzyl glycidol ether, 2,3-two (glycidoxypropyl methyl) styrene, 2; 4-two (glycidoxypropyl methyl) styrene, 2,5-two (glycidoxypropyl methyl) styrene, 2,6-two (glycidoxypropyl methyl) styrene, 2; 3; 4-three (glycidoxypropyl methyl) styrene, 2,3,5-three (glycidoxypropyl methyl) styrene, 2; 3; 6-three (glycidoxypropyl methyl) styrene, 3,4,5-three (glycidoxypropyl methyl) styrene, 2; 4,6-three (glycidoxypropyl methyl) styrene etc.

(a1-2) can enumerate, an oxyethylene group cyclohexene, 1, (for example, セロキサイ De 2000 for 2-epoxy-4 vinyl cyclohexene; ダイセ Le chemical industry (strain) system), 3,4-epoxycyclohexyl methyl (methyl) acrylic ester (for example, サイ Network ロマ one A400; ダイセ Le chemical industry (strain) system), 3,4-epoxycyclohexyl methyl (methyl) acrylic ester (for example, サイ Network ロマ one M100; ダイセ Le chemical industry (strain) system), compound shown in the formula (I) and the compound shown in the formula (II) etc.

[in formula (I) and the formula (II), R ^aAnd R ^bRepresent hydrogen atom independently of one another, or the alkyl of carbon number 1～4, the hydrogen atom that this alkyl comprised can be replaced by hydroxyl.

X ¹And X ²Represent independently of one another singly-bound ,-R ^c-, *-R ^c-O-, *-R ^c-S-, *-R ^c-NH-.

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

* represent bonding position with O.]

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.

Hydrogen atom can be enumerated by the substituted alkyl of hydroxyl, 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, 1,2-propylidene, 1,3-propylidene, 1,4-butylidene, 1,5-pentylidene, 1,6-hexylidene etc.

X ¹And X ²Preferably enumerate singly-bound, methylene, ethylidine, *-CH ₂-O-(* representes the bonding position with O) base, *-CH ₂CH ₂-O-base is more preferably enumerated singly-bound, *-CH ₂CH ₂-O-base.

Compound shown in the formula (I) can be enumerated, the compound shown in formula (I-1)～formula (I-15) etc.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).

Formula (II) but shown in compound enumerative (II-1)～formula (II-15) shown in compound etc.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 compound shown in the formula (I) and the formula (II) can be distinguished independent use.In addition, also can mix by arbitrary ratio.During mixing, its mixture ratio is with molar ratio computing, and preferred formula (I): formula (II) is 5: 95～95: 5, more preferably 10: 90～90: 10, especially preferred 20: 80～80: 20.

Monomer (a2) with epoxy butyl and ethene property unsaturated link more preferably has the monomer of epoxy butyl and (methyl) acryloxy.(a2) can enumerate 3-methyl-3-isobutylene acyl-oxygen ylmethyl oxetanes, 3-methyl-3-acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-methacryloxy methyl oxetanes, 3-ethyl-3-acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloxy ethyl oxetanes, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloyl group oxygen base ethyl oxetanes etc.

Monomer (a3) with tetrahydrofuran base and ethene property unsaturated link more preferably has the monomer of tetrahydrofuran base and (methyl) acryloxy.

(a3) can enumerate acrylic acid tetrahydro furfuryl ester (for example, PVC スコ one ト V#150, Osaka organic chemistry industry (strain) system), methacrylic acid tetrahydro furfuryl ester etc. particularly.

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

(b) can enumerate particularly, for example acrylic acid, methacrylic acid (methacrylate), butenoic acid, neighbour,, to unsaturated monocarboxylic acid classes such as vinylbenzoic acids;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-ethene phthalandione, 4-ethene phthalandione, 3,4,5,6-tetrahydrochysene phthalandione, 1,2,3,6-tetrahydrochysene phthalandione, dimethyl tetrahydro phthalandione, 1, unsaturated dicarboxylic acid classes such as 4-cyclohexane dicarboxylic acid;

Methyl-5-ENB-2; 3-dicarboxylic acid, 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-ethene anhydride phthalic acid, 4-ethene anhydride phthalic acid, 3; 4,5,6-tetrahydrochysene anhydride phthalic acid, 1; 2; 3,6-tetrahydrochysene anhydride phthalic acid, dimethyl tetrahydro anhydride phthalic acid, 5,6-dicarboxyl dicyclo [2.2.1]-2-heptene acid anhydrides unsaturated dicarboxylic acid class acid anhydrides such as (carbic anhydrides);

Mono succinate (2-(methyl) acrylyl oxy-ethyl), the phthalandione list unsaturated list of the polybasic carboxylic acid more than 2 yuan ((methyl) acryloyloxyalkyl) ester classes such as (2-(methyl) acrylyl oxy-ethyls);

Also can enumerate the unsaturated esters of acrylic acid that in a part, contains hydroxyl and carboxyl of α-(hydroxymethyl) acrylic compounds etc.

Wherein, based on the point of copolyreaction property or the deliquescent point in aqueous alkali, preferred acrylic acid, methacrylic acid (methacrylate), maleic anhydride etc.

(c) can enumerate, for example (methyl) methyl acrylate, (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 cyclohexane ester, three ring [5.2.1.0 ^2,6] ten-8-base (methyl) acrylic ester (in this technical field, is commonly referred to (methyl) acrylic acid dicyclo n-pentyl ester.), (methyl) esters of acrylic acid such as dicyclo n-pentyloxy ethyl (methyl) acrylic ester, (methyl) IBOA, (methyl) acrylic acid diamantane ester, (methyl) allyl acrylate, (methyl) acrylic acid alkynes propyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate;

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

Dicarboxylic diesters such as diethyl 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 dicyclo [2.2.1]-2-heptene, 5-ethoxy dicyclo [2.2.1]-2-heptene, 5; 6-dihydroxy dicyclo [2.2.1]-2-heptene, 5; 6-two (hydroxymethyl) dicyclo [2.2.1]-2-heptene, 5; 6-two (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-two (tert-butoxycarbonyl) dicyclo [2.2.1]-2-heptene, 5,6-two (cyclohexyloxy carbonyl) dicyclo [2.2.1]-dicyclo unsaturated compound classes such as 2-heptene;

Dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimide-3-maleimide benzoic ether, N-succinimide-4-maleimide butyric ester, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionic ester, N-(9-acridinyl) maleimide;

Styrene, AMS, a methyl styrene, p-methylstyrene, vinyl toluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic amide, Methacrylamide, vinyl acetate, 1; 3-butadiene, isoprene, 2; 3-dimethyl-1,3-butadiene etc.

Wherein, based on copolyreaction property and stable on heating point, optimization styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, dicyclo [2.2.1]-2-heptene etc.

In the resin [K1], the ratio of the structural unit of different origin is in the entire infrastructure unit that constitutes resin [K1], preferably in following scope.

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

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

When the ratio of the structural unit of resin [K1] was in above-mentioned scope, the solvent resistance of storage stability, development property, cured pattern had the tendency that becomes good.

Resin [K1] but reference example make like the citing document of putting down in writing in the method for record in, the document " Polymer Synthesizing experimental method " (the big grand row work publishing house in Tianjin (strain) chemistry was published on March 1st, 1972 with the 1st edition the 1st printing of people) and the document.

Particularly, can list (a) of ormal weight and (b), in the reaction vessels of packing into such as polymerization initiator and solvent, through use the nitrogen replace oxygen, under deoxygenation conditions, stir, heating, the method that is incubated.In addition, polymerization initiator used herein and solvent etc. do not have special the qualification, can use normally used any compound in this field.For example, polymerization initiator can be enumerated; Azo-compound (2; 2 '-azoisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile) etc.) or organic peroxide (benzoyl peroxide etc.); Solvent be so long as can dissolve each monomer and get final product, and can use as stating solvent etc. behind the solvent of photosensitive polymer combination.

In addition, the multipolymer of acquisition can directly use reacted solution, also can use concentrate or dilution after solution, also can use solid (powder) through method taking-ups such as depositions again.Especially, the solvent during as this polymerization, the solvent (D) through stating after using can directly use reacted solution, and then can simplify manufacturing process.

In the resin [K2], the ratio of the structural unit of different origin is in the entire infrastructure unit that constitutes resin [K2], preferably in following scope.

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

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

When the ratio of the structural unit of resin [K2] was in above-mentioned scope, the solvent resistance of storage stability, development property, cured pattern, thermotolerance and physical strength had the tendency that becomes good.

Resin [K2] can through with for example, the identical method of method put down in writing as the manufacturing approach of resin [K1] makes.

Particularly, can enumerate the (a) and (b) of ormal weight and (c), polymerization initiator and solvent etc. is packed in the reaction vessel, through use the nitrogen replace oxygen, under deoxygenation conditions, stirs, heating, the method that is incubated.The multipolymer that obtains can directly use reacted solution, also can use concentrate or dilution after solution, also can use solid (powder) through method taking-ups such as depositions again.

In the resin [K3], the ratio of the structural unit of different origin is in the entire infrastructure unit that constitutes resin [K3], preferably 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 through with for example, the identical method of method put down in writing as the manufacturing approach of resin [K1] makes.

Resin [K4] can be through obtaining earlier (b) and (c) multipolymer, and the carboxyl that (c) had adds on the cyclic ether that is formed in the carbon number 2～4 that (a) had and obtains.

At first; According to making (b) and multipolymer (c) with the identical method of putting down in writing as the manufacturing approach of [K1] of method; At this moment, the ratio of the structural unit of different origin is in the entire infrastructure unit that constitutes (b) and multipolymer (c), preferably 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 cyclic ether and the origin in the above-mentioned multipolymer that make the carbon number 2～4 that (a) had are in the part reaction of the carboxyl that structural unit comprised and/or the carboxylic acid anhydrides of (c).

(b) with the manufacturing of (c) multipolymer after; And then the atmosphere gas in the flask is replaced as air by nitrogen; Is 0.001～5 quality % with the catalysts of (a), carboxyl and cyclic ether (for example three (dimethylaminomethyl) phenol etc.) by the total amount with respect to (a)～(c); And polymerization inhibitor (for example p-dihydroxy-benzene etc.) etc. is that 0.001～5 quality % joins in the flask by the total amount with respect to (a)～(c), for example, 60～130 ℃ of reactions 1～10 hour down, obtains resin [K4] thus.The reaction conditions of loading method, temperature of reaction and time etc. can consider that manufacturing equipment or polymerization thermal value etc. suitably adjust.In addition, same polymerizing condition can be considered manufacturing equipment or polymerization thermal value etc., suitably adjusts loading method or temperature of reaction.

The use amount of (a) is with respect to (b) at this moment, preferred 5～80 moles of %, more preferably 10～75 moles of %, more preferably 15～70 moles of %.When making it in this scope, has the tendency that the balance of storage stability, development property, solvent resistance, thermotolerance, physical strength and sensitivity improves.

Resin (B) can be enumerated particularly, and 3,4-epoxycyclohexyl methyl (methyl) acrylic ester/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl acrylic ester/resins [K1] such as (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] decyl acrylic ester/(methyl) acrylic acid/N-cyclohexyl maleimide copolymer, 3-methyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes/resins [K2] such as (methyl) acrylic acid/styrol copolymer; (methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/resins [K3] such as (methyl) acrylic copolymer; Addition has addition on the resin, three ring decyl (methyl) acrylic ester/styrene/(methyl) acrylic copolymers of (methyl) glycidyl acrylate to have addition on the resin, three ring decyl (methyl) acrylic ester/(methyl) benzyl acrylate/(methyl) acrylic copolymers of (methyl) glycidyl acrylate that the resins such as resin [K4] etc. of (methyl) glycidyl acrylate are arranged on (methyl) benzyl acrylate/(methyl) acrylic copolymer.Wherein, preferred resin [K1] and resin [K2], more preferably resin [K1], further preferred 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl acrylic ester/(methyl) acrylic copolymer.

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

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

The acid number of resin (B) is preferred 50～150, and more preferably 60～135, further preferred 70～135.With the measured value of the needed potassium hydroxide amount of 1g resin (B) (mg), for example can try to achieve during acid number is meant here through using the potassium hydroxide aqueous solution titration.

The content of resin (B) is with respect to the solid constituent of photosensitive composition, preferred 7～65 quality %, more preferably 13～60 quality %, further preferred 17～55 quality %.When the content of resin (B) is in above-mentioned scope, can form pattern, have the tendency that improves exploring degree and residual film ratio in addition.

Photosensitive composition of the present invention contains optical polymerism compound (C).Optical polymerism compound (C) is meant and can carries out polymeric compounds according to living radical that Photoepolymerizationinitiater initiater (D) is produced and acid etc.; For example can enumerate the compound of ethene property unsaturated link etc., preferred (methyl) acrylate compounds with polymerism.

Wherein, optical polymerism compound (C) preferably has the optical polymerism compound of 3 above ethene property unsaturated links.Such optical polymerism compound can be enumerated, for example tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylic ester, dipentaerythritol five acrylic ester, dipentaerythritol pentamethyl acrylic ester, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylic ester etc.Optical polymerism compound (C) can separately or make up more than 2 kinds and use.

The content of optical polymerism compound (C) is with respect to the solid constituent of photosensitive composition, preferred 7～65 quality %, more preferably 13～60 quality %, further preferred 17～55 quality %.When the content of above-mentioned optical polymerism compound (C) is in above-mentioned scope, have and solidify fully, the film thickness ratio before and after developing improves, and is difficult in pattern, forming undercutting (undercut), connecting airtight property is good, so preferred.

Photosensitive composition of the present invention contains Photoepolymerizationinitiater initiater (D).

Above-mentioned Photoepolymerizationinitiater initiater (D) does not promptly have special restriction so long as the effect through light produces back beginning polymeric compounds such as living radical, acid, can use known polymerization initiator.Photoepolymerizationinitiater initiater (D) can also contain photopolymerization and cause auxiliary agent (D1) when the effect through light of containing produce the compound of living radical, acid etc.It is compound or the sensitizer that is used by the polymerization of the optical polymerism compound of Photoepolymerizationinitiater initiater initiated polymerization in order to promote that photopolymerization causes auxiliary agent (D1).

Photoepolymerizationinitiater initiater (D) is preferably the compound that produces living radical through the effect of light; More preferably contain at least a kind the Photoepolymerizationinitiater initiater that is selected among benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime compound and the double imidazole compound, further preferably contain the Photoepolymerizationinitiater initiater of oxime compound.

Benzene alkyl ketone compound can be enumerated; The oligomer of diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methyl sulphonyl phenyl)-1-acetone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl-1-butanone, 2-dimethylamino-1-(4-morpholino phenyl)-2-(4-aminomethyl phenyl methyl)-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, 2-hydroxy-2-methyl-1-(4-(1-ethylene methacrylic) phenyl)-1-acetone etc., preferred 2-methyl-2-morpholino-1-(4-methyl sulphonyl phenyl)-1-acetone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl-1-butanone etc.Also can use the commercially available article of basic ガキユア 369,907 (above be チバジヤパ Application society system) etc.

Triaizine compounds can be enumerated, and 2,4-two (trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazines, 2; 4-two (trichloromethyl)-6-(4-methoxyl naphthyl)-1,3,5-triazines, 2,4-two (trichloromethyl)-6-piperonyl-1,3; 5-triazine, 2,4-two (trichloromethyl)-6-(4-methoxyl-styrene)-1,3,5-triazines, 2,4-two (trichloromethyl)-6-(2-(5-methylfuran-2-yl) vinyl)-1; 3,5-triazine, 2,4-two (trichloromethyl)-6-(2-(furans-2-yl) vinyl)-1,3; 5-triazine, 2,4-two (trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1,3,5-triazines, 2; 4-two (trichloromethyl)-6-(2-(3, the 4-Dimethoxyphenyl) vinyl)-1,3,5-triazines etc.

The acylphosphine oxide series initiators can be enumerated, and 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.Also can use イ Le ガキユア 819 commercially available article such as (manufacturings of チバジヤパ Application society).

Oxime compound can be enumerated 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-yl] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3; 3-dimethyl-2,4-dioxa cyclopentyl-methyl oxygen base) benzoyl }-9H-carbazole-3-yl] ethane-1-imines etc.Also can use イ Le ガキユア OXE-01, OXE-02 (more than be that チバジヤパ Application society makes), N-1919 commercially available article such as (manufacturings of ADEKA society).

Double imidazole compound can be enumerated, 2,2 '-two (2-chlorphenyls)-4,4 ', 5; 5 '-tetraphenyl double imidazole, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5; 5 '-tetraphenyl double imidazole (for example, consulting japanese patent laid-open 6-75372 communique, japanese patent laid-open 6-75373 communique etc.), 2,2 '-two (2-chlorphenyls)-4,4 ', 5; 5 '-tetraphenyl double imidazole, 2,2 '-two (2-chlorphenyls)-4,4 ', the two imidazoles of 5,5 '-four (alkoxyl phenyls), 2; 2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (dialkoxy phenyl) two imidazoles, 2,2 '-two (2-chlorphenyls)-4; 4 ', the two imidazoles of 5,5 '-four (tri-alkoxy phenyls) (for example, consult the public clear 48-38403 communique of Japanese Patent Laid, Japanese Patent Laid is opened clear 62-174204 communique etc.), 4; 4 ', 5,5 '-the position substituted imidazolinium compounds of phenyl alkoxy phosphinylidyne (for example, consulting japanese patent laid-open 7-10913 communique etc.) etc.Preferable examples has 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole.

Further, Photoepolymerizationinitiater initiater (D) can be enumerated, styrax compounds such as styrax, styrax methyl ether, styrax ethylether, benzoin isobutyl propyl group ether, benzoin isobutyl butyl ether; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulphur, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4, the benzophenone cpd of 6-tri-methyl benzophenone etc.; 9, naphtoquinone compounds such as 10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzil, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.With these with after the photopolymerization stated cause auxiliary agent (D1) (especially amine) combination and use more satisfactory.

Can enumerate through the acidic acid agent of light, for example salt or nitrobenzyl toluenesulfonic acid salt, styrax 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) also can be the compound that light produces living radical and acid simultaneously that passes through as triaizine compounds for example.

Photopolymerization causes auxiliary agent (D1) can enumerate amines, alkoxy anthracene compound, thioxanthones compound, carboxylic acid compound etc.

Amine compound can be enumerated triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl esters, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, benzoic acid-2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid-2-Octyl Nitrite, N; N-dimethyl-p-toluidine, 4; 4 '-two (dimethylamino) benzophenone (common name Michler's keton), 4; 4 '-two (diethylamino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., wherein; Preferred 4,4 '-two (diethylamino) benzophenone.Also can use EAB-F commercially available article such as (hodogaya chemical industry (strain) systems).

The content of Photoepolymerizationinitiater initiater (D) is with respect to total amount 100 mass parts of resin (B) and optical polymerism compound (C), preferred 0.1～30 mass parts, more preferably 1～20 mass parts.When the content of Photoepolymerizationinitiater initiater is in above-mentioned scope, can makes it high sensitivityization, shorten the time shutter, boost productivity.

Can further contain photopolymerization in the photosensitive composition of the present invention and cause auxiliary agent (D1).Photopolymerization cause auxiliary agent (D1) usually with Photoepolymerizationinitiater initiater (D) combination use, be compound or the sensitizer that uses by the polymerization of the optical polymerism compound of Photoepolymerizationinitiater initiater initiated polymerization in order to promote.

Amines can be enumerated triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl esters, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, benzoic acid-2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid-2-Octyl Nitrite, N; N-dimethyl-p-toluidine, 4; 4 '-two (dimethylamino) benzophenone (common name Michler's keton), 4; 4 '-two (diethylamino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., wherein; Preferred 4,4 '-two (diethylamino) benzophenone.Also can use EAB-F commercially available article such as (hodogaya chemical industry (strain) systems).

The alkoxy anthracene compound can be enumerated, and 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.

The thioxanthones compound can be enumerated, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.

Carboxylic acid compound can be enumerated, phenyl sulfonyl acetate, aminomethyl phenyl sulphonyl acetate, ethylphenyl sulfonyl acetate, Methylethyl phenyl sulfonyl acetate, 3,5-dimethylphenyl sulfonyl acetate, methoxyphenyl sulfonyl acetate, Dimethoxyphenyl sulfonyl acetate, chlorphenyl sulfonyl acetate, dichlorophenyl sulfonyl acetate, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.

Photopolymerization causes auxiliary agent (D1) can separately or make up use more than 2 kinds.

When using these photopolymerization to cause auxiliary agent (D1), its use amount is with respect to total amount 100 mass parts of resin (B) and polymerizable compound (C), preferred 0.01～50 mass parts, more preferably 0.1～40 mass parts.In addition, with respect to 1 mole of Photoepolymerizationinitiater initiater (D), preferred 0.01～10 mole, more preferably 0.01～5 mole.The amount that causes auxiliary agent (D1) when polymerization can further form pattern in this scope the time in high sensitivity, has the tendency that improves pattern throughput rate.

Photosensitive composition of the present invention contains solvent (E).

Solvent (E) does not have qualification especially, can use normally used solvent in this field.Can be from for example, select use the ester solvent (contain-COO-solvent), the ether solvents (contain-O-solvent), ether-ether solvent (contain-COO-and-O-solvent) beyond the ester solvent, the ketone solvent (contain-CO-solvent), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) beyond the ester solvent 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 butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, 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-1-butanols, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, 1,4-dioxan, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, anisole, phenetol, methyl anisole etc.

The ether-ether solvent can be enumerated, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate etc.

Ketone solvent can be enumerated, 4-hydroxy-4-methyl-2 pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc.

Alcoholic solvent can be enumerated, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, monoethylene glycol, propylene glycol, glycerine etc.

Aromatic hydrocarbon solvents can be enumerated benzene,toluene,xylene, mesitylene etc.

Amide solvent can be given an example, N, dinethylformamide, DMAC N,N, N-Methyl pyrrolidone etc.

These solvents can separately or make up more than 2 kinds and use.

Among the above-mentioned solvent, based on the point of coating, drying property, the boiling point among the preferred 1atm is at the organic solvent more than 120 ℃, below 180 ℃.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, the flatness during coating is excellent.

The content of solvent in the photosensitive composition (E) is with respect to photosensitive composition, preferred 70～95 quality %, more preferably 75～92 quality %.In other words, preferred 5～30 quality % of the solid constituent in the photosensitive composition, more preferably 8～25 quality %.The content of solvent (E) is in above-mentioned scope, and the flatness during coating becomes well, in addition, do not have the colour saturation deficiency when forming color filter, so display characteristic has the trend that improves.

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

Can enumerate as the silicone-based surfactant, have the surfactant of siloxane bond etc.Particularly, TORAY SILICONE DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, polyether modified silicone oil SH8400 (trade name: eastern レダウコ one ニ Application グ (strain) makes), 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 (manufacturing of モメ Application テイ Block パ Off オ one マ Application スマテリア Le ズジヤパ Application contract commercial firm) etc. are arranged for example.

Above-mentioned fluorine is that surfactant can be enumerated surfactant with fluoro carbochain etc.Specifically can enumerate Off ロラ one De (trade name) FC430, same FC431 (manufacturing of Sumitomo スリ one エ system (strain)), 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) manufacturing), エ Off ト Star プ (trade name) EF301, same EF303, same EF351, same EF352 (the マテリア of Mitsubishi Le electronics changes into (strain) system), サ one Off ロ Application (trade name) S381, same S382, same SC101, same SC105 (Asahi Glass (strain) system), E5844 ((strain) ダイキ Application Off アイ Application ケミ Le institute system) etc.

As above-mentioned silicone-based surfactant, can enumerate surfactant with siloxane bond and fluoro carbochain etc. with fluorine atom.Particularly, メガ Off ア Star Network (registered trademark) R08, same BL20, same F475, same F477, same F443 (DIC (strain) manufacturing) etc. are arranged for example.

These surfactants can be alone or in combination 2 kinds with on use.

The content of surfactant (F); With respect to more than the preferred 0.001 quality % of photosensitive composition, below the 0.2 quality %; More preferably 0.002 quality % above, below the 0.1 quality %, further preferred 0.01 quality % above, below the 0.05 quality %.The content of surfactant (F) can make the flatness of filming improve when above-mentioned scope.

When photosensitive composition of the present invention is the composition that is made up of colorant (A), alkali soluble resin (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D), solvent (E) and surfactant (F); Its coating is excellent, can obtain all excellent multicolour pattern of solvent resistance and beam split.

In the photosensitive composition of the present invention; The content of preferred colorant (A) is 0.5～10 quality %; The content of resin (B) is 1～20 quality %; The content of optical polymerism compound (C) is 1～15 quality %, and the content of Photoepolymerizationinitiater initiater (D) is 0.5～10 quality %, and the content of solvent (E) is 45～97 quality %.In addition, more preferably the content of colorant (A) is 1～7 quality %, and the content of resin (B) is 3～10 quality %; The content of optical polymerism compound (C) is 3～12 quality %; The content of Photoepolymerizationinitiater initiater (D) is 1～5 quality %, and the content of solvent (E) is 66～92 quality %, and the content of further preferred colorant (A) is 2～5 quality %; The content of resin (B) is 4～8 quality %; The content of optical polymerism compound (C) is 5～10 quality %, and the content of Photoepolymerizationinitiater initiater (D) is 2～4 quality %, and the content of solvent (E) is 73～87 quality %.

When using photopolymerization to cause auxiliary agent (D1) in the photosensitive composition of the present invention; With respect to 100 weight portions of the solid constituent in the photosensitive composition; The content that photopolymerization causes auxiliary agent is preferably 0.1～10 mass parts; More preferably 0.5～5 mass parts, further preferred 1～3 mass parts.

When using surfactant (F) in the photosensitive composition of the present invention; With respect to 100 weight portions of the solid constituent in the photosensitive composition; The content of surfactant (F) is preferably 0.001～1 mass parts; More preferably 0.01～0.5 mass parts further is preferably 0.05～1 mass parts.

Photosensitive composition of the present invention can contain various adjuvants such as filling agent, other macromolecular compounds, adhesion promoter, anti-oxidant, ultraviolet light absorber, light stabilizer, chain-transferring agent as required.

As using photosensitive composition of the present invention to form the method for multicolour pattern; Following method is arranged for example, for example, photosensitive composition of the present invention (for example is coated on substrate or other resin bed; Earlier at other photosensitive composition layer that forms on the substrate etc.) on; Remove/volatile ingredients such as dry solvent form dyed layer, are situated between by the photomask method that this dyed layer develops of making public, and use the method for the ink-jet machine that does not need photoetch method etc.

The thickness that film this moment does not have special qualification, can suitably adjust according to employed material, purposes etc., for example is 0.1～30 μ m, preferred 1～20 μ m, further preferred 1～6 μ m.

The coating process of photosensitive composition can be enumerated, for example extrusion coated method, direct photogravure rubbing method, inverse type photogravure rubbing method, CAP rubbing method, chill coating coating (die coating) method etc.In addition, also can use dip coaterd, scraping strip coating machine, rotary coating machine, slit & rotary coating machine, slit coater coating machines such as (also claiming Die Coater, Curtain Flow Coater (showering curtain type plane coating machine), Spinless Coater (non-rotating rubbing method)) to be coated with.

The removing of solvent/drying can be enumerated for example air dry, aeration-drying, drying under reduced pressure, heat drying etc.Preferred 10 ℃～120 ℃ of concrete baking temperature, more preferably 25 ℃～100 ℃.Preferred 10 seconds～60 minutes of drying time, more preferably 30 seconds～30 minutes.Drying under reduced pressure is preferably under the pressure of 50～150pa, carry out in 20～25 ℃ the scope.

Dried coating is situated between and is made public by the photomask that is used to form target pattern.Pattern form on the photomask of this moment does not have special qualification, uses pattern form according to the target purposes.

The employed light source that makes public preferably sends the light source of light of the wavelength of 250～450nm.Can enumerate particularly, mercury vapor lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc. can use the color filter that cuts particular wavelength region to cut and make public, and also can use the BPF. of selecting the specific wavelength territory optionally to take out and make public.

For plane of exposure integral body is shone parallel rays equably, make the correct contraposition of mask and base material, preferably use devices such as mask aligner, step-by-step exposure machine.

After the exposure, can obtain pattern through contact, make for example unexposed dissolving of established part, development with developer solution.Developer solution can be enumerated the WS of alkali compounds (potassium hydroxide, sodium carbonate, TMAH etc.) etc.This developer solution can contain surfactant.

Developing method can use any in paddling process, infusion process, the spray-on process etc.Further, during development, substrate can be with arbitrarily angled inclination.Preferably wash after the development.

Further, according to necessity, can also carry out the back baking.Back baking is preferably 150～230 ℃, 10～240 minutes scope.

Can obtain good filming or pattern such as colour saturation, brightness, contrast, sensitivity, exploring degree, thermotolerance through photosensitive composition of the present invention, these are all useful as color filter.The display device that in addition, can also be applied to these color filters are had as its a part of component parts with known form for example, various all machines relevant such as known liquid crystal indicator, organic El device, solid-state imager with coloured image.

[embodiment]

Below through embodiment photosensitive composition of the present invention is illustrated in greater detail.

" % " in the example reaches " part " as long as there be not special the qualification, is quality % and mass parts.

Synthetic example 1

30 portions of rhodamine Bs (Tokyo changes into industry (strain) system) are dissolved in 288 parts of chloroforms, add 2.3 parts of N, N-dimethyl-4-aminopyridine, 1.75 parts of 10-camphorsulfonic acids, 16.24 parts of diglycidyls are in stirring 1 hour below 20 ℃.When stirring, drip the chloroformic solution that has dissolved 17.41 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochlorides (Tokyo changes into industry (strain) system) in 72 parts of the chloroforms and obtained.After reaction finishes, in this reactant liquor, add the 1N aqueous hydrochloric acid solution and carry out separatory, obtain organic layer.For this organic layer, repeat 2 these operations.Then, in this organic layer, adding 10% saline solution carries out separatory, obtains organic layer.For this organic layer, repeat 2 these operations.After in the organic layer that obtains, adding the magnesium sulphate dehydration, filtration obtains filtrating.Remove from this filtrating through evaporator and to desolvate, the red solid that obtains is carried out drying under following 60 ℃ of decompression, obtain the compound shown in 30 parts of formulas (d-1) (productive rate 89.5%) thus.

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

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

Accurate mass: 534.2

Embodiment 1

After 7.5 parts of 2-amino-4-methyl sulphonyl-6-nitrophenol (CAS No.101861-04-5) adds 65 parts of water, add 1.3 parts of NaOH again and make it dissolving.Ice-cooled 6.1 part of 35% sodium nitrite (with the pure pharmaceutical worker's industry of light (strain) system) WS that adds down then adds 19.4 part of 35% hydrochloric acid bit by bit and makes it dissolving, stirs 2 hours, obtains to contain the suspension of diazo salt.Then add lentamente 5.6 parts of sulfaminic acids (with the pure pharmaceutical worker of light industry (strain) system) are dissolved in 26 parts of WS in the water, suppress excessive sodium nitrite.

Then, 5.6 parts of 3-methyl isophthalic acid-phenyl-5-pyrazolone (with the pure pharmaceutical worker's industry of light (strain) system) is suspended in 70 parts of water, using NaOH adjustment pH is 8.0.Here, the suspension that will contain above-mentioned diazo salt lasts 15 minutes, drips 10% sodium hydroxide solution aptly and makes pH be stabilized to 7.5 scope from 7.After dripping end, further stir and obtained yellow suspension in 30 minutes.Stirred 1 hour.The yellow solid that filters gained is under reduced pressure carried out drying under 60 ℃, obtain the compound shown in 11.7 parts of formulas (p-2) (productive rate 87%).

The compound of 10 parts of formulas (p-2) added dissolving in 100 parts the dimethyl formamide (Tokyo changes into industry (strain) system); After adding 3.1 parts of chromium ammonium suplhates (III), 12 water (with the pure pharmaceutical worker's industry of light (strain) system), 1.1 parts of sodium acetates (with the pure pharmaceutical worker's industry of light (strain) system), reflux 4 hours half.After being cooled to room temperature, reaction solution is injected 1500 part of 20% saline solution,, obtain the compound shown in 13.6 parts of formulas (z-2) (productive rate 63%) filtering Chinese red solid drying under 60 ℃ that the back obtains.

The evaluation of the compound shown in the 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 N-N-methyl-2-2-pyrrolidone N-s.In this solution, add, stirred 2 hours by 2.63 parts of solution that are dissolved in 35 parts of N-N-methyl-2-2-pyrrolidone N-s and obtain of the compound shown in the formula (d-1).After reaction finished, to wherein dripping 300 parts of water, the red solid that leaching is separated out reduced pressure and carries out drying under following 60 ℃, obtains the compound shown in 6.4 parts of formulas (1-27) (productive rate 86.8%) in view of the above.

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

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

Accurate mass: 1381.3

Synthetic example 2

< synthesizing of resin B 1 solution >

The speed of dividing with 0.02L/ pours nitrogen in the flask that possesses stirring machine, thermometer, reflux condensing tube and tap funnel makes it become nitrogen atmosphere gas, adds 305 mass parts ethyl lactates, in the time of stirring, is heated to 70 ℃.Then, be modulated into and dissolved 60 mass parts methacrylic acids, 240 mass parts 3,4-epoxy three ring [5.2.1.0 ^2.6] the decyl acrylic ester (mixes the compound shown in compound shown in the following formula (I-1) and the formula (II-1) with mol ratio 50: 50.) and the solution of 140 mass parts ethyl lactates, this lysate is lasted 4 hours with tap funnel, be added drop-wise to insulation in 70 ℃ flask.On the other hand, with 30 mass parts polymerization initiators 2, the solution that 2 '-azo two (2, the 4-methyl pentane nitrile) is dissolved in 225 mass parts ethyl lactates lasts 4 hours with another tap funnel and is added drop-wise in the flask.After the dropping of polymerization initiator solution finishes, in 70 ℃ of maintenances 4 hours, be cooled to room temperature thereafter, obtaining weight-average molecular weight Mw is 1.3 * 10 ⁴, solid constituent 33 quality %, 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.

Synthetic example 3

< synthesizing of resin B 2 solution >

In the flask that possesses stirring machine, thermometer, backflow cooling tube, tap funnel and gas introduction tube, import the 333g propylene glycol methyl ether acetate.Thereafter, through gas introduction tube nitrogen is imported in the flask, making the atmosphere gas displacement in the flask is nitrogen.Thereafter; After solution in the flask is warming up to 100 ℃; Use tap funnel to last 2 hours and in flask, drip the potpourri that constitutes by N-benzyl maleimide 18.7g, methacrylic acid benzyl ester 70.5g, methacrylic acid 51.7g, methyl methacrylate 90.0g, azoisobutyronitrile 5.2g and propylene glycol methyl ether acetate 182g, drip the end continued and stirred 5 hours down in 100 ℃.

After stirring end; In flask, import air through gas introduction tube; After making the interior atmosphere gas displacement of flask be air; In flask, drop into 28.5g GMA, 1.3g three (dimethylamino methyl) phenol and 0.165g p-dihydroxy-benzene, in 110 ℃ of following sustained responses 6 hours, obtaining weight-average molecular weight Mw was 16 * 10 ³, 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, adopt the GPC method under following condition, to carry out.

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

Chromatographic column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow velocity: 1.0mL/min

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

Injection rate IR: 50 μ L

Detecting device: RI

Proofread and correct and use standard substance: TSK STANDARD POLYSTYRENEF-40, F-4, F-288, A-2500, A-500 (eastern ソ one (strain) system)

Embodiment 2

(modulation of photosensitive composition)

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

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

(C) optical polymerism compound: the potpourri of dipentaerythritol five acrylic ester and dipentaerythritol acrylate (KAYARAD DPHA: Japanese chemical drug (strain) system) 60 parts

(D) Photoepolymerizationinitiater initiater: 12 parts of N-benzoyloxy-1-(4-phenyl sulfonyl phenyl)-1-octanone-2-imines (イ Le ガキユア OXE 01:BASF Japanese firm system)

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

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

(E) solvent: 597 parts of propylene glycol monomethyl ethers

(E) solvent: 43 parts of ethyl lactates

(F) surfactant: polyether modified silicone oil (ト one レシリコ one Application SH8400: eastern レダウコ one ニ Application グ (strain) system) 0.09 part

Mix above-mentioned substance and obtain photosensitive composition.

(formation of pattern)

On 2 inches square glass substrates (イ one グ Le 2000: コ one ニ Application グ society system), be coated with photosensitive composition with spin-coating method, then, under 100 ℃, give baking 3 minutes.After the cooling, make the 100 μ m that are spaced apart between the substrate that has been coated with this photosensitive composition and the quartz glass system photomask, use exposure machine (TME-150RSK: トプコ Application (strain) system), under atmospheric atmosphere gas with 100mJ/cm ²Exposure (365nm benchmark) carry out rayed.In addition, photomask uses the mask of the padding intermittent pattern (Line and Space Pattern) that has formed 100 μ m.After the rayed, this substrate is immersed in contains in the WS that 0.12% nonionic is surfactant and 0.04% potassium hydroxide, in 23 ℃ down dipping developed in 80 seconds, after the washing, in stove, 230 ℃ of back bakings 30 minutes down.After putting cooling, (DEKTAK3: Japanese vacuum technique (strain) system) thickness of the resulting multicolour pattern of mensuration, the result is 2.0 μ m with the determining film thickness device.

(look performance evaluation)

Pattern to acquisition uses colour examining machine (OSP-SP-200: Olympus (strain) is made) to measure beam split, and the XYZ that the isochrome function of use illuminant-C records CIE marks the xy chromaticity coordinate (x, y) (being colourity) and the brightness Y of the immersion front and back in the colour system system.The result sees table 1.

(solvent resistance evaluation)

Except when forming above-mentioned pattern, not using photomask makes public, all the other are implemented same operation and make and film.Filming of acquisition soaked 30 minutes in 23 ℃ N-N-methyl-2-2-pyrrolidone N-; Use colour examining machine (OSP-SP-200: Olympus (strain) system) measure beam split; Xy chromaticity coordinate (Rx, Ry) (being colourity) and brightness RY with before and after the immersion in the XYZ mark colour system system of the isochrome function mensuration CIE of illuminant-C calculate the aberration Δ Eab* that soaks front and back.The more little solvent resistance of aberration Δ Eab* is good more.The result of aberration Δ Eab* sees table 1.

In addition, use cutter (カ Star タ one) and super cutter guide (ス one パ one カ Star タ one ガイ De) (helping very much machine material society system) on filming after the immersion, cut, produce the grid of 100 1mm * 1mm with the interval of 1mm.On this grid, paste the wide adhesive tape (セロテ one プ) (registered trademark) (ニチバ Application (strain) society system) of 24mm; Go up wiping with erasing rubber at adhesive tape (セロテ one プ) (registered trademark); Pay in cured coating film so that adhesive tape (セロテ one プ) (registered trademark) pastes, after 2 minutes, hold the end of adhesive tape (セロテ one プ); On coated surface, keep the right angle, peel off without a break.Afterwards, the range estimation number goes out the number of squares that residual filming on the substrate not have disengaging.Promptly as connecting airtight property, the result sees table 1 to this grid.

Comparative example 1

(A) colorant: 47.5 parts of Orasol Red G (チバジヤパ Application (strain) system)

(B) resin: 16 parts of resin B 2 solution

(C) optical polymerism compound: the potpourri of dipentaerythritol five acrylic ester and dipentaerythritol acrylate (KAYARAD DPHA: Japanese chemical drug (strain) system) 23.9 parts

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

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

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

(E) solvent: 267 parts of propylene glycol monomethyl ethers

(E) solvent: 138 parts of propylene glycol methyl ether acetates

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

Mix above-mentioned substance and obtain photosensitive composition.Photosensitive composition is implemented the evaluation identical with embodiment 1.The result sees table 1.

[table 1]

*) because when in the N-N-methyl-2-2-pyrrolidone N-, soaking, color coating splits away off from glass substrate, thereby can't measure aberration Δ Eab* and connecting airtight property.

Use photosensitive composition of the present invention to form and film and have good solvent resistance.Hence one can see that, according to photosensitive composition of the present invention, can obtain solvent resistance excellent film, pattern and high-quality color filter.

Utilizability on the industry

According to photosensitive composition of the present invention, can obtain solvent resistance good film, pattern and high-quality color filter.

Claims

1. a photosensitive composition contains colorant, resin, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent, and colorant is for containing the colorant of compound shown in the formula (1);

In the formula (1), R ¹～R ¹⁸Represent independently of one another hydrogen atom, halogen atom, carbon number 1～8 1 valency aliphatic alkyl, nitro or-SO ₂R ²⁹

R ²⁹Expression-R ³²,-OH or-NHR ³⁰

R ³⁰1 valency aliphatic alkyl of expression hydrogen atom, carbon number 1～8, can by the substituted cyclohexyl of the alkyl of carbon number 1～4 ,-R ³¹-O-R ³²,-R ³¹-CO-O-R ³²,-R ³¹-O-CO-R ³²Or the aralkyl of carbon number 7～10;

R ³¹The divalent aliphatic alkyl of expression carbon number 1～8;

R ³²1 valency aliphatic alkyl of expression carbon number 1～8;

R ¹⁹And R ²⁰Represent hydrogen atom, methyl, ethyl or amino independently of one another;

M ¹Expression Cr or Co;

R ²¹～R ²⁴Represent 1 valency aliphatic alkyl of hydrogen atom, carbon number 1～8 or 1 valency aromatic hydrocarbyl of carbon number 6～10 independently of one another, the hydrogen atom that this aliphatic alkyl and this aromatic hydrocarbyl comprised can by hydroxyl ,-OR ³², sulfonic group ,-SO ₃Na ,-SO ₃K or halogen atom replace;

R ²⁵And R ²⁶Represent hydrogen atom or methyl independently of one another;

R ²⁷Expression ethylidine, 1,3-propylidene or 1,2-propylidene;

N representes 0～3 integer; When n is the integer more than 2, a plurality of R ²⁷Each other can be identical or different.

2. photosensitive composition according to claim 1, wherein R ¹～R ¹⁸Be independently of one another hydrogen atom, nitro or-SO ₂R ²⁹,

R ²⁹For-R ³²,

R ³²Be 1 valency aliphatic alkyl of carbon number 1～8,

R ¹⁹And R ²⁰Be methyl independently of one another,

R ²¹～R ²⁴Be 1 valency aliphatic alkyl of carbon number 1～8 independently of one another,

R ²⁵And R ²⁶Be hydrogen atom independently of one another,

N is 0.

3. photosensitive composition according to claim 2, wherein R ¹～R ¹⁸Among at least one be hydrogen atom, at least one is a nitro, and at least one is-SO ₂R ²⁹

4. photosensitive composition according to claim 3, wherein R ¹～R ¹⁰Be hydrogen atom independently of one another.

5. photosensitive composition according to claim 4, wherein R ¹¹～R ¹⁸Among at least one be hydrogen atom,

R ¹¹～R ¹⁸Among at least one be nitro, and

R ¹¹～R ¹⁸Among at least one be-SO ₂R ²⁹

6. photosensitive composition according to claim 1, wherein Photoepolymerizationinitiater initiater is to contain at least a Photoepolymerizationinitiater initiater that is selected among benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime compound and the double imidazole compound.

7. photosensitive composition according to claim 1, wherein M ¹Be Cr.

8. color filter is formed by any described photosensitive composition of claim 1～7.

9. a display device contains the described color filter of claim 8.

10. the compound shown in the formula (1),

R ²⁹Expression-R ³²,-OH or-NHR ³⁰

R ³¹The divalent aliphatic alkyl of expression carbon number 1～8;

R ³²1 valency aliphatic alkyl of expression carbon number 1～8;

M ¹Expression Cr or Co;

R ²⁷Expression ethylidine, 1,3-propylidene or 1,2-propylidene;