CN102736412B - Photosensitive composition - Google Patents

Abstract

A kind of photosensitive composition, wherein, comprising colouring agent (A), resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E), and colouring agent (A) is the colouring agent of the salt that contained (1) represents.According to the photosensitive composition, the colour filter of the good film of heat resistance, light resistance, pattern and high-quality can be obtained.

Description

Photosensitive composition

Technical field

The present invention relates to photosensitive composition.

Background technology

Recorded comprising cyanine dyes, resin, optical polymerism chemical combination in Japanese Unexamined Patent Publication JP 2010-168531 publications The photosensitive composition of thing, Photoepolymerizationinitiater initiater and solvent.

Photosensitive composition as film, the pattern etc. of colour filter materials'use.That is, the painting of colour filter Film, pattern etc. are the staining and curing things for solidifying photosensitive composition.

The content of the invention

It is an object of the present invention to provide heat resistance and the more excellent staining and curing thing of light resistance and comprising it The photosensitive composition of colour filter can be obtained.

The present invention provides following [1]~[5].

[1] a kind of photosensitive composition, wherein, comprising colouring agent (A), resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E), and colouring agent (A) is the colouring agent of the salt that contained (1) represents,

[in formula (1), R¹~R¹⁸Hydrogen atom, halogen atom, 1 valency aliphatic of carbon number 1~8 are represented independently of one another Alkyl, nitro or-SO₂R²⁹,

R²⁹Represent-OH ,-NHR³⁰Or-R³²,

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

R³¹The divalent aliphatic alkyl of carbon number 1~8 is represented,

R³²1 valency aliphatic alkyl of carbon number 1~8 is represented,

R¹⁹And R²⁰Hydrogen atom, methyl, ethyl or amino are represented independently of one another,

M¹Cr or Co is represented,

Ring Z¹And ring Z²Represent can there is the aromatic rings of substitution base, R independently of one another²¹And R²²Represent independently of one another Can have the aliphatic alkyl or hydrogen atom of the carbon number 1~12 of substitution base, R²³And R²⁴Can represent independently of one another can The aliphatic alkyl or hydrogen atom of the carbon number 1~12 with substitution base, or R²³With R²⁴Can be integrally formed and form alkylene Base, R²⁵And R²⁶Can independently of one another represent that the aliphatic alkyl or hydrogen of the carbon number 1~12 can with substitution base are former Son, or R²⁵With R²⁶Can be integrally formed and form alkylidene, R²⁷And R²⁸Can independently of one another represent there can be substitution base The aliphatic alkyl or hydrogen atom of carbon number 1~12, or R²⁷With R²⁸Can be integrally formed and form alkylidene, X¹Represent that hydrogen is former Son or chlorine atom.

[2] coloring photosensitive combination according to [1], wherein, Photoepolymerizationinitiater initiater is comprising selected from benzene alkyl ketone At least a kind in compound, triaizine compounds, acylphosphine oxide compound, oxime compound and di- imidazolium compounds of light Polymerization initiator.

[3] coloring photosensitive combination according to [1] or [2], wherein, M¹It is Cr.

[4] coloring photosensitive combination according to [1], wherein, the salt that the salt that formula (1) is represented is represented for formula (1-A),

In formula (1-A), R^21-AAnd R^22-AThe aliphatic alkyl of carbon number 1~4 is represented independently of one another,

R^xAnd R^yHydrogen atom, methyl or trifluoromethyl are represented independently of one another.

[5] a kind of colour filter, its photosensitive composition as any one of [1]~[4] is formed.

[6] a kind of display device, it includes the colour filter described in [5].

Photosensitive composition of the invention, the coloring that can form light resistance and excellent heat resistance is consolidated Compound (for example, film, pattern) such that it is able to obtain the colour filter of the high-quality comprising it.

Photosensitive composition of the invention, comprising colouring agent (A), resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E), and colouring agent (A) is that the anion represented by following formula (A1) (is sometimes referred to as below Be " anion (A1) ") and following formula (A2) represent cation (hereinafter sometimes referred to " cation (A2) ") constitute salt (with Down sometimes referred to as " salt (1) ").

Anion (A1) can be selected according to the color of target colour filter.Salt comprising anion (A1) is preferably molten Fully dissolved in agent.In addition, the salt comprising anion (A1), is preferably dissolved in the aftermentioned developer solution formed for pattern The degree of the pattern can be formed.

It should be noted that because anion (A1) uses resonant structure, therefore, the electric charge of the anion described in formula (A1) The anion being moved is also included in the present invention.

In anion (A1), as 1 valency aliphatic alkyl of carbon number 1~8, can enumerate：Methyl, ethyl, positive third Base, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1- methyl butyls, 1, 1,3,3- tetramethyl butyl, 1,5- dimethylhexanyls, 1,6- dimethyl heptyl, 2- ethylhexyls and 1,1,5,5- tetramethyl oneself Base etc..

In anion (A1), as the alkyl of carbon number 1~4, can enumerate：Methyl, ethyl, n-propyl, isopropyl, Normal-butyl, sec-butyl, tert-butyl group etc..

In anion (A1), as the divalent aliphatic alkyl of carbon number 1~8, can enumerate：Methylene, ethylidene, Propane -1,3- diyls, propane -1,2- diyls, butane-Isosorbide-5-Nitrae-diyl, butane -1,3- diyls, pentane -1,5- diyls, hexane -1, 6- diyls, heptane -1,7- diyls, octane -1,8- diyls etc..

In anion (A1), as be able to can be enumerated by the alkyl-substituted cyclohexyl of carbon number 1~4：2- methyl rings Hexyl, 2- ethylcyclohexyls, 2- propylcyclohexyls, 2- isopropylcyclohexyls, 2- butylcyclohexyls, 4- methylcyclohexyls, 4- second Butylcyclohexyl, 4- propylcyclohexyls, 4- isopropylcyclohexyls, 4- butylcyclohexyls etc..

In anion (A1), as-R³¹-O-R³², can enumerate：Methoxy, ethoxyl methyl, propoxy methyl, Methoxy ethyl, ethoxyethyl group, Among, methoxy-propyl, ethoxycarbonyl propyl, propoxypropyl, 2- oxo -4- first Epoxide butyl, octyloxy propyl group, 3- ethoxycarbonyl propyls, 3- (2- ethyl hexyl oxies) propyl group etc..

In anion (A1), as-R³¹-CO-O-R³², can enumerate：Methoxycarbonyl-methyl, methoxycarbonylethyl, ethoxy Carbonvlmethyl, ethoxycarbonyl-ethyl, propylene carbonyl oxygen methyl, propylene carbonyl oxygen ethyl, butoxycarbonylmethyl, butoxy carbonyl ethyl etc..

In anion (A1), as-R³¹-O-CO-R³², can enumerate：Acetoxy-methyl, Acetoxvethyl, ethyl Carbonyl oxy-methyl, ethyl oxy carbonyl ethyl, propyl group carbonyl oxy-methyl, propyl group carbonyloxy group ethyl, butyl carbonyl oxy-methyl, butyl carbonyl Epoxide ethyl etc..

In anion (A1), as-SO₂R²⁹, can enumerate：Sulfo group；Sulfamoyl；

N- Methylsulfamoyls, N- ethylsulfamovls, N- propylsulfamovs, N- isopropylsulfamoyls base, N- butyl Sulfamoyl, N- isobutyl groups sulfamoyl, N- sec-butyls sulfamoyl, N- tert-butyl groups sulfamoyl, N- amyl groups sulfamoyl, N- (1- ethyl propyls) sulfamoyl, N- (1,1- dimethyl propyl) sulfamoyl, N- (1,2- dimethyl propyl) sulfamoyl, N- (2,2- dimethyl propyl) sulfamoyl, N- (1- methyl butyls) sulfamoyl, N- (2- methyl butyls) sulfamoyl, N- (3- Methyl butyl) sulfamoyl, N- Cyclopentylsulfamoyls base, N- hexyls sulfamoyl, N- (1,3- dimethylbutyl) sulfamoyl, N- (3,3- dimethylbutyl) sulfamoyl, N- heptyl sulfamoyl, N- (1- methylhexyls) sulfamoyl, N- (Isosorbide-5-Nitraes-diformazan Base amyl group) sulfamoyl, N- octyl groups sulfamoyl, N- (2- ethylhexyls) sulfamoyl, N- (1,5- dimethyl) hexyl ammonia sulphur The ammonia sulphur that acyl group, N- (1,1,2,2- tetramethyl butyl) sulfamoyl, N- pi-allyl sulfamoyls etc. are replaced by aliphatic alkyl Acyl group；

N- (2- methoxy ethyls) sulfamoyl, N- (2- ethoxyethyl groups) sulfamoyl, N- (1- methoxy-propyls) ammonia Sulfonyl, N- (3- methoxy-propyls) sulfamoyl, N- (3- ethoxycarbonyl propyls) sulfamoyl, N- (3- propoxypropyls) ammonia sulphur Acyl group, N- (3- isopropoxide propyls) sulfamoyl, N- (3- hexyloxies propyl group) sulfamoyl, N- (2- ethyl hexyl oxies propyl group) Sulfamoyl, N- (3- tert-butoxies propyl group) sulfamoyl, N- (4- octyloxies butyl) sulfamoyl etc. are by-R³¹-O-R³²Substitution Sulfamoyl；

N- (methoxycarbonyl-methyl) sulfamoyl, N- (methoxycarbonylethyl) sulfamoyl, N- (ethoxycarbonylmethyl group) ammonia Sulfonyl, N- (ethoxycarbonyl-ethyl) sulfamoyl, N- (propylene carbonyl oxygen methyl) sulfamoyl, N- (propylene carbonyl oxygen ethyl) ammonia sulphur Acyl group, N- (butoxycarbonylmethyl) sulfamoyl, N- (butoxy carbonyl ethyl) sulfamoyl etc. are by-R³¹-CO-O-R³²Substitution Sulfamoyl；

N- (acetyl-o-methyl) sulfamoyl, N- (Acetoxyethyl) sulfamoyl, N- (ethyl oxy carbonyl methyl) ammonia sulphur Acyl group, N- (ethyl oxy carbonyl ethyl) sulfamoyl, N- (propyl group carbonyl oxy-methyl) sulfamoyl, N- (propyl group carbonyloxy group ethyl) Sulfamoyl, N- (butyl carbonyl oxy-methyl) sulfamoyl, N- (butyl carbonyloxy group ethyl) sulfamoyl etc. are by-R³¹-O-CO- R³²Substituted sulfamoyl；

N- cyclohexylsulfamoyls, N- (2- methylcyclohexyls) sulfamoyl, N- (3- methylcyclohexyls) sulfamoyl, N- The ammonia that (4- methylcyclohexyls) sulfamoyl, N- (4- butylcyclohexyls) sulfamoyl etc. are replaced by the cyclohexyl with substitution base Sulfonyl；

N- benzyls sulfamoyl, N- (1- phenylethyls) sulfamoyl, N- (2- phenylethyls) sulfamoyl, N- (3- benzene Base propyl group) sulfamoyl, N- (4- phenyl butyls) sulfamoyl, N- [2- (2- naphthyls) ethyl] sulfamoyl, N- [2- (4- first Base phenyl) ethyl] sulfamoyl, N- (3- phenyl -1- propyl group) sulfamoyl, N- (3- phenyl -1- methyl-propyls) sulfamoyl Deng sulfamoyl replaced by aralkyl etc..

In anion (A1), as-SO₂R³², can enumerate：It is methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, different Sulfonyl propyl base, normal-butyl sulfonyl, sec-butylsulfonyl, tert. butylsulfonyl, pentylsulfonyl, hexyl sulfonyl, heptyl Sulfonyl, octyl group sulfonyl, 1- methyl butyls sulfonyl, 1,1,3,3- tetramethyl butyl sulfonyl, 1,5- dimethylhexanyl sulphurs Acyl group, 1,6- dimethyl heptyl sulfonyl, 2- ethylhexyls sulfonyl and 1,1,5,5- tetramethylhexyl sulfonyl etc..Its In, preferably methyl sulphonyl and ethylsulfonyl, more preferably methyl sulphonyl.

Due to the tendency that can form the more excellent pattern of heat resistance etc., therefore, R¹~R¹⁸In, preferably with extremely Few 1 nitro.

Additionally, it is preferred that R¹~R⁵In at least one and R⁶~R¹⁰In at least one be-SO₂R²⁹.With multiple-SO₂R²⁹ In the case of, multiple R²⁹Can be the same or different each other.

-SO₂R²⁹For-SO₂H、-SO₂NHR³⁰Or-SO₂R³², preferably-SO₂R³².Wherein, preferably-SO₂CH₃。

Compound of the invention has-SO₂R³²In the case of, preferably R¹¹~R¹⁴In at least one and R¹⁵~R¹⁸In At least one is-SO₂R³².With multiple-SO₂R³²In the case of, multiple R³²Can be the same or different each other.

Cation (A2) can be selected according to the color of target colour filter.Salt comprising cation (A2), preferably exists Fully dissolved in solvent.In addition, the salt comprising cation (A2), preferably dissolves in the aftermentioned developer solution formed for pattern The degree of the pattern can extremely be formed.

It should be noted that because cation (A2) uses resonant structure, therefore, the electric charge of the cation described in formula (A2) The cation being moved is also included in the present invention.

In cation (A2), ring Z¹And ring Z²Represent there can be the aromatic rings of substitution base independently of one another.As above-mentioned virtue Fragrant ring, preferably phenyl ring or naphthalene nucleus.

As above-mentioned phenyl ring and the substitution base of above-mentioned naphthalene nucleus, for example, can enumerate：

Methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, isopentyl, neopentyl, uncle The aliphatic alkyls such as amyl group；

Phenyl, o-tolyl, a tolyl, p-methylphenyl, xylyl, trimethylphenyl, adjacent cumenyl, an isopropylbenzene Base, to aromatic hydrocarbyls such as cumenyls；

Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, penta oxygen The alkoxies such as base；

The aryloxy group such as phenoxy group；

The aralkoxies such as benzyloxy；

The acyloxy such as methoxycarbonyl group, carbethoxyl group, propylene carbonyl oxygen, acetoxyl group, benzoyloxy；

Methylsulfamoyl, DimethylsuIfamoyl, ethylsulfamovl, diethyl amino sulfonyl, n-propyl sulfonamides Base, diη-propyl sulfamoyl, isopropylsulfamoyl base, diisopropyl sulfamoyl, normal-butyl sulfamoyl, di-n-butyl ammonia The alkylsulfamoyl groups such as sulfonyl；

Methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropelsulfonyl, normal-butyl sulfonyl, isobutyl group sulphonyl The alkyl sulphonyls such as base, sec-butylsulfonyl, tert. butylsulfonyl；

The halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom；

Nitro, cyano group.

It should be noted that in the case where such substitution base has hydrogen atom, the hydrogen atom can be for example former by fluorine The halogen atoms such as son, chlorine atom, bromine atoms, iodine atom；Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutyl oxygen The alkoxies such as base, sec-butoxy, tert-butoxy, amoxy；The aryloxy group such as phenoxy group, benzyloxy；Phenyl, o-tolyl, a first Phenyl, p-methylphenyl, xylyl, trimethylphenyl, adjacent cumenyl, a cumenyl, to aromatic hydrocarbyls such as cumenyls； Carboxyl；Cyano group；Nitro；Deng substitution.

From from the viewpoint of dissolubility, ring Z¹And ring Z²The phenyl ring that can be preferably substituted respectively, it is more preferably unsubstituted Phenyl ring.

In cation (A2), X¹Preferably hydrogen atom.

In cation (A2), R²¹And R²²It is independently of one another the aliphatic of the carbon number 1~12 can with substitution base Alkyl or hydrogen atom, the aliphatic alkyl of the carbon number 1~8 preferably without substitution base, more preferably without substitution base The alkyl of carbon number 1~4, particularly preferred methyl.It is preferred that R²¹And R²²It is identical group.

In cation (A2), R²¹And R²²It is the aliphatic alkyl can with the carbon number 1~12 for replacing base Under, as above-mentioned aliphatic alkyl, for example, can enumerate：Methyl, ethyl, vinyl, acetenyl, propyl group, isopropyl, isopropyl Alkenyl, 1- acrylic, 2- acrylic, 2-propynyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, 2- cyclobutenyls, 1,3-butadiene Base, amyl group, isopentyl, neopentyl, tertiary pentyl, 1- methyl amyls, 2- methyl amyls, 2- amylene -4- bases, hexyl, isohesyl, 5- Methylhexyl, heptyl, octyl group.

As the substitution base in the aliphatic alkyl, for example, can enumerate：

Phenyl, o-tolyl, a tolyl, p-methylphenyl, xylyl, trimethylphenyl, adjacent cumenyl, an isopropylbenzene Base, to aromatic hydrocarbyls such as cumenyls；

Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, penta oxygen The alkoxies such as base, phenoxy group, benzyloxy.

Can also enumerate：The halogen groups such as fluoro base, chloro base, bromo base, iodo base；

Carboxyl, nitro, cyano group.

In cation (A2), R²³~R²⁸It is the aliphatic alkyl can with the carbon number 1~12 for replacing base Under, as above-mentioned aliphatic alkyl, for example, can enumerate：Methyl, ethyl, vinyl, acetenyl, propyl group, isopropyl, isopropyl Alkenyl, 1- acrylic, 2- acrylic, 2-propynyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, 2- cyclobutenyls, 1,3-butadiene Base, amyl group, isopentyl, neopentyl, tertiary pentyl, 1- methyl amyls, 2- methyl amyls, 2- amylene -4- bases, hexyl, isohesyl, 5- Methylhexyl, heptyl, octyl group.

As the substitution base in the aliphatic alkyl, for example, can enumerate：

Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, penta oxygen The alkoxies such as base, phenoxy group, benzyloxy.

Can also enumerate：The halogen groups such as fluoro base, chloro base, bromo base, iodo base；

Carboxyl, nitro, cyano group.

As the alkylidene, for example, can enumerate：Methylene, ethylidene, propane -1,2- diyls, propane -1,3- diyls, Butane-Isosorbide-5-Nitrae-diyl, pentane -1,5- diyls, hexane -1,6- diyls.

In cation (A2), R²³~R²⁸The aliphatic of the carbon number 1~12 can with substitution base is represented independently of one another In the case of alkyl or hydrogen atom, can preferably have the alkyl of the carbon number 1~3 of substitution base, can more preferably have and take The methyl of Dai Ji, particularly preferably without the methyl of substitution base.It is preferred that R²³With R²⁴、R²⁵With R²⁶、R²⁷With R²⁸It is identical base Group.

In cation (A2), in R²³With R²⁴It is integrally formed and in the case of forming the alkylidene of carbon number 1~12, makees It is above-mentioned alkylidene, the preferably alkylidene of carbon number 4~7, more preferably pentane -1,5- diyls.

In cation (A2), in R²⁵With R²⁶It is integrally formed and in the case of forming the alkylidene of carbon number 1~12, makees It is above-mentioned alkylidene, the preferably alkylidene of carbon number 4~7, more preferably pentane -1,5- diyls.

As the above-mentioned hydrocarbon ring formed by alkylidene, can enumerate：Cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane Ring etc..In addition, above-mentioned hydrocarbon ring there can be substitution base, as the concrete example of substitution base, can enumerate：Methyl, ethyl, n-propyl, Low alkyl group below the carbon numbers such as isopropyl 3.

In cation (A2), in R²⁷With R²⁸It is integrally formed and in the case of forming the alkylidene of carbon number 1~12, makees It is above-mentioned alkylidene, the preferably alkylidene of carbon number 3~5, more preferably propane -1,5- diyls.

As the above-mentioned hydrocarbon ring formed by alkylidene, can enumerate：Cyclobutane ring, cyclopentene ring, cyclohexene ring, cycloheptene Ring etc..In addition, above-mentioned hydrocarbon ring there can be substitution base, as the concrete example of substitution base, can enumerate：Methyl, ethyl, n-propyl, Low alkyl group below the carbon numbers such as isopropyl 3.

In salt (1), as the preference of the pyrazoles azo-compound of the ligand as anion (A1), can enumerate： Compound that formula (1-a1)~formula (1-a64) is represented etc..

In salt (1), as the preference of anion (A1), can enumerate：Formula (1-b1)~formula (1-b60) represent it is cloudy from Son etc..

In salt (1), as the preference of cation (A2), can enumerate：The sun that formula (1-c1)~formula (1-c36) is represented from Son etc..

Below, the manufacture method to the salt comprising anion (A1) is illustrated.Anion (A1), can be by making (1d) The compound (hereinafter sometimes referred to " compound (1d) ") of expression reacts in organic solvent with chromium compound or cobalt compound Manufacture.

[in formula (1d), R¹~R⁵、R¹¹~R¹⁴And R¹⁹With above-mentioned expression identical meanings].

As the organic solvent used in above-mentioned reaction, can enumerate：Dichloromethane, chloroform, tetrahydrofuran, toluene, second Nitrile etc..

As the compound (1d) of the ligand of the complex anion of salt (1), can be by by diazol and pyrazoles chemical combination Thing carries out the method for diazo coupling to manufacture.For example, the amine for being represented formula (1a) by nitrous acid, nitrite or nitrous acid ester (hereinafter sometimes referred to " amine (1a) ") diazotising, can be using the compound of thus obtained formula (1b) expression as above-mentioned diazonium Salt is used.

[in formula (1a) and formula (1b), R¹¹~R¹⁴With above-mentioned expression identical meanings.A¹- represent it is inorganic or it is organic it is cloudy from Son.]

As above-mentioned inorganic anion, for example, can enumerate：Fluoride ion, chloride ion, bromide ion, iodine Compound ion, perchlorate, hypochlorite ion etc..As above-mentioned organic anion, for example, can enumerate：CH₃COO^-、 C₆H₅COO^-Deng.Can preferably enumerate：Chloride ion, bromide ion, CH₃COO^-Deng.

The compound represented with formula (1c) by the compound for representing formula (1b) carries out diazo coupling in aqueous solvent, The compound (hereinafter sometimes referred to " compound (1d) ") of formula (1d) expression can be manufactured.Reaction temperature is preferably -5 DEG C~60 DEG C, more preferably 0 DEG C~30 DEG C.Reaction time is preferably 1 hour~12 hours, more preferably 1 hour~4 hours.As upper Aqueous solvent is stated, for example, can enumerate：1-METHYLPYRROLIDONE etc..

[in formula (1c), R¹~R⁵And R¹⁹With above-mentioned expression identical meanings.]

Compound (1d) has-SO₂R²⁹, in-SO₂R²⁹For-SO₂NHR³⁰In the case of, can by using with- SO₂NHR³⁰Amine (1a) manufacture, preferably use after amine (1a) with sulfo group carries out coupling reaction, make sulfo group sulfanilamide (SN) Make.For example, synthesis has the azo-compound (hereinafter referred to as " compound (1s) ") of sulfo group in compound (1d), by halogenation Sulfenyl comcoune, makes sulfo group (- SO₃H sulphonyl halogenation (- SO) is carried out₂X；X is halogen atom), sulfonyl halogen compound is obtained, so Afterwards, sulfonyl halogen compound and amine (R are made³⁰NH₂) react, thus, it is possible to make sulfo group carry out sulfanilamide (SN), manufacture compound (1d)。

As the concrete example of compound (1s), can enumerate：Formula (1-a1), formula (1-a2), formula (1-a5)~(1-a20) table The compound that the compound for showing, preferably enumerative (1-a5), (1-a6), (1-a15) and (1-a16) are represented.It is sub- as halogenation Sulfonyl compound, can enumerate：Fluorination thionyl, thionyl chloride, bromination thionyl, iodate thionyl etc., preferably enumerate：Chlorine Change thionyl, bromination thionyl etc., particularly preferably enumerate：Thionyl chloride.The usage amount of halogenation thionyl, relative to compound 1 mole of (1s), preferably 1~10 mole.In addition, when entering water in reaction system, being preferably excessively used halogenation thionyl chemical combination Thing.

Sulphonyl halogenation is carried out in a solvent.As solvent, it is, for example possible to use：The ethers such as Isosorbide-5-Nitrae-dioxane are (special Not preferred ring-type ethers)；Chloroform, dichloromethane, carbon tetrachloride, 1,2- dichloroethanes, dichloroethylene, excessively trichloro ethylene, chloroethene Halogenated hydrocarbons such as alkene, dichloropropane, chlorination pentane, 1,2- Bromofumes etc..The usage amount of solvent, relative to compound (1s) 1 More than mass parts, for example, 3 mass parts (preferably more than 5 mass parts) and below 10 mass parts (preferably below 8 mass parts).

In addition, in sulphonyl halogenation, preferably and N is used, N- dialkylformamides are (for example, DMF, N, N- bis- Ethyl-formamide etc.).In the case where N, N- dialkylformamides is used, its usage amount, relative to halogenation sulfenyl comcoune 1 Mole, for example, 0.05~1 mole.Compound (1s) and N, N- dialkylformamide are pre-mixed in a solvent, then, are added Plus during halogenation sulfenyl comcoune, heating can be suppressed.

Reaction temperature in sulphonyl halogenation, for example, more than 0 DEG C, preferably more than 30 DEG C and less than 70 DEG C, preferably 60 DEG C with Under.Reaction time is, for example, more than 0.5 hour, preferably more than 3 hours and less than 8 hours, preferably less than 5 hours.

The sulfonyl halogen compound for preparing as described above, with amine (R after can separating³⁰NH₂) reaction, it is also possible to do not separate anti- Answer in the state of mixture with amine (R³⁰NH₂) reaction.It should be noted that separate in the case of, for example, by reactant mixture with Water mixes, the crystallization that leaching is separated out.The crystallization of the sulfonyl halogen compound of acquisition, with amine (R³⁰NH₂) before reaction, according to need Can be washed and be dried.

As amine (R³⁰NH₂), including：N-propyl amine, n-butylamine, n-hexyl amine, dimethylhexylamine (1,5- dimethyl Hexyl amine etc.), tetramethyl butyl amine (1,1,3,3- tetramethyl butyl amine etc.), DEHA (2- DEHAs etc.), ammonia Base phenyl butane (3- amino -1- phenyl butanes etc.), isopropoxide propyl amine etc..Amine (R³⁰NH₂) usage amount, relative to sulphonyl 1 mole of halogen compound, is more than 2 moles and less than 10 moles, preferably less than 7 moles.

Sulfonyl halogen compound and amine (R³⁰NH₂) order of addition there is no particular limitation, preferably in sulfonyl halogen compound Addition (dropwise addition) amine (R³⁰NH₂).In addition, sulfonyl halogen compound and amine (R³⁰NH₂) reaction, preferably carry out in a solvent.As Solvent, it is possible to use the solvent same with when preparing sulfonyl halogen compound.

In addition, sulfonyl halogen compound and amine (R³⁰NH₂) reaction, carried out preferably in the presence of base catalyst.As alkali Property catalyst, for example, can enumerate：Tertiary amine (the aliphatic tertiary amine such as triethylamine, triethanolamine；The aromatic nitrile bases such as pyridine) and Secondary amine (the secondary aliphatic amine such as diethylamine；The annular aliphatic such as piperidines secondary amine) etc..In them, preferred tertiary amine, particularly preferred three second The aliphatic tertiary amines such as amine.The usage amount of base catalyst, relative to amine (R³⁰NH₂), it is more than 1.1 moles and less than 6 moles, it is excellent Elect more than 1.1 moles and less than 5 moles as.

Amine (R is added in sulfonyl halogen compound³⁰NH₂) and base catalyst in the case of, during the addition of base catalyst Between point be not particularly limited, amine (R³⁰NH₂) addition before and addition after, it is also possible to amine (R³⁰NH₂) identical when Between put addition.Furthermore it is possible to be added after being pre-mixed with reactive amine, it is also possible to amine (R³⁰NH₂) add respectively.

Sulfonyl halogen compound and amine (R³⁰NH₂) reaction temperature, for example, more than 0 DEG C and less than 50 DEG C, preferably 0 DEG C with Go up and less than 30 DEG C.In addition, the reaction time is 1~5 hour.

As the method for the compound (1d) of target compound, for example, can be listed below as by reactant mixture acquisition Method：Reactant mixture is mixed together with sour (such as acetic acid etc.) and water, is received by the way that the crystallization of precipitation is filtered Collection.After above-mentioned acid preferably previously prepared aqueous acid, reactant mixture is added in the above-mentioned aqueous solution.Addition reaction mixing Temperature during thing, preferably more than 10 DEG C and less than 50 DEG C, more preferably more than 20 DEG C and less than 50 DEG C, more preferably 20 More than DEG C and less than 30 DEG C.Additionally, it is preferred that after reactant mixture is added in aqueous acid, stirring again at the temperature disclosed above Mix about 0.5~2 hour.The crystallization of leaching is preferably cleaned with water etc., is then dried.In addition, as needed, can be by again The methods such as crystallization are further refined.

M in formula (A1)¹It is the anion (A1) of Cr, can be by making compound (1d) with chromium compound in aqueous solvent In react at 70~100 DEG C and to manufacture.It is preferred that making compound (1d) be reacted with chromium compound with 2: 1~4: 1 mol ratio.

As above-mentioned chromium complex, can enumerate：Chromic formate, chromium acetate, chromium chloride, charomic fluoride etc., preferably enumerate chromic formate, Chromium acetate etc..

Below, the manufacture method that can manufacture the salt of the cation (A2) of salt (1) is illustrated.

As the salt comprising cation (A2), can enumerate：The salt of following structure.

[in formula (b), R²¹~R²⁸And X represents identical meanings with formula (1).A^-Represent 1 valency anion.]

As 1 valency anion, can enumerate：Cl^-、Br^-、I^-、ClO₄ ^-、PF₆ ^-Or BF₄ ^-Deng.

Salt comprising cation (A2) can be manufactured by known synthetic method.

Such as J.Mater.Chem., 1999,6 (4), it is described in 559-565, make halogenated alkyl and indole reaction, obtain Compound (b-0), in the presence of a base by the reaction with acton, obtains the cyanines with halide ion as counter ion counterionsl gegenions (b-1).(b-1) counter ion counterionsl gegenions, can by with NaClO₄、NaPF₆、NaBF₄Counter ion counterionsl gegenions from salt exchange reaction to target It is derivative.

Below, the manufacture method to salt (1) is illustrated.

Salt (1) can in a solvent carry out salt friendship by making the salt comprising anion (A1) and the salt comprising cation (A2) Reaction is changed to manufacture.It is preferred that making anion (A1) be reacted with cation (A2) with 1: 1~1: 4 mol ratio.

It is the cobalt complex anion (M in formula (1) in anion (A1)¹It is Co) in the case of, can be by making compound (1d) and cobalt compound are reacted in the aqueous solvent to manufacture at 70~100 DEG C.It is preferred that being made with 2: 1~4: 1 mol ratio Compound (1d) reacts with cobalt compound.

As above-mentioned cobalt compound, can enumerate：Cobalt chloride, cobalt acetate, cobaltous sulfate, three (2,4- pentanedione) cobalts (III) Deng preferably enumerating three (2,4- pentanedione) cobalt (III) etc..

As salt (1), specifically, can enumerate：Compound that formula (1-1)~formula (1-26) is represented etc..

As the form of salt (1), for example, can enumerate：The salt that formula (1-A) is represented.

[in formula (1-A), R^21-AAnd R^22-AThe aliphatic alkyl of carbon number 1~4 is represented independently of one another,

R^xAnd R^yHydrogen atom, methyl or trifluoromethyl are represented independently of one another.]

The content of salt (1), in colouring agent (A), for example, can enumerate：More than 1 mass % and below 100 mass %, or 3 The ratio of more than quality % and 100 below mass %, preferably more than 1 mass % and below 99 mass %, more preferably 1 matter Measure more than % and below 80 mass %, more preferably more than 3 mass % and below 70 mass %.

Colouring agent (A) can contain the dyestuff different from salt (1) while containing salt (1).As the dyestuff, Ke Yilie Lift：The dyestuffs such as the sulphone amide derivative of oil-soluble dyes, acid dyes, the amine salt of acid dyes or acid dyes, for example, can arrange Lift：Compound, the dyeing of dyestuff are categorized as in color index (The Society of Dyers and Colourists publication) Known dyestuff described in notes (Se Ran societies).

Specifically, can enumerate：C.I. solvent yellow 4 (below, omits the record of C.I. solvent yellows, is only remembered by numbering Carry), 14,15,23,24,38,62,63,68,82,94,98,99,162；

C.I. solvent red 45,49,125,130；

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

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, 7,9,17,19；Deng C.I. acid dyes,

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

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

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

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

As the C.I. media Huang 5 of C.I. mordant dyes, 8,10,16,20,26,30,31,33,42,43,45,56,61, 62、65；

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

C.I. medium orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47, 48；

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

Colouring agent (A) contains pigment while can also containing salt (1).

As pigment, can enumerate：Organic pigment, such as the purple face such as C.I. pigment violet 1s, 19,23,29,32,36,38 Material；C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125, 128th, the yellow uitramarine such as 137,138,139,147,148,150,153,154,166,173,194,214；C.I. pigment orange 13, 31st, the orange pigment such as 36,38,40,42,43,51,55,59,61,64,65,71,73；

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215, 216th, red pigments such as 224,242,254,255,264,265 etc..Wherein, preferably comprise selected from C.I. pigment yellow 13s 8,139, 150th, at least a kind in C.I. paratoneres 177,242,254.By the way that comprising above-mentioned pigment, the optimization of transmitted spectrum is easily, resistance to Chemicals become good.

These pigment can be used alone, it is also possible to mixes two or more and uses.

Organic pigment, the pigment for rosin treatment can be implemented as needed, being had acidic groups or basic group using introducing is derived The surface treatment of thing etc., the grafting treatment carried out to surface of pigments using macromolecular compound etc., using sulfuric acid particles method etc. The micronized treatment for carrying out or the cleaning treatment, the ionic impurity that are carried out using organic solvent or water etc. for removing impurity The removing carried out using ion-exchange etc. treatment etc..

Organic pigment preferable particle size is uniform.Decentralized processing is carried out by containing pigment dispersing agent, pigment can be obtained molten The dispersible pigment dispersion of the state being uniformly dispersed in liquid.

As above-mentioned pigment dispersing agent, for example, can enumerate：Cation system, anion system, nonionic system, both sexes, polyester Surfactant of system, many amine systems, acrylic acid series etc. etc..These pigment dispersing agents may be used alone, can also be used in combination 2 More than kind.As pigment dispersing agent, can enumerate：Trade name KP (Shin-Etsu Chemial Co., Ltd's system), Florence (Off The レ Application of ロ mono-) (Kyoeisha Chemical Co., Ltd.'s system), Solsperse (ス of ソ Le ス パ mono-) (Zhe Kanai Co. Ltd. systems (ゼ カ ネ plants)), EFKA (CIBA company systems), Ajisper (ア ジ ス パ mono-) (aginomoto Fine-Tech Co. Ltd. systems), Disperbyk (Bi Ke chemical companies system) etc..

Using in the case of pigment dispersing agent, its usage amount, relative to pigment (A2), preferably 100 mass % are more excellent Elect as more than 5 mass % and below 50 mass %.The usage amount of pigment dispersing agent in above range, with uniformly being divided The tendency of the dispersible pigment dispersion of bulk state.

In the case of pigment being included in colouring agent (A), the content of the pigment, preferably 1~99 mass %, more preferably 10~97 mass %.

The content ratio (mass ratio) of salt (1) and pigment, preferably 1: 99~99: 1, more preferably 3: 97~90: 10.It is logical Cross and be set as such ratio, the optimization of transmitted spectrum becomes easy, obtains high-contrast, high brightness, therefore well.In addition, Heat resistance, chemical-resistant become good.

Particularly salt (1) be selected from C.I. pigment yellow 13s 8, C.I. pigment yellow 13s 9, C.I. pigment yellows 150, C.I. paratoneres 177th, the mass ratio of at least a kind in C.I. paratoneres 242 and C.I. paratoneres 254, preferably 3: 97~90: 10, it is more excellent Elect 3: 97~70 as: 30.

The content of colouring agent (A), relative to the solid constituent in photosensitive composition, preferably 5~60 matter Amount %, more preferably more preferably 8~55 mass %, 10~50 mass %.Here, solid constituent refers in colored photosensitive Property resin combination in, composition in addition to the solvent it is total.The content of colouring agent (A) within the above range when, formed Color depth during colour filter fully, and in the composition can the binder polymer containing requirement, therefore, it can shape Into the sufficient pattern of mechanical strength.

Photosensitive composition of the invention, comprising resin (B).As resin (B), preferably alkali-soluble tree Fat.

As resin (B), for example, can enumerate：Following resin [K1]~[K4] etc..

[K1] there is the ring-type ether structure of carbon number 2~4 and the monomer (a) of ethene unsaturated bond (to be sometimes referred to as below Be " (a) ") and selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides at least a kind (b) (hereinafter sometimes referred to " (b) ") Copolymer.

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

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

[K4] reacted the copolymer of (a) and (b) and (c) obtained from resin.

Resin (B) is by comprising the construction unit from (a), can further improve the heat-resisting of resulting colored pattern The reliabilities such as property, chemical-resistant.

A () refers to the ring-type ether structure with such as carbon number 2~4 (for example, selected from oxirane ring, oxa- ring fourth At least a kind in alkane ring and tetrahydrofuran ring) with the polymerizable compound of ethene unsaturated bond.A () is preferably with carbon The monomer of the cyclic ether of atomicity 2~4 and (methyl) acryloxy.

In addition, in this specification, " (methyl) acrylic acid " is represented selected from least 1 in acrylic acid and methacrylic acid Kind.The statement of " (methyl) acryloyl group " and " (methyl) acrylate " etc. also has same implication.

As (a), for example, can enumerate：Monomer (a1) with Oxyranyle and ethene unsaturated bond (has below When be referred to as " (a1) "), the monomer (a2) (hereinafter sometimes referred to " (a2) ") with oxetanyl and ethene unsaturated bond, Monomer (a3) (hereinafter sometimes referred to " (a3) ") with tetrahydrofuran base and ethene unsaturated bond etc..

(a1), can for example enumerate：With by the monomer (a1-1) of the structure of chain type alkene epoxidation (below sometimes Referred to as " (a1-1) "), with by monomer (a1-2) (hereinafter sometimes referred to " (a1- of the structure of ring type alkene epoxidation 2)”)。

As (a1-1), can enumerate：Glycidyl (methyl) acrylate, Beta-methyl glycidyl (methyl) third Olefin(e) acid ester, β-ethyl glycidyl base (methyl) acrylate, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl Base ether, a vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, the contracting of Alpha-Methyl-neighbour's vinyl benzyl Water glyceryl ether, Alpha-Methyl-a vinylbenzyl glycidyl base ether, Alpha-Methyl-to vinylbenzyl glycidyl base ether, 2, Double (glycidoxypropyl methyl) styrene of 3-, double (glycidoxypropyl methyl) styrene of 2,4-, double (the glycidol oxygen of 2,5- Ylmethyl) styrene, 2,6- double (glycidoxypropyl methyl) styrene, 2,3,4- tri- (glycidoxypropyl methyl) benzene second Alkene, 2,3,5- tri- (glycidoxypropyl methyl) styrene, 2,3,6- tri- (glycidoxypropyl methyl) styrene, 3,4,5- tri- (glycidoxypropyl methyl) styrene, 2,4,6- tri- (glycidoxypropyl methyl) styrene etc..

As (a1-2), can enumerate：VCH list oxide, 1,2- epoxy -4- vinyl cyclohexane (examples Such as, セ ロ キ サ イ De 2000；Daisel chemical industry Co., Ltd's system), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates (for example, the A400 of サ イ Network ロ マ mono-；Daisel chemical industry Co., Ltd's system), (methyl) acrylic acid 3,4- epoxycyclohexyl first Ester is (for example, the M100 of サ イ Network ロ マ mono-；Daisel chemical industry Co., Ltd's system), formula (I) represent compound and formula (II) compound for representing etc..

[in formula (I) and formula (II), R^aAnd R^bThe alkyl of hydrogen atom or carbon number 1~4 is represented independently of one another, The hydrogen atom included in the alkyl can be replaced with hydroxyl.

X¹And X²Singly-bound ,-R are represented independently of one another^c-、*-R^c-O-、*-R^c-S-、*-R^c-NH-。

R³Represent the alkylidene of carbon number 1~6.

* the bonding position with O is represented].

As the alkyl of carbon number 1~4, can enumerate：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, tert-butyl group etc..

Alkyl after being replaced by hydroxyl as hydrogen atom, can enumerate：Hydroxymethyl, 1- hydroxyethyls, 2- hydroxyethyls, 1- hydroxypropyls, 2- hydroxypropyls, 3- hydroxypropyls, 1- hydroxyl -1- Methylethyls, 2- hydroxyl -1- Methylethyls, 1- hydroxyl fourths Base, 2- hydroxybutyls, 3- hydroxybutyls, 4- hydroxybutyls etc..

As R¹And R², preferably enumerate：Hydrogen atom, methyl, hydroxymethyl, 1- hydroxyethyls, 2- hydroxyethyls, it is more excellent Choosing is enumerated：Hydrogen atom, methyl.

As alkylidene, can enumerate：Methylene, ethylidene, propane -1,2- diyls, propane -1,3- diyls, butane -1, 4- diyls, pentane -1,5- diyls, hexane -1,6- diyls etc..

As X¹And X², preferably enumerate：Singly-bound, methylene, ethylidene, *-CH₂- O- (* represents the binding site with O) Base, *-CH₂CH₂- O- bases, more preferably enumerate：Singly-bound, *-CH₂CH₂- O- bases.

As the compound that formula (I) is represented, can enumerate：Compound that formula (I-1)~formula (I-15) is represented etc..It is preferred that arranging Lift：Formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11)~formula (I-15).More preferably enumerate：Formula (I-1), formula (I-7), formula (I-9), formula (I-15).

As the compound that formula (II) is represented, can enumerate：Compound that formula (II-1)~formula (II-15) is represented etc..It is excellent Choosing is enumerated：Formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11)~formula (II-15).It is more excellent Choosing is enumerated：Formula (II-1), formula (II-7), formula (II-9), formula (II-15).

The compound that the compound and formula (II) that formula (I) is represented are represented can be used individually.In addition, they can Mixed with arbitrary ratio.In the case of mixing, the blending ratio is preferably formula (I) with molar ratio computing: formula (II) is 5: 95~ 95: 5, more preferably 10: 90~90: 10, particularly preferably 20: 80~80: 20.

As the monomer (a2) with oxetanyl and ethene unsaturated bond, more preferably with oxetanes The monomer of base and (methyl) acryloxy.As (a2), can enumerate：3- methyl -3- methacryloxymethyl oxa-s Cyclobutane, 3- methyl -3- acryloyloxymethyls oxetanes, 3- ethyl -3- methacryloxymethyl oxa- ring fourths Alkane, 3- ethyl -3- acryloyloxymethyls oxetanes, 3- methyl -3- methacryloxyethyls oxetanes, 3- Methyl -3- acryloyl-oxyethyls oxetanes, 3- ethyl -3- methacryloxyethyls oxetanes, 3- ethyls - 3- acryloyl-oxyethyl oxetanes etc..

As the monomer (a3) with tetrahydrofuran base and ethene unsaturated bond, more preferably with tetrahydrofuran base and The monomer of (methyl) acryloxy.

As (a3), specifically, can enumerate：Tetrahydrofurfuryl acrylate is (for example, VISCOAT (ト of PVC ス Us one) V# 150th, Osaka Organic Chemical Industry Co., Ltd.'s system), tetrahydrofurfuryl methacrylate etc..

As (a), the reliabilities such as the heat resistance of resulting colored pattern, chemical-resistant can further improved Aspect, preferably (a1).In addition, at the excellent aspect of the storage stability of photosensitive composition, more preferably (a1-2)。

As (b), specifically, for example, can enumerate：Acrylic acid, methacrylic acid, crotonic acid, it is o-, m-, to ethene The unsaturated monocarboxylic class such as yl benzoic acid；

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

Methyl -5- ENB -2,3- dicarboxylic acids, 5- carboxyls two ring [2.2.1] hept-2-ene", the ring of 5,6- dicarboxyls two [2.2.1] hept-2-ene", 5- carboxyl -5- methyl bicyclic [2.2.1] hept-2-ene", ring [2.2.1] the hept- 2- of 5- carboxyl -5- ethyls two Alkene, 5- carboxyl -6- methyl bicyclic [2.2.1] hept-2-ene", 5- carboxyl -6- ethyls two ring [2.2.1] hept-2-ene" etc. contain carboxyl Two ring unsaturated compound classes；

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

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

Unsaturated esters of acrylic acid containing hydroxyl and carboxyl as acrylic acid α-(methylol) ester, in same molecule Deng.

In them, from the viewpoint of copolyreaction and in aqueous alkali in dissolubility from the viewpoint of, preferably propylene Acid, methacrylic acid, maleic anhydride etc..

As (c), for example, can enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid N-butyl, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) third Olefin(e) acid dodecane ester, (methyl) lauryl acrylate, stearyl (methyl) acrylate, (methyl) acrylic acid ring pentyl ester, (first Base) cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexyls, three ring [5.2.1.0^2,6] decane -8- base (methyl) acrylic acid Ester (in the technical field, as trivial name, also referred to as the ring pentyl ester of (methyl) acrylic acid two), the cyclopentyloxy of (methyl) acrylic acid two Ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) allyl acrylate, (methyl) propylene (methyl) acrylate such as sour alkynes propyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate Class；

(methyl) acrylate of the hydroxyls such as (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters Class；

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

Two rings [2.2.1] hept-2-ene", 5- methyl bicyclics [2.2.1] hept-2-ene", 5- ethyls two ring [2.2.1] hept-2-ene", 5- hydroxyls two ring [2.2.1] hept-2-ene", 5- hydroxymethyls two ring [2.2.1] hept-2-ene", the rings of 5- (2 '-hydroxyethyl) two [2.2.1] hept-2-ene", 5- methoxyl groups two ring [2.2.1] hept-2-ene", 5- ethyoxyls two ring [2.2.1] hept-2-ene", 5,6- dihydroxies Base two ring [2.2.1] hept-2-ene", 5,6- bis- (hydroxymethyl) two ring [2.2.1] hept-2-ene", 5,6- bis- (2 '-hydroxyethyl) two Ring [2.2.1] hept-2-ene", 5,6- dimethoxys two ring [2.2.1] hept-2-ene", ring [2.2.1] hept- of 5,6- diethoxies two 2- Alkene, 5- hydroxy-5-methyls base two ring [2.2.1] hept-2-ene", 5- hydroxyl -5- ethyls two ring [2.2.1] hept-2-ene", 5- hydroxyl first Base -5- methyl bicyclic [2.2.1] hept-2-ene", 5- tertbutyloxycarbonyls two ring [2.2.1] hept-2-ene", the ring of 5- cyclohexyl oxygen carbonyl two Double (tertbutyloxycarbonyl) two ring [2.2.1] hept- of [2.2.1] hept-2-ene", 5- carbobenzoxies two ring [2.2.1] hept-2-ene", 5,6- The two ring unsaturated compound classes such as double (hexamethylene oxygen carbonyl) two rings [2.2.1] hept-2-ene"s of 2- alkene, 5,6-；

N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, N- succinimidos- 3- maleimidobenzoyls ester, N- succinimido -4- malimidobutanoates, N- succinimido -6- Malaysias The dicarbapentaborane such as acid imide capronate, N- succinimido -3- maleimidopropionic acids ester, N- (9- acridinyls) maleimide Imide derivative class；

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

In them, from from the viewpoint of copolyreaction and heat resistance, preferably styrene, N- benzyl maleimides Amine, N- N-cyclohexylmaleimides, N- benzyl maleimides, two rings [2.2.1] hept-2-ene" etc..

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

Construction unit from (a)；60~98 moles of % (more preferably 65~95 moles %)

Construction unit from (b)；2~40 moles of % (more preferably 5~35 moles %)

The ratio of the construction unit of resin [K1] within the above range when, with storage stability, developability, cured pattern Solvent resistance become good tendency.

Resin [K1], (the big grand row in Tianjin writes sale room strain formula meeting to may be referred to such as document " experimental method of Polymer Synthesizing " Society chemistry is issued with people's the 1st edition the 1st brush on March 1st, 1972) described in method and the citation described in the document enter Row manufacture.

Specifically, following method is illustrated：Put into reaction vessel (a) and (b) of ormal weight, polymerization initiator with And solvent etc., nitrogen displacement oxygen is used, thus, it is stirred under deoxidation, heated, is incubated.It should be noted that using herein Polymerization initiator and solvent etc., there is no particular limitation, arbitrarily can be triggered using polymerization usually used in the field Agent and solvent.For example, as polymerization initiator, can enumerate：Azo-compound (2,2 '-azodiisobutyronitrile, 2,2 '-even Nitrogen double (2,4- methyl pentane nitriles) etc.) or organic peroxide (benzoyl peroxide etc.), as solvent, as long as dissolving each monomer , as the solvent of photosensitive polymer combination, it is possible to use aftermentioned solvent etc..

It should be noted that resulting copolymer, can directly use reacted solution, it is also possible to using concentration or Solution after dilution, it is also possible to use the material obtained in the form of solid (powder) by methods such as reprecipitations.Particularly exist During the polymerization, as solvent, using aftermentioned solvent (D), thus, it is possible to directly use reacted solution such that it is able to simplify Manufacturing process.

In resin [K2], the ratio of the construction unit from various monomers is constituting the entire infrastructure unit of resin [K2] In, preferably in following scope.

Construction unit from (a)；2~95 moles of % (more preferably 5~80 moles %)

Construction unit from (b)；2~40 moles of % (more preferably 5~35 moles %)

Construction unit from (c)；1~65 mole of % (more preferably 1~60 mole %)

The ratio of the construction unit of resin [K2] within the above range when, with storage stability, developability, cured pattern Solvent resistance, heat resistance and mechanical strength become good tendency.

Resin [K2], for example, can manufacture in the same manner as the method recorded as the manufacture method of resin [K1].

Specifically, method can be listed below：(a), (b) and (c), the polymerization of ormal weight are put into reaction vessel Initiator and solvent, use nitrogen displacement oxygen, thus, are stirred under deoxidation, heated, are incubated.Resulting copolymer, Reacted solution can directly be used, it is also possible to use the solution after concentration or dilution, it is also possible to using by reprecipitation etc. The material that method is obtained in the form of solid (powder).

In resin [K3], the ratio of the construction unit from various monomers is constituting the entire infrastructure unit of resin [K3] In, 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], for example, can manufacture in the same manner as the method recorded as the manufacture method of resin [K1].

Resin [K4], can obtain, i.e., as follows：The copolymer of (b) and (c) is obtained, the carbon having at (a) is former The carboxyl that addition (c) has on the cyclic ether of subnumber 2~4.

First, the copolymer of (b) and (c) is manufactured in the same manner as the method recorded as the manufacture method of [K1].The situation Under, the ratio of the construction unit from various monomers in the entire infrastructure unit of (b) with the copolymer of (c) is constituted, preferably exists 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, a part for the carboxyl and/or carboxylic acid anhydrides included in the construction unit from (c) in above-mentioned copolymer is made The cyclic ether reaction of the carbon number 2~4 having with (a).

After copolymer of the manufacture (b) with (c), by atmosphere in flask by nitrogen displacement into air, load in flask The conjunction of catalysts (such as three (dimethylaminomethyl) phenol etc.) relative to (a)~(c) of (a), carboxyl and cyclic ether Measuring the total amount for 0.001~5 mass % and polymerization inhibitor (such as hydroquinones etc.) etc. relative to (a)~(c) is 0.001~5 mass %, such as react 1~10 hour, at 60~130 DEG C thereby, it is possible to obtain resin [K4].Feeding method, The reaction condition such as reaction temperature and time, it may be considered that manufacturing equipment and the caloric value by polymerization generation etc. are suitably adjusted Section.It should be noted that same with polymerizing condition, it is also possible to manufacturing equipment and the caloric value by polymerization generation etc. are considered, to throwing Material method and reaction temperature are suitably adjusted.

The now usage amount of (a), relative to (b), preferably 5~80 moles %, more preferably 10~75 moles % enter one Step is preferably 15~70 moles of %.By setting within the range, with storage stability, developability, solvent resistance, heat-resisting Property, the balance of mechanical strength and speed become good tendency.

As resin (B), specifically, can enumerate：3,4- epoxycyclohexyl-methyls (methyl) acrylate/(methyl) Acrylic copolymer, the ring [5.2.1.0 of 3,4- epoxies three^2.6] resin such as decyl acrylate/(methyl) acrylic copolymer [K1]；Glycidyl (methyl) acrylate/benzyl (methyl) acrylate/(methyl) acrylic copolymer, glycidol Base (methyl) acrylate/styrene/(methyl) acrylic copolymer, the ring [5.2.1.0 of 3,4- epoxies three^2.6] decyl acrylic acid Ester/(methyl) acrylic acid N- N-cyclohexylmaleimides copolymer, 3- methyl -3- (methyl) acryloyloxymethyl oxa- ring fourth The resins [K2] such as alkane/(methyl) acrylic/styrene copolymer；Benzyl (methyl) acrylate/(methyl) acrylic copolymer, The resins [K3] such as styrene/(methyl) acrylic copolymer；On benzyl (methyl) acrylate/(methyl) acrylic copolymer The resin of addition glycidyl (methyl) acrylate, in tricyclodecyl (methyl) acrylate/styrene/(methyl) The resin of addition glycidyl (methyl) acrylate on acrylic copolymer, in tricyclodecyl (methyl) acrylic acid Addition glycidyl (methyl) acrylate on ester/benzyl (methyl) acrylate/(methyl) acrylic copolymer Resins such as resin [K4] etc..Wherein, preferably resin [K1] and resin [K2], more preferably resin [K1], further preferably It is the ring [5.2.1.0 of 3,4- epoxies three^2.6] decyl acrylate/(methyl) acrylic copolymer.

The weight average molecular weight of the polystyrene conversion of resin (B), preferably 3000~100000, more preferably 5000~ 50000, more preferably 5000~35000, particularly preferably 6000~30000, especially preferably 7000~28000.Point Son amount within the above range when, improved with hardness of film, residual film ratio is also high, unexposed portion is in developer solution dissolubility it is good The tendency that good, resolution ratio is improved.

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

The acid number of resin (B), preferably 50~150, more preferably 60~135, more preferably 70~135.Here, Acid number is the value determined as the amount (mg) of the potassium hydroxide required for neutralizing resin (B) 1g, for example can be by using hydrogen-oxygen Change aqueous solutions of potassium to be titrated and tried to achieve.

The content of resin (B), relative to the solid constituent of photosensitive composition, preferably 7~65 mass %, More preferably 13~60 mass %, more preferably 17~55 mass %.The content of resin (B) within the above range when, energy Pattern is enough formed, in addition, the tendency improved with resolution ratio and residual film ratio.

Photosensitive composition of the invention includes photopolymerizable compound (C).Photopolymerizable compound (C), It is the compound that can be polymerized using living radical and acid produced by Photoepolymerizationinitiater initiater (D) etc. by irradiation light, example Such as, can enumerate：Compound of ethene unsaturated bond with polymerism etc., preferably enumerates：(methyl) acrylate chemical combination Thing.

Wherein, as photopolymerizable compound (C), it is however preferred to have more than 3 optical polymerisms of ethene unsaturated bond Compound.As such photopolymerizable compound, for example, can enumerate：Tetramethylol methane tetraacrylate, pentaerythrite tetramethyl Base acrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylates, the acrylic acid of dipentaerythritol six Ester, dipentaerythritol hexamethacrylate etc..Photopolymerizable compound (C) may be used alone, can also be used in combination 2 kinds More than.

The content of photopolymerizable compound (C), relative to the solid constituent of photosensitive composition, preferably 7 ~65 mass %, more preferably 13~60 mass %, more preferably 17~55 mass %.Above-mentioned photopolymerizable compound (C) content within the above range when, fully carried out with solidification, before development after film thickness ratio raising, be difficult in pattern The tendency that embossment (the カ Star ト of ア Application ダ mono-), adaptation become good is introduced, therefore preferably.

Photosensitive composition of the invention includes Photoepolymerizationinitiater initiater (D).

As above-mentioned Photoepolymerizationinitiater initiater (D), as long as living radical, acid etc. are produced by the effect of light, so as to draw The compound of polymerization is sent out, is not particularly limited, it is possible to use known polymerization initiator.Photoepolymerizationinitiater initiater (D) is containing logical The effect for crossing light produces the compound of living radical, acid etc., while photopolymerization initiator auxiliary agent (D1) can be contained.Photopolymerization is drawn Hair auxiliary agent (D1), be for promote by Photoepolymerizationinitiater initiater trigger be polymerized photopolymerizable compound polymerization compound, Or sensitizer.

As Photoepolymerizationinitiater initiater (D), the compound of living radical is produced preferably by the effect of light, more preferably Comprising selected from benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime compound and di- imidazolium compounds In at least a kind of Photoepolymerizationinitiater initiater, the more preferably Photoepolymerizationinitiater initiater comprising oxime compound.

As benzene alkyl ketone compound, can enumerate：Diethoxy acetophenone, 2- methyl -2- morpholinyls -1- (4- methyl Sulfonvlphenyl) propane -1- ketone, 2- dimethylaminos -1- (4- morpholino phenyls) -2- benzyl butane -1- ketone, 2- dimethylaminos Base -1- (4- morpholino phenyls) -2- (4- methylphenylmethyls) butane -1- ketone, 2- hydroxy-2-methyl -1- phenyl-propanes -1- Ketone, benzyl dimethyl ketal, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] propane -1- ketone, 1- hydroxy cyclohexylphenyls Base phenyl ketone, oligomer of 2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) phenyl] propane -1- ketone etc., preferably 2- first Base -2- morpholinyls -1- (4- methylsulfonyl phenyls) propane -1- ketone, 2- dimethylaminos -1- (4- morpholino phenyls) -2- benzyls Base butane -1- ketone etc..Irgacure (イ Le ガ キ ユ ア) 369,907 (being Qi Ba Japanese firms system above) etc. can be used Commercially available product.

As triaizine compounds, can enumerate：2,4- double (trichloromethyl) -6- (4- methoxyphenyls) -1,3,5-triazines, 2,4- double (trichloromethyl) -6- (4- methoxyl groups naphthyl) -1,3,5-triazines, double (trichloromethyl) -6- piperonyl -1 of 2,4-, 3,5- Double (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5-triazines of triazine, 2,4-, double (trichloromethyl) -6- [2- of 2,4- (5- methylfuran -2- bases) ethylidine] -1,3,5-triazines, double (the trichloromethyl) -6- [2- (furans -2- bases) ethylidine] of 2,4- - Double (trichloromethyl) -6- [2- (4- diethylamino -2- aminomethyl phenyls) the ethylidine] -1,3,5-triazines of 1,3,5-triazines, 2,4-, 2,4- double (trichloromethyl) -6- [2- (3,4- Dimethoxyphenyl) ethylidine] -1,3,5-triazines etc..

As acylphosphine oxide series initiators, can enumerate：2,4,6- trimethylbenzoyl diphenyl phosphine oxides etc..Also may be used To use the commercially available products such as Irgacure819 (Qi Ba Japanese firms system).

As oxime compound, can enumerate：N- benzoxies -1- (4- phenyl sulfonyls phenyl) butane -1- ketone -2- is sub- Amine, N- benzoxies -1- (4- phenyl sulfonyls phenyl) octane -1- ketone -2- imines, N- acetoxyl groups -1- [9- ethyl -6- (2- Toluyl) -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- { 2- methyl -4- (3,3- bis- Methyl -2,4- dioxy cyclopentyl-methyls oxygen) benzoyl } -9H- carbazole -3- bases] ethane -1- imines etc..Irgacure can be used The commercially available product such as OXE-01, OXE-02 (being above Qi Ba Japanese firms system), N-1919 (ADEKA company systems).

As di- imidazolium compounds, can enumerate：2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl di- miaow Azoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl di- imidazoles is (for example, referring to Japanese Unexamined Patent Publication 6-75372 Number publication, Japanese Unexamined Patent Publication 6-75373 publications etc.), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl di- imidazoles, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyl) di- imidazoles, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5, 5 '-four (dialkoxy phenyl) di- imidazoles, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) di-s Imidazoles (for example, referring to Japanese Patent Publication 48-38403 publications, Japanese Unexamined Patent Application 62-174204 publications etc.), 4,4 ' 5,5 '- Imidazolium compounds (for example, referring to Japanese Unexamined Patent Publication 7-10913 publications etc.) that the phenyl of position is replaced by alkoxy carbonyl group etc..It is preferred that Enumerate：2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl di- imidazoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5, 5 '-tetraphenyl di- imidazoles, 2,2 '-bis- (2,4- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl di- imidazoles.

In addition, as polymerization initiator (D), can enumerate：Benzoin, benzoin methyl ether, benzoin ethyl ether, benzene idol The benzoin compound such as relation by marriage isopropyl ether, benzoin isobutyl ether；Benzophenone, methyl o-benzoylbenzoate, 4- phenyl two Benzophenone, -4 '-methyldiphenyl sulfide of 4- benzoyls, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4, The benzophenone cpds such as 6- tri-methyl benzophenones；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- EAQs, camphorquinone；10- fourths Base -2- chloro-acridines ketone, benzyl, phenylglyoxalates methyl esters, titanium save compound etc..They preferably with photopolymerization initiator auxiliary agent described later (D1) (special amine) is applied in combination.

Sour acid producing agent is produced as by light, for example, can enumerate：4- hydroxy phenyl dimethyl sulfonium p-methyl benzenesulfonic acid Salt, 4- hydroxy phenyl dimethyl sulfoniums hexafluoro antimonate, 4- acetoxyl group phenyl dimethyl sulfoniums tosilate, 4- acetoxyl groups Phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine The salts such as tosilate, diphenyl iodine hexafluoro antimonate, nitrobenzyl tosylate class, benzoin toluene sulphur Barbiturates etc..

Photoepolymerizationinitiater initiater (D), for example can also be as triaizine compounds by light while producing living radical With the compound of acid.

As photopolymerization initiator auxiliary agent (D1), can enumerate：Amines, alkoxy anthracene compound, thioxanthone compounds, Carboxylic acid compound etc..

As amine compound, can enumerate：Triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylaminos Methyl benzoate, EDMAB, 4- dimethylaminobenzoic acids isopentyl ester, benzoic acid 2- dimethylaminos Ethyl ester, 4- dimethylaminobenzoic acid 2- Octyl Nitrites, N, N- dimethyl-p-toluidines, 4,4 '-bis- (dimethylamino) hexichol Ketone (common name michaelis ketone), 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (ethylmethylamino) benzophenone etc., Wherein, preferably 4,4 '-bis- (diethylamino) benzophenone.EAB-F (Baotugu Chemical Industrial Co., Ltd can also be used System) etc. commercially available product.

The content of Photoepolymerizationinitiater initiater (D), relative to resin (B) and the matter of total amount 100 of photopolymerizable compound (C) Amount part, more preferably preferably 0.1~30 mass parts, 1~20 mass parts.The content of Photoepolymerizationinitiater initiater is within the above range When, ISO is carried out, the time for exposure shortens, and productivity ratio is improved.

In photosensitive composition of the invention, photopolymerization initiator auxiliary agent (D1) can also be contained.Photopolymerization is drawn Hair auxiliary agent (D1), is generally applied in combination with Photoepolymerizationinitiater initiater (D), is for promoting to trigger polymerization by Photoepolymerizationinitiater initiater The compound or sensitizer of the polymerization of photopolymerizable compound.

As photopolymerization initiator auxiliary agent (D1), can enumerate：Amines, alkoxy anthracene compound, thioxanthone compounds, Carboxylic acid compound etc..

As amines, can enumerate：Triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylamino benzene Methyl formate, EDMAB, 4- dimethylaminobenzoic acids isopentyl ester, benzoic acid 2- dimethylaminoethyls Ester, 4- dimethylaminobenzoic acid 2- Octyl Nitrites, N, N- dimethyl-p-toluidines, 4,4 '-bis- (dimethylamino) hexichol first Ketone (common name michaelis ketone), 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (ethylmethylamino) benzophenone etc., its In, preferably 4,4 '-bis- (diethylamino) benzophenone.EAB-F (Baotugu Chemical Industrial Co., Ltd can also be used System) etc. commercially available product.

As alkoxy anthracene compound, can enumerate：9,10- dimethoxy anthracenes, EDMO, 9, 10- diethoxies anthracene, 2- ethyl -9,10- diethoxies anthracene, 9,10- dibutoxies anthracene, 2- ethyl -9,10- dibutoxy anthracenes Deng.

As thioxanthone compounds, can enumerate：ITX, ITX, 2,4- diethyl thiophenes Ton ketone, the clopenthixal ketones of 2,4- bis-, the chloro- 4- propoxythioxanthones of 1- etc..

As carboxylic acid compound, can enumerate：PhenylSulphon guanidine-acetic acid, methylphenylsulfonyl acetic acid, ethylphenyl sulphur Acyl acetic acid, Methylethyl phenyl sulfonyl acetic acid, 3,5-dimethylphenyl sulfonyl acetic acid, methoxy phenylsulfonyl acetic acid, two Methoxy phenylsulfonyl acetic acid, Chlorophenylsulfonyl acetic acid, dichlorophenyl sulfonyl acetic acid, N-phenylglycine, benzene oxygen second Acid, naphthylthio acetic acid, N- naphthyls glycine, naphthoxy acetic acid etc..

Photopolymerization initiator auxiliary agent (D1) may be used singly or in combination of two or more.

In the case of using these photopolymerization initiator auxiliary agents (D1), its usage amount, relative to resin (B) and polymerism The mass parts of total amount 100 of compound (C), more preferably preferably 0.01~50 mass parts, 0.1~40 mass parts.In addition, phase For 1 mole of Photoepolymerizationinitiater initiater (D), more preferably preferably 0.01~10 mole, 0.01~5 mole.Polymerization triggers auxiliary agent (D1) amount within the range when, pattern can be formed with more ISO, have the tendency that figuratum productivity ratio is improved.

Photosensitive composition of the invention includes solvent (E).

Solvent (E), there is no particular limitation, it is possible to use usually used solvent in the field.For example, can be molten from ester Ether solvents (solvent of the intramolecular comprising-O- structures) beyond agent (solvent of the intramolecular comprising-COO- structures), ester solvent, ether (intramolecular includes-CO- to ketone solvent beyond ester solvent (solvent of the intramolecular comprising-COO- structures and-O- structures), ester solvent The solvent of structure), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent, the middle selection such as dimethyl sulfoxide (DMSO) use.

As ester solvent, can enumerate：Methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-isobutyric alkanoic acids methyl esters, second Acetoacetic ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, butyric acid second Ester, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, acetic acid ring Hexanol ester, gamma-butyrolacton etc..

As ether solvents, can enumerate：Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, second two Alcohol single-butyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl group -3- methyl Butanol, tetrahydrofuran, oxinane, Isosorbide-5-Nitrae-dioxolanes, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol first Benzyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl phenyl ethers anisole, phenetole, methylanisole etc..

As ether-ether solvent, can enumerate：Methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, second Ethoxyacetic acid methyl esters, ethoxy ethyl acetate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxy-propionic acid first Ester, 3- ethoxyl ethyl propionates, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethoxies Base methyl propionate, 2- ethoxyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, 3- methoxybutyls acetic acid esters, 3- methyl -3- methoxybutyls acetic acid esters, propylene glycol monomethyl ether, propane diols list second Base ether acetic acid ester, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, two Ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetic acid esters etc..

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

As alcoholic solvent, can enumerate：It is methyl alcohol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols, sweet Oil etc..

As aromatic hydrocarbon solvents, can enumerate：Benzene,toluene,xylene, mesitylene etc..

As amide solvent, can enumerate：DMF, DMA, N- crassitudes Ketone etc..

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

In above-mentioned solvent, from from the viewpoint of coating, drying property, the boiling point under preferably 1atm is more than 120 DEG C and 180 Organic solvent below DEG C.Wherein, preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3- second Epoxide ethyl propionate, ethylene glycol single methyl ether, diethylene glycol monomethyl ether, TC, 4- hydroxy-4-methyls- 2 pentanone, DMF, 1-METHYLPYRROLIDONE etc., more preferably propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetic acid ester, ethyl lactate, 3- ethoxyl ethyl propionates etc..During comprising these solvents, flatness during coating is excellent.

The content of the solvent (E) in photosensitive composition, relative to photosensitive composition, preferably It is 70~95 mass %, more preferably 75~92 mass %.In other words, the solid constituent of photosensitive composition, excellent Elect 5~30 mass %, more preferably 8~25 mass % as.The content of solvent (E) within the above range when, it is flat during coating Property become good, in addition, color depth will not be not enough when forming colour filter, therefore, become good tendency with characterization.

In photosensitive composition of the invention, surfactant (F) can also be contained.As surfactant (F), can enumerate：Silicone based surfactants, fluorine system surfactant and the silicon-type surface with fluorine atom are lived Property agent etc..They can have polymerizable group on side chain.

As silicone based surfactants, can enumerate：Surfactant with polysiloxanes key etc..It is specific and Speech, can enumerate：Toray silicone (Application of mono- レ シ リ Us of ト one) DC3PA, Toray silicone SH7PA, Toray silicone DC11PA、Toray silicone SH21PA、Toray silicone SH28PA、Toray silicone SH29PA, Toray silicone SH30PA, organic silicon modified by polyether oil SH8400 (trade names：The eastern ニ Application of レ ダ ウ Us one グ Co. Ltd. systems), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemial Co., Ltd System), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (モ Contract commercial firm of the マ Application ス マ テ リ ア Le ズ of メ Application テ イ Block パ Off オ mono- Japan system) etc..

As above-mentioned fluorine system surfactant, can enumerate：Surfactant with fluorocarbon chain etc..Specifically, may be used To enumerate：Florado (De of Off ロ ラ mono-) (trade name) FC430, Florado FC431 (Sumitomo 3M Co. Ltd. systems), Megafac (メ カ Off ア Star Network) (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30, Megafac RS-718-K (Dainippon Ink Chemicals's system), F-top (エ Off ト Star Off プ) (trade name) EF301, F-top EF303, F-top EF351, F-top EF352 (Mitsubishi's マ テ リ ア Le Electronization is into Co. Ltd. system), Sulfone (the Off ロ Application of サ mono-) (trade name) S381, Sulfone S382, Sulfone (Co., Ltd.'s タ イ キ Application Off ア イ Application ケ ミ カ Le grinds for SC101, Sulfone SC105 (Asahi Glass Co., Ltd's system), E5844 Study carefully made) etc..

As the above-mentioned silicone based surfactants with fluorine atom, can enumerate：With polysiloxanes key and fluorine Surfactant of carbochain etc..Specifically, can enumerate：Megafac (registration mark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (Dainippon Ink Chemicals's system) etc..

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

The content of surfactant (F), relative to photosensitive composition, preferably more than 0.001 mass % And 0.2 below mass %, preferably more than 0.002 mass % and below 0.1 mass %, more preferably more than 0.01 mass % and Below 0.05 mass %.The content of surfactant (F) within the above range when, the flatness of film can be made to become good.

Photosensitive composition of the invention, is comprising colouring agent (A), alkali soluble resin (B), optical polymerism During the composition of compound (C), Photoepolymerizationinitiater initiater (D), solvent (E) and surfactant (F), coating can be obtained excellent Good, solvent resistance and the excellent colored pattern of light splitting.

Photosensitive composition of the invention, as needed, can contain filler, other macromolecule chemical combination The various additives such as thing, closely sealed accelerator, antioxidant, ultra-violet absorber, light stabilizer, chain-transferring agent.

As the method using photosensitive composition of the invention formation colored pattern, for example, can enumerate Following method：By photosensitive composition of the invention in substrate or other resin beds (for example, being initially formed on substrate Other photosensitive compositions layer etc.) on be coated with, by the volatile ingredients such as solvent remove, dry, formed dyed layer, across Photomask exposes the dyed layer, the method developed；It is used without method of photolithographic ink-jet apparatus etc..

The thickness of film now, can suitably be adjusted according to material, purposes for using etc., for example, 0.1~30 μm, excellent Elect 1~20 μm, more preferably 1~6 μm as.

The coating method of photosensitive composition, for example, can enumerate：Extrusion coating methods, direct intaglio plate coating Method, reverse gravure coating process, CAP rubbing methods, die coating method etc..Alternatively, it is also possible to using dip coaterd, wire rod coating, dip coated machine, Spin coater, slit ＆ spin coaters, slit coater (otherwise referred to as die coating machine, without spin curtain curtain coater, coating machine) etc. are coated with Machine is coated.

The removing of solvent, drying, for example, can enumerate：Natural drying, aeration-drying, drying under reduced pressure, heat drying etc.. Specific drying temperature, more preferably preferably 10~120 DEG C, 25~100 DEG C.Drying time, preferably 10 seconds~60 minutes, More preferably 30 seconds~30 minutes.

Drying under reduced pressure, is preferably carried out under the pressure of 50~150Pa in the range of 20~25 DEG C.

Dried film, is exposed across for forming the photomask of target pattern.The figure on photomask now Case shape, uses the pattern form of suitable intended applications.

As the light source used in exposure, the light source of the light of the wavelength of 250~450nm is preferably produced.Specifically, may be used To enumerate：Mercury vapor lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc., it is possible to use the filtering of cut-out particular range of wavelengths Device is cut off, or is optionally taken out using the pass-band filter for taking out particular range of wavelengths, is exposed.

Can equably irradiate parallel rays to whole plane of exposure, or be masked and be properly positioned with base material, therefore, it is excellent Choosing uses the devices such as mask aligner, stepper motor.

After exposure, contacted with developer solution, dissolve established part, for example unexposed portion, developed, thereby, it is possible to To pattern.As developer solution, can enumerate：Alkali compounds (potassium hydroxide, sodium carbonate, TMAH etc.) it is water-soluble Liquid etc..The developer solution can contain surfactant.

Developing method can be any one in paddling process, infusion process, spray-on process etc..In addition, in development by substrate Skewed at any angle.Preferably washed after development.

In addition, as needed, being bakeed after can carrying out.Bakee afterwards for example at 150~230 DEG C, preferably 10~240 minutes In the range of.

Photosensitive composition of the invention, can obtain the good film of heat resistance, light resistance, pattern And the colour filter of high-quality.Furthermore it is possible to possess these colour filters or pattern as the aobvious of a part for its component parts The institutes related to various rendered images such as showing device, such as known liquid crystal display device, organic el device, solid-state imager Have in equipment, utilized in known form.

Embodiment

Hereinafter, photosensitive composition of the invention is explained in more detail by embodiment.

" % " and " part " in example is unless otherwise specified, then quality % and mass parts.

Synthesis example 1

Methyl iodide (and Wako Pure Chemical Industries are added 2, in 3,3- 63 parts of trimethyls -3H- indoles (and Wako Pure Chemical Industries system) System) 65 parts, carry out being heated to reflux for 6 hours at 140 DEG C.After cooling, 120 parts of ether, the precipitation produced by leaching, with cold are added Acetone is cleaned, and then, is dried under reduced pressure, and obtains iodate 1- methyl -2,3,3- 102 parts of trimethyl -3H- indiums (86%). Then, 470 parts of pyridine, 64 parts and iodate 1- methyl -2 of triethylamine, 3,3- 100 parts of trimethyl -3H- indiums and orthoformic acid second are made 64 parts of ester (and Wako Pure Chemical Industries system) reacts 1 hour at 120 DEG C.After cooling, 800 parts of ether is slowly added to, will thus obtained Precipitation be filtrated to get.After being recrystallized to the solid using ethanol, thus 60 DEG C of drying under reduced pressure 24 hours, obtain 145 parts of cyanine compound (d-1) (90%).

The identification of the compound that formula (d-1) is represented

(mass spectrum) ionization mode=ESI+：M/z=357.3 [M-I^-]⁺

Exact Mass：484.1

65 parts of water is added in 7.5 parts of 2- amino -4- methyl sulphonyl -6- nitrophenols (CAS No.101861-04-5) Afterwards, 1.3 parts of NaOH is added, it is dissolved.Under ice-cold, 35% natrium nitrosum (Wako Pure Chemical Industries, Ltd.'s system) is added 6.1 parts of the aqueous solution, it is then, a small amount of repeatedly to add 19.4 parts of 35% hydrochloric acid, it is dissolved, stir 2 hours, obtain comprising diazonium The suspension of salt.Then, it is slowly added to make 5.6 parts of amido sulfuric acid (Wako Pure Chemical Industries, Ltd.'s system) to be dissolved in 26 parts of water The aqueous solution, consume excessive natrium nitrosum.

Then, 5.6 parts of Edaravone (Wako Pure Chemical Industries, Ltd.'s system) is made in 70 parts of water Middle suspension, using NaOH, pH is adjusted to 8.0.The suspension comprising above-mentioned diazol was added dropwise thereto with 15 minutes, Suitably additional 10% sodium hydroxide solution makes pH reach 7 to 7.5 scope.After completion of dropwise addition, then stir within 30 minutes, by This, obtains the suspension of yellow.Stirring 1 hour.The yellow solid that will be filtrated to get is dried at 60 DEG C under reduced pressure, is obtained 11.7 parts of the compound (yield 87%) that formula (to 2) is represented.

10 parts of the compound of formula (p-2) is added in 100 parts of dimethylformamide (Tokyo HuaCheng Industry Co., Ltd's system), Dissolved, (and light is pure to add 3.1 parts of chromium ammonium suplhate (III) 12 hydrate (Wako Pure Chemical Industries, Ltd.'s system), sodium acetate Medicine Industrial Co., Ltd system) 1.1 parts, then, be heated to reflux within 4 and a half hours.After being cooled to room temperature, by reaction solution to Injected in 20% 1500 parts of saline solution, resulting orange red solid is dried at 60 DEG C after filtering, obtain formula (z-2) 13.6 parts of the compound (yield 63%) of expression.

The identification of the compound that formula (z-2) is represented

(mass spectrum) ionization mode=ESI-：M/z=882.1 [M-Na⁺]^-

Exact Mass：905.1

4 parts of the compound that formula (z-2) is represented is set to be dissolved in 70 parts of METHYLPYRROLIDONE.Added in the solution The solution of 2 parts of the compound of formula (d-1) expression is dissolved with 15 parts of METHYLPYRROLIDONE, is stirred 2 hours.After stirring, 300 parts of water is slowly added dropwise, the red solid of precipitation is collected by filtration, then, by drying under reduced pressure, at 60 DEG C, thus, Obtain 4.5 parts of the compound (yield 88%) of formula (1-27) expression.

Synthesis example 2

<The synthesis of resin solution B1>

In the flask for possessing mixer, thermometer, reflux cooler and dropping funel nitrogen was passed through with 0.02L/ minutes Gas, forms nitrogen atmosphere, loads 305 parts of ethyl lactate, and 70 DEG C are heated to while being stirred.Then, in methacrylic acid 60 parts, the ring [5.2.1.0 of 3,4- epoxies three^2.6] the decyl acrylate (compound and formula (II- for representing following formula (I-1) 1) compound for representing is mixed with mol ratio as 50: 50) dissolving in 240 parts and 140 parts of ethyl lactate, solution is prepared, The lysate was added drop-wise in insulation to 70 DEG C of flask using dropping funel with 4 hours.On the other hand, will be in ethyl lactate Polymerization initiator 2 is dissolved in 225 parts, the solution of 30 parts of 2 '-azo double (2,4- methyl pentane nitriles) used dropping funel with 4 hours It is added drop-wise in flask.After the completion of dropwise addition of the solution of polymerization initiator, kept for 70 DEG C 4 hours, it is then cooled to room temperature, obtains Weight average molecular weight Mw is 1.3 × 10⁴, the mass % of solid constituent 33, the solution of resin B 1 of solution acid number 34mg-KOH/g.By above-mentioned Solid constituent and solution acid number are calculated, and the solid constituent acid number of resin B 1 is 100mg-KOH/g.

Synthesis example 3

<The synthesis of resin solution B2>

The third two are imported in possessing mixer, thermometer, backflow cooling tube, the flask of dropping funel and gas introduction tube 333 parts of alcohol monomethyl ether acetate.Then, nitrogen is imported in flask by gas introduction tube, atmosphere in flask is replaced as Nitrogen.Then, after the solution in flask being warming up into 100 DEG C, will be comprising 18.7 parts of N- benzyl maleimides, benzyl methyl third 70.5 parts of olefin(e) acid ester, 51.7 parts of methacrylic acid, 90.0 parts of methylmethacylate, 5.2 parts of azodiisobutyronitrile and third The mixture that 182 parts of glycol monomethyl ether acetic acid esters, was added drop-wise in flask using dropping funel with 2 hours, after completion of dropwise addition, Continue to stir 5 hours at 100 DEG C.

After stirring terminates, directed the air into flask by gas introduction tube, after atmosphere in flask is replaced as into air, will Glycidyl methacrylate 28.5g, 0.165 part of input of 1.3 parts of three dimethylaminomethyl phenol and hydroquinones In flask, reaction is set to continue 6 hours at 110 DEG C, it is 16 × 10 to obtain weight average molecular weight Mw³, solid constituent 31%, acid number The solution of resin B 2 of 80mg-KOH/g (solid constituent conversion).

The measure of the polystyrene conversion weight average molecular weight on above-mentioned resin, using GPC method, enters under the following conditions OK.

Device；HLC-8120GPC (TOSOH Co., Ltd's system)

Chromatographic column；TSK-GELG2000HXL

Column temperature；40℃

Solvent；THF

Flow velocity；1.0mL/min

Test solution solid component concentration；0.001~0.01%

Injection rate；50μL

Detector；RI

Correction standard substance；TSK polystyrene standards

F-40, F-4, F-288, A-2500, A-500 (TOSOH Co., Ltd's system)

Embodiment 1

[preparation of photosensitive composition]

By (A) salt (1)：30 parts of the compound that formula (1-27) is represented

(B) resin：40 parts of resin B 1 (solid constituent conversion)

(C) photopolymerizable compound：The mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate (KAYARAD DPHA；Nippon Kayaku K. K's system) 60 parts

(D) Photoepolymerizationinitiater initiater：N- benzoxies -1- (4- phenyl sulfonyls phenyl) octane -1- ketone -2- imines (Irgacure OXE 01；BASF Japanese firms system) 12 parts

(D) Photoepolymerizationinitiater initiater：2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) butane -1- ketone (Irgacure369；BASF Japanese firms system) 6 parts

(D2) photopolymerization initiator auxiliary agent：4,4 '-bis- (diethylamino) benzophenone (EAB-F；Hodogaya chemical strain formula meeting Society's system) 2 parts

(E) solvent：528 parts of propylene glycol monomethyl ether

(E) solvent：69 parts of propylene glycol monomethyl ether

(F) surfactant：Organic silicon modified by polyether oil (Toray silicone SH8400；The eastern ニ Application of レ ダ ウ Us one グ Co. Ltd. systems) 0.09 part

Mixing, obtains photosensitive composition.

[formation of pattern]

In the glass substrate (Eagle (the グ Le of イ mono-) 2000 of 2 inch squares；The ニ Application グ company systems of U one) on use spin-coating method After coating photosensitive composition, prebake 3 minutes at 100 DEG C.After cooling, the coloring phototonus resin group will be coated with The substrate of compound is set to 100 μm with the interval of quartz glass photomask, uses exposure machine (TME-150RSK；ト プ Us Application strain formula Commercial firm's system), with 100mJ/cm under air atmosphere²Light exposure (365nm benchmark) carry out light irradiation.In addition, as photomask, Use the mask of line and space (the line and space) pattern for foring 100 μm.After light irradiation, by the substrate at 23 DEG C It is impregnated into 80 seconds in the aqueous solution comprising nonionic surfactants 0.12% and potassium hydroxide 0.04%, is developed, water After washing, bakeed 30 minutes after carrying out at 230 DEG C in an oven.After letting cool, film thickness measuring device (DEKTAK3 is used；Japanese vacuum Technology Co. Ltd. system)) determine obtained by pattern thickness, be as a result 2.0 μm.

[Evaluation of Heat Tolerance]

In above-mentioned pattern is formed, in addition to not using photomask to be exposed, same operation is carried out, make and apply Film.After being preserved 2 hours at resulting film in an oven 230 DEG C, colour examining machine (OSP-SP-200 is used；Olympus strain Formula commercial firm system) light splitting is determined, the xy colors before and after the heat resistant test in the XYZ color specification systems of CIE are determined using the color matching function of illuminant-C Degree coordinate (Rx, Ry) (i.e. colourity) and brightness RY, calculate the aberration Δ Eab* before and after heat resistant test.Eab* is smaller for aberration Δ, Heat resistance is better.The result of aberration Δ Eab* is shown in table 1.

[Investigation on Photodegradation]

In above-mentioned pattern is formed, in addition to not using photomask to be exposed, same operation is carried out, make and apply Film.By resulting film, in xenon lamp, (Toyo Seiki makes institute's Co. Ltd. system：サ Application テ ス ト CPS+) preservation 48 is small down for irradiation Shi Hou, uses colour examining machine (OSP-SP-200；Olympus Co., Ltd's system) light splitting is determined, using the color matching function of illuminant-C, survey Determine xy chromaticity coordinates (Rx, Ry) (i.e. colourity) and the brightness RY before and after the heat resistant test in the XYZ color specification systems of CIE, calculate resistance to Aberration Δ Eab* before and after heat test.Eab* is smaller for aberration Δ, and heat resistance is better.The result of aberration Δ Eab* is shown in table 1.

Comparative example 1

By (A) colouring agent：10.2 parts of the compound that formula (d-1) is represented

(B) resin：40 parts of resin solution B1 (solid constituent conversion)

(C) photopolymerizable compound：The mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate (KAYARAD DPHA；Nippon Kayaku K. K's system) 60 parts

(D) Photoepolymerizationinitiater initiater：N- benzoxies -1- (4- phenyl sulfonyls phenyl) octane -1- ketone -2- imines (Irgacure OXE 01；BASF Japanese firms system) 12 parts

(D) Photoepolymerizationinitiater initiater：2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) butane -1- ketone (Irgacure 369；BASF Japanese firms system)

6 parts

(D2) photopolymerization initiator auxiliary agent：4,4 '-bis- (diethylamino) benzophenone (EAB-F；Hodogaya chemical strain formula meeting Society's system) 2 parts

(E) solvent：445 parts of N, dinethylformamide

(E) solvent：60 parts of propylene glycol monomethyl ether

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

(F) surfactant：0.1 part of Magfac F475 (Dainippon Ink Chemicals's system)

Mixing, obtains photosensitive composition.On photosensitive composition, similarly to Example 1 Evaluated.Show the result in table 1.

Table 1

The film formed using photosensitive composition of the invention, confirms there is good heat resistance, fast light Property.It follows that the colour filter of display good heat resistance, sunproof pattern and high-quality can be obtained.

The possibility utilized in industry

Photosensitive composition of the invention, can obtain the good film of heat resistance, light resistance, pattern And the colour filter of high-quality.

Claims (6)

1. a kind of photosensitive composition, wherein, comprising colouring agent A, resin B, photopolymerizable compound C, photopolymerization Initiator D and solvent E, and colouring agent A is the colouring agent of the salt that contained (1) represents,

In formula (1), R¹~R¹⁸Independently of one another represent hydrogen atom, halogen atom, 1 valency aliphatic alkyl of carbon number 1~8, Nitro or-SO₂R²⁹,

R²⁹Represent-OH ,-NHR³⁰Or-R³²,

R³⁰Hydrogen atom, 1 valency aliphatic alkyl of carbon number 1~8 are represented,

R³²1 valency aliphatic alkyl of carbon number 1~8 is represented,

R¹⁹And R²⁰Hydrogen atom, methyl, ethyl or amino are represented independently of one another,

M¹Cr or Co is represented,

Ring Z¹And ring Z²Phenyl ring, R are represented independently of one another²¹And R²²Represent there can be the carbon atom of substitution base independently of one another The aliphatic alkyl or hydrogen atom of number 1~12, R²³And R²⁴Can independently of one another represent there can be the carbon number of substitution base 1~12 aliphatic alkyl or hydrogen atom, or R²³With R²⁴Can be integrally formed to form alkylidene, R²⁵And R²⁶Can be only each other On the spot represent the aliphatic alkyl or hydrogen atom of the carbon number 1~12 can with substitution base, or R²⁵With R²⁶Can be integrally formed Form alkylidene, R²⁷And R²⁸The aliphatic alkyl of the carbon number 1~12 can with substitution base can independently of one another be represented Or hydrogen atom, or R²⁷With R²⁸Can be integrally formed to form alkylidene, X¹Represent hydrogen atom or chlorine atom.

2. photosensitive composition according to claim 1, wherein,

The Photoepolymerizationinitiater initiater D is comprising selected from benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime At least a kind in compound and di- imidazolium compounds of Photoepolymerizationinitiater initiater.

3. photosensitive composition according to claim 1, wherein,

M¹It is Cr.

4. photosensitive composition according to claim 1, wherein,

The salt that the salt that formula (1) is represented is represented for formula (1-A),

In formula (1-A), R^21-AAnd R^22-AThe aliphatic alkyl of carbon number 1~4 is represented independently of one another.

5. a kind of colour filter, it is formed as the photosensitive composition described in claim 1.

6. a kind of display device, it includes the colour filter described in claim 5.