CN101349865B

CN101349865B - Photosensitive compositions, curable compositions, color filters, and method for manufacturing the same

Info

Publication number: CN101349865B
Application number: CN2008101338344A
Authority: CN
Inventors: 土村智孝
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2007-07-17
Filing date: 2008-07-17
Publication date: 2012-10-03
Anticipated expiration: 2028-07-17
Also published as: CN101349865A; JP5274132B2; JP2009042751A

Abstract

A photosensitive composition includes a compound represented by Formula (I) and a curable composition contains the compound of Formula (I) and a polymerizable compound. A compound is represented by a Formula (1) and a photocurable composition contains the compound of Formula (1) and a polymerizable compound. In Formula (I), R, R1 and R2 each independently represent a hydrogen atom or a monovalent substituent. In Formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

Description

Photosensitive composite, curable compositions, color filter and prepare the method for color filter

Technical field

The present invention relates to photosensitive composite, curable compositions is used for the curable compositions of color filter, color filter and their preparation method.The invention still further relates to new oxime compound, photopolymerisable compositions is used for the photopolymerisable compositions of color filter, color filter and their preparation method, solid imaging element and original edition of lithographic printing plate.

Background technology

Photonasty or photopolymerisable compositions can comprise polymerizable compound and the Photoepolymerizationinitiater initiater that for example contains alkene formula unsaturated link.Therefore this photonasty or photopolymerisable compositions are used for for example light solidity printing ink, photosensitive printing version, color filter and various photoresist in they polymerization and curing during by photoirradiation.In the photonasty or photopolymerisable compositions of other type, for example, using light time generation acid, and described acid plays catalyst action.Particularly; This composition can be used for forming images, the material of false proof or detected energy-roentgen dose X; Wherein utilize the color reaction of pigment precursors in the presence of the acid that plays catalyst action that produces; Perhaps can be used for the positive corrosion-resisting agent that uses in the manufacturing of semiconductor, TFT, color filter, micro-mechanical piece etc., the decomposition reaction under the acid that plays catalyst action that wherein is utilized in generation exists.

In recent years; In various application, required photonasty or the photopolymerisable compositions responsive, and can show highly sensitive requirement to this short wavelength light source to this compound (for example photopolymerization initiating agent) and increase day by day short wavelength (365nm or 405nm) light source more.Yet, the common poor stability of super-sensitive Photoepolymerizationinitiater initiater.Therefore, require Photoepolymerizationinitiater initiater not only to have the sensitivity of raising but also have in time stability.

In this case, for example at United States Patent (USP) 4,255; 513 and 4; 590,145 and open (JP-A) 2000-80068 of Japanese patent application and 2001-233842 in, proposed to use the oxime ester compound conduct to be used for the Photoepolymerizationinitiater initiater of photonasty or photopolymerisable compositions.Yet these known oxime ester compounds are low and unsatisfactory aspect the sensitivity in the absorbance of 365nm or 405nm wavelength.At present, required photonasty or photopolymerisable compositions not only to have high stability in time, and the light of short wavelength such as 365nm or 405nm has been had high sensitivity.For example, JP-A 2006-195425 discloses a kind of painted irradiation-sensitive compositions that is used for color filter that contains oxime compound.Yet stability in time and short wavelength's sensitivity of this component are still not enough.Tone rendering property after the pattern that has also required painted irradiation-sensitive compositions to have raising forms, and strong request suppresses coloring over time.

On the other hand, in order to improve the light gathering of solid imaging element such as CCD, and in order to improve picture quality through improving the look separation property, the color filter that has required to be used for imageing sensor has high colour saturation and little thickness.If add a large amount of coloured materials to obtain high colour saturation, then sensitivity maybe be not enough and can not verily reproduce the shape of the precise image pattern 2.5 μ m below, pattern defect consequently on product, often occurs.For fear of these defectives, must carry out photoirradiation with high-energy more, time shutter that this will rectificate and cause the remarkable decline of throughput rate.In this case, the painted irradiation-sensitive compositions that requires to be used for color filter has the coloured material (colorant) of high-load and has high sensitivity, forms performance to obtain excellent pattern.

Summary of the invention

An object of the present invention is to provide a kind of light to 365nm or 405nm wavelength has high sensitivity and has the high photosensitive composite and the curable compositions of stability in time.Another object of the present invention provides a kind of curable compositions that is used for color filter; The curable compositions that wherein is used for color filter has high stability in time and excellent pattern and forms performance; Can solidify with high sensitivity, and can form the colored pattern that has outstanding adhesion with carrier.A purpose more of the present invention provides a kind of color filter; It is to use the curable compositions preparation that is used for color filter; Have the excellent pattern shape and comprise the colored pattern that has outstanding adhesion with carrier, and provide a kind of can be with the method for this color filter of produced with high productivity.

As the result of further investigation, the inventor finds: uses special oxime compound in acquisition to being effective aspect stable in time aspect the high absorbance of the light of 365nm or 405nm wavelength and providing high.Curable compositions according to the present invention comprises the compound by following formula (I) expression.

In formula (I), R, R ¹And R ²Represent hydrogen atom or monovalence substituting group independently of one another.Compound by formula (I) expression preferably has the molar absorptivity more than 20,000 at 365nm or 405nm.

In photosensitive composite of the present invention, the compound of being represented by formula (I) is preferably the compound by following formula (I-I) expression.

In formula (I-I), R ¹And R ²Represent hydrogen atom or monovalence substituting group independently of one another, M representes divalent linker, and R ³And R ⁴Represent hydrogen atom or monovalence substituting group independently of one another.R ³And R ⁴Can mutually combine and form ring.

In photosensitive composite of the present invention, the compound of being represented by formula (I) is preferably the compound by following formula (I-II) expression.

In formula (I-II), R ¹And R ²Represent hydrogen atom or monovalence substituting group independently of one another, M representes divalent linker, and Ar ¹Expression hydrocarbon cyclic base group or heterocyclic group.

Curable compositions of the present invention can comprise compound and the polymerizable compound by formula (I) expression.Particularly, the compound by formula (I) expression is preferably the compound by formula (I-I) expression, the compound of more preferably being represented by formula (I-II).The curable compositions of invention preferably comprises and is selected from least a of the group be made up of sensitizer, mercaptan compound and colorant.

The curable compositions that is used for color filter according to the present invention comprises the above-mentioned curable compositions of the present invention.Color filter according to the present invention comprises establishes carrier at last colored pattern, and said colored pattern is to use the above-mentioned curable compositions that is used for color filter to prepare.The method that is used to prepare color filter according to the present invention comprises: the curable compositions that will be used for color filter is coated on the carrier to form the curable compositions layer; The curable compositions layer is passed through mask exposure; Develop to form colored pattern with composition layer exposure.

According to the present invention, can provide a kind of light to have high sensitivity and have the high photosensitive composite and the curable compositions of stability in time 365nm or 405nm wavelength.According to the present invention, a kind of curable compositions that is used for color filter can be provided, it has high stability in time and excellent pattern and forms performance, and can and can form the colored pattern that has outstanding adhesion with carrier with high sensitivity curing.According to the present invention, a kind of color filter can be provided, it is to obtain through the curable compositions that use is used for color filter, and it has the excellent pattern shape and comprises the colored pattern that has outstanding adhesion with carrier.Also provide a kind of can be with the method for this color filter of produced with high productivity.

Another object of the present invention provides a kind of photopolymerisable compositions; Its light to 365nm or 405nm wavelength has high sensitivity; Have high stability in time and can form can suppress in time pass through heat due to painted cured film, and a kind of new oxime compound that is suitable for this photopolymerisable compositions is provided.A purpose more of the present invention provides a kind of photopolymerisable compositions that is used for color filter; Wherein said composition has high stability in time and excellent pattern and forms performance; Can solidify with high sensitivity, and can form the colored pattern that has outstanding adhesion with carrier.A purpose more of the present invention provides a kind of color filter; It is to use the photopolymerisable compositions preparation that is used for color filter; And it has the excellent pattern shape and comprises the colored pattern that has outstanding adhesion with carrier; And provide a kind of and can a kind of solid imaging element that comprises this color filter also be provided with the method for this color filter of produced with high productivity.A purpose more of the present invention provides a kind of original edition of lithographic printing plate, and it comprises through using the photographic layer of said photopolymerisable compositions preparation, and has high-caliber sensitivity, stability and printability resistance in time.

As the result of further investigation, the inventor finds: use oxime compound with new structure obtaining aspect the high absorbance of the light of 365nm or 405nm wavelength and realizing that high is effective aspect stable in time.< 1>a kind of compound by following formula (1) expression:

wherein; In formula (1); R and B represent the monovalence substituting group independently of one another; A representes divalent organic group, and Ar representes aryl.< 2>compound of < 1 >; Wherein said compound is represented by following formula (2):

wherein; In formula (2), R and X represent the monovalence substituting group independently of one another, and A and Y represent divalent organic group independently of one another; Ar representes aryl, and n representes 0 to 5 integer.< 3>compound of < 1>or < 2 >; Wherein said compound is represented by following formula (3):

wherein; In formula (3), R and X represent the monovalence substituting group independently of one another, and A representes divalent organic group; Ar representes aryl, and n representes 0 to 5 integer.< 4>a kind of photopolymerisable compositions comprises: (A) compound of any one in < 1>to < 3 >; (B) polymerizable compound.< 5>photopolymerisable compositions of < 4 >, described photopolymerisable compositions also comprise (C) colorant.< 6>photopolymerisable compositions of < 4>or < 5 >, wherein (C) colorant is a pigment, and said photopolymerisable compositions also comprises (D) pigment dispersing agent.< 7>photopolymerisable compositions of < 5>or < 6 >, wherein (C) colorant is a black colorant.< 8>a kind of photopolymerisable compositions that is used for color filter, it comprises in < 5>to < 7>photopolymerisable compositions of any one.< 9>a kind of color filter, it comprises the colored pattern that is arranged on the carrier, and wherein said colored pattern is to use the photopolymerisable compositions of < 8>to prepare.< 10>a kind of method that is used to prepare color filter, said method comprises: the photopolymerisable compositions of < 8>is coated on the carrier to form the photopolymerisable compositions layer; Said photopolymerizable composition is passed through mask exposure; Develop to form colored pattern with composition layer exposure.< 11>a kind of solid imaging element, it comprises the color filter of < 9 >.< 12>a kind of original edition of lithographic printing plate, it comprises the photographic layer that is arranged on the carrier, and wherein said photographic layer comprises the photopolymerisable compositions (that is, comprise in < 1>to < 3>compound of any one and the photopolymerisable compositions of polymerizable compound) of < 4 >.

According to the present invention, a kind of photopolymerisable compositions can be provided, its light to 365nm or 405nm wavelength has high sensitivity, and it has high stability in time and can form the painted cured film due to heating that pass through that can suppress in time.A kind of new oxime compound that is suitable for this photopolymerisable compositions also is provided.According to the present invention; A kind of photopolymerisable compositions that is used for color filter can be provided; Wherein said composition has high stability in time and excellent pattern and forms performance, can solidify with high sensitivity, and can form the colored pattern that has outstanding adhesion with carrier.According to the present invention, a kind of color filter can be provided, it is to use the photopolymerisable compositions preparation that is used for color filter, and it has the excellent pattern shape and comprises the colored pattern that has outstanding adhesion with carrier.Can also provide a kind of can be with the method for this color filter of produced with high productivity, and the solid imaging element that comprises this color filter.According to the present invention, a kind of original edition of lithographic printing plate can be provided, it comprises the photographic layer that uses the photopolymerisable compositions preparation, and has high-caliber sensitivity, stability and printability resistance in time.

Description of drawings

Fig. 1 is the UV absorption spectrum of compound 1, and compound 1 is according to special oxime compound of the present invention; With Fig. 2 be the UV absorption spectrum of compound 7, compound 7 is according to special oxime compound of the present invention.

Embodiment

Photosensitive composite of the present invention comprises the compound (following be called in some cases " special oxime compound ") by formula (I) expression.Describe special oxime compound below in detail as the component of photosensitive composite of the present invention.

(a) special oxime compound in one embodiment of the invention, (a) special oxime compound is represented by formula (I):

In formula (I), R, R ¹And R ²Represent hydrogen atom or monovalence substituting group independently of one another.

In formula (I), the substituting group that R representes can be can have substituent aromatic yl group maybe can have substituent heterocyclic group, and any in the group shown in preferably.

In these groups, M, R ³, R ⁴And Ar ¹Have with formula (I-I) shown in after a while separately and the M (I-II), R ³, R ⁴And Ar ¹Identical definition, and preferred embodiment is also identical.

In formula (I), R ¹And R ²Have separately with formula (I-I) in R ¹And R ²Identical definition, and preferred embodiment is also identical.

In the present invention, the special oxime compound of preferably being represented by formula (I) is more than 20,000 at the molar absorptivity of 365nm or 405nm.If special oxime compound has so high absorptivity for such short wavelength's light, then can improve the sensitivity of the photosensitive composite that contains special oxime compound to short-wavelength light.

In the present invention, special oxime compound is preferably represented by following formula (I-I).

In formula (I-I), R ¹And R ²Represent hydrogen atom or monovalence substituting group independently of one another; M representes divalent linker; R ³And R ⁴Represent hydrogen atom or monovalence substituting group independently of one another; And R ³And R ⁴Can mutually combine and form ring.

By R ¹The monovalence substituting group of expression is preferably monovalence nonmetallic atom group, as described below those.By R ¹The instance of the monovalence nonmetallic atom group of expression comprises optional substituted alkyl, optional substituted aryl, optional substituted thiazolinyl, optional substituted alkynyl; Optional substituted alkyl sulphinyl, optional substituted aryl sulfonyl kia, optional substituted alkyl sulphonyl, optional substituted aryl sulfonyl; Optional substituted acyl group, optional substituted alkoxy carbonyl group, optional substituted aryloxy carbonyl; Optional substituted phosphono (phosphinoyl), optional substituted heterocyclic radical, optional substituted alkylthio group carbonyl; Optional substituted arylthio carbonyl, optional substituted dialkyl amino carbonyl and optional substituted dialkyl amido sulfenyl carbonyl.

Optional substituted alkyl is preferably the alkyl that contains 1 to 30 carbon atom, and the example comprises methyl, ethyl, propyl group, butyl, hexyl; Octyl group, decyl, dodecyl, octadecyl, isopropyl, isobutyl; Sec-butyl, the tert-butyl group, 1-ethyl pentyl group, cyclopentyl, cyclohexyl, trifluoromethyl; The 2-ethylhexyl, phenacyl, 1-naphthoyl methyl, 2-naphthoyl methyl, 4-methyl mercapto phenacyl, 4-thiophenyl phenacyl; 4-dimethylamino phenacyl, 4-cyanic acid phenacyl, 4-toluyl methyl, 2-toluyl methyl, 3-fluorobenzoyl methyl, 3-trifluoromethyl benzoyl methyl and 3-nitrobenzene formyl methyl.

An optionally substituted aryl group is preferably 6 to 30 carbon atoms, an aryl group, and examples thereof include? Phenyl, biphenyl, 1 - naphthyl, 2 - naphthyl group, 9 - anthryl group, 9 - phenanthryl 1 - pyrene group, a 5 - four-phenyl, 1 - indenyl group, a 2 - azulenyl group, 9 - fluorenyl, terphenyl, quadruple phenyl, o - tolyl, m - tolyl, p - toluene group, xylyl group, o - cumene group, a - cumene group, the - cumenyl,?

group, and cyclopentadienyl group, binaphthyl group, a naphthyl group triple, quadruple naphthyl group, a heptyl triene and a leukotriene heptyl group, a biphenylene group, indacenyl? group, fluoranthenyl group, acenaphthyl, aceanthrylenyl, phenalenylgroup, fluorenyl, anthracenyl group, biphenyl anthracene group, anthryl group triple, quadruple anthracene base, anthraquinone, phenanthrene, benzo phenanthrene, pyrene,?

group, and the four phenyl, seven Yao group (pleiadenyl), Pi group, perylene group, pentyl Fenji and pentaphenylbenzaldehyde, tetra-phenyl group, a hexyl Fenji and hexaphenyl, Rubine province group, halo phenyl, biphenyl, trinaphthyl, heptyl Fenji and seven phenyl, anthracenyl and egg phenyl skin.

Optional substituted thiazolinyl is preferably the thiazolinyl that contains 2 to 10 carbon atoms, and the example comprises vinyl, allyl and styryl.

Optional substituted alkynyl is preferably the alkynyl that contains 2 to 10 carbon atoms, and the example comprises ethinyl, propinyl and propargyl.

Optional substituted alkyl sulphinyl is preferably the alkyl sulphinyl that contains 1 to 20 carbon atom, and the example comprises methylsulfinyl, ethyl sulfinyl, propyl group sulfinyl; The isopropyl sulfinyl, butyl sulfinyl, hexyl sulfinyl, cyclohexyl sulfinyl; The octyl group sulfinyl, 2-ethylhexyl sulfinyl, capryl sulfinyl; Dodecane acyl group sulfinyl, octadecanoyl sulfinyl, cyano methyl sulfinyl and methoxy sulfinyl.

Optional substituted aryl sulfonyl kia is preferably the aryl sulfonyl kia that contains 6 to 30 carbon atoms, and the example comprises the phenyl sulfinyl, 1-naphthyl sulfinyl, 2-naphthyl sulfinyl; 2-chlorphenyl sulfinyl, 2-aminomethyl phenyl sulfinyl, 2-methoxyphenyl sulfinyl, 2-butoxy phenyl sulfinyl; 3-chlorphenyl sulfinyl, 3-trifluoromethyl sulfinyl, 3-cyano-phenyl sulfinyl; 3-nitrobenzophenone sulfinyl, 4-fluorophenyl sulfinyl, 4-cyano-phenyl sulfinyl; 4-methoxyphenyl sulfinyl, 4-methyl mercapto phenyl sulfinyl, 4-thiophenyl phenyl sulfinyl and 4-dimethylaminophenyl sulfinyl.

Optional substituted alkyl sulphonyl is preferably the alkyl sulphonyl that contains 1 to 20 carbon atom, and the example comprises methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base; The isopropyl sulfonyl, butyl sulfonyl, hexyl sulfonyl, cyclohexyl sulfonyl; The octyl group sulfonyl, 2-ethylhexyl sulfonyl, capryl sulfonyl, dodecane acyl group sulfonyl; The octadecanoyl sulfonyl, cyano methyl sulfonyl, methoxy sulfonyl and perfluoroalkyl group sulfonyl.

Optional substituted aryl sulfonyl is preferably the aryl sulfonyl that contains 6 to 30 carbon atoms, and the example comprises phenyl sulfonyl, 1-naphthyl sulfonyl, 2-naphthyl sulfonyl; 2-chlorphenyl sulfonyl, 2-aminomethyl phenyl sulfonyl, 2-methoxyphenyl sulfonyl, 2-butoxy phenyl sulfonyl; 3-chlorphenyl sulfonyl, 3-trifluoromethyl sulfonyl, 3-cyano-phenyl sulfonyl; 3-nitrobenzophenone sulfonyl, 4-fluorophenyl sulfonyl, 4-cyano-phenyl sulfonyl; 4-methoxyphenyl sulfonyl, 4-methyl mercapto phenyl sulfonyl, 4-thiophenyl phenyl sulfonyl and 4-dimethylaminophenyl sulfonyl.

Optional substituted acyl group is preferably the acyl group that contains 2 to 20 carbon atoms, and the example comprises acetyl group, propiono, bytyry, trifluoromethyl carbonyl; Valeryl, benzoyl, 1-naphthoyl, 2-naphthoyl, 4-methylthio phenyl formoxyl; 4-thiophenyl benzoyl, 4-dimethylamino benzoyl, 4-diethylamino benzoyl, 2-chlorobenzene formacyl, 2-methyl benzoyl; 2-methoxybenzoyl base, 2-butyl phenyl ether formoxyl, 3-chlorobenzene formacyl, 3-trifluoromethyl benzoyl; 3-cyanic acid benzoyl, 3-nitro benzoyl, 4-fluoro benzoyl, 4-cyanic acid benzoyl and 4-methoxybenzoyl base.

Optional substituted alkoxy carbonyl group is preferably the alkoxy carbonyl group that contains 2 to 20 carbon atoms, and the example comprises methoxycarbonyl, ethoxy carbonyl; Propoxycarbonyl, butoxy carbonyl, hexyloxy carbonyl; Carbonyl octyloxy, the last of the ten Heavenly stems oxygen base carbonyl, octadecane oxygen base carbonyl and trifluoromethyl oxygen base carbonyl.

The instance of optional substituted aryloxy carbonyl comprises phenyloxycarbonyl, 1-naphthyl oxygen base carbonyl, 2-naphthoxy carbonyl, 4-methyl mercapto phenyl oxygen base carbonyl; 4-thiophenyl phenyl oxygen base carbonyl, 4-dimethylaminophenyl oxygen base carbonyl, 4-diethylamino phenyl oxygen base carbonyl, 2-chlorphenyl oxygen base carbonyl; 2-aminomethyl phenyl oxygen base carbonyl, 2-methoxyphenyl oxygen base carbonyl, 2-butoxy phenyl oxygen base carbonyl; 3-chlorphenyl oxygen base carbonyl, 3-trifluoromethyl oxygen base carbonyl, 3-cyano-phenyl oxygen base carbonyl; 3-nitrobenzophenone oxygen base carbonyl, 4-fluorophenyl oxygen base carbonyl, 4-cyano-phenyl oxygen base carbonyl and 4-methoxyphenyl oxygen base carbonyl.

Optional substituted phosphono is preferably the phosphono that contains 2 to 50 carbon atoms altogether, and the example comprises dimethyl phosphine acyl group, diethyl phosphonyl; The dipropyl phosphono, diphenylphosphine acyl group, dimethoxy phosphono; The diethoxy phosphonium mesitoyl base; Dibenzoyl phosphono and two (2,4, the 6-trimethylphenyl) phosphonos.

Optional substituted heterocyclic radical is preferably to contain and is selected from nitrogen, oxygen, the aromatics of at least one atom of sulphur and phosphorus atoms or aliphatic heterocyclic radical.Instance comprises thienyl, benzo [b] thienyl, naphtho-[2,3-b] thienyl, thianthrene group, furyl, pyranose, isobenzofuran-base, chromene base; Xanthyl, phenol oxathiin base, 2H-pyrrole radicals, pyrrole radicals, imidazole radicals, pyrazolyl, pyridine radicals, pyrazinyl, pyrimidine radicals; Pyridazinyl, indolizine base, isoindolyl, 3H-indyl, indyl, 1H-indazolyl, purine radicals, 4H-quinolizine base, isoquinolyl; Quinolyl, phthalazinyl, 1,5-phthalazinyl, quinoxalinyl, quinazolyl, cinnolines base, pteridyl, 4aH-carbazyl; Carbazyl, B-carboline base, phenanthridinyl, acridinyl, perimidinyl, phenanthroline base, phenazinyl, phenarsazine base, isothiazolyl; Phenothiazinyl ， isoxazolyl, furazan base ， phenoxazine group, isochroman base, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl; Imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, iso-dihydro-indole-group, quininuclidinyl, morpholinyl and thioxanthene ketone group.

The instance of optional substituted alkylthio group carbonyl comprises the methyl mercapto carbonyl, rosickyite base carbonyl, the butylthio carbonyl, own sulfenyl carbonyl, hot sulfenyl carbonyl, the last of the ten Heavenly stems sulfenyl carbonyl, octadecane sulfenyl carbonyl and trifluoromethylthio carbonyl.

The instance of optional substituted arylthio carbonyl comprises 1-naphthalene sulfenyl carbonyl, 2-naphthalene sulfenyl carbonyl, 4-methylthio phenyl sulfenyl carbonyl, 4-thiophenyl thiophenyl carbonyl; 4-dimethylamino thiophenyl carbonyl, 4-diethylamino thiophenyl carbonyl, 2-chlorobenzene sulfenyl carbonyl; 2-methylbenzene sulfenyl carbonyl, 2-methoxybenzene sulfenyl carbonyl, 2-butyl phenyl ether sulfenyl carbonyl; 3-chlorobenzene sulfenyl carbonyl, 3-trifluoromethyl thiophenyl carbonyl, 3-cyanic acid thiophenyl carbonyl; 3-nitrophenylsulfenyl carbonyl, 4-fluorobenzene sulfenyl carbonyl, 4-cyanic acid thiophenyl carbonyl and 4-methoxybenzene sulfenyl carbonyl.

The instance of optional substituted dialkyl amino carbonyl comprises the dimethylamino carbonyl, diethylamino carbonyl, dipropyl amino carbonyl and dibutylamino carbonyl.

The instance of optional substituted dialkyl amido sulfenyl carbonyl comprises dimethylamino sulfenyl carbonyl, amino sulfenyl carbonyl of dipropyl and dibutylamino sulfenyl carbonyl.

In order to obtain high sensitivity, R ¹Be preferably acyl group, particularly, preferred especially acetyl group, propiono, benzoyl or toluyl groups.

By R ²The monovalence substituting group of expression is preferably selected from following: the optional substituted alkyl that contains 1 to 20 carbon atom; The thiazolinyl that contains 1 to 20 carbon atom; Halogen atom; Aryl; The naphthenic base that contains 3 to 8 carbon atoms; The alkanoyl that contains 2 to 20 carbon atoms; The alkoxy carbonyl group that contains 2 to 12 carbon atoms; Aryloxy carbonyl; CN;-CONR ⁰¹R ⁰², R wherein ⁰¹And R ⁰²Represent alkyl or aryl independently of one another; The haloalkyl that contains 1 to 4 carbon atom;-S (O) ₁Alkyl;-S (O) ₂Alkyl;-S (O) ₂Aryl;-S (O) ₂Aryl; The diaryl phosphono; Two (C ₁To C ₄Alkoxy)-phosphono; The dialkyl phosphine acyl group; Or heterocyclic group.Consider sensitivity, preferred alkyl, thiazolinyl, haloalkyl or cyanic acid are as R ²

The divalent linker of being represented by M can be a phenylene, naphthylene, and the phenylene carbonyl, the naphthylene carbonyl, the group (A) below perhaps, (B), (C) or (D).

At (A), (B), (C) with (D) in, X is a singly-bound ,-O-,-S-,-NR ⁵-or-CO-, and Y is-O--S-,-NR ⁵-,-CO-or-CH ₂-, R wherein ⁵Represent hydrogen atom, contain the alkyl of 1 to 20 carbon atom, contain the hydroxy alkyl of 2 to 4 carbon atoms, contain the alkoxyalkyl of 2 to 10 carbon atoms, contain the thiazolinyl of 2 to 5 carbon atoms, contain the naphthenic base of 3 to 8 carbon atoms, phenyl-C ₁To C ₃Alkyl contains the alkanoyl of 1 to 8 carbon atom, contains the enoyl-of 3 to 12 carbon atoms; Benzoyl; Phenyl or naphthyl, each can be unsubstituted or substituted by following group for these groups: the alkyl of 1 to 12 carbon atom, benzoyl or contain the alkoxy of 1 to 12 carbon atom.Particularly, any shown in below M is preferably in the structure.

R ³And R ⁴Represent hydrogen atom or monovalence substituting group independently of one another.R ³And R ⁴Can mutually combine and form ring.By R ³And R ⁴The substituent instance of monovalence of expression comprises optional substituted alkyl, optional substituted aryl, optional substituted thiazolinyl, optional substituted alkynyl, optional substituted alkyl sulphinyl; Optional substituted aryl sulfonyl kia, optional substituted alkyl sulphonyl, optional substituted aryl sulfonyl, optional substituted acyl group, optional substituted alkoxy carbonyl group; Optional substituted aryloxy carbonyl, optional substituted phosphono, optional substituted heterocyclic radical, optional substituted alkylthio group oxygen base, optional substituted arylthio oxygen base; Optional substituted alkoxy, optional substituted aryloxy group, optional substituted alkylthio group carbonyl, optional substituted arylthio carbonyl; Optional substituted dialkyl amino carbonyl, optional substituted dialkyl amido sulfenyl carbonyl, carboxylic acid group, sulfonic group; Cyanic acid, halogen atom, optional substituted amino, and their any combination.Consider sensitivity improving and stable in time, preferred especially hydrogen atom, alkoxy carbonyl group, cyanic acid or phenyl are as R ³Or R ⁴R ³And R ⁴Combination be preferably below shown in combination.In the combination below, symbol * is illustrated in the formula (I-I) and R ³And R ⁴Adjacent and be included in the position that the carbon atom in two keys is combined.

R ³And R ⁴Can mutually combine and form aliphatic series or aromatic ring.The instance of said ring comprises aliphatic series or aromatic hydrocarbon ring and contains heteroatomic heterocycle.These rings can combine to form polycyclic fused ring.Aliphatic series or aromatic hydrocarbon ring can be five-, six-or seven-membered hydrocarbon ring, more preferably five-or six-unit ring, preferred especially five-unit ring.Heterocycle can contain as heteroatomic sulphur, oxygen or nitrogen-atoms, and the more preferably heterocycle of sulfur atom-containing.When the condensation through aliphatic series and/or aromatic hydrocarbon ring formed polycyclic fused ring, polycyclic fused ring can be, for example, and the condensed ring that obtains through 1 to 4 phenyl ring condensation, or through at least one phenyl ring and at least one five-condensed ring that first unsaturated cyclic condensation obtains.When condensed ring comprises when containing heteroatomic heterocycle, condensed ring can be, for example; Through at least one sulfur-bearing; The condensed ring of five of oxygen or nitrogen-atoms-unit's ring and at least one phenyl ring condensation acquisition, or through at least one sulfur-bearing, six of oxygen or nitrogen-atoms-unit encircles the condensed ring that obtains with at least one phenyl ring condensation.

At R ³And R ⁴The instance of the ring that can form when mutually combining comprises: phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, fluorenes ring, benzo phenanthrene ring, aphthacene ring, cyclohexyl biphenyl; Pyrrole ring, furan nucleus, thiphene ring, dithiolane ring, oxirane ring, diepoxide for example ring, thiirane ring, pyrrolidine ring; Piperidine ring, imidazole ring ， isoxazole ring, benzo dithiol Huan ， oxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring benzoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring; The coumarone ring, benzothiophene ring, benzo dithiole ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazines ring; 1,5-diaza naphthalene nucleus, quinoxaline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridines ring; The acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, fen oxathiin (phenoxathiin) ring, phenothiazine ring and azophenlyene ring.Wherein, preferred especially dithiolane ring, benzo dithiol ring, benzothiazole ring, benzimidazole ring and benzoxazole ring.

In formula (I-I), preferred R ³And R ⁴Mutually combining to form contains heteroatomic hydrocarbon ring or heterocycle, and the alkene part is deactivated through isomerization when being suppressed at extinction.

According to special oxime compound of the present invention more preferably by the compound of following formula (I-II) expression.

In formula (I-II), R ¹And R ²Represent hydrogen atom or monovalence substituting group independently of one another; M representes divalent linker; And Ar ¹Expression hydrocarbon cyclic base group or heterocyclic group.R in the formula (I-II) ¹, R ²Have separately and the R in formula (I-I) with M ¹, R ²The definition identical with M, and preferred embodiment is also identical.

By Ar ¹Shown in below the hydrocarbon cyclic base group of expression or heterocyclic radical are preferably in the group any.In the group below, symbol * is illustrated in the formula (I-II) and Ar ¹The position of adjacent two keys.

Instance according to special oxime compound of the present invention includes but not limited to, below shown in compound.By the examples for compounds of formula (I-I) expression comprise have below shown in R ¹, R ², M, R ³And R ⁴The compound of any combination of respective instance.In the instance of following M, symbol * is illustrated in the position that is attached in the formula (I-I) on the carbon atom adjacent with M.At following R ³And R ⁴Instance in, symbol * is illustrated in the formula (I-I) and R ³And R ⁴The position of two keys that the ring that forms when mutually combining is adjacent.

The instantiation of special oxime compound is as follows.But the present invention never is limited to these instantiations.

In the present invention, special oxime compound can have maximum absorption wavelength in the wavelength coverage of 350nm to 500nm, more preferably in 360nm to 480nm scope, have absorbing wavelength.Particularly, special oxime compound preferably has high absorbance at 365nm and 455nm.Therefore, compare with conventional oxime compound, described special oxime compound has absorption at longer wavelength zone, thereby can show high sensitivity when its light time that is exposed to from 365nm or 405nm light source.

In the present invention, consider sensitivity, special oxime compound is preferably 10,000 to 300,000 at the molar absorptivity of 365nm or 405nm, and more preferably 15,000 to 300,000, be preferably 20,000 to 200,000 especially.The molar absorptivity of special oxime compound is to use ultraviolet-visible spectrophotometer (trade name: CARRY-5 Spectrophotometer, made by Varian Inc.), in ethyl acetate solvent, under the concentration of 0.01g/L, measures.

In the present invention, for example, special oxime compound can be synthetic through for example method described below.

Formula; (I-I) synthetic

formula of the compound of expression; (I-II) synthetic

of the compound of expression

Based on the quality of the total solid of photosensitive composite, the content of special oxime compound in photosensitive composite of the present invention can be 0.1 to 30 quality %, more preferably 1 to 25 quality %, preferred especially 2 to 20 quality %.Can use single special compound of planting, maybe can make up and use two or more special oxime compounds.

Photosensitive composite of the present invention contains special oxime compound, and therefore the light to 365nm or 405nm wavelength has high sensitivity.Special oxime compound has highly hydrophobic structure, so suppressed hydrolysis etc.Therefore, the photosensitive composite that contains special oxime compound has excellent stability in time.

Photosensitive composite of the present invention, it has high stability in time as stated and to the high sensitivity of short-wavelength light, can be used for moulding resin, curtain coating resin, light-moulding resin; Encapsulant, the dentistry polymeric material, printing-ink, paint, galley is used photoresist; Color proof is used in printing, and color filter is used resist, and black matrix is used resist, the use in printed circuit board resist, and semiconductor production is used resist; Microelectronics is used resist, is used to make the resist of micro-mechanical piece, insulating material, holographic material, waveguide material; Be coated with material outward, bonding agent, tackifier, contact adhesive and release coat agent.Photosensitive composite of the present invention also is suitable for other application, in these are used, through with energy-ray for example photoirradiation produce acid, the acid that produces then plays catalyst action.For example, it can also be used for Image forming material, and anti-counterfeiting technology and energy-ray dosage detect, and wherein is utilized in the color reaction of pigment precursors under the existence of the acid that plays catalyst action of generation; And for example be used for making, semiconductor, TFT, the positive corrosion-resisting agent of color filter and micro-mechanical piece wherein is utilized in the decomposition reaction under the existence of acid of a catalyst action of generation.

In the present invention, special oxime compound is by photolysis and play the Photoepolymerizationinitiater initiater effect that causes and promote the polymerizable compound polymerization.Particularly, special oxime compound has excellent sensitivity to 365nm or 405nm light source, can produce good effect when therefore in photosensitive composite, being used as Photoepolymerizationinitiater initiater.Therefore, photosensitive composite of the present invention can comprise the special oxime compound as Photoepolymerizationinitiater initiater that makes up with polymerizable compound.Such composition is the curable compositions form of polymerization and curing with photoirradiation the time preferably.Curable compositions as the preferred aspect of photosensitive composite of the present invention (curable compositions of the present invention) is described below, but it is not intended to limit scope of the present invention.

Curable compositions curable compositions of the present invention comprises (a) special oxime ester and (b) polymerizable compound.In curable compositions of the present invention, based on the quality of the total solid of curable compositions, (a) content of special oxime ester is preferably 0.1 to 30 quality %, and more preferably 1 to 25 quality % is preferably 2 to 20 quality % especially.Can use single special oxime compound of planting, maybe can make up and use two or more special oxime compounds.Provide the description of (b) curable compound below, i.e. the description of the solvent of curable compositions of the present invention and other optional components.The various optional components of describing after a while can also be used to form any photosensitive composite that is different from said curable compositions, look their function and decide.

(b) but the polymerizable compound that polymerizable compound can be used in the curable compositions of the present invention can be the compound that contains the addition polymerization of at least one alkene formula unsaturated double-bond; And can be selected from and contain the unsaturated end key of at least one alkene formula separately, the compound of preferred two unsaturated end keys of above alkene formula.This compounds is extensively known in the related industries field, and these compounds can be used for the present invention and not special restriction.The chemical species of these compounds can be monomer or prepolymer, particularly dipolymer, trimer or oligomer, perhaps their any potpourri or any multipolymer.The instance of monomer and multipolymer thereof comprises unsaturated carboxylic acid (like acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid and maleic acid), their ester and their acid amides.Preferred unsaturated carboxylic acid and the ester of aliphatic polyol compound or the acid amides of unsaturated carboxylic acid and aliphatic polyamines of using.Also preferred the use contained the esters of unsaturated carboxylic acids of nucleophilic displacement of fluorine base such as hydroxyl, amino or sulfydryl or the addition reaction product of acid amides and simple function or polyfunctional isocyanate or epoxy compound, and the dehydration condensation product of this ester or acid amides and simple function or polyfunctional carboxylic acids.Further preferably contain the esters of unsaturated carboxylic acids of close electric substituting group such as NCO or epoxy radicals or the addition reaction product of acid amides and simple function or polyfunctional alcohol, acid amides or mercaptan, and contain the esters of unsaturated carboxylic acids of halogen group or leaving group such as tosyloxy or the substitution reaction product of acid amides and simple function or polyfunctional alcohol, acid amides or mercaptan.Other instance of preferred compound comprises the compound that replaces the unsaturated carboxylic acid in the above-mentioned instance to obtain with unsaturated phosphonic acids, styrene, vinyl ether etc.

The instance of the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid comprises acrylic ester such as glycol diacrylate, triethylene glycol diacrylate, 1,3 butyleneglycol diacrylate; The tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate; Trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylic ester, hexanediyl ester, 1; 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate; Tetramethylol methane tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol acrylate; The D-sorbite triacrylate, D-sorbite tetraacrylate, D-sorbite five acrylic ester; D-sorbite six acrylic ester, three (acryloxy ethyl) isocyanuric acid ester, the triacrylate of polyester acrylic ester oligomer and isocyanuric acid ester EO-modification.

The instance of the monomer of said ester also comprises methacrylate such as tetramethylene glycol dimethylacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate; Trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate; The 1,3 butylene glycol dimethylacrylate, hexanediol dimethacrylate; Dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylic ester; The dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylic ester, D-sorbite trimethyl acrylic ester; D-sorbite tetramethyl acrylic ester, two [right-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethane and two [right-(methacryloxy ethoxy) phenyl] dimethylmethanes.

The instance of the monomer of said ester also comprises: itaconate such as ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1; 3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate; The tetramethylene glycol diitaconate, pentaerythrite diitaconate and D-sorbite four itaconates; Crotonates such as ethylene glycol bisthioglycolate crotonates, tetramethylene glycol two crotonatess, pentaerythrite two crotonatess and D-sorbite four crotonatess; Iso-crotonic acid ester such as ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters and D-sorbite four iso-crotonic acid esters; And maleate such as ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate and D-sorbite four maleates.

The instance of other ester comprises the aliphatic alcohol esters described in Japan patent applicant announce (JP-B) No.51-47334 and the JP-A No.57-196231; JP-A Nos.59-5240; The compound that contains the aromatics skeleton described in 59-5241 and the 02-226149, and the compound that contains amino described in the JP-A No.01-165613.Can also use the potpourri of the monomer that is selected from above-mentioned ester monomer.

The instance of the monomer of the acid amides of aliphatic polyamines compound and unsaturated carboxylic acid comprises di-2-ethylhexylphosphine oxide-acrylic amide; Di-2-ethylhexylphosphine oxide-Methacrylamide, 1, the 6-hexylidene is two-acrylic amide; 1; The 6-hexylidene is two-Methacrylamide, and diethylene triamine three acrylic amides, xylylene bisacrylamide and xylylene pair Methacrylamides.The instance of other preferred amide monomer comprises the compound that contains the cyclohexylidene structure described in the JP-B No.54-21726.

But the carbamate compounds of the addition polymerization that the addition reaction of also preferably passing through isocyanates and hydroxyl prepares; The example comprises the vinyl carbamate compound described in the JP-B No.48-41708, and this compound has plural polymerizable vinyl and is to prepare through being added to the polyisocyanate compounds that in molecule, contains two above NCOs by the vinyl monomer of the hydroxyl of following formula (A) expression in molecule.

CH ₂=C (R ⁴) COOCH ₂CH (R ⁵) OH (A) in formula (A), R ⁴And R ⁵Represent H or CH separately ₃

JP-A No.51-37193 further preferably; Urethane acrylate described in JP-B No.02-32293 and the JP-B No.02-16765; And JP-B Nos.58-49860,56-17654, the carbamate compounds that contains the oxirane skeleton described in 62-39417 and the 62-39418.Can also use Nos.63-277653 at JP-A, but the disclosed compound that in molecule, has the addition polymerization of amino or sulfide based structural among 63-260909 and the 01-105238, and acquisition has the photopolymerisable compositions of excellent speed of photoresponse.

Other instance comprises polyfunctional acrylic ester and methacrylate; Like polyester acrylate and epoxy acrylate (for example at JP-A No.48-64183, those disclosed among JP-B No.49-43191 and the JP-B No.52-30490) through epoxy resin and (methyl) acrylic acid prepared in reaction; And JP-B Nos.46-43946, the vinyl phosphonic acid compounds described in special unsaturated compound described in 01-40337 and the 01-40336 and the JP-A No.02-25493.In some cases, preferably use the structure that contains perfluoroalkyl described in the JP-A No.61-22048.Can also use Japan, Vol.20, No.7, light solidity monomer and the oligomer described in 300 to 308 pages (1984) at Journal of the AdhesionSociety of.

But how to use the details of the compound of addition polymerization, as should using which kind of structure, whether should their be used separately or combination is used or should be added how many amounts, can freely confirm according to the final performance design of curable compositions.For example, can select them from following viewpoint.Consider sensitivity, preferably each molecule has the structure of higher unsaturated group mass contg, and the structure of preferred in many cases difunctionality or higher official ability.In order to increase the curing film strength, preferred three-or higher official can structure.Use have varying number functional group and/or dissimilar polymerizable groups compound (for example; Be selected from acrylic ester; Methacrylate, distyryl compound, the compound of vinyl ether compound) the method for combination also all be effective for control sensitivity and intensity.But the compound of how selecting and using addition polymerization is for also being important factor with the compatibility of other component (like Photoepolymerizationinitiater initiater, colorant (pigment and/or dyestuff) and binder polymer) of curable compositions or to the dispersiveness of other component.For example, in some cases, through use low-purity compound or through using two or more combination of compounds can improve compatibility.Also can select particular structural to improve adhesion to the hard surface of carrier etc.

(c) sensitizer curable compositions of the present invention can contain sensitizer, and purpose is to improve the free-radical generating efficient of radical initiator or obtains longer wavelength photoreceptor.Can be used for sensitizer of the present invention and be preferably based on electron transport mechanism or the special oxime compound of energy transfer mechanism sensitization (a).

Be used for sensitizer of the present invention and can belong to any of following compound group, and can have the absorbing wavelength in 300nm to 450nm scope.Instance comprises multi-nucleus aromatic compound (like phenanthrene, anthracene, Bi ， perylene, benzophenanthrene and 9,10-dialkoxy anthracene); Xanthene class (like luciferin, eosin, erythrosine, rhodamine B and rose-red), thioxanthene ketone (like isopropyl thioxanthone, diethyl thioxanthone and clopenthixal ketone); Cyanine class (like thia-carbonyl cyanine and oxa-carbocyanine), merocyanine class (like merocyanine and first merocyanine), phthalocyanines, thiazide (like thionine, methylene blue and toluidine blue), acridine is (like acridine orange; Chloroflavin and acridine yellow), anthraquinone class (like anthraquinone), square acids (squaliums) (like square acid), acridine orange, Coumarins (like 7-diethylamino-4-methylcoumarin), ketone cumarin; Phenothiazines, azophenlyene class, styryl benzene class, azo-compound, diphenyl methane, triphenyl methane; The diphenylethyllene benzene class, carbazoles, porphyrin, spiro-compound, quinoline a word used for translation ketone, indigo; Compound of styryl, pyrylium compound, pyrroles's methylene (pyrromethene) compound, Pyrazolotriazole compound, benzothiazole compound, barbituric acid derivatives; The thiobarbituricacid derivant, aromatic ketone compound such as acetophenone, benzophenone, thioxanthones and Michler's keton, and heterogeneous ring compound such as N-Fang oxazolidinone.The instance of preferred sensitizer comprises the compound by following formula (e-1) to (e-4) expression.

In formula (e-1), A ¹Expression sulphur atom or NR ⁵⁰, R ⁵⁰The expression alkyl or aryl, L ¹The expression nonmetallic atom group, itself and A ¹With with L ¹Adjacent carbon atom forms the alkalescence nuclear of pigment, R together ⁵¹And R ⁵²Represent hydrogen atom or monovalence nonmetallic atom group independently of one another, and R ⁵¹And R ⁵²Can mutually combine forms the acid core of pigment, and W representes oxygen atom or sulphur atom.

In formula (e-2), Ar ¹And Ar ²Represent aryl independently of one another and via-L ²-interconnect, wherein-L ²-expression-O-or-S-, and W have with formula (e-1) in identical definition.

In formula (e-3), A ²Expression sulphur atom or NR ⁵⁹L ³The expression nonmetallic atom group, itself and A ²With with L ³Adjacent carbon atom forms the alkalescence nuclear of pigment together; R ⁵³, R ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷And R ⁵⁸Represent the monovalence nonmetallic atom group independently of one another; And R ⁵⁹The expression alkyl or aryl.

In formula (e-4), A ³And A ⁴Independently of one another expression-S-or-NR ⁶²R ⁶²Represent substituted or unsubstituted alkyl is substituted or unsubstituted aryl; L ⁴And L ⁵Represent nonmetallic atom group independently of one another, itself and adjacent A ³Or A ⁴And and L ⁴Or L ⁵Adjacent carbon atom forms the alkalescence nuclear of pigment together; And R ⁶⁰And R ⁶¹Represent the monovalence nonmetallic atom group independently of one another, maybe can mutually combine forms aliphatic series or aromatic ring.

Consider the efficiency of light absorption in dark part or cause decomposing efficiency; Quality based on solid; Sensitizer content of (or in (1) photopolymerisable compositions) in curable compositions of the present invention is preferably 0.1 to 20 quality %, more preferably 0.5 to 15 quality %.Can use single sensitizer of planting, maybe can make up and use two or more sensitizers.

Preferably be contained in sensitizer in the curable compositions of the present invention and can be and be selected from by the compound of following formula (II) expression with by in the compound of following formula (III) expression at least one.Can use the single compound of planting that is selected from these sensitizers, maybe can make up and use the two or more compounds that are selected from these sensitizers.

In formula (II), R ¹¹And R ¹²Represent the monovalence substituting group independently of one another, R ¹³, R ¹⁴, R ¹⁵And R ¹⁶Represent hydrogen atom or monovalence substituting group independently of one another, n representes 0 to 5 integer, the integer of n ' expression 0 to 5, and n and n ' are not 0 simultaneously.When n is 2 or during bigger value, there are a plurality of R ¹¹, and they can be identical or different.When n ' is 2 or during bigger value, there are a plurality of R ¹², and they can be identical or different.Formula (II) can be represented any isomeride because of existing two keys to produce.

Compound by formula (II) expression is preferably 500mol at the molar absorptivity ε of 365nm wavelength ^-1Lcm ^-1More than, 3000mol more preferably ^-1Lcm ^-1More than, most preferably be 20000mol ^-1Lcm ^-1More than.If all in above-mentioned scope, then sensitivity improves effect and aspect efficiency of light absorption, can uprise molar absorptivity ε at each wavelength, this is preferred.

Preferred embodiment by the compound of formula (II) expression includes but not limited to, below illustrational compound.In this manual, some chemical formulas are structural formulas of simplifying, and wherein solid line is represented alkyl, only if point out element and substituting group clearly.In the instance below, Me representes methyl, and Et representes ethyl, and Bu representes butyl, and n-Bu representes normal-butyl, and Ph representes phenyl.

In formula (III), A representes optional substituted aromatics or heterocyclic group; X ²The expression oxygen atom, sulphur atom or-N (R ²³)-; Y representes oxygen atom, sulphur atom or=N (R ²³); R ²¹, R ²²And R ²³Represent hydrogen atom or monovalence nonmetallic atom group independently of one another; And A, R ²¹, R ²²And R ²³Can mutually combine and form more than one aliphatic series or aromatic ring.

In formula (III), R ²¹, R ²²And R ²³Represent hydrogen atom or monovalence nonmetallic atom group independently of one another.By R ²¹, R ²²Or R ²³The monovalence nonmetallic atom group of expression is preferably substituted or unsubstituted alkyl; Substituted or unsubstituted aryl; Substituted or unsubstituted thiazolinyl, substituted or unsubstituted aromatic heterocycle residue, substituted or unsubstituted alkoxy; Substituted or unsubstituted alkylthio group, hydroxyl or halogen atom.

In compound by formula (III) expression, consider the raising of Photoepolymerizationinitiater initiater decomposition efficiency, Y be preferably oxygen atom or=N (R ²³).R ²³Represent hydrogen atom or monovalence nonmetallic atom group independently of one another.Y most preferably is=N (R ²³).

Preferred embodiment by the compound of formula (III) expression includes but not limited to, below the compound of (VI1) to (VI124).In the present invention, clearly stipulate by the isomeride that the existence of the two keys between acid core and alkalescence nuclear causes, and structure also is not limited to specific isomeride.Therefore, any isomeride all can be used for the present invention.

(d) auxiliary sensitizer curable compositions of the present invention preferably contains (d) auxiliary sensitizer.In the present invention, auxiliary sensitizer has further raising to (a) the special oxime compound or (c) effect of the sensitivity of the active irradiation of sensitizer, and/or the effect that suppresses of the polymerization of (b) polymerizable compound that suppresses to be caused by oxygen.

The instance of auxiliary sensitizer comprises amine, like M.R.Sander etc., and Journal of PolymerSociety; Vol.10,3173 pages (1972), JP-B No.44-20189; JP-A Nos.51-82102,52-134692,59-138205; 60-84305,62-18537 and 64-33104, and the compound described in the Research Disclosure33825.Instantiation comprises triethanolamine, right-the dimethylaminobenzoic acid ethyl ester, right-formoxyl xylidin and right-methyl mercapto xylidin.

Other instance of auxiliary sensitizer comprises mercaptan and thioether; Like JP-A No.53-702, the disulfide compound described in mercaptan compound described in JP-B No.55-500806 and the JP-A No.05-142772 and the JP-A No.56-75643; And instantiation comprises 2-mercaptobenzothiazole; The 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline and β-mercaptonaphthalene.

Other instance of auxiliary sensitizer also comprises amino-acid compound (like N-phenylglycine); Organometallics described in the JP-BNo.48-42965 (like tributyltin acetate); Hydrogen described in the JP-B No.55-34414 is given the sulphur compound (like trithiane) described in body and the JP-A No.06-308727.

In order under the situation of balance between polymer growth and the chain transfer, to improve solidification rate; Quality based on the total solid of curable compositions (or photopolymerisable compositions (1)); The content of auxiliary sensitizer is preferably 0.1 to 30 quality %; 1 to 25 quality % more preferably, also 1.5 to 20 quality % more preferably.

Curable compositions of the present invention (or photopolymerisable compositions (1)) preferably contains the mercaptan compound as auxiliary sensitizer.The mercaptan compound that can be included in the curable compositions of the present invention (or photopolymerisable compositions (1)) is preferably the compound by following formula (IV) expression.

In formula (IV), X representes sulphur atom, oxygen atom or-N (R ⁴³)-; R ⁴³The expression hydrogen atom contains the alkyl of 1 to 5 carbon atom or contains the aryl of 6 to 13 carbon atoms; R ⁴¹And R ⁴²Represent hydrogen atom independently of one another, contain 1 to 5 carbon atom alkyl, contain the hydroxy alkyl of 1 to 3 carbon atom; Optional quilt contains the substituted phenyl of alkoxy of 1 to 8 carbon atom, and nitro has the alkoxy carbonyl group of the alkyl that contains 1 to 8 carbon atom; Phenyloxycarbonyl, acetyl group or carboxyl, or R ⁴¹, R ⁴²And the two keys between them can form phenyl ring together; And R ⁴¹And R ⁴²Between two keys can be hydrogenated.

Mercaptan compound can for example be selected from JP-A No.53-702, the compound described in JP-B No.55-500806 and the JP-A No.05-142772.

In the present invention, mercaptan compound is preferably the compound by following formula (V) expression.

In formula (V), R representes alkyl or aryl, and A representes to form with N=C-N the atomic group of heterocycle.

In formula (V), R representes alkyl or aryl.Alkyl can be the straight chain that contains 1 to 20 carbon atom, and side chain or cyclic alkyl more preferably contain the straight chained alkyl of 1 to 12 carbon atom, contains the branched alkyl of 3 to 12 carbon atoms or contains the cyclic alkyl of 5 to 10 carbon atoms.The instance of alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl; Octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl; Octadecyl, eicosyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl; Neopentyl, 1-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl and 2-norborny.

Aryl can have single ring architecture, has the structure of the condensed ring that forms through 1 to 3 phenyl ring condensation or has the structure through at least one phenyl ring and at least one five-condensed ring that first unsaturated cyclic condensation forms.The example comprises phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl and fluorenyl.Particularly, more preferably phenyl or naphthyl.

Alkyl or aryl can also have at least one substituting group.The substituent instance that can introduce comprises straight chain, side chain or the cyclic alkyl that contains 1 to 20 carbon atom, contains straight chain, side chain or the ring-type thiazolinyl of 2 to 20 carbon atoms, contains the alkynyl of 2 to 20 carbon atoms, contains the aryl of 6 to 20 carbon atoms; The acyloxy that contains 1 to 20 carbon atom contains the alkoxy-carbonyl oxy of 2 to 20 carbon atoms, contains the aryloxycarbonyl oxygen base of 7 to 20 carbon atoms, contains the carbamoyloxy of 1 to 20 carbon atom; Phosphoamide (carbonanmide) base that contains 1 to 20 carbon atom contains the sulfoamido of 1 to 20 carbon atom, contains the carbamyl of 1 to 20 carbon atom, sulfamoyl; The substituted sulfamoyl that contains 1 to 20 carbon atom contains the alkoxy of 1 to 20 carbon atom, contains the aryloxy group of 6 to 20 carbon atoms, contains the aryloxy carbonyl of 7 to 20 carbon atoms; The alkoxy carbonyl group that contains 2 to 20 carbon atoms contains the N-acyl group sulfamoyl of 1 to 20 carbon atom, contains the N-sulfamoyl carbamyl of 1 to 20 carbon atom, contains the alkyl sulphonyl of 1 to 20 carbon atom; The aryl sulfonyl that contains 6 to 20 carbon atoms contains the alkoxycarbonyl amino of 2 to 20 carbon atoms, and the aryloxycarbonyl that contains 7 to 20 carbon atoms is amino, amino; The substituted amino that contains 1 to 20 carbon atom contains the imino group of 1 to 20 carbon atom, contains the ammonium (ammonio) of 3 to 20 carbon atoms, carboxyl; Sulfo group, the oxygen base, sulfydryl contains the alkyl sulphinyl of 1 to 20 carbon atom; The aryl sulfonyl kia that contains 6 to 20 carbon atoms contains the alkylthio group of 1 to 20 carbon atom, contains the arylthio of 6 to 20 carbon atoms; The uride base that contains 1 to 20 carbon atom contains the heterocyclic group of 2 to 20 carbon atoms, contains the acyl group of 1 to 20 carbon atom; Sulfamoyl is amino, and the substituted sulfamoyl that contains 1 to 2 carbon atom is amino, contains the silicyl of 2 to 20 carbon atoms; NCO, isocyano group, halogen atom is (like fluorine; The chlorine or bromine atom), cyanic acid, nitro and base.

In formula (V), A representes to form with N=C-N the atomic group of heterocycle.At least one atom that forms said atomic group can comprise and is selected from carbon, nitrogen, hydrogen, the atom in sulphur and the selenium atom.The heterocycle that is formed by A and N=C-N can also have at least one substituting group.The substituent instance that can introduce can comprise be incorporated into abovementioned alkyl or aryl in those identical substituting groups.

In the present invention, mercaptan compound more preferably by following formula (VI) or (VII) expression compound.

In formula (VI), R ¹The expression aryl, and X representes hydrogen atom, halogen atom, alkoxy, alkyl or aryl.

In formula (VII), R ²The expression alkyl or aryl, and X representes hydrogen atom, halogen atom, alkoxy, alkyl or aryl.

In formula (VI) with (VII), halogen atom is preferably fluorine, chlorine, bromine or iodine atom.

In formula (VI) with (VII), alkoxy can be a methoxyl, ethoxy, propoxyl group, isopropoxy; Butoxy, amoxy, own oxygen base, dodecyloxy, benzyloxy; Allyloxy, phenethyl oxygen base, carboxyl ethoxy, methoxycarbonyl ethyl oxygen base, ethoxy carbonyl ethyl oxygen base; Methoxy ethoxy, phenoxy group ethoxy, methoxy ethoxy ethoxy, ethoxy ethoxy ethoxy, morpholino ethoxy; The morpholino propoxyl group, allyloxy ethoxy ethoxy, phenoxy group, toloxyl, xylyloxy; oxygen base, cumenyl oxygen base, methoxyphenyl oxygen base, ethoxyl phenenyl oxygen base; Chlorphenyl oxygen base, bromophenyl oxygen base, acetoxyl group, benzoyloxy or naphthoxy.

In formula (VI) with (VII), alkyl have with formula (V) in the identical definition of alkyl represented by R, and their preferable range is also identical.In formula (VI) with (VII), aryl have with formula (V) in the identical definition of aryl represented by R, and their preferable range is also identical.

In formula (VI) with (VII), each group can also have at least one substituting group.Those that mention as the substituting group that in formula (R), can introduce the alkyl or aryl of representing by R above substituent instance comprises.

In formula (VI) with (VII), consider the solubleness in PGMEA, X is preferably hydrogen atom.In formula (VI), consider sensitivity and the solubleness in PGMEA, R ¹Most preferably be phenyl.In formula (VII), consider sensitivity and the solubleness in PGMEA, R ²More preferably methyl, ethyl, phenyl or benzyl.

By formula (VI) with (VII) in the compound of expression, consider the solubleness in PGMEA, most preferably by the compound of formula (VII) expression.

The preferred embodiment that can be used for the mercaptan compound in the embodiment of the present invention includes but not limited to, below illustrational compound.In this manual, following chemical formula is the structural formula of simplifying, and wherein solid line is represented alkyl, only if spell out element and substituting group.In the instance below, Me representes methyl.

Solubility: 20g / L or more Solubility: 20g / L or more Solubility: 20g / L or more?

Solubility: 20g / L or more? Solubility: 20g / L or more Solubility: 20g / L or more?

Solubility: 20g / L or more Solubility: 20g / L or more?

Solubility: 20g / L or more Solubility: 20g / L or more

solubility: 20g / L or more solubility: 20g / L or more solubility: 20g / L or more? solubility: 20g / L or more solubility: 20g / L or more

Solubility: 20g / L less solubility: less than 20g / L ? solubility: less than 20g / L?

Solubility: less than 20g / L solubility: less than 20g / L ? solubility: less than 20g / L?

Solubility: less than 20g / L solubility: less than 20g / L

Consider the coating homogeneity, the solubleness of these mercaptan compounds in the PGMEA solvent is preferably more than the 20g/L, 20g/L to 50g/L more preferably, also 20g/L to 40g/L more preferably.

The solubleness measuring method in this manual, the solubleness of mercaptan compound is as giving a definition.Concrete mercaptan compound is joined in 5mL propylene glycol methyl ether acetate (PGMEA) solvent and stirred one hour at 25 ℃.In this process, can in solvent, the maximum of consoluet concrete mercaptan compound be considered to solubleness.

These mercaptan compounds can pass through J.Appl.Chem., and 34, the method described in the 2203-2207 (1961) is synthetic.

Can only will singly plant mercaptan compound and use separately, and maybe can make up and use two or more mercaptan compounds.When using the combination of mercaptan compound; Mercaptan compound can comprise two or more by above-mentioned various in the compound of any expression; Can comprise maybe that respectively the compound represented by different formulas (in one embodiment; For example, can at least a compound and at least a compound of a compounds of free style (VII) expression that selects of a compounds of free style (VI) expression of selecting be made up use).

When curable compositions of the present invention (or photopolymerisable compositions (1)) when containing mercaptan compound; Consider under the situation of the balance between polymer growth and the chain transfer and improve solidification rate; Quality (or photopolymerisable compositions (1)) based on the total solid of curable compositions; The content of mercaptan compound is preferably 0.5 to 30 quality %, 1 to 25 quality % more preferably, also 3 to 20 quality % more preferably.

(e) colorant curable compositions of the present invention can contain (e) colorant.When adding colorant, can obtain to have the painted curable compositions that needs color.Curable compositions of the present invention contains (a) has excellent sensitivity to short wavelength light source such as 365nm or 406nm light source special oxime compound.Therefore, even curable compositions of the present invention when it contains the colorant of high concentration, also can solidify with high sensitivity.

To being used for the not special restriction of colorant of the present invention.Can use in various known conventional dyestuffs and the pigment a kind of, or two or more potpourri, it can suitably be selected according to the purposes of curable compositions.When the curable compositions that the present invention is painted is used to prepare color filter, can adopt the colour such as the R of the colour element that is used to form color filter, the colorant of G or B, or be generally used for forming the black colorant of black matrix.

Describing the colorant that can be used for curable compositions of the present invention below in detail, is that example is described with the colorant that is suitable for color filter.The color pigment that will use can be various known conventional inorganic or organic pigments.No matter pigment is inorganic or organic, preferred higher transparency.Be in this viewpoint, the preferred pigments particle is littler.When also considering operating performance, the particle mean size of pigment is preferably 0.01 μ m to 0.1 μ m, more preferably 0.01 μ m to 0.05 μ m.

The instance of inorganic pigment comprises metallic compound, and its representative instance comprises metal oxide and metal complex salts.Instantiation comprises iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, the oxide of metals such as antimony, and the composite oxides of above-mentioned metal.

The instance of organic pigment comprises: C.I. pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199; C.I. pigment orange 36,38,43,71; C.I. pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270; C.I. pigment violet 19,23, and 32,39; C.I. pigment blue 1,2,15,15:1,15:3,15:6,16,22,60,66; C.I. pigment Green 7,36,37; C.I. pigment brown 25,28; C.I. pigment black 1,7; And carbon black.

In the present invention, especially preferably use the pigment that in their structure, has alkaline N atom.The pigment that contains alkaline N atom shows polymolecularity in curable compositions of the present invention (or photopolymerisable compositions (1)).Although its reason is also not fully aware of, according to thinking that the high-affinity between photonasty polymerizable components and the pigment has effect.

In the present invention, the instance of the preferred pigment that uses includes but not limited to, below listed pigment.

C.I. pigment yellow 11,24, and 108,109,110,138,139,150,151,154,167,180,185; C.I. pigment orange 36,71; C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264; C.I. pigment violet 19,23, and 32; C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66; With C.I. pigment black 1.

Can only use and singly plant combination that organic pigment maybe can use multiple organic pigment to improve excitation.Some instances of said combination are described below.For example, can be with anthraquinone pigment, the yellow pigment of the red pigment of more than one in perylene dye and the diketopyrrolo-pyrrole pigment and bisdiazo, the isoindoline yellow uitramarine, quinone phthalein ketone (quinophthalone) yellow uitramarine or perylene red pigment are mixed.For example, anthraquinone pigment can be that C.I. paratonere 177 ， perylene dyes can be C.I. paratonere 155 or C.I. paratonere 224, and diketopyrrolo-pyrrole pigment can be a C.I. paratonere 254.Consider colorrendering quality, preferably C.I. pigment yellow 13 9 is used to form potpourri.The quality ratio of yellow uitramarine and red pigment (yellow uitramarine/red pigment) is preferably in 5/100 to 50/100 scope.If this quality ratio is below 4/100, possibly is difficult to be suppressed at the light transmission in 400nm to the 500nm scope, and can not improves excitation in some cases.If this ratio is more than 51/100, then the advantage wavelength possibly move to more short wavelength side, makes possibly observe in some cases from the bigger deviation of NTSC target tone.Particularly, quality ratio is most preferably in 10/100 to 30/100 scope.Under the situation of the red pigment combinations of difference, can regulate its quality ratio according to tone.

The viridine green of halo phthalocyanine color can use separately, perhaps with the yellow pigment of bisdiazo, quinone phthalein ketone yellow uitramarine, the form of the potpourri of azomethine yellow uitramarine or isoindoline yellow uitramarine is used.For example, preferably with the C.I. pigment Green 7,36 or 37 and the C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185 mix.The quality ratio of yellow uitramarine and viridine green (yellow uitramarine/viridine green) is preferably in 5/100 to 150/100 scope.If quality ratio is lower than 5/100, possibly be difficult to be suppressed at the light transmission in 400nm to the 450nm scope, make and can not improve excitation in some cases.If ratio is higher than 150/100, then the advantage wavelength possibly move to more long wavelength side, makes possibly observe in some cases from the bigger deviation of NTSC target tone.Particularly, quality ratio is preferably in 30/100 to 120/100 scope.

The blue pigment of phthalocyanine color can use separately or to use with the form of the potpourri of dioxazine purple pigment.For example, preferably with the C.I. pigment blue 15: 6 mix with the C.I. pigment Violet 23.The quality ratio of violet pigment and blue pigment (violet pigment/blue pigment) is preferably in 0/100 to 30/100 scope, more preferably below 10/100.

Carbon, titanium carbide (titanium carbon), iron oxide and titanium dioxide can use separately or use with its form of mixtures, as the pigment that is used for black matrix, and the combination of preferred carbon and titanium carbide.The quality ratio of titanium carbide and carbon (titanium carbide/carbon) is preferably 0/100 to 60/100.If ratio is more than 61/100, possibly reduce dispersiveness in some cases.

In the present invention, when colorant is dyestuff, can obtain the painted composition that uniform dissolution wherein has dyestuff.The instance that can be used as the dyestuff of the colorant in the curable compositions of the present invention includes but not limited to, is used for the known dye of conventional color filter.The instance of operable dyestuff is included in JP-A Nos.64-90403,64-91102,01-94301 and 06-11614, Jap.P. No.2592207, United States Patent(USP) Nos. 4,808,501; 5,667,920 and 5,059,500, and JP-A Nos.05-333207,06-35183; 06-51115,06-194828,08-211599,04-249549,10-123316,11-302283,07-286107; 2001-4823,08-15522,08-29771,08-146215,11-343437,08-62416,2002-14220; 2002-14221,2002-14222,2002-14223,08-302224,08-73758, disclosed dyestuff among 08-179120 and the 08-151531.

As for chemical constitution, can use the pyrazoles azo dyes, aniline azo dyes, triphenhlmethane dye; Anthraquinone dye, Anthrapyridone dyestuff, benzal dyestuff, oxonol dye; The Pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dye, phenothiazine dyestuff; Pyrrolo-pyrazoles azomethine dyes, xanthene dye, phthalocyanine dye, benzopyran dyes and bipseudoindoxyl dye.

Comprise in the resist system of water or alkaline developer (alkali development) at some, can preferably use acid dyes and/or its derivant, to remove bonding agent and/or the dyestuff in the irradiation part not fully through developing.Can effectively use other dyestuff such as direct dyes, basic-dyeable fibre, mordant dye, acid mordant dyes, azo dyes, disperse dyes, oil-soluble dyes, food dye and/or their derivant.

Can use any acid dyes that contains acidic-group such as sulfonic group or carboxylic acid group.Can consider all must performance like the solubleness in organic solvent or developer, form the ability of salt with alkali compounds, absorbance with the interaction of other component in the composition, photostability and thermotolerance, is selected acid dyes.The instance of acid dyes includes but not limited to following dyestuff: the purple N of acid alizarine: acid black 1,2,24,48; Blue VRS, 7,9,15,18,23,25,27,29,40,45,62,70,74,80,83,86,87,90,92,103,112,113,120,129,138,147,158,171,182,192,243,324:1; Acid chrome violet K; Acid fuchsin; Acid green 1,3,5,9,16,25,27,50; Acid orange 6,7,8,10,12,50,51,52,56,63,74,95; 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; 176,183,198,211,215,216,217,249,252,257,260,266,274; Acid violet 6B, 7,9,17,19; Indian yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184,243; Food yellow 3; And the derivant of these dyestuffs.

The instance of preferred especially acid dyes comprises acid black 24; Acid blue 23,25,29,62,80,86,87,92,138,158,182,243,324:1; Acid orange 8,51,56,63,74; Azogeramine, 4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; Acid violet 7; Indian yellow 17,25,29,34,42,72,76,99,111,112,114,116,184,243; ACID GREEN 25; Derivant with these dyestuffs.Also preferred the use and above-mentioned different acid dyes such as azo, xanthene and phthalocyanine dye.Also preferably use acid dyes such as C.I. solvent blue 44,38, C.I. solvent orange 45, rhodamine B and rhodamine 110, and the derivant of these acid dyess.

Particularly, preferred colorant is selected from triarylmethane dye, anthraquinone dye, azomethine dyes, benzal dyestuff; Oxonol dye, cyanine dye, phenothiazine dyestuff, pyrrolo-pyrazoles azomethine dyes; Xanthene dye, phthalocyanine dye, benzopyran dyes, bipseudoindoxyl dye; Pyrazoles azo dyes, aniline azo dyes, Pyrazolotriazole azo dyes, pyridone azo dyes and Anthrapyridone dyestuff.

Can be used for colorant of the present invention and be preferably particle mean size (unit: nm) satisfy relational expression 20≤r≤300, more preferably 125≤r≤250, the dyestuff or the pigment of preferred especially 30≤r≤200.The pigment that has a this particle mean size r through use can obtain to have hard contrast than and the redness and the green pixel of high transmission rate.As the term " particle mean size " that here uses is meant the particle mean size of the secondary that primary particle (the single thin crystalline substance) gathering through pigment forms.Preferred the making of size-grade distribution (below, abbreviate " size-grade distribution " as) that is used for the secondary of pigment of the present invention: all in the secondarys more than the 70 quality %, more preferably drop on more than the 80 quality % in (particle mean size ± 100) nm.

Pigment with above-mentioned particle mean size and size-grade distribution can prepare through following method: this method comprises mixes commercially available pigment and another optional pigment (having the particle mean size greater than 300nm usually) and dispersion; The preferred pigment mixed liquor of conduct and spreading agent and solvent grinds them with muller such as ball mill or tumbling mill simultaneously.The pigment that obtains is the dispersible pigment dispersion form normally.

Based on the quality of the total solid of curable compositions, the content of the colorant in the curable compositions of the present invention is preferably 25 to 95 quality %, 30 to 90 quality % more preferably, also 40 to 80 quality % more preferably.If colorant content is too low, when using curable compositions to prepare color filter, possibly be difficult to obtain suitable colourity.If colorant content is too high, then photocuring possibly fully not carry out, and film strength possibly reduce or in the alkali developing process development latitude possibly narrow down.But, have high efficiency of light absorption owing to be used for (a) of the present invention special oxime compound, even when curable compositions contains the colorant of high concentration, also can produce sensitivity significantly and improve effect.

If necessary, curable compositions of the present invention can contain the optional components of more than one following detailed description.Other component that curable compositions of the present invention can contain is described below.

Can use any known Photoepolymerizationinitiater initiater that is different from special oxime compound in other Photoepolymerizationinitiater initiater curable compositions of the present invention, only otherwise weakening effect of the present invention gets final product.The Photoepolymerizationinitiater initiater that can use with the combination of special oxime compound causing and to promote described after a while curable compound polymeric compounds, and is preferably had absorption by photolysis in 300 to 500nm wavelength coverages.The instance of Photoepolymerizationinitiater initiater comprises organohalogen compounds, oxadiazole (oxydiazole) compound, carbonyls, ketal compound; The benzoin compound, acridine compound, organic peroxide compounds, azo-compound; Coumarin compound, triazo-compound, Metallocenic compound, united imidazole; The organic boronic ester compounds, disulfonic acid compound, oxime ester compound, salt compound and acylphosphanes (oxide) compound.

When spreading agent contains the pigment of conduct (e) colorant when curable compositions of the present invention, preferably spreading agent is joined in the composition to improve dispersing of pigments property.

The instance that can be used for spreading agent of the present invention (pigment dispersing agent) comprise polymeric dispersant (like daiamid and salt thereof, poly carboxylic acid and salt thereof, HMW unsaturated acid ester; The polyurethane of modification, the polyester of modification, modification gather (methyl) acrylic ester; (methyl) acrylic copolymer and naphthalene sulfonic acids formalin condensed polymer); And polyxyethylated phosphate, polyoxyethylene alkyl amine, alkanolamine and pigment derivative.According to structure, polymeric dispersant can further be divided into linear polymer, the polymkeric substance of end-modification, graft polymer and block polymer.

Polymeric dispersant is adsorbed on the surface of pigments and plays and prevents to reassociate effect.Therefore, for the block polymer that surface of pigments has the anchor part, the polymkeric substance of graft polymer and end-modification is a preferred construction.On the other hand, pigment derivative has the effect that promotes polymeric dispersant absorption through the modified pigment surface.

The instance that can be used for pigment dispersing agent of the present invention comprises DISPERBYK 101 (daiamid phosphate), 107 (carboxylates), 110 (multipolymers that contain acidic-group); 130 (polyamide), 161,162; 163,164,165; 166 and 170 (heavy polymers), and BYK-P104 and P105 (HMW unsaturated polyester carboxylic acid), they are all made by BYK Chemie; EFKA 4047,4050,4010 and 4165 (polyurethane dispersants), and EFKA 4330; 4340 (segmented copolymers), 4400,4402 (polyacrylate of modification); 5010 (polyesteramides), 5765 (HMW polycarboxylates), 6220 (fatty acid polyesters); 6745 (phthalocyanine derivates) and 6750 (AZOpigments derivant), they are all made by EFKA; By Ajinomoto Fine-Techno Co., AJISPER PB821 and PB822 that Inc. makes; FLOWLENTG-710 (oligourethane) and POLYFLOW Nos.50E and 300 (acrylic copolymer), they all are by Kyoeisha Chemical Co., Ltd. makes; DISPARLON KS-860,873SN, 874, #2150 (aliphatic poly carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705 and DA-725, they all are by Kusumoto Chemicals, Ltd. makes; DEMOL RN, N (naphthalene sulfonic acids formalin condensed polymer), MS; C, SN-B (aromatic sulfonic acid formalin condensed polymer), HOMOGENOL L-18 (HMW poly carboxylic acid); EMULGEN 920,930,935 and 985 (polyoxyethylene nonylplenyl ethers); And ACETAMIN 86 (stearylamine acetate), they are all made by Kao Corporation; SOLSPERSE 5000 (phthalocyanine derivates), 22000 (AZOpigments derivants), 13240 (polyesteramines); 3000,17000,27000 (polymkeric substance that have the functional moiety endways); 24000; 28000,32000 and 38500 (graft polymer), they are all made by The Lubrizol Corporation; And NIKKOLT106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylene monostearate), they all are by Nikko Chemicals Co., Ltd makes.

Can only use single spreading agent of planting, maybe can make up and use two or more spreading agents.In the present invention, especially preferably pigment derivative and polymeric dispersant combination are used.

In the present invention, based on the quality of pigment, the content of spreading agent is preferably 1 to 80 quality %, 5 to 70 quality % more preferably, also 10 to 60 quality % more preferably.For example, when using polymeric dispersant, its content is preferably 5 to 100 quality % of pigment, more preferably 10 to 80 quality %.When using pigment derivative, its content is preferably 1 to 30 quality % of pigment, and more preferably 3 to 20 quality % are preferably 5 to 15 quality % especially.

In the present invention; When using pigment as colorant and use spreading agent; Consider and solidify sensitivity and color density that based on the quality of the total solid of curable compositions, the total content of colorant and spreading agent is preferably 30 to 90 quality %; 40 to 85 quality % more preferably, also 50 to 80 quality % more preferably.

Binder polymer if necessary can also use binder polymer in curable compositions of the present invention (or photopolymerisable compositions (1)), purpose is to improve membrane property etc.The preferred line style organic polymer that uses is as bonding agent.Can use any known " line style organic polymer ".For can water or weak alkaline aqueous solution develop, the preferred selection dissolves in or the line style organic polymer of swellable in water or weak alkaline aqueous solution.Can not only be used as film forming agent but also consider developer such as water according to application, the line style organic polymer is selected and used to weak alkaline aqueous solution or organic solvent.For example, when using water-soluble organic polymer, can carry out water development.The instance of line style organic polymer is included in the free radical polymerization product that contains hydroxy-acid group in the side chain; Like JP-ANo.59-44615, JP-B Nos.54-34327,58-12577 and 54-25957; And JP-A Nos.54-92723; Those that describe among 59-53836 and the 59-71048, particularly, through the homopolymerization of carboxylic monomer or the resin of copolymerization; The resin that the homopolymerization of the monomer through containing acid anhydrides or hydrolysis, half esterization or the half amideization of copolymerization and acid anhydrides unit subsequently prepare, and epoxy acrylate through preparing with unsaturated monocarboxylic and/or anhydride modified epoxy resin.The instance of carboxylic monomer comprises acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and 4-carboxyl styrene.The instance that contains the monomer of acid anhydrides comprises maleic anhydride.Instance also is included in the acid cellulose derivant that has hydroxy-acid group in the side chain.In addition, also can use cyclic acid anhydride to add to the product in the polymkeric substance of hydroxyl.

When used alkali soluble resins is multipolymer, can also use the monomer that is different from above-mentioned monomer as will be by the compound of copolymerization.The instance of other monomer comprises the compound of following (1) to (12):

(1) contains the acrylic ester and the methacrylate of aliphatic hydroxide radical; Like acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 3-hydroxy propyl ester; Acrylic acid 4-hydroxyl butyl ester; 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester and methacrylic acid 4-hydroxyl butyl ester; (2) alkyl acrylate, like methyl acrylate, ethyl acrylate, propyl acrylate; Butyl acrylate, isobutyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate; 2-EHA, 2-ethyl hexyl acrylate, benzyl acrylate, acrylic acid 2-chloroethene ester; Glycidyl acrylate, acrylic acid 3,4-epoxycyclohexyl methyl esters, vinyl acrylate; Acrylic acid 2-phenyl ethene (2-phenylviyl) ester, acrylic acid 1-propylene ester, allyl acrylate, acrylic acid 2-allyl oxygen base ethyl ester and acrylic acid alkynes propyl ester;

(3) alkyl methacrylate, like methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate; Butyl methacrylate, isobutyl methacrylate, methacrylic acid pentyl ester, hexyl methacrylate; Methacrylic acid 2-Octyl Nitrite, 2-Propenoic acid, 2-methyl-, octyl ester, benzyl methacrylate, methacrylic acid 2-chloroethene ester; GMA, methacrylic acid 3,4-epoxycyclohexyl methyl esters, metering system vinyl acetate; Methacrylic acid 2-phenyl vinyl acetate, methacrylic acid 1-propylene ester, allyl methacrylate, methacrylic acid 2-allyl oxygen base ethyl ester and methacrylic acid alkynes propyl ester; (4) acrylic amide and methacryl amine, like acrylic amide, Methacrylamide, N hydroxymethyl acrylamide; The N-ethyl acrylamide, N-hexyl methyl acrylic amide, N-cyclohexyl acrylic amide, N-hydroxyethyl acrylic amide; N phenyl acrylamide, N-nitrobenzophenone acrylic amide, N-ethyl-N phenyl acrylamide, vinyl acrylic amide; The vinyl Methacrylamide, N, N-diallyl acrylic amide; N, N-diallyl Methacrylamide, allyl acrylic amide and allyl methyl acrylic amide;

Vinyl ether, like ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl group vinyl ether and Vinyl phenyl ether; (6) vinyl esters, like vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate; (7) phenylethylene, like styrene ,-methyl styrene, methyl styrene, 1-chloro-4-methyl-benzene and right-acetoxy-styrene; (8) vinyl ketone, like methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone and phenyl vinyl ketone; (9) alkene, like ethene, propylene, isobutylene, butadiene and isoprene;

(10) N-vinylpyrrolidone, vinyl cyanide, methacrylonitrile etc.; (11) unsaturated acid imide, like maleimide, N-acryloyl group acrylic amide, N-acetyl group Methacrylamide, N-propiono Methacrylamide and N-(right-chlorobenzene formacyl) Methacrylamide; And (12) have heteroatomic methacrylic acid monomer at alpha-position, the compound described in Japanese patent application Nos. 2001-115595 and 2001-115598.

Consider excellent balance between film strength, sensitivity and the development property; Particularly preferably be (methyl) acrylic resin that on side chain, has allyl or vinyl esters group and carboxyl; Described in JP-A Nos.2000-187322 and the 2002-62698 at the alkali soluble resins that has two keys on the side chain with at the alkali soluble resins that on side chain, has amide group described in the JP-ANo.2001-242612.

JP-B Nos.07-12004; 07-120041,07-120042 and 08-12424, JP-A Nos.63-287944; 63-287947 and 01-271741; And the urethane adhesive polymkeric substance that in side chain, has acidic-group and two keys described in urethane adhesive polymkeric substance that contains acidic-group described in the Japanese patent application No.10-116232 and the JP-A No.2002-107918 is being favourable aspect printability resistance or the low exposure performance, because they have very high intensity.Contain acidic-group, acetal-modification, poly (vinyl alcohol) binder polymkeric substance; As European patent Nos.993966 and 1204000 with JP-A No.2001-318463 described in those; Also be preferred, because they have excellent balance between film strength and development property.Available water-soluble line style organic polymer also comprises polyvinylpyrrolidone and polyethylene oxide.Alcohol soluble nylon or 2, the polyethers of 2-pair-(4-hydroxy phenyl)-propane and chloropropylene oxide also is useful for improving the curing film strength.

The weight-average molecular weight that can be used for the binder polymer of one embodiment of the invention is preferably more than 5,000, and more preferably 10,000 to 300,000, and number-average molecular weight is preferably more than 1,000, more preferably 2,000 to 250,000.Polydispersity (weight-average molecular weight/number-average molecular weight) is preferably more than 1, and more preferably 1.1 to 10.These binder polymers can be any in random, block or the graft polymer.

Can be used for binder polymer of the present invention can use known conventional method synthetic.The instance of the solvent that can be used for synthesizing comprises tetrahydrofuran, ethylidene bichloride, cyclohexanone, methyl ethyl ketone, acetone, methyl alcohol; Ethanol, glycol monoethyl ether, ethylene glycol monoethyl ether, acetate 2-methoxyl ethyl ester, diethylene glycol dimethyl ether, 1-methoxyl-2-propyl alcohol; Acetate 1-methoxyl-2-propyl ester, N, dinethylformamide, DMAC N,N; Toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide and water.Can only use known solvent maybe can use the potpourri of two or more solvents.Can be used in the method for binder polymer of the present invention synthetic, can use compound known such as azo initiator and peroxide initiator as radical polymerization initiator.

Polymerization inhibitor preferably adds a spot of thermal polymerization inhibitor to be suppressed at the unnecessary thermal polymerization of (b) polymerizable compound in curable compositions preparation or the storage process in the present invention.The instance that can be used for thermal polymerization inhibitor of the present invention comprises quinhydrones, and is right-metoxyphenol, di-t-butyl-p-Cresol; 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, benzoquinones; 4; 4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol) and N-nitroso-phenyl-azanol cerium.

Based on the quality of the total solid of curable compositions, the content of thermal polymerization inhibitor is preferably about 0.01 to about 5 quality %.If necessary, can add behenic acid or advanced higher fatty acid derivative such as behenamide in case block-polymerization of inducing suppresses, and in can the dry run after coating localization to the surface of filming.Based on whole composition, the content of advanced higher fatty acid derivative is preferably about 0.5 to about 10 quality %.

Adhesion improver curable compositions of the present invention can contain the adhesion improver to improve the adhesion to hard surface such as carrier surface.The adhesion improver can be a silane coupling agent, titanium coupling agent etc.

The instance of silane coupling agent comprises γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) aminopropyl dimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; The gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane; γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl-triethoxysilicane, γ-isocyanato-propyl trimethoxy silicane, γ-isocyanato-propyl-triethoxysilicane; N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane hydrochloride, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, amino silane; γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, MTMS; MTES, vinyltriacetoxy silane, γ-r-chloropropyl trimethoxyl silane; Hexamethyldisilazane, γ-anilino-propyl trimethoxy silicane, vinyltrimethoxy silane; VTES, vinyl three ('beta '-methoxy ethoxy) silane, chlorination octadecyl dimethyl [3-(trimethoxysilyl) propyl group] ammonium; Gamma-chloropropylmethyldimethoxysilane, γ-sulfydryl propyl group methyl dimethoxysilane, methyl trichlorosilane; Dimethyldichlorosilane, trimethyl chlorosilane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, diallyl trimethoxy silane, tetraethoxysilane; Two (trimethoxysilyl) hexane, phenyltrimethoxysila,e, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxywerene werene; N-(3-methacryloxy 2-hydroxypropyl)-3-aminopropyltriethoxywerene werene, (methacryloxy methyl) methyldiethoxysilane and (acryloyl-oxy ylmethyl) methyl dimethoxysilane.Particularly; Preferred γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, γ-acryloxy propyl trimethoxy silicane; γ-acryloxy propyl-triethoxysilicane; γ-Qiu Jibingjisanjiayangjiguiwan, γ-An Jibingjisanyiyangjiguiwan and phenyltrimethoxysila,e, and γ-methacryloxypropyl trimethoxy silane most preferably.

Based on the quality of the total solid of curable compositions (or photopolymerisable compositions (1)), the content of adhesion improver is preferably 0.5 to 30 quality %, more preferably 0.7 to 20 quality %.

Thinning agent can use any thinning agent as curable compositions of the present invention in the various organic solvents.The instance of operable organic solvent comprises acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylidene bichloride, tetrahydrofuran; Toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether; Diacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, glycol monomethyl isopropyl ether; Ethylene glycol monomethyl ether acetate, 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Diethylene glycol dimethyl ether, diethyl carbitol, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate 3-methoxyl propyl ester; N, dinethylformamide, dimethyl sulfoxide, gamma-butyrolacton, methyl lactate and ethyl lactate.Can only use a kind of solvent maybe can use the potpourri of two or more solvents.Solid content with respect to organic solvent is preferably 2 to 60 quality %.

Other adjuvant in addition can also be with the adjuvant of the known physical property that is used for modified solidified film, and like inorganic filler, plastifier and lipophilization agent add in the curable compositions of the present invention.The instance of plastifier comprises dioctyl phthalate, phthalic acid two (dodecyl) ester, triethylene glycol dieaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate and triacetyl glycerine.When using bonding agent,, can add plastifier with the amount below the 10 quality % based on the gross mass of polymerizable compound and binder polymer.

Curable compositions of the present invention contains (a) special oxime compound, therefore can and have high storage stability with high sensitivity curing.When curable compositions of the present invention being coated to hard material surface and solidifying, cured product can show the outstanding adhesion to the surface.The curable compositions of the invention described above can be preferred for Image forming material field such as three-dimensional light moulding material, holographic material, color filter; Photoresist, lithography material and color proof, and aforesaid printing ink; Paint, cementing agent, smears and dental material.Particularly, of the present invention comprising (a), special oxime ester, (b) polymerizable compound were preferably used as color filter with curable compositions (curable compositions that is used for color filter of the present invention) with (e) curable compositions of colorant.

Provide below color filter and preparation method thereof color filter according to the present invention and the description for preparing the method for color filter.Color filter of the present invention comprises carrier and uses the colored pattern that is used for the curable compositions preparation of color filter of the present invention.Describe color filter of the present invention below in detail together with its preparation method (method that is used to prepare color filter of the present invention).

The method that is used to prepare color filter of the present invention may further comprise the steps: the curable compositions that is used for color filter of the present invention is coated on the carrier to form colored curable composition layer (following also abbreviate as " the colored curable composition layer forms step "); With the colored curable composition layer through mask exposure (following also abbreviate as " step of exposure "); And the composition layer of exposure developed to form colored pattern (following also abbreviate as " development step ").

Particularly, directly or under the intercalary situation of another layer, be coated to carrier (substrate) and go up to form photopolymerisable compositions layer (the colored curable composition layer forms step) with the curable compositions that is used for color filter of the present invention; With film through the exposure of special pattern mask with cured coating film by irradiation part (step of exposure); And will be coated with film development with liquid developer and comprise the patterned film of the pixel of respective color (three kinds or four kinds of colors), thereby prepare color filter of the present invention with formation.Each step that is used to prepare the method for color filter of the present invention is described below.

< the colored curable composition layer forms step>forms in the step at the colored curable composition layer, and the curable compositions that is used for color filter of the present invention is coated on the carrier to form the colored curable composition layer.

The instance that can be used for the carrier of this step comprises the soda-lime glass substrate, PYREX (registered trademark) glass substrate, quartz glass substrate and through with nesa coating attached to the substrate that obtains on arbitrary above-mentioned glass substrate, these substrates are used for LCD etc.; And the photoelectricity conversion substrate that is used for image device, like silicon substrate and complementary metal oxide semiconductor (CMOS) (CMOS).In some cases, these substrates can have the separated black streaking of pixel.If necessary, can on carrier, form undercoat, prevent the material diffusion or substrate surface is flattened with the adhesion of improvement with the upper strata.

The curable compositions that is used for color filter of the present invention can be coated to carrier through various coating processes, described coating process such as slot coated, ink ejecting method, rotary coating, curtain coating coating, roller coat and serigraphy.

The thickness that curable compositions is filmed is preferably 0.1 μ m to 10 μ m, 0.2 μ m to 5 μ m more preferably, also 0.2 μ m to 3 μ m more preferably.

The curable compositions that is used for color filter the coating on the carrier usually under 70 to 110 ℃ condition dry 2 to 4 minutes to form the colored curable composition layer.

< step of exposure>forms the colored curable composition layer on the colored curable composition layer that forms in the step through mask exposure in step of exposure, make a cured coating film by the irradiation part.Exposure is preferably through carrying out with radiant rays irradiation.Particularly, the preferred radiant rays that uses ultraviolet ray as g-line or i-line as the usefulness of making public, and more preferably high-pressure sodium lamp.Irradiation intensity is preferably 5mJ to 1500mJ, and more preferably 10mJ to 1000mJ most preferably is 10mJ to 800mJ.

< development step>can carry out alkali and develop (development step) after step of exposure, makes and can be dissolved in the alkaline aqueous solution by the unexposed portion that step of exposure produces.In this step, only stay the part of photocuring.Liquid developer is preferably the organic basic developer that does not damage following circuit etc.Develop and carried out 20 to 90 seconds 20 ℃ to 30 ℃ temperature usually.

The instance that is used for the alkali of liquid developer comprises ammoniacal liquor and organic basic compound such as ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrroles, piperidines and 1,8-diazabicyclo-[5,4,0]-7-undecylene.Can use with pure water and alkali is diluted to the concentration of 0.001 to 10 quality %, preferred 0.01 to 1 quality % and the alkaline aqueous solution for preparing.When use comprises the liquid developer of this alkaline aqueous solution, after development, wash (flushing) usually with pure water.

If necessary, the method for preparing color filter of the present invention can also be included in and carry out after the formation of curable compositions layer step, step of exposure and the development step, through the step that heats and/or colored pattern is solidified in exposure.

Can the colored curable composition layer be formed step, the corresponding required tone of step of exposure and development step (and optional curing schedule) repeats for several times, thereby can prepare the color filter with required tone.

Color filter of the present invention is to use the curable compositions that is used for color filter of the present invention to prepare.Therefore, in color filter, colored pattern and support substrate have outstanding adhesion, and cured compositions has excellent anti-development property.Therefore, exposure sensitivity is high, and the adhesion of exposed portion and substrate is excellent, and can form the high resolution design with required shape of cross section.Therefore, color filter of the present invention is suitable for LCD and solid imaging element such as CCD, is particularly suitable for having high resolution CCD device or the cmos device that surpasses 1 mega pixel.For example, can with color filter of the present invention be placed on CCD each pixel light receiving part and assemble between the lenticule.

< novel oxime compound>novel oxime compound of the present invention is by following formula (1) expression (below be also referred to as " novel oxime compound ").

In formula (1), R and B represent the monovalence substituting group independently of one another, and A representes divalent organic group, and Ar representes aryl.The substituent instance of representing by R of monovalence with in above-mentioned formula (I-I) by R ¹The monovalence of expression is substituent, and those are identical, and their preferred embodiment is also identical with scope.

In order to improve sensitivity, R is acyl group more preferably, particularly, and preferred acetyl group propiono, benzoyl or toluyl groups.

The monovalence substituting group of being represented by B can be optional substituted aryl, optional substituted heterocyclic radical, optional substituted aryl carbonyl or optional substituted heterocycle carbonyl, and any in the structure shown in below preferred especially.In the structure below, Y, X and n have and the Y in the formula of describing after a while (2) separately, the definition that X is identical with n, and preferred embodiment is also identical.

The divalent organic group of being represented by A can be the alkylidene of optional substituted 1 to 12 carbon atom, optional substituted cyclohexylidene or optional substituted alkynylene.The substituent instance that can introduce these groups comprises: halogen atom such as fluorine, chlorine, bromine or iodine atom; Alkoxy such as methoxyl, ethoxy or tert-butoxy; Aryloxy group such as phenoxy group or right-toloxyl; Alkoxy carbonyl group such as methoxycarbonyl group, butoxy carbonyl or carbobenzoxy; Acyloxy such as acetoxyl group, propionyloxy or benzoyloxy; Acyl group such as acetyl group, benzoyl, isobutyryl, acryloyl group, methacryl or methoxalyl base; Alkylthio group such as methyl mercapto or uncle's butylthio; Arylthio such as thiophenyl or right-toluene sulfenyl; Alkyl amino such as methylamino or cyclohexyl are amino; Dialkyl amido such as dimethylamino, diethylamino, morpholino or piperidino; Arylamino such as phenyl amino or right-tolyl are amino; Alkyl such as methyl, ethyl, the tert-butyl group or dodecyl; Aryl such as phenyl, right-tolyl, xylyl, cumenyl, naphthyl, anthryl or phenanthryl; Hydroxyl, carboxyl, formoxyl, sulfydryl, sulfo group, mesyl, ptoluene-sulfonyl, amino, nitro, cyanic acid, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphono, trimethyl ammonium, dimethyl sulfonium base and triphenyl phenacyl Phosphonium base.Particularly, A is preferably unsubstituted alkylidene, by alkyl (like methyl, ethyl; The tert-butyl group or dodecyl) substituted alkylidene, by the substituted alkylidene of thiazolinyl (like vinyl or allyl), or by aryl (like phenyl; Right-tolyl, xylyl, cumenyl; Naphthyl, anthryl, phenanthryl or styryl) substituted alkylidene.

The aryl of being represented by Ar preferably has 6 to 30 carbon atoms and can have one or more substituting groups.Examples include phenyl, biphenyl, 1 - naphthyl, 2 - naphthyl group, 9 - anthryl group, 9 - phenanthryl group, 1 - pyrene group, a 5 - four-phenyl, 1 - indenyl group, a 2 - azulenyl 9 - fluorenyl, terphenyl, quadruple phenyl, o - tolyl, m - tolyl, p - tolyl, xylyl, o - cumene group, a - cumene group, the - cumene base,?

group, and cyclopentadienyl group, binaphthyl group, a naphthyl group triple, quadruple naphthyl group, a heptyl a triene and triene heptyl group, a biphenylene group, indacenyl? group, fluoranthenyl group, acenaphthyl, aceanthrylenyl, phenalenyl? group, fluorenyl group, an anthryl group, together anthracene group, anthryl group triple, quadruple anthryl group, anthraquinone group, phenanthryl, benzo phenanthryl, pyrenyl,?

group, four-phenyl, seven Yao group, Pi group, perylene group, pentyl Fenji, pentacene group, tetramethylene group, hexyl Fenji and hexaphenyl, Rubine province group, halo phenyl, biphenyl, trinaphthyl group, a heptyl Fenji and seven phenyl, anthracenyl and egg phenyl skin.Particularly, consider sensitivity is provided and/or suppress by long-time heating cause painted, preferred substituted or unsubstituted phenyl.

The substituent instance of substituted phenyl comprises halogen atom such as fluorine, chlorine, bromine or iodine atom; Alkoxy such as methoxyl, ethoxy or tert-butoxy; Aryloxy group such as phenoxy group or right-toloxyl; Alkylthio group oxygen base such as methyl mercapto oxygen base, ethylmercapto group oxygen base or uncle's butylthio oxygen base; Arylthio oxygen base such as thiophenyl oxygen base or right-toluene sulfenyl oxygen base; Alkoxy carbonyl group such as methoxycarbonyl group, butoxy carbonyl or carbobenzoxy; Acyloxy such as acetoxyl group, propionyloxy or benzoyl oxygen base; Acyl group such as acetyl group, benzoyl, isobutyryl, acryloyl group, methacryl or methoxalyl base; Alkylthio group such as methyl mercapto or uncle's butylthio; Arylthio such as thiophenyl or right-toluene sulfenyl; Alkyl amino such as methylamino or cyclohexyl are amino; Dialkyl amido such as dimethylamino, diethylamino, morpholino base or piperidino; Arylamino such as phenyl amino or right-tolyl are amino; Alkyl such as ethyl, the tert-butyl group or dodecyl; Hydroxyl, carboxyl, formoxyl, sulfydryl, sulfo group, mesyl, ptoluene-sulfonyl, amino, nitro, cyanic acid, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphono, trimethyl ammonium, dimethyl sulfonium base or triphenyl phenacyl Phosphonium base.

In formula (1), consider sensitivity, the SAr structure optimization of forming by substituent A r and adjacent S be following shown in the structure any.

Novel oxime compound of the present invention is preferably the compound by following formula (2) expression.

In formula (2), R and X represent the monovalence substituting group independently of one another, and A and Y represent divalent organic group independently of one another, and Ar representes aryl, and n representes 0 to 5 integer.

In formula (2), R, A and Ar have and R in formula (1), definition that A is identical with Ar separately, and preferred embodiment is also identical.

The monovalence substituting group of being represented by X can be optional substituted alkyl, optional substituted aryl, optional substituted thiazolinyl, optional substituted alkynyl; Optional substituted alkoxy, optional substituted aryloxy group, optional substituted alkylthio group oxygen base, optional substituted arylthio oxygen base; Optional substituted acyloxy, optional substituted alkylthio group, optional substituted arylthio, optional substituted alkyl sulphinyl; Optional substituted aryl sulfonyl kia, optional substituted alkyl sulphonyl, optional substituted aryl sulfonyl, optional substituted acyl group; Optional substituted alkoxy carbonyl group, optional substituted carbamyl, optional substituted sulfamoyl, optional substituted amino; Optional substituted phosphono, optional substituted heterocyclic radical, halogen group etc.

Optional substituted alkyl is preferably the alkyl that contains 1 to 30 carbon atom, and instance comprises methyl, ethyl, propyl group, butyl, hexyl; Octyl group, decyl, dodecyl, octadecyl, isopropyl, isobutyl; Sec-butyl, the tert-butyl group, 1-ethyl pentyl group, cyclopentyl, cyclohexyl, trifluoromethyl; The 2-ethylhexyl, phenacyl, 1-naphthoyl methyl, 2-naphthoyl methyl, 4-methyl mercapto phenacyl, 4-thiophenyl phenacyl; 4-dimethylamino phenacyl, 4-cyanic acid phenacyl, 4-toluyl methyl, 2-toluyl methyl, 3-fluorobenzoyl methyl, 3-trifluoromethyl benzoyl methyl and 3-nitrobenzene formyl methyl.

An optionally substituted aryl group is preferably 6 to 30 carbon atoms, an aryl group, and examples thereof include phenyl, biphenyl, 1 - naphthyl, 2 - naphthyl group, 9 - anthryl group, 9 - phenanthryl, 1 - pyrene group, a 5 - four-phenyl, 1 - indenyl group, a 2 - azulenyl group, 9 - fluorenyl group, a terphenyl group, quadruple phenyl, o - tolyl, m - tolyl, p - tolyl , di? tolyl, o - cumene group, a - cumene group, the - cumenyl,?

group, and cyclopentadienyl group, binaphthyl group, a naphthyl group triple, quadruple naphthyl group, a heptyl triene and a leukotriene heptyl group, a biphenylene group, indacenyl? group, fluoranthenyl group, acenaphthyl, aceanthrylenyl, phenalenyl? group, fluorenyl, anthracenyl, together two anthryl, triple anthryl group, four Union anthryl, anthraquinone, phenanthrene, benzo phenanthrene, pyrene group,?

group, and the four phenyl, seven Yao group, Pi group, perylene group, pentyl Fenji and pentaphenylbenzaldehyde four phenylene , hexyl Fenji and hexaphenyl, Rubine province group, halo phenyl, biphenyl, trinaphthyl, heptyl Fenji and seven phenyl, anthracenyl and egg phenyl skin.

Optional substituted alkoxy is preferably the alkoxy that contains 1 to 30 carbon atom, and the example comprises methoxyl, ethoxy, propyl group oxygen base, isopropyl oxygen base; Butoxy, isobutoxy, sec-butoxy, tert-butoxy, amoxy; Isoamoxy, own oxygen base, heptan the oxygen base, octyloxy, 2-ethyl hexyl oxy; The last of the ten Heavenly stems oxygen base, dodecyloxy, octadecane oxygen base, ethoxy carbonyl methyl, 2-ethyl hexyl oxy carbonyl methyl oxygen base; Amino carbonyl methyl oxygen base, N, N-dibutylamino carbonyl methyl oxygen base, N-methylamino carbonyl methyl oxygen base; N-ethylamino carbonyl methyl oxygen base, N-octyl group amino carbonyl methyl oxygen base, N-methyl-N-benzylamino carbonyl methyl oxygen base, benzyloxy and cyano methyl oxygen base.

Optional substituted aryloxy group is preferably the aryloxy group that contains 6 to 30 carbon atoms, and the example comprises phenoxy group, 1-naphthoxy, 2-naphthoxy, 2-chlorophenoxy; The 2-methylphenoxy, 2-methoxyl phenoxy group, 2-phenoxy butoxy base, 3-chlorophenoxy; The 3-4-trifluoromethylphenopendant, 3-cyano-benzene oxygen, 3-nitro-phenoxy, 4-fluorophenoxy; 4-cyano-benzene oxygen, 4-methoxyl phenoxy group, 4-dimethylamino phenoxyl, 4-methyl mercapto phenoxy group and 4-thiophenyl phenoxy group.

Optional substituted alkylthio group oxygen base is preferably the thio alkoxy that contains 1 to 30 carbon atom, and the example comprises methyl mercapto oxygen base, ethylmercapto group oxygen base, rosickyite base oxygen base, different rosickyite base oxygen base; Butylthio oxygen base, isobutyl sulfenyl oxygen base, secondary butylthio oxygen base, uncle's butylthio oxygen base, penta sulfenyl oxygen base; Isoamyl sulfenyl oxygen base, own sulfenyl oxygen base, heptan sulfenyl oxygen base, hot sulfenyl oxygen base; The own sulfenyl oxygen of 2-ethyl base, the last of the ten Heavenly stems sulfenyl oxygen base, dodecane sulfenyl oxygen base, octadecane sulfenyl oxygen base and benzylthio oxygen base.

Optional substituted arylthio oxygen base is preferably the arylthio oxygen base that contains 6 to 30 carbon atoms, and the example comprises thiophenyl oxygen base, 1-naphthalene sulfenyl oxygen base, 2-naphthalene sulfenyl oxygen base; 2-chlorobenzene sulfenyl oxygen base, 2-methylbenzene sulfenyl oxygen base, 2-methoxybenzene sulfenyl oxygen base, 2-butyl phenyl ether sulfenyl oxygen base; 3-chlorobenzene sulfenyl oxygen base, 3-trifluoromethyl thiophenyl oxygen base, 3-cyanic acid thiophenyl oxygen base; 3-nitrophenylsulfenyl oxygen base, 4-fluorobenzene sulfenyl oxygen base, 4-cyanic acid thiophenyl oxygen base; 4-methoxybenzene sulfenyl oxygen base, 4-dimethylamino thiophenyl oxygen base, 4-methylthio phenyl sulfenyl oxygen base and 4-thiophenyl thiophenyl oxygen base.

Optional substituted acyloxy is preferably the acyloxy that contains 2 to 20 carbon atoms, and the example comprises acetoxyl group, propionyloxy, butyryl acyloxy, penta acyloxy, trifluoromethyl ketonic oxygen base, benzoyl oxygen base, 1-naphthyl carbonyl oxygen base and 2-naphthyl carbonyl oxygen base.

Optional substituted alkylthio group is preferably the alkylthio group that contains 1 to 20 carbon atom, and the example comprises methyl mercapto, ethylmercapto group, rosickyite base; Different rosickyite base, butylthio, own sulfenyl, hexamethylene sulfenyl; Hot sulfenyl, the own sulfenyl of 2-ethyl, caprinoyl sulfenyl; Dodecanoyl sulfenyl, stearyl sulfenyl, cyanomethylthio and methoxy methyl sulfenyl.

Optional substituted arylthio is preferably the arylthio that contains 6 to 30 carbon atoms, and the example comprises thiophenyl, 1-naphthalene sulfenyl, 2-naphthalene sulfenyl, 2-chlorobenzene sulfenyl; 2-methylbenzene sulfenyl, 2-methoxybenzene sulfenyl, 2-butyl phenyl ether sulfenyl, 3-chlorobenzene sulfenyl; 3-trifluoromethyl thiophenyl, 3-cyanic acid thiophenyl, 3-nitrophenylsulfenyl, 4-fluorobenzene sulfenyl; 4-cyanic acid thiophenyl, 4-methoxybenzene sulfenyl, 4-methylthio phenyl sulfenyl, 4-thiophenyl thiophenyl and 4-dimethylamino thiophenyl.

Optional substituted alkyl sulphonyl is preferably the alkyl sulphonyl that contains 1 to 20 carbon atom, and the example comprises methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base; The isopropyl sulfonyl, butyl sulfonyl, hexyl sulfonyl, cyclohexyl sulfonyl; The octyl group sulfonyl, 2-ethylhexyl sulfonyl, capryl sulfonyl; Dodecane acyl group sulfonyl, octadecanoyl sulfonyl, cyano methyl sulfonyl and methoxy sulfonyl.

Optional substituted alkoxy carbonyl group is preferably the alkoxy carbonyl group that contains 2 to 20 carbon atoms, and the example comprises methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl; Butoxy carbonyl, hexyloxy carbonyl, carbonyl octyloxy, the last of the ten Heavenly stems oxygen base carbonyl; Octadecane oxygen base carbonyl, phenyloxycarbonyl, trifluoromethyl oxygen base carbonyl, 1-naphthoxy carbonyl; 2-naphthoxy carbonyl, 4-methyl mercapto phenyl oxygen base carbonyl, 4-thiophenyl phenyl oxygen base carbonyl, 4-dimethylaminophenyl oxygen base carbonyl; 4-diethylamino phenyl oxygen base carbonyl, 2-chlorphenyl oxygen base carbonyl, 2-aminomethyl phenyl oxygen base carbonyl, 2-methoxyphenyl oxygen base carbonyl; 2-butoxy phenyl oxygen base carbonyl, 3-chlorphenyl oxygen base carbonyl, 3-trifluoromethyl oxygen base carbonyl, 3-cyano-phenyl oxygen base carbonyl; 3-nitrobenzophenone oxygen base carbonyl, 4-fluorophenyl oxygen base carbonyl, 4-cyano-phenyl oxygen base carbonyl and 4-methoxyphenyl oxygen base carbonyl.

Optional substituted carbamyl is preferably the carbamyl that contains 1 to 30 carbon atom altogether, and the example comprises N-methylamino formoxyl, N-ethylamino formoxyl, N-propyl group carbamyl; N-butyl carbamyl, N-hexyl carbamyl, N-cyclohexyl carboxyamide base, N-octyl group carbamyl; N-decyl carbamyl, N-octadecyl carbamyl, N-phenyl amino formoxyl, N-2-aminomethyl phenyl carbamyl; N-2-chlorphenyl carbamyl, N-2-isopropyl phenyl carbamyl, N-2-(2-ethylhexyl) phenyl amino formoxyl, N-3-chlorphenyl carbamyl; N-3-nitrobenzophenone carbamyl, N-3-cyano-phenyl carbamyl, N-4-methoxyphenyl carbamyl; N-4-cyano-phenyl carbamyl, N-4-methyl mercapto phenyl carbamyl, N-4-thiophenyl phenyl amino formoxyl; N-methyl-N-phenyl amino formoxyl, N, N-formyl-dimethylamino; N, N-dibutylamino formoxyl and N, N-diphenyl amino formoxyl.

Optional substituted sulfamoyl is preferably the sulfamoyl that contains 0 to 30 carbon atom altogether, and the example comprises sulfamoyl, the N-alkylsulfamoyl group; The N-ammonia aryl sulfonyl, N, N-dialkyl sulfamine; N, N-ammonia diaryl sulfonyl and N-alkyl-N-ammonia aryl sulfonyl.More specifically, instance comprises N-methyl sulfamoyl, N-ethyl sulfamoyl, N-propyl group sulfamoyl, N-butyl sulfamoyl; N-hexyl sulfamoyl, N-cyclohexyl sulfamoyl, N-octyl group sulfamoyl, N-2-ethylhexyl sulfamoyl, N-decyl sulfamoyl; N-octadecyl sulfamoyl, N-phenyl sulfamoyl base, N-2-aminomethyl phenyl sulfamoyl, N-2-chlorphenyl sulfamoyl; N-2-methoxyphenyl sulfamoyl, N-2-isopropyl phenyl sulfamoyl, N-3-chlorphenyl sulfamoyl, N-3-nitrobenzophenone sulfamoyl; N-3-cyano-phenyl sulfamoyl, N-4-methoxyphenyl sulfamoyl, N-4-cyano-phenyl sulfamoyl, N-4-dimethylaminophenyl sulfamoyl; N-4-methyl mercapto phenyl sulfamoyl, N-4-thiophenyl phenyl sulfamoyl base, N-methyl-N-phenyl sulfamoyl base, N; N-dimethylamino sulfonyl, N, N-dibutylamine sulfonyl and N, N-diphenyl sulfamoyl.

Optional substituted amino is preferably the amino that contains 0 to 50 carbon atom altogether, and instance comprises-NH ₂, the N-alkyl amino, the N-arylamino, the N-acylamino-, the N-sulfuryl amino, N, the N-dialkyl amido, N, the N-ammonia diaryl base, N-alkyl-N-arylamino and N, N-disulfonyl base is amino.More specifically, instance comprises the N-methylamino, the N-ethylamino, and the N-propyl group is amino, and the N-isopropyl is amino, and the N-butyl is amino, and the N-tert-butyl group is amino; The N-hexyl is amino, and the N-cyclohexyl is amino, and the N-octyl group is amino, and the N-2-ethylhexyl is amino, and the N-decyl is amino, and the N-octadecyl is amino, the N-benzylamino; The N-phenyl amino, the N-2-aminomethyl phenyl is amino, and the N-2-chlorphenyl is amino, and the N-2-methoxyphenyl is amino, and the N-2-isopropyl phenyl is amino, N-2-(2-ethylhexyl) phenyl amino; The N-3-chlorphenyl is amino, and the N-3-nitrobenzophenone is amino, and the N-3-cyano-phenyl is amino, and the N-3-trifluoromethyl is amino, and the N-4-methoxyphenyl is amino, and the N-4-cyano-phenyl is amino; The N-4-trifluoromethyl is amino, and N-4-methyl mercapto phenyl is amino, N-4-thiophenyl phenyl amino, and the N-4-dimethylaminophenyl is amino, N-methyl-N-phenyl amino, N; The N-dimethylamino, N, N-diethylamino, N, N-dibutylamino, N; The N-diphenyl amino, N, the N-diacetyl is amino, N, the N-dibenzoyl is amino, N; N-(dibutyl carbonyl) amino, N, N-(dimethyl methyl acyl group) amino, N, N-(diethyl sulfonyl) amino, N; N-(dibutyl sulfonyl) amino, N, N-(diphenyl sulfonyl) amino, morpholino, 3,5-thebaine generation and carbazyl.

Optional substituted heterocyclic radical is preferably and contains nitrogen, oxygen, the aromatics of sulphur or phosphorus atoms or aliphatic heterocyclic radical.Instance comprises thienyl, benzo [b] thienyl, naphtho-[2,3-b] thienyl, thianthrene group, furyl, pyranose, isobenzofuran-base, chromene base; Xanthyl, phenol oxathiin base, 2H-pyrrole radicals, pyrrole radicals, imidazole radicals, pyrazolyl, pyridine radicals, pyrazinyl, pyrimidine radicals; Pyridazinyl, indolizine base, isoindolyl, 3H-indyl, indyl, 1H-indazolyl, purine radicals, 4H-quinolizine base, isoquinolyl; Quinolyl, phthalazinyl, 1,5-phthalazinyl, quinoxalinyl, quinazolyl, cinnolines base, pteridyl, 4aH-carbazyl; Carbazyl, B-carboline base, phenanthridinyl, acridinyl, perimidinyl, phenanthroline base, phenazinyl, phenarsazine base, isothiazolyl; Phenothiazinyl ， isoxazolyl, furazan base ， phenoxazine group, isochroman base, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl; Imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, iso-dihydro-indole-group, quininuclidinyl, morpholinyl and thioxanthene ketone group.

Halogen group can be a fluorine atom, chlorine atom, bromine atoms, iodine atom etc.

Optional substituted alkyl, optional substituted aryl, optional substituted thiazolinyl, optional substituted alkynyl; Optional substituted alkoxy, optional substituted aryloxy group, optional substituted alkylthio group oxygen base, optional substituted arylthio oxygen base; Optional substituted acyloxy, optional substituted alkylthio group, optional substituted arylthio; Optional substituted alkyl sulphinyl, optional substituted aryl sulfonyl kia, optional substituted alkyl sulphonyl; Optional substituted aryl sulfonyl, optional substituted acyl group, optional substituted alkoxy carbonyl group; Optional substituted carbamyl, optional substituted sulfamoyl, they itself can further be replaced optional substituted amino or optional substituted heterocyclic radical by arbitrary other substituting group.

This other substituent instance comprises halogen group such as fluorine, chlorine, bromine or iodine atom; Alkoxy such as methoxyl, ethoxy or tert-butoxy; Aryloxy group such as phenoxy group or right-toloxyl; Alkoxy carbonyl group such as methoxycarbonyl group, butoxy carbonyl or carbobenzoxy; Acyloxy such as acetoxyl group, propionyloxy or benzoyloxy; Acyl group such as acetyl group, benzoyl, isobutyryl, acryloyl group, methacryl or methoxalyl base; Alkylthio group such as methyl mercapto or uncle's butylthio; Arylthio such as thiophenyl or right-toluene sulfenyl; Alkyl amino such as methylamino or cyclohexyl are amino; Dialkyl amido such as dimethylamino, diethylamino, morpholino or piperidino; Arylamino such as phenyl amino or right-tolyl are amino; Alkyl such as methyl, ethyl, the tert-butyl group or dodecyl; Aryl such as phenyl, right-tolyl, xylyl, cumenyl, naphthyl, anthryl or phenanthryl; Hydroxyl, carboxyl, formoxyl, sulfydryl, sulfo group, mesyl, ptoluene-sulfonyl, amino, nitro, cyanic acid, trifluoromethyl, trichloromethyl, trimethyl silyl, phosphinico, phosphono, trimethyl ammonium, dimethyl sulfonium base or triphenyl phenacyl Phosphonium base.

Wherein, consider improvement in solvent solubleness and in the absorption efficiency of long wavelength region, X is preferably optional substituted alkyl; Optional substituted aryl, optional substituted thiazolinyl, optional substituted alkynyl; Optional substituted alkoxy; Optional substituted aryloxy group, optional substituted alkylthio group oxygen base, optional substituted arylthio oxygen base or optional substituted amino.In formula (2), n representes 0 to 5, preferred 0 to 2 integer.

Structure shown in below the instance of the divalent organic group of being represented by Y comprises.In the structure below, symbol * is illustrated in the position that is attached to the key of the carbon atom adjacent with Y in the formula (2).

Consider raising sensitivity, preferred especially below shown in structure.

Novel oxime compound of the present invention is preferably the compound by following formula (3) expression.

In formula (3), R and X represent the monovalence substituting group independently of one another, and A representes divalent organic group, and Ar representes aryl, and n representes 0 to 5 integer.

R in formula (3), X, A, Ar and n have and the R in formula (2) separately, X, and A, the definition that Ar is identical with n, and preferred embodiment is also identical.

Novel oxime examples for compounds of the present invention includes but not limited to, below shown in compound.

Novel oxime compound of the present invention has maximum absorption wavelength in 350nm to 500nm wavelength coverage, more preferably in 360nm to 480nm wavelength coverage, have maximum absorption wavelength.Particularly, the novel oxime compound preferably has high absorbance at 365nm and 455nm.Therefore, compare with conventional oxime compound, the novel oxime compound has absorption at longer wavelength zone, thereby can show high sensitivity when its light time that is exposed to from 365nm or 405nm light source.

Consider sensitivity, novel oxime compound of the present invention is preferably 10,000 to 300,000 at the molar absorptivity of 365nm or 405nm, and more preferably 15,000 to 300,000, be preferably 20,000 to 200,000 especially.The molar absorptivity of novel oxime compound is to use ultraviolet-visible spectrophotometer (trade name: CARRY-5 Spectrophotometer, made by Varian Inc.), in ethyl acetate solvent, under the concentration of 0.01g/L, measures.

For example, novel oxime compound of the present invention can be synthetic through for example method described below, but synthetic method is not limited thereto.

Synthetic

by the compound of formula (2) expression

Based on the quality of the total solid of photopolymerisable compositions of the present invention, the content of novel oxime compound in photopolymerisable compositions of the present invention is preferably 0.1 to 30 quality %, more preferably 1 to 25 quality %, preferred especially 2 to 20 quality %.Can use single new compound of planting, maybe can make up and use two or more novel oxime compounds.

Novel oxime compound of the present invention is by photolysis and play the Photoepolymerizationinitiater initiater effect that causes and promote the polymerizable compound polymerization.Particularly, the novel oxime compound has high sensitivity to 365nm or 405nm light source, therefore when photopolymerisable compositions is used as Photoepolymerizationinitiater initiater, can produce good effect.Novel oxime compound of the present invention can also be used for following application.Application example comprises printing-ink such as screen printing ink, offset printing or flexographic ink and UV-curable ink; The white of timber or metal or colored paint cover; Powdery paints is especially for the coating material of paper, timber, metal or plastics; Building or pavement marker; The graph copying technology; Hologram recording material; The image recording technology; The manufacturing of the printing plate precursor that develops with organic solvent or alkaline aqueous solution; Be used to make the daylight-hardenable coatings of serigraphy mask; Dentistry is filled up composition; Tackifier; Pressure-sensitive adhesive; Laminated resin; The etching resist that is used for wet method and dry film; Solder resist; Electroplate or permanent resist; Light-the forming electrolyte that is used for printed circuit board (PCB) and electronic circuit; Various displays; Optical switch; Grating (interference grating); The manufacturing of optical circuit; The manufacturing of the three-dimensional objects that carries out through extensive curing (in transparent mould UV solidify) or stereolithography technology (for example, like United States Patent(USP) No. 4,575,330 is said); The manufacturing of compound substance (like the optional styrene-Ji polyester that contains spun glass and/or other fiber and other auxiliary agent) or other thick-layer composition; The resist of electronic unit and integrated circuit coating or sealing usefulness; Optical fiber or optical lens are as being used to make the coating of contact lens or Fresnel lens; The manufacturing of Medical Devices, instrument (aids) or implant; And make like Deutsche Bundespatent No.19,700,064 and European patent No.678, the thermic property gel described in 534.

Novel oxime compound of the present invention can also particularly produce acid during photoirradiation with energy-ray at it.Therefore, it can be used for using the acid of generation other application as catalyzer.For example, it can be used for being utilized in the definition technique of the color reaction of pigment precursors under the existence of the acid that plays catalyst action of generation, anti-counterfeiting technology; The material that is used for the detected energy roentgen dose X; With the existence decomposition reaction down of the acid that plays catalyst action that is utilized in generation, at manufacturing semiconductor, TFT; The positive corrosion-resisting agent that uses in the color filter, micro-mechanical piece etc.

As stated, novel oxime compound of the present invention can be used as Photoepolymerizationinitiater initiater.Therefore, it can be preferably and the polymerizable compound combination to form photopolymerisable compositions (photopolymerisable compositions of the present invention) through polymerization and curing with photoirradiation.

Photopolymerisable compositions photopolymerisable compositions of the present invention comprises (A) novel oxime compound and (B) polymerizable compound.Photopolymerisable compositions of the present invention has high sensitivity and has high stability in time the light of 365nm or 405nm wavelength.In addition, it can form and wherein can suppress the painted cured film in time that caused by heating.Although do not know its detailed mechanism, the novel oxime compound has the structure that by photolysis the time, can suppress the free radical reorganization, so it can produce more a large amount of free radicals to obtain high sensitivity.Because free radical reorganization is suppressed, in the long-time heating process, can suppress the reaction between the novel oxime compound decomposition product molecule according to thinking, thereby suppress by this reaction cause painted.

In the present invention, can use aberration Δ Eab ^*Estimate in time painted of the cured film that causes by heating.Can use the Co. by Otsuka Electronics, the MCPD-3000 that Ltd makes measures aberration Δ Eab ^*The condition that is used to estimate can be following.At first; Form cured film through following steps: in ultrahigh pressure mercury lamp proximity printing system (by Hitachi High-Tech Electronics Engineering Co.; Ltd. make) or i-line stepping exposure system (trade name: FPA-3000i5; Make by Canon Inc.) (365nm) in, with 10mJ/cm ²To 2500mJ/cm ²Different exposures in the scope are made public photopolymerisable compositions of the present invention.Cured film is developed as required, then 200 ℃ of heating 1 hour.Measure the aberration Δ Eab of cured film before and after heating ^*Thereby, heat aging that can the evaluate cure film-induce painted.When using photopolymerisable compositions of the present invention, the aberration Δ Eab before and after the heating ^*Can be below 5.

Photopolymerizable composition of the present invention can be used for various application, like moulding resin, and curtain coating resin, light-moulding resin, encapsulant; The dentistry polymeric material, printing-ink, paint, galley is used photoresist, and color proof is used in printing; Color filter is used photopolymerisable compositions, and black matrix is used resist, the use in printed circuit board resist, and semiconductor production is used resist, and microelectronics is used resist; Be used to make the resist of micro-mechanical piece, insulating material, holographic material, waveguide material; Be coated with material outward, tackifier, tackifier, contact adhesive and release coat agent.

The photopolymerisable compositions (2) that adopt to be fit to forms the photopolymerisable compositions (1) of color filter etc. and the photographic layer that is fit to the formation original edition of lithographic printing plate is below described photopolymerisable compositions of the present invention as an example.

The novel oxime compound (A) of photopolymerisable compositions (1) (1)-(A) novel oxime compound photopolymerisable compositions (1) can play the polymerization initiator effect.Based on the quality of the total solid of composition, the novel oxime compounds content in the photopolymerisable compositions (1) is preferably 0.5 to 40 quality %, 1 to 35 quality % more preferably, also 1.5 to 30 quality % more preferably.

In photopolymerisable compositions (1), can also use any known Photoepolymerizationinitiater initiater that is different from the novel oxime compound, only otherwise reducing effect of the present invention gets final product.The Photoepolymerizationinitiater initiater that can use with novel oxime compound combination by photolysis to cause and to promote above-mentioned polymerizable compound polymeric compounds.Preferred its has absorption in 300 to 500nm wavelength coverages.The instance of Photoepolymerizationinitiater initiater comprises organohalogen compounds, oxadiazole compound, carbonyls, ketal compound; The benzoin compound, acridine compound, organic peroxide compounds, azo-compound; Coumarin compound, triazo-compound, Metallocenic compound, united imidazole; The organic boronic ester compounds, disulfonic acid compound, oxime ester compound, salt compound and acylphosphanes (oxide) compound.

(1)-(B) to can be used for those of instance, preferred embodiment and scope and foregoing curable composition of polymerizable compound of photopolymerisable compositions (1) identical for polymerizable compound.

(1)-(C) colorant photopolymerisable compositions (1) can contain (C) colorant.When adding colorant, can obtain the painted photopolymerisable compositions of required color.Photopolymerisable compositions (1) contains (A) has excellent sensitivity to short wavelength light source such as 365nm or 406nm light source novel oxime compound.Therefore, even when it contains the colorant of high concentration, also can solidify with high sensitivity.

To the not special restriction of the colorant that is used for photopolymerisable compositions (1).Can use a kind of in various known conventional dyestuffs and the pigment, or two or more potpourris, it can suitably be selected according to the purposes of photopolymerisable compositions.When the photopolymerisable compositions that the present invention is painted is used to prepare color filter, can adopt the colour such as the R of the colour element that is used to form color filter, the colorant of G or B, or be generally used for forming the black colorant of black matrix.。

Being described in of colorant that is used for the foregoing curable composition is applicable to the colorant that is used for photopolymerisable compositions (1) on the whole.

When using photopolymerisable compositions (1) to form black film such as black matrix, employed colorant can be black (black colorant).In the present invention, can use various known black colorants such as black pigment and black dyes.For with the high optical density of a small amount of acquisition, preferred especially carbon black, black oxidation titanium, titanium dioxide, iron oxide, manganese oxide, graphite etc.Wherein, preferably contain in carbon black and the black oxidation titanium at least one.Can only use single black colorant of planting, maybe can use the potpourri of two or more black colorants.

In order to reduce the residue in the developing process, the particle mean size of black colorant (average primary particle size) is preferably less, and particularly, it is preferably below the 30nm.In order to reduce the residue in the developing process in the technology that needs high-resolution color filter in manufacturing, average primary particle size is preferably 5 to 25nm, and more preferably 5 to 20nm, is preferably 5 especially to 15nm.

Although to the not special restriction of the content of black colorant in photopolymerisable compositions (1) total solid, preferred its high as far as possible film that has high light intensity with formation.Particularly, it is preferably 25 to 80 quality %, and more preferably 30 to 75 quality % are preferably 35 to 70 quality % especially.If the black colorant agent content is too low, must increase film thickness to obtain high optical density.If the black colorant agent content is too high, then photocuring possibly fully not carry out, film strength possibly reduce or in the alkali developing process development latitude possibly narrow down.

For photopolymerisable compositions (1), can make up and use multiple black colorant.In the time will comprising carbon black and use as the multiple black colorant combination of key component; The quality ratio of carbon black and other black colorant (carbon black: other black colorant) be preferably 95: 5 to 60: 40; More preferably 95: 5 to 70: 30, also more preferably 90: 10 to 80: 20.The quality of other black colorant refers to the gross mass of other black colorant.When the quality ratio of carbon black and other black colorant is 95: 5 to 60: 40, can prevents the gathering in the photopolymerisable compositions (1), thereby can promote uniform and stable preparation of filming.

The instance that is applicable to carbon black of the present invention comprises the carbon black #2400 that is made by Mitsubishi Chemical Corporation, #2350, #2300, #2200, #1000, #980, #970, #960, #950; #900, #850, MCF88, #650, MA600, MA7, MA8, MA11, MA100; MA220, IL30B, IL31B, IL7B, IL11B, IL52B, #4000, #4010, #55; #52, #50, #47, #45, #44, #40, #33, #32, #30; #20, #10, #5, CF9, #3050, #3150, #3250, #3750, #3950; Diablack A, Diablack N220M, Diablack N234, Diablack I, Diablack LI, DiablackII, Diablack N339, Diablack SH, Diablack SHA; Diablack LH, Diablack H, DiablackHA, Diablack SF, Diablack N550M, Diablack E, Diablack G, Diablack R, DiablackN760M and Diablack LP (trade name); By the carbon black Thermax N990 that Cancarb makes, N991, N907, N908, N990, N991 and N908 (trade name); By Asahi Carbon Co., the carbon black Asahi#80 that Ltd. makes, Asahi#70, Asahi#70L, Asahi F-200; Asahi#66, Asahi#66HN, Asahi#60H, Asahi#60U; Asahi#60, Asahi#55, Asahi#50H, Asahi#51; Asahi#50U, Asahi#50, Asahi#35, Asahi#15 and Asahi Thermal (trade name); By the carbon black Color Black Fw 200 that Degussa makes, Color Black Fw2, Color Black Fw2V, Color BlackFw1; Color Black Fw18, Color Black S170, Color Black S160, Special Black 6; Special Black 5, Special Black 4, Special Black 4A; Printex U, Printex V, Printex140U and Printex 140V (trade name).

In the present invention, preferred carbon black has insulativity.Carbon black with insulativity is meant the carbon black that when measuring the specific insulation of its powder with following method, shows insulativity.For example, this carbon black contains through absorption, coating or chemical bond (grafting) and is deposited on the lip-deep organic compound of carbon black particle.

The multipolymer (the quality mean molecular weight is 30,000) of carbon black and benzyl methacrylate and methacrylic acid (mol ratio is 70: 30) is distributed to 20: 80 mass ratioes forms coating fluid in the propylene glycol monomethyl ether.The thickness of coating fluid with 1.1mm is coated on the chrome substrate of 10cm * 10cm, is filming of 3 μ m to form build.To film and on electric hot plate, further heat about 5 minutes in 220 ℃.Afterwards; According to JIS K 6911, use high resistivity meter (trade name: HIRESTER UP (MCP-HT450) is made by MitsubishiChemical Corporation); Under the environment of 23 ℃ and 65% relative humidity, through applying the specific insulation that voltage measurement is filmed.The specific insulation of carbon black is preferably 10 ⁵More than the Ω cm, more preferably 10 ⁶More than the Ω cm, also more preferably 10 ⁷More than the Ω cm.

The instance of operable carbon black also comprises JP-A Nos.11-60988,11-60989,10-330643,11-80583,11-80584, the carbon black of the resin-coating described in 09-124969 and the 09-95625.

The instance that is applicable to black oxidation titanium of the present invention comprises the 12S that is made by Mitsubishi ChemicalCorporation, 13M, 13M-C and 13R-N (trade name) and by Ako Kasei Co., the TILACK D (trade name) of Ltd manufacturing.

Contain the photopolymerisable compositions of the present invention that can be selected from above-mentioned black colorant and be preferred for forming black film such as black matrix.Black film has light-proofness or anti-reflective, therefore can be used for preparing antireflection or photomask and black matrix.

Based on the total solid quality of photopolymerisable compositions, the content of colorant is preferably 30 to 95 quality % in the photopolymerisable compositions (1), 40 to 90 quality % more preferably, also 50 to 80 quality % more preferably.If colorant content is too low, then when using photopolymerisable compositions (1) preparation color filter, possibly be difficult to obtain suitable colourity.If colorant content is too high, then photocuring possibly fully not carry out, and film strength possibly reduce or in the alkali developing process development latitude possibly narrow down.But, have high efficiency of light absorption owing to be used for (A) of the present invention novel oxime compound, even when photopolymerisable compositions contains the colorant of high concentration, also can produce sensitivity significantly and improve effect.

(1)-(D) pigment dispersing agent preferably adds in the composition (D) pigment dispersing agent to improve dispersing of pigments property when photopolymerisable compositions (1) contains pigment as (C) colorant.

Being described in of spreading agent that is used for curable compositions is applicable to fully on the whole and can be used for the present invention's pigment dispersing agent of (comprising photopolymerizable composition (1)).

In photopolymerisable compositions (1), based on the quality of pigment, the content of spreading agent is preferably 1 to 80 quality %, 5 to 70 quality % more preferably, also 10 to 60 quality % more preferably.For example, when using polymeric dispersant, its content is preferably 5 to 100 quality % of pigment, more preferably 10 to 80 quality %.When using pigment derivative, its content is preferably 1 to 30 quality % of pigment, and more preferably 3 to 20 quality % are preferably 5 to 15 quality % especially.

When in photopolymerisable compositions (1), using as the pigment of colorant and spreading agent; Consider and solidify sensitivity and color density; Total solid quality based on photopolymerisable compositions; The total content of colorant and spreading agent is preferably 30 to 90 quality %, 40 to 85 quality % more preferably, also 50 to 80 quality % more preferably.

If necessary, any in the optional components that details below photopolymerisable compositions (1) can also contain.The optional components that can add in the photopolymerisable compositions (1) is described below.

(1)-(E) sensitizer photopolymerisable compositions (1) can contain sensitizer, is used to improve the free-radical generating efficient of radical initiator or make wavelength photoreceptor longer.Can be used for sensitizer of the present invention preferably improves (A) novel oxime compound based on electronics-transfer mechanism or energy-transfer mechanism sensitivity.

Being described in of (c) sensitizer in the curable compositions is applicable to the sensitizer that in photopolymerisable compositions (1), uses on the whole.

(1)-(F) auxiliary sensitizer photopolymerisable compositions (1) preferably also contains (F) auxiliary sensitizer.In the present invention, auxiliary sensitizer have further raising (A) novel oxime compound or (E) sensitizer to the effect of the sensitivity of active irradiation, or the effect that suppresses of (B) polymerizable compound polymerization that suppresses to cause by oxygen.

(d) auxiliary being described in of sensitizer is applicable to this auxiliary sensitizer that can be used for photopolymerisable compositions (1) on the whole in the curable compositions.

(1)-(G) binder polymer if necessary can also use binder polymer to improve membrane property etc. in photopolymerisable compositions (1).Be used for the description of the binder polymer of curable compositions, comprise the description that is used for its synthetic radical polymerization initiator, be applicable to the bonding agent that in photopolymerisable compositions (1), uses on the whole.

(1)-(H) polymerization inhibitor preferably adds photopolymerisable compositions (1) to be suppressed at the unnecessary thermal polymerization of (B) polymerizable compound in preparation or the photopolymerisable compositions storage process with the small amount of thermal polymerization inhibitor.The instance that can be used for thermal polymerization inhibitor of the present invention comprises those that describe for curable compositions.

Based on the total solid quality of photopolymerisable compositions (1), the content of thermal polymerization inhibitor is preferably about 0.01 to about 5 quality %.If necessary, can add behenic acid or advanced higher fatty acid derivative such as behenamide, suppress with the polymerization that prevents to cause, and can localize to the surface of filming in the dry run after coating by oxygen.Based on the quality of whole composition, the content of advanced higher fatty acid derivative is preferably about 0.5 to about 10 quality %.

(1)-(I) adhesion improver photopolymerisable compositions (1) can contain the adhesion improver to improve the adhesion to the surface of hard surface such as carrier etc.The instance of adhesion improver comprise for curable compositions described those.Particularly; Preferred embodiment comprises γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, γ-acryloxy propyl trimethoxy silicane; γ-acryloxy propyl-triethoxysilicane; γ-Qiu Jibingjisanjiayangjiguiwan, γ-An Jibingjisanyiyangjiguiwan and phenyltrimethoxysila,e, and γ-methacryloxypropyl trimethoxy silane most preferably.

Based on the quality of photopolymerisable compositions (1) total solid, the content of adhesion improver is preferably 0.5 to 30 quality %, more preferably 0.7 to 20 quality %.

(1)-(J) thinning agent can use in the various organic solvents any as being used for the thinning agent of photopolymerisable compositions (1).The instance of operable organic solvent comprises: acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylidene bichloride, tetrahydrofuran; Toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether; Diacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, glycol monomethyl isopropyl ether; Ethylene glycol monomethyl ether acetate, 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Diethylene glycol dimethyl ether, diethyl carbitol, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate 3-methoxyl propyl ester; N, dinethylformamide, dimethyl sulfoxide, gamma-butyrolacton, methyl lactate and ethyl lactate.Can only use single solvent of planting, perhaps can use the potpourri of two or more solvents.Solid content with respect to organic solvent is preferably 2 to 60 quality %.

(1)-(K) other adjuvant in addition can also be with the additives known of the physical property that is used to improve cured film, and like inorganic filler, plastifier and lipophilization agent add in the photopolymerisable compositions (1).The instance of plastifier comprises dioctyl phthalate, phthalic acid two (dodecyl) ester, triethylene glycol dieaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate and triacetyl glycerine.When using bonding agent,, can add plastifier with the amount below the 10 quality % based on the gross mass of polymerizable compound and binder polymer.

Photopolymerisable compositions (1) contains (A) novel oxime compound, therefore can and have high storage stability with high sensitivity curing.Can also be suppressed at painted in time in the heating process.When photopolymerisable compositions (1) being coated to hard material surface and solidifying, cured film can show the outstanding adhesion with the surface.Therefore, preferably will comprise (A) novel oxime compound, (B) polymerizable compound and (C) photopolymerisable compositions of colorant (1) with the photopolymerisable compositions (photopolymerisable compositions that is used for color filter of the present invention) that acts on color filter.

Novel oxime compound in photopolymerisable compositions (2) (2)-(A) the novel oxime compound photopolymerisable compositions (2) can play the polymerization initiator effect.Based on the total solid quality of composition, the content of novel oxime compound in photopolymerisable compositions (2) is preferably 0.5 to 40 quality %, 1 to 35 quality % more preferably, also 1.5 to 30 quality % more preferably.

Can also in photopolymerisable compositions (2), use any known polymerization initiator different, only otherwise weakening effect of the present invention gets final product with the novel oxime compound.The instance of other polymerization initiator comprises (a) aromatic ketone, (b) aromatics salt compound, (c) organic peroxide; (d) thio-compounds, (e) six aryl united imidazoles, (f) ketoxime ester compounds; (g) boric acid ester compound, (h) azine (azinium) compound, (i) Metallocenic compound; (j) active ester compound and (k) compound of carbon containing-halogen bond.More specifically, can use the polymerization initiator of describing in [0081] to [0139] section of JP-A No.2006-78749.

(2)-(B) the polymerizable compound instance that can be included in (B) polymerizable compound in the photopolymerisable compositions (2) comprise above-mentioned for curable compositions or photopolymerisable compositions (1) but the compound of described addition polymerization.

But how to use the details of the compound of addition polymerization, as should using which kind of structure, whether should their be used separately or combination is used or should be added how many amounts, can freely confirm according to the final performance design of photosensitive material.For example, can select them from following viewpoint.Consider film speed, preferably each molecule has the structure of higher unsaturated group mass contg, and the structure of preferred in many cases difunctionality or higher official ability.Promptly solidify film strength in order to increase image section, preferred three-or higher official can structure.Use have varying number functional group and/or dissimilar polymerizable groups compound (for example; Be selected from acrylic ester; Methacrylate, distyryl compound, the compound of vinyl ether compound) the method for combination also all be effective for control photosensitivity and intensity.High-molecular weight compounds or highly hydrophobic compound can have high film speed or form high-strength membrane, but consider developing powder or the deposition in liquid developer, are not preferred in some cases.

But the compound of how selecting and using addition polymerization is for also being important factor with the compatibility of other component (like binder polymer, initiating agent and colorant) of photographic layer or to the dispersiveness of other component.For example, in some cases, through use low-purity compound or through using two or more combination of compounds can improve compatibility.Also can select particular structural to improve to carrier the adhesion of external coating etc.Consider sensitivity, but the content of the compound of addition polymerization in photographic layer is high more favourable approximately.But if undesirable being separated can appear in too high levels, the production technology problem that is caused by the viscosity of photographic layer (the production fault that causes like transfer or adhesion by the photosensitive material component) precipitates from liquid developer etc.

From these viewpoints, based on the total solid quality of photopolymerisable compositions (2), but the content of the compound of addition polymerization is preferably 5 to 80 quality %, more preferably 25 to 75 quality %.But but can only use the compound of single kind addition polymerization or the compound of two or more addition polymerizations can make up use.But as for the compound that how to use addition polymerization, can consider the polymerization inhibition degree, resolution, mist formation performance, change of refractive, surface viscosity or other viewpoint that cause by oxygen, can freely select suitable structure, composition or content.In some cases, can also use the layer structure or the coating process of undercoat or external coating.

(2)-(C) binder polymer photopolymerisable compositions (2) preferably contains binder polymer.In view of improving membrane property, can contain binder polymer.Can use and have any binder polymer that improves the membrane property function.

Preferably contain line style organic polymer weight polymers as binder polymer.This line style organic polymer weight polymers that will use can limit not especially, and can be any line style organic polymer.For can water or weak alkaline aqueous solution develop, the preferred selection dissolves in or the line style organic polymer weight polymers of swellable in water or weak alkaline aqueous solution.Not only be used as film forming agent but also consider developer such as water, line style organic polymer weight polymers is selected and used to the regulation of weak alkaline aqueous solution or organic solvent.For example, when using the water soluble organic polymer weight polymers, can carry out water development.The instance of this line style organic polymer weight polymers is included in the polyaddition products that has the carboxylic acid group in the side chain, like JP-A No.59-44615, and JP-B Nos.54-34327; 58-12577 and 54-25957, and JP-A Nos.54-92723, those described in 59-53836 and the 59-71048; Methacrylic acid copolymer particularly, acrylic copolymer, itaconic acid copolymer; The crotonic acid multipolymer, the maleic acid of maleic acid and partial esterification.Instance also is included in the acid cellulose derivant that has hydroxy-acid group in the side chain.In addition, also can use cyclic acid anhydride to add to the product on the addition polymer of hydroxyl.

Particularly; Preferably (methyl) benzyl acrylate and (methyl) but the multipolymer of the vinyl monomer of acrylic acid and optional any other addition polymerization; (methyl) allyl acrylate and (methyl) but the multipolymer of the vinyl monomer of acrylic acid and optional any other addition polymerization because they have excellent balance between film strength, sensitivity and development property.

Can also contain the binder polymer of amide containing key or the binder polymer of amido-containing acid ester key.The binder polymer of amide containing key or amino-formate bond is preferably the line style organic polymer weight polymers of amide containing key or amino-formate bond.The line style organic polymer weight polymers of this amide containing key or amino-formate bond can be an any kind.For can water or weak alkaline aqueous solution develop, preferably select to dissolve in or swellable high-molecular linear organic polymer in water or weak alkaline aqueous solution, amide containing key or amino-formate bond.Can not only be used as film forming agent but also consider developer such as water weak alkaline aqueous solution or organic solvent, the line style organic polymer weight polymers of selection and use amide containing key or amino-formate bond according to application.For example, when using water soluble polymer amount organic polymer, can carry out water development.The preferred line style organic polymer weight polymers that uses the bonding agent of the amide-containing of in JP-A No.11-171907, describing as amide containing key or amino-formate bond is because it not only has excellent development property but also has high film strength.

JP-B Nos.07-120040; 07-120041; 07-120042 and 08-12424, JP-A Nos.63-287944,63-287947 and 01-271741; And the urethane adhesive polymkeric substance of describing among the Japanese patent application No.10-116232 that contains acidic-group is being favourable aspect printability resistance or the low exposure property, because they have very high intensity.The bonding agent of the amide containing key described in the also preferred JP-A No.11-171907 is because it not only has excellent development property but also has high film strength.

Operable water-soluble line style organic polymer weight polymers also comprises polyvinylpyrrolidone and polyethylene oxide.Alcohol soluble nylon or 2, the polyethers of 2-pair-(4-hydroxy phenyl)-propane and chloropropylene oxide also is useful for improving the curing film strength.

Can the binder polymer of any amount be mixed in the photopolymerisable compositions (2).Consider image intensity etc., based on the quality of photographic layer total solid, the content of binder polymer is preferably 30 to 85 quality %.But the compound of addition polymerization and the quality ratio of binder polymer are preferably in 1/9 to 7/3 scope.

In a preferred exemplary, but employed binder polymer is water insoluble basically alkaline bleach liquor soluble.This can eliminate for the disagreeableness organic solvent of developer environment for use or with its consumption and be restricted to low-down level.In this method of application, can consider image intensity and development property, suitably select the acid number (acid content of the every gram polymkeric substance that shows with the chemical equivalent numerical table) and the molecular weight of binder polymer.Acid number is preferably 0.4 to 3.0meq/g, and more preferably 0.6 to 2.0meq/g, and molecular weight is preferably 3,000 to 500,000, and more preferably 10,000 to 300,000.

(2)-(D) sensitizer photopolymerisable compositions (2) preferably contains sensitizer and as novel oxime compound of polymerization initiator etc.The instance that can be used for sensitizer of the present invention comprise spectral sensitization dyestuff and pigment maybe can be through absorbing from the light of light source and with the interactional dyestuff of polymerization initiator.

The instance of preferred spectral sensitization dyestuff or pigment comprises polynuclear aromatic compound (like Bi ， perylene and benzophenanthrene), and the xanthene class (like luciferin, eosin; Erythrosine, rhodamine B and rose-red), cyanine class (like thia-carbonyl cyanine and oxa-carbocyanine); Merocyanine class (like merocyanine and first merocyanine), thiazide (like thionine, methylene blue and toluidine blue); Acridine (like acridine orange, chloroflavin and acridine yellow), phthalocyanines (like phthalocyanine and metal phthalocyanine); Porphyrin class (like tetraphenylporphyrin and central metal-substituted porphyrin), chlorophyll class (like chlorophyll, chlorophyllin and central metal-substituted chlorophyll); Metal complex (compound as shown below), anthraquinone class (like anthraquinone), and square acids (like square acid).

The instance of preferred spectral sensitization dyestuff or pigment is included in the compound of describing in [0144] to [0202] section of JP-A No.2006-78749.

The instance that can be used for the sensitizer of photopolymerisable compositions (2) also comprises above-mentioned those that describe for curable compositions or photopolymerisable compositions (1).

Can only use single sensitizer of planting, maybe can make up and use two or more sensitizers.In photopolymerisable compositions (2), and the mol ratio of all polymerization initiators and sensitizing dyestuff (all polymerization initiators: sensitizing dyestuff) can be 100: 0 to 1: 99, more preferably 90: 10 to 10: 90, most preferably 80: 20 to 20: 80.

(2)-(E) auxiliary sensitizer can be with having the further known compound that improves the sensitivity effect or have an effect that polymerization that inhibition causes by oxygen suppresses as in the auxiliary sensitizer adding photopolymerisable compositions (2).

The instance of auxiliary sensitizer also comprise above-mentioned be used for curable compositions or photopolymerisable compositions (1) described those.Other instance comprises the phosphorus compound described in the JP-A No.06-250387 (diethyl phosphite etc.) and described Si-H of Japanese patent application No.06-191605 and Ge-H compound.

When sensitizer was assisted in use, in photopolymerisable compositions (2), based on the polymerization initiator of 1 mass parts, the amount of auxiliary sensitizer was suitably 0.01 to 50 mass parts.

(2)-(F) polymerization inhibitor preferably adds in the photopolymerisable compositions (2) a spot of thermal polymerization inhibitor to be suppressed at the unnecessary thermal polymerization of the compound that contains polymerisable alkene formula unsaturated double-bond in preparation of compositions or the storage process.The instance of thermal polymerization inhibitor comprises quinhydrones, and is right-metoxyphenol, di-t-butyl-p-Cresol, 1,2,3,-thrihydroxy-benzene; Tert-butyl catechol, benzoquinones, 4; 4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol) and N-nitroso-phenyl-azanol cerium.

Based on the quality of composition, the content of polymerization inhibitor is preferably about 0.01 to about 5 quality %.If necessary, can add behenic acid or advanced higher fatty acid derivative such as behenamide in case block-polymerization of inducing suppresses, and can localize to the surface of photographic layer in the dry run after coating.Based on whole composition, the content of advanced higher fatty acid derivative is preferably about 0.5 to about 10 quality %.

(2)-(G) colorant etc. can add dyestuff or pigment in the composition in order to form painted photographic layer.This can improve the version checking ability of so-called galley, as the adaptability of making a plate the visual of back photographic layer and the image density measuring machine being measured.Many dyestuffs as colorant can reduce the sensitivity of the photographic layer of photopolymerization.Therefore, particularly, preferably use pigment as colorant.The instance of colorant comprises pigment such as phthalocyanine color, AZOpigments, carbon black and titanium dioxide; With dyestuff such as ethyl violet, crystal violet, azo dyes, anthraquinone dye and cyanine dye.The content of dyestuff or pigment be preferably composition about 0.5 to about 5 quality %.

(2)-(H) other adjuvant in addition, can also with the additives known of the physical property that is used for changing cured film such as inorganic filler or plastifier with can improve printing ink and join composition in the lip-deep fixed lipophilization agent of photographic layer.

The instance of plastifier comprises dioctyl phthalate, phthalic acid two (dodecyl) ester, triethylene glycol dieaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate and triacetyl glycerine.When using bonding agent,, can add plastifier with the amount below the 10 quality % based on the compound that contains alkene formula unsaturated double-bond and the gross mass of bonding agent.

In order to improve film strength (printability resistance), can also be with the UV initiating agent or the thermal cross-linking agent adding composition that are used for improving heating of development back and/or exposure effect.

< color filter and preparation method thereof>describes below the preparation method according to color filter of the present invention and color filter.Color filter of the present invention comprises the colored pattern that is arranged on the carrier, and said colored pattern is to use the photopolymerisable compositions that is used for color filter of the present invention to prepare.Describe in detail below color filter of the present invention and preparation method thereof (the present invention is used to prepare the method for color filter).

The method that the present invention is used to prepare color filter may further comprise the steps: the photopolymerisable compositions that is used for color filter of the present invention is coated on the carrier to form painted photopolymerisable compositions layer (following also abbreviate as " painted photopolymerisable compositions layer forms step "); With painted photopolymerisable compositions layer through mask exposure (following also abbreviate as " step of exposure "); Develop to form colored pattern (following also abbreviate as " development step ") with composition layer exposure.

Particularly, the present invention be used for color filter photopolymerisable compositions directly or under the intercalary situation of another layer, be coated to carrier (substrate) and go up to form photopolymerisable compositions layer (painted photopolymerisable compositions layer forms step); With film through the exposure of special pattern mask with cured coating film by irradiation part (step of exposure); And will be coated with film development with liquid developer and comprise the patterned film of the pixel of respective color (three kinds or four kinds of colors), thereby prepare color filter of the present invention with formation.Each step that is used to prepare the method for color filter of the present invention is described below.

Painted photopolymerisable compositions layer forms step and forms in the step at painted photopolymerisable compositions layer, and the photopolymerisable compositions that the present invention is used for color filter is coated on the carrier to form painted photopolymerisable compositions layer.

The photopolymerisable compositions that the present invention is used for color filter can be coated to carrier through various coating processes, described coating process such as slot coated, ink ejecting method, rotary coating, curtain coating coating, roller coat and serigraphy.

The thickness of filming that is used for the photopolymerisable compositions of color filter is preferably 0.1 μ m to 10 μ m, 0.2 μ m to 5 μ m more preferably, also 0.2 μ m to 3 μ m more preferably.When preparation is used for the color filter of solid imaging element, consider resolution and development property, the thickness of filming that is used for the photopolymerisable compositions of color filter is preferably 0.35 μ m to 1.5 μ m, more preferably 0.40 μ m to 1.0 μ m.

The photopolymerisable compositions that will be used for color filter the coating on the carrier usually under 70 to 110 ℃ condition dry 2 to 4 minutes to form painted photopolymerisable compositions layer.

Step of exposure forms painted photopolymerisable compositions layer on the painted photopolymerisable compositions layer that forms in the step through mask exposure in step of exposure, make a cured coating film by the irradiation part.Exposure is preferably through carrying out with radiant rays irradiation.Particularly, the preferred radiant rays that uses ultraviolet ray as g-line or i-line as the usefulness of making public, and more preferably high-pressure sodium lamp.Irradiation intensity is preferably 5mJ to 1500mJ, and more preferably 10mJ to 1000mJ most preferably is 10mJ to 800mJ.

Development step can be carried out alkali and develop (development step) after step of exposure, makes and can be dissolved in the alkaline aqueous solution by the unexposed portion that step of exposure produces.In this step, only stay the part of photocuring.Liquid developer is preferably the organic basic developer that does not damage following circuit etc.Develop and carried out 20 to 90 seconds 20 ℃ to 30 ℃ temperature usually.

If necessary, the method for preparing color filter of the present invention can also be included in carries out after the formation of photopolymerisable compositions layer step, step of exposure and the development step, through the step of heating and/or exposure curing colored pattern.

Can painted photopolymerisable compositions layer be formed step, the corresponding required tone of step of exposure and development step (and optional curing schedule) repeats for several times, thereby can prepare the color filter with required tone.

Although described the method that the present invention prepares color filter based on exemplary; In said exemplary; The photopolymerisable compositions that the present invention is used for color filter is used to form the technology of the colored pattern of color filter; But this exemplary is not intended to restriction scope of the present invention.For example, can also the photopolymerisable compositions that the present invention is used for color filter be used to form black matrix, said black matrix is used for colored pattern (pixel) in sunder in color filter.Color filter preparation method's of the present invention painted photopolymerisable compositions layer forms step, and step of exposure and development step (and optional curing schedule) can also be used on substrate, forming the technology of black matrix.Particularly; The present invention that use contains black colorant such as carbon black or black oxidation titanium is used for the photopolymerisable compositions of color filter; Carry out painted photopolymerisable compositions layer as stated and form step; Step of exposure and development step (and optional curing schedule), thus black matrix (black pattern) on substrate, formed.

The photopolymerisable compositions that color filter of the present invention is to use the present invention to be used for color filter prepares.Therefore, in color filter, colored pattern and support substrate have outstanding adhesion, and cured compositions has excellent anti-development property.Therefore, exposure sensitivity is high, and the adhesion of exposed portion and substrate is excellent and can form the high resolution design with required shape of cross section.Therefore, color filter of the present invention is suitable for LCD and solid imaging element such as CCD, is particularly suitable for having high resolution CCD device or the cmos device that surpasses 1 mega pixel.Particularly, color filter of the present invention is preferred for solid imaging element.For example, can with color filter of the present invention be placed on CCD each pixel light receiving part and assemble between the lenticule.

Provide the description of original edition of lithographic printing plate of the present invention below < original edition of lithographic printing plate >.Original edition of lithographic printing plate comprises carrier and photographic layer, and said photographic layer places on the carrier and contains photopolymerisable compositions of the present invention.If necessary, original edition of lithographic printing plate can also comprise that any other layer is like protective seam and middle layer.Because original edition of lithographic printing plate contains photopolymerisable compositions of the present invention in photographic layer, therefore have high sensitivity, stability and printability resistance in time.Each element of original edition of lithographic printing plate of the present invention is described below.

The photographic layer photographic layer is the layer that contains photopolymerisable compositions of the present invention.Particularly; Can form photographic layer through following method; Said method comprises uses photopolymerisable compositions (2) (preferred embodiment of photopolymerisable compositions of the present invention) as the composition that is used to form photographic layer (below be also referred to as " photographic layer-formation composition "); The coating fluid that will contain said composition is coated on the carrier and dry coating, forms photographic layer.

For photographic layer-formation composition is coated on the carrier, each component that can be included in the composition is used with the form in various organic solvents.The instance that can be used for the solvent of this method comprises acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylidene bichloride, tetrahydrofuran; Toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether; Diacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, glycol monomethyl isopropyl ether; Ethylene glycol monomethyl ether acetate, 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Diethylene glycol dimethyl ether, diethyl carbitol, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate 3-methoxyl propyl ester; N, dinethylformamide, dimethyl sulfoxide, gamma-butyrolacton, methyl lactate and ethyl lactate.Can only use single potpourri that solvent maybe can use two or more solvents of planting.Coating solution has the solid content of 2 to 50 quality % aptly.

Preferably according to the coating weight of application choice photographic layer on carrier, because it can be to the sensitivity of photographic layer and/or development property and exposure film strength and/or printability resistance produced effect mutually.If coating weight is too little, then printability resistance maybe be not enough.If coating weight is too big, then sensitivity possibly descend, and makes the essential time shutter to increase, and possibly increase development time unfavourably.As a fundamental purpose of the present invention, promptly be used for the lithographic plate of scan exposure, in mass coating weight can suitably be 0.1g/m after drying ²To 10g/m ², 0.5g/m more preferably ²To 5g/m ²

Carrier is in original edition of lithographic printing plate of the present invention, and carrier preferably has water-wetted surface.The hydrophilic support that can be used for lithographic plate from known routine is selected hydrophilic support, and not special restriction.Carrier is preferably the flaky material of dimensionally stable, and the example comprises paper, and lamination has the paper of plastics (like tygon, polypropylene or polystyrene); Sheet metal (like aluminium, zinc or copper sheet), plastic foil is (like the film of following material: cellulose diacetate, cellulose triacetate; Cellulose propionate, cellulose butyrate, cellulose acetate-butyrate, cellulose nitrate; Polyethylene glycol phthalate, tygon, polystyrene; Polypropylene, polycarbonate or Pioloform, polyvinyl acetal), with and laminated or vapour deposition the as above paper or the plastic foil of listed metal are arranged.If necessary, suitable known physical and/or chemical treatment are carried out in surface that can these materials, to improve water wettability, improve intensity etc.

Preferred paper, polyester film or aluminium flake are as carrier.Preferred especially aluminium flake, relatively cheap and can highly-hydrophilic or strong surface be provided through carrying out surface treatment because it has excellent size stability, said surface treatment can be carried out as required.The polyethylene glycol phthalate film of describing among the JP-B No.48-18327 that comprises also is preferred with the composite sheet that combines the aluminium flake on it.

The preferred embodiment of aluminium flake comprises the fine aluminium sheet and comprises the aluminum alloy sheet of aluminium as key component and a spot of other element.Can also use its laminated or vapour deposition that the plastic foil of aluminium is arranged.This instance that is included in other element in the aluminium alloy comprises silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium.The content of other element in alloy is at most below the 10 quality %.In the present invention, preferred especially fine aluminium.Yet, aspect refining techniques, be difficult to prepare pure aluminium fully, therefore, can contain other element of trace.Be used for aluminium flake of the present invention and be not limited to have special composition, and can from the aluminium flake of any known conventional material, suitably select.Be preferred for aluminium flake of the present invention thickness can for about 0.1mm to about 0.6mm, be preferably 0.15mm to 0.4mm, be preferably 0.2mm to 0.3mm especially.

When carrier has the metal surface, particularly aluminium when surface, preferably carry out surface treatment such as surface roughening (granulation), the dipping in the WS of sodium silicate, potassium fluorozirconate, phosphate etc., or anodic oxidation.

Can carry out the surface roughening of aluminium flake through the whole bag of tricks, like the method for mechanically roughened surface, the method on the method for electrochemical dissolution and roughened surface and chemistry and selective dissolution surface.Mechanically roughened can be that known mechanical means such as ball polishes, brush polishing, air blast polishing and rag wheel polishing.Electrochemical surface roughening method can be carried out under interchange or direct current in the electrolytic solution of hydrochloric acid, nitric acid etc.As disclosed among the JP-A No.54-63902, can also make up the combination of using two kinds of methods.Before the aluminium flake surface roughening, if necessary, can use surfactant, organic solvent or alkaline aqueous solution carry out degreasing to remove rolling oil from the surface.

Preferred use behind the surface roughening in sodium silicate aqueous solution impregnated aluminium flake.Also preferably use and pass through the aluminium flake anodized and impregnated aluminium flake in alkali metal silicate aqueous solution described in the JP-B No.47-5125.For example; Can carry out anodic oxidation in order to following method: electric current is flow through serve as the aluminium flake of anode, said electrolytic solution contains mineral acid, the WS of more than one of organic acid or its salt or non-aqueous solution; Said mineral acid such as phosphoric acid; Chromic acid, sulfuric acid and boric acid, organic acid such as oxalic acid and sulfaminic acid.

U.S.No.3, the silicate electro-deposition of describing in 658,662 also is effective.

Can also use disclosed surface treatment among JP-B No.46-27481 and JP-A Nos.52-58602 and the 52-30503, wherein the carrier of electrolysis granulation handled being used in combination with anodic oxidation and sodium silicate.

In a kind of preferred processing, of JP-A No.56-28893, order is carried out the mechanical surface roughening, chemical etching, and the electrolysis granulation, anodic oxidation and sodium silicate are handled.

After these are handled, preferably carry out the undercoat coating.Undercoat can comprise water soluble resin such as polyvinyl phosphonic acids, in side chain, contains sulfonic polymkeric substance or multipolymer, or polyacrylic acid; Water-soluble metal salt (like Firebrake ZB); Weld; Or amine salt.

Also preferably use the substrate of the sol-gel-processing described in JP-A No.07-154983, wherein covalent bond can be carried out the functional group of free radical addition reaction.

In another preferred embodiment, can form the water tolerance hydrophilic layer as superficial layer on the carrier arbitrarily.The instance of this superficial layer comprises United States Patent(USP) No. 3; 055; 295 with JP-A No.56-13168 described in the layer that comprises inorganic pigment and bonding agent; Hydrophilic swellability layer described in the JP-A No.09-80744 and Japanese patent application country announce the titanium dioxide described in (disclosing) No.08-507727, the sol gel film of polyvinyl alcohol (PVA) or silicate.

Carry out these hydrophilic treated, not only can make the carrier surface hydrophiling, and can prevent to settle the unfavorable reaction of the photopolymerisable compositions on it and the adhesion of raising photographic layer.

Protective seam original edition of lithographic printing plate of the present invention preferably also is included in the protective seam on the photographic layer.Protective seam can prevent that micromolecular compound such as alkaline matter or airborne oxygen from getting into photographic layer, and can be exposed in the air, the image in the photographic layer that described micromolecular compound suppresses to be caused by exposure-form reaction.Therefore, preferred protective seam has such characteristic: protective seam is low to the perviousness of micromolecular compound such as oxygen, does not suppress the transmission of exposure light basically, with photographic layer excellent tack is arranged, and can remove through the development treatment after the exposure easily.

Like United States Patent(USP) No. 3,458,311 with JP-ANo.55-49729 in describe in detail, carried out the improvement of protective seam.For example, can preferably the water-soluble polymeric compounds with higher crystallinity be used for protective seam.The instance of this material comprises water-soluble polymers such as polyvinyl alcohol (PVA), polyvinylpyrrolidone, acid cellulose, gelatin, Arabic gum and polyacrylic acid.Particularly, use polyvinyl alcohol (PVA), can obtain at fundamental characteristics like resistance oxygen property and the best result aspect the property removed of developing as key component.

The polyvinyl alcohol (PVA) that is used for protective seam can be by ester, and at least a part replaces in ether and the acetal, as long as it has unsubstituted vinyl alcohol units to produce necessary resistance oxygen property and water-soluble.Polyvinyl alcohol (PVA) can partly have at least one other copolymerization component.Particularly, can and can have the quality mean molecular weight in 300 to 2400 scopes with hydrolyzed pva to 71 to the degree of 100mol%.The instance of polyvinyl alcohol (PVA) comprises the Co. by Kuraray, the PVA-105 that Ltd makes, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124; PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204; PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE; PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613 and L-8.

Can consider to hinder oxygen property, through the property removed of developing, mist formation property, tack or mar-resistance, the component (selection of PVA, the use of adjuvant etc.) of selection protective seam, coating weight etc.Usually, the percent hydrolysis of employed PVA high more (unsubstituted vinyl alcohol units content is high more in the protective seam) or film thickness are big more, and resistance oxygen property level is high more, and this is favourable to sensitivity.When excessive increase resistance oxygen property, possibly go wrong as produce or storage process in unnecessary polyreaction with becoming the image exposure process in unnecessary mist formation or the thickening of image line.With the adhesion of image section and mar-resistance also be very important for the operating performance of galley.The method that applies protective seam for example is described in detail in, United States Patent(USP) No. 3,458,313 with JP-ANo.55-49729 in.

Protective seam can also have other function.For example; Can with effective transmission in 350nm to the 450nm scope that is used to make public light and effectively be absorbed in the colorant (like water-soluble dye) of the light more than the 500nm; Join in the protective seam, make and further to improve safety light adaptability and non-desensitization.

Other layer can also provide other layer, as layer that is used to improve adhesion between photographic layer and the carrier and the removing property of pass through to develop that is used to improve unexposed photographic layer layer.For example can through adding contain the diazonium structure compound or can be relatively consumingly and interactional compound of substrate such as phosphinic acid compounds, or, improve adhesiveness or printability resistance through the undercoat of this compound is provided.On the other hand, can be through adding hydrophilic polymer such as polyacrylic acid or gathering sulfonic acid or, improve the development property or the soil resistance of non-image part through the undercoat of this polymkeric substance is provided.

Plate-making becomes the exposure of image ground with original edition of lithographic printing plate usually, through using liquid developer to remove unexposed portion, forms image then.

Can any known exposure method be used for original edition of lithographic printing plate of the present invention and not restriction.The wavelength of light source is preferably 350nm to 450nm, particularly, and preferred InGaN semiconductor laser.Exposure mechanism can be any system such as inner drum system, the mechanism of outside drum system or tack system.Can the highly-water-soluble component be used for photographic layer, make this layer can be dissolved in neutral water or the alkalescent water.Can the lithographic plate with this structure be carried out after being installed on the printing machine in machine (on-press) exposure and development.

The available LASER Light Source in 350nm to 450nm scope comprises following laser instrument.

Gas laser comprises Ar ion laser (364nm, 351nm, 10mW to 1W), Kr ion laser (356nm, 351nm, 10mW to 1W and He-Cd laser instrument (1 to 100mW for 441nm, 325nm); Solid-state laser comprises Nd:YAG (YVO ₄) and the combination of the combination (355nm, 5mW to 1W) of SHG crystal (twice) and Cr:LiSAF and SHG crystal (430nm, 10mW); Semiconductor laser comprises KNbO ₃Toroidal cavity resonator (430nm; 30mW), the semi-conductive combination of waveguide type wavelength converter spare and AlGaAs or InGaAs (380 to 450nm, and 5 to 100mW); (300 to 350nm for the semi-conductive combination of waveguide type wavelength converter spare and AlGaInP or AlGaAs; 5 to 100mW) and AlGaInN laser instrument (350 to 450nm, and 5 to 30mW); Other laser instrument comprises pulsed laser such as N ₂Laser instrument (337nm, 0.1 to 10mJ pulse) and XeF laser (351nm, 10 to 250mJ pulses).

Wherein, consider wavelength characteristic and cost, preferred especially AlGaInN semiconductor laser (commercially available InGaN semiconductor laser (400 to 410nm, and 5 to 30mW).

For scan exposure type lithographic plate exposure system, can use inner drum, outside drum or tack system as exposure mechanism, and can use above-mentioned all light sources except that pulsed laser as light source.In fact, consider material sensitivity and the relation between the plate-making time, preferred especially following exposure system.

Use single single beam exposure system of planting the inside drum system of gas or solid-state laser light source; Use the multiple beam exposure system of the tack system of many (more than 10) semiconductor laser; Multiple beam exposure system with the outside drum system that uses many (more than 10) semiconductor laser.

For aforesaid laser direct rendering type lithographic plate, equality (eq1): XS=nqt sets up usually, wherein X (J/cm ²) be the sensitivity of photosensitive material, S (cm ²) be the exposure area of photosensitive material, q (W) is the power of a LASER Light Source, n is the number of LASER Light Source, and t (s) is a total exposure time.

Under the situation of (i) inner drum system (single beam), equality (eq2): fZt=Lx sets up usually, and wherein (radian/s) is the gyro frequency of laser to f, and Lx (cm) is the subscan length of photosensitive material, and (point/cm) is a resolution to Z, and t (s) is a total exposure time.

Under the situation of (ii) outside drum system (multiple beam), equality (eq3): FZnt=Lx sets up usually, and wherein (radian/s) is the gyro frequency of drum to F; Lx (cm) is the subscan length of photosensitive material; (point/cm) is a resolution to Z, and t (s) is a total exposure time, and n is the quantity of light beam.

In (iii) tack system (multiple beam) is under the situation, and equality (eq4): HZnt=Lx sets up usually, and wherein (radian/s) is the gyro frequency of polygon mirror to H; Lx (cm) is the subscan length of photosensitive material; (point/cm) is a resolution to Z, and t (s) is a total exposure time, and n is the quantity of light beam.

The resolution that the actual print version is required (2560dpi), the size of sheet (A1/B1, in subscan length 42 inches), the sensitometric characteristic of about 20 conditions of exposures hourly and photopolymerisable compositions of the present invention (wavelength photoreceptor and about 0.1mJ/cm ²Sensitivity) in the substitution equality, show photosensitive material of the present invention should be preferably and the combination of multiple beam exposed type semiconductor laser use.Also consider operating performance and cost, advise photosensitive material of the present invention most preferably with semiconductor laser, the combination of the multiple beam exposure system of outside drum system is used.

Other instance of the light source that can be used for making public comprises UHV (ultra-high voltage), high pressure, middle pressure and low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, various visible and Ultra-Violet Laser lamps, fluorescent light, in tungsten lamp and the daylight any.

The liquid developer that is suitable for original edition of lithographic printing plate of the present invention comprises the developer described in the JP-B No.57-7427.Appropriate developer comprises: inorganic alkaline agents such as sodium silicate, potassium silicate, NaOH; Potassium hydroxide, lithium hydroxide, tertiary sodium phosphate; Sodium hydrogen phosphate, triammonium phosphate, diammonium hydrogen phosphate; Sodium metasilicate, the WS of soda mint and ammoniacal liquor, and the WS of organic basic reagent such as monoethanolamine and diethanolamine.Can add alkaline reagent, make the concentration of alkaline solution can be 0.1 to 10 quality %, preferred 0.5 to 5 quality %.

If necessary, alkaline aqueous solution can contain a spot of surfactant or organic solvent such as benzylalcohol, 2-phenoxetol or butoxy ethanol.The instance of this adjuvant is included in United States Patent(USP) Nos. 3,375, and 171 and 3,615, those described in 480.

Liquid developer described in JP-A Nos.50-26601 and 58-54341 and JP-B Nos.56-39464 and the 56-42860 also is excellent.

Liquid developer described in the preferred especially JP-ANo.2002-202616, it contains by the non-ionic compound of formula (VIII) expression and has 11.5 to 12.8 pH and 3 to 30mS/cm conductivity.Formula (VIII): A-W

In formula (VIII), A representes that the logP of A-H is the so hydrophobic organic group more than 1.5, and the W logP that representes W-H is less than such nonionic hydrophilic organic group of 1.0.The liquid developer component be described in detail in JP-A No.2002-202616's [0024] to [0067] section in.

Effectively, add non-ionic compound, make its concentration in liquid developer become 0.1 to 15 quality %, preferred 1.0 to 8.0 quality % by formula (VIII) expression.

If necessary, the method for making galley by original edition of lithographic printing plate also be included in before the exposure in the exposure process or exposure and develop between the whole surface of heating.This heating can promote the image in the photographic layer to form reaction, thereby can obtain as improving sensitivity or printability resistance and making the stable benefit of sensitivity.In addition, can be on image, effectively carrying out whole face exposure or the back heating of whole surface after the development, to improve the intensity or the printability resistance of image.Usually, heating is preferably carried out under the temperate condition below 150 ℃ before the development.Below 150 ℃, non-image part can not have the mist formation problem.Heating after very strong condition should be used to develop.This condition is usually in 200 to 500 ℃ of scopes.More than 200 ℃, can fully obtain the image reinforced effects.Below 500 ℃, the problem like carrier deterioration and image section thermal decomposition can not appear.

Embodiment

Use embodiment more specifically to describe the present invention below.But, the invention is not restricted to these embodiment.Under the situation that does not depart from aim of the present invention, many replacements, variation and improvement are possible.

Following table 1 and 2 has shown the details of special oxime compound (compound 1 to 8) that uses in embodiment and the comparative example and the compound (comparative compound 1 to 3) that is used for comparison.

Table 1

Table 2

Synthetic embodiment 1: the N-hydroxyoxime of structure shown in below will having corresponding to the compound 1 of special oxime compound synthetic (10.00g, 19.0mmol) and triethylamine (2.31g 22.8mmol) is dissolved among the 200ml THF and is cooled to 0 ℃.Then to dripping acetyl chloride wherein (1.79g, 22.8mmol).Potpourri in stirring at room after 1 hour, to wherein adding 100ml distilled water, and is used ethyl acetate extraction with organic layer.Remove through decompression distillation desolvate after, the residue that obtains with silica gel chromatography (ethyl acetate/hexane=1/4) purifying, is obtained having the compound 1 (9.5g, 88% productive rate) of the structure shown in following.

compound 1

Use ultraviolet-visible spectrophotometer (trade name: CARRY-5 Spectrophotometer, made by Varian), the compound 1 that in ethyl acetate solution, obtains with the measurement of concetration of 0.01g/L is found to be 29,059 at the molar absorptivity of 365nm.The structure of the compound of confirming with NMR to obtain 1. ¹H-NMR，400MHz，CDCl ₃：8.54(s，1H)，8.41(s，1H)，8.04(d，1H，J＝8.0Hz)，7.79(d，1H，J＝8.0Hz)，7.45(d，1H，J＝9.6Hz)，7.43(d，1H，9.6Hz)，6.68(s，1H)，4.41(q，2H，J＝7.2Hz)，4.14-4.04(m，1H)，3.94-3.87(m，1H)，2.53(s，3H)，2.31(s，3H)，1.95-1.24(m，?23H)。Fig. 1 has also shown the UV absorption spectrum of the compound 1 (0.01g/L is in ethyl acetate) that obtains.

Synthetic embodiment 2: the N-hydroxyoxime of structure shown in below will having corresponding to the compound 7 of special oxime compound synthetic (10.00g, 22.9mmol) and triethylamine (2.78g 27.5mmol) is dissolved among the 200ml THF and is cooled to 0 ℃.Then to dripping acetyl chloride wherein (2.16g, 27.5mmol).Potpourri in stirring at room after 1 hour, to wherein adding 100ml distilled water, and is used the ethyl acetate extraction organic layer.Remove through decompression distillation desolvate after, the crystal of deposition use recrystallizing methanol, obtain following shown in the compound 7 (9.2g, 84% productive rate) of structure.

compound 7

Use ultraviolet-visible spectrophotometer (trade name: Carry-5 Spectrophotometer, made by Varian), the compound 7 that in ethyl acetate solution, obtains with the measurement of concetration of 0.01g/L is found to be 21,380 at the molar absorptivity of 405nm.The structure of the compound of confirming with NMR to obtain 7. ¹H-NMR，400MHz，CDCl ₃：9.47(s，1H)，8.73(d，1H，J＝12.0Hz)，8.55(s，1H)，8.13(s，1H)，8.07-8.02(m，3H)，7.82-7.79(m，2H)，7.52(d，1H，J＝8.8Hz)，7.46(d，1H，J＝8.8Hz)，4.44(q，2H，J＝7.2Hz)，2.58(s，3H)，2.33(s，3H)，1.50(t，3H，J＝7.2Hz)。Fig. 2 has also shown the UV absorption spectrum of the compound 7 (0.01g/L is in ethyl acetate) that obtains.

Shown in the table 1 and 2 and separately corresponding to the compound 2,3,4,5,6 and 8 of special oxime compound be adopt with synthetic embodiment 1 or 2 in the similar method of method that adopts synthetic.

Structure shown in below comparative compound 1 to 3 shown in the table 2 has.

Embodiment 1-1 < preparation of photosensitive composite 1 and evaluation>is described below and prepares photosensitive composite 1, and estimates its sensitivity.Prepare uniform composition; It contains the compound 1 of 0.08mmol as special oxime compound; 1g is as the tetramethylol methane tetraacrylate of free redical polymerization compound, and 1g is as the polymethylmethacrylate (molecular weight about 996,000 of adhesive resin; Make by Aldrich) and 16g as the cyclohexanone of solvent.The composition that obtains as coating fluid, is coated on the glass sheet and 40 ℃ of dryings 10 minutes, forms thick the filming of 1.5 μ m with spin coater.With 21 √, 2 hierarchical table (step tablet) (by Dainippon Screen Mfg.Co., the progressive series of greys film that Ltd. makes) be placed on film on.To film is exposed to from the light of 500mW high-pressure sodium lamp (being made by Ushio Inc.) 30 seconds through heat-ray-intercepting filtrator (heat-ray-cutting filter), then in toluene dipping 60 seconds to develop.According to hierarchical table, the MEASUREMENTS OF THIN full solidification and not the progression during dissolving as sensitivity.As a result, sensitivity is the 8th grade.Progression is big more, and sensitivity is high more.

Embodiment 1-2 to 1-8 and comparative example 1-1 to 1-3 adopt with embodiment 1-1 in identical method prepare photosensitive composite 2 to 8 respectively; Difference is; Use compound 1 that each compound 2 to 8 shown in the table 1 of 0.08mmol replaces 0.08mmol as special oxime compound, and estimate the progression of sensitivity with the mode identical with embodiment 1-1.

The evaluation result of embodiment 1-1 to 1-8 and comparative example 1-1 to 1-3 is shown in the following table 3.

Table 3

	Special oxime compound or comparative compound	Sensitivity progression
			Embodiment 1-1	Compound 1	8
Embodiment 1-2	Compound 2	8
			Embodiment 1-3	Compound 3	8
Embodiment 1-4	Compound 4	8
			Embodiment 1-5	Compound 5	8
Embodiment 1-6	Compound 6	7
			Embodiment 1-7	Compound 7	7
Embodiment 1-8	Compound 8	6
			Comparative example 1-1	Comparative compound 1	5
Comparative example 1-2	Comparative compound 2	5
			Comparative example 1-3	Comparative compound 3	4

The negativity colored curable composition (A-1) that the preparation preparation of embodiment 2-11. colored curable composition A-1 contains colorant (pigment) is as the curable compositions that is used to form color filter.Use this colored curable composition to prepare color filter.

1-1. preparation dispersible pigment dispersion (P1) will be by the C.I. pigment green 36 of 40 mass parts and the pigment composition of C.I. pigment yellow 219 (mass ratio is 30/70); 10 mass parts (counting 4.51 mass parts with solid content) are as the BYK 2001 (DISPERBYK of spreading agent; Make by BYK-Chemie; Count 45.1 quality % with solid content) and the liquid mixture formed as the 3-ethoxyl ethyl propionate of solvent of 150 mass parts in ball mill, mixes and disperseed 15 hours, prepare dispersible pigment dispersion (P1).

Through dynamic light scattering measurement, the particle mean size of the pigment in the dispersible pigment dispersion that obtains (P1) is 200nm.

1-2. the component of the composition A-1 of preparation colored curable composition A-1 (coating fluid) shown in will be following is mixed and dissolving, with formation colored curable composition A-1.

< composition A-1>dispersible pigment dispersion (P1) 600 mass parts alkali soluble resinss 200 mass parts (benzyl methacrylate/methacrylic acid/methacrylic acid hydroxyl ethyl ester (mol ratio is 80/10/10) multipolymer (Mw:10; 000) the special oxime compound of polyfunctional monomer dipentaerythritol acrylate 60 mass parts: compound 1 60 mass parts solvents: propylene glycol methyl ether acetate 1; 000 mass parts surfactant (trade name: TETRANIC 150R1, BASF) 1 mass parts γ-methacryloxypropyl triethoxysilane 5 mass parts

2. preparation color filter 2-1. forms the colored curable composition A-1 that contains pigment that the curable compositions layer will obtain as resist solution.Through under the described below condition of slot coated resist solution being coated on the glass substrate of 550mm * 650mm, let it leave standstill then 10 minutes.Then with solution drying and prebake (100 ℃, 80 seconds) under vacuum, form curable compositions film (curable compositions layer).

The opened gap at (slot coated condition) dispense tip top: 50 μ m coating speeds: the space between 100mm/ substrate second and the dispense tip: 150 μ m coating thicknesses (dry thickness): 2 μ m coating temperatures: 23 ℃

2-2. exposure becomes image ground to make public to the light from the 2.5kW ultrahigh pressure mercury lamp on the curable compositions layer with developing then.After exposure, with the whole surface of exposure composition layer with 10% WS covering of the organic developer of liquid (trade name: CD, by Fuji FilmElectronics Materials Co., Ltd. makes) and let it leave standstill 60 seconds.

2-3. thermal treatment sprays on the composition layer pure water with the flush away liquid developer then.Then composition is heated 1 hour (afterwards curing) in 220 ℃ stove, thereby obtain the color filter on glass substrate with colored pattern.

3. performance evaluation is described below to following aspect and estimates: the storage stability of colored curable composition and exposure sensitivity; Use said colored curable composition to be formed on the development property of the painted patterning product on the glass substrate; The painted patterning product and the adhesion of substrate, and the shape of cross section of patterning product.Gathering of evaluation result is shown in Table 4.

3-1. the storage stability of colored curable composition after 1 month, is visually being estimated the deposition degree of material: A: do not observe deposition in room temperature storage with colored curable composition according to following standard; B: observe deposition slightly; C: observe deposition.

3-2. the exposure sensitivity of colored curable composition is dry then to the glass substrate through spin-applied with colored curable composition, forming thickness is filming of 1.0 μ m.The spin coating condition is 300rpm spin coating 5 seconds 800rpm spin coating 20 seconds then.Drying condition is 100 ℃ of dryings 80 seconds.Use the proximity printing system be equipped with ultrahigh pressure mercury lamp (by Hitachi High-Tech ElectronicsEngineering Co., Ltd. makes) then, with at 10mJ/cm ²To 1,600mJ/cm ²Different exposures in the scope are the test light mask of 2.0 μ m through live width, with the exposure of filming that obtains.Filming of will making public then developed 60 seconds at 25 ℃ with liquid developer 60%CD-2000 (by Fuji Film Electronics MaterialsCo., Ltd. makes).Afterwards, with this film with flowing water flushing 20 seconds, spraying-drying then, thereby completion patterning.As for the evaluation of exposure sensitivity, 95% minimum exposure amount when above that will be in step of exposure becomes film thickness (100%) before the exposure with thickness after the development in the zone of photoirradiation is evaluated as the exposure requirement.The more little expression sensitivity of exposure requirement is high more.

3-3. development property; The shape of cross section of pattern; After curing after described in the 2-3 part " thermal treatment " with the adhesion of substrate; Through the commonsense method of use optical microscope and the surface and the shape of cross section of SEM photography observation substrate, to estimate development property, with the adhesion of substrate and the shape of cross section of pattern.The details of evaluation method is described below.

Whether there is residue in the zone (unexposed portion) of < development property>observation photoirradiation of no use in step of exposure, to estimate development property.Estimate according to following standard: A: do not observe residue at unexposed portion; B: observe residue slightly at unexposed portion, but the residue level is being actually acceptable; C: obviously observe residue at unexposed portion.

Observe whether there is pattern defect with the adhesion of substrate, and according to the adhesion of following standard evaluation and substrate: A: do not observe pattern defect; B: almost do not observe and observing pattern defect in part; C: obviously observe many pattern defects.

The shape of cross section of pattern) shape of cross section of O&A pattern.The shape of cross section of pattern is preferably rectangle, most preferably forward direction-taper.Preferably not oppositely-conical by its shape.The result is shown in Table 4.

Embodiment 2-2 to 2-15 and comparative example 2-1 to 2-3 prepare colored curable composition A-2 to A-15 and A '-1 to A '-3 and color filter with the mode identical with embodiment 2-1; Difference is to use the 60 mass parts compounds 1 (special oxime compound) among the composition A-1 that the respective compound of the amount shown in the following table 4 replaces in preparation colored curable composition A-1, using, and further adds the sensitizer and/or the auxiliary sensitizer of kind shown in the table 4 and amount in each at embodiment 2-9 to 2-15.Mode with identical with embodiment 2-1 is estimated equally.The result is shown in Table 4.

Sensitizer A1 to A3 shown in the table 4 and auxiliary sensitizer F1 to F3 are following compounds:

A1:4, the two diethylamino benzophenone A2 of 4-: diethyl thioxanthone

F1:2-mercaptobenzimidazole F2:2-mercaptobenzothiazoler F3:N-phenyl-2-mercaptobenzimidazole

The result of table 4 shows that the colored curable composition that contains each embodiment of special oxime compound (each in the compound 1 to 8) has high storage stability (stability in time).Also be apparent that; These colored curable compositions have high sensitivity when exposure; Show high development property in the process of colored pattern forming color filter, and form the colored pattern that has excellent and adhesion substrate and have the shape of cross section of excellence.

Embodiment 3-11. prepare that resist liquid mixes the component of composition described below and dissolving to form resist liquid.Composition propylene glycol methyl ether acetate (PGMEA) 19.20 mass parts ethyl lactates 36.67 mass parts resins 30.51 mass parts (40%PGMEA solution dipentaerythritol acrylate (polymerizable compound) 12.20 mass parts polymerization inhibitors (right-metoxyphenol) the 0.0061 mass parts fluorine surfactant 0.83 mass parts (F-475 of benzyl methacrylate/methacrylic acid/2-hydroxyethyl methacrylate (mol ratio is 60/22/18) multipolymer of resist liquid; By Dainippon Ink and Chemicals; Incorporated makes) Photoepolymerizationinitiater initiater 0.586 mass parts (TAZ-107 (trihalomethyl group triazine-Ji Photoepolymerizationinitiater initiater); By Midori Kagaku Co., Ltd. makes)

2. preparing the silicon wafer substrate with undercoat heats 6 inches silicon wafers 30 minutes in 200 ℃ stove.Resist liquid is coated on the silicon wafer 2 μ m with the dry thickness that 2 μ m are provided, then in 220 ℃ stove heating with dry 1 hour to form undercoat.As a result, obtain to have the silicon wafer substrate of undercoat.

3. preparation colored curable composition B-1 contains the colored curable composition B-1 of colorant (dyestuff) with compound and the dissolving of the composition B-1 shown in following with formation.

Monomer (polymerizable compound) 7.0 mass parts (potpourri of pentaerythritol triacrylate and dipentaerythritol acrylate (3: 7)) compounds 1 (special oxime compound) 2.5 mass parts propoxylated glycerols (glycerol propxylate) 0.5 mass parts (the number-average molecular weight Mn:1 of composition B-1 cyclohexanone 80 mass parts colorant C.I. Blue VRSs 08 7.5 mass parts colorant C.I. solvent yellow 16s 2 2.5 mass parts free redical polymerizations; 500, molar absorptivity ε=0)

4. the evaluation of the storage stability of colored curable composition B-1 (coating fluid) after 1 month, is visually being estimated the deposition degree of material in room temperature storage with colored curable composition B-1 according to following standard.The result is shown in Table 5.A: do not observe deposition; B: observe deposition slightly; C: observe deposition.

5. use colored curable composition B-1 to prepare color filter and estimate the colored curable composition B-1 for preparing in the 3.th part is coated on the undercoat of the silicon wafer substrate with undercoat that obtains in the 2.th part, form the light solidity and film.Then with film with 100 ℃ electric hot plate heating (prebake) 120 seconds so that the dry thickness of 0.9 μ m to be provided.Use i-line stepping exposure system (trade name: FPA-3000i5+, by Cannon Inc. make) then, with 10 to 1,600mJ/cm ²Exposure in the scope through having the mask of the square island of 2 μ m pattern, uses wavelength as the light of 365nm this film to be made public.The silicon wafer substrate of filming that will have then behind the irradiation is installed in rotary spray developing machine (trade name: Model DW-30; By Chemitronics Co.; Ltd. on horizontal rotating table manufacturing); And carried out oar formula development treatment 60 seconds with CD-2000 (by Fuji Film Electronics Materials Co., Ltd. makes) at 23 ℃, on silicon wafer substrate, to form colored pattern.

The silicon wafer substrate that will have colored pattern through vacuum cup is fixed on the horizontal rotating table.Through using nozzle, colored pattern is used from the pure water spray irrigation of rotation center top supply, simultaneously through the revolution rotation silicon wafer substrate of spinner, then with colored pattern spraying-drying with 50rpm.As a result, obtain to comprise substrate and the color filter that forms colored pattern above that.

95% minimum exposure amount when above that < size of exposure sensitivity and pattern>will be in step of exposure becomes film thickness (100%) before the exposure with thickness after the development in the zone of photoirradiation is evaluated as the exposure requirement.The more little expression sensitivity of exposure requirement is high more.In the method, use linear measure longimetry SEM (trade name: S-9260A is made by HitachiHigh-Technologies Corporation) to measure the size of colored pattern.Pattern dimension near 2 μ m shows abundant curing more, and sensitivity is high more.The result is shown in Table 5.

Development property, with the shape of cross section of the adhesion of substrate and pattern according to the method that adopts among the embodiment 2-1 and standard evaluation development property, with the adhesion of substrate and the shape of cross section of pattern.The result is shown in the following table 5.

Embodiment 3-2 to 3-9 prepares colored curable composition B-2 to B-9 and B ' 3-1 to B ' 3-3 and color filter with comparative example 3-1 to 3-3 with the mode identical with embodiment 3-1; Difference is to use the 2.5 mass parts compounds 1 (special oxime compound) among the composition B-1 that every kind of compound shown in the following table 5 replaces in preparation colored curable composition B-1, using, and in embodiment 3-9, further is added in the sensitizer and the auxiliary sensitizer of kind shown in the table 5 and amount.Mode with identical with embodiment 3-1 is estimated equally.The result is shown in Table 5.

Sensitizer A1 to A3 shown in the table 5 and auxiliary sensitizer F1 to F3 are aforesaid compounds.

Embodiment 3-10 contains the colored curable composition C-1 of colorant (pigment) with following compound and the dissolving that is used for composition C-1 with formation.

Monomer (polymerizable compound) 7.0 mass parts (potpourri of pentaerythritol triacrylate and dipentaerythritol acrylate (3: 7)) compounds 1 (special oxime compound) 2.5 mass parts propoxylated glycerols, 0.5 mass parts (number-average molecular weight Mn:1,500) of < composition C-1>cyclohexanone 80 mass parts colorant C.I. paratoneres 254 6.0 mass parts colorant C.I. pigment yellow 13s 9 4.0 mass parts free redical polymerizations

Embodiment 3-11 to 3-18 and comparative example 3-5 to 3-8 prepare colored curable composition C-2 to C-9 and C '-1 to C '-3 with the mode identical with embodiment 3-10; Difference is to use shown in the following table 6 the 2.5 mass parts compounds 1 (special oxime compound) among the composition C-1 that every kind of compound of amount replaces in preparation colored curable composition C-1, using, and in embodiment 3-16 to 3-18, further adds the sensitizer and the auxiliary sensitizer of kind shown in the table 6 and amount.

Estimate every kind of colored curable composition that obtains with the mode identical with embodiment 3-1.The result is shown in Table 6.

Sensitizer A1 to A3 shown in the table 6 and auxiliary sensitizer F1 to F3 are above-mentioned compounds.

Table 5 shows that with 6 result the colored curable composition that contains each embodiment of special oxime compound (each in the compound 1 to 8) has high storage stability (stability in time).Be apparent that also these colored curable compositions the time have high sensitivity in exposure, in forming the process of color filter, have high development property, and form and have excellent and the colored pattern of adhesion substrate with the shape of cross section of excellence with colored pattern.

Table 7 and 8 below the details that are used for the novel oxime compound (compound 31 to 38) of embodiment and are used for the comparative compound (comparative compound 31 to 34) of comparative example are shown in.

Table 7

Table 8

Compound 31 to 34 in the table 7, they are synthetic through following method separately corresponding to the novel oxime compound.

Synthetic embodiment 3: corresponding to the compound 31 of novel oxime compound synthetic at first, according to the scheme synthetic compound A shown in following.(100.0g 0.512mol) is dissolved in the chlorobenzene of 260ml with ethyl carbazole.After solution is cooled to 0 ℃, to wherein add aluminum chloride (70.3g, 0.527mol).Subsequently, (81.5g 0.527mol), is warming to potpourri room temperature and stirred 3 hours wherein to drip neighbour-tolyl chloride 40 minutes introversions.After potpourri is cooled to 0 ℃, in potpourri, add aluminum chloride (75.1g, 0.563mol).In 40 minutes, (79.4g 0.563mol), is warming to potpourri room temperature and stirred 3 hours to drip the 4-chlorobutanoylchloride.The 35 quality % aqueous hydrochloric acid solutions of 156ml and the mixed solution of 392ml distilled water are cooled to 0 ℃, and to dropwise reaction solution wherein.Through behind the solid of suction filtration precipitation separation, with solid with distilled water and methanol wash and use the acetonitrile recrystallization, obtain having following shown in the compd A (164.4g, 77% productive rate) of structure.

Scheme according to shown in following is used compd A synthetic compound B.With compd A (20.0g 47.9mmol) is dissolved among the THF of 64ml, and with 4-chlorobenzene mercaptan (7.27g, 50.2mmol) and sodium iodide (0.7g 4.79mmol) joins in the solution.Subsequently, (2.0g 50.2mmol) adds in the reactant liquor and refluxed 2 hours with NaOH.After potpourri was cooled to 0 ℃, (11.1g 57.4mmol), was warming to potpourri room temperature and stirred 2 hours wherein to drip SM-28 20 minutes introversions.After potpourri was cooled to 0 ℃, (6.73g 57.4mmol), was warming to potpourri room temperature and stirred 3 hours in 20 minutes, to drip isoamyl nitrite.With 120ml acetone diluted reactant liquor, and will be added drop-wise in the dilution at the 0.1N of 0 ℃ of cooling aqueous hydrochloric acid solution.Through behind the solid of suction filtration precipitation separation, solid is washed with distilled water, use the acetonitrile recrystallization then, obtain below having shown in the compd B (17.0g, 64% productive rate) of structure.

Subsequently, use compd B synthetic compound 31 according to the scheme shown in following.(18.0g 32.4mmol) is dissolved in the N-Methyl pyrrolidone of 90ml, and (3.94g 38.9mmol) adds in the solution with triethylamine with compd B.After potpourri was cooled to 0 ℃, (3.05g 38.9mmol), was warming to potpourri room temperature and stirred 2 hours dripping acetyl chloride in 20 minutes.Reactant liquor is added drop-wise in the 150ml of 0 ℃ of cooling distilled water.Through behind the solid of suction filtration precipitation separation, the 200ml washed with isopropyl alcohol that solid is used in 0 ℃ of cooling is dry then, obtain below having shown in the compound 31 (19.5g, 99% productive rate) of structure.

The structure of the compound of confirming through NMR to obtain 31. ¹H-NMR，400MHz，CDCl ₃：8.86(s，1H)，8.60(s，1H)，8.31(d，1H，J＝8.0Hz)，8.81(d，1H，J＝8.0Hz)，7.51-7.24(m，10H)，7.36(q，2H，7.4Hz)，3.24-3.13(m，4H)，2.36(s，3H)，2.21(s，3H，1.50(t，3H，7.4Hz)。

Synthetic embodiment 4: corresponding to the compound 32 of novel oxime compound synthetic will be following shown in the oxime compound C of structure (17.6g 32.4mmol) is dissolved in the N-Methyl pyrrolidone of 90ml, and (3.94g is 38.9mmol) in the adding solution with triethylamine.After potpourri was cooled to 0 ℃, (3.05g 38.9mmol), was warming to potpourri room temperature and stirred 2 hours dripping acetyl chloride in 20 minutes.Reactant liquor is added drop-wise in the 150ml of 0 ℃ of cooling distilled water.After passing through the solid of suction filtration precipitation separation, the 200ml washed with isopropyl alcohol that solid is used in 0 ℃ of cooling is dry then, obtains compound 32 (17.5g, 92% productive rate).

The structure of the compound of confirming through NMR to obtain 32. ¹H-NMR，400MHz，CDCl ₃：8.89(s，1H)，8.65(s，1H)，8.32(d，1H，J＝8.8Hz)，8.10(d，1H，J＝8.8Hz)，7.86(d，1H，J＝7.0Hz)，7.56-7.49(m，4H)，7.30-7.23(m，4H)，4.46(q，2H，J＝7.2Hz)，3.24-3.14(m，4H)，2.21(s，3H)，2.17(s，3H)，1.51(t，3H，J＝7.2Hz)。

Synthetic embodiment 5: corresponding to the compound 33 of novel oxime compound synthetic will be following shown in the oxime compound D of structure (17.3g 32.4mmol) is dissolved in the N-Methyl pyrrolidone of 90ml, and (3.94g is 38.9mmol) in the adding solution with triethylamine.After potpourri was cooled to 0 ℃, (3.05g 38.9mmol), was warming to potpourri room temperature and stirred 2 hours dripping acetyl chloride in 20 minutes.In the distilled water of the 150ml that reactant liquor is added drop-wise to 0 ℃ of cooling.After passing through the solid of suction filtration precipitation separation, the 200ml washed with isopropyl alcohol that solid is used in 0 ℃ of cooling is dry then, obtains compound 33 (18.5g, 99% productive rate).

The structure of the compound of confirming through NMR to obtain 33. ¹H-NMR，400MHz，CDCl ₃：8.86(s，1H)，8.59(s，1H)，8.33(d，1H，J＝8.4Hz)，8.07(d，1H，J＝8.4Hz)，7.50-7.26(m，8H)，7.11(d，2H，J＝9.2Hz)，4.34(q，2H，J＝7.4Hz)，3.19-3.14(m，4H)，2.37(s，3H)，2.31(s，3H)，2.18(s，3H)，1.49(t，3H，J＝7.4Hz)。

Synthetic embodiment 6: (17.7g 32.4mmol) is dissolved in the N-Methyl pyrrolidone of 90ml to the oxime compound E of structure shown in below will having corresponding to the compound 34 of novel oxime compound synthetic, and (3.94g 38.9mmol) adds in the solution with triethylamine.After potpourri was cooled to 0 ℃, (3.05g 38.9mmol), was warming to potpourri room temperature and stirred 2 hours dripping acetyl chloride in 20 minutes.In the distilled water of the 150ml that reactant liquor is added drop-wise to 0 ℃ of cooling.After passing through the solid of suction filtration precipitation separation, the 200ml washed with isopropyl alcohol that solid is used in 0 ℃ of cooling is dry then, obtains compound 34 (17.5g, 92% productive rate).

The structure of the compound of confirming through NMR to obtain 34. ¹H-NMR，400MHz，CDCl ₃：8.05(d，1H，J＝8.8Hz)，7.78(d，1H，J＝8.8Hz)，7.74(d，1H，J＝8.0Hz)，7.42-7.26(m，10H)，3.19-3.08(m，4H)，2.35(s，3H)，2.17(s，3H)。

Shown in the table 7 and 8 and separately corresponding to the compound 35 to 38 of special oxime compound with synthetic with synthetic embodiment 3 to 6 similar modes.

Structure shown in below comparative compound 31 to 33 shown in the table 8 has separately.

The preparation of embodiment 4-1 photopolymerisable compositions 1 and evaluation are described below and prepare photopolymerisable compositions 1, and estimate its sensitivity.Prepare uniform composition; It contains the compound 31 of 0.08mmol as the novel oxime compound; 1g is as the tetramethylol methane tetraacrylate of free redical polymerization compound, and 1g is as the polymethylmethacrylate (molecular weight about 996,000 of adhesive resin; Make by Aldrich) and 16g as the cyclohexanone of solvent.The composition that obtains as coating fluid, is coated on the glass sheet and 40 ℃ of dryings 10 minutes, forms thick the filming of 1.5 μ m with spin coater.With 21 √, 2 hierarchical table (by Dainippon Screen Mfg.Co., the progressive series of greys film that Ltd. makes) be placed on film on.To film is exposed to from the light of 500mW high-pressure sodium lamp (being made by Ushio Inc.) 30 seconds through heat-ray-intercepting filtrator, then in toluene dipping 60 seconds to develop.According to hierarchical table, the MEASUREMENTS OF THIN full solidification and not the progression during dissolving as sensitivity.As a result, sensitivity is the 9th grade.Progression is big more, and sensitivity is high more.

Embodiment 4-2 to 4-8 prepares photopolymerisable compositions 2 to 12 with comparative example 4-1 to 4-4 respectively with the mode identical with embodiment 4-1; The compound 31 that each compound 32 to 38 that difference is the 0.08mmol shown in the use table 7 and 8 and comparative compound 31 to 34 replace 0.08mmol is as special oxime compound, and estimates the progression of sensitivity with the mode identical with embodiment 4-1.

The evaluation result of embodiment 4-1 to 4-8 and comparative example 4-1 to 4-4 is shown in the following table 9.

Table 9

	Special oxime compound or comparative compound	The polymerisable compound numbering	Sensitivity progression
				Embodiment 4-1	Compound 31	1	9
Embodiment 4-2	Compound 32	2	8
				Embodiment 4-3	Compound 33	3	9
Embodiment 4-4	Compound 34	4	7
				Embodiment 4-5	Compound 35	5	9
Embodiment 4-6	Compound 36	6	9
				Embodiment 4-7	Compound 37	7	6
Embodiment 4-8	Compound 38	8	6
				Comparative example 4-1	Comparative compound 31	9	5
Comparative example 4-2	Comparative compound 32	10	5
				Comparative example 4-3	Comparative compound 33	11	4
Comparative example 4-4	Comparative compound 34	12	5

Embodiment 5-11. prepares painted photopolymerisable compositions A-1 and prepares the photopolymerisable compositions that the painted photopolymerisable compositions of negativity (A-1) conduct that contains colorant (pigment) is used to form color filter.Use this painted photopolymerisable compositions to prepare color filter.

The particle mean size of pigment is 200nm in the dispersible pigment dispersion (P1) that obtains through dynamic light scattering measurement.

1-2. prepare painted photopolymerisable compositions A-1 (coating fluid) component of the composition A-1 shown in following is mixed and dissolving, to form painted photopolymerisable compositions A-1.

Composition A-1 dispersible pigment dispersion (P1) 600 mass parts alkali soluble resinss 200 mass parts (benzyl methacrylate/methacrylic acid/methacrylic acid hydroxyl ethyl ester (mol ratio is 80/10/10) multipolymer (Mw:10; 000)) polyfunctional monomer dipentaerythritol acrylate 60 mass parts novel oxime compounds: compound 31 60 mass parts solvents: propylene glycol methyl ether acetate 1; 000 mass parts surfactant (trade name: Tetranic 150R1, BASF) 1 mass parts γ-methacryloxypropyl triethoxysilane 5 mass parts

2. preparation color filter 2-1. forms the painted photopolymerisable compositions A-1 that contains pigment that the photopolymerisable compositions layer will obtain as resist solution.Through under the described below condition of slot coated resist solution being coated on the glass substrate of 550mm * 650mm, let it leave standstill then 10 minutes.Then with solution drying and prebake (100 ℃, 80 seconds) under vacuum, form photopolymerisable compositions film (photopolymerisable compositions layer).

The opened gap at slot coated condition dispense tip top: 50 μ m coating speeds: the space between 100mm/ substrate second and the dispense tip: 150 μ m coating thicknesses (dry thickness): 2 μ m coating temperatures: 23 ℃

2-2. exposure becomes image ground to make public to the light from the 2.5kW ultrahigh pressure mercury lamp on the photopolymerisable compositions layer with developing then.After exposure, with the whole surface of exposure composition layer with 10% WS covering of the organic developer of liquid (trade name: CD, by Fuji FilmElectronics Materials Co., Ltd. makes) and let it leave standstill 60 seconds.

3. performance evaluation is described below to following aspect and estimates: the storage stability of painted photopolymerisable compositions and exposure sensitivity; Use said painted photopolymerisable compositions to be formed on the development property of the painted patterning product on the glass substrate; Painted patterning product because of long-time heating cause painted; The painted patterning product and the adhesion of substrate, and the shape of cross section of patterning product.Gathering of evaluation result is shown in Table 10.

3-1. the painted photopolymerisable compositions of storage stability after 1 month, is visually being estimated the deposition degree of material: A: do not observe deposition in room temperature storage with painted photopolymerisable compositions according to following standard; B: observe deposition slightly; C: observe deposition.

3-2. the painted photopolymerisable compositions of exposure sensitivity is dry then to the glass substrate through spin-applied with painted photopolymerisable compositions, forming thickness is filming of 1.0 μ m.The spin coating condition is 300rpm spin coating 5 seconds 800rpm spin coating 20 seconds then.Drying condition is 100 ℃ of dryings 80 seconds.Use the proximity printing system be equipped with ultrahigh pressure mercury lamp (by Hitachi High-TechElectronics Engineering Co., Ltd. makes) then, with at 10mJ/cm ²To 1,600mJ/cm ²Different exposures in the scope are the exposure of filming that the test light mask of 2.0 μ m will obtain through live width.Filming of will making public then developed 60 seconds at 25 ℃ with liquid developer 60%CD-2000 (by Fuji Film ElectronicsMaterials Co., Ltd. makes).Afterwards, this film is washed 20 seconds spray dryings then with flowing water, form thereby accomplish pattern.As for the evaluation of exposure sensitivity, 95% minimum exposure amount when above that will be in step of exposure becomes film thickness (100%) before the exposure with thickness after the development in the zone of photoirradiation is evaluated as the exposure requirement.The more little expression sensitivity of exposure requirement is high more.

Whether there is residue in the zone (unexposed portion) of development property observation photoirradiation of no use in step of exposure, to estimate development property.Estimate according to following standard: A: do not observe residue at unexposed portion; B: observe residue slightly at unexposed portion, but the residue level is being actually acceptable; C: obviously observe residue at unexposed portion.

The composition layer (colored pattern) that will make public and develop through the painted evaluation of forcing heat aging heated 1 hour in 200 ℃ on electric hot plate; And with Otsuka Electronics Co., the MCPD-3000 (trade name) that Ltd. makes estimates the aberration Δ Eab before and after the heating according to following standard ^*: A: Δ Eab ^*≤5B:5＜ ^*Δ Eah ^*＜8 C: Δ Eab ^*>=8

Observe whether there is pattern defect with the adhesion of substrate, and according to the adhesion of following standard evaluation and substrate: A: do not observe pattern defect; B: almost do not have and observing pattern defect in part; C: obviously observe many pattern defects.

The shape of cross section of the shape of cross section O&A pattern of pattern.The shape of cross section of pattern is preferably rectangle, most preferably forward direction-taper.Preferably not oppositely-conical by its shape.The result is shown in Table 10.

Embodiment 5-2 to 5-15 and comparative example 5-1 to 5-4 prepare painted photopolymerisable compositions A-2 to A-15 and A '-1 to A '-4 and color filter with the mode identical with embodiment 5-1; Difference is to use the 60 mass parts compounds 31 (novel oxime compound) among the composition A-1 that every kind of compound of the amount shown in the following table 10 replaces in the painted photopolymerisable compositions A-1 of preparation, using, and further adds the kind described in the table 10 and the sensitizer and/or the auxiliary sensitizer of amount at embodiment 5-9 to 5-15 in each.Estimate with the mode identical equally with embodiment 5-1.The result is shown in Table 10.

Sensitizer A1 to A3 shown in the table 10 and auxiliary sensitizer F1 to F3 are following compounds:

A1:4, the two diethylamino benzophenone A2 of 4-: diethyl thioxanthone

The result of table 10 shows that the painted photopolymerisable compositions that contains each embodiment of novel oxime compound (each of compound 31 to 38) has high storage stability (stability in time).Also be apparent that; These painted photopolymerisable compositions have high sensitivity when exposure; In forming the process of color filter, has high development property with colored pattern; Show that the gained colored pattern is repressed painted in the heat aging process, and form colored pattern with excellent and adhesion substrate and excellent shape of cross section.

Embodiment 6-11. prepare that resist liquid mixes the component of combinations thing and dissolving to form resist liquid.Composition propylene glycol methyl ether acetate (PGMEA) 19.20 mass parts ethyl lactates 36.67 mass parts resins 30.51 mass parts (40%PGMEA solution dipentaerythritol acrylate (polymerizable compound) 12.20 mass parts polymerization inhibitors (right-metoxyphenol) the 0.0061 mass parts fluorine surfactant 0.83 mass parts (F-475 of benzyl methacrylate/methacrylic acid/2-hydroxyethyl methacrylate (mol ratio is 60/22/18) multipolymer of resist liquid; By Dainippon Ink and Chemicals; Incorporated makes) Photoepolymerizationinitiater initiater 0.586 mass parts (TAZ-107 (trihalomethyl group triazine-Ji Photoepolymerizationinitiater initiater); By Midori Kagaku Co., Ltd. makes)

2. preparing the silicon wafer substrate with undercoat heats 6 inches silicon wafers 30 minutes in 200 ℃ stove.Resist liquid is coated on the silicon wafer so that the dry thickness of 2 μ m to be provided, then in 220 ℃ stove heating and dry 1 hour to form undercoat.As a result, obtain to have the silicon wafer substrate of undercoat.

3. prepare compound and the dissolving of painted photopolymerisable compositions B-1, contain the painted photopolymerisable compositions B-1 of colorant (dyestuff) with formation following composition B-1.

Monomer (polymerizable compound) 7.0 mass parts (pentaerythritol triacrylate and dipentaerythritol acrylate (3: 7) potpourri) compound 31 (novel oxime compound) 2.5 mass parts propoxylated glycerols 0.5 mass parts (the number-average molecular weight Mn:1 of composition B-1 cyclohexanone 80 mass parts colorant C.I. Blue VRSs 08 7.5 mass parts colorant C.I. solvent yellow 16s 2 2.5 mass parts free redical polymerizations; 500, molar absorptivity ε=0)

4. the evaluation of painted photopolymerisable compositions B-1 (coating fluid) storage stability after 1 month, is visually being estimated the deposition degree of material in room temperature storage with painted photopolymerisable compositions B-1 according to following standard.The result is shown in Table 11.A: do not observe deposition; B: observe deposition slightly; C: observe deposition.

5. use painted photopolymerisable compositions B-1 to prepare color filter and estimate the painted photopolymerisable compositions B-1 for preparing in the 3rd part is coated on the undercoat of the silicon wafer substrate with undercoat that obtains in the part 2, form the light solidity and film.To film then with 100 ℃ electric hot plate heating (prebake) 120 seconds, so that the dry thickness of 0.9 μ m to be provided.Use i-line stepping exposure system (trade name: FPA-3000i5+, by Cannon Inc. make) then, with 10 to 1,600mJ/cm ²Exposure in the scope through having the mask of the square island of 2 μ m pattern, uses wavelength as the light of 365nm this film to be made public.The silicon wafer substrate of filming that will have then behind the irradiation is installed in rotary spray developing machine (trade name: Model DW-30; By Chemitronics Co.; Ltd. horizontal rotating table manufacturing); And carry out the oar formula with CD-2000 (by Fuji Film Electronics Materials Co., Ltd. makes) at 23 ℃ and developed 60 seconds, on silicon wafer substrate, to form colored pattern.

The silicon wafer substrate that will have colored pattern through vacuum cup is fixed on the horizontal rotating table.Use nozzle, colored pattern is used from the pure water spray irrigation of rotation center top supply, simultaneously through the revolution rotation silicon wafer substrate of spinner, then with colored pattern spraying-drying with 50rpm.As a result, obtain to comprise substrate and the color filter that forms colored pattern above that.

95% minimum exposure amount when above that the size of exposure sensitivity and pattern will be in step of exposure becomes film thickness (100%) before the exposure with thickness after the development in the zone of photoirradiation is evaluated as the exposure requirement.The more little expression sensitivity of exposure requirement is high more.In the method, use linear measure longimetry SEM (trade name: S-9260A is made by HitachiHigh-Technologies Corporation) to measure the size of colored pattern.Pattern dimension near 2 μ m shows that abundant curing and sensitivity are high more more.The result is shown in Table 11.

Development property, through heat ageing painted, with the shape of cross section of the adhesion of substrate and pattern according to method that adopts among the embodiment 5-1 and standard, estimate development property, through heat ageing painted, with the adhesion of substrate and the shape of cross section of pattern.The result is shown in the following table 11.

Embodiment 6-2 to 6-9 and comparative example 6-1 to 6-4 prepare painted photopolymerisable compositions B-2 to B-9 and B '-1 to B '-4 and color filter with the mode identical with embodiment 6-1; Difference is; 2.5 mass parts compounds 31 (novel oxime compound) among the composition B-1 that every kind of compound of amount shown in the use table 11 replaces in the painted photopolymerisable compositions B-1 of preparation, using, and in embodiment 6-9, further add the sensitizer and the auxiliary sensitizer of kind shown in the table 11 and amount.Also estimate with the mode identical with embodiment 6-1.The result is shown in Table 11.

Sensitizer A3 shown in the table 11 and auxiliary sensitizer F3 are above-mentioned compounds.

Embodiment 6-10 contains the painted photopolymerisable compositions C-1 of colorant (pigment) with compound and the dissolving of combinations thing C-1 with formation.

Composition C-13-ethoxyl ethyl propionate (solvent) 17.9 mass parts colorants: dispersion liquid 26.7 mass parts of C.I. paratonere 254 (solid content: 15 quality %; Pigment content in the solid: colorant 60%): dispersion liquid 17.8 mass parts of C.I. pigment yellow 13 9 (solid content: 15 quality %, the pigment content in the solid: the monomer of free redical polymerization (polymerizable compound) 3.5 mass parts (pentaerythritol triacrylate and dipentaerythritol acrylate (3: 7) potpourri) compound 31 (novel oxime compound) 0.5 mass parts benzyl methacrylate/methacrylic acid copolymer, 2.0 mass parts (mol ratio is 70/30) 60%)

Embodiment 6-11 to 6-20 and comparative example 6-5 to 6-8 prepare painted photopolymerisable compositions C-2 to C-11 and C '-1 to C '-4 with the mode identical with embodiment 6-10; Difference is; 0.5 mass parts compound 31 (novel oxime compound) among the composition C-1 that every kind of compound of the amount shown in the table 12 replaces in the painted photopolymerisable compositions C-1 of preparation, using below using, and further add the sensitizer and the auxiliary sensitizer of kind shown in the table 12 and amount in each at embodiment 6-18 to 6-20.

Estimate the painted photopolymerisable compositions that each obtains with the mode identical with embodiment 6-1.The result is shown in Table 12.

Sensitizer A1 shown in the table 12 and A3 and auxiliary sensitizer F2 and F3 are above-claimed cpds.

Embodiment 6-21 contains the painted photopolymerisable compositions D-1 of colorant (pigment) with following compound and the dissolving that is used for composition D-1 with formation.

Composition D-13-ethoxyl ethyl propionate (solvent) 17.9 mass parts colorants: dispersion liquid 33.34 mass parts of C.I. paratonere 254 (solid content: 15 quality %; Pigment content in the solid: colorant 60%): dispersion liquid 22.23 mass parts of C.I. pigment yellow 13 9 (solid content: 15 quality %, the pigment content in the solid: the monomer of free redical polymerization (polymerizable compound) 2.5 mass parts (pentaerythritol triacrylate and dipentaerythritol acrylate (3: 7) potpourri) compound 31 (novel oxime compound) 0.5 mass parts benzyl methacrylate/methacrylic acid copolymer, 2.0 mass parts (mol ratio is 70/30) 60%)

Embodiment 6-22 to 6-28 and comparative example 6-9 to 6-12 prepare painted photopolymerisable compositions D-2 to D-8 and D '-1 to D '-4 with the mode identical with embodiment 6-21; Difference is, uses the 0.5 mass parts compound 31 (novel oxime compound) among the composition D-1 that every kind of compound shown in the following table 13 of 0.5 mass parts replaces in the painted photopolymerisable compositions D-1 of preparation, using.

Estimate every kind of painted photopolymerisable compositions that obtains with the mode identical with embodiment 6-1.The result is shown in Table 13.

Table 11 shows that the painted photopolymerisable compositions that contains each embodiment of novel oxime compound (each in the compound 31 to 38) has high storage stability (stability in time) to 13 result.Also be apparent that; These painted photopolymerisable compositions have high sensitivity when exposure; In forming the process of color filter, has high development property with colored pattern; And form colored pattern with excellent and adhesion substrate and excellent shape of cross section, and in time painted in heating process not.Table 13 shows that also even when pigment content is high relatively, the composition of each embodiment still has the high sensitivity when exposure.

Embodiment 7-1 to 7-7 and comparative example 7-1 and 7-3 prepare the water slurry granulation of the surface of the carrier aluminium that 0.30mm is thick (1S level) sheet with nylon bruss (No.8) and 800 order float stones, and water fully washs then.With aluminium flake through with it after the etching in 60 seconds of 10% sodium hydrate aqueous solution of 70 ℃ dipping, it is washed with flowing water, use 20%HNO then ₃Solution neutralizes and uses water washing.Then in 1% aqueous solution of nitric acid under following condition with the surperficial electrolysis roughening of aluminium flake: at VA=12.7V, apply sinusoidal ac, the anode electric weight is 300C/dm ²Through measuring, the surfaceness that obtains is 0.45 μ m (in Ra).Subsequently, with the 30%H of aluminium flake at 55 ℃ ₂SO ₄Flood 2 minutes in the WS with decontamination (desmutting).Then with the 20%H of aluminium flake at 33 ℃ ₂SO ₄In the WS at 5A/dm ²Current density under anodization 50 seconds, wherein negative electrode is placed on the granulation surface, thus formation thickness is 2.7g/m ²Anodization layer.As a result, obtain original edition of lithographic printing plate and use carrier.

The photosensitive layer coating liquid that the formation photographic layer will have following composition is coated on the carrier that obtains so that 1.4g/m to be provided ²Drying coated amount and 95 ℃ of dryings, form photographic layer.

Photosensitive layer coating liquid forms that but compound (compound shown in the following table 14) 0.80 mass parts binder polymer (compound shown in the following table 14) the 0.90 mass parts sensitizer (compound shown in the following table 14) of addition polymerization does not have or the special oxime compound of 0.10 mass parts or the auxiliary sensitizer (compound shown in the following table 14) of comparative compound (compound shown in the following table 14) 0.05 mass parts do not have or 0.25 mass parts fluorine surfactant, 0.02 mass parts (Magafac F-177 (trade name); By Dainippon Ink and Chemicals, Incorporated makes) thermal polymerization inhibitor 0.03 mass parts (N-nitrosohydroxylamines aluminium salt) ε class copper phthalocyanine dispersion 0.2 mass parts methyl ethyl ketone 16.0 mass parts propylene glycol monomethyl ethers 16.0 mass parts

The formation protective seam is coated to the WS of 3 quality % polyvinyl alcohol (PVA) (saponification degree is 98 moles of %, and the degree of polymerization is 550) on the photographic layer that obtains, so that 2g/m to be provided ²Drying coated quality and 100 ℃ of dryings 2 minutes, form protective seam.

As above-mentioned process result, obtain the original edition of lithographic printing plate of embodiment and comparative example respectively.

Plate-making is carried out exposure-processed described below and development treatment to each original edition of lithographic printing plate.

Exposure use 405nm (wavelength) ultraviolet LD (trade name: Violet Boxer, make by FFEI Ltd.), at 50 μ J/cm ²Exposure, 4, under the condition of 000dpi and 175 line/inches original edition of lithographic printing plate is carried out scan exposure to solid images (solid image) and 1-99% dot image (being spaced apart 1%).

Developer 1 shown in below the use of developing is equipped with and arrangement (finishing) gummy liquid (trade name: FP-2W; Make by FUJIFILM Corporation) automatic processor (trade name: LP-850P2 is made by FUJIFILMCorporation) carry out standard program.Reach on the sheet surface under 100 ℃ the condition and preheat.The developer temperature is 30 ℃, and the time of in developer, flooding is about 15 seconds.

Developer 1 have below shown in composition, 25 ℃ pH be 11.5 and conductivity be 5mS/cm.

Composition potassium hydroxide 0.15g polyoxyethylene phenyl ether (n=13) 5.0gCHELEST 400 (sequestrant) the 0.1g water 94.75g of developer 1

Estimate sensitivity and the storage stability of estimating original edition of lithographic printing plate through following method.The result gathers and is presented in the table 14.

1. the evaluation of sensitivity makes public original edition of lithographic printing plate under these conditions.After exposure, immediately galley is developed to form image under these conditions.Use some area measurement instrument (Gretag Macbeth) to measure the area of 50%-half tone dot.Numerical value shows that more greatly sensitivity is high more.

2. the test of image section printability resistance is used by the printing machine R201 (trade name) of Roland DG Corporation manufacturing with by DainipponInk and Chemicals, and " GEOS-G (N) " printing ink that Incorporated makes adopts the printing of said original edition of lithographic printing plate.Observe the solid images part of each printed matter, use the quantity of the printed matter that before image begins to fade, obtains, to confirm printability resistance.Numerical value shows that more greatly printability resistance is high more.

The evaluation of storage stability (variable quantity of forced aging) with each original edition of lithographic printing plate with the sealing of the plain pape of aluminium kraft and insertion and it was left standstill 4 days at 60 ℃.Afterwards, through with identical method measurement point area during sensitivity is estimated.Calculating after 60 ℃ leave standstill 4 days the some area and leave standstill the poor of some area before 4 days at 60 ℃, confirm the some area change (Δ %) of forced aging.The absolute value of this numerical value is more little, shows that the influence of forced aging is more little, and promptly stability is high more in time.

Above table 14 show that each the original edition of lithographic printing plate of embodiment 7-1 to 7-7 that in photographic layer, contains novel oxime compound of the present invention has high-caliber sensitivity, stability and printability resistance in time.On the contrary, comparative example 7-1 to 7-3 each original edition of lithographic printing plate sensitivity, stability and printability resistance all are lower than the sensitivity of the lithographic plate of embodiment, stability and printability resistance in time in time.

In table 14, sensitizer A1 to A3 and auxiliary sensitizer F2 and F3 are aforesaid compounds, and comparative compound LD-5 be 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.Structure shown in below polymerizable compound M, N and O shown in the table 14 and binder polymer B1, B2 and B3 have.

0 The following mixture of isomers?

Embodiment 8-1 to 8-24 and comparative example 8-1 to 8-16 prepare the black photopolymerisable compositions and prepare carbon black dispersion liquid A and with two rollers the composition 1 shown in following is carried out the high viscosity dispersion treatment, are 70 to form viscosity, the dispersion liquid of 000mPas.Then the composition 2 shown in following is joined in the dispersion liquid, with homogenizer with potpourri 3,000rpm stirred 3 hours.Adopt 0.3mm zirconia bead, in dispersion machine (trade name: DISPERMAT is made by Getzmann), the mixture solution that obtains carried out little-dispersion treatment 4 hours, with preparation carbon black dispersion liquid A (below be called CB dispersion liquid A).In this was handled, the viscosity of mixture solution was 37mPas.

Composition 1 average primary particle size is the carbon black (pigment black 7) of 15nm: 23 parts of benzyl methacrylate-methacrylic acid copolymer 45% solution (BzMA/MAA=70/30 in propylene glycol methyl ether acetate; Mw:30,000): 1.2 parts of 22 parts of SOLSPERSE 5000 (making) by Zeneca Ltd.

45% solution (the BzMA/MAA=70/30 of composition 2 benzyl methacrylates-methacrylic acid copolymer in propylene glycol methyl ether acetate; Mw:30,000): 22 parts of propylene glycol methyl ether acetates: 200 parts

Preparation black oxidation titanium dispersion liquid A uses two rollers that the composition 3 shown in following is carried out the high viscosity dispersion treatment, is 40 to form viscosity, the 000mPas dispersion liquid.Randomly can use the kneading 30 minutes of kneader before the high viscosity dispersion treatment.

Composition 3 average primary particle size are the black oxidation titanium 13M-C (pigment black 35 of 75nm; Make by Mitsubishi MaterialsCorporation): 39 parts of (methyl) benzyl acrylate-(methyl) acrylic copolymer solution (BzMA/MAA=70/30 in propylene glycol methyl ether acetate; Mw:30; 000, solid content: 40 quality %): 8 parts of SOLSPERSE 5000 (making): 1 part by Zeneca Ltd.

Then the composition shown in following 4 is added in the dispersion liquid that obtains, with homogenizer with potpourri 3,000rpm stirred 3 hours.Adopt 0.3mm zirconia bead, in the dispersion machine (trade name: DISPERMAT is made by Getzmann) mixture solution that obtains carried out little-dispersion treatment 4 hours with preparation black oxidation titanium dispersion liquid A (below be called TB dispersion liquid A).In this was handled, the viscosity of mixture solution was 7.0mPas.

Composition 4 (methyl) benzyl acrylate-solution (BzMA/MAA=70/30 of (methyl) acrylic copolymer in propylene glycol methyl ether acetate; Mw:30; 000, solid content: 40 quality %): 8 parts of propylene glycol methyl ether acetates: 200 parts

Preparation black photopolymerisable compositions E-1 to E-24 and E '-1 mix the component that is used for composition E-a shown in following to E '-16 at mixer, with each to the E '-8 of formation black photopolymerisable compositions E-1 to E-14 and E '-1.

Composition E-a methacrylate-acrylic copolymer; (alkali soluble resins): 1.6 mass parts dipentaerythritol acrylates: the tetramethylol methane tetraacrylate of 2.3 mass parts ethoxyquins: CB dispersion liquid A below 0.8 mass parts shown in the table 15 or TB dispersion liquid A:24 mass parts propylene glycol methyl ether acetate: 10 mass parts ethyl-3-ethoxy-c acid esters: 8 mass parts novel oxime compounds; (compound shown in the table 15): the amount shown in the table 15 is assisted sensitizer; (F3 shown in top): do not have or 0.1 mass parts

The component that is used for composition E-b shown in following is mixed at stirrer, to form each to the E '-16 of black photopolymerisable compositions E-15 to E-24 and E '-9.

Composition E-b dipentaerythritol acrylate: CB dispersion liquid A below 2.3 mass parts shown in the table 16 or TB dispersion liquid A:24 mass parts propylene glycol methyl ether acetate: 10 mass parts ethyl-3-ethoxy-c acid esters: 8 mass parts novel oxime compounds; (compound shown in the table 16): the amount shown in the table 16 is assisted sensitizer; (F3 shown in top): do not have or 0.1 mass parts

Evaluation is described below the black photopolymerisable compositions E-1 to E-24 that obtains and E '-1 respectively to E '-16 and estimates.The result gathers and is shown in the table 15 and 16.

The evaluation of exposure sensitivity is confirmed through following method and is estimated black photopolymerisable compositions E-1 to E-24 and E '-1 to each exposure sensitivity of E '-16.

Use black photopolymerisable compositions E-1 to E-24 and E '-1 to the E '-16 each and through spin coating it evenly is coated on the silicon wafer, the rotational speed of controlling spin coating makes that the thickness of coating becomes 1.0 μ m after being to heat-treat 120 seconds on 120 ℃ the electric hot plate in surface temperature with coating.By i-line steeper (trade name: FPA-3000iS+, by Canon Inc. make), with at 10mJ/cm ²To 5,100mJ/cm ²Different exposures in the scope are through having the mask of 10nm L & S (line and space) pattern, the exposure of filming that the 1.0 μ m that obtain are thick.After the exposure, use the oar formula development treatment 60 seconds that 0.3% tetramethylammonium hydroxide (TMAH) WS carries out 23 ℃ to filming.Then through the rotary spray device, with this film with pure water rinsing 20 seconds and further wash with pure water.Afterwards, remove the water droplet of deposition with high-speed air, and with the substrate air dry, thereby the patterning image of acquisition black.According to following standard, each painted patterning image that obtains with the optics microscopic evaluation.

Measurement is evaluated as the exposure requirement with 95% minimum exposure amount when above that thickness after the development in the zone of photoirradiation becomes film thickness (100%) before the exposure in step of exposure.The more little expression sensitivity of exposure is high more.

Black photopolymerisable compositions E-1 to E-24 and in time stable (storage stability) of E '-1 that the evaluation of storage stability (stability) in time obtains through following method evaluation to E '-16.With black photopolymerisable compositions E-1 to E-24 and E '-1 to each comfortable room temperature storage of E '-16 after 1 month, visually estimate the deposition degree of material: A according to following standard: do not observe deposition; B: observe deposition slightly; C: observe deposition.

Black photopolymerisable compositions E-1 to E-24 that the evaluation of development property obtains through following method evaluation and E '-1 are to the development property of E '-16.Whether observation exists residue in the zone (unexposed portion) of the step of exposure photoirradiation of no use that is used for the sensitivity evaluation, to estimate development property.Estimate according to following standard: A: do not observe residue at unexposed portion; B: observe residue slightly at unexposed portion, but the residue level is in fact acceptable; C: obviously observe residue at unexposed portion.

Table 15 and 16 shows that the black photopolymerisable compositions that contains each embodiment of novel oxime compound has high storage stability (stability in time).Be apparent that also, compare that these black photopolymerisable compositions have the high sensitivity when exposure and the height development property of unexposed portion, even therefore adopt lower exposure also can form excellent black pattern (colored pattern) with comparative example.

Claims

1. photosensitive composite, described photosensitive composite comprise the compound by following formula (I-I) expression:

Wherein, in formula (I-I), R ¹Expression contains the acyl group of 2 to 20 carbon atoms, R ²Expression contains the alkyl of 1 to 20 carbon atom, and M representes divalent linker, and said divalent linker is a phenylene, naphthylene, and the phenylene carbonyl, the naphthylene carbonyl, the group (A) below perhaps, (B), (C) or (D),

At (A), (B), (C) with (D) in, X is a singly-bound ,-O-,-S-,-NR ⁵-or-CO-, and Y is-O--S-,-NR ⁵-,-CO-or-CH ₂-, R wherein ⁵Represent hydrogen atom, contain the alkyl of 1 to 20 carbon atom, contain the hydroxy alkyl of 2 to 4 carbon atoms, contain the alkoxyalkyl of 2 to 10 carbon atoms, contain the thiazolinyl of 2 to 5 carbon atoms, contain the naphthenic base of 3 to 8 carbon atoms, phenyl-C ₁To C ₃Alkyl contains the alkanoyl of 1 to 8 carbon atom, contains the enoyl-of 3 to 12 carbon atoms; Benzoyl, phenyl or naphthyl, each can be unsubstituted or substituted by following group for these groups: the alkyl of 1 to 12 carbon atom; Benzoyl or contain the alkoxy of 1 to 12 carbon atom

R ³And R ⁴Represent hydrogen atom independently of one another, alkoxy carbonyl group, cyanic acid or phenyl, and R ³And R ⁴Can mutually combine and form five-, six-or seven-first aliphatic series or aromatic hydrocarbon ring or contain heteroatomic heterocycle, and these rings can combine to form polycyclic fused ring,

Perhaps comprise compound by following formula (I-II) expression:

Wherein, in formula (I-II), R ¹, R ²Definition and the middle R of formula (I-I) with M ¹, R ²Identical with the definition of M, and Ar ¹Be in the group shown in following any, wherein, symbol * is illustrated in the formula (I-II) and Ar ¹The position of adjacent two keys:

2. curable compositions, described curable compositions comprise by the compound of following formula (I-I) expression or by the compound and the polymerizable compound of following formula (I-II) expression:

3. the described curable compositions of claim 2, said curable compositions also comprises sensitizer.

4. the described curable compositions of claim 2, said curable compositions also comprises mercaptan compound.

5. the described curable compositions of claim 2, said curable compositions also comprises colorant.

6. curable compositions that is used for color filter, the said curable compositions that is used for color filter comprises the described curable compositions of claim 5.

7. color filter, said color filter comprises the colored pattern that is arranged on the carrier, and wherein said colored pattern is to use claim 6 described curable compositions preparation.

8. method for preparing color filter, said method comprises:

The described curable compositions of claim 6 is coated on the carrier to form the curable compositions layer;

Said curable compositions layer is passed through mask exposure; With

The composition layer of exposure is developed to form colored pattern.