CN107614485A - Oxime ester compound and the polymerization initiator containing the compound - Google Patents

Oxime ester compound and the polymerization initiator containing the compound Download PDF

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CN107614485A
CN107614485A CN201680030952.5A CN201680030952A CN107614485A CN 107614485 A CN107614485 A CN 107614485A CN 201680030952 A CN201680030952 A CN 201680030952A CN 107614485 A CN107614485 A CN 107614485A
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cycloalkyl
alkyl
aralkyl
carbon
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柳泽智史
伊香贺贵之
竹内良智
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Adeka Corp
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Asahi Denka Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/56—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation

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Abstract

A kind of oxime ester compound, it is represented by following logical formula (I)s, and the R in following logical formula (I)s1、R2、R3、R4、R5、R6、R7、R8、R9And R10In it is at least one be group represented by following logical formula (II)s.Above-mentioned oxime ester compound preferably comprises the group represented by 2 formula above (II).It is also preferred that the R in following logical formula (I)s6、R7、R8、R9And R10In it is at least one be COR13。

Description

Oxime ester compound and the polymerization initiator containing the compound
Technical field
The present invention relates to the new oxime ester compound useful as the polymerization initiator used in polymerizable composition, polymerizable composition, contain There is the polymerization initiator of above-mentioned oxime ester compound, make to be formed containing ethylenically unsaturated compounds in above-mentioned polymerization initiator Polymerizable composition, polymerizable composition, make the coloured polymerized composition that is further formed in above-mentioned polymerizable composition, polymerizable composition containing colorant and by Above-mentioned polymerizable composition, polymerizable composition or above-mentioned coloured polymerized composition and the solidfied material obtained.
Background technology
Polymerizable composition, polymerizable composition is to be added in ethylenically unsaturated compounds obtained from polymerization initiator, by irradiating energy Ray (light) is measured, its polymerizing curable can be made, thus available for light curable inks, photosensitive printing version, various photoresists Agent etc..
As the polymerization initiator for above-mentioned polymerizable composition, polymerizable composition, propose in patent document 1~4 and be esterified using oxime Compound.
But in the oxime ester compound described in patent document, the gratifying oxime ester compound of sensitivity energy is in general Dissolubility in solvent or polymerizable composition, polymerizable composition is low, exist polymerization initiator in polymerizable composition, polymerizable composition for low concentration, solvent and The species or amount of polymerizable compound, which are restricted etc., has the problem of limitation in the design of polymerizable composition, polymerizable composition.In addition, deposit In following problem：The sensitivity of the high oxime ester compound of solubility in general solvent or polymerizable composition, polymerizable composition not can be very It is satisfactory.
Prior art literature
Patent document
Patent document 1：US6596445(B1)
Patent document 2：US2006/241259(A1)
Patent document 3：US2004/170924(A1)
Patent document 4：US2011/170209(A1)
The content of the invention
Up to the present the problem to be solved in the present invention is also without high sensitivity and the high polymerization initiator of dissolubility.
Therefore, it is useful it is an object of the present invention to provide the polymerization initiator high as high sensitivity, dissolubility new Compound and the polymerization initiator and polymerizable composition, polymerizable composition for having used the compound.
The present invention is by providing the new oxime ester compound and gathering containing the oxime ester compound that following logical formula (I)s represent Initiator is closed, realizes above-mentioned purpose.
(in formula, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12(R is also recited as below1~R12) independently Ground represents group, hydrogen atom, halogen atom, nitro, cyano group, hydroxyl, carboxyl, the R represented by following logical formula (II)s13、OR13、 SR13、NR14R15、COR13、SOR13、SO2R13Or CONR14R15,
R13、R14And R15Separately represent the cycloalkanes that alkyl, carbon number that carbon number is 1~20 are 3~20 The aralkyl that aryl that cycloalkyl-alkyl that base, carbon number are 4~20, carbon number are 6~20, carbon number are 7~20 Or carbon number is 2~20 to contain heterocyclic radical,
R13、R14And R15Cycloalkyl that alkyl that represented carbon number is 1~20, carbon number are 3~20, carbon are former The aralkyl or carbon atom that aryl that cycloalkyl-alkyl that subnumber is 4~20, carbon number are 6~20, carbon number are 7~20 The hydrogen atom containing heterocyclic radical that number is 2~20 is sometimes by halogen atom, nitro, cyano group, hydroxyl, amino, carboxyl, methacryl Base, acryloyl group, epoxy radicals, vinyl, vinyl ether, sulfydryl, NCO substitute, R containing heterocyclic radical13、R14And R15Institute The cycloalkyl alkane that cycloalkyl that alkyl that the carbon number of expression is 1~20, carbon number are 3~20, carbon number are 4~20 The aralkyl or carbon number that base, carbon number are 7~20 be 2~20 containing the methylene in heterocyclic radical sometimes also by-O- ,- CO-、-COO-、-OCO-、-NR16-、-NR16CO-、-S-、-CS-、-SO2- ,-SCO- ,-COS- ,-OCS- or-CSO- substitution,
R16Represent that cycloalkyl, carbon number that alkyl, carbon number that hydrogen atom, carbon number are 1~20 are 3~20 are The aralkyl that the aryl or carbon number that 4~20 cycloalkyl-alkyl, carbon number are 6~20 are 7~20,
Ring A1And ring A2Condense and form the aromatic rings that carbon number is less than 30,
R1、R2、R3、R4、R5、R6、R7、R8、R9And R10(R is also recited as below1~R10) in it is at least one be following formulas (II) group represented by,
M is A1Positive integer below the quantity of desirable substituent,
During m >=2, multiple R11It is sometimes each different,
N is A2Positive integer below the quantity of desirable substituent,
During n >=2, multiple R12It is sometimes each different,
R1And R2、R2And R3、R3And R4、R4And R5、R6And R7、R7And R8、R8And R9、R9And R10、R11And R12Sometimes also it is bonded And ring is formed, R during m >=211And R11Sometimes also it is bonded and forms ring, R during n >=212And R12Sometimes also it is bonded and forms ring.)
(in formula, R17And R18It is 1~20 separately to represent hydrogen atom, halogen atom, nitro, cyano group, carbon number Alkyl, carbon number be 3~20 cycloalkyl, carbon number be 4~20 cycloalkyl-alkyl, carbon number be 6~20 The aralkyl or carbon number that aryl, carbon number are 7~20 are 2~20 to contain heterocyclic radical,
R17And R18Cycloalkyl that alkyl that represented carbon number is 1~20, carbon number are 3~20, carbon number The aralkyl or carbon number that the aryl for being 6~20 for 4~20 cycloalkyl-alkyl, carbon number, carbon number are 7~20 be 2~20 hydrogen atom containing heterocyclic radical sometimes by halogen atom, nitro, cyano group, hydroxyl, amino, carboxyl, methylacryloyl, Acryloyl group, epoxy radicals, vinyl, vinyl ether, sulfydryl, NCO substitute, R containing heterocyclic radical17And R18Represented Cycloalkyl-alkyl that cycloalkyl that alkyl that carbon number is 1~20, carbon number are 3~20, carbon number are 4~20, carbon The aralkyl or carbon number that atomicity is 7~20 be 2~20 containing the methylene in heterocyclic radical sometimes also by-O- ,-CO- ,- COO-、-OCO-、-NR19-、-NR19CO-、-S-、-CS-、-SO2- ,-SCO- ,-COS- ,-OCS- or-CSO- substitution,
R19Represent that cycloalkyl, carbon number that alkyl, carbon number that hydrogen atom, carbon number are 1~20 are 3~20 are The aralkyl that the aryl or carbon number that 4~20 cycloalkyl-alkyl, carbon number are 6~20 are 7~20,
K represents 0 or 1.)
In addition, the present invention provides a kind of polymerizable composition, polymerizable composition, it contains above-mentioned polymerization initiator and ethylenic unsaturationization Compound.
In addition, the present invention provides a kind of coloured polymerized composition, it is to make further to contain in above-mentioned polymerizable composition, polymerizable composition There is colorant and formed.
In addition, the present invention provides a kind of solidfied material, it is by above-mentioned polymerizable composition, polymerizable composition or above-mentioned coloured polymerized composition And obtain.
Embodiment
Hereinafter, the oxime ester compound of the present invention and the polymerization containing the oxime ester compound are drawn according to preferred embodiment Hair agent is described in detail.
The oxime ester compound of the present invention is the new compound that above-mentioned logical formula (I) represents.In the oxime ester compound, because of oxime Double bond and geometric isomer be present, but they are not distinguished.
I.e., in this manual, the compound and its exemplary compounds that above-mentioned logical formula (I) represents represent both mixtures Or any one party, however it is not limited to represent the structure of isomers.
As the R in above-mentioned logical formula (I), (II) and logical formula (III) described later13~R19The carbon number of expression is 1~20 Alkyl, such as can enumerate methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, isopentyl, Tertiary pentyl, hexyl, heptyl, octyl group, iso-octyl, 2- ethylhexyls, t-octyl, nonyl, isononyl, decyl, isodecyl, hendecane Base, dodecyl, myristyl, cetyl, octadecyl and eicosyl etc..
R in so-called above-mentioned logical formula (I), (II) and logical formula (III) described later13~R19The carbon number of expression is 3~20 Cycloalkyl, refer to saturation monocyclic or saturation polycycle alkyl with 3~20 carbon atoms, for example, can enumerate cyclopropyl, Cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydro naphthyl, octahydro and ring penta Diene and bicyclic [1.1.1] amyl group etc..
R in so-called above-mentioned logical formula (I), (II) and logical formula (III) described later13~R19The carbon number of expression is 4~20 Cycloalkyl-alkyl, refer to the group with 4~20 carbon atoms that the hydrogen atom of alkyl is substituted by cycloalkyl to obtain.Such as can Enumerate Cvclopropvlmethvl, CYCLOBUTYLETHYL, cyclopentyl-methyl, cyclopentyl ethyl, cyclopentylpropyi, cyclohexyl methyl, cyclohexyl Ethyl, cyclohexylbutyl, CycloheptylmethyI, cyclooctyl methyl, cyclononyl ethyl, cyclodecyl ethyl, adamantyl propyl group and ten Hydrogen naphthylpropyl etc..
As the R in above-mentioned logical formula (I), (II) and logical formula (III) described later13~R19The carbon number of expression is 6~20 Aryl, such as phenyl, tolyl can be enumerated, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, by abovementioned alkyl substitute 1 Phenyl, xenyl, naphthyl, anthryl more than individual etc..
As the R in above-mentioned logical formula (I), (II) and logical formula (III) described later13~R19The carbon number of expression is 7~30 Aralkyl, such as benzyl, α-methylbenzyl, alpha, alpha-dimethylbenzyl, phenylethyl and naphthylpropyl etc. can be enumerated.
As the R in above-mentioned logical formula (I), (II) and logical formula (III) described later13~R15、R17And R18The carbon number of expression Contain heterocyclic radical for 2~20, such as pyrrole radicals, pyridine radicals, pyridyl-ethyl group, pyrimidine radicals, pyridazinyl, piperazinyl, piperazine can be enumerated Piperidinyl, pyranose, pyranose ethyl, pyrazolyl, triazine radical, triazine ylmethyl, pyrrolidinyl, quinolyl, isoquinolyl, imidazoles Base, benzimidazolyl, triazolyl, furyl (furyl), furyl (furanyl), benzofuranyl, thienyl (thienyl), thienyl (thiophenyl), benzothienyl, thiadiazolyl group, thiazolyl, benzothiazolyl, oxazolyls, benzene And oxazolyl, isothiazolyl, isoxazolyl, indyl, long Luo Lidingji, morpholinyl, thio-morpholinyl, 2-Pyrrolidone -1- Base, 2- piperidones -1- bases, the epoxide imidazolidine -3- bases of 2,4- bis- and the oxygen base oxazolidine -3- bases of 2,4- bis- etc..
In above-mentioned logical formula (I), R1And R2、R2And R3、R3And R4、R4And R5、R6And R7、R7And R8、R8And R9、R9And R10Have When be also bonded and form ring,
Multiple R during m >=211Also it is bonded sometimes each other and forms ring,
Multiple R during n >=212Also it is bonded sometimes each other and forms ring,
In addition, the R in logical formula (III) described later1And R2、R2And R3、R3And R4、R4And R5、R6And R7、R7And R8、R8And R9、 R9And R10、R20And R21、R22And R23、R23And R24And R24And R25Sometimes also it is bonded and forms ring,
As such ring, pentamethylene ring, cyclohexane ring, cyclopentene ring, phenyl ring, pyrrolidine ring, pyrrole ring, piperazine can be enumerated 5~7 yuan of rings such as piperazine ring, piperidine ring, morpholine ring, thiomorpholine ring, tetrahydro pyridine ring, lactonic ring, lactam nucleus and naphthalene nucleus, anthracene nucleus Deng condensed ring etc..
Ring A1And ring A2Condense and form the aromatic rings that carbon number is less than 30.
As ring A1And ring A2, can separately enumerate phenyl ring, non-phenyl ring aromatic backbone, heteroaromatic skeleton with And ring A1And ring A2Condense and turn into the skeleton of aromatic rings.
As the ring A in above-mentioned logical formula (I)1And ring A2Represented non-benzene aromatic backbone, can include such as ring fourth two Alkene, cyclo-octatetraene and tropone etc..
As the ring A in above-mentioned logical formula (I)1And ring A2Represented heteroaromatic skeleton, can include such as furans, Thiophene, pyrroles, pyrazoles, imidazoles, triazole, pyridine, pyridazine, pyrimidine and pyrazine etc..
As the ring A in above-mentioned logical formula (I)1And ring A2Condense as the skeleton of aromatic rings, azulenes etc. can be enumerated.
Ring A is included as in above-mentioned logical formula (I)1And ring A2Condensed ring preferred concrete example, following condensed ring can be enumerated No.1~No.107, from the few aspect of oxime ester compound excellent in stability and coloring, more preferably condensed ring No.1~No.16. But, the present invention is not by any restrictions of following condensed ring.
As the R that can substitute in above-mentioned logical formula (I), (II) and logical formula (III) described later1~R12、R17And R18And R in above-mentioned logical formula (I), (II) and logical formula (III) described later13~R15、R17And R18Hydrogen atom halogen atom, can enumerate Fluorine, chlorine, bromine, iodine.
Oxime ester compound represented by above-mentioned logical formula (I) comprising the group represented by 2 formula above (II) as It is high sensitivity during polymerization initiator, it is advantageous to.
R in logical formula (I)6、R7、R8、R9And R10In it is at least one be COR13Oxime ester compound as polymerization trigger It is high sensitivity during agent, it is advantageous in R13For phenyl when, absorbing wavelength is good and resulting during as polymerization initiator consolidates The transparency of compound uprises, so more preferably.
R in logical formula (I)1、R2、R3、R4、R5And R11In it is at least one be oxime ester compound represented by logical formula (II) It is easy to manufacture, and the excellent in stability of oxime ester compound, it is advantageous to.
In the oxime ester compound of the present invention, lead to the compound sensitivity height that formula (III) represents, dissolubility is high, easy to manufacture, institute With preferred.
(in formula, R1~R10、R20、R21、R22、R23、R24And R25Separately represent group represented by logical formula (II), Hydrogen atom, halogen atom, nitro, cyano group, hydroxyl, carboxyl, R13、OR13、SR13、NR14R15、COR13、SOR13、SO2R13Or CONR14R15,
R13、R14And R15Separately represent the cycloalkanes that alkyl, carbon number that carbon number is 1~20 are 3~20 The aralkyl that aryl that cycloalkyl-alkyl that base, carbon number are 4~20, carbon number are 6~20, carbon number are 7~20 Or carbon number is 2~20 to contain heterocyclic radical,
R13、R14And R15Cycloalkyl that alkyl that represented carbon number is 1~20, carbon number are 3~20, carbon are former The aralkyl or carbon atom that aryl that cycloalkyl-alkyl that subnumber is 4~20, carbon number are 6~20, carbon number are 7~20 The hydrogen atom containing heterocyclic radical that number is 2~20 is sometimes by halogen atom, nitro, cyano group, hydroxyl, amino, carboxyl, methacryl Base, acryloyl group, epoxy radicals, vinyl, vinyl ether, sulfydryl, NCO substitute, R containing heterocyclic radical13、R14And R15Institute The cycloalkyl alkane that cycloalkyl that alkyl that the carbon number of expression is 1~20, carbon number are 3~20, carbon number are 4~20 The aralkyl or carbon number that base, carbon number are 7~20 be 2~20 containing the methylene in heterocyclic radical sometimes also by-O- ,- CO-、-COO-、-OCO-、-NR16-、-NR16CO-、-S-、-CS-、-SO2- ,-SCO- ,-COS- ,-OCS- or-CSO- substitution,
R16Represent that cycloalkyl, carbon number that alkyl, carbon number that hydrogen atom, carbon number are 1~20 are 3~20 are The aralkyl that the aryl or carbon number that 4~20 cycloalkyl-alkyl, carbon number are 6~20 are 7~20,
R1~R10In it is at least one be group represented by logical formula (II),
R17And R18Separately represent hydrogen atom, halogen atom, nitro, cyano group, carbon number be 1~20 alkyl, Aryl that cycloalkyl-alkyl that cycloalkyl that carbon number is 3~20, carbon number are 4~20, carbon number are 6~20, carbon The aralkyl or carbon number that atomicity is 7~20 are 2~20 to contain heterocyclic radical,
R17And R18Cycloalkyl that alkyl that represented carbon number is 1~20, carbon number are 3~20, carbon number The aralkyl or carbon number that the aryl for being 6~20 for 4~20 cycloalkyl-alkyl, carbon number, carbon number are 7~20 be 2~20 hydrogen atom containing heterocyclic radical sometimes by halogen atom, nitro, cyano group, hydroxyl, amino, carboxyl, methylacryloyl, Acryloyl group, epoxy radicals, vinyl, vinyl ether, sulfydryl, NCO, carboxyl substitute, R containing heterocyclic radical17And R18Institute The cycloalkyl alkane that cycloalkyl that alkyl that the carbon number of expression is 1~20, carbon number are 3~20, carbon number are 4~20 The aralkyl or carbon number that base, carbon number are 7~20 be 2~20 containing the methylene in heterocyclic radical sometimes also by-O- ,- CO-、-COO-、-OCO-、-NR19-、-NR19CO-、-S-、-CS-、-SO2- ,-SCO- ,-COS- ,-OCS- or-CSO- substitution,
R19Represent that cycloalkyl, carbon number that alkyl, carbon number that hydrogen atom, carbon number are 1~20 are 3~20 are The aralkyl that the aryl or carbon number that 4~20 cycloalkyl-alkyl, carbon number are 6~20 are 7~20,
R1And R2、R2And R3、R3And R4、R4And R5、R6And R7、R7And R8、R8And R9、R9And R10、R20And R21、R22And R23、R23 And R24And R24And R25Sometimes also it is bonded and forms ring,
K represents 0 or 1.)
By the R in logical formula (III)8For COR13And R13For aromatic hydrocarbyl or the oxime ester compound of aromatic heterocycle It is high sensitivity during as polymerization initiator, it is advantageous to by R13When being used as polymerization initiator for the oxime ester compound of phenyl, Absorbing wavelength is good, and the transparency of the solidfied material of gained uprises, so more preferably.
R in logical formula (III)3To lead to, the synthesis of the oxime ester compound of the group represented by formula (II) is easy and stability is good It is good, it is advantageous to.
As the preferable concrete example of the oxime ester compound of the invention represented by above-mentioned logical formula (I), can enumerate following Compound N o.1~No.181.From synthesis easily, stability is high, polymerization initiator as polymerizable composition, polymerizable composition when sensitivity it is high, Absorbing wavelength is good, and the transparent high aspect of the solidfied material of gained is set out, the chemical combination represented by more preferably logical formula (III) Thing No.1~No.36.But the present invention is not by any restrictions of following compound.
In the oxime ester compound of the invention represented by above-mentioned logical formula (I), in formula, R3To lead to the change represented by formula (II) The synthetic method of compound is not particularly limited, but in k=0, the reaction equation according to following [changing 26] can be included, by following The method that is synthesized of method.
That is, by making known commercially available secondary amine compound be reacted with halogenated aryl to obtain tertiary amine compound, by making Tertiary amine compound and acyl chloride reaction and obtain assimilation compound 1, closed by making assimilation compound 1 be reacted with hydroxylamine hydrochloride to obtain oximate Thing 1.Then, by being reacted oxime compound 1 and acid anhydrides or acyl chlorides, obtain of the invention represented by above-mentioned logical formula (I) Oxime ester compound 1.
In the oxime ester compound of the invention represented by above-mentioned logical formula (I), in formula, R1、R2、R4、R5、R6、R7、R8、R9、 R10、R11And R12It can also be carried out according to the method described above with leading to the synthesis for the compound that formula (II) represents.
Oxime compound and oxime ester compound can also use the method system described in No. 4223071 publications of Japan Patent Make.
[changing 26]
(in formula, R1、R2、R4、R5、R6、R7、R8、R9、R10、R11、R12、R17、R18、A1And A2With above-mentioned logical formula (I) and (II) It is identical.)
In the oxime ester compound of the invention represented by above-mentioned logical formula (I), in formula, R3To lead to the change represented by formula (II) The synthetic method of compound is not particularly limited, but in k=1, the reaction equation according to following [changing 27] can be included, by following The method that is manufactured of method.
That is, by making known commercially available secondary amine compound be reacted with halogenated aryl to obtain tertiary amine compound, by making Tertiary amine compound and acyl chloride reaction and obtain assimilation compound 2, by making assimilation compound 2 be reacted with isobutyl nitrite to obtain oxime Compound 2.Then, by being reacted oxime compound 2 and acid anhydrides or acyl chlorides, this hair represented by above-mentioned logical formula (I) is obtained Bright oxime ester compound 2.
In the oxime ester compound of the invention represented by above-mentioned logical formula (I), in formula, R1、R2、R4、R5、R6、R7、R8、R9、 R10、R11And R12It can also be carried out according to the method described above with leading to the synthesis for the compound that formula (II) represents.
Oxime compound and oxime ester compound can also use the method system described in No. 4223071 publications of Japan Patent Make.
[changing 27]
(in formula, R1、R2、R4、R5、R6、R7、R8、R9、R10、R11、R12、R17、R18、A1And A2With above-mentioned logical formula (I) and (II) It is identical.)
The new oxime ester compound of present invention mentioned above triggers as radical polymerization initiator, particularly photopolymerization Agent or thermal polymerization are useful.In addition, the new oxime ester compound of the present invention can also be suitable as generated base alkaline agent and increasing Feel agent.
The oxime ester compound of the present invention can be together used in combination by the polymerization initiator of the present invention with other polymerization initiators.As Can and other polymerization initiators, previously known compound can be used, for example, can include benzophenone, phenyl connection Benzophenone, 1- hydroxyl -1- 2-benzoyl-cyclohexanes, benzoin, benzil dimethyl ketal, 1- benzyl -1- dimethylaminos -1- (4 ' - Morpholino benzoyl) propane, 2- morpholinyls -2- (4 '-methyl mercapto) benzoyls propane, thioxanthones, the chloro- 4- propoxyl group of 1- Thioxanthones, isopropyl thioxanthone, diethyl thioxanthone, EAQ, 4- benzoyls -4 '-dimethyl diphenyl sulfide, benzoin Butyl ether, 2- hydroxyl -2- benzoyls propane, 2- hydroxyls -2- (4 '-isopropyl) benzoyls propane, 4- butylbenzoyls three Chloromethanes, 4- phenoxybenzoyls dichloromethane, methyl benzoylformate, 1,7- double (9 '-acridinyl) heptane, the positive fourths of 9- Double (the 2 '-morpholino isobutyryl) carbazoles of base -3,6-, double (the trichloromethyl)-s-triazine of 2- methyl -4,6-, 2- phenyl -4,6- are double Double (the trichloromethyl)-s-triazine of (trichloromethyl)-s-triazine, 2- naphthyls -4,6-, 2,2- double (2- chlorphenyls) -4,5,4 ', 5 ' - Tetraphenyl -1-2 '-bisglyoxaline, 4,4- azodiisobutyronitriles, triphenylphosphine, camphorquinone, N-1414, N-1717, N-1919, NCI- 831st, NCI-930 (ADEKA systems), IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (BASF systems) and benzoyl peroxide etc., when using these other polymerization initiators, its usage amount is preferably set to the present invention's 1 mass of the usage amount of oxime ester compound times is following.In addition, these polymerization initiators can use a kind or be applied in combination 2 kinds with On.
The content of oxime ester compound of the invention in the polymerization initiator of the present invention is preferably 30~100 mass %, more Preferably 50~100 mass %.
It is unsaturated containing above-mentioned polymerization initiator and ethylenic as required composition in the polymerizable composition, polymerizable composition of the present invention Compound.
As above-mentioned ethylenically unsaturated compounds, it is not particularly limited, can uses and be used for polymerizable composition, polymerizable composition in the past Compound, such as ethene, propylene, butylene, isobutene, vinyl chloride, vinylidene chloride, vinylidene, tetrafluoro second can be included The unsaturated fatty hydrocarbons such as alkene；(methyl) acrylic acid, α-chloro-acrylicacid, itaconic acid, maleic acid, citraconic acid, fumaric acid, Na Di Gram acid, crotonic acid, iso-crotonic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, mono succinate [2- (methyl) acryloyl-oxyethyl] ester, phthalic acid list [2- (methyl) acryloyl-oxyethyl] ester, ω-carboxyl gather in oneself Ester list (methyl) acrylate etc. has list (methyl) acrylate of the polymer of carboxyl and hydroxyl in two ends；Hydroxyethyl (methyl) acrylate-malate, hydroxypropyl (methyl) acrylate-malate, bicyclopentadiene-malate or The unsaturated polyacids such as multifunctional (methyl) acrylate with 1 carboxyl and more than 2 (methyl) acryloyl group；(first Base) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) glycidyl acrylate, following chemical combination Thing No.A1~No.A4, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) third Enoic acid ter-butyl ester, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) third The different nonyl ester of olefin(e) acid, (methyl) stearyl acrylate ester, (methyl) lauryl acrylate, (methyl) methoxyethyl acrylate, (first Base) acrylate methyl esters, (methyl) acrylate, (methyl) acrylic-amino propyl ester, (first Base) acrylate propyl ester, (methyl) ethoxyethyl acrylate, poly- (ethyoxyl) ethyl ester of (methyl) acrylic acid, (first Base) acrylate, butoxy ethoxy ethyl ester, (methyl) ethylhexyl acrylate, (methyl) acrylate, (methyl) Acrylic acid tetrahydrofuran ester, (methyl) vinyl acrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, second Glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, poly- second two Alcohol two (methyl) acrylate, propane diols two (methyl) acrylate, BDO two (methyl) acrylate, 1,6- oneself two Alcohol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite four (methyl) acrylic acid Ester, pentaerythrite three (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, three [(methyl) acryloyls Base ethyl] the unsaturated monoacid and polyalcohol or polyhydric phenols such as isocyanuric acid ester, polyester (methyl) acrylate oligomer ester； The metal salt of the unsaturated polyacids such as (methyl) zinc acrylate resin, (methyl) Magnesium Acrylate Prepared；Maleic anhydride, itaconic anhydride, citraconic acid Acid anhydride, methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, trialkyl tetrabydrophthalic anhydride, 5- (2,5- dioxos Tetrahydrofuran base) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, trialkyl tetrabydrophthalic anhydride-maleic anhydride addition The acid anhydrides of the unsaturated polyacid such as thing, dodecenyl succinic anhydride, methylnadic anhydride；(methyl) acrylamide, methylene Double (methyl) acrylamides of base, diethylenetriamines three (methyl) acrylamide, xyxylene double (methyl) acrylamide, α-chlorine For the acid amides of the unsaturated monoacid and polyamine such as acrylamide, N-2- hydroxyethyls (methyl) acrylamide；Methacrylaldehyde etc. is no Saturated aldehyde；The unsaturated nitriles such as (methyl) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, allyl cyanide；Styrene, 4- first Base styrene, 4- ethyl styrenes, 4- methoxy styrenes, 4-Vinyl phenol, 4- chlorostyrenes, divinylbenzene, ethene Base toluene, vinyl benzoic acid, vinylphenol, vinyl sulfonic acid, 4- vinylbenzenesulfonic acids, vinyl benzyl methyl ether, second The unsaturated aromatic compound such as alkenyl benzyl glycidyl ether；The beta-unsaturated ketones such as methyl vinyl ketone；Vinyl amine, pi-allyl The unsaturated amine compounds such as amine, NVP, vinylpiperidine；The vinyl alcohols such as allyl alcohol, crotonyl alcohol；Vinyl The vinyl ethers such as methyl ether, EVE, n-butyl vinyl ether, IVE, allyl glycidyl ether； The unsaturated acyl imines such as maleimide, N-phenylmaleimide, N- N-cyclohexylmaleimides；Indenes, 1- methyl indenes etc. Indene；The aliphatic conjugated diene class such as 1,3-butadiene, isoprene, chlorobutadiene；Polystyrene, poly- (methyl) acrylic acid first Ester, poly- (methyl) n-butyl acrylate, there is single (methyl) acryloyl group in the end of the polymer molecular chains such as polysiloxanes Macromonomer class；Vinyl chloride, vinylidene chloride, divinyl succinate base ester, diallyl phthalate, tricresyl phosphate allyl Ester, Triallyl isocyanurate, vinyl sulfide, vinyl imidazole, Yi Xi oxazolins, vinyl carbazole, vinylpyridine Pyrrolidone, vinylpyridine, the vinyl carbamate chemical combination of the vinyl monomer of hydroxyl and polyisocyanate compounds The vinyloxirane of thing, the vinyl monomer of hydroxyl and polyepoxides.
In them, for list (methyl) acrylate in polymer of two ends with carboxyl and hydroxyl, with 1 carboxylic Multifunctional (methyl) acrylate, unsaturated monoacid and the polyalcohol or polynary of base and more than 2 (methyl) acryloyl group For the ester of phenol, the polymerization initiator of the oxime ester compound containing the present invention is suitable.
These ethylenically unsaturated compounds can be used alone or mix two or more use, and works as and mix two or more In use, they can also be copolymerized in advance and be used as copolymer.
Compound N o.A1
Compound N o.A2
Compound N o.A3
Compound N o.A4
In addition, assigning the purpose of alkali-developable for the polymerizable composition, polymerizable composition to the present invention, can also use has carboxyl Deng the ethylenically unsaturated compounds (being also recited as the compound with alkali-developable below) of acidic group.As with alkali-developable Compound, be just not particularly limited as long as being soluble in aqueous alkali, but can for example include Japanese Unexamined Patent Publication 2004- The copolymer of resin and acrylate described in No. 264414 publications, phenol, cresol novolac epoxy, there are more officials The polyphenyl methylmethane type ring oxygen tree fat of epoxy radicals, Epocryl and and then multi-anhydride can be made to act on epoxy third Resin etc. obtained from alkene acid ester resin.
Commercially available product can be used as above-mentioned ethylenically unsaturated compounds, such as Kayarad DPHA, DPEA- can be enumerated 12nd, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (Japanese chemical drug system), SPC-1000, SPC-3000 (Showa electricity Work system), ARONIX M-140, M-215, M-350, M-450 (East Asia synthesis system), NK ESTER A-DPHA-TMPT, A-DCP, A-HD-N, A-9300, TMPT, DCP, NPG and HD-N (Xin Zhong villages chemical industry system) etc..
The content of the above-mentioned polymerization initiator used in the polymerizable composition, polymerizable composition of the present invention is not particularly limited, but relative to The above-mentioned mass parts of ethylenically unsaturated compounds 100, preferably 0.5~70 mass parts, more preferably 0.5~50 mass parts, most Preferably 0.5~30 mass parts.
The coloured polymerized composition of the present invention further contains colorant in above-mentioned polymerizable composition, polymerizable composition.
As above-mentioned colorant, pigment, dyestuff and natural pigment etc. can be included.These colorants can be used alone or Mix two or more use.
As above-mentioned pigment, such as nitroso compound can be used；Nitro compound；Azo-compound；Diazo compounds Thing；Oxa anthracene compound；Quinoline compound；Anthraquinone compounds；Coumarin compound；Phthalocyanine compound；Isoindolinone chemical combination Thing；Isoindoline compounds；Quinoline azone compound；Anthanthrone compound；Purple cyclic ketones (perynone) compound；Perylene Compound；Pyrrolo-pyrrole-dione compound；Thioindigo compound；Dioxazine compound；Triphenylmethane compounds；Quinophthalone Compound；Naphthalene tetracarboxylic acid；The metal complex of azo dyes, cyanine dye；Mordant pigment；Obtained with oven process, channel process or pyrolysis method The carbon blacks such as the carbon black or acetylene black, Ketjen black or the lampblack that arrive；Above-mentioned carbon black is adjusted or covered with epoxy resin and is obtained Material, above-mentioned carbon black is subjected to decentralized processing with resin in a solvent in advance, and it is adsorbed 20~200mg/g resin and Obtained material, above-mentioned carbon black is subjected to the processing of acid or basic surface obtained from material, average grain diameter be more than 8nm and DBP oil absorptions are below 90ml/100g material, from CO, CO in the volatile ingredient at 950 DEG C2The whole oxygen amount calculated is every 100m2The surface area of carbon black is more than 9mg material；Graphite, ketjenblack EC, activated carbon, carbon fiber, CNT, spiral Shape carbon fiber, carbon nanohorn, carbon aerogels, fullerene；Nigrosine, pigment black 7, titanium are black；Chrome oxide green, milori blue, cobalt green, Cobalt blue, manganese systems, ferrocyanide, phosphate ultramarine, the native indigo plant in general Shandong, ultramarine, cerulean blue, guignet's green, emerald green, lead sulfate, chromium The organic or inorganic pigment such as Huang, zinc yellow, iron oxide (red iron oxide (III)), cadmium red, synthesis iron oxide black, umber (amber).This A little pigment can be used alone or a variety of be used in mixed way.
As above-mentioned pigment, commercially available pigment can also be used, can include for example paratonere 1,2,3,9,10,14, 17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、 177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、 254；Pigment orange 13,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,65,71；Pigment yellow 1,3, 12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、 120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、 185；Pigment Green 7,10,36；Pigment blue 15,15：1、15：2、15：3、15：4、15：5、15：6、22、24、56、60、61、62、 64；Pigment violet 1,19,23,27,29,30,32,37,40,50 etc..
As above-mentioned dyestuff, azo dyes, anthraquinone dye, indigoid dye, triarylmethane dye, oxa- can be included Anthracene dyes, alizarin dyes, acridine dye, Stilbene dyestuff, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamines dye Dyestuffs such as Liao, oxazine dyes, phthalocyanine dye, cyanine dye etc., they a variety of can also be used in mixed way.
In the coloured polymerized composition of the present invention, the content of above-mentioned colorant relative to 100 mass parts above-mentioned ethylene linkage Formula unsaturated compound, preferably 50~350 mass parts, more preferably 100~250 mass parts.
In above-mentioned coloured polymerized composition, polymerization initiator can also be added as needed on, can dissolve or disperses alkene The solvent of keyed unsaturated compound and colorant.Such as MEK, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl can be enumerated The ketones such as base ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, 2-HEPTANONE；Ether, dioxanes, tetrahydrofuran, 1,2- dimethoxy-ethanes, The ether series solvents such as 1,2- diethoxyethane, dimethyl ether；Methyl acetate, ethyl acetate, n-propyl acetate, acetic acid Isopropyl ester, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, 2,2,4- trimethyl -1,3- pentanediol lists The ester series solvents such as isobutyrate (texanol)；The cellosolve series solvent such as glycol monoethyl ether, ethylene glycol monoethyl ether；Methanol, second The alcohol series solvents such as alcohol, XOR normal propyl alcohol, XOR n-butanol, amylalcohol；Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetic acid Ester, propane diols -1- monomethyl ether -2- acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, 3- methoxyl group butyl ether acetic acid esters, ethyoxyl second The ether-ether series solvent such as ether propionic ester；The BTX series solvents such as benzene,toluene,xylene；The aliphatic such as hexane, heptane, octane, hexamethylene Hydrocarbon system solvent；The terpenic series hydrocarbon ils such as turpentine oil, D- limonenes, firpene；(Cosmo Guia Hills oil is public by Mineral spirits, Swazol#310 Department), the alkane hydrocarbon system solvent such as Solvesso#100 (Exxon chemical companies)；Carbon tetrachloride, chloroform, trichloro ethylene, dichloromethane The halogenated aliphatic hydrocarbon system solvents such as alkane, 1,2- dichloroethanes；The halogenated aromatic hydrocarbon system solvent such as chlorobenzene；Carbitol series solvent；Benzene Amine；Triethylamine；Pyridine；Acetic acid；Acetonitrile；Carbon disulfide；DMF；DMA；N- methyl pyrroles Pyrrolidone；Dimethyl sulfoxide；Water etc., these solvents can use a kind, or be used as mixed solvent of more than two kinds.
In them, ketone, ether-ether series solvent etc. are particularly propane diols -1- monomethyl ether -2- acetic acid esters, cyclohexanone etc. and caused The compatibility of ethylenically unsaturated compounds and polymerization initiator is good in polymerizable composition, polymerizable composition, thus preferably.
, can be in the polymerizable composition, polymerizable composition and coloured polymerized composition of the present invention as long as not damaging the effect of the present invention Be added as needed on polymer (being also recited as polymer below) in addition to ethylenically unsaturated compounds, inorganic compound, Dispersant, chain-transferring agent, the sensitizer (being also recited as sensitizer below) in addition to the oxime ester compound of the present invention, surface-active Agent, silane coupler, melamine, levelling agent, potentiality additive, the monomer in addition to ethylenically unsaturated compounds, disappear Infusion, thickener, thixotropic agent, fire retardant, plasticizer, stabilizer, polymerization inhibitor, ultra-violet absorber, organic filler, antioxygen Various resin additives such as agent, antistatic agent, flowing regulator and adhesion promoters etc..
By being used together above-mentioned polymer with ethylenically unsaturated compounds, the characteristic of solidfied material can also be improved.Make For the polymer, such as polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate can be included Copolymer, poly- (methyl) acrylic acid, styrene-(methyl) acrylic copolymer, (methyl) acrylic acid-methacrylic acid methyl esters Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl base co-polymer, Corvic, ABS resin, nylon 6, nylon 66th, nylon 12, polyurethane resin, makrolon polyvinyl butyral resin, cellulose esters, polyacrylamide, saturated polyester, phenolic aldehyde Resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, epoxy resin etc., wherein it is preferred that polystyrene, (first Base) acryl acid-methyl methacrylate copolymer, epoxy resin.
In the polymerizable composition, polymerizable composition and coloured polymerized composition of the present invention, the content of above-mentioned polymer is relative to 100 The above-mentioned ethylenically unsaturated compounds of mass parts, preferably 0~500 mass parts.
As above-mentioned inorganic compound, can include for example nickel oxide, iron oxide, yttrium oxide, titanium oxide, zinc oxide, The metal oxides such as magnesia, calcium oxide, potassium oxide, silica, aluminum oxide；Layered clay mineral, milori blue, carbonic acid Calcium, magnesium carbonate, cobalt system, manganese systems, glass powder (particularly glass dust (glass frit)), mica, talcum, kaolin, ferrous iron Cyanide, various metal sulfates, sulfide, selenides, alumina silicate, calcium silicates, aluminium hydroxide, platinum, gold, silver, copper etc..
In them, preferably glass dust, titanium oxide, silica, layered clay mineral, silver etc..
It is strong that these inorganic compounds may be used as such as filler, antireflection agent, conductive agent, stabilizer, fire retardant, machinery Spend enhancer, special wavelength absorbent, anti-ink agent etc..
In the polymerizable composition, polymerizable composition and coloured polymerized composition of the present invention, the content of above-mentioned inorganic compound relative to The above-mentioned ethylenically unsaturated compounds of 100 mass parts, preferably 0~1000 mass parts, more preferably 0~800 mass parts.This Outside, these inorganic compounds can use one kind or two or more.
As above-mentioned dispersant, as long as can make that colorant or inorganic compound be scattered, stabilized dispersant, just do not have Limitation, commercially available dispersant can be used, such as BYK Chemie BYK series.Especially it is possible to it is preferred that use by having The macromolecule dispersing agent that the polyester, polyethers or polyurethane for having basic functionality are formed；With nitrogen-atoms as basic functionality, simultaneously And the dispersant that the functional group with nitrogen-atoms is amine and/or its quaternary salt and amine value is 1~100mgKOH/g.
It is general to use the compound containing sulphur atom as above-mentioned chain-transferring agent or sensitizer.Such as sulphur can be included For glycolic, thiomalic acid, thiosalicylic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acids, 3- mercaptobutyric acids, N- (2- mercaptopropionyls Base) glycine, 2- mercaptonicotinic acids, 3- [N- (2- mercaptoethyls) carbamoyl] propionic acid, 3- [N- (2- mercaptoethyls) amino] Propionic acid, N- (3- mercapto radical propionyl groups) alanine, mistabrom, 3- thiohydracrylic acids, 4- sulfydryl fourths sulfonic acid, dodecyl (4- methyl mercaptos) phenyl ether, 2 mercapto ethanol, 3- sulfydryls -1,2-PD, 1- sulfydryl -2- propyl alcohol, 3- sulfydryl -2- butanol, mercapto Base phenol, 2-MEA, 2- mercaptoimidazoles, 2-mercaptobenzimidazole, 2- sulfydryl -3- pyridones, 2-mercaptobenzothiazole, The sulfhydryl compounds such as TGA, trimethylolpropane tris (3-thiopropionate), pentaerythrite four (3-thiopropionate), incite somebody to action Disulphide, iodoacetic acid, iodopropionic acid, ethylene iodohydrin, 2- iodine ethyl sulfonic acid, 3- iodine propane sulfonic acid obtained from sulfhydryl compound oxidation Deng iodo-alkyl compound, trimethylolpropane tris (3- mercaptoisobutanoics acid esters), butanediol double (3- mercaptoisobutanoics acid esters), oneself two The double thiopropionates of mercaptan, the mercaptan of the last of the ten Heavenly stems two, Isosorbide-5-Nitrae-dimethyl sulfydryl benzene, butanediol, the double thioglycolic acid esters of butanediol, ethylene glycol Double thioglycolic acid esters, trimethylolpropane tris thioglycolic acid esters, butanediol double thiopropionate, trimethylolpropane tris sulphur For propionic ester, trimethylolpropane tris thioglycolic acid esters, pentaerythrite tetrathio propionic ester, pentaerythrite tetrathio glycolic Ester, the thiopropionate of trihydroxy ethyl three, diethyl thioxanthone, diisopropylthioxanthone, following compound N o.C1, tri-thiol The aliphatic multi-functional thiol compounds such as propionic acid three (2- ethoxys) isocyanuric acid ester, Showa electrician KARENZ MT BD1, PE1, NR1 etc..
Compound N o.C1
As above-mentioned surfactant, the fluorine surface-actives such as perfluoralkyl phosphate, perfluoroalkyl carboxylate can be used Agent；The anion such as higher aliphatic acid alkali metal salt, alkylsulfonate, alkyl sulfate system surfactant；Higher amines halate, The cation such as quaternary ammonium salt system surfactant；Polyethylene glycol alkyl ether, cithrol, sorbitol anhydride fatty acid The nonionic surfactants such as ester, glycerine monofatty ester；Amphoteric surfactant；The surface-actives such as silicone-based surfactant Agent, they can also combine use.
As above-mentioned silane coupler, the silane coupler that for example SHIN-ETSU HANTOTAI's chemistry is made can be used, wherein, preferably use KBE-9007, KBM-502, KBE-403 etc. have the silane coupler of NCO, methylacryloyl or epoxy radicals.
As above-mentioned melamine compound, can include (poly-) melamine methylol, (poly-) methylol glycoluril, Active methylol (CH in the nitrogen compounds such as (poly-) methylolbenzoguanamine, (poly-) methylolurea2OH yls) whole or one Divide (at least two) compound etc. obtained from alkyl etherified.
Here, as the alkyl for forming alkyl ether, methyl, ethyl or butyl can be included, mutually can also may be used with identical With difference.In addition, not alkyl etherified methylol can be self condensed in an intramolecular, intermolecular can also be contracted two Close, as a result form oligomer composition.
Specifically, HMMM, six butoxymethyl melamines, tetramethoxymethyl can be used Glycoluril, four butoxymethyl glycolurils etc..
Wherein, preferably HMMM, six butoxymethyl melamines etc. are by alkyl etherified trimerization Cyanamide.
As above-mentioned levelling agent, commercially available product can be used.As the levelling agent of commercially available product, can enumerate such as BYK-300, BYK-301、BYK-302、BYK-306、BYK-307、BYK-310、BYK-313、BYK-315、BYK-320、BYK-322、BYK- 323、BYK-325、BYK-330、BYK-331、BYK-333、BYK-337、BYK-341、BYK-344、BYK-345、BYK-346、 BYK-347、BYK-348、BYK-349、BYK-370、BYK-375、BYK-377、BYK-378、BYK-UV3500、BYK- UV3510、BYK-UV3570、BYK-340、BYK-3550、BYK-SILCLEAN3700、BYK-SILCLEAN3720、BYK- DYNWET800 (BYK Chemie Japan systems) Polyflow No.3, Polyflow No.50HF, Polyflow No.54, Polyflow No.64HF、Polyflow No.75、Polyflow No.77、Polyflow No.85HF、Polyflow No.90、Polyflow No.95、Polyflow No.ATF-2、Glanol 100、Glanol 115、Glanol 400、 Glanol 410, Glanol 420, Glanol 440, Glanol 450, Glanol B-1484 (common prosperity society chemistry system), L- 7001、L-7002、L-7006、56ADDITIVE、57ADDITIVE、67ADDITIVE、8032ADDITIVE、FZ-2105、FZ- 2110th, FZ-2122 and FZ-2123 (Toray-Dow corning systems) etc..
So-called above-mentioned potentiality additive, be in normal temperature, light exposure process and prebake conditions process to be not active, by Heat or heated in the presence of acid/base catalyst at 80~200 DEG C at 100~250 DEG C, protection group is departed from and is activated Additive.And the effect obtained, anti-oxidant, ultraviolet radiation absorption, soil resistance, being coated property can be enumerated as by activation And adaptation etc..
, can be preferably using the additive described in WO2014/021023 pamphlets as above-mentioned potentiality additive.
Commercially available product can be used as above-mentioned potentiality additive, such as ADEKA ARKLS GPA-5001 etc. can be enumerated.
In the polymerizable composition, polymerizable composition and coloured polymerized composition of the present invention, above-mentioned ethylenically unsaturated compounds, sheet (but above-mentioned polymer, inorganic compound, colorant and solvent removes any condition beyond the oxime ester compound and colorant of invention Usage amount outside) can properly select according to its application target, be not particularly limited, but preferably with respect to 100 mass The above-mentioned ethylenically unsaturated compounds of part are added up to below 50 mass parts.
The polymerizable composition, polymerizable composition and coloured polymerized composition of the present invention can be used in photo-curable coating or varnish；Light Curability bonding agent；Printing-ink；Dental composition；The photoresist of electronic engineering；Platedresist；Etch against corrosion Agent；Solder resist；And it is used for the resist for forming structure in LCD manufacturing process；For enclosing the combination of Electrical and Electronic part Thing；Solder resist；Magnetic recording material；Plating mask；Etching mask；For manufacturing the material of three-dimensional body by stereolithography Material；Decoloring material for image recording material；Use the decoloring material of the image recording material of microcapsules；Printed wiring board Use photo anti-corrosion agent material；UV and the photo anti-corrosion agent material of visible laser through image system；Tellite is gradually Dielectric layer in stacking forms the various uses such as the middle photo anti-corrosion agent material used or diaphragm, not special to its purposes Limitation.
The polymerizable composition, polymerizable composition and coloured polymerized composition of the present invention can also be in order to form liquid crystal display panel The purpose of sept and used to form vertical alignment-type liquid crystal display device projection.Especially as shape simultaneously Projection and the polymerizable composition, polymerizable composition and coloured polymerized composition of sept into vertical alignment-type liquid crystal display device are that have .
Above-mentioned liquid crystal display panel is preferably formed with sept by following processes：(1) this hair is formed on substrate The process of the film of bright polymerizable composition, polymerizable composition, (2) are irradiated across the mask with defined pattern form to the film radiates Process that roasting procedure, (4) after the process of line, (3) exposure are developed the envelope after exposure, (5) by after development The process that the envelope is heated.
The polymerizable composition, polymerizable composition of the invention and coloured polymerized composition that with the addition of anti-ink agent are used as ink-jetting style Next door formed resin combination be useful, said composition may be used as colour filter, particularly preferably as profile angle be 50 ° with On ink-jet color filter next door.It is preferable to use fluorine system surfactant and fluorine system is included as the anti-ink agent The composition of surfactant.
The present invention polymerizable composition, polymerizable composition and coloured polymerized composition by containing organic and/or inorganic materials (inorganic compound) and It may be used as photosensitive paste composition.The photosensitive paste composition can be used for the next door to form plasma display The roast patterns such as pattern, dielectric pattern, electrode pattern and black matrix pattern.
The manufacture method of the solidfied material obtained by the polymerizable composition, polymerizable composition or coloured polymerized composition of the present invention is recorded In following.
The polymerizable composition, polymerizable composition or coloured polymerized composition of the present invention can pass through spinner, sized roller applicator, rod coaters, mould Apply device, curtain coaters, various printings, means known to impregnating are applied to soda-lime glass, quartz glass, semiconductor substrate, gold In the support substrates such as category, paper, plastics.After being temporarily implemented in the support substrates such as film, then it is transferred to others In support substrate, its usability methods is not limited.
The light of the energy-ray used when solidifying as the polymerizable composition, polymerizable composition or coloured polymerized composition for making the present invention Source, can utilize from ultrahigh pressure mercury lamp, high-pressure sodium lamp, medium pressure mercury lamp, low pressure mercury lamp, mercury vapour arc lamp, xenon arc lamp, carbon arc lamp, What metal halide lamp, fluorescent lamp, tungsten lamp, Excimer lamp, bactericidal lamp, light emitting diode, CRT light sources etc. obtained has 2000 angstroms The high-energy rays such as electromagnetic wave energy or electron beam, X ray, radioactive ray to 7000 angstroms of wavelength, can preferably be included The ultrahigh pressure mercury lamp of 300~450nm of wavelength light, mercury vapour arc lamp, carbon arc lamp, xenon arc lamp etc. can be sent.
And then by using laser as exposure light source, then just can be direct from computer digital information without using mask The raising of productivity ratio can not only be realized by forming the laser directly method of drawing of image, can also realize resolution ratio and positional precision etc. Improve, thus be useful, as the laser, preferably using 340~430nm wavelength light, but quasi-molecule can also be used Laser, nitrogen laser, argon ion laser, helium cadmium laser, He-Ne laser, krypton ion laser, various semiconductors swash Light device and YAG laser etc. can be sent from visible to the laser of the light of region of ultra-red.During using above-mentioned laser, in this hair The absorbable sensitizing from visible to the infrared region can be added in bright polymerizable composition, polymerizable composition or coloured polymerized composition Pigment.
The solidfied material obtained by the polymerizable composition, polymerizable composition or coloured polymerized composition of the present invention can be used in printing electricity Base board；In the liquid crystal display cells of the colored display such as colour television set, PC monitors, portable information terminal, digital camera Colour filter；The colour filter of ccd image sensor；The electrode material of plasma display；Powdery paints；Galley；Magnetic Recording materials；Milli machine part；Waveguide；Optical switch；Color test system；Glass fiber cable coatings；Image recording material； Fine circuits；Decoloring material；Diaphragm；Dielectric film；The various uses such as optical element, its purposes is not particularly limited.
Embodiment
Hereinafter, enumerate embodiment and the present invention is described in more detail in comparative example, but the present invention is not by these embodiments etc. Limit.
Manufacture on the above-claimed cpd No.1 and its intermediate of the oxime ester compound as the present invention is shown in following.
<Step 1：The manufacture of intermediate 1>
By nonox (8.76g, 39.9mmol), 4- bromines benzophenone (10.4g, 39.9mmol), tertiary amoxy sodium Toluene (150ml) suspension of (8.79g, 79.8mmol), bi triphenyl phosphine palladium (0.9g, 3.99mmol) stirs 5 at 100 DEG C Hour.After being cooled to room temperature, diatomite, silica gel are added in reaction solution and is stirred 30 minutes, is filtered, at 40 DEG C under decompression Solvent is distilled off, following intermediates 1 (15.0g) are obtained as tan solid.Intermediate 1 is used for following anti-without refined Ying Zhong.
<Step 2：The manufacture of intermediate 2>
In intermediate 1 (15.0g, 37.5mmol) nitromethane (150ml) solution, under ice cooling, 4, second is added Acyl chlorides (6.19g, 78.8mmol), aluminium chloride (10.5g, 78.5mmol), stir 6.5 hours at the same temperature.And then add Chloroacetic chloride (12.4g, 158mmol), aluminium chloride (20.1g, 151mmol), are stirred at room temperature 2 hours.Reaction solution is poured into In ice bath cooling water, extracted using ethyl acetate.After with watery hydrochloric acid, organic layer is cleaned, carry out 4 times washing, under decompression 40 DEG C are distilled off solvent.By acetone/2- propyl alcohol carry out partial crystallization and obtain cream colored solid following intermediates 2 (8.0g, 44%).
<Step 3：The manufacture of intermediate 3>
In intermediate 2 (8.0g, 16.5mmol) ethanol (56mL) solution add hydroxylamine hydrochloride (2.53g, 36.4mmol), sodium acetate (3.57g, 43.5mmol), water (30ml), it is being heated to reflux lower stirring 4.3 hours.It is cooled to room temperature Afterwards, extracted using ethyl acetate, organic layer cleaned 3 times with saturated aqueous common salt, solvent is distilled off at 40 DEG C under decompression, Obtain following intermediates 3 (11.6g).Intermediate 3 is used in following reaction without refined.
<Step 4：The manufacture of compound N o.1>
In intermediate 3 (11.6g, 22.5mmol) chloroform (50ml) solution, under ice cooling, 4, triethylamine is added (4.78g, 47.2mmol), chloroacetic chloride (3.53g, 45.0mmol), an evening is stirred at room temperature.Under ice cooling, 4, water is added And after carrying out water-oil separating, organic layer is washed 5 times.Solvent is distilled off at 40 DEG C under decompression, with ethyl acetate/hexane=1/ 2 (v/v) cut is attached in silica gel column chromatography instrument, obtain the compound N of object as yellow amorphous o.1 (1.1g, 8.2%).Analysis result is shown in 1~table of table 3.
Manufacture on the above-claimed cpd No.182 and its intermediate of the oxime ester compound as the present invention is shown in following.
<Step 1：The manufacture of intermediate 4>
By nonox (22.27g, 102mmol), bromobenzene (15.95g, 102mmol), tertiary amoxy sodium (22.37g, 203mmol), toluene (100ml) suspension of bi triphenyl phosphine palladium (0.26g, 0.5mmol) stirs 2 hours at 100 DEG C.It is cold But to after room temperature, adding diatomite, silica gel in reaction solution and stirring 30 minutes, filtered, removed under decompression in 40 DEG C of distillations Solvent is removed, following intermediates 4 (30.0g) are obtained as tan solid.Intermediate 4 is used in following reaction without refined.
<Step 2：The manufacture of intermediate 5>
In 1,2- dichloroethanes (50ml) solution of intermediate 4 (12.2g, 41.3mmol), under ice cooling, 4, add Chloroacetic chloride (10.2g, 130mmol), aluminium chloride (17.8g, 134mmol), stir 4 hours, stir at room temperature at the same temperature Mix 3 hours.And then under ice cooling, 4, chloroacetic chloride (10.2g, 130mmol), aluminium chloride (17.8g, 134mmol) are added, Stir 2.5 hours, be stirred at room temperature 4 hours at identical temperature.Reaction solution is poured into ice bath cooling water, entered using chloroform Row extraction.After organic layer is cleaned with watery hydrochloric acid, 5 washings are carried out, solvent is distilled off at 40 DEG C under decompression.With acetic acid second The cut of ester/hexane=3/7 (v/v) is attached in silica gel column chromatography instrument, obtains following intermediates 5 (4.06g, 23.3%).
<Step 3：The manufacture of intermediate 6>
In intermediate 5 (4.06g, 9.63mmol) ethanol (32mL) solution add hydroxylamine hydrochloride (2.21g, 31.7mmol), sodium acetate (3.16g, 38.5mmol), water (16ml), it is being heated to reflux lower stirring 4 hours.After being cooled to room temperature, Extracted using ethyl acetate, organic layer is cleaned 3 times with saturated aqueous common salt, solvent is distilled off at 40 DEG C under decompression, obtains To following intermediates 6 (4.84g).Intermediate 6 is used in following reaction without refined.
<Step 4：The manufacture of compound N o.182>
In intermediate 6 (4.84g, 11.5mmol) chloroform (19ml) solution, under ice cooling, 4, triethylamine is added (3.16g, 31.2mmol), chloroacetic chloride (2.38g, 30.3mmol), is stirred at room temperature 2 hours.Under ice cooling, 4, water is added And after carrying out water-oil separating, organic layer is washed 5 times.Solvent is distilled off at 40 DEG C under decompression, with ethyl acetate/hexane=1/ 1 (v/v) cut is attached in silica gel column chromatography instrument, obtains the compound N of object as yellow amorphous o.182 (0.78g, 13.7%).Analysis result is shown in 1~table of table 3.
Manufacture on the above-claimed cpd No.183 and its intermediate of the oxime ester compound as the present invention is shown in following.
<Step 1：The manufacture of intermediate 7>
In 1,2- dichloroethanes (50ml) solution of intermediate 4 (15.9g, 53.9mmol), under ice cooling, 4, add Propionyl chloride (30.16g, 226.2mmol), aluminium chloride (30.16g, 8.5), are stirred at room temperature 1 hour.Reaction solution is poured into In ice bath cooling water, extracted using ethyl acetate.After with watery hydrochloric acid, organic layer is cleaned, carry out 5 times washing, under decompression 40 DEG C are distilled off solvent, are attached to the cut of ethyl acetate/hexane=1/3 (v/v) in silica gel column chromatography instrument, obtain it is following in Mesosome 7 (11.83g).
<Step 2：The manufacture of intermediate 8>
35% hydrochloric acid is added in intermediate 7 (10.0g, 21.5mmol) dimethylformamide (20mL) solution (8.99g, 86.0mmol), isobutyl nitrite (8.90g, 86.0mmol), is stirred at room temperature 12 hours.Use ethyl acetate Extracted, organic layer is washed 5 times, solvent is distilled off at 40 DEG C under decompression, obtains following intermediates 8 (16.43g).In Mesosome 8 is used in following reaction without refined.
<Step 3：The manufacture of compound N o.183>
In intermediate 8 (16.43g) THF (40ml) solution, under ice cooling, 4, addition triethylamine (4.67g, 45.3mol), chloroacetic chloride (3.56g, 45.3mmol), stir within 1 hour.Under ice cooling, 4, water and ethyl acetate are added simultaneously After carrying out water-oil separating, organic layer is washed 5 times.Solvent is distilled off at 40 DEG C under decompression, with ethyl acetate/hexane=2/3 (v/v) cut is attached in silica gel column chromatography instrument, obtain the compound N of object as yellow amorphous o.183 (4.6g, 8.2%).Analysis result is shown in 1~table of table 3.
Table 1
Oxime ester compound Decomposition point (DEG C) Solubility (wt%) in PGMEA
Embodiment 1 Compound N is o.1 258 30
Embodiment 2 Compound N is o.182 258 38
Embodiment 3 Compound N is o.183 197 46
Comparative example 1 Comparative compound No.1 - 7.5
Comparative compound No.1
Table 2
Table 3
The modulation of [embodiment 4~6 and comparative example 2] polymerizable composition, polymerizable composition
Each composition is modulated according to the formula of table 4, obtains polymerizable composition, polymerizable composition (embodiment 4~6 and comparative example 2).In addition, table In numeral represent mass parts.As polymerization initiator, be used alone compound N o.1, compound N o.182, compound No.183 and comparative compound No.1.
In addition, the symbol of each composition in table represents following compositions.
(there are the ethylenically unsaturated compounds of acidic group；Showa electrician system)
Table 4
Embodiment 4 Embodiment 5 Embodiment 6 Comparative example 2
A-1 0.5
A’-2 0.5
A-3 0.5
A-4 0.5
B-1 54.8 54.8 54.8 54.8
B-2 13 13 13 13
C-1 30.5 30.5 30.5 30.5
D-1 0.6 0.6 0.6 0.6
D-2 0.1 0.1 0.1 0.1
D-3 0.5 0.5 0.5 0.5
It is total 100 100 100 100
[evaluation example 4~6 and comparative evaluation example 2]
On above-described embodiment 4~6 and the polymerizable composition, polymerizable composition of comparative example 2, line width sensitivity has been carried out by following methods Evaluation.Show the result in table 5.
(line width sensitivity)
2ml anti-corrosion liquids are added drop-wise on glass substrate, using spinner in 500rpm × 2 second → 900rpm × 5 second → 1 second Film is carried out under the conditions of clock is inclined, is air-dried 5 minutes.After air-drying, substrate is positioned in heating plate, entered under 90 DEG C × 90 seconds Row prebake conditions, cooled down afterwards under 23 DEG C × 40 seconds.To the substrate that cools via mask (line and gap) with the μ of gap 20 M simultaneously uses exposure machine in 10mJ/cm2~80mJ/cm2In the range of with 10mJ/cm2Interval carry out pattern exposure.Use alkalescence Developer solution, develop 27~28 seconds.Afterwards, the line width and thickness after measure before and after baking (230 DEG C × 30 points).Will be in mask open Line width is set to line width sensitivity as 20 μm of light exposure in 20 μm.
Table 5
Evaluate example 4 Evaluate example 5 Evaluate example 6 Comparative evaluation example 2
Line width sensitivity (mJ/cm2) ＜ 20 ＜ 20 20 30
It is clear and definite by above-mentioned table 1, table 4 and table 5, oxime ester compound of the invention and existing oxime ester compound (compared with chemical combination Thing No.1) to compare, the solubility in PGMEA is high, and light exposure is small, i.e. line width sensitivity is excellent.
<Blue pigment dispersion liquid No.1 manufacture>
Use DISPERBYK-161 (12.5 mass parts；BYK Chemie Japan systems) dispersant is used as, by pigment blue 15 : 6 (15 mass parts) are used as colorant, it is scattered in PGMEA (72.5 mass parts) using ball mill.
The modulation of [embodiment 7~9 and comparative example 3] coloured polymerized composition
Each composition is modulated according to the formula of table 6, obtains coloured polymerized composition (embodiment 7~9 and comparative example 3).This Outside, the numeral in table represents mass parts.As polymerization initiator, be used alone compound N o.1, compound N o.182, compound No.183 and comparative compound No.1.
In addition, the symbol of each composition in table represents following compositions.
(there are the ethylenically unsaturated compounds of acidic group；Showa electrician system)
Table 6
Embodiment 7 Embodiment 8 Embodiment 9 Comparative example 3
A-1 0.9
A′-2 0.9
A-3 0.9
A-4 0.9
B-3 25 25 25 25
B-4 3 3 3 3
C-1 45 45 45 45
D-1 0.4 0.4 0.4 0.4
D-2 0.1 0.1 0.1 0.1
E-1 25.6 25.6 25.6 25.6
It is total 100.0 100.0 100.0 100.0
[evaluation example 7~9 and comparative evaluation example 3]
On obtained coloured polymerized composition, the evaluation of line width sensitivity has been carried out by method similar to the above. Show the result in table 7.
Table 7
Evaluate example 7 Evaluate example 8 Evaluate the comparative evaluation example 3 of example 9
Oxime ester compound Compound N is o.1 Compound N is o.182 Compound N o.183 comparative compound No.1
Line width sensitivity (mJ/cm2) ＜ 20 ＜ 20 3040
It is clear and definite by above-mentioned table 6 and table 7, when the oxime ester compound of the present invention is used as into polymerization initiator, it can obtain sensitivity Excellent coloured polymerized composition.Because photoetching is excellent, so the polymerization initiator especially as colour filter is useful 's.
Therefore, oxime ester compound of the invention is in the polymerization initiator as polymerizable composition, polymerizable composition, due to cooperation from High by degree, photoetching is excellent, so being useful.
Industrial applicability
The present invention oxime ester compound as high sensitivity used in polymerizable composition, polymerizable composition and dissolubility it is high polymerization initiation Agent is useful.

Claims (10)

1. a kind of oxime ester compound, it is represented by following logical formula (I)s,
In formula (I), R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12(R is also recited as below1~R12) separately Represent group, hydrogen atom, halogen atom, nitro, cyano group, hydroxyl, carboxyl, the R represented by following logical formula (II)s13、OR13、SR13、 NR14R15、COR13、SOR13、SO2R13Or CONR14R15,
R13、R14And R15Separately represent the cycloalkyl, carbon that alkyl, carbon number that carbon number is 1~20 are 3~20 The aralkyl or carbon that aryl that cycloalkyl-alkyl that atomicity is 4~20, carbon number are 6~20, carbon number are 7~20 are former Subnumber is 2~20 to contain heterocyclic radical,
R13、R14And R15Cycloalkyl that alkyl that represented carbon number is 1~20, carbon number are 3~20, carbon number The aralkyl or carbon number that the aryl for being 6~20 for 4~20 cycloalkyl-alkyl, carbon number, carbon number are 7~20 be 2~20 hydrogen atom containing heterocyclic radical sometimes by halogen atom, nitro, cyano group, hydroxyl, amino, carboxyl, methylacryloyl, Acryloyl group, epoxy radicals, vinyl, vinyl ether, sulfydryl, NCO substitute, R containing heterocyclic radical13、R14And R15Institute's table The cycloalkyl alkane that cycloalkyl that alkyl that the carbon number shown is 1~20, carbon number are 3~20, carbon number are 4~20 The aralkyl or carbon number that base, carbon number are 7~20 be 2~20 containing the methylene in heterocyclic radical sometimes also by-O- ,- CO-、-COO-、-OCO-、-NR16-、-NR16CO-、-S-、-CS-、-SO2- ,-SCO- ,-COS- ,-OCS- or-CSO- substitution,
R16Represent cycloalkyl, carbon number that alkyl, carbon number that hydrogen atom, carbon number are 1~20 are 3~20 be 4~ The aralkyl that the aryl or carbon number that 20 cycloalkyl-alkyl, carbon number are 6~20 are 7~20,
Ring A1And ring A2Condense and form the aromatic rings that carbon number is less than 30,
R1、R2、R3、R4、R5、R6、R7、R8、R9And R10(R is also recited as below1~R10) in it is at least one be following logical formula (II)s Represented group,
M is A1Positive integer below the quantity of desirable substituent,
During m >=2, multiple R11It is sometimes each different,
N is A2Positive integer below the quantity of desirable substituent,
During n >=2, multiple R12It is sometimes each different,
R1And R2、R2And R3、R3And R4、R4And R5、R6And R7、R7And R8、R8And R9、R9And R10、R11And R12Sometimes also it is bonded and shape Cyclization, R during m >=211And R11Sometimes also it is bonded and forms ring, R during n >=212And R12Sometimes also it is bonded and forms ring,
In formula (II), R17And R18It is 1~20 separately to represent hydrogen atom, halogen atom, nitro, cyano group, carbon number The virtue that cycloalkyl-alkyl that cycloalkyl that alkyl, carbon number are 3~20, carbon number are 4~20, carbon number are 6~20 The aralkyl or carbon number that base, carbon number are 7~20 are 2~20 to contain heterocyclic radical,
R17And R18Cycloalkyl that alkyl that represented carbon number is 1~20, carbon number are 3~20, carbon number be 4~ The aralkyl or carbon number that aryl that 20 cycloalkyl-alkyl, carbon number are 6~20, carbon number are 7~20 are 2~20 The hydrogen atom containing heterocyclic radical sometimes by halogen atom, nitro, cyano group, hydroxyl, amino, carboxyl, methylacryloyl, acryloyl Base, epoxy radicals, vinyl, vinyl ether, sulfydryl, NCO substitute, R containing heterocyclic radical17And R18Represented carbon atom Count the cycloalkyl-alkyl, carbon number that the alkyl for 1~20, the cycloalkyl that carbon number is 3~20, carbon number are 4~20 Aralkyl or carbon number for 7~20 be 2~20 containing the methylene in heterocyclic radical sometimes also by-O- ,-CO- ,-COO- ,- OCO-、-NR19-、-NR19CO-、-S-、-CS-、-SO2- ,-SCO- ,-COS- ,-OCS- or-CSO- substitution,
R19Represent cycloalkyl, carbon number that alkyl, carbon number that hydrogen atom, carbon number are 1~20 are 3~20 be 4~ The aralkyl that the aryl or carbon number that 20 cycloalkyl-alkyl, carbon number are 6~20 are 7~20,
K represents 0 or 1.
2. oxime ester compound according to claim 1, it is characterised in that it is included represented by 2 formula above (II) Group.
3. oxime ester compound according to claim 1 or 2, it is characterised in that the R in logical formula (I)6、R7、R8、R9And R10In It is at least one be COR13。
4. according to oxime ester compound according to any one of claims 1 to 3, it is characterised in that the R in logical formula (I)1、R2、R3、 R4、R5And R11In it is at least one be group represented by logical formula (II).
5. according to oxime ester compound according to any one of claims 1 to 3, it is represented by following logical formula (III)s,
In formula (III), R1~R10、R20、R21、R22、R23、R24And R25Separately represent group represented by logical formula (II), Hydrogen atom, halogen atom, nitro, cyano group, hydroxyl, carboxyl, R13、OR13、SR13、NR14R15、COR13、SOR13、SO2R13Or CONR14R15,
R13、R14And R15Separately represent the cycloalkyl, carbon that alkyl, carbon number that carbon number is 1~20 are 3~20 The aralkyl or carbon that aryl that cycloalkyl-alkyl that atomicity is 4~20, carbon number are 6~20, carbon number are 7~20 are former Subnumber is 2~20 to contain heterocyclic radical,
R13、R14And R15Cycloalkyl that alkyl that represented carbon number is 1~20, carbon number are 3~20, carbon number The aralkyl or carbon number that the aryl for being 6~20 for 4~20 cycloalkyl-alkyl, carbon number, carbon number are 7~20 be 2~20 hydrogen atom containing heterocyclic radical sometimes by halogen atom, nitro, cyano group, hydroxyl, amino, carboxyl, methylacryloyl, Acryloyl group, epoxy radicals, vinyl, vinyl ether, sulfydryl, NCO substitute, R containing heterocyclic radical13、R14And R15Institute's table The cycloalkyl alkane that cycloalkyl that alkyl that the carbon number shown is 1~20, carbon number are 3~20, carbon number are 4~20 The aralkyl or carbon number that base, carbon number are 7~20 be 2~20 containing the methylene in heterocyclic radical sometimes also by-O- ,- CO-、-COO-、-OCO-、-NR16-、-NR16CO-、-S-、-CS-、-SO2- ,-SCO- ,-COS- ,-OCS- or-CSO- substitution,
R16Represent cycloalkyl, carbon number that alkyl, carbon number that hydrogen atom, carbon number are 1~20 are 3~20 be 4~ The aralkyl that the aryl or carbon number that 20 cycloalkyl-alkyl, carbon number are 6~20 are 7~20,
R1~R10In it is at least one be group represented by logical formula (II),
R17And R18Separately represent that hydrogen atom, halogen atom, nitro, cyano group, the alkyl that carbon number is 1~20, carbon are former Aryl that cycloalkyl-alkyl that cycloalkyl that subnumber is 3~20, carbon number are 4~20, carbon number are 6~20, carbon atom Number is 2~20 to contain heterocyclic radical for 7~20 aralkyl or carbon number,
R17And R18Cycloalkyl that alkyl that represented carbon number is 1~20, carbon number are 3~20, carbon number be 4~ The aralkyl or carbon number that aryl that 20 cycloalkyl-alkyl, carbon number are 6~20, carbon number are 7~20 are 2~20 The hydrogen atom containing heterocyclic radical sometimes by halogen atom, nitro, cyano group, hydroxyl, amino, carboxyl, methylacryloyl, acryloyl Base, epoxy radicals, vinyl, vinyl ether, sulfydryl, NCO, carboxyl substitute, R containing heterocyclic radical17And R18Represented Cycloalkyl-alkyl that cycloalkyl that alkyl that carbon number is 1~20, carbon number are 3~20, carbon number are 4~20, carbon The aralkyl or carbon number that atomicity is 7~20 be 2~20 containing the methylene in heterocyclic radical sometimes also by-O- ,-CO- ,- COO-、-OCO-、-NR19-、-NR19CO-、-S-、-CS-、-SO2- ,-SCO- ,-COS- ,-OCS- or-CSO- substitution,
R19Represent cycloalkyl, carbon number that alkyl, carbon number that hydrogen atom, carbon number are 1~20 are 3~20 be 4~ The aralkyl that the aryl or carbon number that 20 cycloalkyl-alkyl, carbon number are 6~20 are 7~20,
R1And R2、R2And R3、R3And R4、R4And R5、R6And R7、R7And R8、R8And R9、R9And R10、R20And R21、R22And R23、R23And R24 And R24And R25Sometimes also it is bonded and forms ring,
K represents 0 or 1.
6. oxime ester compound according to claim 5, it is characterised in that the R in logical formula (III)1、R2、R3、R4And R5In At least one is the group represented by logical formula (II).
7. a kind of polymerization initiator, it contains oxime ester compound according to any one of claims 1 to 6.
8. a kind of polymerizable composition, polymerizable composition, it contains the polymerization initiator and ethylenically unsaturated compounds described in claim 7.
9. a kind of coloured polymerized composition, it is to make further to contain colorant in the polymerizable composition, polymerizable composition described in claim 8 And formed.
10. a kind of solidfied material, it is as coloured polymerized described in the polymerizable composition, polymerizable composition described in claim 8 or claim 9 Composition and obtain.
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