CN1171122C - Optical polymerism composition - Google Patents
Optical polymerism composition Download PDFInfo
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- CN1171122C CN1171122C CNB00134577XA CN00134577A CN1171122C CN 1171122 C CN1171122 C CN 1171122C CN B00134577X A CNB00134577X A CN B00134577XA CN 00134577 A CN00134577 A CN 00134577A CN 1171122 C CN1171122 C CN 1171122C
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Abstract
The present invention provides an optical polymerism composition in a free radical optical polymerism system composition form, which can simultaneously ensure high sensitivity and good storage stability. The composition has maximum sensitivity and has good prospects in imaging techniques. The optical polymerism composition comprises an optical polymerism group containing compound with a special structure and an optical polymerism initiator.
Description
Technical field
The present invention relates to the optical polymerism material, this material can be used for image forming material, for example three-dimensional imaging, holography, lithographic plate, color proof, photoresist and color filter, or be used for light-cured resin material such as printing ink, coating and bonding agent.More particularly, the present invention relates to be suitable for use as the optical polymerism composition that can carry out the lithographic plate of so-called direct plate-making, described plate can directly be made a plate from the digital signal of computing machine etc. with various laser.
Background technology
At present, the miniature laser of highoutput is easy to obtain, and it can be that emission wavelength is from 300 to 1200nm ultraviolet light, solid state laser, semiconductor laser or the gas laser of visible or infrared light.These laser instruments are particularly suitable for directly being used as the light source that imprinting is used the plate-making at the digital laser from computing machine etc.
For various laser sensitive imprinting materials have been carried out big quantity research, the representative example of imprinting material comprises following material.
First kind is that wavelength photoreceptor is 760nm or the higher material that can pass through the infrared laser imprinting, for this kind material, known material is a United States Patent (USP) 4,708, the acid catalyst cross-linking type egative film imprinting material of describing among positive plate-making imprinting material of describing in 925 and the JP-A-8-276558.
Second kind is to be 300 to 700nm the ultraviolet light or the imprinting material of visible laser sensitivity to wavelength, for this kind material, a large amount of imprinting materials are known, and for example United States Patent (USP) 2,850,445 and JP-B-44-20189 in the radical polymerization type egative film imprinting material put down in writing.
On the other hand, be that the short-wavelength light below the 300nm or the material of electron beam sensitive are very important photo anti-corrosion agent materials to wavelength.In recent years, the integrated level of integrated circuit is more and more higher, and in the production of the semiconductor chip of super LSI etc., essential processing live width is at the ultra-fine grating below half micron.In order to meet this requirement, being used for photolithographic exposure device needs can the shorter and shorter light of emission wavelength, and research use far ultraviolet or excited molecule laser beam (XeCl for example, KrF, ArF).Even begin to attempt using electron beam to form ultra-fine grating.In follow-on grating formation technology, electron beam is very promising light source.
These image forming materials have a problem that needs solution jointly, and this problem is exactly that at energy exposure zone and non-irradiation area, what degree the ON-OFF of image can expand to, that is to say how to reach the hypersensitivity and the shelf stability of image forming material simultaneously.
Usually, the susceptibility of free radical photopolymerization system is very high, but owing to the inhibiting effect of airborne oxygen to polymerization, susceptibility can reduce greatly.For this reason, adopted the method that oxygen barrier can be provided on imaging layer.But, after oxygen barrier is provided, then can be owing to dark polymerization produce mist, thus the shelf stability of destroying.Therefore, be difficult to the susceptibility and the shelf stability that reach high simultaneously in the past, conventional technology all can not obtain satisfied result always.Therefore, need in the past unknown new technology.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of optical polymerism composition that can guarantee the free radical photopolymerization set of systems compound form of hypersensitivity and good shelf stability simultaneously, the susceptibility of said composition is the highest, is very promising in imaging technique.Specifically, the purpose of this invention is to provide a kind of be suitable for use as can by from the numerical data of computing machine etc. with the solid state laser of emission ultraviolet rays, visible light ray or infrared-ray or the optical polymerism composition of the lithographic plate that the semiconductor laser imprinting is directly made a plate.
Through big quantity research, the inventor finds, when use has the compound of particular polymeric group in optical polymerism composition, can achieve the above object.More particularly, the present invention has following formation.
Contain the compound with structure shown in the following general formula (I) and the optical polymerism composition of Photoepolymerizationinitiater initiater:
[changing 2]
X wherein
1And X
2Represent heteroatoms or the group or the halogen atom that connect with heteroatoms independently of one another, R
aAnd R
bRepresent hydrogen atom, halogen atom, cyano group or organic residue independently of one another, X
1And X
2, R
aAnd R
b, or X
1And R
aOr R
bCan lump together the formation ring texture each other.
Usually, modal radical polymerization compound is monomer, oligomer or the polymkeric substance of the acrylate group, acrylic acid amides group, methacrylate based group or the methacrylic acid amide group that contain high polymerism.But their polymerization meeting when such compound is used for optical polymerism composition, can't reach the purpose that obtains hypersensitivity and shelf stability simultaneously owing to oxygen is suppressed.
With regard to the constituent of polymkeric substance, the compound (monomer) that has the α-methacryl of heteroatoms replacement or the methacryl of α-halogen-replacement is known, and these groups all have the polymerism suitable with the group of acrylic-type.With equally substituting group is arranged but low itaconic acid group or the alpha-alkyl acryloyl group of polymerism is different at the α bit strip, the heteroatoms that these compounds replace as the polymerism of polymkeric substance constituent because at alpha-position or the electronic effect and the steric effect of halogen atom are improved.
The inventor finds, when in optical polymerism composition, containing when alpha-position is used with Photoepolymerizationinitiater initiater by the compound of the polymerizable groups of heteroatoms or halogen atom replacement, the conventional existing problem of radical polymerization compound, to be oxygen described above can reduce greatly to the inhibiting effect of polymerization, and can obtain required hypersensitivity of optical polymerism composition and splendid shelf stability simultaneously.
It is not clear to the inhibiting mechanism of polymerization to reduce oxygen; but; the compound that the present invention is used with structure shown in the formula (I); because the substituent effect of its alpha-position; though the aggregation growth rate constant is not as the conventional acryloyl group or the height of methacryl base type, it is very little to stop rate constant, therefore; when chain elongation, be difficult to react, thereby this compound is not subject to the influence that oxygen suppresses polymerization with oxygen.
Embodiment
The used compound of the present invention is characterised in that this compound has the structure shown in the formula (I) and contains at least one polymerizable group.
Structure shown in the formula (I) can be the substituting group of monovalence substituting group or divalence or higher valence link, perhaps, and the R in formula (I)
a, R
b, X
1And X
2When all representing end group, this structure itself just can be a compound.When the structure shown in the formula (I) is the substituting group of monovalence substituting group or divalence or higher valence link, the R in the formula (I)
a, R
b, X
1And X
2In have at least one to have one or more keys.In addition, X
1And X
2Can be respectively the linking group with n connectable position, its end can connect the group shown in n the formula (I) (n is the integer greater than 2) (polymer).
In addition, compound can also pass through X
1And X
2In at least one combine with polymer chain.In other words, can use the form that in the side chain of polymer chain, has structure shown in the formula (I).The example of polymer chain comprises at linear organic high molecular polymer described below.Its concrete example comprises the polymkeric substance based on vinyl, for example polyurethane, novolaks and polyvinyl alcohol, polycarboxylated styrene, polystyrene, poly-(methyl) acrylate, poly-(methyl) acrylic acid amides and polyacetal.These polymkeric substance can be homopolymer, also can be multipolymers.
In formula (I), X
1And X
2Represent heteroatoms or halogen atom respectively, but also can be end group or can be that linking group and other substituting group (as mentioned above, substituting group comprises the structure and polymer chain of formula (I)) are connected.The preferred non-metallic atom of heteroatoms, its concrete example comprises oxygen atom, sulphur atom, nitrogen-atoms and phosphorus atoms.The example of halogen atom comprises chlorine atom, bromine atoms, iodine atom and fluorine atom.
X
1Preferably halogen atom is perhaps worked as X
1When representing linking group and having another substituting group to be connected with it; preferred its is expressed as follows group; the for example phosphonate groups of the phosphono of the sulfonyl of the sulfinyl of the amino of the sulfydryl of the hydroxyl of hydroxyl, replacement, sulfydryl, replacement, amino, replacement, sulfo group, sulfonate group, replacement, replacement, phosphono, replacement, phosphonate groups, replacement, nitro or heterocyclic group (condition is that substituting group connects by heteroatoms).
X
2Preferably halogen atom is perhaps worked as X
2When representing linking group and having another substituting group to be connected with it, preferably it is expressed as follows group, for example the amino of the sulfydryl of the hydroxyl of hydroxyl, replacement, sulfydryl, replacement, amino, replacement or heterocyclic group (condition is that substituting group connects by heteroatoms).
Work as X
1And X
2When representing linking group and having another substituting group to be connected with it, this group can represent that its end can connect the group shown in n the formula (I) (n is the integer greater than 2) by eliminating the linking group with n connectable position that n hydrogen atom forms from group.
In addition, X
1And X
2Also can lump together the formation ring texture each other.
R
aAnd R
bRepresent that independently of one another hydrogen atom, halogen atom, cyano group or organic residue for example can have substituting group and can contain the alkyl of unsaturated link, the hydroxyl of replacement, the sulfydryl of replacement, the amino of replacement, the carbonyl or the carboxylate group of replacement.In addition, R
aAnd R
bAlso can lump together the formation ring texture each other.
Each substituent X in the formula (I)
1, X
2, R
aAnd R
bExample as described below.
The example that can have substituting group and can contain the alkyl of unsaturated link comprises the alkynyl group of alkenyl, alkynyl group and replacement of aryl, alkenyl, the replacement of alkyl, aryl, the replacement of alkyl, replacement.
Alkyl comprises the alkyl of the straight chain, side chain or the ring-type that contain 1-20 carbon atom, and its concrete example 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.Wherein, preferably contain 1-12 carbon atom straight chained alkyl, contain the branched alkyl of 3-12 carbon atom and contain the cyclic alkyl of 5-10 carbon atom.
The alkyl that replaces combines with alkylidene by substituting group and forms.Substituting group is the monovalence non-metal atom group except that hydrogen atom; its preferred example comprise halogen atom (for example-F;-Br;-Cl;-I); hydroxyl; alkoxy; aryloxy group; sulfydryl; alkylthio group; arylthio; the alkyl dimercapto; the aryl dimercapto; amino; the N-alkyl amino; N; the N-dialkyl amido; the N-arylamino; N; the N-ammonia diaryl base; N-alkyl-N-arylamino; acyloxy; carbamoyloxy; N-alkyl carbamoyloxy base; N-arylamino formyloxy; N; N-dialkyl amido formyloxy; N; N-ammonia diaryl base formyloxy; N-alkyl-N-arylamino formyloxy; alkylsulfonyloxy; aryl-sulfonyl oxygen; the acyl sulfenyl; acyl amino; N-alkyl acyl amino; N-aryl-acyl amino; urea groups; N '-alkyl urea groups; N '; N '-dialkyl group urea groups; N '-aryl-ureido; N '; N '-diaryl urea groups; N '-alkyl-N '-aryl-ureido; N-alkyl urea groups; the N-aryl-ureido; N '-alkyl-N-alkyl urea groups; N '-alkyl-N-aryl-ureido; N '; N '-dialkyl group-N-alkyl urea groups; N '; N '-dialkyl group-N-aryl-ureido; N '-aryl-N-alkyl urea groups; N '-aryl-N-aryl-ureido; N '; N '-diaryl-N-alkyl urea groups; N '; N '-diaryl-N-aryl-ureido; N '-alkyl-N '-aryl-N-alkyl urea groups; N '-alkyl-N '-aryl-N-aryl-ureido; alkoxycarbonyl amido; aryloxy carbonyl amino; N-alkyl-N-alkoxycarbonyl amido; N-alkyl-N-aryloxy carbonyl amino; N-aryl-N-alkoxycarbonyl amido; N-aryl-N-aryloxy carbonyl amino; formoxyl; acyl group; carboxyl and conjugate base group (hereinafter referred to as carboxylate radical); alkoxy carbonyl group; aryloxy carbonyl; carbamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formoxyl; the N-aryl-amino-carbonyl; N, N-ammonia diaryl base formoxyl; N-alkyl-N-aryl-amino-carbonyl; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; sulfo group (SO
3H) and conjugate base group (hereinafter referred to as sulfonate group); the alkoxy sulfonyl; aryloxy sulfonyl; amino sulfinyl; N-alkyl amino sulfinyl; N; N-dialkyl amido sulfinyl; N-arylamino sulfinyl; N; N-ammonia diaryl base sulfinyl; N-alkyl-N-arylamino sulfinyl; sulfamoyl; the N-alkylsulfamoyl group; N; the N-dialkyl sulfamine; the N-ammonia aryl sulfonyl; N, N-ammonia diaryl sulfonyl; N-alkyl-N-ammonia aryl sulfonyl; N-acyl group sulfamoyl and conjugate base group thereof; N-alkyl sulphonyl sulfamoyl (SO
2NHSO
2(alkyl)) and conjugate base group, N-aryl sulfonyl sulfamoyl (SO
2NHSO
2(allyl)) and conjugate base group, N-alkyl sulfonyl-amino formoxyl (CONHSO
2(alkyl)) and conjugate base group, N-aryl-sulfonyl-amino-carbonyl (CONHSO
2(allyl)) and conjugate base group, alkoxysilane group (Si (O alkyl)
3), aryloxy silane base (Si (O allyl)
3), silicol base (Si (OH)
3) and conjugate base group, phosphono (PO
3H
2) and conjugate base group (hereinafter referred to as phosphonate radical), dialkyl phosphine acyl group (PO
3(alkyl)
2), diaryl phosphono (PO
3(aryl)
2), alkylaryl phosphono (PO
3(alkyl) (aryl)), monoalkyl phosphono (PO
3H (alkyl)) and conjugate base group (hereinafter referred to as the alkylphosphines acid group), single aryl phosphine acyl group (PO
3H (aryl)) and conjugate base group (hereinafter referred to as the aryl phosphine acid group), phosphonato (OPO
3H
2) and conjugate base group (hereinafter referred to as phosphonate radical oxygen base), dialkyl phosphine acyloxy (OPO
3(alkyl)
2), diaryl phosphonato (OPO
3(aryl)
2), alkylaryl phosphonato (OPO
3(alkyl) (aryl)), monoalkyl phosphonato (OPO
3H (alkyl)) and conjugate base group (hereinafter referred to as alkylphosphines acid group oxygen base), single aryl phosphine acyloxy (OPO
3H (aryl)) and conjugate base group (hereinafter referred to as aryl phosphine acid group oxygen base), cyano group, nitro, aryl, alkenyl and alkynyl group.
In these substituting groups; the object lesson of alkyl comprises above-mentioned alkyl, and the object lesson of aryl comprises phenyl; xenyl; naphthyl; tolyl; xylyl; trimethylphenyl; cumyl; chlorphenyl; bromophenyl; chloromethyl phenyl; hydroxy phenyl; methoxyphenyl; ethoxyl phenenyl; Phenoxyphenyl; the acetoxyl group phenyl; the benzoyloxy phenyl; the methyl mercapto phenyl; the thiophenyl phenyl; the methylamino phenyl; dimethylaminophenyl; the acetyl-amino phenyl; carboxyl phenyl; the methoxycarbonyl group phenyl; the ethoxyl phenenyl carbonyl; the carbobenzoxy phenyl; N-phenyl amino formoxyl phenyl; phenyl; nitrobenzophenone; cyano-phenyl; the sulfo group phenyl; the sulfonate radical phenyl; phosphono phenyl and phosphonate radical phenyl.The example of alkenyl comprises vinyl, 1-propenyl, 1-butenyl group, cinnamyl and 2-chloro-1-vinyl, and the example of alkynyl group comprises ethinyl, 1-propinyl, 1-butynyl, TMS ethinyl and phenylacetylene base.
Acyl group (R
4CO-) example comprises wherein R
4It is the group of hydrogen atom or abovementioned alkyl, aryl, alkenyl or alkynyl group.
The example of the alkylidene in the alkyl that replaces comprises from the above-mentioned alkyl that contains 1 to 20 carbon atom eliminates the organic residue of the formed divalence of any one hydrogen atom, preferably contain 1 to 12 carbon atom straight-chain alkyl-sub-, contain the branched alkylidene of 3 to 12 carbon atoms and contain the cyclic alkylidene of 5 to 10 carbon atoms.The examples of groups of the alkyl that replaces comprises chloromethyl; bromomethyl; the 2-chloroethyl; trifluoromethyl; methoxy; methoxyethoxyethyl; the allyloxy methyl; phenoxymethyl; methylthiomethyl; toluene sulfenyl methyl; the ethylamino ethyl; the diethylamino propyl group; the morpholino propyl group; acetoxy-methyl; the benzoyloxy methyl; N-cyclohexyl carboxyamide oxygen base ethyl; N-phenyl amino formyloxy ethyl; the acetyl-amino ethyl; N-methyl benzoyl aminopropyl; the 2-oxoethyl; the 2-oxopropyl; the carboxyl propyl group; the methoxycarbonyl group ethyl; the methoxycarbonyl group methyl; the methoxycarbonyl group butyl; ethoxycarbonylmethyl group; the butoxy carbonyl methyl; the allyloxycarbonyl methyl; the benzyloxycarbonyl group methyl; the methoxycarbonyl group phenyl methyl; trichloromethyl carbonyl acyl methyl; the allyloxycarbonyl butyl; chlorobenzene oxygen carbonyl methyl; the carbamyl ylmethyl; N-methylamino formoxyl ethyl; N, N-dipropyl carbamyl ylmethyl; N-(methoxyphenyl) carbamyl ethyl; N-methyl-N-(sulfo group phenyl) carbamyl ylmethyl; the sulfo group propyl group; the sulfo group butyl; the sulfonate radical butyl; the sulfamoyl butyl; N-ethyl sulfamoyl methyl; dipropyl sulfamoyl propyl group; N-tolyl sulfamoyl propyl group; N-methyl-N-(phosphono phenyl) sulfamoyl octyl group;
[changing 3]
CH
3CONHSO
2CH
2CH
2CH
2CH
2-、
The phosphono butyl; the phosphonate radical hexyl; the diethyl phosphonyl butyl; diphenylphosphine acyl group propyl group; methylphosphine acyl group butyl; methylphosphine acid group butyl; tolylphosphine acyl group hexyl; tolylphosphine acid group hexyl; the phosphonato propyl group; phosphonate radical oxygen Ji Dingji; benzyl; phenethyl; α-Jia Jibianji; 1-methyl isophthalic acid-phenylethyl; right-methyl-benzyl; cinnamyl; allyl; 1-propenyl methyl; the 2-butenyl group; the 2-methacrylic; 2-metering system ylmethyl; 2-propynyl; 2-butynyl and 3-butynyl.
The example of aryl includes the fused rings of 1-3 phenyl ring formation and by phenyl ring and 5 yuan of fused rings that unsaturated ring forms, the example of its group comprises phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl and fluorenyl, preferred phenyl and naphthyl.
The aryl that replaces combines with aryl by substituting group and forms, and is included in other monovalence non-metal atom group of having on the one-tenth ring carbon atom of above-mentioned aryl except that hydrogen atom as substituent group.The example of preferred substituted comprises the alkyl of above-mentioned alkyl, replacement and the substituting group of substituted alkyl.The example of the aryl of particularly preferred replacement comprises xenyl; tolyl; xylyl; trimethylphenyl; cumyl; chlorphenyl; bromophenyl; fluorophenyl; chloromethyl phenyl; trifluoromethyl; hydroxy phenyl; methoxyphenyl; the methoxy ethoxy phenyl; the allyloxy phenyl; Phenoxyphenyl; the methyl mercapto phenyl; toluene sulfenyl phenyl; the thiophenyl phenyl; the ethylamino phenyl; the diethylamino phenyl; the morpholino phenyl; the acetoxyl group phenyl; the benzoyloxy phenyl; N-cyclohexyl carboxyamide oxygen base phenyl; N-phenyl amino formyloxy phenyl; the acetyl-amino phenyl; N-methyl benzoyl aminophenyl; carboxyl phenyl; the methoxycarbonyl group phenyl; the allyloxycarbonyl phenyl; chlorobenzene oxygen carbonyl phenyl; the carbamyl phenyl; N-methylamino formoxyl phenyl; N; N-dipropyl carbamyl phenyl; N-(methoxyphenyl) carbamyl phenyl; N-methyl-N-(sulfo group phenyl) carbamyl phenyl; the sulfo group phenyl; the sulfonate radical phenyl; the sulfamoyl phenyl; N-ethyl sulfamoyl phenyl; N, N-dipropyl sulfamoyl phenyl; N-tolyl sulfamoyl phenyl; N-methyl-N-(phosphono phenyl) sulfamoyl phenyl; the phosphono phenyl; the phosphonate radical phenyl; the diethyl phosphonyl phenyl; diphenylphosphine acyl group phenyl; methylphosphine acyl group phenyl; methylphosphine acid group phenyl; tolylphosphine acyl group phenyl; tolylphosphine acid group phenyl; allyl; 1-propenyl methyl; the 2-butenyl group; 2-methacrylic phenyl; 2-methylpropenyl phenyl; 2-propenyl phenyl; 2-butynyl phenyl and 3-butynyl phenyl.
The example of alkenyl comprises above-mentioned alkenyl.The alkenyl that replaces is combined by the displacement hydrogen atom with alkenyl by substituting group and forms.Substituent example comprises the substituting group of the alkyl of above-mentioned replacement, and the example of alkenyl comprises above-mentioned alkenyl.Preferred substituted alkenyl base comprises:
[changing 4]
CH
3O
2CCH
2CH＝CHCH
2-、
HO
2CCH
2CH＝CHCH
2-、
CH
2＝CH-CH＝CH-CH
2-、 Cl-CH
2CH＝CHCH
2-、
HS-CH
2CH＝CHCH
2-
The example of alkynyl group comprises above-mentioned alkynyl group.The alkynyl group that replaces is combined by the displacement hydrogen atom with alkynyl group by substituting group and forms.Substituent example comprises the substituting group of the alkyl of above-mentioned replacement, and the example of alkynyl group comprises above-mentioned alkynyl group.
Heterocyclic group comprises the univalent perssad that forms by a hydrogen atom of eliminating on the heterocycle, and by eliminating a hydrogen atom from above-mentioned univalent perssad again and it is combined the univalent perssad that forms (heterocyclic group of replacement) with the substituting group of above-mentioned substituted alkyl.The preferred example of heterocycle comprises:
[changing 5]
[changing 6]
Oxygen base (the R that replaces
5CO-) comprise wherein R
5It is the group of other monovalence non-metallic atom except that hydrogen atom.The example of the preferred oxygen base that replaces comprises alkoxy, aryloxy group, acyloxy, carbamoyloxy, N-alkyl carbamoyloxy base, N-arylamino formyloxy, N, N-dialkyl amido formyloxy, N, N-ammonia diaryl base formyloxy, N-alkyl-N-arylamino formyloxy, alkylsulfonyloxy, aryl-sulfonyl oxygen, phosphonato and phosphonate radical oxygen base.The alkyl in these groups and the example of aryl comprise the alkyl of above-described alkyl and replacement and the aryl of aryl and replacement.Acyl group (R in the acyloxy
6CO-) example comprises wherein R
6It is the group of aryl of alkyl, aryl or the replacement of above-described alkyl, replacement.In these substituting groups, more preferably alkoxy, aryloxy group, acyloxy and aryl-sulfonyl oxygen.The object lesson of the preferred oxygen base that replaces comprises methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, amoxy, own oxygen base, lauryl oxygen base, benzyloxy, allyloxy, the benzene ethoxy, the carboxyl ethoxy, the methoxycarbonyl group ethoxy, the carbethoxyl group ethoxy, methoxy ethoxy, the phenoxy group ethoxy, the methoxy ethoxy ethoxy, ethoxy ethoxy ethoxy, the morpholino ethoxy, the morpholino propoxyl group, the allyloxy ethoxy ethoxy, phenoxy group, toloxyl, xylyloxy, the front three phenoxy group, isopropyl benzene oxygen base, the methoxyl phenoxy group, ethoxy phenoxy, chlorophenoxy, the bromine phenoxy group, acetoxyl group, benzoyloxy, naphthoxy, the phenyl sulfonyloxy, phosphonato and phosphonate radical oxygen base.
Sulfydryl (the R of operable replacement
7S-) example comprises wherein R
7It is the group of other monovalence non-metallic atom except that hydrogen atom.The preferred sulfydryl that replaces comprises alkylthio group, arylthio, alkyl dimercapto, aryl dimercapto and acyl sulfenyl.The alkyl in these groups and the example of aryl comprise the alkyl of above-described alkyl and replacement and the aryl of aryl and replacement.Acyl group (R in the acyl sulfenyl
6CO-) R
6With described above identical.Wherein, more preferably alkylthio group and arylthio.The sulfydryl that replaces comprises methyl mercapto, ethylmercapto group, thiophenyl, ethoxy ethylmercapto group, carboxyl ethylmercapto group and methoxycarbonyl group thio group.
Amino (the R that replaces
8NH-, (R
9) (R
10) N-) and example comprise wherein R
8, R
9And R
10It is respectively the group of other monovalence non-metallic atom except that hydrogen atom.The preferred example of the amino that replaces comprises the N-alkyl amino; N; the N-dialkyl amido; the N-arylamino; N; the N-ammonia diaryl base; N-alkyl-N-arylamino; acyl amino; N-alkyl acyl amino; N-aryl-acyl amino; urea groups; N '-alkyl urea groups; N '; N '-dialkyl group urea groups; N '-aryl-ureido; N '; N '-diaryl urea groups; N '-alkyl-N '-aryl-ureido; N-alkyl urea groups; the N-aryl-ureido; N '-alkyl-N-alkyl urea groups; N '-alkyl-N-aryl-ureido; N '; N '-dialkyl group-N-alkyl urea groups; N '; N '-dialkyl group-N '-aryl-ureido; N '-aryl-N-alkyl urea groups; N '-aryl-N-aryl-ureido; N '; N '-diaryl-N-alkyl urea groups; N ', N '-diaryl-N-aryl-ureido; N '-alkyl-N '-aryl-N-alkyl urea groups; N '-alkyl-N '-aryl-N-aryl-ureido; alkoxycarbonyl amido; aryloxy carbonyl amino; N-alkyl-N-alkoxycarbonyl amido; N-alkyl-N-aryloxy carbonyl amino; N-aryl-N-alkoxycarbonyl amido and N-aryl-N-aryloxy carbonyl amino.
The alkyl in these groups and the example of aryl comprise the alkyl of above-described alkyl and replacement and the aryl of aryl and replacement, the acyl group (R in acylamino-, N-alkyl amido and the N-aryl acylamino-
6CO-) R
6With described above identical.Wherein, preferred N-alkyl amino, N, N-dialkyl amido, N-arylamino and acylamino-.The example of the preferred amino that replaces comprises methylamino, ethylamino, diethylamino, morpholino group, piperidino, pyrrolidinyl, phenyl amino, benzamido and acetyl-amino.
Carbonyl (the R of operable replacement
11-CO-) example comprises wherein R
11It is the group of monovalence non-metallic atom.The example of the preferred carbonyl that replaces comprises formoxyl, acyl group, carboxyl, alkoxy carbonyl group, aryloxy carbonyl, carbamyl, N-alkyl-carbamoyl, N; N-dialkyl amido formoxyl, N-aryl-amino-carbonyl, N, N-ammonia diaryl base formoxyl and N-alkyl-N '-aryl-amino-carbonyl.The alkyl in these groups and the example of aryl comprise the alkyl of above-described alkyl and replacement and the aryl of aryl and replacement.Wherein, the preferred carbonyl that replaces comprises formoxyl, acyl group, carboxyl, alkoxy carbonyl group, aryloxy carbonyl, carbamyl, N-alkyl-carbamoyl, N; N-dialkyl amido formoxyl and N-aryl-amino-carbonyl, more preferably formoxyl, acyl group, alkoxy carbonyl group and aryloxy carbonyl.The object lesson of the preferred carbonyl that replaces comprises formoxyl, acetyl group, benzoyl, carboxyl, methoxycarbonyl group, allyloxycarbonyl, N-methylamino formoxyl, N-phenyl amino formoxyl, N, N-diethylamino formoxyl and morpholino carbonyl.
Sulfinyl (the R of operable replacement
12-SO-) example comprises wherein R
12It is the group of monovalence non-metallic atom.Its preferred example comprises alkyl sulphinyl, aryl sulfonyl kia, amino sulfinyl, N-alkyl amino sulfinyl, N; N-dialkyl amido sulfinyl, N-arylamino sulfinyl, N, N-ammonia diaryl base sulfinyl and N-alkyl-N-arylamino sulfinyl.Alkyl in these groups and aryl comprise the alkyl of above-described alkyl and replacement and the aryl of aryl and replacement.Wherein, more preferably alkyl sulphinyl and aryl sulfonyl kia.The object lesson of the sulfinyl that replaces comprises hexyl sulfinyl, benzyl sulfinyl and tolyl sulfinyl.
Sulfonyl (the R that replaces
13-SO
2-) example comprise wherein R
13It is the group of monovalence non-metallic atom.Its preferred example comprises alkyl sulphonyl and aryl sulfonyl.Alkyl in these groups and aryl comprise the alkyl of above-described alkyl and replacement and the aryl of aryl and replacement.The object lesson of the sulfonyl that replaces comprises butyl sulfonyl and chlorphenyl sulfonyl.
Sulfonate group (SO
3-) be meant above-described sulfo group (SO
3H) conjugate base anionic group, usually, sulfonate group is preferably used with counter cation.The example of counter cation comprises known kation, more particularly, comprises various (for example ammonium, Liu, Phosphonium, iodine, aziniums) and metallic ion (for example, Na
+, K
+, Ca
2+, Zn
2+).
Carboxylate radical (CO
2-) be meant above-described carboxyl (CO
2H) conjugate base anionic group, usually, carboxylate group is preferably used with counter cation.The example of counter cation comprises known kation, more particularly, comprises various (for example ammonium, Liu, Phosphonium, iodine, aziniums) and metallic ion (for example, Na
+, K
+, Ca
2+, Zn
2+).
The phosphono that replaces is meant that its preferred example comprises dialkyl phosphine acyl group, diaryl phosphono, alkylaryl phosphono, monoalkyl phosphono and single aryl phosphine acyl group by replace the formed compound of one or two hydroxyl on the phosphono with other organic oxo group.Wherein, preferred dialkyl phosphine acyl group and diaryl phosphono.The example of its group comprises diethyl phosphonyl, dibutyl phosphono and diphenylphosphine acyl group.
Phosphonate radical (PO
3 2-,-PO
3H-) be meant by phosphono (PO
3H
2) the acid formed conjugate base anionic group that dissociates for the first time or dissociate for the second time of acid, usually, phosphonate groups is preferably used with counter cation.The example of counter cation comprises known kation, more particularly, comprises various (for example ammonium, Liu, Phosphonium, iodine, aziniums) and metallic ion (for example, Na
+, K
+, Ca
2+, Zn
2+).
Phosphonate radical (the PO that replaces
3 2-,-PO
3H-) be a hydroxyl wherein to be arranged by the conjugate base anionic group of the phosphono of the above-mentioned replacement that organic oxo group replaced.Its concrete example comprises above-mentioned monoalkyl phosphono (PO
3H (alkyl)) conjugate base and single aryl phosphine acyl group (PO
3H (aryl)) conjugate base.Usually, the phosphonate groups of replacement is preferably used with counter cation.The example of counter cation comprises known kation, more particularly, comprises various (for example ammonium, Liu, Phosphonium, iodine, aziniums) and metallic ion (for example, Na
+, K
+, Ca
2+, Zn
2+).
By with X
1And X
2, R
aAnd R
bOr X
1And R
aOr R
bThe formed ring texture of combination with one another is as described below.By with X
1And X
2, R
aAnd R
bOr X
1And R
aOr R
bThe formed aliphatics ring of combination with one another comprises 5-, 6-, 7-or 8-unit aliphatics ring, more preferably 5-or 6-unit aliphatics ring.The aliphatics ring can also become ring carbon atom to be replaced by heteroatoms (for example oxygen atom, sulphur atom, nitrogen-atoms) having a substituting group (substituent example comprises the substituting group on the alkyl of above-mentioned replacement) or a part on the carbon atom that constitutes ring.In addition, the part of aliphatics ring can also constitute the part of aromatic ring.
Object lesson with compound of structure shown in the formula (I) is as follows.
[table 1]
I) single function fundamental mode (A group)
Table-1
[table 2]
-1 (continuing) of table
[table 3]
-1 (continuing) of table
[table 4]
-1 (continuing) of table
[table 5]
(B group) table-2
[table 6]
Ii) 2 function fundamental modes (C group)
Table-3
[table 7]
-3 (continuing) of table
[table 8]
-3 (continuing) of table
[table 9]
(D group)
Table-4
[table 10]
-4 (continuing) of table
[table 11]
-4 (continuing) of table
[table 12]
Iii) more than the 3 function fundamental modes (E group)
Table-5
[table 13]
-5 (continuing) of table
[table 14]
-5 (continuing) of table
[table 15]
The F group
Table-6
[table 16]
-6 (continuing) of table
[changing 7]
Iv) polymer electrolyte
[changing 8]
[changing 9]
[changing 10]
[changing 11]
[changing 12]
V) other
The H group
[changing 13]
The J group
[changing 14]
Compound of the present invention contains multi-functional fundamental mode (dual-functional group or greater functionality fundamental mode or the polymer-type) compound of structure shown in two or more formulas (I) particularly preferably in molecule or contains the compound of the combination of structure shown in the formula (I) and another kind of radical polymerization group, and it can play the effect of multi-functional base to photopolymerization.
In optical polymerism composition of the present invention, compound with structure shown in the formula (I) uses as the compound that has addition polymerization alkene unsaturated link, this compound can use separately or use with two or more array configuration, perhaps to use with the following known potpourri that has the compound of addition polymerization alkene unsaturated link.
The known example that has the compound of addition polymerization alkene unsaturated link comprises unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid) and the ester of aliphatic polyol compound and the acid amides of above-mentioned unsaturated carboxylic acid and aliphatic polyamine compound.
The object lesson of the ester monomer of aliphatic polyol compound and unsaturated carboxylic acid comprises acrylate, glycol diacrylate for example, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, 1, the 4-butanediol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris-(acryloxy propyl group) ether, the methyltrimethylolmethane triacrylate, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol diacrylate, dipentaerythritol acrylate, the sorbierite triacrylate, the sorbierite tetraacrylate, sorbierite five acrylate, sorbierite six acrylate, three (acryloxy ethyl) cyanonitroacetamide ester and polyester-acrylate oligomer;
Methacrylate, for example 1, the 4-butanediol dimethylacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the methyltrimethylolmethane trimethyl acrylic ester, ethylene glycol dimethacrylate, the 1,3 butylene glycol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, the sorbierite trimethyl acrylic ester, sorbierite tetramethyl acrylate, two [right-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethane and two [right-(acryloxy-ethoxy) phenyl] dimethylmethane; Itaconate is ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3 butylene glycol diitaconate, 1 for example, 4-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, pentaerythrite diitaconate and sorbierite four itaconates; Crotonates is ethylene glycol bisthioglycolate crotonates, 1 for example, 4-butylene glycol two crotonatess, pentaerythrite two crotonatess and sorbierite four crotonatess; The iso-crotonic acid ester is ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters and sorbierite four iso-crotonic acid esters for example; Maleate is ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate and sorbierite four maleates for example; And the potpourri of these ester monomers.The object lesson of the amide monomer that aliphatic polyamine compound and unsaturated carboxylic acid form comprises, methylene diacrylamine, methylene DMAA, 1,6-hexylidene diacrylamine, 1,6-hexylidene DMAA, diethylene triamine three acrylamides, two methylene phenyl diacrylamines and two methylene phenyl DMAAs.
Other example comprises the vinyl urethane compound of describing among the JP-B-48-41708 that contains two or more polymerizable vinyl in a molecule, and this compound is by making vinyl monomer that has hydroxyl shown in the formula (A) and the polyisocyanate compounds addition that has two or more isocyanate groups in a molecule:
CH
2＝C(R)COOCH
2CH(R’)OH (A)
Wherein R and R ' represent H or CH respectively
3
In addition, the urethane acrylate that can also use multi-functional basic acrylate and methacrylate for example to describe among the JP-A-51-37193; The polyester acrylate of describing among JP-A-48-64183, JP-B-49-43191 and the JP-B-52-30490; And epoxy acrylate by epoxy resin and the reaction of (methyl) acrylic acid are made.In addition, can also use " Japanese bonding agent meeting will " (Journal of Japan AdhesiveSociety), 20 volumes, photo-curing monomer or the oligomer described among the No.7,300-308 page or leaf (1984).In the present invention, the chemical species that these monomers all can polymkeric substance (dimer, tripolymer or oligomer) or its potpourri use.
Contain all polymerizable compounds, comprise that the consumption of the compound of the compound of structure shown in (I) that has formula is generally 1 to 99.99%, preferred 5 to 90.0%, more preferably 10 to 70% (" % " used herein is meant " weight % (wt%) ") are in the general assembly (TW) of each composition of optical polymerism composition.
But the content with The compounds of this invention of structure shown in the formula (I) in containing the compound of all polymerizable groups is 0.005 to 100wt%, and preferred 1 to 100wt%, and more preferably 30 to 100wt%.If content is lower than 0.005wt%, then possibly can't reach effect of the present invention.
Optical polymerism composition of the present invention, wherein, described composition is 300 to 1 by wavelength, the laser light source sensitization of 200nm.
Optical polymerism composition of the present invention, wherein, the molecular weight with described compound of structure shown in the formula (I) is 4,000-100,000.
Below Photoepolymerizationinitiater initiater used in the optical polymerism composition of the present invention will be described.
The example of preferred Photoepolymerizationinitiater initiater comprises (a) aromatic ketone, (b) aromatic series salt, (c) organic peroxide, (d) thio-compounds, (e) Hexaarylbiimidazole compound, (f) ketoxime ester compounds, (g) borate compound, (h) azinium compound, (i) Metallocenic compound, (j) active ester compounds and (k) has the compound of carbon-halogen bond.
The example of preferred aromatic ketone (a) comprises having benzophenone skeleton or J.P.Fouassier and J.F.Rabek, the compound of the thioxanthones skeleton of describing in " radiation in polymer science and the technology is solidified " (Radiation Curing in PolymerScience and Technology) 77-117 page or leaf (1993), for example:
[changing 15]
[changing 16]
[changing 17]
The example of preferred aromatic ketone (a) comprises the benzoin ether of describing among α-sulfo-benzophenone of describing among the JP-B-47-6416, the JP-B-47-3981, for example
[changing 18]
The benzoin compound of the alpha-substituted of describing among the JP-B-47-22326, for example
[changing 19]
The dialkoxy benzophenone compound of describing among the aroyl phosphate derivatives of describing among the benzoin derivatives of describing among the JP-B-47-23664, the JP-A-57-30704, the JP-B-60-26483, for example
[changing 20]
The benzoin ether of describing among JP-B-60-26403 and the JP-A-62-81345, for example
[changing 21]
The alpha-amido benzophenone compound of describing among JP-B-1-34242, United States Patent (USP) 4,318,791 and the European patent 0284561A1, for example
[changing 22]
Right-two (dimethylamino benzoyl) benzene compound of describing among the JP-A-2-211452, for example
[changing 23]
The aromatic ketone compound that the sulphur of describing among the JP-A-61-194062 replaces, for example
[changing 24]
The acylphosphanes sulfide of describing among the JP-B-2-9597, for example
[changing 25]
The acylphosphanes compound of describing among the JP-B-2-9596, for example
[changing 26]
The coumarin compound of describing among thioxanthones compound of describing among the JP-B-63-61950 and the JP-B-59-42864.
The aromatic series salt that comprises periodic table of elements V, VI and VII family element, particularly N, P, As, Sb, Bi, O, S, Se, Te and I as the example of the aromatic series salt (b) of another example.The example of aromatic series salt comprises the compound of describing among JP-B-52-14277, JP-B-52-14278 and the JP-B-52-14279.Its concrete example comprises following compound.
[changing 27]
[changing 28]
[changing 29]
[changing 30]
In addition, can also use diazo salt as follows.
[changing 31]
(diazo salt or quinonediazide)
[changing 32]
The example that is used as another example organic peroxide (c) of Photoepolymerizationinitiater initiater in the present invention comprises nearly all compound that has one or more o-o bonds in molecule, its example comprises methyl ethyl ketone peroxide, the cyclohexanone superoxide, 3,3, the 5-trimethyl hexanone peroxide, methyl cyclohexanone peroxide, acetylacetone peroxide, 1,1-two (t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane, 1,1-two (t-butylperoxy) cyclohexane, 2,2-two (t-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide hydrogen, the diisopropyl benzene hydrogen peroxide, the paramethane hydrogen peroxide, 2,5-dimethylhexane-2,5-diperoxy hydrogen, 1,1,3, the 3-tetramethyl butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl group cumyl peroxide, dicumyl peroxide, two (tert-butyl peroxide isopropyl) benzene, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, 2, the 5-oxanoyl superoxide, succinyl peroxide, benzoyl peroxide, peroxidating 2, the 4-dichloro-benzoyl, between peroxidating-toluoyl, diisopropyl peroxydicarbonate, two-2-ethylhexyl peroxide, two carbonic esters, two-2-ethoxyethyl group peroxide, two carbonic esters, dimethoxy isopropyl peroxy carbonates, two (3-methyl-3-methoxyl butyl) peroxide two carbonic esters, the t-butyl peroxy acetic acid esters, the t-butyl peroxy pivalate, t-butyl peroxy neodecanoic acid ester, the t-butyl peroxy caprylate, t-butyl peroxy-3,5,5-tri-methyl hexanoic acid ester, the t-butyl peroxy laurate, tertiary carbonate, 3,3 ', 4,4 '-four-(t-butyl peroxy carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(tertiary pentyl peroxide carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(uncle's hexyl peroxide carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(uncle's octyl group peroxide carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(cumyl peroxide carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(right-isopropyl cumyl peroxide carbonyl)-benzophenone, carbonyl two (tert-butyl peroxide dihydro biphthalate) and carbonyl two (peroxidating uncle hexyl dihydro biphthalate).
Wherein, preferred ester superoxide, for example 3,3 ', 4,4 '-four-(t-butyl peroxy carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(tertiary pentyl peroxide carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(uncle's hexyl peroxide carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(uncle's octyl group peroxide carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(cumyl peroxide carbonyl)-benzophenone, 3,3 ', 4,4 '-four-(right-isopropyl cumyl peroxide carbonyl)-benzophenone and di-t-butyl diperoxy isophthalic acid ester.
In the present invention as another example thio-compounds (d) of Photoepolymerizationinitiater initiater as shown in the formula shown in [II],
[changing 33]
R wherein
20The aryl of expression alkyl, aryl or replacement, R
21Expression hydrogen atom or alkyl, or R
20And R
21Expression formation can be lumped together each other and heteroatomic 5, the 6 or 7 yuan of non-metallic atoms that ring is required that are selected from oxygen atom, sulphur atom and nitrogen-atoms can be contained.
Alkyl in the formula [II] preferably contains the alkyl of 1-4 carbon atom.Aryl preferably contains the aryl of 6-10 carbon atom, and for example phenyl and naphthyl, the aryl of replacement comprise by halogen atom chlorine, alkyl methyl or the alkoxy above-mentioned aryl that replaces of methoxyl and ethoxy for example for example for example.R
21The alkyl that preferably contains 1-4 carbon atom.The object lesson of the thio-compounds shown in the formula [II] comprises compound.
[table 17]
The example that is used as another example Hexaarylbiimidazole (e) of Photoepolymerizationinitiater initiater in the present invention comprises the lophine dipolymer described in JP-B-45-37377 and the JP-B-44-86516, for example 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (neighbour-bromophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (neighbours, right-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-four (-methoxyphenyl)-diimidazole, 2,2 '-two (neighbour, neighbour '-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (o-nitrophenyl)-4,4 ', 5,5-tetraphenyl diimidazole, 2,2 '-two (neighbour-aminomethyl phenyl)-4,4 ', 5,5-tetraphenyl diimidazole and 2,2 '-two (neighbour-trifluorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole.
In the present invention as the example of another example ketoxime ester (f) of Photoepolymerizationinitiater initiater comprise 3-benzoyloxy imino group fourth-2-ketone, 3-acetoxyl group imino group fourth-2-ketone, 3-propionyloxy imino group fourth-2-ketone, 2-acetoxyl group imino group penta-3-ketone, 2-acetoxyl group imino group-1-phenyl third-1-ketone, 2-benzoyloxy imino group-1-phenyl third-1-ketone, 3-right-tosyloxy imino group fourth-2-ketone and 2-ethoxy carbonyl oxygen base-imino group-1-phenyl third-1-ketone.
The example that is used as another example borate (g) of Photoepolymerizationinitiater initiater in the present invention comprises the compound shown in the following formula [III]:
[changing 34]
R wherein
22, R
23, R
24And R
25Can be identical or different, represent replacement or unsubstituted alkyl, replacement or unsubstituted aryl, replacement or unsubstituted alkenyl, replacement or unsubstituted alkynyl group or replacement or unsubstituted heterocyclic group respectively, R
22, R
23, R
24And R
25In two or more groups can lump together the formation ring texture, condition is R
22, R
23, R
24And R
25In have at least one to be to replace or unsubstituted alkyl Z
+Expression alkali metal cation or quaternary ammonium cation.R
22, R
23, R
24Or R
25The alkyl of expression comprises the alkyl of straight chain, side chain or ring-type, preferably contains 1 to 18 carbon atom.Its concrete example comprises methyl, ethyl, propyl group, isopropyl, butyl, amyl group, hexyl, octyl group, stearyl, cyclobutyl, cyclopentyl and cyclohexyl.The alkyl that replaces comprises the abovementioned alkyl that is replaced by following substituting group, and described substituting group is, for example halogen atom (for example-Cl ,-Br), cyano group, nitro, aryl (preferred phenyl), hydroxyl,
[changing 35]
R wherein
26And R
27Represent hydrogen atom independently of one another, contain 1-14 carbon atom alkyl or aryl ,-COOR
28, R wherein
28The expression hydrogen atom, contain 1-14 carbon atom alkyl or aryl ,-OCOR
29Or-OR
30, R wherein
29And R
30Expression contains the alkyl or aryl of 1-14 carbon atom respectively.R
22, R
23, R
24Or R
25That the aryl of expression comprises is single-, two-and three-cyclophane base, for example phenyl and naphthyl; The aryl that replaces comprises by the substituting group described in the alkyl of above-mentioned replacement or contains the above-mentioned aryl of the alkyl replacement of 1-14 carbon atom.R
22, R
23, R
24Or R
25The alkenyl of expression comprises that the alkenyl of the straight chain, side chain and the ring-type that contain 2-18 carbon atom respectively, the substituting group of the alkenyl of replacement comprise the substituting group described in the alkyl of above-mentioned replacement.R
22, R
23, R
24Or R
25The alkynyl group of expression comprises straight chain and the side chain alkynyl group that contains 2-28 carbon atom respectively, and the substituting group of the alkynyl group of replacement comprises the substituting group described in the alkyl of above-mentioned replacement.R
22, R
23, R
24Or R
25The heterocyclic group of expression comprises more than 5 yuan, preferred 5 to the 7 yuan heterocyclic group that contains at least one N, S or O, and described heterocyclic group can contain the substituting group described in ring that condenses and the alkyl that can have above replacement.
The object lesson of compound comprises United States Patent (USP) 3,567 shown in the formula [III], 435 and 4,343,891 and European patent 109,772 and 109,773 described in compound and following compound.
[changing 36]
The example that is used as another example azinium salt compound (h) of Photoepolymerizationinitiater initiater in the present invention comprises the compound that contains the N-O key described in JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143537 and the JP-B-46-42363.
The example that is used as another example Metallocenic compound (i) of Photoepolymerizationinitiater initiater in the present invention comprises the cyclopentadiene titanium compound described in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249 and the JP-A-2-4705 and JP-A-1-304453 and JP-A-1-152109 iron-propadiene complex.
Specific cyclopentadienyl titanium compounds include dicyclopentadienyl-Ti-dichloride, dicyclopentadiene
Alkenyl-Ti-biphenyl, dicyclopentadienyl-Ti-two ,3,4,5,6 - pentafluoro - phen-1 - yl, dicyclopentadiene
Two base-Ti-2 ,3,5,6 - tetrafluoro - phen-1 - yl, dicyclopentadienyl-Ti-two 4,6 - trifluoro - phen-1 -
Yl, dicyclopentadienyl-Ti-2 ,6 - difluoro - phen-1 - yl, dicyclopentadienyl-Ti-2 ,4 - difluoro
- Phen-1 - yl, dimethyl-cyclopentadienyl-Ti-two ,3,4,5,6 - pentafluoro - phen-1 - yl, dimethylcyclopentadienyl
Two cyclopentadienyl-Ti-2,3,5,6 - tetrafluoro - phen-1 - yl, dimethyl-cyclopentadienyl-Ti-2 ,4 - difluoro -
Phen-1 - yl, bis (cyclopentadienyl) - bis [2,6 - difluoro-3 - (pyrrol-1 - yl) phenyl] - titanium, bis (cyclopentadienyl
Enyl)-bis [2,6 - difluoro-3 - (methyl - sulfonyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-
-3 - (N-dibutyl alloyl amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-ethyl-
Acetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-methyl-acetylamino) phenyl
Yl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-ethyl-propionylamino) - phenyl] titanium, bis (ring
Pentadienyl) bis [2,6 - difluoro -3 - (N-ethyl - (2,2 - dimethylbutyl) amino) phenyl] titanium, bis (ring
Pentadienyl) bis [2,6 - difluoro -3 - (N-butyl - (2,2 - dimethylbutyl) amino) phenyl] titanium, bis (ring
Pentadienyl) bis [2,6 - difluoro -3 - (N-pentyl - (2,2 - dimethyl - butanoyl) amino) phenyl] titanium,
(Cyclopentadienyl) bis [2,6 - difluoro -3 - (N-hexyl) - (2,2 - dimethylbutyl) phenyl] - titanium, di (cyclo
Cyclopentadienyl) bis [2,6 - difluoro -3 - (N-methylbutanoyl-amino) phenyl] titanium, bis (cyclopentadienyl) - two
[2,6 - difluoro -3 - (N-methyl-pentanoyl-amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 -
(N-ethyl-cyclohexyl carbonyl amino) phenyl] titanium, bis (cyclopentadienyl) - bis [2,6 - difluoro -3 - (N-ethyl-
Isobutyryl-amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-ethyl-acetyl - amino)
Phenyl] titanium, bis (cyclopentadienyl) bis (2,6 - difluoro-3 - (2,2,5,5 - tetramethyl-1 ,2,5 - aza-
disilolidin-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (octyl sulfonamido)
Phenyl] titanium, bis (cyclopentadienyl) - bis [2,6 - difluoro-3 - (4 - methylphenyl) phenyl] titanium,
(Cyclopentadienyl) bis [2,6 - difluoro-3 - (4 - phenyl-lauryl - sulfonyl amino) phenyl] titanium, bis (cyclopentadienyl
Enyl)-bis [2,6 - difluoro-3 - (4 - (1 - pentyl - heptyl) phenyl - sulfonyl) phenyl] titanium, bis (cyclopentadienyl
Enyl)-bis [2,6 - difluoro-3 - (ethylsulfonyl) phenyl] - titanium, bis (cyclopentadienyl) bis - [2,6 -
Fluoro-3 - ((4 - bromophenyl) sulfonyl amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (2 - naphthyl
Yl) phenyl] - titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (hexadecyl sulfonylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-methyl - (4 - dodecylphenyl) - sulfonamide
Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-methyl-4 - (1 - pentyl-heptyl)-phenyl)
Sulfonyl amino)] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-hexyl - (4 - methylphenyl) sulfonylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (pyrrolidin-2 ,5 - dione-- yl) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (3,4 - dimethyl-3 - pyrrolidine-2 ,5 - dione-- yl) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (o-phthalimido) phenyl] titanium, bis (cyclopentadienyl
Enyl)-bis [2,6 - difluoro-3 - butoxycarbonyl, isobutoxycarbonyl - amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -
Fluoro-3 - (ethoxycarbonyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - ((2 - chloro-ethoxy)
Carbonyl - amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (phenoxycarbonyl - amino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (3 - phenyl thiourea yl) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6 - difluoro-3 - (3 - butyl thiourea yl) phenyl] - titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 -
(3 - phenyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (3 - butyl) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N, N-diacetyl amino) phenyl] - titanium, bis (cyclopentadienyl
Dienyl) bis [2,6 - difluoro-3 - (3,3 - dimethyl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6 -
Difluoro-3 - (acetylamino) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (butylamino) benzene
Yl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (decyl) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6 - difluoro-3 - (XVIII) phenyl] - titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (iso-
Butyl-amino) phenyl] titanium, bis (cyclopentadienyl) - bis [2,6 - difluoro-3 - (2 - ethylhexyl) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (2 - methyl butyric acid - amino) phenyl] titanium, bis (cyclopentadienyl
Dienyl) bis [2,6 - difluoro-3 - (pivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -
3 - (2,2 - dimethyl - butyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (2 - ethyl
-2 - methyl-heptyl) phenyl] - titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (cyclo - hexyl-ylcarbonyl
Amino) phenyl] titanium, bis (cyclopentadienyl) - bis [2,6 - difluoro-3 - (2,2 - dimethyl-3 - chloro amido
Yl) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (3 - phenyl-propionylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (2 - chloro-2 - methyl - 3 - chloropropyl acyl amino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (3,4 - xylene amido) - phenyl] titanium, bis (cyclopentadienyl
Dienyl) bis [2,6 - difluoro-3 - (4 - ethyl-benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis
[2,6 - difluoro-3 - (2,4,6 - methanesulfonyl-amino-carbonyl) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -
Difluoro-3 - (benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(3 - phenyl-
Propyl) benzoylamino) phenyl] - titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(3 - heptyl
Yl) -2,2 - dimethyl-pentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-iso-
Butyl - (4 - methyl-benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-isobutyryl
-Benzoyl amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-cyclohexyl - methyl New
Pentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(oxoran-2-yl) benzene
Formyl - amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(3 - ethyl-heptyl) -
2,2 - dimethylbutanoyl amino) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(3 - phenyl
Propyl - (4 - methyl-benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-
(Oxoran-2-ylmethyl) - (4 - methyl-benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -
Fluoro -3 - (N-(4 - methyl-benzoyl) benzoyl-amino) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -
Difluoro -3 - (N-(4 - toluyl - methyl) - (4 - methyl-benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6 - difluoro -3 - (N-butyl-benzoylamino)-phenyl] - titanium, bis (cyclopentadienyl) bis [2,6 -
Fluoro -3 - (N-(butyl - (4 - methyl-benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 -
(N-(hexyl - (4 - methyl-benzoyl) amino) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-
(2,4 - dimethyl-pentyl) -2,2 - dimethylbutanoyl amino) - phenyl] titanium, bis (cyclopentadienyl) bis
[2,6 - difluoro-3 - (2,4 - dimethyl-pentyl) -2,2 - dimethyl-pentanoyl-amino) phenyl] - titanium, bis (cyclopentadienyl
Dienyl) bis [2,6 - difluoro-3 - ((4 - methyl-benzoyl) amino) - phenyl] titanium, bis (cyclopentadienyl) bis
[2,6 - difluoro-3 - (2,2 - dimethyl-pentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-
-3 - (2,2 - dimethyl-3 - ethoxy - propionylamino)-phenyl] titanium, bis (cyclopentadienyl) - bis [2,6 -
Fluoro-3 - (2,2 - dimethyl-3 - propoxylated allyl group - amino) phenyl] titanium, bis (cyclopentadienyl) bis
[2,6 - difluoro -3 - (N-allyl-acetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -
3 - (2 - amino-ethyl butyric acid) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-cyclohexyl-
Methyl-benzoyl amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-cyclohexyl - methyl
- (4 - methyl-benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-2-ethyl hexyl)
Benzoylamino) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-isopropyl-benzoyl amino
Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(3 - phenyl-propyl) -2,2 - dimethyl -
Pentanoylamino] titanium diphenyl, bis (cyclopentadienyl) - bis [2,6 - difluoro -3 - (N-hexyl-benzoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-cyclohexyl - methyl -2,2 - dimethyl-valeryl
Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-butyl-benzoylamino)-phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(2 - ethylhexyl) -2,2 - dimethyl-pentanoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-hexyl-2 ,2 - dimethyl-pentyl group - group)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-isopropyl-2 ,2 - dimethyl ammonium valeryl
Yl) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(3 - phenylpropyl) pivaloylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-butyl-2 ,2 - dimethyl-pentanoyl-amino) phenyl
Yl] titanium, bis (cyclopentadienyl) bis (2,6 - difluoro -3 - (N-(2 - methoxyethyl) amino-benzoyl) - benzene
Yl] titanium, bis (cyclopentadienyl) bis (2,6 - difluoro -3 - (N-benzyl-benzoyl - amino) phenyl] titanium,
(Cyclopentadienyl) bis [2,6 - difluoro -3 - (N-benzyl-4 - (methyl-benzoyl) - amino) phenyl] titanium, bis (ring
Pentadienyl) bis [2,6 - difluoro -3 - (N-(2 - methoxyethyl) - (4 - methyl-benzoyl) amino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(4 - methylphenyl) -2,2 - dimethyl - pentanoylamino)
Phenyl] titanium, bis (cyclopentadienyl) - bis [2,6 - difluoro -3 - (N-(2 - methoxyethyl) -2,2 - dimethyl -
Pentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-cyclohexylmethyl - (2 - ethyl
2 - methyl - heptyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-Butyl
(4 - chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-hexyl-- (2 -
Ethyl-2 - methyl - butyryl amino) phenyl] titanium, bis (cyclopentadienyl) - bis [2,6 - difluoro -3 - (N-cyclohexyl
Yl -2,2 - dimethyl-pentyl group - amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-
(Oxoran-2-ylmethyl) -2,2 - dimethyl-pentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis
[2,6 - difluoro -3 - (N-cyclohexyl - (4 - chlorobenzoyl) amino) phenyl] - titanium, bis (cyclopentadienyl) bis
[2,6 - difluoro -3 - (N-cyclohexyl - (2 - chloro-benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis
[2,6 - difluoro-3 - (3,3 - dimethyl-2 - butanone-1-aza ring - yl) phenyl] titanium, bis (cyclopentadienyl) bis
(2,6 - difluoro-3 - isocyanato-phenyl) - titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-ethyl -
(4 - methylphenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-hexyl--
(4 - methylphenyl) amino-phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-Butyl - (4 -
Methylphenyl sulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-iso-butyl - (4 -
Tolyl - sulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) - bis [2,6 - difluoro -3 - (N-Butyl -
(2,2 - dimethyl-3 - chloro - propionyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 -
(N-(3 - phenyl - propyl) -2,2 - dimethyl-3 - chloropropyl) amino) phenyl] - titanium, bis (cyclopentadienyl)
Bis [2,6 - difluoro -3 - (N-cyclohexyl-methyl - (2,2 - dimethyl-3 - chloropropyl) amino) - phenyl] titanium,
(Cyclopentadienyl) bis [2,6 - difluoro -3 - (N-iso-butyl - (2,2 - dimethyl-3 - chloropropyl) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-butyl - (2 - chloro - methyl - 2 - methyl - 3 - chloropropyl acyl) amino
Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (butyl-thio-carbonylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (phenylthio-carbonyl) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6 - difluoro-3 - isocyanato-phenyl) - titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-ethyl -
(4 - methylphenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-hexyl--
(4 - methylphenyl sulfonyl) - amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-Butyl -
(4 - methylphenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-isobutyl -
(4 - methylphenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-Butyl -
(2,2 - dimethyl-3 - chloro - propionyl) amino) phenyl] titanium, bis (cyclopentadienyl) - bis [2,6 - difluoro-3 -
(N-(3 - phenyl-propionyl) -2,2 - dimethyl-3 - chloropropyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6 - difluoro -3 - (N-cyclohexyl-methyl - (2,2 - dimethyl-3 - chloropropyl) amino) phenyl] - titanium,
(Cyclopentadienyl) bis [2,6 - difluoro -3 - (N-iso-butyl - (2,2 - dimethyl-3 - chloropropyl) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-butyl - (2 - chloro-2 - methyl - 3 - chloropropyl) amino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (butyl-thio-carbonylamino) phenyl] titanium,
(Cyclopentadienyl) bis [2,6 - difluoro-3 - (phenylthio-carbonyl) phenyl] - titanium, bis (cyclopentadienyl dimethyl
Enyl)-bis [2,6 - difluoro -3 - (N-hexyl-2 ,2 - dimethylbutanoyl) amino) phenyl] titanium, di (meth ring
Pentadienyl) bis [2,6 - difluoro -3 - (N-hexyl-2 ,2 - dimethylbutanoyl amino) phenyl] titanium, (meth
Cyclopentadienyl) bis [2,6 - difluoro -3 - (N-ethyl-acetylamino) phenyl] - titanium, bis (methylcyclopentadienyl
Yl) bis [2,6 - difluoro -3 - (N-ethyl-propionylamino)-phenyl] titanium, bis (trimethylsilyl pentadienyl) bis
[2,6 - difluoro -3 - (N-butyl-2 ,2 - dimethyl - propionylamino)-phenyl] titanium, bis (cyclopentadienyl) bis
[2,6 - difluoro -3 - (N-(2 - methoxyethyl) amino trimethylsilyl) - phenyl] titanium, bis (cyclopentadienyl
Yl) bis [2,6 - difluoro -3 - (N-butyl dimethylsilyl hexyl amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6 - difluoro -3 - (N-ethyl - (1,1,2 - tolyl methyl - propyl) phenyl amino dimethylsilyl]
Titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (3 - ethoxy-3 - methyl - 2 - butanone-1-aza ring -
Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (3 - allyloxy-3 - methyl - N
Heterocyclic butanone-1 - yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (3 - chloro-3 - methyl -
2 - butanone-1-aza ring - yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-benzyl-2, 2 -
Dimethyl-propionylamino)-phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-benzyl-2 ,2 - dimethyl
Ylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (5,5 - dimethyl-2 - pyrrolidine
One-1 - yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (6,6 - diphenyl-2 - piperidin-one-1 -
Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-2, 3 - dihydro-1 ,2 - benzisothiazol -
3 - one (1,1 - dioxide) -2 - yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-hexyl-
- (4 - chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-hexyl-- (2 -
Chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-isopropyl-- (4 - chloro-
Benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(4 - methylphenyl - A
Yl) - (4 - chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-(4 - A
Methyl-phenyl) - (2 - chloro-benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 -
(N-Butyl - (4 - chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-
Benzyl-2 ,2 - dimethyl-pentanoylamino) - phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-
(2 - ethylhexyl)-4 - methylphenyl - sulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-
-3 - (N-(3 - oxa-heptyl) - benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro -
3 - (N-(3,6 - dioxa-decyl)-benzoyl-amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-
-3 - (Trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (trifluoro-acetic
Acyl amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (2 - chloro-benzoyl) - amino) phenyl
Yl] titanium, bis (cyclopentadienyl) bis [2,6 - difluoro-3 - (4 - chlorobenzoyl) amino) phenyl] titanium, bis (ring
Pentadienyl) bis [2,6 - difluoro -3 - (N-(3,6 - dioxa-decyl) -2,2 - dimethyl-pentanoyl-amino) phenyl]
Titanium, bis (cyclopentadienyl) bis (2,6 - difluoro -3 - (N-(3,7 - dimethyl-7 - methoxy - octyl) benzoyl
Ylamino) phenyl] titanium and bis (cyclopentadienyl) bis [2,6 - difluoro -3 - (N-cyclohexyl-benzoylamino) -
Phenyl] titanium.
...
Comprise the active sulfonic acid esters of describing among the imino group sulfonate compound described among the JP-B-62-6223 and JP-B-63-14340 and the JP-A-59-174831 as the example of the active ester compounds of another example (j) of Photoepolymerizationinitiater initiater in the present invention.
Another example as Photoepolymerizationinitiater initiater is the compound (k) that has carbon-halogen bond in the present invention, and its preferred example comprises the compound shown in [IV] to [X].
[changing 37]
Compound shown in the formula [IV]:
X wherein
2The expression halogen atom, Y
2Expression-C (X
2)
3,-NH
2,-NHR
32,-NR
32Or-OR
32(R wherein
32The aryl of alkyl, aryl or the replacement of expression alkyl, replacement), R
31Expression-C (X
2)
3, alkyl, replacement alkyl, aryl, the aryl of replacement or the alkenyl of replacement.
[changing 38]
Compound shown in the formula [V]:
R wherein
33Alkoxy, nitro or the cyano group of the aryl of the alkenyl of the alkyl of expression alkyl, replacement, alkenyl, replacement, aryl, replacement, halogen atom, alkoxy, replacement, X
3The expression halogen atom, n represents 1 to 3 integer.
[changing 39]
Compound shown in the formula [VI]:
R
34-Z
2-CH
(2-m)X
m 3R
35 [VI]
R wherein
34The aryl of expression aryl or replacement, R
35Expression
[changing 40]
Or halogen, Z
2Expression-C (=O)-,-C (=S)-or-SO
2-, R
36And R
37The aryl of alkenyl, aryl or replacement of representing alkyl, alkenyl, the replacement of alkyl, replacement respectively, R
38Have with formula [IV] in R
32Identical implication, X
3The expression halogen atom, m represents 1 or 2.
[changing 41]
Compound shown in the formula [VII]:
R wherein
39Expression replaces or unsubstituted aryl or replacement or unsubstituted heterocyclic group, R
40The tri haloalkyl or three halogenated alkenyls of 1-3 carbon atom of expression implication, p represents 1,2 or 3.
[changing 42]
The carbonyl methylene heterogeneous ring compound that has trihalomethyl group shown in the formula [VIII]:
Wherein L represents hydrogen atom or CO-(R
41)
q(C (X
4)
3)
rShown substituting group, Q are represented sulphur atom, selenium atom, oxygen atom, dialkyl group methylene, 1, and 2-alkenylene, 1,2-phenylene or N-R group, M are represented to replace or unsubstituted alkylidene or alkenylene or 1 2-arlydene, R
42Expression alkyl, aralkyl or alkoxyalkyl, R
41Expression carbocyclic ring or heterocycle divalence aromatic group, X
4Expression chlorine atom, bromine atoms or iodine atom, q=0 and r=1 or q=1 and r=1 or 2.
[changing 43]
4-halo-5-(halogenated methyl-phenyl)-oxazole derivants shown in the formula [IX]:
X wherein
5The expression halogen atom, t represents the integer of 1-3, s represents the integer of 1-4, R
43Expression hydrogen atom or CH
3-tX
5 tGroup, R
44Expression replaces or the undersaturated organic group of unsubstituted s-valency.
[changing 44]
2-(halogenated methyl-phenyl) shown in the formula [X]-4-halo-oxazole derivants:
X wherein
6The expression halogen atom, v represents the integer of 1-3, u represents the integer of 1-4, R
45Expression hydrogen atom or CH
3-vX
6 vGroup, R
46Expression replaces or the undersaturated organic group of unsubstituted u-valency.
The object lesson that has the carbon-halogen bond compound comprises: Wakabayashi etc. for example, " communication of Japanese chemical association " (Bull.Chem.Soc.Japan), 42, the compound of describing in 2924 (1969), 2-phenyl-4 for example, 6-two (trichloromethyl)-S-triazine, 2-(right-chlorphenyl)-4,6-two (trichloromethyl)-S-triazine, 2-(right-tolyl)-4,6-two (trichloromethyl)-S-triazine, 2-(right-methoxyl-phenyl)-4,6-two (trichloromethyl)-S-triazine, 2-(2 ', 4 '-dichlorophenyl)-4,6-two (trichloromethyl)-S-triazine, 2,4,6-three (trichloromethyl)-S-triazine, 2-methyl-4,6-two (trichloromethyl)-S-triazine, 2-n-nonyl-4,6-two (trichloromethyl)-S-triazine and 2-(a, a, β-three chloroethyl)-4,6-two (trichloromethyl)-S-triazine; BrP 1,388, the compound of record in 492,2-styryl-4 for example, 6-two (trichloromethyl)-S-triazine, 2-(p-methylstyrene base)-4,6-two (trichloromethyl)-S-triazine, 2-(p-methoxystyrene base)-4,6-two (trichloromethyl)-S-triazine and 2-(p-methoxystyrene base)-4-amino-6-trichloromethyl-S-triazine; The compound of putting down in writing among the JP-A-53-133428,2-(4-methoxynaphthalene formyl-1-yl)-4 for example, 6-two-trichloromethyl-S-triazine, 2-(4-ethoxy naphthalene formyl-1-yl)-4,6-two-trichloromethyl-S-triazine, 2-[4-(2-ethoxyethyl group)-naphthalene formyl-1-yl]-4,6-two-trichloromethyl-S-triazine, 2-(4,7-dimethoxy-naphthalene formyl-1-yl)-4,6-two-trichloromethyl-S-triazine and 2-(acenaphthene acyl-5-yl)-4,6-two-trichloromethyl-S-triazine; Deutsche Bundespatent 3,337, the compound of describing in 024, for example
[changing 45]
Deng and other.
Compound as follows:
[changing 46]
F.C.Schafer etc., " organic chemistry magazine " (J.Org.Chem.), 29, the compounds of describing in 1527 (1964), 2-methyl-4 for example, 6-two (trisbromomethyl)-S-triazine, 2,4,6-three (trisbromomethyl)-S-triazine, 2,4,6-three (trisbromomethyl)-S-triazine, 2-amino-4-methyl-6-trisbromomethyl-S-triazine and 2-methoxyl-4-methyl-6-trichloromethyl-S-triazine; The compound of describing among the JP-A-62-58241, for example:
[changing 47]
[changing 48]
The compound of describing among the JP-A-5-281728, for example:
[changing 49]
Compound as follows, described compound can be by those skilled in the art according to M.P.Hutt, E.F.Elslager and L.M.Herbel, " heterocyclic chemistry magazine " (Journal of HeterocyclicChemistry), 7 (No.3), after 511 pages, the synthetic method of describing in (1970) is synthetic easily:
[changing 50]
[changing 51]
[changing 52]
[changing 53]
[changing 54]
[changing 55]
Deutsche Bundespatent 2,641, the compound of describing in 100, for example 4-(4-methoxyl-styrene)-6-(3,3,3-tri chloropropene base)-2-pyrone and 4-(3,4,5-trimethoxy styryl)-6-trichloromethyl-2-pyrone; Deutsche Bundespatent 3,333, the compound of describing in 450, for example
[changing 56]
R wherein
41The expression phenyl ring, R
42Expression alkyl, aralkyl or alkoxyalkyl.
[table 18]
| R 42 | M | L | q | (CX 4 3) r | |
| 1 2 3 4 5 6 7 | C 2H 5CH 2C 6H 5C 2H 5C 2H 5C 2H 5CH 2C 6H 5C 2H 4OCH 3 | 1,2-phenylene 1,2-phenylene 1,2-phenylene 1,2-phenylene 5-CH 3-1,2 phenylenes 1,2-phenylene 1,2-phenylene | H H H H H H H | 1 1 1 1 0 0 1 | 4-CCl 34-CCl 33-CCl 34-CF 3CCl 3CCl 34-CCl 3 |
Deutsche Bundespatent 3,021, the compound of describing in 590:
[changing 57]
[changing 58]
Deutsche Bundespatent 3,021, the compound of describing in 599, for example
[changing 59]
Be used for Photoepolymerizationinitiater initiater of the present invention at these, more preferably (a) aromatic ketone, (b) aromatic series salt, (c) organic peroxide, (e) Hexaarylbiimidazole, (i) Metallocenic compound and (k) have the compound of carbon-halogen bond, the compound shown in first-selected aromatic series salt compounded of iodine, aromatic series diazo salt, cyclopentadiene titanium compound and the formula [IV].
Be used for that Photoepolymerizationinitiater initiater of the present invention can use separately or use with two or more array configuration.
The sensitizing dye that can be used as one of the component of photopolymerizable composition of the present invention comprise can absorb from the light of light source and with the interactional spectral sensitizing dye of Photoepolymerizationinitiater initiater and dyestuff or pigment.
The example of preferred spectral sensitizing dye or dyestuff comprises polynuclear aromatic compound (pyrene perylene for example, benzophenanthrene), xanthene (fluorescence for example, eosin, erythrosine, rhodalline B, rose bengal), cyanines indigo plant (thia carbon cyanines (thiacarbocyanine) for example, oxa-carbon cyanines (oxacarbocyanine)), merocyanine class (merocyanine for example, carbon merocyanine (carbomerocyanine)), thiazide (for example, thionine, methylene blue, toluidine blue), acridine (for example, acridine orange, chloroflavin, acriflavine), the phthalocyanine dye class (for example, phthalocyanine dye, the metal-phthalocyanine dyestuff), the porphyrin class (for example, tetraphenylporphyrin, the porphyrin of central authorities' metal-replacement), the chlorophyll class (for example, chlorophyll, chlorophyllin, the chlorophyll of central authorities' metal-replacement), metal complex, for example
[changing 60]
Anthraquinone class (for example, anthraquinone) and squaliums (for example, squalium).The example of preferred spectral sensitizing dye or dyestuff comprises the dyestuff of the styrene-based base of describing among the JP-B-37-13034, for example
[changing 61]
The dye of positive ion of describing among the JP-A-62-143044, dyestuff
[changing 62]
The quinoxaline salt of describing among the JP-B-59-24147, for example
[changing 63]
The new methylene blue of describing among the JP-A-64-33104, for example
[changing 64]
The anthraquinone class of describing among the JP-A-64-56767, for example
[changing 65]
The benzo xanthene dyestuff of describing among the JP-A-2-1714; The acridine of describing among JP-A-2-226148 and the JP-A-2-226149, for example
[changing 66]
The pyralium salt of describing among the JP-B-40-28499, for example
[changing 67]
The blue class of the cyanines of describing among the JP-B-46-42363, for example
[changing 68]
The benzofurans of describing among the JP-A-2-63053, for example
[changing 69]
The conjugation ketone dyes of describing among JP-A-2-85858 and the JP-A-2-21654, for example
[changing 70]
The dyestuff of describing among the JP-A-57-10605; The azepine cinnamylidene derivant of describing among the JP-B-2-30321,
For example
[changing 71]
The dyestuff of describing among the JP-A-1-287105 based on cyanines indigo plant, for example
[changing 72]
Describe among JP-A-62-31844, JP-A-62-31848 and the JP-A-62-143043 based on the xanthene dyestuff,
For example
[changing 73]
The aminobenzene vinyl ketones of describing among the JP-B-59-28325, for example
[changing 74]
Merocyanine dyes shown in the following formula of describing among the JP-B-61-9621 [1] to [8], for example
[changing 75]
Wherein, in formula [3] in [8], X
8Aryl, aryloxy group, aralkyl or the halogen atom of the alkyl of expression hydrogen atom, alkyl, replacement, alkoxy, aryl, replacement, in formula [2], Ph represents phenyl, in formula [1] in [8], R
48, R
49And R
50Can be identical or different, represent alkyl, alkenyl, the aryl of alkyl, replacement, the aryl or aralkyl of replacement respectively); Dyestuff shown in the following formula of describing among the JP-A-2-179643 [9] to [11], for example
[changing 76]
Wherein A represents oxygen atom, sulphur atom, selenium atom, tellurium atom, alkyl-or the nitrogen-atoms of aryl-replacement or carbon atom that dialkyl group replaces, Y
3The alkoxy carbonyl group of aryl, aralkyl, acyl group or the replacement of the alkyl of expression hydrogen atom, alkyl, replacement, aryl, replacement, R
51And R
52Represent hydrogen atom respectively, contain the alkyl of 1-18 carbon atom or contain 1-18 carbon atom and have the alkyl of following group as substituent replacement, described substituting group is R
53O-,
[changing 77]
-(CH
2CH
2O) W-R
53Or halogen atom (for example, F, Cl, Br, I) (R wherein
53Expression hydrogen atom or contain the alkyl of 1-10 carbon atom, B represents dialkyl amido, hydroxyl, acyloxy, halogen atom or nitro), w represents the integer of 0-4, x represents the integer of 1-20); Merocyanine dyes shown in the following formula of describing among the JP-A-2-244050 [12]:
[changing 78]
R wherein
54And R
55Represent alkyl, alkoxy carbonyl group, the aryl of hydrogen atom, alkyl, replacement, the aryl or aralkyl of replacement independently of one another, A
2Expression oxygen atom, sulphur atom, selenium atom, tellurium atom, alkyl-or the nitrogen-atoms of aryl-replacement or the carbon atom of dialkyl group-replacement, X
9Expression forms the required non-metal atom group of 5 member heterocyclic ring containing nitrogens, Y
4The phenyl that expression replaces, the polynuclear aromatic family of unsubstituted replacement ring or the alkyl heteroaromatic rings that does not replace or replace, Z
3Amino, acyl group or the alkoxy carbonyl group of the aryl of the alkyl of expression hydrogen atom, alkyl, replacement, aryl, replacement, aralkyl, alkoxy, alkylthio group, arylthio, replacement, and Z
3And Y
4Can lump together each other and form ring, its preferred example is as follows:
[changing 79]
Merocyanine dyes shown in the formula of describing among the JP-B-59-28326 [13]:
[changing 80]
R wherein
56And R
57Can be identical or different, represent alkyl, the aryl of hydrogen atom, alkyl, replacement, the aryl or aralkyl of replacement respectively, X
10The substituting group of expression Hammett ' s Φ value from-0.9 to+0.5; Merocyanine dyes shown in the following formula of describing among the JP-A-59-89303 [14]:
[changing 81]
R wherein
58And R
59Represent alkyl, the aryl of hydrogen atom, alkyl, replacement, the aryl or aralkyl of replacement respectively, X
11The substituting group of expression Hammett ' s Φ value from-0.9 to+0.5; Y
5Aryl, aralkyl, acyl group or the alkoxy carbonyl group of the alkyl of expression hydrogen atom, alkyl, replacement, aryl, replacement, its preferred example is as follows:
[changing 82]
Merocyanine dyes shown in the following formula of describing among the Japanese patent application No. 6-269047 [15]:
[changing 83]
R wherein
60, R
21, R
62, R
63, R
68, R
69, R
70And R
71Represent phosphono, the phosphonate groups of sulfonyl, phosphono, the replacement of sulfinyl, the replacement of carbonyl, sulfo group, sulfonate group, the replacement of amino, the replacement of sulfydryl, amino, the replacement of hydroxyl, sulfydryl, the replacement of aryl, hydroxyl, the replacement of alkyl, aryl, the replacement of hydrogen atom, halogen atom, alkyl, replacement, phosphonate groups, cyano group or the nitro of replacement independently of one another, or R
60And R
61, R
61And R
62, R
62And R
63, R
68And R
69, R
69And R
70Or R
70And R
71Can lump together each other and form aliphatics or aromatic ring, R
64The aryl of alkyl, aryl or the replacement of expression hydrogen atom, alkyl, replacement, R
65Expression replaces or unsubstituted alkenyl alkyl or replacement or unsubstituted alkynyl group alkyl, R
66And R
67Represent alkyl, aryl, the aryl of replacement or the carbonyl of replacement of hydrogen atom, halogen atom, alkyl, replacement independently of one another, its preferred example comprises:
[changing 84]
Dyestuff shown in the following formula of describing among the Japanese patent application No. 7-164583 [16] based on chromene:
[changing 85]
R wherein
72To R
75Represent hydrogen atom, halogen atom, alkyl, aryl, hydroxyl, alkoxy or amino independently of one another, R
72To R
75Can be respectively and R
72To R
75Combinable carbon atom lumps together and forms the ring that contains non-metallic atom, R
76Expression hydrogen atom, alkyl, aryl, heteroaryl, cyano group, alkoxy, carboxyl or alkenyl, R
77Expression R
76Shown group or-Z-R
76, Z represents carbonyl, sulfonyl, sulfinyl or arlydene dicarbapentaborane, R
76And R
77Can lump together and form the ring that contains non-metallic atom; A represents O atom, S atom, NH or has substituent N atom; B represent the O atom or=(G2) (wherein G1 and G2 can be identical or different for C (G1); represent hydrogen atom, cyano group, alkoxy carbonyl group, aryloxy carbonyl, acyl group, aryl carbonyl, alkylthio group, arylthio, alkyl sulphonyl, aryl sulfonyl or fluorosulfonyl respectively; condition is that G1 and G2 are not hydrogen atom simultaneously, and G1 and G2 can lump together with carbon atom form the ring that contains non-metallic atom).
In addition, following infrared absorbent (dyestuff or pigment) also is suitable for use as sensitizing dye.
The example of preferred dyestuff comprises the blue dyestuff of the cyanines of describing among JP-A-58-125246, JP-A-59-84356, JP-A-59-202829 and the JP-A-60-78787, and the blue dyestuff of the cyanines of describing in the BrP 434,875.
In addition, can also use United States Patent (USP) 5,156, the near infrared absorption sensitizer of describing in 938.In addition, can also use United States Patent (USP) 3,881, aryl benzo (sulfo-) pyralium salt of the replacement of describing in 924; The cyclonite thiapyran salt of describing among the JP-A-57-142645 (United States Patent (USP) 4,327,169); The pyrylium compound of describing among JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, JP-A-59-84248, JP-A-59-84249, JP-A-59-146063 and the JP-A-59-146061; The blue dyestuff of the cyanines of describing among the JP-A-59-216146; United States Patent (USP) 4,283, the pyralium salt of describing among the five methine thiapyran salt of describing in 475 and JP-B-5-13514 and the JP-B-5-19702.
The example of other preferred dyestuff comprises United States Patent (USP) 4,756, the formula of describing in 993 (I) and (II) shown in hear-infrared absorption dye and EP-A-916513 in the phthalocyanine dye described.
In addition, can also use the anionic infrared absorbing agents of describing among the Japanese patent application No. 10-79912.Term anionic infrared absorbing agents be meant in parent nucleus cation structure not and contain anion structure can obviously absorb ultrared dyestuff.Its example comprises (c1) negative ion metal complex, (c2) negative ion carbon black, (c3) negative ion phthalocyanine dye and (c4) compound shown in the following formula 6.In these negative ion infrared absorbing agents, counter ion counterionsl gegenions are univalent cation or the multivalent cations that contain proton.
[changing 86]
[G
a-M-G
b]
mX
M+Formula (6)
In the literary composition used negative ion metal complex (c1) be meant in the complex part can obvious light-absorbing central atom and part to do as a whole be the metal complex of anionic property.
The example of negative ion carbon black (c2) comprises and is connected with anionic group such as sulfonic acid, carboxylic acid or phosphonyl group as substituent carbon black.These groups can be by being incorporated into carbon black in the carbon black with predetermined acid oxidase, referring to " carbon black handbook (Carbon Black Handbook), the 3rd edition, 12 pages, carbon black association publishes and distributes (April 5 nineteen ninety-five).
Negative ion phthalocyanine dye (c3) be meant that (c2) described anionic group combines with the phthalocyanine dye skeleton as substituting group and phthalocyanine dye to do as a whole be the phthalocyanine dye of anionic property.
Below will describe the compound shown in the formula 6 (c4) in detail.G
a -The expression anion substituent, G
bSubstituent in the expression, X
mThe negative ion of expression 1-m valency comprises proton, and m represents the integer of 1-6, and M represents conjugated chain.Conjugated chain M can have substituting group or ring structure.Conjugated chain M can be represented by the formula:
[changing 87]
R wherein
1, R
2And R
3Represent hydrogen atom, halogen atom, cyano group, alkyl, aryl, alkenyl, alkynyl group, carbonyl, sulfydryl, sulfonyl, sulfinyl, hydroxyl or amino independently of one another, R
1, R
2And/or R
3Can lump together the formation ring structure each other, n represents the integer of 1-8.
The example of the preferred anionic surfactants infrared absorbing agents shown in the formula 6 comprises that following compd A-1 is to A-5.
[changing 88]
In addition, also can use following kation infrared absorbing agents CA-1 to CA-44.
[changing 89]
[changing 90]
[changing 91]
[changing 92]
[changing 93]
[changing 94]
[changing 95]
[changing 96]
[changing 97]
[changing 98]
[changing 99]
[changing 100]
[changing 101]
[changing 102]
[changing 103]
In these structural formulas, T
-Expression monovalence counter anion, preferred halide anion (for example, F
-, Cl
-, Br
-, I
-), Lewis acid anion (for example, BF
4 -, PF
6 -, SbCl
6 -, ClO
4 -), alkyl sulfonic acid salt anionic or aryl sulfonic acid salt anionic.
Alkyl in the alkyl sulfonic acid is the alkyl that contains straight chain, side chain or the ring-type of 1 to 20 carbon atom, and its concrete example 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.Wherein, preferably contain 1 to 12 carbon atom straight chained alkyl, contain the branched alkyl of 3 to 12 carbon atoms and contain the cyclic alkyl of 5 to 10 carbon atoms.
Aryl in the aryl sulfonic acid is to contain the aryl of a phenyl ring or condense the aryl that forms by 2 or 3 phenyl ring or phenyl ring and 5 yuan of unsaturated rings, and its concrete example comprises phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl and fluorenyl, preferred phenyl and naphthyl.
In addition, can also use following nonionic infrared absorbing agents NA-1 to NA-12.
[changing 104]
[changing 105]
[changing 106]
[changing 107]
In these compounds, more preferably negative ion infrared absorbing agents A-1, kation infrared absorbing agents CA-7, CA-30, CA-40 and CA-42, and nonionic infrared absorbing agents NA-11.
Except that these dyestuffs, for example " dyestuff handbook (Handbook of Dyes), Yuki Gosei Kagaku Kyokai publishes the known dye of describing in (1970) can also to use commercially available dyestuff and document.Its concrete example comprises dyestuff, dyestuff azo dyes, metal complex salts azo dyes, pyrazolone azo dyes, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine dye, carbonium dyestuff, quinoneimine dye, methine dyes, diimmonium (diimmonium) dyestuff, ammonium dyestuff, squarylium dyestuff and metal mercaptide salt dyestuff.
Except that those can be as the pigment of sensitizing dye, can also use commercially available pigment and " Colour Index handbook (C.I.Handbook), " up-to-date pigment handbook (Handbook of LatestPigments), Nippon Ganryo Gijutsu Kyokai publishes (1977), " up-to-date pigment applications technology " (Latest Pigment Application Technology), the pigment of describing in CMC (1986) and " ink technique " (Printing Ink Technology), CMC (1984).The kind of pigment comprises that mineral black, yellow pigment, orange pigment, brown pigment, red, purple dye, blue pigment, green pigment, fluorescent pigment, metallic powdery pigment and polymkeric substance are in conjunction with pigment.The object lesson of operable pigment comprises AZO pigments, the pigment based on phthalocyanine dye, anthraquinone pigment, perylene dye He perylene ketone pigment, thioindigo pigment, quinacridone pigment, two _ piperazine pigment, isoindolinone pigment, quinophthalone pigment, mordant pigment, azine pigment, nitroso pigments, nitropigments, natural pigment, fluorescent pigment, inorganic pigment and the carbon black of insoluble azo colour, azo lake pigment, the AZO pigments that condenses, chelating.In these pigment, preferred carbon black.
These pigment can carry out surface treatment before use, also can not handle.
Surface treatment can be by coated with resins or wax from the teeth outwards method, connect the method for surfactant and the method that active material (for example silane coupling agent, epoxy compound and polyisocyanate) combines with surface of pigments carried out.These surface-treated methods are recorded in " character of metallic soap and application " (Properties and Application of Metal Soap), Saiwai Shobo, " ink technique " (Printing Ink Technology), CMC (1984) and " up-to-date pigment applications technology " (Latest Pigment Application Technology), CMC (1986).
The granularity of pigment is preferably 0.01 to 10 μ m, more preferably 0.05 to 1 μ m, still more preferably 0.1 to 1 μ m.If the granularity of pigment is less than 0.01 μ m, then with regard to the stability of the coating solution that is used for the picture record layer, dispersion liquid is disadvantageous, and when it surpasses 10 μ m, is disadvantageous with regard to the homogeneity of picture record layer then.
For dispersing of pigments, can adopt dispersion technology known in the production of printing ink or toner.The example of dispersion machine comprises ultrasonic decollator, sand mill, attitor, pearl mill, micronizer, bowl mill, impeller decollator, KD mill, colloid mill, dynatron (dynatron), three millings (threeroll mill) and pressure kneader.These mechanical write ups are in " up-to-date pigment applications technology " (Latest Pigment Application Technology), CMC (1986).
The preferred example that is used for sensitizing dye of the present invention comprises the benzopyran dyes of describing among the merocyanine dyes described among the merocyanine dyes described among the merocyanine dyes described among the merocyanine dyes described among the merocyanine dyes described among merocyanine dyes that JP-B-61-9621 describes, the JP-A-2-179643, the JP-A-2-244050, the JP-B-59-28326, the JP-A-59-89303, the Japanese patent application No. 6-269047 and the Japanese patent application No. 7-164583.
In addition, can also use the infrared absorbing agents of describing among the JP-A-11-209001.
Being used for sensitizing dye of the present invention can use separately or being used in combination with two or more.Optical polymerism composition of the present invention can also contain the auxiliary sensitizer of known compound conduct with the polymerization inhibit feature that strengthens susceptibility or prevent to cause owing to oxygen.
The example of auxiliary sensitizer comprises amine, M.R.Sander " polymkeric substance can will " (Journal ofPolymer Society) for example, Vol.10,3173 pages (1972), JP-B-44-20189, JP-A-51-82102, JP-A-52-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104 and " research is announced " (Research Disclosure), the compound of describing among the No.33825.Its concrete example comprises triethanolamine, (dimethylamino)-ethyl benzoate, to the formoxyl xylidin with to the methyl mercapto xylidin.
Other example of auxiliary sensitizer comprises mercaptan and sulfide, for example the di-sulphide compounds of describing among mercaptan compound of describing among JP-A-53-702, JP-B-55-500806 and the JP-A-5-142772 and the JP-A-56-75643.Its concrete example comprises 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline and β-mercaptonaphthalene.
Other example of auxiliary sensitizer (for example also comprises amino-acid compound, N-phenylglycine), Si-H and the Ge-H compound of describing among phosphorus compound of describing among the sulphur compound of describing among the hydrogen donor of describing among the organometallics of describing among the JP-B-48-42965 (for example tributyltin acetate), the JP-B-55-34414, the Japanese patent application No. 5-91089 (for example trithiane), the Japanese patent application No. 5-32147 (for example, diethyl phosphite) and the Japanese patent application No. 6-191605.
In composition of the present invention, the consumption of Photoepolymerizationinitiater initiater is 0.01 to 60wt%, and preferred 1 to 30wt%, in the weight of optical polymerism composition all the components.
When using sensitizing dye, the mol ratio of Photoepolymerizationinitiater initiater and sensitizing dye is 100: 0 to 1: 99 in the optical polymerism composition, preferred 90: 10 to 10: 90, and first-selected 80: 20 to 20: 80.
When using above-mentioned auxiliary sensitizer, for every weight portion Photoepolymerizationinitiater initiater, the suitable consumption of auxiliary sensitizer is 0.01 to 50 weight portion, more preferably 0.02 to 20 weight portion, first-selected 0.05 to 10 weight portion.
Optical polymerism composition of the present invention preferably contains linear organic high molecular polymer as bonding agent." linear organic high molecular polymer " can be any polymkeric substance, as long as it is the linear organic high molecular polymer that can mix with the optical polymerism unsaturated allyl compound.Preferred use can water development or can in water or alkalescence water, the dissolving or the linear organic high molecular polymer of swelling of alkalescence water development.Linear organic high molecular polymer is not only the film forming agent as composition, but also plays developer, and its selection depends on that used is water, alkalescence water or organic solvent.For example, when using high molecular weight water soluble polymer, can carry out water development.The example of these organic high molecular polymers comprises, the addition polymer that on side chain, has carboxylic acid function's base, the maleic acid of methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid and partial esterification for example is referring to JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048.In addition, can also use the acid cellulose derivant that on side chain, has carboxylic acid function's base.In addition, also can use by cyclic acid anhydride being added to the polymkeric substance that obtains on the addition polymer that has hydroxyl.Wherein, preferred [(methyl) benzyl acrylate/(methyl) acrylic acid/other addition polymerization sex ethylene base monomer, multipolymer and [(methyl) acrylic acid allyl ester/(methyl) acrylic acid/other addition polymerization sex ethylene base monomer, multipolymer if necessary] if necessary].In addition, polyvinylpyrrolidone and polyoxyethylene also can be used as the water-soluble linear organic polymer.In order to increase the curing film strength, can also use pure dissolubility formamide and 2, the polyethers of 2-two (4-hydroxy phenyl) propane and chloropropylene oxide.
Linear organic high molecular polymer can any amount be mixed in the whole composition.But,, then can have a negative impact at the aspects such as intensity of form image if its consumption has surpassed 90% of composition all the components weight.The amount of mixing is preferably 30 to 85%.The weight ratio of optical polymerism unsaturated allyl compound and linear organic high molecular polymer is preferably 1/9 to 7/3, and more preferably 3/7 to 5/5.
When the compound of structure shown in the used formula that has (I) of the present invention was the macromolecule type, compound itself can play the effect of bonding agent, therefore, and the bonding agent shown in optical polymerism composition, can not containing.When with compound and binder combination use, polymer electrolyte polymerizable compound of the present invention and bonding agent can be used with above-mentioned weight ratio.
Polymer inhibitor:
In the present invention, except that basis, also preferred add a spot of thermal polymerization inhibitor with the compound that prevents to have the polymerizable alkylene unsaturated double-bond in the production of photopolymerizable composition or deposit unnecessary thermal polymerization takes place in the process.The example of suitable thermal polymerization inhibitor comprises quinhydrones, p methoxy phenol, BHT, trihydroxy benzene, tert-butyl catechol, benzoquinones, 4,4 '-sulfo-two (3 methy 6 tert butyl phenol), 2,2 '-methylene two (4-methyl-6-tert butyl-phenol) and N-nitroso-phenyl hydramine cerium salt.The amount of the thermal polymerization inhibitor that adds is preferably about 0.01 to about 5wt%, in the weight of whole composition.In addition, as needs, also can add advanced higher fatty acid derivative for example the docosanoic acid acid amides so that the uneven surface that is present in photosensitive layer in its dry run after coating, to prevent because the polymerization inhibiting effect that oxygen causes.The addition of advanced higher fatty acid derivative be preferably whole composition about 0.5 to about 10wt%.
Colorant etc.:
In addition, also can add dyestuff or pigment so that photosensitive layer is painted.By adding these materials, can after plate-making, make the visual adaptability of improving or making the galley check of galley, for example improve for the adaptability of visual opacimeter.Preferred colorant is a pigment, descends because many dyestuffs can cause the susceptibility of optical polymerism system photosensitive layer.The object lesson of colorant comprises pigment, for example phthalocyanine dye, AZO pigments, carbon black and titanium dioxide; Dyestuff, for example blue dyestuff of ethyl violet, crystal violet, azo dyes, anthraquinone dye and cyanines.The addition of dyestuff or pigment be preferably whole composition 0.5 to 5wt%.
Other adjuvant:
In order to improve the physical property of cured layer, can also add inorganic filler or other known additives, for example plastifier and the ink absorbent that can improve the inking on photosensitive layer surface.
The example of plastifier comprises dioctyl phthalate, phthalic acid two-dodecyl ester, triethylene glycol dieaprylate, dimethyl EGP ethylene glycol phthalate, three cresols phthalic esters, dioctyl adipate, dibutyl sebacate and triacetyl glycerine, when using bonding agent, the addition of plastifier can be 10wt% or lower, in the compound that has the alkene unsaturated double-bond and the general assembly (TW) of bonding agent.
In addition, in order to improve the following film strength that will describe (printing life-span), can also add the UV initiating agent that can strengthen the heating/exposure effect after the development, thermal cross-linking agent etc.
In addition, in order to improve the bounding force between photosensitive layer and the carrier or to increase the developer removability of unexposed photosensitive layer, can add adjuvant or the middle layer is provided.For example, when add or applied with carrier between have relatively than the compound bottom of strong interaction, when for example having the compound of diazonium structure and phosphine compound, can improve cohesive and print the life-span.On the other hand, when adding or having applied hydrophilic polymer such as polyacrylic acid and poly-sulfonic acid bottom, can improve the development and the resistance of increase of non-developing regional to dyeing.
Be coated on the carrier after optical polymerism composition of the present invention is dissolved in various types of organic solvents.Operable solvent comprises acetone, MEK, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, the propylene glycol monomethyl ether, propylene glycol monoethyl ether, diacetone, cyclohexanone, diacetone alcohol, methyl glycol acetate, ethyl cellosolve acetate, ethylene glycol one isopropyl ether, ethylene glycol monobutyl ether acetic acid ester, 3-methoxyl-propyl alcohol, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, 3-methoxy propyl yl acetate, N, dinethylformamide, dimethyl sulfoxide, gamma-butyrolacton, methyl lactate and ethyl lactate.These solvents can be used singly or in combination.Solid concentration in the coating solution can be from 2 to 50wt%.
The coverage of photosensitive layer on carrier mainly influences the susceptibility of photosensitive layer, development, intensity and the printing life-span of exposed film, therefore, should select suitable coverage according to purposes.If coverage is too little, then can't obtain the sufficiently long printing life-span, and coverage is when excessive, then susceptibility can reduce, and the time shutter is prolonged, and develops and also need the longer time.To the lithographic plate (fundamental purpose of the present invention) that is used for scan exposure, coverage is preferably about 0.1 to about 10g/m
2, more preferably 0.5 to 5g/m
2, with dry weight basis.
Carrier:
In order to obtain lithographic plate, preferably provide photosensitive layer having on the carrier of hydrophilic surface as one of fundamental purpose of the present invention.For this reason, can have no restrictedly to use any known hydrophilic carrier that is used for lithographic plate.Used carrier is the dry plate sample material of dimensionally stable preferably.Its example comprises paper, the paper with plastics (for example tygon, polypropylene, polystyrene) laminations, metal (for example aluminium, zinc, copper) thin slice, plastic foil (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate-butyrate, cellulose nitrate, polyethylene terephthalate, tygon, polystyrene, polypropylene, polycarbonate, polyvinyl acetal) and with above-mentioned metal laminate or deposited the paper or the plastic foil of above-mentioned metal thereon.As needs, also known suitable physical or chemical treatment can be carried out in the surface of these carriers, to produce water wettability, to improve intensity etc.
In these carriers, preferred paper, polyester film and aluminium sheet, more preferably aluminium sheet, because its dimensionally stable and more cheap relatively, and can produce water wettability and the splendid surface of intensity by surface treatment when needed.In addition, also preferably use passing through of describing among the JP-B-48-18327 that aluminium sheet is combined in the compound foil that obtains on the polyethylene terephthalate film.
The preferred pure aluminium sheet of aluminium sheet or mainly contain aluminium and contain the alloy sheets of trace extraneous element.In addition, also can use with aluminium lamination plastic foil that press or that deposited aluminium thereon.The example of contained extraneous element comprises silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium in the aluminium alloy.The content of extraneous element mostly is 10wt% or lower most in the alloy.In the present invention, preferred fine aluminium still, with regard to smelting process, is difficult to produce pure aluminium fully, therefore, can use the aluminium that contains the trace extraneous element.Therefore, the composition of the aluminium sheet that the present invention is used is not specific, can use to contain conventional known and aluminium sheet common used material.Be used for preferred its thickness of aluminium sheet of the present invention and be 0.1 to 0.6mm, more preferably 0.15 to 0.4mm, and preferred especially 0.2 to 0.3mm.
When carrier has metal surface, particularly aluminium when surface, preferably carrier is carried out surface treatment, for example surface coarsening (system line), be immersed in sodium silicate, potassium fluorozirconate or the potassium phosphate aqueous solution, or carry out anodic oxidation.
The surface coarsening of aluminium sheet is undertaken by the whole bag of tricks, for example, dissolves and the method for alligatoring or the method on the surface that chemical dissolution is selected with the method for the mechanical alligatoring in surface, with surface electrochemistry.In the mechanical surface alligatoring, can adopt known method, for example ball polishing, scratch brushing, blast (blast polishing) or polishing (buff polishing).The electrochemical surface alligatoring can be by carrying out alternating current or direct current by electrolytic solution example hydrochloric acid or nitric acid.These two kinds of surface coarsenings are handled and can be united use according to the description among the JP-A-54-63902.Before aluminium sheet being carried out the surface coarsening processing, as needs, aluminium sheet can be carried out degreasing with for example surfactant, organic solvent or alkaline aqueous solution and handle, to remove lip-deep stone roller oil.
In addition, preferred employing is carried out the surface coarsening processing with aluminium sheet and carry out immersion treatment then in sodium silicate aqueous solution.Can also aluminium sheet be carried out anodized in alkali metal silicate aqueous solution, carry out immersion treatment then according to the description among the JP-B-47-5125.Anodized by at electrolytic solution, for example mineral acid as phosphoric acid, chromic acid, sulfuric acid or boric acid, in the moisture or non-aqueous solution of organic acid such as oxalic acid or sulfaminic acid or its salt, on aluminium sheet, apply electric current and finish as anode.These are moisture or non-aqueous solution can use separately or use with two or more array configuration wherein.
Also can use United States Patent (USP) 3,658, the silicate electro-deposition method of describing in 662.
Also can adopt and disclosedly among JP-B-46-27481, JP-A52-58602 and the JP-A-52-30503 carrier is carried out electrolysis system line and anodized and sodium silicate handle and combine described above.
Also can adopt carrier is carried out successively machinery system line, chemical etching, electrolysis system line, anodized and the sodium silicate described among the JP-A-56-28893 to handle.
In addition, after above-mentioned processing, also can be with carrier with water soluble resin such as polyvinylphosphonic acid, the polymkeric substance that on side chain, has the sulfonate functional base or multipolymer, polyacrylic acid or water-soluble metal salt (for example Firebrake ZB) or carry out internal coating with weld or amine salt and handle.
Also can adopt the bottom of the sol-gel processing of describing among the Japanese patent application No. 5-304358, on this bottom, have the functional group that can carry out addition reaction by free radical.
Other preferred example comprises the carrier that obtains as superficial layer by the hydrophilic layer that waterproof is provided on any carrier.The example of superficial layer comprises, United States Patent (USP) 3,055,295 and JP-A-56-13168 in the sol gel film that contains titanium dioxide, polyvinyl alcohol (PVA) and silicic acid described among the water wettability swell layer described in the layer that contains inorganic pigment and bonding agent, JP-A-9-80744 described and the JP-W-8-507727 (term used herein " JP-W " is meant " not unexamined open international patent application ").
Hydrophilicity-imparting treatment not only can make the carrier surface possess hydrophilic property, but also can prevent that the optical polymerism composition that applies from disadvantageous reaction taking place thereon, can also improve the bounding force of photosensitive layer simultaneously.
[protective seam]
In the present invention, the lithographic plate that is used for scan exposure is exposed to air through regular meeting, therefore, can provide layer protective layer again on optical polymerism composition.Protective seam can stop (the imaging reactions when these materials can suppress to expose in the photosensitive layer) such as alkaline matters that exist in the air to sneak into photosensitive layer, thereby can expose in air.Therefore, protective seam is need be to the perviousness of micromolecular compound low and preferably can also not suppress passing through of the light that is used to expose substantially, and photosensitive layer is had splendid bounding force and is easy to be removed in the development step of exposure.Protective seam usually all like this design, at United States Patent (USP) 3,458,311 and JP-A-55-49729 in have a detailed description.The material that can be used as protective seam is to have good relatively crystalline water-soluble polymers.Its concrete example comprises water-soluble polymers such as polyvinyl alcohol (PVA), polyvinylpyrrolidone, acid cellulose, gelatin, Arabic gum and polyacrylic acid.Wherein, preferably use polyvinyl alcohol (PVA), because can for example the isolated characteristic of oxygen and development removability produce optimal results to fundamental property as principal ingredient.The polyvinyl alcohol (PVA) that is used for protective seam has the isolated characteristic and water-soluble of required oxygen, and therefore, as long as it contains unsubstituted vinyl alcohol unit, its part just can use ester, ether or acetal to replace.Equally, a part can contain other multipolymer composition.The example of operable polyvinyl alcohol (PVA) comprise degree of hydrolysis be 71 to 100mol% and weight-average molecular weight be 300 to 2,400 those.Its concrete example comprises PVA-105, 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 Kuraray Co., the L-8 that Ltd produces.
The selection of composition of protective seam (for example use of the selection of PVA, adjuvant) and coated weight thereof need be considered isolated characteristic and development removability, atomizing, cohesive and the erasibility to small-molecule substance.Usually, the thickness of the hydrolysis of PVA higher than more (that is, protective seam has higher unsubstituted vinyl alcohol unit content) and layer is big more, and the isolated property of small-molecule substance is just strong more, is favourable more with regard to susceptibility.But,, then producing or raw material may cause unnecessary polyreaction when depositing, or in the image exposure process, may produce thickening of unnecessary atomizing or picture lines if the isolated property of small-molecule substance is strengthened terrifically.In addition, with regard to the operation of galley, also be very important to the cohesive and the erasibility of image region.That is to say that when the hydrophilic layer that will contain water-soluble polymers was laminated on the lipophilic polymer layer, this layer meeting was owing to bounding force is easy to be stripped from inadequately.In order to address this problem, to have proposed various suggestions and strengthened this cohesive between two-layer.For example, United States Patent (USP) 292,501 and 44,53 have described 20 to 60wt% acrylic emulsion or water soluble vinyl pyrrolidone-vinyl acetate copolymer have been mixed in the hydrophilic polymer that mainly contains polyvinyl alcohol (PVA) then the technology of its lamination on polymeric layer, obtain sufficiently high cohesive thus.These known technology all can be used for protective seam of the present invention.The coating process write up of protective seam is in for example United States Patent (USP) 3,458,311 and JP-A-55-49729.
In addition, also can give protective seam other function.For example, when using laser, make photo-sensitive composition that the light of optical source wavelength is demonstrated splendid susceptibility sometimes wittingly as light source, and insensitive to the light of other wavelength.When the light of light emitted 750nm or higher region of ultra-red, galley can be used in bright room, still, the sensitization meeting in addition shortwave light for example take place under the light of fluorescent light.In this case, preferred adding can be guaranteed the colorant (for example water-soluble dye) that source light sees through well and absorbing wavelength is lower than the light of 700nm effectively.
In another example of the light source that uses emission 450nm or lower ultraviolet region light, galley can be used under the light of basic security.But composition is sometimes by 500nm or higher visible sensitization.In this case, can use can guarantee that source light sees through well and effectively absorbing wavelength can not cause any reduction of susceptibility so that safety lamp is suitable for more as the colorant (for example water-soluble dye) of 500nm or higher light.
When the photosensitive material that adopt to use optical polymerism composition of the present invention during as image forming material, usually photosensitive material is carried out the imaging exposure, develop to remove unexposed zone on the photosensitive layer with developer then, obtain image thus.When using optical polymerism composition to produce lithographic plate, preferably use the developer of describing among the JP-B-57-7427.Developer can be for example aqueous solution or the ammoniacal liquor of sodium silicate, potassium silicate, NaOH, potassium hydroxide, lithium hydroxide, sodium phosphate, dibastic sodium phosphate (sodium secondaryphosphate), ammonium phosphate, ammonium hydrogen phosphate (ammonium secondary phosphate), sodium silicate, sodium borate of inorganic alkaline agents, or the aqueous solution of organic basic reagent such as monoethanolamine or diethanolamine.Alkaline reagent with concentration be 0.1 to 10wt%, the form of preferred 0.5 to 5wt% alkaline solution adds.
As needs, above-mentioned alkaline solution can contain low quantity of surfactant or organic solvent, for example benzylalcohol, 2-phenoxetol or butoxy ethanol.Its example comprises United States Patent (USP) 3,375, those that describe in 171 and 3,615,480.
In addition, the developer of describing among JP-A-50-26601, JP-A-58-54341, JP-B-56-39464 and the JP-B-56-42860 also is extraordinary.
As needs, in the plate-making process of the original edition of lithographic printing plate that has suitably applied optical polymerism composition of the present invention, can before exposure or in the exposure process or from the process that is exposed to development, heat whole surface.By heating, can quicken the imaging reaction in the photosensitive layer and obtain favourable result, for example, improve susceptibility and printing life-span and make susceptibility stable.In addition, in order to improve image intensity and printing life-span, it also is effective after development the whole surface of image being carried out the back heating or exposed.If temperature is too high, the problems such as atomizing of non-image areas then may appear.Adding after development pined for, and can use very harsh condition, and temperature is generally 200 to 500 ℃.If temperature is lower, then possibly can't obtain sufficiently high image and strengthen effect, on the contrary,, then can go out the thermal decomposition of the rotten or imagery zone of expression vector if temperature is too high.
In the exposure of the lithographic plate that is used for scan exposure of the present invention, can have no restrictedly to use various known methods.The light source preferred laser can obtain and operable wavelength is that the example of 350 to 450nm laser light source comprises at present:
Gas laser, for example Argon ion laser (364nm, 351nm are from 10mW to 1W), krypton ion laser (356nm, 351nm are from 10mW to 1W) and He-Cd laser instrument (441nm, 325nm, from 1 to 100mW);
Solid state laser, for example Nd:YAG (YVO
4) with the composition of the combination (355nm is from 5mW to 1W) of SHG crystallization x2 and Cr:LiSAF and SHG crystallization (430nm, 10mW);
Semiconductor laser, for example KNbO
3, the ring resonant cavity (430nm, 30mW), guided wave type wavelength sensing element and AlGaAs or the semi-conductive combination of InGAAs (from 380 to 450nm, from 5 to 100mW) and AlGaInN (from 350 to 450nm, from 5 to 30mW); With
Pulsed laser, for example N
2Laser instrument (337nm, pulse: from 0.1 to 10mJ) and XeF (351nm, pulse: from 10 to 250mJ).
Wherein, with regard to wavelength characteristic and cost, preferred AIGaInN semiconductor laser (commercially available InGaN N-type semiconductor N laser instrument: from 400 to 410nm, from 5 to 30mW).
In addition, the light source as emission 450 to the 700nm light that can adopt can use Ar
+Laser instrument (488nm), YAG-SHG laser instrument (532nm), He-Ne laser instrument (633nm), He-Cd laser instrument and red laser diode (from 650 to 690nm), as the emission 700 to 1 that can adopt, the light source of 200nm light, can use semiconductor laser (from 800 to 850nm) and Nd-YAG laser instrument (1,064nm).
In addition, can also use mercury lamp, chemical lamp, carbon arc lamp, xenon of various UHV (ultra-high voltage), high pressure, middle pressure or low pressure etc., metal halide lamp, Ultra-Violet Laser lamp (for example, ArF excimer laser instrument, KrF excimer laser instrument) and radioactive ray for example electron beam, X ray, ion beam and far ir ray.Wherein, preferred 350nm or higher laser light source are because they are comparatively cheap.
Exposure mechanism can be any in inside surface rotor system, the outer drum system peace plate system.The component that is used for photosensitive layer of the present invention can have high water-soluble, and photosensitive layer is dissolved in neutral or the subalkaline water.For having this structure lithographic plate, can adopting galley is assembled to the system that exposes and develop then on the printing machine on machine.
Except the lithographic plate that is used for exposing uses, optical polymerism composition of the present invention can also have no restrictedly to be widely used in the known field that can use light-cured resin.For example, when the present invention being used for the liquid optical polymerism composition when (, can unite and use the cationically polymerizable compound), can obtain the light building material of hypersensitivity as needs.In addition, the change of index of refraction can obtain hologram material when utilizing polymerization.The change of surface adhesion when utilizing photopolymerization, the present invention can be used for various transmission materials (for example, exfoliated photochromics, toner development photochromics).The photocuring, electronic material that the present invention also can be used for microcapsules for example photoresist production and be used for photo-curing material as China ink, coating material and bonding agent.
Hereinafter with reference to embodiment the present invention is explained in more detail, still, the present invention should be interpreted as to only limit to these embodiment.
＜have The compounds of this invention synthetic of structure shown in the formula (I) 〉
Formula (I) compound is easy to from the compound that contains acryloyl group accordingly according to " adhesion technique " (Adhesion Technology), Vol.14, and No.4, continuous Vol.37, method of describing in the 2nd page (1995) is synthetic.
Synthetic embodiment 1: compd A-1
Methyl acrylate (1.5mol), 37% formlinata aquae concentratac (1.0mol) and tetrahydrofuran (100ml) are joined in the flask.(0.135mol) and with potpourri stir to wherein adding DABCO (1,4-diazabicyclo [2,2,2] octane).React after 24 hours, add 40ml 1N hydrochloric acid/200ml water and, use dried over mgso, filter then that concentrating under reduced pressure obtains compd A-1, yield 30% the reactant liquor ethyl acetate extraction.
The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 2: compd A-12
Compd A-1 (1.0mol) and tetrahydrofuran (100ml) are joined in the flask.To wherein adding NaH (1.0mol) gradually, stir after 30 minutes down with ice-cooled, with 1 hour time dropping benzyl bromide a-bromotoluene (1.0mol).Potpourri is returned to room temperature to be stirred 3 hours then.After the reaction, add 200ml water and, use dried over mgso, filter under reduced pressure fully concentrated then obtain compd A-12, yield 80% the reactant liquor ethyl acetate extraction.
The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 3: compd A-17
Compd A-1 (1.0mol), ethyl acetate (100ml), pyridine (1.0mol) and DMAP (4-dimethylaminopyridine) (0.1mol) are joined in the flask.With ice-cooled down, with 1 hour time to dripping acetyl chloride (1.0mol) wherein, then potpourri is returned to room temperature and stirred 3 hours.After the reaction, add 200ml water and, use dried over mgso, filter under reduced pressure fully concentrated then obtain compd A-17, yield 95% the reactant liquor ethyl acetate extraction.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 4: compd A-22
Compd A-1 (1.0mol), ethyl acetate (100mol), pyridine (1.0mol) and DMAP (4-dimethylaminopyridine) (0.1mol) are joined in the flask.With ice-cooled down, with 1 hour time to wherein dripping paratoluensulfonyl chloride (1.0mol), then potpourri is returned to room temperature and stirred 3 hours.After the reaction, add 200ml water and, use dried over mgso, filter under reduced pressure fully concentrated then obtain compd A-22, yield 90% the reactant liquor ethyl acetate extraction.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 5: compd A-33
With 2-(bromomethyl) acrylic acid (producing) by Aldrich (1.0mol) and chloroform (100ml) join in the flask.With ice-cooled down, with 1 hour time to wherein dripping SOCl
2(1.0mol), then potpourri is returned to room temperature and stirring 2 hours.To wherein adding normal butyl alcohol (2.0mol), room temperature reaction is after 24 hours, with the reactant liquor concentrating under reduced pressure, to wherein adding 200ml water,, use dried over mgso with the solution ethyl acetate extraction that forms, filter under reduced pressure fully to concentrate then and obtain compd A-33, yield 90%.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 6: compd A-27
With 2-(bromomethyl) acrylic acid (producing) by Aldrich (1.0mol) and chloroform (100ml) join in the flask.With ice-cooled down, with 1 hour time to wherein dripping SOCl
2(1.0mol), then potpourri is returned to room temperature and stirring 2 hours.To wherein adding methyl alcohol (2.0mol), room temperature reaction with the reactant liquor concentrating under reduced pressure, to wherein adding 200ml water, with the solution ethyl acetate extraction that forms, was used dried over mgso after 24 hours, filtered under reduced pressure fully concentrated then.To wherein adding ethyl acetate (100ml) and 2-mercaptobenzothiazole (1.0mol), in 30 minutes, dripping triethylamine (1.0mol) with ice-cooled time then.To wherein adding 200ml water, with the solution ethyl acetate extraction that forms, use dried over mgso, filter under reduced pressure fully concentrated then obtain compd A-27, yield 80%.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 7: compd A-38
With 2-(bromomethyl) acrylic acid (producing) by Aldrich (1.0mol) and chloroform (100ml) join in the flask.With ice-cooled down, with 1 hour time to wherein dripping SOCl
2(1.0mol), then potpourri is returned to room temperature and stirring 2 hours.To wherein adding methyl alcohol (2.0mol), room temperature reaction with the reactant liquor concentrating under reduced pressure, to wherein adding 200ml water, with the solution ethyl acetate extraction that forms, was used dried over mgso after 24 hours, filtered under reduced pressure fully concentrated then.To wherein adding ethyl acetate (100ml) and morpholine (1.0mol), in 30 minutes, dripping triethylamine (1.0mol) with ice-cooled time then.Potpourri was stirred 5 hours,,, use dried over mgso, filter under reduced pressure fully concentrated then obtain compd A-38, yield 70% the solution ethyl acetate extraction that forms to wherein adding 200ml water.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 8: compd B-5
A-1 (1.5mol) and acetone (100ml) are joined in the flask.To wherein adding isocyanic acid normal-butyl (1.0mol) and di-n-butyl tin two lauric acid salt (0.001mol), then with potpourri stirring at room 8 hours.To wherein adding 200ml water, with the solution ethyl acetate extraction that forms, use dried over mgso, filter under reduced pressure fully concentrated then.To wherein adding tetrahydrofuran (100ml), adding NaH (1.0mol) gradually with ice-cooled time then.Stir after 1 hour, add p methoxy phenol (0.01mol) and potpourri was stirred 10 hours under 80 ℃ bath temperature.After the stirring, add 200ml water and, use dried over mgso, filter the solution ethyl acetate extraction that forms, under reduced pressure fully concentrated, separate (hexane/ethyl acetate=9/1) by silica gel column chromatography, concentrating under reduced pressure obtains compd B-5 then, yield 20%.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 9: Compound C-1
With 1,6 hexanediol diacrylate (producing) by Nakamura Kagaku (0.75mol), 37% formlinata aquae concentratac (1.0mol) and tetrahydrofuran (100ml) join in the flask.
To wherein adding DABCO (0.135mol) and potpourri being stirred.React after 24 hours, add 40ml 1N hydrochloric acid/200ml and, use dried over mgso the reactant liquor ethyl acetate extraction, filter, under reduced pressure fully concentrated, separate (hexane/ethyl acetate=9/1) by silica gel column chromatography, concentrating under reduced pressure obtains Compound C-1 then, yield 20%.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 10: Compound D-7
Compd A-1 (1.0mol), ethyl acetate (100ml), pyridine (1.0mol) and DMAP (4-dimethylaminopyridine) (0.1mol) are joined in the flask.With ice-cooled down, with 1 hour time to wherein dripping succinyl dichloro (0.5mol), then potpourri is returned to room temperature and stirred 3 hours.After the reaction, add 20ml water and, use dried over mgso, filter under reduced pressure fully concentrated then obtain Compound D-7, yield 80% the reactant liquor ethyl acetate extraction.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 11: compd E-4
With tetramethylol methane tetraacrylate (producing) by Nakamura Kagaku (0.375mol), 37% formlinata aquae concentratac (1.0mol) and tetrahydrofuran (100ml) join in the flask.
To wherein adding DABCO (0.135mol) and potpourri being stirred.React after 24 hours, add 40ml 1N hydrochloric acid/200ml water and, use dried over mgso the reactant liquor ethyl acetate extraction, filter, under reduced pressure fully concentrated, separate (hexane/ethyl acetate=9/1) by silica gel column chromatography, concentrating under reduced pressure obtains compd E-4 then, yield 10%.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 12: compound F 17-hydroxy-corticosterone-3
Compd A-1 (1.0mol), ethyl acetate (100ml), pyridine (1.0mol) and DMAP (4-dimethylaminopyridine) (0.1mol) are joined in the flask.With ice-cooled down, with 1 hour time to wherein dripping benzene tricarbonic acid's acyl chlorides (0.34mol), then potpourri is returned to room temperature and stirred 3 hours.After the reaction, add 200ml water and, use dried over mgso, filter under reduced pressure fully concentrated then obtain compound F 17-hydroxy-corticosterone-3, yield 70% the reactant liquor ethyl acetate extraction.The structure of compound confirms by NMR, MASS and IR.
Synthetic embodiment 13: compound G-5
Compd A-1 (0.8mol), acetone (100ml), pyridine (1.0mol) and DMAP (4-dimethylaminopyridine) (0.1mol) are joined in the flask.With under ice-cooled, to wherein adding the 30wt% weight-average molecular weight is 20,000 polyacrylamide solutions of chlorine is (in compd A-1, can provide the amount of 1.0mol COCl group), this solution makes by acryloyl chloride and thermal polymerization V-601 (being produced by Wako Junyaku) are carried out radical polymerization.Potpourri is returned to room temperature and stirred 24 hours.After the reaction, add 200ml water and potpourri is continued stirring 24 hours.Reactant liquor is added drop-wise in 100ml 1N hydrochloric acid/1L water, isolates polymer precipitation, be dissolved in ethyl acetate and use dried over mgso, be about the p methoxy phenol of 500ppm to wherein adding concentration.It is 30% that the solution decompression that forms is concentrated into solid concentration.Obtain compound G-5 thus, yield 90%.The structure of compound confirms by GPC, NMR and IR.
Synthetic embodiment 14: compound G-13
With 2-(bromomethyl) acrylic acid (producing) by Aldrich (0.8mol) and chloroform (100ml) join in the flask.With ice-cooled down, with 1 hour time to wherein dripping SOCl
2(0.8mol).Potpourri is returned to room temperature and stirred 2 hours.Behind the concentrating under reduced pressure, to wherein adding acetone (100ml), adding weight-average molecular weight is 4,000 novolaks are (in 2-(bromomethyl) acrylic acid, can provide the amount of 1.0mol OH group), described novolaks are synthetic in the presence of the oxalic acid catalyzer by metacresol, right-phenol-formaldehyde A and formalin.Wherein drip triethylamine (0.8mol) with time of 1 hour then.Reaction was added drop-wise to reactant liquor in 100ml 1N hydrochloric acid/1L water after 24 hours under the room temperature, isolated polymer precipitation, was dissolved in ethyl acetate and used dried over mgso, was about the p methoxy phenol of 200ppm to wherein adding concentration.It is 30% that the solution decompression that forms is concentrated into solid concentration.Obtain compound G-13 thus, yield 80%.The structure of compound confirms by GPC, NMR and IR.
All specifically described compounds all can be synthetic according to the mode identical with above description.
The embodiment 1 of optical polymerism composition
(preparation of carrier)
The aluminium sheet that 0.3mm is thick with the tap water flushing, is used in the 20wt% nitric acid and washing by carried out etching in 25 seconds in 60 ℃ of immersions in 10wt% NaOH, washes with water then.In the 1wt% aqueous solution of nitric acid, use sine wave alternating current with 300 coulombs/dm the plate that obtains
2Anode time electric weight carry out electrolysis system line and handle.Subsequently, aluminium sheet was soaked 5 hours in 40 ℃ in the 1wt% sodium hydrate aqueous solution, in the 30wt% aqueous sulfuric acid in 60 ℃ of dismutase-4s 0 second, then at 2A/dm
2Current density under in the 20wt% aqueous sulfuric acid anodic oxidation to obtain thickness in 2 hours be 2.7g/m
2Anodic oxide coating.Recording surfaceness is 0.3 μ m (according to the Ra indication of JISB0601).
At the back side of the bottom of so handling, apply following sol gel reaction solution and made in 100 ℃ of dryings that to have dry coating weight thereon be 70mg/m in 1 minute by bar-shaped coater
2The carrier of back coating.
Sol gel reaction solution:
Silicon ethyl acid esters 50 weight portions
Water 20 weight portions
Methyl alcohol 15 weight portions
Phosphoric acid 0.05 weight portion
These are fully mixed and stir, in about 5 minutes, begin heat release.React after 60 minutes, add the coating solution of following formulations prepared from solutions back coating.
The resin of tri hydroxybenzaldehyde condensation (molecular weight: 2,000) 4 weight portions
Repefral 5 weight portions
Fluorochemical surfactant (N-butyl PFO sulfonamide ethyl acrylate/poly-0.7 weight portion
The ethylene oxide acrylate copolymer, molecular weight: 20,000)
The methyl alcohol silicon dioxide gel is (by Nissan Chemical Industry, 50 weight portions
Ltd. produce methyl alcohol: 30wt%)
Methyl alcohol 800 weight portions
(preparation of photosensitive layer)
On the aluminium sheet of so handling, apply optical polymerism composition and make dried coated weight reach 1.5g/m with following composition
2, formed photosensitive layer in 1 minute in 100 ℃ of dryings then.
(forming the solution of photosensitive layer)
Compound [X] or contrast (shown in the following Table A) 1.5g of having polymerizable groups of the present invention
Photoepolymerizationinitiater initiater [Y] (shown in the following Table A) 0.3g
Polymer adhesive [Z] (shown in the following Table A) 2.0g
Polymerisable compound [R] (shown in the following Table A) 5g (referring to Table A)
Adjuvant [S] (shown in the following Table A) 0.4g
(Megafac F-177 is by Dai-Nippon Ink ﹠amp for fluorine-containing surfactant; 0.03g
Chemicals, Inc. produces)
Thermal polymerization inhibitor (N-nitroso-phenyl hydramine aluminium salt) 0.01g
Dispersible pigment dispersion 2.0g
The composition of dispersible pigment dispersion
Form: 15: 6 15 weight portions of blue pigment
ALMA/methacrylic acid copolymer 10 weight portions
(copolymerization mol ratio: 83/17)
Cyclohexanone 15 weight portions
Methoxy propyl yl acetate 20 weight portions
Propylene glycol monomethyl ether 40 weight portions
MEK 20g
Propylene glycol monomethyl ether 20g
(preparation of protective seam)
In certain embodiments, on photosensitive layer, apply and contain the 3wt% polyvinyl alcohol (PVA) (saponification degree: 98mol%, the degree of polymerization: aqueous solution 550) is to reach 2g/m
2The dry-coated weight of covering, then in 100 ℃ of dryings 2 minutes.
(assessment of susceptibility)
Change the susceptibility that light source is assessed the photochromics that so obtains by exposure wavelength according to various photochromicss.
For example, photochromics is exposed in air, it is soaked in the developer solution that has following composition under 25 ℃ develop for 10 seconds then with the semiconductor laser of 400nm, the FD-YAG laser instrument of 632nm and the semiconductor laser of 830nm.From forming the required minimum exposure amount of image, calculate the susceptibility under the various conditions of exposures, unit is mJ/cm
2Resulting numerical value is more little, and susceptibility is high more.But along with the difference of optical source wavelength, the energy that each photon had is different, and briefly, wavelength can be finished sensitization more usually under less exposure.Therefore, the susceptibility between the different exposure is more nonsensical, and table B has provided in the difference between comparing embodiment and the Comparative Examples under the identical conditions of exposure.The result is shown in table B.
(composition of developer solution)
DP-4 (by Fuji Photo Film Co., Ltd. produces) 65.0g
Water 880.0g
Lipomin A (20% aqueous solution is produced by Lion) 50.0g
(assessment of shelf stability)
The above photochromics that obtains was placed 3 days down in hot conditions (60 ℃) before using laser explosure.Photochromics after these are deposited according to above identical mode with laser explosure and calculate the required energy of imprinting.Can at high temperature be deposited the energy of front and back from the numerical value that calculates than (energy before the energy/high temperature after high temperature is deposited is deposited).With regard to production, this energy ratio is preferably 1.1 or lower.Adopt this energy ratio, can also obtain good shelf stability.
The result of this assessment is shown in following table B.
[table 19]
Table-A: photochromics
X Y Z R (r) S contains or does not contain protective seam light source (nm)
Embodiment 1 C-1 Y-1 Z-1 does not have and has 400
Embodiment 2 C-9 Y-1 Z-1 do not have and have 400
" 3 D-17 Y-2 Z-2 do not have S-1 400
4 D-18 Y-2 Z-2 do not have S-2 400
5 E-2 Y-1 Z-2 do not have S-3 400
6 E-20 Y-2 Z-1 do not have S-4 400
7 F-3 Y-1 Z-1 do not have S-3 400
8 F-8 Y-1 Z-2 R-1 (0.5) S-1 have 400
9 G-1 Y-1 do not have R-1 (0.1) S-1 and have 400
10 G-3 Y-1 do not have R-2 (1.0) nothing and have 400
11 H-1 Y-2 Z-1 do not have and have 400
12 J-1 Y-1 Z-2 do not have and have 400
Have 400 Bi More example 1 xc-1 Y-1 Z-1 nothing
Have 400 Bi More example 2 xc-9 Y-1 Z-1 nothing
" 3 xd-17 Y-2 Z-2 do not have S-1 400
4 xd-18 Y-2 Z-2 do not have S-2 400
5 xe-2 Y-1 Z-2 do not have S-3 400
6 xe-20 Y-2 Z-1 do not have S-4 400
7 xf-3 Y-1 Z-1 do not have S-3 400
8 xf-8 Y-1 Z-2 R-1 (0.5) S-1 have 400
9 xg-1 Y-1 do not have R-1 (1.0) S-1 and have 400
10 xg-3 Y-1 do not have R-2 (1.0) nothing and have 400
11 xh-1 Y-2 Z-1 do not have and have 400
12 xj-1 Y-1 Z-2 do not have and have 400
Embodiment 13 C-2 Y-3 Z-1 R-1 (0.5) do not have and have 532
Embodiment 14 C-8 Y-3 Z-1 do not have and have 532
" 15 D-13 Y-4 Z-1 do not have S-1 532
16 D-15 Y-4 Z-2 do not have S-2 532
17 E-1 Y-5 Z-2 do not have S-3 532
18 E-21 Y-4 Z-1 do not have S-4 532
19 F-4 Y-5 Z-1 do not have S-3 532
20 F-10 Y-3 Z-2 do not have S-2 532
21 G-2 Y-4 do not have R-1 (1.0) S-2 and have 532
22 G-10 Y-3 do not have R-2 (1.0) nothing and have 532
23 H-2 Y-3 Z-1 do not have and have 532
24 J-3 Y-3 Z-2 do not have and have 532
[table 20]
Table-A (continuing): photochromics
X Y Z R (r) S contains or does not contain protective seam light source (nm)
Have 532 Bi More example 13 xc-2 Y-3 Z-1 R-1 (0.5) nothing
Have 532 Bi More example 14 xc-8 Y-3 Z-1 nothing
" 15 xd-13 Y-4 Z-1 do not have S-1 532
16 xd-15 Y-4 Z-2 do not have S-2 532
17 xe-1 Y-5 Z-2 do not have S-3 532
18 xe-21 Y-4 Z-1 do not have S-4 532
19 xf-4 Y-5 Z-1 do not have S-3 532
20 xf-10 Y-3 Z-2 do not have S-2 532
21 xg-2 Y-4 do not have R-1 (1.0) S-2 and have 532
22 xg-10 Y-3 do not have R-2 (1.0) nothing and have 532
23 xh-2 Y-3 Z-1 do not have and have 532
24 xj-3 Y-3 Z-2 do not have and have 532
Embodiment 25 C-3 Y-6 Z-1 R-1 (0.5) do not have 830
Embodiment 26 C-10 Y-6 Z-1 do not have 830
" 27 D-4 Y-6 Z-1 do not have S-5 is not had 830
28 D-18 Y-7 Z-2 do not have S-5 is not had 830
29 E-7 Y-7 Z-2 do not have S-6 is not had 830
30 E-9 Y-8 Z-1 do not have S-7 is not had 830
31 F-5 Y-8 Z-1 do not have 830
32 F-11 Y-8 Z-2 do not have 830
33 G-5 Y-8 do not have R-1 (1.0) and do not have 830
34 G-12 Y-9 do not have R-2 (1.0) and do not have 830
35 H-1 Y-9 Z-1 do not have 830
36 J-7 Y-9 Z-2 do not have 830
Do not have 830 Bi More example 25 xc-3 Y-6 Z-1 R-1 (0.5)
Do not have 830 Bi More example 26 xc-10 Y-6 Z-1
" 27 xd-4 Y-6 Z-1 do not have S-5 is not had 830
28 xd-18 Y-7 Z-2 do not have S-5 is not had 830
29 xe-7 Y-7 Z-2 do not have S-6 is not had 830
30 xe-9 Y-8 Z-1 do not have S-7 is not had 830
31 xf-5 Y-8 Z-1 do not have 830
32 xf-11 Y-8 Z-2 do not have 830
33 xg-5 Y-8 do not have R-1 (1.0) and do not have 830
34 xg-12 Y-9 do not have R-2 (1.0) and do not have 830
35 xh-1 Y-9 Z-1 do not have 830
36 xj-7 Y-9 Z-2 do not have 830
[table 21]
Table-B: evaluation result
Susceptibility (mJ/cm2) shelf stability (ratio)
Embodiment 1 0.05 1.05
″ 2 0.1 1.0
3 0.1 1.0
4 0.1 1.05
5 0.1 1.0
6 0.1 1.0
7 0.1 1.05
8 0.05 1.1
9 0.05 1.1
10 0.05 1.05
11 0.1 1.05
12 0.1 1.05
Bi More example 1 0.2 2.0
″ 2 0.2 2.0
3 0.2 1.5
4 0.2 1.5
5 0.25 1.5
6 0.3 1.5
7 0.2 2.0
8 0.3 1.5
9 0.15 2.0
10 0.15 2.0
11 0.3 1.5
12 0.2 2.0
Embodiment 13 0.15 1.0
″ 14 0.1 1.0
15 0.1 1.0
16 0.1 1.05
17 0.1 1.0
18 0.1 1.0
19 0.15 1.1
20 0.1 1.1
21 0.1 1.05
22 0.1 1.0
23 0.15 1.05
24 0.1 1.05
[table 22]
Table-B (continuing): evaluation result
Susceptibility (mJ/cm
2) shelf stability (ratio)
Bi More example 13 0.3 1.5
″ 14 0.3 1.5
15 0.2 1.5
16 0.2 1.5
17 0.3 1.5
18 0.4 1.5
19 0.3 2.0
20 0.3 1.5
21 0.2 2.5
22 0.3 2.0
23 0.3 1.5
24 0.3 1.5
Embodiment 25 100 1.05
″ 26 100 1.0
27 100 1.0
28 90 1.0
29 110 1.1
30 100 1.0
31 110 1.0
32 100 1.0
33 90 1.1
34 90 1.1
35 100 1.0
36 100 1.0
Bi More example 25 150 1.5
″ 26 250 1.5
27 150 1.5
28 200 1.5
29 300 2.0
30 200 2.0
31 150 2.0
32 150 2.0
33 150 1.5
34 200 1.5
35 300 2.0
36 200 2.0
[changing 108]
Compound among the embodiment
[changing 109]
Z-1
Benzyl methacrylate/methacrylic acid copolymer=70/30mol%, Mw:30,000
Z-2
ALMA/methacrylic acid copolymer=80/20mol%, Mw:40,000
R-1
Tetramethylol methane tetraacrylate (ATMMT)
R-2
Dipentaerythritol acrylate (DPHA)
[changing 110]
[changing 111]
[changing 112]
Compound in the comparative example
[changing 113]
[changing 114]
[changing 115]
[changing 116]
[changing 117]
From table B as can be seen, photochromics of the present invention has very high susceptibility and good shelf stability.
The embodiment 2 of optical polymerism composition
Upward applying the optical polymerism composition solution with following composition at PET (polyethylene terephthalate) is 2.0g/m to reach dry coating weight
2, formed photosensitive layer in 1 minute in 80 ℃ of dryings then.
(optical polymerism composition solution)
Compound [S] or contrast (shown in the following table C) 1.5g of having polymerizable groups of the present invention
CGI-784 (produce by Ciba Geigy, contain the initiating agent of cyclopentadienyltitanium) 0.2g
Polymethylmethacrylate (Mw:30,000, Mw/Mn=1.3) 2.0g
(Megafac F-177 is by Dai-Nippon Ink﹠amp for fluorine-containing surfactant; 0.03g
Chemicals, Inc. produces)
MEK 20g
1-methoxyl-2-propyl alcohol 20g
(assessment of susceptibility)
The photochromics that so makes is cut into the square of 10cm * 10cm, and the light with high-pressure sodium lamp shines to produce 300mJ/cm on photochromics it in air then
2Susceptibility.Then, measure the weight (Wi g) of photochromics.Then, in soaking 10 minutes in MEK/1-methoxyl-2-propyl alcohol=50wt%/50wt% under 25 ℃, with solvent develop and dry, (Wf g) then weighs with it.
State of cure with following formula definition is good or bad with sensitivity assessment.
State of cure (%)=100-(Wi-Wf)/2 (%)
State of cure is more near 100%, and susceptibility is high more.The result is as shown in following table C.
Table C: assessment result
[table 23] table-C: evaluation result
[X] state of cure (%)
Embodiment 37 A-4 40
″ 38 B-5 40
39 C-1 70
40 D-1 70
41 E-1 70
42 F-1 60
43 G-8 70
44 H-1 80
45 J-12 60
Bi More example 37 xa-1 0
″ 38 xb-5 0
39 xc-1 0
40 xd-1 0
41 xe-1 0
42 xf-1 0
43 xg-8 5
44 xh-1 0
45 xj-12 0
From table C as can be seen, even optical polymerism composition of the present invention also can solidify when not having the antioxygen protective seam, be not subjected to the influence of oxygen and susceptibility very high.
According to the present invention, the optical polymerism composition of the free radical photopolymerization set of systems compound form that can guarantee hypersensitivity and good shelf stability simultaneously can be provided, the susceptibility of said composition is the highest, is very promising in imaging technique.Specifically, can provide a kind of be suitable for use as can by from the numerical data of computing machine etc. with the solid state laser of emission ultraviolet rays, visible light ray or infrared-ray or the optical polymerism composition of the lithographic plate that the semiconductor laser imprinting is directly made a plate.
Claims (14)
1. contain the compound with structure shown in the following general formula (I) and the optical polymerism composition of Photoepolymerizationinitiater initiater:
[changing 1]
X wherein
1And X
2Represent heteroatoms or the group or the halogen atom that connect with heteroatoms independently of one another, R
aAnd R
bRepresent hydrogen atom, halogen atom, cyano group or organic residue independently of one another, X
1And X
2, R
aAnd R
b, or X
1And R
aOr R
bCan lump together the formation ring texture each other.
2. the described optical polymerism composition of claim 1, wherein, described composition is 300 to 1 by wavelength, the laser light source sensitization of 200nm.
3. the described optical polymerism composition of claim 2, wherein, described composition also contains sensitizing dye.
4. the described optical polymerism composition of claim 1, wherein, the described compound with structure shown in the formula (I) has the structure shown at least two kinds of formulas (I).
5. the described optical polymerism composition of claim 1, wherein, the described compound with structure shown in the formula (I) has the structure shown at least three kinds of formulas (I).
6. the described optical polymerism composition of claim 1, wherein, the molecular weight with described compound of structure shown in the formula (I) is 4,000-100,000.
7. the described optical polymerism composition of claim 1, wherein, the X in the formula (I)
2It is methoxyl.
8. the described optical polymerism composition of claim 1, wherein, the X in the formula (I)
1Contain O, S, N or OCO.
9. the described optical polymerism composition of claim 1, wherein, the X in the formula (I)
1Contain O.
10. the described optical polymerism composition of claim 1, wherein, the X in the formula (I)
1Contain OCO.
11. the described optical polymerism composition of claim 1, wherein, described composition also contains acrylate or methacrylate compound.
12. the described optical polymerism composition of claim 1, wherein, the amount with described compound of structure shown in the formula (I) is 10 to 70wt%, in the weight of all the components.
13. the described optical polymerism composition of claim 1, wherein, described composition also contains the linear organic high molecular polymer with alkali-soluble.
14. contain the original edition of lithographic printing plate of the described optical polymerism composition of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00134577XA CN1171122C (en) | 2000-12-12 | 2000-12-12 | Optical polymerism composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00134577XA CN1171122C (en) | 2000-12-12 | 2000-12-12 | Optical polymerism composition |
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|---|---|
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| CN1171122C true CN1171122C (en) | 2004-10-13 |
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ID=4596292
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026019A (en) * | 2015-09-15 | 2018-05-11 | 捷恩智株式会社 | Polymerism polar compound, liquid-crystal composition and liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100470365C (en) * | 2001-01-12 | 2009-03-18 | 富士胶片株式会社 | Positive imaging material |
| JP2004012706A (en) * | 2002-06-05 | 2004-01-15 | Fuji Photo Film Co Ltd | Planographic printing plate original plate |
| KR100995612B1 (en) * | 2007-07-05 | 2010-11-22 | 주식회사 엘지화학 | Method of Producing Polymerized Toner |
| EP2356182B1 (en) * | 2008-11-12 | 2015-05-06 | Basf Se | Radiation curable coating materials |
| CN105392634B (en) * | 2013-07-18 | 2017-10-13 | 富士胶片株式会社 | Original edition of lithographic printing plate and its method for platemaking |
| US11685808B2 (en) * | 2020-06-11 | 2023-06-27 | Novoset, Llc | Oligomer resin compositions |
-
2000
- 2000-12-12 CN CNB00134577XA patent/CN1171122C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026019A (en) * | 2015-09-15 | 2018-05-11 | 捷恩智株式会社 | Polymerism polar compound, liquid-crystal composition and liquid crystal display element |
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|---|---|
| CN1319784A (en) | 2001-10-31 |
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