JPH06157623A - Polymerizable composition and method for polymerization - Google Patents

Abstract

PURPOSE:To obtain a compsn. which can be photo-or thermally polymerized in a short time by compounding a radical-polymerizable ethylenically unsatd. compd. with a specific polymn. initiator. CONSTITUTION:A polymerizable compsn. is obtd. by compounding 100 pts.wt. radical-polymerizable ethylenically unsatd. compd., 0.01-30 pts.wt. (oxo)sulfonium complex of the formula (wherein R<1> and R<2> are each an optionally substd. aryl; R<3> is an optionally substd. alkyl, aryl, alicyclic, alkenyl, alkynyl, alkoxy, aryloxy, alkylthio, or amino group; R<4> is 0 a lone electron pair; and R<5> to R<8> are each an optionally substd. alkyl, aryl, alkenyl, or alkynyl group, etc.) having a reduction potential by an electrochemical measurement of -1.3eV or higher, and, if necessary, 0.01-10 pts.wt. sensitizer which absorbs arbitrary rays of light in the region 4 from ultraviolet to near-infrared rays.

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a polymerizable composition and a polymerization method. More specifically, the polymerizable composition can be polymerized in a short time by applying light and / or heat. Photosensitive printing plate material that requires high sensitivity,
The present invention relates to a polymerizable composition and a polymerization method useful in the fields of direct printing plate materials, photoresists, hologram materials, inks, sealants, adhesives, pressure-sensitive adhesives, adhesives and the like.

[0002]

2. Description of the Related Art Heretofore, many examples have been reported in which various sulfonium compounds or oxosulfonium compounds are used as a polymerization initiator of a polymerizable composition. Regarding this, "Applications and Markets of UV / EB Curing Technology", edited by Radtech Research Group, p. 79 (1989, CMC),
Supervised by Kunihiro Ichimura, “Application of new photofunctional polymers”, (19
1988, CMC) and JVCrivello, "Advances
in Polymer Science ", Volume 62, Initiators-Poly-Re
actions-Optical Activity, (1984, Springer-Verla
g) etc.

For example, JP-A-2-196812 discloses a polymerizable composition containing benzylsulfonium, and JP-B-63-2081 discloses a polymerizable composition containing triphenylsulfonium hexafluorophosphate.
Japanese Patent Application Laid-Open No. 59-140203 discloses a polymerizable composition containing a triaryl and diarylsulfonium compound, and European Patent No. 395969 discloses a polymerizable composition containing an oxosulfonium compound.
Japanese Patent Publication No. 483 discloses a polymerizable composition containing various sulfonium compounds and oxosulfonium compounds using tetrabenzoporphyrin as a sensitizer.

In all of the sulfonium compounds and oxosulfonium compounds reported in these publications and patents, the anion part thereof is BF ₄ , PF ₆ , SbF ₆ , S.
It is composed of inorganic anions such as bCl ₆ and ClO ₄ or anions of organic acids such as sulfonic acids such as trifluoromethylsulfate and p-toluenesulfonate, or carboxylic acids.

In both of these sulfonium compounds and oxosulfonium compounds, the carbon-sulfur bond portion of the sulfonium cation is decomposed by giving heat and / or light energy to generate radicals and / or cations. It is believed to polymerize the polymerizable composition.

On the other hand, there is disclosed an example in which a complex having an organic boron anion (borate) is used as a polymerization initiator of a polymerizable composition.

For example, JP-A-2-4804 and JP-A-2-3460 disclose a polymerizable composition containing a metal borate complex, and USP No. 4343891 discloses a polymerizable composition containing an ammonium borate complex. JP-A-6
Japanese Patent Publication No. 2-143044 discloses a polymerizable composition containing a cationic dye-borate complex.

In any of these complexes having an organic boron anion, the carbon-boron bond portion of the borate anion portion is decomposed by applying heat and / or light energy to generate a radical, and this action causes the polymerizable composition to undergo polymerization. It is believed to polymerize things.

Recently, as an example of using an iodonium cation as a counter cation of a complex having an organic boron anion as a polymerization initiator of a polymerizable composition, JP-A-2-16645 has been proposed.
JP-A-2-157760 discloses a polymerizable composition containing a diaryl iodonium tetraaryl borate.
Japanese Patent Laid-Open No. 3-704 and Japanese Patent Laid-Open No. 3-704 disclose a polymerizable composition containing a diaryliodonium alkyltriarylborate.

As an example of using a sulfonium cation as a counter cation of a complex having an organic boron anion as a polymerization initiator of a polymerizable composition, US Pat.
A polymerizable composition containing dithiolium tetraphenylborate described in No. 3 is disclosed in JP-A-2-157760, and a polymerizable composition containing diaryl and triphenylsulfonium butyltriphenylborate is disclosed.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to generate active radicals by applying light and / or heat energy to polymerize a compound having a radical-polymerizable ethylenically unsaturated bond in a short time. And a highly sensitive polymerizable composition and a method for polymerizing the same. Polymerizable composition useful in the fields of photosensitive printing plate materials, direct printing plate materials, photoresists, hologram materials, inks, sealants, adhesives, pressure sensitive adhesives, adhesives, etc., which require high sensitivity And to provide a polymerization method.

In the field of industrial application intended by the present invention, the problems of the polymerizable composition disclosed in the prior art are listed below.

First, Japanese Patent Application Laid-Open No. 2-196812,
JP-A-63-2081, JP-A-59-140203
Publication, European Patent No. 35969 and Japanese Patent Publication
Various sulfoni described in JP-A-3-55483
Polymerization with Ruthenium and Oxosulfonium Compounds
The anionic part of each of the functional compositions is BF_Four , PF
₆ , SbF₆ , SbCl₆ , ClO_Four Inorganic anio such as
Or trifluoromethylsulfuric acid, p-toluenesulfur
Sulfonic acid such as phonate or organic acid such as carboxylic acid
It is composed of anions. But these ani
Since ON does not contribute to radical generation,
Is insufficient.

Polymerization containing complexes having various organic boron anions described in JP-A-2-4804, JP-A-2-3460, USP No. 4343891, and JP-A-62-143044. The sex composition is
In each case, the cation itself does not contribute to the generation of radicals, and the sensitivity is insufficient.

Further, the polymerizable compositions containing complexes having various organic boron anions described in JP-A-2-166451 and US Pat. No. 3,567,453 all have a tetraarylborate anion structure. Anions having such a structure do not efficiently generate radicals, and are insufficient in sensitivity.

Further, the polymerizable compositions containing the diaryliodonium alkyltriarylborate described in JP-A-2-157760 and JP-A-3-704 are thermally unstable and storage stable. The problem is that it is not good.

Further, the polymerizable composition containing diaryl and triphenylsulfonium butyl triphenyl borate described in JP-A-2-157760 has a low reduction potential of these diaryl and triphenyl sulfonium butyl triphenyl borate. Therefore, radicals are not efficiently generated, and sensitivity is insufficient.

Therefore, it has been desired to develop a polymerization initiator and a polymerizable composition capable of solving these problems.

[0019]

The present inventors have accomplished the present invention as a result of earnest studies to solve the above problems in consideration of the various problems. That is, the present invention provides that (A) a compound having a radically polymerizable ethylenically unsaturated bond and (B) a polymerization initiator have a reduction potential of -1.
A polymerizable composition containing a sulfonium complex or an oxosulfonium complex represented by the general formula (1) having a value of 3 eV or more, and an active radical generated by applying light and / or heat energy The method is a method for polymerizing the above-mentioned polymerizable composition, which comprises subjecting the composition to superposition polymerization. General formula (1) (However, R ¹ and R ² are an aryl group which may have a substituent, R ³ is an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent Optionally alicyclic group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted alkoxy group, optionally substituted aryloxy A group selected from a group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, and an amino group which may have a substituent, and R ⁴ represents an oxygen atom or a lone electron pair. ,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, a substituent A group selected from an alkynyl group which may have a group and an alicyclic group which may have a substituent, and R ⁵ , R ⁶ , R ⁷ and R ⁸
Not all of the aryl groups may have a substituent at the same time. )

First, the polymerization initiator represented by the general formula (1) will be described. R ¹ and R ² of the general formula (1)
Is an aryl group which may have a substituent, and examples thereof include a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like. It may be further substituted with another substituent, and as such a substituent, for example,
Halogen group such as fluorine atom, chlorine atom, bromine atom, iodine atom, alkoxy group such as methoxy group, ethoxy group, tert-butoxy group, phenoxy group, aryloxy group such as p-tolyloxy group, methoxycarbonyl group, butoxycarbonyl group Group, acetoxy group, ester group such as benzoyloxy group, acetyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group, acyl group such as phenacyl group, methylthio group, alkylthio group such as tert-butylthio group, phenylthio group, arylthio groups such as p-tolylthio group, alkylamino groups such as methylamino group, cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, piperidino group, phenylamino group, p-tolylamino group, etc. A Ruamino group, a methyl group, an ethyl group, tert- butyl group, an alkyl group such as a dodecyl group,
Phenyl group, p-tolyl group, xylyl group, cumenyl group,
In addition to aryl groups such as naphthyl group, anthryl group and phenanthryl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, tri group Examples thereof include a fluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumyl group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group.

R ^{3 in the} general formula (1) is an alkyl group which may have a substituent, an aryl group which may have a substituent, an alicyclic group which may have a substituent, a substituent An alkenyl group which may have an alkynyl group which may have a substituent,
Alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylthio group which may have a substituent, arylthio group which may have a substituent, and which has a substituent Is a group selected from optionally amino group, specifically, as the alkyl group which may have a substituent, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec-butyl group, te
rt-butyl group, hexyl group, octyl group, decyl group,
Dodecyl group, octadecyl group, allyl group, benzyl group,
Acetonyl group, phenacyl group, salicyl group, anisyl group, cyanomethyl group, chloromethyl group, bromomethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, menthyl group, pinanyl group, etc., an aryl group which may have a substituent Are, for example, phenyl group, p
Examples of the alicyclic group which may have a substituent include a tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group and a phenanthryl group, for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group, a bornyl group, 1 Examples of the alkenyl group which may have a substituent include a cyclohexenyl group and the like, for example, vinyl group, 1-propenyl group, 1
-Butenyl group, 3,3-dicyano-1-propenyl group and the like, the alkynyl group which may have a substituent, for example,
Examples of the alkoxy group which may have a substituent include an ethenyl group, a 1-propynyl group, a 2-tert-butylethenyl group, a 2-phenylethenyl group and the like.
Examples of the aryloxy group which may have a substituent include an ert-butoxy group, a benzyloxy group and the like, for example, a phenoxy group, a p-tolyloxy group, a p-fluorophenoxy group, a p-cyanophenoxy group and the like are substituted. As the alkylthio group which may have a group, for example, a methylthio group,
Examples of the arylthio group such as an ethylthio group and a butylthio group which may have a substituent include, for example, a phenylthio group,
P-tolylthio group, p-cyanophenylthio group and the like, the amino group which may have a substituent is, for example, an amino group, a methylamino group, a dimethylamino group, a cyclohexylamino group, an anilino group, a piperidino group, Morpholino group and the like, the hydrogen atom of these groups may be further substituted with other substituents, such substituents include, for example, fluorine atom, chlorine atom, bromine atom, iodine atom and the like. Halogen group, methoxy group, ethoxy group, ter
Alkoxy group such as t-butoxy group, phenoxy group, p-
Aryloxy group such as tolyloxy group, methoxycarbonyl group, butoxycarbonyl group, acetoxy group, ester group such as benzoyloxy group, acetyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group, acyl group such as phenacyl group, methylthio Base, te
alkylthio groups such as rt-butylthio group, phenylthio groups, arylthio groups such as p-tolylthio group, alkylamino groups such as methylamino group and cyclohexylamino group,
Dimethylamino group, diethylamino group, morpholino group,
Dialkylamino group such as piperidino group, phenylamino group, arylamino group such as p-tolylamino group, methyl group, ethyl group, tert-butyl group, alkyl group such as dodecyl group, phenyl group, p-tolyl group, xylyl group , Cumenyl group, naphthyl group, anthryl group, aryl groups such as phenanthryl group, and the like, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group,
p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group,
Examples thereof include a diphenylsulfoniumyl group, a triphenylphenacylphosphoniumyl group, a phenyliodoniumyl group and the like.

In the general formula (1), R ⁴ is either an oxygen atom or a lone electron pair, and when R 4 is an oxygen atom, it corresponds to the oxosulfonium complex of the present invention, and R ⁴ is a lone electron pair. In this case, it corresponds to the sulfonium complex of the present invention.

Further, in the substituents R ⁵ , R ⁶ , R ⁷ and R ⁸ on the borate anion in the general formula (1), the alkyl group which may have a substituent is, for example, a methyl group or an ethyl group. , Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, te
Examples of the aryl group which may have a substituent include a rt-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an allyl group, and a benzyl group. -Tolyl group, xylyl group, mesityl group, cumenyl group, p-methoxyphenyl group, naphthyl group, 2,4-bis (trifluoromethyl)
Examples of the alkenyl group which may have a substituent include a phenyl group, a p-fluorophenyl group, a p-chlorophenyl group, a p-bromophenyl group and the like, for example, a vinyl group, a 1-propenyl group, a 1-butenyl group and the like. However, examples of the alkynyl group which may have a substituent include an ethenyl group and 2-t.
Examples of the alicyclic group which may have a substituent include an ert-butylethenyl group and a 2-phenylethenyl group, for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group,
Examples thereof include a bornyl group and a 1-cyclohexenyl group, but the present invention is not limited thereto.

Therefore, R ^{1 to} R ⁸ in the general formula (1) are
May have any combination of the groups shown above, but its reduction potential is -1.3 in the electrochemical measurement.
It must be a sulfonium complex or an oxosulfonium complex showing a value of eV or more.

The "reduction potential" in this specification means
The value refers to a saturated calomel electrode (SCE) as a reference electrode.

Whether or not the sulfonium complex or oxosulfonium complex of the present invention shows a reduction potential of -1.3 eV or more in electrochemical measurement is determined by an electrochemical measurement such as polarography or cyclic voltammetry. It can be easily determined by the method.

Further, the reduction potentials of some sulfonium compounds are described in Journal of American Chemical Society (J. Am. Chem. Soc.), Vol. 106, p. 4121 (1984), Journal of American.・ Chemical Society (J. Am. Chem. Soc.), Vol. 111, 1
328 (1989) and JV Crivello, "Advances
in Polymer Science ", Volume 62, Initiators-Poly-Re
actions-Optical Activity, (1984, Springer-Verla
g) and its references.

The polymerization initiator of the present invention has a reduction potential of −
It preferably has a value of 1.2 eV or more, more preferably has a reduction potential of −1.0 eV or more, and most preferably has a reduction potential of −0.8 eV or more. The reason for this will be described in detail below.

First, in order to obtain a highly sensitive polymerizable composition, it is necessary to efficiently polymerize the compound having a radical-polymerizable ethylenically unsaturated bond in the polymerizable composition. It is required that the polymerization initiator in the polymerizable composition be efficiently decomposed by light and / or heat energy to generate radicals.

On the other hand, it is considered that there is a close relationship between the reduction potential when the sulfonium complex is decomposed by electrochemical reduction and the photochemical reduction potential. The Journal of American Chemical Society (J.Am.Ch
em.Soc.), 106, 4121 (1984), Journal of American Chemical Society.
(J. Am. Chem. Soc.), 111, 1328 (1989).
Year) and JV Crivello, "Advances in Polymer Scienc
e ", Volume 62, Initiators-Poly-Reactions-Optical Ac
tivity, (1984, Springer-Verlag) and its references.

Therefore, in order to efficiently decompose the sulfonium complex or oxosulfonium complex, which is a polymerization initiator, to generate a radical, the reduction potential thereof is -1.3e.
It was necessary to set the value to V or more.

To achieve this object, a sulfonium complex or an oxosulfonium complex composed of a combination of an unsubstituted alkyl group and an unsubstituted aryl group cannot be used, and therefore, a radically polymerizable ethylenically unsaturated bond is required. It is difficult to efficiently polymerize the compound.

Actually, in the actual measurement value by cyclic voltammetry, in the case of the triphenylsulfonium compound,
Its reduction potential is -1.44 eV, and that of dimethylphenylsulfonium compounds is -1.66 eV.
4 eV and such a sulfonium cation is
It is unlikely that the electrons will be efficiently received (reduced) and decomposed to generate radicals.

Similarly, sulfonium compounds such as triphenylsulfonium, p-methoxyphenyldiphenylsulfonium and bis (p-chlorophenyl) methylsulfonium described in JP-A-2-157760 have a reduction potential of the present invention. It is not included in the sulfonium complex or the oxosulfonium complex showing a value of −1.3 eV or more.

On the other hand, focusing on the substituents on the boron of the general formula (1), the structure in which all of R ⁵ , R ⁶ , R ⁷ and R ⁸ are aryl groups which may have a substituent at the same time is as follows: Such structures are not preferred because the bonds between these groups and boron do not cleave efficiently and do not generate radicals.

A preferred structure in the general formula (1) is that R ³ is an allyl group which may have a substituent, a benzyl group which may have a substituent or a phenacyl group which may have a substituent. In any of the above, R ⁵ is an alkyl group which may have a substituent, and R ⁶ , R ⁷ and R ⁸ are aryl groups which may have a substituent.

As a more preferred structure, the substituent of R ³ is an allyl group which may have a substituent, a benzyl group which may have a substituent or a phenacyl group which may have a substituent, Atom, chlorine atom, bromine atom and other halogen groups, trofluoromethyl group, cyano group, nitro group, acetyl group, methoxycarbonyl group, benzoyl group, phenoxycarbonyl group and other ester groups, mesyl group, benzenesulfonyl group, p- A structure in which an electron-withdrawing group represented by a sulfonyl group such as a toluenesulfonyl group is

The reason for this is that it is required to enhance the decomposition efficiency of the polymerization initiator represented by the general formula (1) by light and / or heat, and R ³ is an allyl group which may have a substituent, When a benzyl group which may have a substituent or a phenacyl group which may have a substituent is introduced, these groups preferentially and efficiently decompose from a sulfonium or oxosulfonium cation to generate a radical. It can be considered that the sensitivity is improved.

R ³ is an acetonyl group, cyanomethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 3,3-dicyano-1-propenyl group, sulfomethyl group, mesyl group,
p-toluenesulfonylmethyl group, trimethylammoniumylmethyl group, dimethylsulfoniumylmethyl group, p
Preferred examples of the structure include-(diphenylsulfoniumyl) phenyl group, triphenylphenacylphosphoniumylmethyl group and phenyliodoniumylethynyl group.

Therefore, as the polymerization initiator corresponding to the general formula (1) of the present invention, the cation moiety is diphenylbenzylsulfonium, diphenyl (p-chlorobenzyl) sulfonium, diphenyl (p-bromobenzyl) sulfonium, diphenyl (p- Cyanobenzyl) sulfonium, bis (p-tert-butylphenyl) benzylsulfonium, bis (p-methylphenyl) (p-chlorobenzyl) sulfonium, bis (p-methoxyphenyl) (p-bromobenzyl) sulfonium, bis (p −
Chlorophenyl) (p-cyanobenzyl) sulfonium, diphenylphenacylsulfonium, diphenyl (p-chlorophenacyl) sulfonium, diphenyl (p-bromophenacyl) sulfonium, diphenyl (p-methoxyphenacyl) sulfonium, diphenyl (p-cyanophenacyl) sulfonium , Bis (pt
ert-butylphenyl) phenacylsulfonium, bis (p-methoxyphenyl) (p-chlorophenacyl)
Sulfonium, bis (p-chlorophenyl) (p-bromophenacyl) sulfonium, bis (p-methylphenyl) (p-methoxyphenacyl) sulfonium, bis (p-tert-butylphenyl) (p-cyanophenacyl) sulfonium, diphenylallylsulfonium ,
Diphenyl (2-methyl-3,3-dicyano-2-propenyl) sulfonium, diphenyl (2-phenyl-
3,3-dicyano-2-propenyl) sulfonium, diphenyl [2-phenyl-3,3-bis (methoxycarbonyl) -2-propenyl] sulfonium, bis (p-
Chlorophenyl) allylsulfonium, bis (p-te)
rt-Butylphenyl) (2-methyl-3,3-dicyano-2-propenyl) sulfonium, bis (p-methylphenyl) (2-phenyl-3,3-dicyano-2-propenyl) sulfonium, bis (p- Methoxyphenyl) [2-phenyl-3,3-bis (methoxycarbonyl) -2-propenyl] sulfonium, diphenylacetonylsulfonium, diphenylcyanomethylsulfonium, diphenylmethoxycarbonylmethylsulfonium, diphenylethoxycarbonylmethylsulfonium, diphenylbutoxycarbonylmethyl Sulfonium, diphenylsulfomethylsulfonium, diphenylmesylsulfonium, diphenyl-p-toluenesulfonylmethylsulfonium, diphenyl (trimethylammoniumylmethyl) sulfone , Diphenyl (dimethylsulfoniumylmethyl) sulfonium, diphenyl [p- (diphenylsulfoniumyl) phenyl] sulfonium, diphenyl (triphenylphenacylphosphoniumiumylmethyl) sulfonium, diphenyl (phenyliodoniumylethynyl) sulfonium, diphenyl Benzyloxosulfonium, diphenyl (p-chlorobenzyl) oxosulfonium, diphenyl (p-cyanobenzyl) oxosulfonium, bis (p-tert-butylphenyl) benzyloxosulfonium, bis (p
-Methoxyphenyl) (p-bromobenzyl) oxosulfonium, bis (p-chlorophenyl) (p-cyanobenzyl) oxosulfonium, diphenylphenacyloxosulfonium, diphenyl (p-chlorophenacyl) oxosulfonium, diphenyl (p-bromophenacyl) ) Oxosulfonium, diphenyl (p-methoxyphenacyl) oxosulfonium, diphenyl (p-
Cyanophenacyl) oxosulfonium, bis (pt)
ert-butylphenyl) phenacyloxosulfonium, bis (p-methoxyphenyl) (p-chlorophenacyl) oxosulfonium, bis (p-chlorophenyl) (p-bromophenacyl) oxosulfonium, bis (p-methylphenyl) (p -Methoxyphenacyl)
Oxosulfonium, bis (p-tert-butylphenyl) (p-cyanophenacyl) oxosulfonium,
Diphenylallyloxosulfonium, diphenyl (2
-Methyl-3,3-dicyano-2-propenyl) oxosulfonium, diphenyl (2-phenyl-3,3-dicyano-2-propenyl) oxosulfonium, diphenyl [2-phenyl-3,3-bis (methoxycarbonyl) -2-propenyl] oxosulfonium, bis (p
-Chlorophenyl) allyloxosulfonium, bis (p-tert-butylphenyl) (2-methyl-3,
3-dicyano-2-propenyl) oxosulfonium,
Bis (p-methylphenyl) (2-phenyl-3,3-
Dicyano-2-propenyl) oxosulfonium, bis (p-methoxyphenyl) [2-phenyl-3,3-bis (methoxycarbonyl) -2-propenyl] oxosulfonium, diphenylacetonyloxosulfonium, diphenylcyanomethyloxosulfonium, Diphenylmethoxycarbonylmethyloxosulfonium,
Diphenylethoxycarbonylmethyloxosulfonium, diphenylbutoxycarbonylmethyloxosulfonium, diphenylsulfomethyloxosulfonium,
Diphenylmesyloxosulfonium, diphenyl-p
-Toluenesulfonylmethyloxosulfonium, diphenyl (trimethylammoniumylmethyl) oxosulfonium, diphenyl (dimethylsulfoniumylmethyl) oxosulfonium, diphenyl [p- (diphenylsulfoniumyl) phenyl] oxosulfonium, diphenyl (triphenylphenacylphosphonium Sulfonium and oxosulfonium cations such as niumylmethyl) oxosulfonium and diphenyl (phenyliodoniumylethynyl) oxosulfonium, and an anion part of tert-butyltriethylborate, phenyltriethylborate, tert-butyltributylborate, phenyltributylborate, Tributyl benzyl borate, diethyl dibutyl borate, methyl triphenyl borate, ethyl Li tetraphenylborate, propyl triphenyl borate, isopropyl triphenyl borate, butyl triphenyl borate, sec- butyl triphenyl borate, tert- butyl triphenyl borate, neopentyl tilt Li tetraphenylborate, allyl triphenyl borate, benzyl triphenyl borate,
Vinyl triphenyl borate, ethynyl triphenyl borate, butyl trimesityl borate, butyl tri (p
-Methoxyphenyl) borate, butyltri (p-fluorophenyl) borate, butyltri (p-chlorophenyl) borate, butyltri (p-bromophenyl) borate, butyltris [3,5-bis (trifluoromethyl) phenyl] borate, sec- Butyltri (p-
Methoxyphenyl) borate, sec-butyltri (p
-Fluorophenyl) borate, sec-butyltri (p-chlorophenyl) borate, sec-butyltri (p-bromophenyl) borate, sec-butyltris [3,5-bis (trifluoromethyl) phenyl] borate, tert-butyltri (p) -Methoxyphenyl) borate, tert-butyltri (p-fluorophenyl) borate, tert-butyltri (p-chlorophenyl) borate, tert-butyltri (p-bromophenyl) borate, tert-butyltris [3.
Examples thereof include a sulfonium complex and an oxosulfonium complex formed by a combination with a borate anion such as borate anion such as 5-bis (trifluoromethyl) phenyl] borate.

Therefore, specific examples of the sulfonium complex or oxosulfonium complex corresponding to the compound (1) of the present invention include diphenylbenzylsulfonium butyl triphenyl borate, diphenyl (p-chlorobenzyl) sulfonium butyl tris (p-methoxyphenyl). Borate, diphenyl (p-bromobenzyl) sulfonium butyl tris (p-fluorophenyl) borate, diphenyl (p-cyanobenzyl) sulfonium butyl triphenyl borate, bis (p-tert-butylphenyl) benzyl sulfonium butyl tris (p-
Bromophenyl) borate, bis (p-chlorophenyl) (p-cyanobenzyl) sulfoniumbutyltriphenylborate, diphenyl (p-cyanobenzyl) sulfoniumphenyltributylborate, diphenyl (p-cyanobenzyl) sulfoniumdibutyldiphenylborate, diphenyl (p -Cyanobenzyl) sulfonium vinyltriphenylborate, diphenyl (p-
Cyanobenzyl) sulfonium-sec-butyltriphenylborate, diphenyl (p-cyanobenzyl) sulfoniumcyclohexyltriphenylborate, diphenylphenacylsulfoniumbutyltriphenylborate, diphenyl (p-chlorophenacyl) sulfoniumbutyltriphenylborate, diphenyl ( p-Bromophenacyl) sulfonium butyltriphenylborate, diphenyl (p-methoxyphenacyl) sulfoniumbutyltriphenylborate, diphenyl (p-cyanophenacyl) sulfoniumcyclohexyltris (p
-Methoxyphenyl) borate, bis (p-tert-)
Butylphenyl) phenacylsulfonium-sec-butyltris (p-fluorophenyl) borate, bis (p-methoxyphenyl) (p-chlorophenacyl) sulfoniumdibutyldiphenylborate, bis (p-chlorophenyl) (p-bromophenacyl) sulfoniumbenzyl Triphenylborate, bis (p-methylphenyl) (p-methoxyphenacyl) sulfonium-te
rt-butyltriphenylborate, bis (p-ter
t-Butylphenyl) (p-cyanophenacyl) sulfonium benzyltributylborate, diphenylallylsulfoniumbutyltriphenylborate, diphenyl (2-methyl-3,3-dicyano-2-propenyl) sulfonium-2-phenylethynyltriphenylborate, diphenyl (2-phenyl-3,3-dicyano-2
-Propenyl) sulfonium butyl triphenylborate, diphenyl [2-phenyl-3,3-bis (methoxycarbonyl) -2-propenyl] sulfonium-se
c-Butyltriphenylborate, bis (p-chlorophenyl) allylsulfoniumphenyltriethylborate, bis (p-tert-butylphenyl) (2-methyl-3,3-dicyano-2-propenyl) sulfonium di (sec-butyl) Diphenyl borate, bis (p-
Methylphenyl) (2-phenyl-3,3-dicyano-
2-propenyl) sulfonium butyl triphenyl borate, diphenyl acetonyl sulfonium butyl triphenyl borate, diphenyl cyanomethyl sulfonium butyl triphenyl borate, diphenyl methoxycarbonylmethyl sulfonium butyl triphenyl borate, diphenyl sulfomethyl sulfonium methyl tris (p-fluorophenyl) Borate, diphenyl-p-
Toluenesulfonyl methyl sulfonium dicyclohexyl diphenyl borate, diphenyl (trimethylammoniumylmethyl) sulfonium bis (butyl triphenyl borate), diphenyl (triphenylphenacyl phosphonium umilumyl methyl) sulfonium bis (butyl triphenyl borate), diphenyl (phenyliodonium mil) Ethynyl) sulfonium bis (butyltriphenylborate), diphenylbenzyloxosulfoniumbutyltriphenylborate, diphenyl (p-cyanobenzyl) oxosulfoniumbutyltriphenylborate, diphenyl (p-cyanobenzyl) oxosulfonium-sec-butyltriphenylborate , Diphenyl (p-cyanobenzyl) oxosulfonium cyclohexyl tris (p- Luorophenyl) borate, diphenylphenacyloxosulfonium butyltriphenylborate, diphenyl (p-chlorophenacyl) oxosulfonium-sec-butyltris (p-fluorophenyl) borate, bis (p-tert-butylphenyl) phenacyloxosulfonium octyl Tris (p-fluorophenyl) borate, diphenylallyloxosulfonium butyltriphenylborate, diphenyl (2-phenyl-3,3-dicyano-2-propenyl) oxosulfonium-tert-butyltriphenylborate, diphenylmethoxycarbonylmethyloxosulfonium Butyltriphenylborate, diphenyl (trimethylammoniumylmethyl) oxosulfonium bis (butyltriphenylborate) ), Diphenyl (such as triphenyl phenacyl oxo phosphonium Niu mill methyl) oxosulfonium bis (butyl triphenyl borate) and the like, but the invention is not limited to these examples.

Many of these sulfonium complexes or oxosulfonium complexes of the general formula (1) do not usually absorb light in a wavelength longer than the ultraviolet region, and thus have poor activity in the near-ultraviolet to near-infrared light. Substituents R ^{1 to} R excluding R ^4
8 naphthyl group, anthranyl group, phenanthryl group,
By introducing a condensed polycyclic aromatic ring group such as anthryl group and pyrenyl group, and other appropriate substituents, it is possible to give an absorption band even in the visible region and to make it active in the wavelength region longer than the visible region. Is.

Further, by combining with a sensitizer having absorption of ultraviolet to near-infrared light to form a composition, the activity against light from ultraviolet to near-infrared region is enhanced, and the polymerization sensitivity is extremely high. It can be a composition.

Specific examples of such a sensitizer include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, and benzoin derivatives. , Fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, thioxanthene derivative, xanthone derivative, thioxanthone derivative, coumarin derivative,
Polymethine dyes such as ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triaryls Methane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, Annulene derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran Conductor, metal arene complexes, organic ruthenium complexes, and the like, other more specifically, Ogawara Shilla ed, "dye Handbook" (1986, Kodansha), Okawara Shilla ed., "Chemistry of Functional Dyes" (198
1 year, CMC), edited by Tadaburo Ikemori et al., "Special Functional Materials" (1986, CMC), but not limited to these, and from ultraviolet. Examples thereof include dyes and sensitizers that absorb light in the near-infrared region, and two or more of these may be used in any proportion as necessary.

The compound having a radically polymerizable ethylenically unsaturated bond in the polymerizable composition of the present invention may be a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule. Any substance may be used, and it has a chemical form such as a monomer, an oligomer or a polymer. Only one of these may be used, or a system in which two or more kinds are mixed at an arbitrary ratio may be used in order to improve the desired properties.

Examples of such a compound having a radical-polymerizable ethylenically unsaturated bond include acrylic acid,
Unsaturated carboxylic acids such as methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, urethanes, amides and anhydrides, acrylonitrile, styrene and various unsaturated polyesters,
Radical polymerizable compounds such as unsaturated polyethers, unsaturated polyamides and unsaturated polyurethanes are mentioned, but the present invention is not limited thereto.

Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, Neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate , Pentaerythritol triacrylate, pen Erythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, acrylic acid derivatives such as epoxy acrylate, methyl methacrylate, n-butyl methacrylate , 2-ethylhexyl methacrylate, lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene Methacrylic acid derivatives such as lenglycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, allyl glycidyl ether, diallyl phthalate, triallyl triaryl Examples thereof include derivatives of allyl compounds such as melitate, and more specifically, Shinzo Yamashita et al., “Handbook of Crosslinking Agents” (1981, Taiseisha) and Kiyomi Kato,
"UV / EB Curing Handbook (Raw Materials)", (198
5 years, Polymer Society), edited by Radtech, "UV
Application and Market of EB Curing Technology ", p. 79, (1989,
CMC), Kiyoshi Akamatsu, "Practical Technology of New Photosensitive Resins", (1987, CMC), Takeshi Endo, "Refinement of Thermosetting Polymers", (1986, CMC), Commercially available products described in “Polyester Resin Handbook” by Eiichiro Takiyama, (1988, Nikkan Kogyo Shimbun) or radically polymerizable or crosslinkable monomers, oligomers and polymers known in the art can be mentioned.

The sulfonium and oxosulfonium complex represented by the general formula (1) of the present invention is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the compound having an ethylenically unsaturated bond capable of radical polymerization. , And more preferably 0.1 to 10 parts by weight.

The polymerizable composition of the present invention is mixed with a binder such as an organic high-molecular polymer, and a glass plate, an aluminum plate,
It can be used by coating it on other metal plates or polymer films such as polyethylene terephthalate.

Binders usable by mixing with the polymerizable composition of the present invention include polyacrylates and poly-α.
-Polymers and copolymers of alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, polyvinyl esters and the like, and more specifically, polymethacrylates, polymethacrylates Methylmethacrylate, polyethylmethacrylate, polyvinylcarbazole, polyvinylpyrrolidone, polyvinylbutyral,
Polyvinyl acetate, novolac resin, phenol resin, epoxy resin, alkyd resin and others, supervised by Akamatsu Kiyoshi, "Practical technology of new photosensitive resin", (CMC,
1987) and "10188 chemical products", 657-7
Examples include organic high molecular polymers known in the art described on page 67 (Chemical Industry Daily, 1988).

The polymerizable composition of the present invention can be used in combination with another polymerization initiator for the purpose of further improving the sensitivity.

Other polymerization initiators that can be used in combination with the polymerizable composition of the present invention include JP-B-59-1281, JP-B-61-9621 and JP-A-60-.
Triazine derivatives described in JP-A-60104, JP-A-59
-1504 and organic peroxides described in JP-A-61-243807, JP-B-43-23684, JP-B-44-6413 and JP-B-47-160.
4 and diazonium compounds described in USP No. 3567453, organic azide compounds described in USP No. 2848328, USP No. 2852379 and USP No. 2940853, JP-B-36-22062, JP-B-37-13109, and JP-B-37-13109. Kosho 38-18
No. 015 and Japanese Patent Publication No. 45-9610, ortho-quinone diazides, Japanese Patent Publication No. 55-39162.
Publication No. 59-140203 and "Macromolecules", Volume 10, No. 1
Various onium compounds including the iodonium compound described on page 307 (1977), JP-A-59-1422.
Azo compounds described in JP-A-05, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, "Journal of Imaging Science (J.Imag.Sci.)", Volume 30, 174
Page (1986), metal allene complexes, JP-A-61-1
No. 151197, entitled "Coordination Chem Review".
istry Review) ", Vol. 84, pp. 85-277 (1
1988) and a transition metal complex containing a transition metal such as ruthenium described in JP-A-2-182701, an aluminate complex described in JP-A-3-209477,
A borate compound described in JP-A-2-157760,
JP-A-55-127550 and JP-A-60-
2,4,5-triarylimidazole dimer and carbon tetrabromide described in JP-A-202437 and JP-A-59-1073.
The organic halogen compounds described in JP-A-44-44 are listed, and these polymerization initiators are contained in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the compound having a radically polymerizable ethylenically unsaturated bond. Is preferred.

Further, the polymerizable composition of the present invention may contain a thermal polymerization inhibitor for the purpose of preventing polymerization during storage.

Specific examples of the thermal polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. These thermal polymerization inhibitors are compounds 100 having a radically polymerizable ethylenically unsaturated bond.
It is preferably added in the range of 0.001 to 5 parts by weight with respect to parts by weight.

Further, for the purpose of further promoting the polymerization, the polymerizable composition of the present invention may be added with a polymerization accelerator represented by amine, thiol, disulfide and the like, a chain transfer catalyst and the like.

Specific examples of the polymerization accelerator and the chain transfer catalyst that can be added to the polymerizable composition of the present invention include amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, USP. U.S. Pat. No. 4,414,312 and Japanese Patent Application Laid-Open No. 64-13144, disulfides described in Japanese Patent Application Laid-Open No. 2-291156, U.
Examples thereof include thiones described in SP No. 3558322 and JP-A No. 64-17048, O-acyl thiohydroxamates and N-alkoxypyridine thiones described in JP-A No. 2-291560.

The polymerizable composition of the present invention further comprises an oxygen scavenger or reducing agent such as dyes, organic and inorganic pigments, phosphines, phosphonates, phosphites, antifoggants, antifading agents and antihalation agents, depending on the purpose. , Optical brightener,
Surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, ultraviolet absorbers, foaming agents, antifungal agents, antistatic agents,
You may use it, mixing with a magnetic substance and the additive which gives various other characteristics, a diluting solvent, etc.

During the polymerization reaction, the polymerizable composition of the present invention is exposed to ultraviolet rays, visible light, near infrared rays, etc. in a solvent inert to these polymerization initiators and compounds having a radical-polymerizable ethylenically unsaturated bond. Light energy and /
Alternatively, it is possible to obtain a desired polymer by carrying out polymerization by heating or applying heat energy with a thermal head or the like. The definitions of ultraviolet rays, near ultraviolet rays, visible light, near infrared rays, infrared rays, etc. in the present specification are based on "Iwanami Rikagaku Jiten 4th Edition" (1987, Iwanami) edited by Ryogo Kubo et al.

Therefore, the polymerizable composition of the present invention comprises a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, and helium cadmium. Laser, helium neon laser, krypton ion laser, various semiconductor lasers, YA
By applying various light sources such as G laser, light emitting diode, CRT light source, and plasma light source and / or light energy and / or heat energy by heating or a thermal head, the intended polymer or cured product can be obtained.

Therefore, various inks, various printing plate materials, photoresists,
It can be applied to various recording media such as electrophotographic materials, direct printing plate materials, hologram materials and other photosensitive materials and microcapsules, as well as adhesives, pressure-sensitive adhesives, adhesives, sealants and various paints. .

[0061]

The sulfonium and oxosulfonium complex represented by the general formula (1) used in the present invention is excited by application of light and / or heat energy and further decomposed to generate a free radical. result,
It is considered to polymerize the compound having an ethylenically unsaturated bond capable of radical polymerization.

Further, these sulfonium and oxosulfonium complexes represented by the general formula (1) usually do not show absorption in a wavelength longer than the visible region, and therefore have no activity for visible to near infrared light. Poorly, the substituents R ^{1 to} R ^{8 other} than R ⁴ in the general formula (1) are condensed polycyclic aromatic ring groups such as naphthyl group, anthranyl group, phenanthryl group, anthryl group and pyrenyl group, coumarino group and other suitable substitutions. By introducing a group or by combining with the above-mentioned suitable sensitizer, it functions as a polymerizable composition having extremely high sensitivity to light in the near-ultraviolet to near-infrared region.

Although the detailed photoreaction mechanism is not clear, the reaction mechanism is such that, when a sensitizer is used, there is an intermolecular reaction between the sensitizer and the polymerization initiator represented by the general formula (1). When the polymerization initiator represented by the general formula (1) alone is used by electron transfer or intermolecular energy transfer,
The intramolecular electron transfer or intramolecular energy transfer causes cleavage of the binding sites of both the cation part and the anion part of the polymerization initiator represented by the general formula (1), and as a result, a free radical is generated. It is considered to cause the polymerization or crosslinking reaction of the compound having a polymerizable ethylenically unsaturated bond.

Further, by devising a substituent on the sulfonium or oxosulfonium cation, crystallinity, stability, and solubility in various organic solvents can be improved, and further, it is more ethylenic than conventional sulfonium complexes. It gives good results for the improvement of sensitivity to the polymerization of a polymerizable composition containing a compound having a saturated bond.

[0065]

EXAMPLES The present invention is described in detail below with reference to examples, but the present invention is not limited to the following. In the examples, “part” means “part by weight”.

(Examples 1 to 39 and Comparative Examples 1 to 3) 50 parts of pentaerythritol triacrylate as a compound having a radical-polymerizable ethylenically unsaturated bond and diphenylphenacylsulfonium butyl triphenyl of the present invention as a polymerization initiator. 1 part of borate was dissolved in 100 parts of 1,1,1-trichloroethane as a diluting solvent, and this mixture was coated on a glass plate to a thickness of about 5 microns,
This was dried in a hot air oven at 70 ° C. for 2 minutes, and then a polyethylene terephthalate film having a thickness of about 25 μm was further adhered onto the sample to prepare a sample. The sample was held in an oven at 150 ° C. for 10 minutes, whereupon it cured and gave apparently a polymerization product.

Next, instead of diphenylphenacylsulfoniumbutyltriphenylborate, as a polymerization initiator, diphenylphenacyloxosulfoniumbutyltriphenylborate, diphenylbenzylsulfoniumbutyltriphenylborate, diphenylbenzyloxosulfoniumbutyltriphenylborate, diphenyl -P-chlorophenacylsulfonium butyl triphenyl borate, diphenyl-p-chlorobenzyl sulfonium butyl triphenyl borate, diphenyl-p
-Cyanobenzylsulfonium butyl triphenyl borate, bis (tert-butyl phenyl) phenacyl sulfonium butyl triphenyl borate, diphenyl phenacyl sulfonium butyl tris (p-methoxyphenyl) borate, diphenyl phenacyl sulfonium butyl tris (p-fluorophenyl) Borate, diphenylphenacylsulfonium vinyl triphenylborate, diphenylphenacylsulfonium benzyltriphenylborate, diphenylphenacylsulfonium-
tert-Butyltriethylborate, diphenylphenacylsulfoniumphenyltriethylborate, phenyl (9-anthryl) phenacylsulfoniumbutyltriphenylborate, diphenylallylsulfoniumbutyltriphenylborate, diphenylcyanomethylsulfoniumbutyltriphenylborate, diphenylethoxycarbonylmethylsulfonium Butyltriphenylborate, diphenylvinylsulfonium butyltriphenylborate, diphenylphenoxyoxosulfonium butyltriphenylborate, diphenylethylthiosulfonium butyltriphenylborate, diphenyl-N-phenylaminosulfonium butyltriphenylborate, 1-naphthylphenylbenzylmethylsulfonium Buchi Samples containing triphenylborate and diphenyl (2-phenyl-3,3-dicyano-2-propenyl) sulfoniumbutyltriphenylborate were prepared and similar experiments were carried out. In each case, the sample was cured. Clearly, a polymerization product was given, but no polymerization product was observed when these sulfonium or oxosulfonium complexes were not included.

Instead of pentaerythritol triacrylate as a radically polymerizable ethylenically unsaturated compound, butoxyethyl acrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate. , Trimethylolpropane triacrylate, n-
Prepare each sample containing butyl methacrylate, allyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate However, when the same experiment was performed respectively, the samples were cured in each case and apparently gave a polymerization product.

As a comparative example, instead of diphenylphenacylsulfonium butyltriphenylborate, known diphenylphenacylsulfonium tetrafluoroborate, diphenylphenacyloxosulfonium hexafluorophosphate, diphenylbenzylsulfonium tetrafluoroborate were used as polymerization initiators. When each of the samples containing the same was prepared and subjected to the same experiment, no polymerization product was obtained under the same conditions in any case.

(Examples 40 to 78 and Comparative Examples 4 to 6)
50 parts of pentaerythritol triacrylate as a compound having a radical-polymerizable ethylenically unsaturated bond and 1 part of diphenylphenacylsulfonium butyl triphenylborate of the present invention as a polymerization initiator as a diluent solvent 1,1,1-trichloroethane 100 parts Dissolves in
This mixture was coated on a glass plate to a thickness of about 5 μm, dried in a hot air oven at 70 ° C. for 2 minutes, and then a 10% polyvinyl alcohol aqueous solution was applied thereon to a thickness of about 5 μm. Then, the sample was dried again in a hot air oven at 70 ° C. for 2 minutes to prepare a sample.
When this sample was irradiated with a 500 mW high pressure mercury lamp for 30 seconds, it cured and gave apparently a polymerization product.

Next, instead of diphenylphenacylsulfoniumbutyltriphenylborate, as a polymerization initiator, diphenylphenacyloxosulfoniumbutyltriphenylborate, diphenylbenzylsulfoniumbutyltriphenylborate, diphenylbenzyloxosulfoniumbutyltriphenylborate, diphenyl -P-chlorophenacylsulfonium butyl triphenyl borate, diphenyl-p-chlorobenzyl sulfonium butyl triphenyl borate, diphenyl-p
-Cyanobenzylsulfonium butyl triphenyl borate, bis (tert-butyl phenyl) phenacyl sulfonium butyl triphenyl borate, diphenyl phenacyl sulfonium butyl tris (p-methoxyphenyl) borate, diphenyl phenacyl sulfonium butyl tris (p-fluorophenyl) Borate, diphenylphenacylsulfonium vinyl triphenylborate, diphenylphenacylsulfonium benzyltriphenylborate, diphenylphenacylsulfonium-
tert-Butyltriethylborate, diphenylphenacylsulfoniumphenyltriethylborate, phenyl (9-anthryl) phenacylsulfoniumbutyltriphenylborate, diphenylallylsulfoniumbutyltriphenylborate, diphenylcyanomethylsulfoniumbutyltriphenylborate, diphenylethoxycarbonylmethylsulfonium Butyltriphenylborate, diphenylvinylsulfonium butyltriphenylborate, diphenylphenoxyoxosulfonium butyltriphenylborate, diphenylethylthiosulfonium butyltriphenylborate, diphenyl-N-phenylaminosulfonium butyltriphenylborate, 1-naphthylphenylbenzylmethylsulfonium Buchi Samples containing triphenylborate and diphenyl (2-phenyl-3,3-dicyano-2-propenyl) sulfoniumbutyltriphenylborate were prepared and similar experiments were carried out. In each case, the sample was cured. Clearly, a polymerization product was given, but no polymerization product was observed when these sulfonium or oxosulfonium complexes were not included.

Further, butoxyethyl acrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate instead of pentaerythritol triacrylate as the compound having a radical-polymerizable ethylenically unsaturated bond. , Trimethylolpropane triacrylate, n-
Prepare each sample containing butyl methacrylate, allyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate However, when the same experiment was performed respectively, the samples were cured in each case and apparently gave a polymerization product.

As a comparative example, instead of diphenylphenacylsulfonium butyltriphenylborate, known diphenylphenacylsulfonium tetrafluoroborate, diphenylphenacyloxosulfonium hexafluorophosphate, diphenylbenzylsulfonium tetrafluoroborate were used as polymerization initiators. When each of the samples containing the same was prepared and subjected to the same experiment, no polymerization product was obtained under the same conditions in any case.

(Examples 79 to 101 and Comparative Examples 7-1)
4) 360 parts of 1,1,2,2-tetrachloroethane as a diluting solvent, 20 parts of polymethyl methacrylate as a binder, 20 parts of pentaerythritol triacrylate as a compound having a radically polymerizable ethylenically unsaturated bond, and a sensitizer 3,3'-carbonyl-bis (7-diethylamino coumarin (compound (a)) sulfonium or oxosulfonium of the present invention shown in table 1 below as a polymerization initiator to a solution 2g consisting of 1 part iodonium complex 1.2 × 10 ^{- 5} mol was added to make a photosensitizing solution, which was coated on a glass plate with a thickness of about 2 μm by a spin coater, and a 10% polyvinyl alcohol aqueous solution as an oxygen blocking layer was further applied on the glass plate by a spin coater with a thickness of about 5 μm. The beam diameter was 1.5 m on this photosensitive plate.
m Argon ion laser light (488 nm) was exposed for different irradiation times, followed by development treatment with water and toluene to give a curing spot diameter equivalent to the laser beam diameter as exposure energy. It was shown to. As a comparative example, known diphenylphenacylsulfonium tetrafluoroborate as a polymerization initiator, diphenylphenacyloxosulfonium hexafluorophosphate,
The sensitivity when using tetrabutylammonium butyl triphenylborate, copper bis (butyltriphenylborate) and triphenylsulfonium butyltriphenylborate, and diphenyliodonium hexafluorophosphate is also shown in Table 1. As is clear from the results shown in Table 1, when the sulfonium or oxosulfonium complex of the present invention is used as the polymerization initiator, the sensitivity is improved as compared with the case where a known polymerization initiator is used. Recognize.

[0075]

[Table 1]

Compound (a)

[0077]

[Chemical 1]

(Examples 102 and 103 and Comparative Example 1)
5, 16) 360 parts of 1,1,2,2-tetrachloroethane as a diluting solvent, 20 parts of polymethyl methacrylate as a binder, 20 parts of pentaerythritol triacrylate as a compound having a radically polymerizable ethylenically unsaturated bond, the following 2 g of a solution consisting of 1 part of the sensitizer shown in Table 2 was used as a polymerization initiator to diphenylphenacylsulfonium butyl triphenylborate of the present invention 1.
2 × 10 ⁻⁵ mol was added to obtain a photosensitive solution. This photosensitive solution is applied to a glass plate with a thickness of about 2 μm by a spin coater,
Further, a 10% polyvinyl alcohol aqueous solution as an oxygen barrier layer was applied thereon by a spin coater to a thickness of about 5 μm to obtain a photosensitive plate. This photosensitive plate was exposed to an argon ion laser beam (514 nm) or a helium neon laser beam (633 nm) having a beam diameter of 1.5 mm while changing the irradiation time, and then developed with water and toluene to have a laser beam diameter equal to that of the laser beam. The exposure energy that gives the size of the cured spot is shown in Table 2 as the sensitivity. As a comparative example, Table 2 also shows the sensitivity when a known triphenylsulfonium butyl triphenyl borate was used as a polymerization initiator. As is clear from the results in Table 2, when the diphenylphenacylsulfonium butyl triphenyl borate of the present invention is used as the polymerization initiator, the sensitivity is higher than that when the known triphenyl sulfonium butyl triphenyl borate is used. You can see that it is improving.

[0079]

[Table 2]

Compound (b)

[Chemical 2]

Compound (c)

[Chemical 3]

(Examples 104 to 107 and Comparative Example 17)
24) 1,1,2,2-tetrachloroethane (360 parts) as a diluting solvent, polymethyl methacrylate (20 parts) as a binder, trimethylolpropane triacrylate (20 parts) as a compound having a radically polymerizable ethylenically unsaturated bond, and sensitization As a polymerization initiator, 2 g of a solution containing 1 part of the sensitizer shown in Table 3 below was used as a polymerization initiator.
1.2 × 10 ⁻⁵ mol of diphenylphenacylsulfonium butyltriphenylborate of the present invention shown in the table was added to prepare a photosensitive solution. Approximately 2μ of this photosensitizer with a spin coater
A glass plate having a thickness of m was coated with a 10% polyvinyl alcohol aqueous solution as an oxygen barrier layer with a spin coater to a thickness of about 5 μm to obtain a photosensitive plate. This photosensitive plate was exposed to an argon ion laser beam (488 nm or 514 nm) having a beam diameter of 1.5 mm while changing the irradiation time, and then developed with water and toluene to perform a curing spot diameter equal to the laser beam diameter. Table 3 shows the exposure energy for giving the sensitivity. As comparative examples, Table 3 also shows the sensitivity when a known triphenylsulfonium butyl triphenylborate was used as the polymerization initiator and when the polymerization initiator was not included. As is clear from the results in Table 3, when the diphenylphenacylsulfonium butyltriphenylborate of the present invention was used as a polymerization initiator, when a known polymerization initiator was used and when no polymerization initiator was contained, It can be seen that the sensitivity is improved in all cases.

[0083]

[Table 3]

Compound (d)

[Chemical 4]

Compound (e)

[Chemical 5]

Compound (f)

[Chemical 6]

Compound (g)

[Chemical 7]

(Examples 108 to 210 and Comparative Example 2)
5, 26) In order to confirm the storage stability of the polymerizable composition, the present polymerizable composition of Examples 1 to 103, in the dark,
The sample was left in a constant temperature room at 25 ° C for 1 month, but no change was observed in any case. As a comparative example, a similar experiment was conducted using a polymerizable composition containing known diphenyliodonium butyltriphenylborate and bis (p-tert-butylphenyl) iodoniumbutyltriphenylborate instead of the present polymerization initiator. In each of the polymerizable compositions, thickening was observed. From these, it is understood that the storage stability of the polymerizable composition containing the polymerization initiator of the present invention is improved as compared with the case of using the known polymerization initiator.

[0089]

INDUSTRIAL APPLICABILITY The sulfonium and oxosulfonium complexes represented by the general formula (1) of the present invention are effective as a polymerization initiator of a compound having an ethylenically unsaturated bond capable of radical polymerization, and a polymerizable compound containing them. The composition is polymerized in a short time by applying light and / or heat energy,
It is possible to cure.

Therefore, the polymerizable composition of the present invention contains a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, and helium cadmium. Laser, helium neon laser, krypton ion laser, various semiconductor lasers, YA
The target polymer or cured product can be obtained by applying various light sources such as G laser, light emitting diode, CRT light source, and plasma light source, and light energy, or by applying heat energy such as heating or a thermal head.

Therefore, a photosensitive printing plate material requiring high sensitivity,
It is extremely useful for direct printing plate materials, photoresists, hologram materials, various recording media using microcapsules, and fields such as inks, sealants, adhesives, pressure-sensitive adhesives and adhesives.

Claims (4)

[Claims] 1. A compound having a radical-polymerizable ethylenically unsaturated bond (A) and a general formula (B) in which the polymerization initiator has a reduction potential of -1.3 eV or more in an electrochemical measurement. A sulfonium complex or an oxosulfonium complex represented by 1),
A polymerizable composition and a polymerization method comprising: General formula (1) (However, R ¹ and R ² are an aryl group which may have a substituent, R ³ is an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent Optionally alicyclic group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted alkoxy group, optionally substituted aryloxy Group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an amino group which may have a substituent, and R ⁴ represents an oxygen atom or a lone electron pair. ,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, a substituent A group selected from an alkynyl group which may have a group and an alicyclic group which may have a substituent, and R ⁵ , R ⁶ , R ⁷ and R ⁸
Not all of the aryl groups may have a substituent at the same time. ) 2. The polymerizable composition according to claim 1, which comprises (C) a sensitizer that absorbs arbitrary light in the ultraviolet to near-infrared region. 3. In the general formula (1), R ³ is any of an allyl group which may have a substituent, a benzyl group which may have a substituent or a phenacyl group which may have a substituent. Wherein R ⁵ is an optionally substituted alkyl group and R ⁶ , R ⁷ and R ⁸ are optionally substituted aryl groups. 2. The polymerizable composition according to any one of 2 above. 4. A polymerization method characterized in that the polymerizable composition according to any one of claims 1 to 3 is produced by generating active radicals by applying light and / or heat energy.