JP2884902B2 - Polymerizable composition and polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerizable composition and a polymerization method. More specifically, a compound having a radically polymerizable ethylenically unsaturated bond is polymerized in a short time by light and / or heat, and is, for example, an ink, a photosensitive printing plate, a photoresist, a direct plate material, a hologram material, a sealing material. The present invention relates to a polymerizable composition and a polymerization method for obtaining a cured product having good physical properties in the fields of a stopper, an adhesive, and the like.

[0002]

2. Description of the Related Art There have been reported many examples in which various sulfonium and oxosulfonium compounds are used as initiators for cationic polymerization. For example, see, for example, "Application of UV / EB curing technology and Market, ”p. 79 (1989, CMC) and JV
CRIVELLO, "ADVANCES IN POLYMER SCIENCE", No. 62
Volume, INITIATORS-POLY-REACTIONS-OPTICAL ACTIVITY, (1
984, SPRINGER-VERLAG) etc.

On the other hand, in recent years, examples have been reported in which these sulfonium and oxosulfonium compounds are used as an initiator for radical polymerization.
No. 81 discloses triphenylsulfonium hexafluorophosphate, JP-A-59-140203 discloses triaryl and diarylsulfonium compounds, and JP-A-63-243102 discloses various sulfonium and oxosulfonium compounds.

The sulfonium and oxosulfonium compounds reported in these literatures and patents are thought to decompose the carbon-sulfur bond of the sulfonium cation by the action of heat or light to generate radicals.
In any case, the anion part is BF ₄ , PF ₆ , SbF
_6, SbCl _6, ClO _4, etc. of inorganic anion or trifluoromethyl sulfate and an anion of an organic acid such as sulfonic or carboxylic acids, such as p- toluenesulfonate.

[0005] However, examples of using a sulfonium compound having an anion portion comprising an organic boron anion (borate) as a polymerization initiator include dithiolium tetraphenyl borate described in US Pat. No. 3,567,453 and triphenyl described in JP-A-2-157760. Only about sulfonium triphenyl (n-butyl) borate is known.

On the other hand, examples of using a complex having an organoboron anion as an initiator for radical polymerization include metal borate complexes described in JP-A-2-4804 and JP-A-2-3460, and US Pat. No. 4,434,891. Ammonium borate complex is disclosed in JP-A-62-14304.
JP-A-2-157760, JP-A-2-166451 and JP-A-3-704 disclose diaryliodonium borates, etc., as the cationic dye-borate anion complex described in No. 4 It is considered that the carbon-boron bonding portion of the borate anion is decomposed by the action of heat or light to generate a radical.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to propose a highly sensitive radical polymerizable polymerizable composition which can be polymerized in a short time by light and / or heat, and a polymerization method thereof. It is an object of the present invention to provide a cured material having good physical properties, for example, a recording medium such as an ink, a sealant, or a photosensitive printing plate, a photoresist, a direct printing plate material, or a hologram material requiring high sensitivity. Further, a compound having a radically polymerizable ethylenically unsaturated bond is polymerized under certain conditions, and practical oligomers and polymers such as adhesives are industrially provided, and the polymerizable composition and the polymerization method are provided. To provide.

[0008] The problems of the polymerizable composition disclosed in the prior art in the industrial application field aimed at by the present invention are listed below.

First, triaryl and diaryl sulfonium compounds described in JP-B-63-2081 and JP-A-59-140203, and JP-A-63-24310.
The use of various sulfonium and oxosulfonium compounds of No. 2 as initiators for radical polymerization has been studied, but all of these have an anion moiety of BF
₄ , PF ₆ , SbF ₆ , SbCl ₆ , ClO _{4 and} other inorganic anions or trifluoromethyl sulfate, p-toluenesulfonate and other sulfonic acids or carboxylic acids and other organic acid anions, these anion portions It does not contribute to radical generation and is insufficient in sensitivity.

[0010] Japanese Patent Application Laid-Open No. Sho 62-143044 discloses that
Cationic dye-borate anion complexes are disclosed, but all of these have absorption in the visible light region, and therefore they are decomposed under a normal fluorescent lamp or the like, and the cationic dye-borate anion complex is decomposed. It is necessary to operate in the dark consistently from the synthesis of ionic complex, cationic dye-
Since the light absorption wavelength range of the borate anion complex depends on its cationic dye moiety, it is necessary to synthesize a complex having sensitivity to the desired light absorption wavelength range, and the absorbance for the light to be exposed. When the content of the cationic dye-borate anion complex in the polymerizable composition is increased in order to increase the content, the borate moiety that generates radicals is also contained accordingly, and the degree of polymerization of the polymerizable substance is reduced. There are various problems such as a cause of lowering the sensitivity and insufficient sensitivity.

Also, metal borate complexes described in JP-A-2-4804 and JP-A-2-3460, US Pat.
All of the ammonium borate complexes described in 43891 are insufficient in sensitivity.

Further, diaryliodonium borate described in JP-A-2-157760, JP-A-2-166451 and JP-A-3-704 is thermally unstable, and triphenylene described in JP-A-2-157760 is disclosed.
Rusulfonium borate or diarylsulfonium borate is problematic in that it has a low reduction potential, does not efficiently generate radicals, and is insufficient in sensitivity.

Therefore, development of a polymerization initiator and a polymerizable composition which can solve these problems has been desired.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems in consideration of the above problems, and as a result, have reached the present invention. That is, the present invention relates to a compound having a radically polymerizable ethylenically unsaturated bond capable of being polymerized in a short time by light and / or thermal energy, and a sulfonium and an oxosulfonium represented by the following general formula (1) as a polymerization initiator. A polymerizable composition comprising a complex is provided. General formula (1)

Embedded image (However, at least one of R ¹ , R ² and R ³ is any of an allyl group optionally having a substituent, a benzyl group optionally having a substituent or a phenacyl group optionally having a substituent. And the others are each independently an alkyl group optionally having a substituent, an aryl group optionally having a substituent, an alkenyl group optionally having a substituent, A good alkynyl group, an alicyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, A group selected from an arylthio group which may have a substituent and an amino group which may have a substituent, R ⁴ is an oxygen atom or a lone electron pair, and R ⁵ is an alkyl which may have a substituent A group wherein R ⁶ , R ⁷ and R ⁸ are each independently
The following shows an aryl group which may have a substituent. ). Further, the present invention provides a polymerizable composition comprising the above polymerizable composition and a sensitizer that absorbs arbitrary light in the ultraviolet to near infrared region. Further, the present invention provides a method for polymerizing a polymerizable composition, characterized in that active radicals are generated by applying light and / or thermal energy to each of the two polymerizable compositions to cause polymerization.

First, the polymerization initiator represented by the general formula (1) will be described. In the substituents R ¹ , R ² and R ³ on the sulfonium or oxosulfonium cation in the general formula (1), the alkyl group which may have a substituent includes a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, isobutyl group, sec
-Butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, allyl, benzyl, acetonyl, phenacyl, salicyl, anisyl, cyanomethyl, chloromethyl Group, bromomethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, menthyl group, pinanyl group, etc., as the aryl group which may have a substituent, phenyl group, p-tolyl group, xylyl group, mesityl group, Cumenyl group, p-methoxyphenyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group,
p-cyanophenyl, 2,4-bis (trifluoromethyl) phenyl, p-fluorophenyl, p-chlorophenyl, p-dimethylaminophenyl, p-phenylthiophenyl, etc. have a substituent. Examples of the alkenyl group which may be a vinyl group, a 1-propenyl group,
Butenyl group, 3,3-dicyano-1-propenyl group and the like, as the alicyclic group which may have a substituent, cyclopentyl group, cyclohexyl group, norbornyl group, bornyl group, 1-cyclohexenyl group and the like, Examples of the optionally substituted alkoxyl group include a methoxy group, a tert-butoxy group, and a benzyloxy group. Examples of the optionally substituted aryloxy group include a phenoxy group, a p-tolyloxy group, and a p-tolyloxy group. Examples of the alkylthio group which may have a substituent such as a fluorophenoxy group and a p-nitrophenoxy group include methylthio group, ethylthio group and butylthio group, and examples of the arylthio group which may have a substituent include phenylthio group. Group, p-tolylthio group, p-cyanophenylthio group, etc., as an amino group which may have a substituent,
Examples include an amino group, a methylamino group, a dimethylamino group, a cyclohexylamino group, an anilino group, a piperidino group, a morpholino group, and the like. Further, R ¹ , R ² and R ³ represent a cyclic structure in which the two groups are bonded. For example, a tetramethylene group, a pentamethylene group, 1,4-
Examples include an alkylene group which may have a substituent such as a dichlorotetramethylene group, an ethylenedioxy group, a diethylenedioxy group, an adipoyl group, an ethylenedithio group, and the like, but the present invention is not limited thereto.

Further, in the substituents R ⁵ , R ⁶ , R ⁷ and R ⁸ on the borate anion in the general formula (1),
Examples of the alkyl group which may have a substituent include a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group,
Pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, allyl group, benzyl group, etc.
Examples of the aryl group which may have a substituent include a phenyl group, a p-tolyl group, a xylyl group, a mesityl group, a cumenyl group, a p-methoxyphenyl group, a naphthyl group, and 2,4-bis (trifluoromethyl) phenyl Group, p-fluorophenyl group, p-chlorophenyl group, p-bromophenyl group and the like.

In the formula (1), a particularly preferred structure is that at least one of R ¹ , R ² and R ³ is an allyl group which may have a substituent, or a benzyl group which may have a substituent. Or a phenacyl group which may have a substituent, R ⁵ is an alkyl group which may have a substituent, and R ⁶ , R ⁷ and R ⁸ may have a substituent The structure is an aryl group.

For this reason, it is required to increase the efficiency of decomposition of the polymerization initiator represented by the general formula (1) by light and / or heat, and at least one of R ¹ , R ² and R ³ is required. By introducing 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, these groups are converted from a sulfonium or oxosulfonium cation. It is considered that decomposition occurs preferentially and efficiently to generate radicals, and improvement in sensitivity is recognized.

This can be predicted by measuring the reduction potential of the polymerization initiator by a method such as polarography or cyclic voltammetry. A polymerization initiator having a higher reduction potential is more likely to receive electrons, and thus is more efficient. It is thought to decompose to generate radicals.

The reduction potential of some sulfonium compounds is determined by the Journal of American Chemical Society (J.AM.CHEM.SOC.), Vol. 106, p. 4121 (1984), Journal of American Chemical Society.・ Chemical Society (J.AM.CHEM.SOC.), Volume 111, 1
328 pages (1989) and JVCRIVELLO, "ADVANCES
IN POLYMER SCIENCE, Vol. 62, INITIATORS-POLY-REA
CTIONS-OPTICAL ACTIVITY, (1984, SPRINGER-VERLAG)
And its cited references.

For example, as measured by cyclic voltammetry, the reduction potential of the methylphenylphenacylsulfonium cation is -0.73 eV, and the reduction potential of the methylphenyl p-cyanobenzylsulfonium cation is -0.95 eV. On the other hand, the reduction potential of the triphenylsulfonium cation is -1.44 eV.
And the reduction potential as compared with the above-mentioned sulfonium cation, the sensitivity in preparing a polymerizable composition is low, and thus the reduction potential of the sulfonium cation is reduced.
Such combinations of substituents R ¹ , R ² and R ³ are preferred.
Not good.

In the general formula (1), the substituent R ⁵ on the borate anion is an alkyl group which may have a substituent, and R ⁶ , R ⁷ and R ⁸ may have a substituent. When the structure is an aryl group, the substituent R ⁵ on the borate anion, that is, the alkyl group which may have a substituent is considered to be cleaved preferentially and efficiently, and an improvement in sensitivity is observed.

When all of R ⁵ , R ⁶ , R ⁷ and R ⁸ are simultaneously an aryl group which may have a substituent, the borate anion is not efficiently cleaved, and such a structure is not preferred.

Therefore, as a preferable structure in the general formula (1), at least one of R ¹ , R ² and R ³ is an allyl group, a 2-cyano-1-propenyl group,
3,3-dicyano-2-phenyl-1-propenyl group,
Benzyl group, p-fluorobenzyl group, p-chlorobenzyl group, p-bromobenzyl group, p-cyanobenzyl group, p-nitrobenzyl group, p-methoxybenzyl group,
p-tert-butylbenzyl group, p-dimethylaminobenzyl group, m-cyanobenzyl group, 2,4-dicyanobenzyl group, 2,4,6-trimethylbenzyl group, phenacyl group, p-fluorophenacyl group, p -Chlorophenacyl group, p-bromophenacyl group, p-cyanophenacyl group, p-nitrophenacyl group, m-methoxyphenacyl group, 2,4-dicyanophenacyl group, and R ⁵ is a methyl group, an ethyl group, Propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-
Butyl group, pentyl group, neopentyl group, hexyl group,
An octyl group, a decyl group, a dodecyl group, an allyl group, a benzyl group, etc., wherein R ⁶ , R ⁷ and R ⁸ are phenyl, p-tolyl, xylyl, mesityl, p-methoxyphenyl, p-methoxyphenyl, -Fluorophenyl group, p-chlorophenyl group, p-bromophenyl group, and 3,5-bis (trifluoromethyl) phenyl group.

Therefore, as the polymerization initiator corresponding to the general formula (1) of the present invention, the cation moiety is dimethylbenzylsulfonium, di-tert-butylbenzylsulfonium, didodecylbenzylsulfonium, dimethyl (p
-Chlorobenzyl) sulfonium, dibutyl (p-bromobenzyl) sulfonium, dimethyl (p-cyanobenzyl) sulfonium, dimethylphenacylsulfonium, di-tert-butylphenacylsulfonium, dimethyl (p-chlorophenacyl) sulfonium, dimethyl ( p-bromophenacyl) sulfonium, dimethyl (p-methoxyphenacyl) sulfonium, dimethyl (p-cyanophenacyl) sulfonium, dimethyl (2
-Phenyl-3,3-dicyanoprop-2-enyl) sulfonium, methylphenylbenzylsulfonium, methylphenyl (p-cyanobenzyl) sulfonium, methylphenylphenacylsulfonium, methylphenyl (2-phenyl-3,3-dicyanoprop-2) -Enyl) sulfonium, tetramethylenephenacylsulfonium, tribenzylsulfonium, dimethylallylsulfonium, dibutylallylsulfonium, diallylphenacylsulfonium, dimethylbenzyloxosulfonium, dimethylphenacyloxosulfonium, methylphenylbenzyloxosulfonium, methylphenylphenacyloxo Each sulfonium and oxosulfonium cation such as sulfonium and the anion part are methyltriphenyl vole , Ethyl triphenyl borate,
Propyl triphenyl borate, isopropyl triphenyl borate, butyl triphenyl borate, sec-
Butyl triphenyl borate, tert-butyl triphenyl borate, neopentyl triphenyl borate,
Butyl tri (p-methoxyphenyl) borate, butyl tri (p-fluorophenyl) borate, butyl tri (p-chlorophenyl) borate, butyl tri (p-bromophenyl) borate, butyl tris [3,5-bis (trifluoromethyl) phenyl] borate , Sec-
Butyl tri (p-methoxyphenyl) borate, sec
-Butyl tri (p-fluorophenyl) borate, se
c-butyl tri (p-chlorophenyl) borate, se
c-butyl tri (p-bromophenyl) borate, se
c-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 [3,5-bis (trifluoromethyl ) Phenyl] borate and the like, and sulfonium complexes and oxosulfonium complexes composed of a combination with borate anions such as each borate anion.

Accordingly, specific examples of the sulfonium complex or oxosulfonium complex corresponding to the compound (1) of the present invention include dimethyl (p-chlorobenzyl) sulfonium methyltriphenylborate and dibutyl (p-
Bromobenzyl) sulfonium isopropyltriphenylborate, dimethyl (p-cyanobenzyl) sulfoniumbutyltriphenylborate, dimethylphenacylsulfoniumbutyltriphenylborate, dimethylphenacylsulfonium-sec-butyltriphenylborate, di-tert-butylphenacyl Sulfonium-sec-butyltriphenylborate, dimethyl (p
-Chlorophenacyl) sulfonium-tert-butyltriphenylborate, dimethyl (2-phenyl-3,
3-dicyanoprop-2-enyl) sulfoniumbutyltri (p-methoxyphenyl) borate, methylphenyl (p-cyanobenzyl) sulfonium-sec-butyltri (p-fluorophenyl) borate, methylphenyl (2-phenyl-3,3 -Dicyanoprop-2-enyl) sulfonium-tert-butyltri (p-bromophenyl) borate, tetramethylenephenacylsulfonium-sec-butyltriphenylborate, dimethylallylsulfoniumbutyltriphenylborate,
Tetramethylene-p-cyanobenzylsulfonium-s
ec-butyltri-p-fluorophenylborate, dimethylbenzyloxosulfoniumbutyltriphenylborate, dimethylphenacyloxosulfonium-s
ec-butyltri (p-chlorophenyl) borate, methylphenylbenzyloxosulfonium-tert-
Examples thereof include butyl tri (p-methoxyphenyl) borate and methylphenylphenacyloxosulfonium-tert-butyl tri (p-fluorophenyl) borate, but the present invention is not limited to these examples.

Most of these sulfonium complexes or oxosulfonium complexes of the general formula (1) generally show no absorption at wavelengths longer than the ultraviolet region and thus have poor activity from near ultraviolet to near infrared light. Substituents R ^{1 to} R except 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 suitable substituents, it is possible to have an absorption band up to the visible region and to have activity even in the wavelength region longer than visible. It is.

Further, by forming a composition in combination with a sensitizer having absorption for ultraviolet to near-infrared light, the activity with respect to light in the ultraviolet to near-infrared region is enhanced, and a very sensitive polymerizable compound is obtained. It can be a composition.

Specific examples of such sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, and benzoin derivatives. , Fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives,
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, triaryl Methane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetrafilin derivative, Anulene 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
One year, CMC), edited by Tadasaburo Ikemori et al., "Specially Functional Materials" (1986, CMC), but are not limited thereto. Dyes and sensitizers that absorb light in the near-infrared region may be mentioned. If necessary, two or more of these may be used in any ratio.

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

Examples of such radically polymerizable compounds having an ethylenically unsaturated bond include acrylic acid,
Methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, unsaturated carboxylic acids such as maleic acid and their salts, esters, urethanes, amides and anhydrides, acrylonitrile, styrene, and various other unsaturated polyesters,
Examples include radically polymerizable compounds such as unsaturated polyethers, unsaturated polyamides, and unsaturated polyurethanes, but the present invention is not limited to these.

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 Pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 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, polypro Methacrylic acid derivatives such as lenglycol dimethacrylate, trimethylolethanetrimethacrylate, trimethylolpropanetrimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, etc., allyl glycidyl ether, diallyl phthalate, triallyl tri Derivatives of allyl compounds such as melitate, etc., and more specifically, edited by Shinzo Yamashita et al., "Crosslinking Agent Handbook", (1981, Taiseisha), edited by Kato Kiyomi,
"UV / EB Curing Handbook (Raw Materials)", (198
5th year, Polymer Publishing Association), edited by Radtech Research Group, “UV ・
Application and Market of EB Curing Technology ", p. 79, (1989,
(CMC), edited by Kiyoshi Akamatsu, "Practical technology of new photosensitive resin", (1987, CMC), edited by Tsuyoshi Endo, "Precision of thermosetting polymer", (1986, CMC), Commercially available products described in Eiichiro Takiyama, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun) or radically polymerizable or crosslinkable monomers, oligomers, and polymers known in the industry.

The sulfonium and oxosulfonium complex represented by the general formula (1) of the present invention is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the radically polymerizable compound having an ethylenically unsaturated bond. 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 weight polymer, and is mixed with a glass plate or an aluminum plate.
It can be used by coating it on other metal plates or polymer films such as polyethylene terephthalate.

The binder usable as a mixture with the polymerizable composition of the present invention includes polyacrylates and poly-α.
-Alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, polymers such as polyvinyl esters, copolymers, and more specifically, polymethacrylate, polymethacrylate Methyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral,
Polyvinyl acetate, novolak resin, phenolic resin, epoxy resin, alkyd resin, etc., supervised by Kiyoshi Akamatsu, "Practical technology of new photosensitive resin", (CMC,
1987) and "10188 Chemical Products", 657-7
An organic polymer known in the art described on page 67 (Kagaku Kogyo Nippo, 1988) can be used.

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 which can be used in combination by mixing with the polymerizable composition of the present invention include JP-B-59-1281,
JP-B-61-9621 and JP-A-60-6010
4, the organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413.
No., JP-B-47-1604 and USP No. 3567.
No. 453, USP 2848
No. 328, US Pat. No. 2,852,379 and US Pat. No. 2,908,583;
-22062, JP-B-37-13109, JP-B-3
Ortho-quinonediazides described in JP-B-8-18015 and JP-B-45-9610, JP-B-55-39162.
And various onium compounds including iodonium compounds described in JP-A-59-142205, and "MACROMOLECULES", Vol. 10, p. 1307 (1977). Azo compounds described in JP-A-1-54440, EP 109851, EP 126712.
Issue, “Journal of Imaging Science
(J.IMAG.SCI.), Vol. 30, p. 174 (1986)
Metal allene complexes described, titanocenes described in JP-A-61-151197, "COORDINATION CHEMISTRY REVIEW", Vol. 84, pp. 85-277 (1988), and JP-A-2- Transition metal complexes containing a transition metal such as ruthenium described in 182701, aluminate complexes described in JP-A-3-209777, borate compounds described in JP-A-2-157760, JP-A-55-127550 and JP-A-55-127550. 2,4,5-triarylimidazole dimer, carbon tetrabromide described in JP-A-60-202037;
And organic polymerization compounds described in JP-A-107344. These polymerization initiators are used in an amount of 0.1 to 100 parts by weight of a radically polymerizable compound having an ethylenically unsaturated bond.
It is preferably contained in the range of 01 to 10 parts by weight.

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 radically polymerizable ethylenically unsaturated bonds.
It is preferably added in the range of 0.001 to 5 parts by weight based on parts by weight.

The polymerizable composition of the present invention may further contain a polymerization accelerator represented by an amine, a thiol, a disulfide, or the like, a chain transfer catalyst, or the like for the purpose of further promoting the polymerization.

Specific examples of polymerization accelerators and chain transfer catalysts that can be added to the polymerizable composition of the present invention include, for example, amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, USP Thiols described in JP-A-4414312 and JP-A-64-13144, disulfides described in JP-A-2-291561, U.S. Pat.
And thiones described in Japanese Patent Application Laid-Open No. 2-170560 and O-acylthiohydroxamate and N-alkoxypyridinethiones described in JP-A-2-291560.

The polymerizable composition of the present invention may further comprise, depending on the purpose, dyes, organic and inorganic pigments, oxygen scavengers such as phosphines, phosphonates, phosphites and the like, reducing agents, antifoggants, fading inhibitors, antihalation agents. , Optical brightener,
Surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, ultraviolet absorbers, foaming agents, antifungal agents, antistatic agents,
It may be used by mixing with a magnetic substance, other additives imparting various properties, a diluting solvent, and the like.

In the polymerization reaction, the polymerizable composition of the present invention may be used in a solvent inert to these polymerization initiators and a compound having a radically polymerizable ethylenically unsaturated bond, such as ultraviolet light, visible light or near infrared light. Light energy and / or
Alternatively, the polymer can be polymerized by applying heat energy by heating or a thermal head or the like to obtain a desired polymer. The definition of ultraviolet light, near ultraviolet light, visible light, near infrared light, infrared light, and the like in this specification is based on Iwanami Physical and Chemical Dictionary, 4th Edition, edited by Ryogo Kubo et al. (Iwanami, 1987).

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

Therefore, various inks, various printing plate materials, photoresist,
It can be applied to various recording media such as photosensitive materials such as electrophotography, direct printing plate materials, hologram materials and microcapsules, as well as adhesives, adhesives, adhesives, sealants and various paints. .

[0046]

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

The sulfonium and oxosulfonium complexes represented by the general formula (1) usually do not absorb at wavelengths longer than the visible region, and therefore have an activity with respect to visible to near-infrared light. Although it is scarce, condensed polycyclic aromatic ring groups such as naphthyl group, anthranyl group, phenanthryl group, anthryl group, pyrenyl group and other suitable substituents are substituted for the substituents R ^{1 to} R ⁸ except R ⁴ in the general formula (1). When introduced or combined with an appropriate sensitizer described above, 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, an intermolecular reaction between the sensitizer and the polymerization initiator represented by the general formula (1) is performed. When the polymerization initiator represented by the general formula (1) is used alone by electron transfer or intermolecular energy transfer,
Due to intramolecular electron transfer or intramolecular energy transfer, cleavage of both binding sites of the cation portion and the anion portion of the polymerization initiator represented by the general formula (1) occurs, and as a result, free radicals are generated. It is thought to cause a polymerization or crosslinking reaction of the compound having a polymerizable ethylenically unsaturated bond.

By devising a substituent on the sulfonium or oxosulfonium cation, improved crystallinity, stability and solubility in various organic solvents can be obtained. Good results can be obtained with respect to improvement in sensitivity to polymerization of a polymerizable composition containing a compound having a saturated bond.

[0050]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited only to the following examples. In the examples, “parts” indicates “parts by weight”.

(Examples 1 to 29 and Comparative Examples 1 to 3) 50 parts of pentaerythritol triacrylate as a compound having a radically polymerizable ethylenically unsaturated bond and 1 part of dimethylphenacylsulfonium butyl triphenyl borate as a polymerization initiator Was dissolved in 100 parts of dioxane as a diluting solvent.
The sample was applied to a thickness of micron and 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 thereon to prepare a sample. When the sample was held in an oven at 150 ° C. for 10 minutes, the sample cured and clearly gave a polymerized product.

Next, instead of dimethylphenacylsulfonium butyltriphenylborate, dimethylphenacyloxosulfoniumbutyltriphenylborate, dimethylbenzylsulfoniumbutyltriphenylborate, dimethylbenzyloxosulfoniumbutyltriphenylborate, dimethylbenzyloxosulfoniumbutyltriphenylborate are used as polymerization initiators. -P-
Chlorophenacylsulfonium butyl triphenyl borate, dimethyl-p-chlorobenzylsulfonium butyl triphenyl borate, dimethyl-p-cyanobenzylsulfonium butyl triphenyl borate, di-te
rt-butylphenacylsulfoniumbutyltriphenylborate, dimethylphenacylsulfoniumbutyltri (methoxyphenyl) borate, dimethylphenacylsulfoniumbutyltri (p-fluorophenyl) borate, dimethylphenacylsulfoniumbenzyltriphenylborate, tetramethylenephenacyl Includes sulfonium butyl triphenyl borate, dimethyl allyl sulfonium butyl triphenyl borate, p-acetoxy phenyl benzyl methyl sulfonium butyl triphenyl borate, phenylmethyl (2-phenyl-3,3-dicyanoprop-2-enyl) sulfonium butyl triphenyl borate Each sample was prepared and subjected to similar experiments.In each case, the sample cured and apparently polymerized It gave Narubutsu but the polymerization product in the case that does not contain these sulfonium or oxosulfonium complex was observed.

In addition to pentaerythritol triacrylate as a radical polymerizable compound having an ethylenically unsaturated bond, 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 similar experiments were respectively performed, in each case, the sample was cured and clearly gave a polymerization product.

As a comparative example, each of the polymerization initiators containing dimethylphenacylsulfonium tetrafluoroborate, dimethylphenacyloxosulfonium hexafluorophosphate and dimethylbenzylsulfonium tetrafluoroborate as polymerization initiators instead of dimethylphenacylsulfoniumbutyltriphenylborate was used. Samples were prepared and subjected to similar experiments. In each case, no polymerization product was obtained under the same conditions.

(Examples 30 to 58 and Comparative Examples 4 to 6) 50 parts of pentaerythritol triacrylate as a compound having a radically polymerizable ethylenically unsaturated bond and 1 part of dimethylphenacylsulfonium butyl triphenylborate as a polymerization initiator Was dissolved in 100 parts of dioxane as a diluting solvent.
After drying in a hot air oven at 70 ° C. for 2 minutes, a 10% aqueous solution of polyvinyl alcohol was applied thereon to a thickness of about 5 μm, and this was again heated with hot air at 70 ° C. A sample was prepared which was dried in an oven for 2 minutes. When this sample was irradiated with a 500 mW high pressure mercury lamp for 30 seconds, it hardened and clearly gave a polymerization product.

Next, instead of dimethylphenacylsulfoniumbutyltriphenylborate, polymerization initiators such as dimethylphenacyloxosulfoniumbutyltriphenylborate, dimethylbenzylsulfoniumbutyltriphenylborate, dimethylbenzyloxosulfoniumbutyltriphenylborate, dimethylbenzyl -P-
Chlorophenacylsulfonium butyl triphenyl borate, dimethyl-p-chlorobenzylsulfonium butyl triphenyl borate, dimethyl-p-cyanobenzylsulfonium butyl triphenyl borate, di-te
rt-butylphenacylsulfoniumbutyltriphenylborate, dimethylphenacylsulfoniumbutyltri (methoxyphenyl) borate, dimethylphenacylsulfoniumbutyltri (p-fluorophenyl) borate, dimethylphenacylsulfoniumbenzyltriphenylborate, tetramethylenephenacyl Includes sulfonium butyl triphenyl borate, dimethyl allyl sulfonium butyl triphenyl borate, p-acetoxy phenyl benzyl methyl sulfonium butyl triphenyl borate, phenylmethyl (2-phenyl-3,3-dicyanoprop-2-enyl) sulfonium butyl triphenyl borate Each sample was prepared and subjected to similar experiments.In each case, the sample cured and apparently polymerized It gave Narubutsu but the polymerization product in the case that does not contain these sulfonium or oxosulfonium complex was observed.

In addition to pentaerythritol triacrylate as a radical polymerizable compound having an ethylenically unsaturated bond, butoxyethyl acrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tetraacrylate, diventerythritol hexaacrylate <br/> 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 similar experiments were respectively performed, in each case, the sample was cured and clearly gave a polymerization product.

As a comparative example, each of the polymerization initiators containing dimethylphenacylsulfonium tetrafluoroborate, dimethylphenacyloxosulfonium hexafluorophosphate and dimethylbenzylsulfonium tetrafluoroborate as polymerization initiators instead of dimethylphenacylsulfoniumbutyltriphenylborate was used. Samples were prepared and subjected to similar experiments. In each case, no polymerization product was obtained under the same conditions.

(Examples 59 to 77 and Comparative Examples 7 to 9) 360 parts of methyl ethyl ketone as a diluting solvent, 20 parts of polymethyl methacrylate as a binder, and 20 parts of pentaerythritol triacrylate as a compound having a radically polymerizable ethylenically unsaturated bond As a sensitizer, 2 g of a solution comprising 1 part of 3,3′-carbonylbis (7-diethylaminocoumarin (compound (a)) was added to a sulfonium or oxosulfonium complex 1.2 × as shown in Table 1 below as a polymerization initiator. 10 ^-5 mol was added to give a photosensitive solution. at this photosensitive solution was coated on a glass plate to a thickness of about 2μm by a spin coater, further spin coater 10% aqueous solution of polyvinyl alcohol as an oxygen blocking layer on the It was applied to a thickness of about 5 μm to form a photosensitive plate having a beam diameter of 1. After exposure to 5 mm argon ion laser light (488 nm) for different irradiation times, development processing was performed with water and toluene, and the exposure energy that gave a cured spot diameter equivalent to the laser beam diameter was used as a sensitivity. As comparative examples, Table 1 also shows the sensitivities when known polymerization initiators such as dimethylphenacylsulfonium tetrafluoroborate, dimethylphenacyloxosulfonium tetrafluoroborate and tetrabutylammonium butyltriphenylborate were used. As is clear from the results in Table 1, when a sulfonium or oxosulfonium complex represented by the general formula (1) is used as a polymerization initiator, known dimethylphenacylsulfonium tetrafluoroborate and dimethylphenacyloxo are used. Sulfonium tetrafluo It can be seen that the sensitivity neither than with the borate and tetrabutylammonium butyltriphenyl borate the polymerization initiator is improved.

[0060]

Compound (a)

Embedded image

Examples 78 and 79: 360 parts of methyl ethyl ketone 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,
To 2 g of a solution comprising 1 part of the sensitizer shown in the table, 1.2 × 10 ⁻⁵ mol of dimethylphenacylsulfoniumbutyltriphenylborate was added as a polymerization initiator to prepare a photosensitive solution.
This photosensitive solution was applied on a glass plate to a thickness of about 2 μm using a spin coater, and an oxygen barrier layer was further formed thereon as an oxygen barrier layer.
% Polyvinyl alcohol aqueous solution was applied to a thickness of about 5 μm by a spin coater to obtain a photosensitive plate. An argon ion laser beam (514 n) having a beam diameter of 1.5 mm is applied to this photosensitive plate.
m) or helium-neon laser light (633 nm) for different exposure times, and then developed with water and toluene to give a cured spot diameter equivalent to the laser beam diameter. It was shown to.

[0063]

Compound (b)

Embedded image Compound (c)

Embedded image

Reference Example 1 Differential scanning calorimetry (DSC) was performed to compare and study the thermal stability of the polymerization initiator. As a sample, dimethylphenacylsulfoniumbutyltriphenylborate, which is a polymerization initiator of the present invention, was measured from room temperature to about 300 ° C. at a heating rate of 10 ° C./min. The result is shown in FIG. Next, diphenyliodonium butyltriphenylborate, which is a known polymerization initiator, was measured under the same conditions, and the results are shown in FIG.
The temperature at which the DSC curve changes with the decomposition of the polymerization initiator is as low as 152 ° C. for dimethylphenacylsulfoniumbutyltriphenylborate (FIG. 1) and 112 ° C. for diphenyliodoniumbutyltriphenylborate (FIG. 2). It can be understood that dimethylphenacylsulfoniumbutyltriphenylborate, which is the polymerization initiator of the present invention, is more thermally stable.

[0066]

Industrial Applicability The sulfonium and oxosulfonium complexes represented by the general formula (1) of the present invention are effective as a polymerization initiator for radically polymerizable compounds having an ethylenically unsaturated bond. The composition can be polymerized and cured by application of light and / or thermal energy.

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

Therefore, it is coated on a substrate together with a binder or the like and used as a plate material, a photoresist, an electrophotograph, a direct plate material, a photosensitive plate such as a hologram material, a core material such as a microcapsule, and various recording media and adhesives. It is possible to apply to.

[Brief description of the drawings]

FIG. 1 shows a DSC curve of dimethylphenacylsulfonium butyltriphenylborate which is a polymerization initiator of the present invention.

FIG. 2 shows a DSC curve of a known polymerization initiator, diphenyliodoniumbutyltriphenylborate.

Continuation of front page (56) References JP-A-2-157760 (JP, A) JP-A-59-147001 (JP, A) JP-A-58-37004 (JP, A) JP-A-2-178303 (JP, A) JP-A-2-196812 (JP, A) JP-A-56-8428 (JP, A) JP-A-61-50959 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) C08F 4/00 C08F 4/42-4/52 C08F 2/46-2/50

Claims (3)

(57) [Claims] 1. A polymerizable composition comprising a radically polymerizable compound having an ethylenically unsaturated bond and a sulfonium or oxosulfonium complex represented by the general formula (1) as a polymerization initiator, a general formula (1) Formula 1 (However , at least one of R ¹ , R ² and R ³ is
An allyl group which may have a substituent or a group which may have a substituent.
Phenyl or an optionally substituted phenacyl group
Each other independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, Alkynyl group, alicyclic 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 A group selected from an arylthio group which may have a substituent and an amino group which may have a substituent, R ⁴ is an oxygen atom or a lone electron pair, and R ⁵ is a group which may have a substituent. A
The alkyl group, ^R 6, ^{R 7} and ^{R 8} are each independently,
The following shows an aryl group which may have a substituent . ). 2. A polymerizable composition according to claim 1 Symbol placement, and a sensitizer which absorbs any light toward the near-infrared region from ultraviolet Tona
That heavy polymerizable composition. Against 3. A process according to claim 1 or claim 2 Symbol placement of the polymerizable composition, according to claim 1 or claim, characterized in that to produce by polymerizing an active radicals by providing a light and / or heat energy 3. A method for polymerizing the polymerizable composition according to 2 .