JPH0782307A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable composition with high sensitivity which polymerizes in a short time upon exposure to an actinic ray by mixing a radical-polymerizable ethylenic compound with specific compounds as photopolymerization initiators. CONSTITUTION:This composition comprises a radical-polymerizable ethylenic compound and, as photopolymerization initiators, at least one styryl dye represented by any of formulae I to III [wherein R<1> to R<3> each is a (substituted) alkyl or a (substituted) aralkyl; X is O, S, Se, NH, CH=CH, or C(CH3)2 and forms, in cooperation with the N atom of N-R<1>, a five- or sixmembered heterocycle which may have a fused benzene ring; Y is a halogen, NO3, BF4, PF6, AsF6, ClO4, SbF6, CF3SO3, or CH3C6H4SO3; and n is 1 or 2] and a diaryliodonium salt represented by formula IV (wherein R<4> and R<5> each is H, a lower alkyl, a lower alkoxy, cyano, nitro, or a halogen; and Z is a halogen, BF4, PF6, AsF6, SbF6 ClO4, C6H5SO3, p-CH3C6H4SO3, etc.).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photopolymerizable composition. More specifically, a compound having a radically polymerizable ethylenically unsaturated bond is polymerized in a short time by exposure to actinic rays, and, for example, ink, a photosensitive printing plate, a photoresist, a direct printing plate material, a proofing material for plate making, The present invention relates to a photopolymerizable composition for obtaining a cured product having good physical properties in the fields of hologram materials, sealants, adhesives, stereolithography materials and the like.

[Prior art]

In recent years, various photopolymerization initiators have been devised and put into practical use in order to improve the sensitivity characteristics to a visible light source. From such a viewpoint, a photopolymerization initiator system characterized by a combination of a diaryliodonium salt and various sensitizers has been proposed. For example, Japanese Patent Application Laid-Open No. 60-88005 (Japanese Patent Publication No. 3-62162) discloses a combination with a 3-ketocoumarin compound, but it has a high sensitivity but a wide wavelength range, especially for red light. It was desired to impart photosensitivity. Japanese Patent Application Laid-Open No. 60-78442 (Japanese Patent Publication No. 3-44287) discloses a combination with a porphyrin derivative, but it has been desired to improve the sensitivity characteristic to red light. JP-A-63-243
No. 102 (Japanese Patent Publication No. 3-55483) discloses a combination with a tetrabenzoporphyrin derivative, but there is a problem in practical use because an industrial production method of the tetrabenzoporphyrin derivative has not been established. Also, it has been desired to impart photosensitivity to short wavelength light. JP-A-60-76740 (JP-B-3-9453) and JP-A-60-96604 (JP-B-3-3).
No. 62164) discloses a combination with a rhodanine derivative, but further improvement in sensitivity characteristics has been desired. JP-A-60-92302 (Japanese Patent Publication No. 3-62)
163) and Japanese Patent Application Laid-Open No. 60-258204 (Japanese Patent Publication No. 36604/1990), a combination with a dialkylaminophenyl derivative is disclosed. However, the sensitivity characteristics are further improved and the sensitivity to red light is further improved. Grant was desired. Further, JP-A-3-704 proposes a photopolymerization initiator comprising a combination of various sensitizing dyes with a diaryl iodonium salt having an organic borate salt as a special diaryliodonium salt. Have not been proposed at all for the styryl dye proposed in the present invention.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to propose a highly sensitive radical-polymerizable photopolymerizable composition which can be polymerized in a short time by exposure to actinic radiation. To provide a cured product having good physical properties, for example, an ink, a sealant, and a recording medium such as a photosensitive printing plate requiring high sensitivity, a proof material, a photoresist, a direct printing plate material, and a hologram material. It is in.

[0004]

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 is represented by the general formula (1) to the general formula (3) as a compound having a radical-polymerizable ethylenically unsaturated bond, which can be polymerized in a short time by exposure to actinic radiation, and a photopolymerization initiator. At least one styryl dye and a diaryl iodonium salt represented by the general formula (4).

[0005]

[Chemical 3] (In the formula, R ¹ , R ² and R ³ each independently represent an alkyl group which may have a substituent or an aralkyl group which may have a substituent, Z represents an oxygen atom, a sulfur atom, A selenium atom, an NH group, a CH═CH group, or a C (CH ₃ ) ₂ group, and X represents a 5-membered ring or a 6-membered ring hetero group which may further have a condensed benzene ring together with N—R ^1. Form a ring, and Y is halogen, NO ₃ , BF ₄ , PF ₆ , A
sF ₆ , ClO ₄ , SbF ₆ , CF ₃ SO ₃ or CH ₃ C ₆
H ₄ SO ₃ and n is an integer of 1 or 2. )

[0006]

[Chemical 4](In the formula, R^Four, R^FiveIs a hydrogen atom, a lower alkyl group, a lower alkyl
Rucoxy group, cyano group, nitro group or halogen atom
, X is halogen, BF_Four, PF₆, AsF₆, Sb
F₆, ClO_Four, C₆H_FiveSO₃, P-CH₃C₆H_FourSO₃,
p-CF₃C₆H_FourSO ₃, N-C_FourH₉C₆H_FourB is shown)

First, the compound having a radically polymerizable ethylenically unsaturated bond in the photopolymerizable composition of the present invention means a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule. Any material may be used as long as 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 can be mentioned.

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.

Next, the styryl dye of the photopolymerization initiators of the present invention will be described. The styryl dye in the present invention is represented by the general formulas (1) to (3).

[0011]

[Chemical 5] (In the formula, R ¹ , R ² and R ³ each independently represent an alkyl group which may have a substituent or an aralkyl group which may have a substituent, X represents an oxygen atom, a sulfur atom, A selenium atom, an NH group, a CH═CH group, or a C (CH ₃ ) ₂ group, and X represents a 5-membered ring or a 6-membered ring hetero group which may further have a condensed benzene ring together with N—R ^1. Form a ring, and Y is halogen, NO ₃ , BF ₄ , PF ₆ , A
sF ₆ , ClO ₄ , SbF ₆ , CF ₃ SO ₃ or CH ₃ C ₆
H ₄ SO ₃ and n is an integer of 1 or 2. )

The following compounds may be mentioned as specific examples of such styryl dyes. 2- (p-dimethylaminostyryl) -1-ethylpyridinium iodide, 2- [4- (p-dimethylaminophenyl)-
1,3-Butadienyl] -1-ethylpyridinium iodide, 2-{[5,5-dimethyl-3- (p-dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl} -1-ethylpyridinium park Lorate, 2-{[5,5-dimethyl-3- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -2-
Cyclohexene-1-ylidene] methyl} -1-ethylpyridinium perchlorate, 2-{[4- (p-dimethylaminostyryl) -2H-benzopyran-2-ylidene] methyl} -1-ethylpyridinium perchlorate, 2- {[4- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -2H-benzopyran-
2-ylidene] methyl} -1-ethylpyridinium perchlorate, 4- (p-dimethylaminostyryl) -1
-Ethylpyridinium iodide, 4- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -1
-Ethylpyridinium iodide, 4-{[5,5-dimethyl-3- (p-dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl} -1-ethylpyridinium perchlorate, 4-{[5 5-dimethyl-3- [4- (p-dimethylaminophenyl) -1,3
-Butadienyl] -2-cyclohexene-1-ylidene] methyl} -1-ethylpyridinium perchlorate, 4-{[4- (p-dimethylaminostyryl) -2
H-benzopyran-2-ylidene] methyl} -1-ethylpyridinium perchlorate, 4-{[4- [4-
(P-Dimethylaminophenyl) -1,3-butadienyl] -2H-benzopyran-2-ylidene] methyl}-
1-ethylpyridinium perchlorate, 2- (p-dimethylaminostyryl) -3-methylbenzoxazolium iodide, 2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -3-methyl Benzoxazolium iodide, 2- (p-diethylaminostyryl) -3-methylbenzoxazolium iodide, 2- (p-julolidylstyryl) -3-ethylbenzoxazolium iodide, 2- { [5,5-Dimethyl-3- (p-dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl} -3-methylbenzoxazolium iodide, 2-{[5,5-dimethyl-3- [4- (p-dimethylaminophenyl) -1,
3-Butadienyl] -2-cyclohexene-1-ylidene] methyl} -3-methylbenzoxazolium iodide, 2-{[4- (p-dimethylaminostyryl)-
2H-benzopyran-2-ylidene] methyl} -3-ethylbenzoxazolium tetrafluoroborate, 2
-{[4- [4- (p-dimethylaminophenyl)-
1,3-Butadienyl] -2H-benzopyran-2-ylidene] methyl} -3-ethylbenzoxazolium tetrafluoroborate, 2- (p-dimethylaminostyryl) -3-methylnaphtho [2,1-d] oxa Zolium iodide, 2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -3-methylnaphtho [2,1-d] oxazolium iodide, 2-
{[5,5-Dimethyl-3- (p-dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl}
-3-Methylnaphtho [2,1-d] oxazolium iodide, 2-{[4- (p-dimethylaminostyryl)
-2H-benzopyran-2-ylidene] methyl} -3-
Ethylnaphtho [2,1-d] oxazolium tetrafluoroborate, 5,5-dichloro-2-{[5,5-dimethyl-3- [4- (p-dimethylaminophenyl)-
1,3-Butadienyl] -2-cyclohexene-1-ylidene] methyl} -3-methylbenzoxazolium perchlorate, 2- (p-dimethylaminostyryl)-
3-ethylbenzothiazolium iodide, 2- [4-
(P-Dimethylaminophenyl) -1,3-butadienyl] -3-ethylbenzothiazolium iodide, 2-
(P-Dimethylaminostyryl) -3-benzylbenzothiazolium iodide, 2-{[5,5-dimethyl-
3- (p-dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl} -3-methylbenzothiazolium iodide, 2-{[5,5-dimethyl-3-
[4- (p-Dimethylaminophenyl) -1,3-butadienyl] -2-cyclohexene-1-ylidene] methyl} -3-methylbenzothiazolium iodide, 2-
{[4- (p-Dimethylaminostyryl) -2H-benzopyran-2-ylidene] methyl} -3-ethylbenzothiazolium tetrafluoroborate, 2-{[4-
[4- (p-Dimethylaminophenyl) -1,3-butadienyl] -2H-benzopyran-2-ylidene] methyl} -3-ethylbenzothiazolium tetrafluoroborate, 2- (p-dimethylaminostyryl)- 3-methylnaphtho [2,1-d] thiazolium iodide, 2
-[4- (p-Dimethylaminophenyl) -1,3-butadienyl] -3-methylnaphtho [2,1-d] thiazolium iodide, 2-{[5,5-dimethyl-3-
(P-Dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl} -3-methylnaphtho [2,1
-D] thiazolium iodide, 2-{[4- (p-dimethylaminostyryl) -2H-benzopyran-2-ylidene] methyl} -3-ethylnaphtho [2,1-d] thiazolium tetrafluoroborate , 5,5-Dichloro-2-{[5,5-dimethyl-3- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -2-cyclohexene-1-ylidene] methyl} -3- Methylbenzothiazolium perchlorate, 2- (p-dimethylaminostyryl) -3-ethylbenzoselenazolium iodide, 2- [4- (p-dimethylaminophenyl)
-1,3-Butadienyl] -3-ethylbenzoselenazolium iodide, 2-{[5,5-dimethyl-3-
(P-Dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl} -3-methylbenzoselenazolium iodide, 2-{[5,5-dimethyl-3-
[4- (p-Dimethylaminophenyl) -1,3-butadienyl] -2-cyclohexene-1-ylidene] methyl} -3-methylbenzoselenazolium iodide, 2
-{[4- (p-dimethylaminostyryl) -2H-benzopyran-2-ylidene] methyl} -3-ethylbenzoselenazolium tetrafluoroborate, 2-{[4
-[4- (p-Dimethylaminophenyl) -1,3-butadienyl] -2H-benzopyran-2-ylidene] methyl} -3-ethylbenzoselenazolium tetrafluoroborate, 2- (p-dimethylaminostyryl) -3
-Methylnaphtho [2,1-d] selenazolium iodide, 2- [4- (p-dimethylaminophenyl) -1,
3-Butadienyl] -3-methylnaphtho [2,1-d]
Selenazolium iodide, 2-{[5,5-dimethyl-3- (p-dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl} -3-methylnaphtho [2,1-d] selenazolium Iodide, 2-{[4
-(P-Dimethylaminostyryl) -2H-benzopyran-2-ylidene] methyl} -3-ethylnaphtho [2,2
1-d] selenazolium tetrafluoroborate, 5,
5-dichloro-2-{[5,5-dimethyl-3- [4-
(P-Dimethylaminophenyl) -1,3-butadienyl] -2-cyclohexene-1-ylidene] methyl}-
3-methylbenzoselenazolium perchlorate, 2-
(P-Dimethylaminostyryl) -1-ethylquinolinium iodide, 2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -1-ethylquinolinium iodide, 2- [4 -(P-Dimethylaminophenyl) -1,3-butadienyl] -6-dimethylamino-1-ethylquinolinium perchlorate, 2-
{[5,5-Dimethyl-3- (p-dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl}
-1-ethylquinolium iodide, 2-{[5,5-
Dimethyl-3- [4- (p-dimethylaminophenyl)
-1,3-Butadienyl] -2-cyclohexene-1-
Ylidene] methyl} -1-ethylquinolium iodide, 2-{[4- (p-dimethylaminostyryl) -2
H-benzopyran-2-ylidene] methyl} -1-ethylquinolium tetrafluoroborate, 2-{[4-
[4- (p-dimethylaminophenyl) -1,3-butadienyl] -2H-benzopyran-2-ylidene] methyl} -1-ethylquinolium tetrafluoroborate,
4- (p-dimethylaminostyryl) -1-ethylquinolinium iodide, 4- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -1-ethylquinolinium iodide, 4- {[5,5-dimethyl-3-
(P-Dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl} -1-ethylquinolium iodide, 4-{[5,5-dimethyl-3- [4- (p-
Dimethylaminophenyl) -1,3-butadienyl]-
2-Cyclohexene-1-ylidene] methyl} -1-ethylquinolium iodide, 4-{[4- (p-dimethylaminostyryl) -2H-benzopyran-2-ylidene] methyl} -1-ethylquinolium tetra Fluoroborate, 4-{[4- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -2H-benzopyran-2-ylidene] methyl} -1-ethylquinolium tetrafluoroborate, 2- ( p-dimethylaminostyryl) -1,3,3-trimethyl-3H-indolium iodide, 2- [4- (p-dimethylaminophenyl)
-1,3-Butadienyl] -1,3,3-trimethyl-
3H-indolium iodide, 2-{[5,5-dimethyl-3- (p-dimethylaminostyryl) -2-cyclohexene-1-ylidene] methyl} -1,3,3-trimethyl-3H-indolium Iodide, 2-
{[5,5-Dimethyl-3- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -2-cyclohexene-1-ylidene] methyl} -1,3,3-trimethyl-3H-indo Lithium iodide, 2-{[4-
(P-Dimethylaminostyryl) -2H-benzopyran-2-ylidene] methyl} -1,3,3-trimethyl-
3H-indolium tetrafluoroborate, 2-
{[4- [4- (p-dimethylaminophenyl) -1,
3-Butadienyl] -2H-benzopyran-2-ylidene] methyl} -1,3,3-trimethyl-3H-indolium tetrafluoroborate.

Next, the diaryliodonium salt used in the present invention will be described. The diaryliodonium salt in the present invention is represented by the general formula (4).

[0014]

[Chemical 6] (In the formula, R ⁴ and R ⁵ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a cyano group, a nitro group or a halogen atom, and Z is a halogen ion, BF ₄ ⁻ , PF ₆ ⁻ , As.
F ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , C ₆ H ₅ SO ₃ ⁻ , p-CH _{3
^{C 6 H 4 SO 3 -,}} p-CF 3 C 6 H 4 SO 3 -, n-C 4 H 9 C 6
H ₄ B ^- shows a)

Examples of such diaryliodonium salts include "Macromolecules (Macromolecules).
les), vol. 10, p. 1307 (1977).
Year) and JP-A-3-704, for example, diphenyliodonium, ditolyliodonium, phenyl (p-methoxyphenyl) iodonium,
Bis (m-nitrophenyl) iodonium, bis (p-
tert-butylphenyl) iodonium, bis (p-
(Cyrophenyl) iodonium chloride, bromide, boron tetrafluoride salt, boron hexafluoride salt, phosphorus hexafluoride salt, arsenic hexafluoride salt, antimony hexafluoride salt, perchlorate salt, benzenesulfonate salt, p-toluenesulfonate, p-trifluoromethylbenzenesulfonate, n
-Butyl triphenyl boron salt and the like are exemplified.

The compounding amount of the styryl dye in the present invention is
It is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the compound having a radically polymerizable ethylenically unsaturated bond, but it is formed on the substrate as a photosensitive film. It is necessary to adjust the blending amount so that the optical density at the irradiation wavelength of the light source used does not exceed 2, and more preferably the optical density does not exceed 1 in general. desired.

The amount of the diaryliodonium salt used in the present invention is 0.01 to 30 with respect to 100 parts by weight of the compound having a radically polymerizable ethylenically unsaturated bond.
Weight part is preferable, and 0.1 to 10 weight part is more preferable.

Further, the photopolymerizable composition of the present invention is mixed with a binder such as an organic or inorganic polymer, and applied on a glass plate, an aluminum plate, other metal plates, or a polymer film such as polyethylene terephthalate. It is possible to use. Examples of binders that can be used by mixing with the photopolymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes. Examples thereof include polymers and copolymers such as polyvinyl esters, and more specifically, polymethacrylate, polymethylmethacrylate, polyethylmethacrylate, polyvinylcarbazole, polyvinylpyrrolidone, polyvinylbutyral, polyvinylacetate, novolac resin, phenol resin. , Epoxy resin, alkyd resin and others, supervised by Kiyoshi Akamatsu, "Actual technology of new photosensitive resin"
(CMC, 1987) and "10188 Chemical Products", pp. 657-767 (Chemical Industry Daily, 1988).
(Year) and known polymer polymers in the art.

The photopolymerizable composition of the present invention can be used in combination with another photopolymerization initiator for the purpose of further improving the sensitivity. Other photopolymerization initiators that can be used in combination with the photopolymerizable composition of the present invention include, for example, JP-B-59-1281.
Japanese Examined Patent Publication No. 61-9621 and Japanese Patent Laid-Open No. 60-6010.
4, triazine derivatives, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413
No. 4, Japanese Patent Publication No. 47-1604 and USP No. 3567.
No. 453 diazonium compound, USP 2848
No. 328, USP No. 2852379, and USP No. 2940853, organic azide compounds, JP-B-36.
-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 3
8-18015 and the ortho-quinone diazides described in JP-B-45-9610, JP-B-55-39162
No. 59-140203 and "Macromolecules", No. 10
Vol., P. 1307 (1977), various onium compounds other than diaryl iodonium compounds, JP-A-59-59.
Azo compounds described in JP-A-142205, JP-A-1-544
40, European Patent No. 109851, European Patent No. 126712, "Journal of Imaging Science (J.Imag.Sci.)", No. 3
0, page 174 (1986), metal allene complexes, Japanese Patent Application No. 4-56831 and Japanese Patent Application No. 4-8953.
No. 5, (oxo) sulfonium organoboron complex, the titanocenes described in JP-A No. 61-151197, “Coordination Chemistry Review (Coord).
Ination Chemistry Review
w) ", Vol. 84, pp. 85-277 (1988).
And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701, JP-A-3-209
Aluminate complex described in JP-A No. 477/1982
550 and 2,4,5-triarylimidazole dimers described in JP-A-60-202437, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, and the like. The initiator is preferably contained in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the compound having a radical-polymerizable ethylenically unsaturated bond.

The photopolymerizable 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 photopolymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The thermal polymerization inhibitor is a compound 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.

The photopolymerizable composition of the present invention may further contain a polymerization accelerator represented by amine, thiol, disulfide, etc., a chain transfer catalyst, etc. for the purpose of further promoting the polymerization. Specific examples of the polymerization accelerator and the chain transfer catalyst that can be added to the photopolymerizable composition of the present invention include, for example, N-phenylglycine, triethanolamine,
Amines such as N, N-diethylaniline, USP No. 44
14312 and thiols described in JP-A No. 64-13144, disulfides described in JP-A No. 2-291561, USP No. 3558322, and JP-A No. 64-1704.
No. 8, thiones, O-acyl thiohydroxamates and N-alkoxypyridine thiones described in JP-A-2-291560.

The photopolymerizable composition of the present invention further comprises, according to purposes, an oxygen scavenger or reducing agent such as dyes, organic and inorganic pigments, phosphines, phosphonates and phosphites, an antifoggant, an antifading agent and an antihalation agent. Agents, optical brighteners, surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, UV absorbers, foaming agents, antifungal agents, antistatic agents, magnetic materials and various other properties. You may use it, mixing with the additive to add, a diluent solvent, etc.

The photopolymerizable composition of the present invention comprises a low pressure mercury lamp,
Medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser,
The desired polymer or cured product can be obtained by exposure using various light sources such as a light emitting diode, a CRT light source, and a plasma light source. Therefore, various inks, various printing plate materials, various proof materials, photoresists, electrophotography, direct printing plate materials, etc.
It can be applied to various recording media such as photosensitive materials such as hologram materials and microcapsules, as well as adhesives, pressure-sensitive adhesives, adhesives, sealants and various paints.

[0024]

EXAMPLES The present invention will be described in detail below with reference to examples. In the examples, “part” means “part by weight”.

Example 1 Pentaerythritol triacrylate 100 as a compound having a radically polymerizable ethylenically unsaturated bond
Parts, 5 parts of a styryl dye (STY-1), and 5 parts of diphenyliodonium hexafluoroborate (compound (a)) as a polymerization initiator to 2500 parts of tetrachloroethane together with 100 parts of polymethyl methacrylate (PMMA) which is a binder component. Dissolve and coat this mixture on a glass plate to a thickness of about 2 microns, which is applied at 60 ° C.
After drying in a hot air oven for 2 minutes, 1% of polyvinyl alcohol (PVA) is further formed thereon as an oxygen inhibition layer.
The PVA layer was peeled off by exposing a photosensitive plate coated with a 0% aqueous solution with 514 nm light of an Ar ion laser having a beam diameter of 1.2 mm while changing the irradiation time, and then developed with toluene. Table 1 also shows the minimum exposure dose (gelation sensitivity) at which gelation starts and the exposure dose (spot sensitivity) that gives a spot diameter equivalent to that of the laser beam.

[0026]

[Chemical 7]

Embodiments 2 to 6 STY-1 in Embodiment 1 is replaced with STY-2 to STY.
In place of -6 nm and using 488 nm light of Ar ion laser in Example 3 and 647 nm light of Kr ion laser in Example 6, sensitivity when operated in the same manner as in Example 1 was used. The results are shown in Table 1.

[0028]

[Chemical 8]

[0029]

[Table 1]

Examples 7 to 9 Table 2 shows the sensitivities when operated in the same manner as in Example 1 except that the diaryl iodonium salt in Example 1 was changed to the compounds (b) to (d). .

[0031]

[Chemical 9]

[0032]

[Table 2]

[0033]

The combination of the styryl dyes represented by the general formulas (1) to (3) and the diaryl iodonium salt represented by the general formula (4) of the present invention is radically polymerizable. It is effective as a photopolymerization initiator for a compound having an ethylenically unsaturated bond, and a photopolymerizable composition containing them can be polymerized and cured by application of light energy.

Therefore, the photopolymerizable composition of the present invention is
Low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, super-high pressure mercury lamp,
Xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YA
By applying light energy from various light sources such as a G laser, a light emitting diode, a CRT light source, and a plasma light source, a desired polymer or cured product can be obtained.

Therefore, it is coated on a substrate together with a binder or the like and used as a core material for a photosensitive plate such as a printing plate material, photoresist, electrophotography, direct printing plate material, proof material, hologram material, or microcapsule, and various recording media. It can also be applied to adhesives.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03F 7/027 502 7/029 7/038 H01L 21/027 (72) Inventor Yen Yasuko Central Tokyo 2-3-13 Kyobashi, Tokyo Toyo Inki Manufacturing Co., Ltd.

Claims (1)

[Claims] 1. A radically polymerizable ethylenically unsaturated bond
A compound having a general formula (1) as a photopolymerization initiator
Ishi At least one styryl represented by the general formula (3)
Dye, and diaryl iodo represented by the general formula (4)
A photopolymerizable composition comprising a titanium salt. [Chemical 1](In the formula, R¹, R²And R³Are each independently a substituent
May have an alkyl group or may have a substituent
Represents an aralkyl group, X is an oxygen atom, a sulfur atom,
Group atom, NH group, CH = CH group, or C (CH₃)₂Basis
And X is NR¹Condensation with the nitrogen atom of the group
5-membered ring and 6-membered ring which may further have a benzene ring
Form a heterocycle. Y is halogen, NO₃, B
F_Four, PF₆, AsF₆, ClO_Four, SbF₆, CF₃SO₃
Or CH₃C₆H_FourSO₃Where n is an integer of 1 or 2
Indicates. ) [Chemical 2](In the formula, R^Four, R^FiveIs a hydrogen atom, a lower alkyl group, a lower alkyl
Rucoxy group, cyano group, nitro group or halogen atom
, Z is halogen, BF_Four, PF₆, AsF₆, Sb
F₆, ClO_Four, C₆H_FiveSO₃, P-CH₃C₆H_FourSO₃,
p-CF₃C₆H_FourSO ₃, N-C_FourH₉C₆H_FourB is shown)