JP2001206903A - Polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization initiator which gives a colorless cured product after the irradiation of light and exhibits high sensitivity to UV light. SOLUTION: This polymerizable composition characterized by comprising (A) a polymerization initiator represented by the general formula (1) [R1 and R4 are each a 1 to 8C primary alkyl; R2 and R3 are each a halogen, a 1 to 6C alkyl or a 1 to 6C alkoxy; Ar is an aryl; (p) is an integer of 0 to 3; (q) is an integer of 0 to 4] and (B) a radically polymerizable compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymerizable composition. More specifically, free radicals are generated by irradiation with energy rays, particularly UV light, and radical polymerizable compounds are cured in a short time. For example, molding resins, casting resins, stereolithography resins, sealants, and dental Polymerized resin, printing ink,
Paint, photosensitive resin for printing plate, color proof for printing, resist for color filter, dry film resist,
Printed circuit board resist, semiconductor photoresist, microelectronic resist, hologram material,
The present invention relates to a polymerizable composition for obtaining a polymer or a cured product having good physical properties in the fields of overcoat materials, adhesives, pressure-sensitive adhesives, release agents, optical recording media, various devices, and the like.

[0002]

2. Description of the Related Art Photopolymerization initiators which cause the polymerization of acrylates and the like by irradiation with UV light are used in a wide range of fields, and commercially available photopolymerization initiators are described in Photopolymer Gathering Association, "Photosensitive Material List Book". ", 55-72
Page, 1996 (Bunshin Publishing).

In recent years, research on photopolymerization initiators having higher sensitivity than these commercially available photopolymerization initiators has been actively conducted, and one of them is a site that absorbs light and generates free radicals in the molecule. A photopolymerization initiator having both a site and an active site has been proposed. This is based on the idea that by causing the two sites to coexist in the same molecule, a photoinduced electron transfer reaction or a light energy transfer reaction between these two sites is likely to occur, and as a result, the generation efficiency of free radicals is increased. Is based on

[0004] For example, the following publications are known as photopolymerization initiators comprising a dye cation as a site for absorbing light and a borate anion generating free radicals. U.S. Pat. No. 4,772,530. Journal of America
n Chemical Society, Vol. 110, 2326-232
8 pages (1988, published by the American Chemical Society).

[0005] The following publications are known as photopolymerization initiators composed of an ammonium cation having a benzophenone structure, a coumarin structure or a naphthalene structure as a light absorbing site and a borate anion. PCT Patent WO97 / 16406. Journal of American Chem
ical Society, Vol. 117, 11369-11370
Page (1995, published by The Chemical Society of America). Macromolecules
29, 8047-8052 (1996, published by The Chemical Society of America). Macromolecules, Vol. 31, 951
954 pages (1998, published by the American Chemical Society). Macromol
ecules, Vol. 32, pp. 328-330 (1999,
Published by the American Chemical Society). Journal of Organic Chemistry,
64, 458-463 (American Chemical Society, 1999).

[0006]

For example, the above-mentioned photopolymerization initiator comprising a dye cation and a borate anion is:
It was developed mainly for the purpose of increasing the sensitivity to visible light, and its sensitivity to UV light is not sufficient.
Further, since the dye cation is used, there is a disadvantage that coloring of a cured product obtained after light irradiation is inevitable.

Further, an ammonium cation having a benzophenone structure, a coumarin structure, or a naphthalene structure,
For the photopolymerization initiator consisting of borate anions,
Although the coloring of the cured product is small, the sensitivity to UV light is insufficient, and a polymerization initiator exhibiting even higher sensitivity has been required.

[0008]

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 provides a polymerization initiator (A) represented by the general formula (1) and a radical polymerizable compound (B)
It is a polymerizable composition characterized by comprising.

General formula (1)

[0010]

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(Where R ¹ and R ⁴ are primary alkyl groups having 1 to 8 carbon atoms, R ² and R ³ are halogen groups,
-C6 alkyl group, C1-C6 alkoxyl group, A
r represents an aryl group, p represents an integer of 0 to 3, and q represents an integer of 0 to 4. )

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

First, the polymerization initiator (A) of the present invention will be described. The polymerization initiator (A) of the present invention
It is characterized by having a thioxanthone structure highly sensitive to V light. That is, the thioxanthone site is excited by irradiation with UV light, causing an electron transfer reaction from a borate anion as a counter anion,
The resulting boranyl radical is efficiently decomposed to generate free radicals.

Here, the substituent R ¹ in the general formula (1)
And a primary alkyl group having 1 to 8 carbon atoms represented by R ⁴ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, Octyl groups and the like can be mentioned.

The halogen groups represented by R ² and R ³ are fluorine, chlorine and bromine, and the alkyl groups having 1 to 6 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, Isobutyl group, sec-butyl group, tert-butyl group, hexyl group, etc.
As the alkoxyl group of 6, a methoxy group, an ethoxy group,
Examples include a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a hexyloxy group. Further, the aryl group represented by Ar includes a phenyl group,
o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, 1-naphthyl group and the like, p-methoxyphenyl group,
Examples thereof include an aryl group substituted with a halogen group such as an m-fluorophenyl group or an alkoxyl group, but the present invention is not limited thereto.

The combination of these substituents changes the solubility in the radically polymerizable compound (B) described later and the light absorption characteristics. Among them, the following compounds (1) to (5) are preferable as the polymerization initiator (A) of the present invention.
Compound (14) can be mentioned (where Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group).

Compound (1)

[0018]

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Compound (2)

[0020]

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Compound (3)

[0022]

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Compound (4)

[0024]

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Compound (5)

[0026]

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Compound (6)

[0028]

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Compound (7)

[0030]

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Compound (8)

[0032]

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Compound (9)

[0034]

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Compound (10)

[0036]

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Compound (11)

[0038]

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Compound (12)

[0040]

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Compound (13)

[0042]

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Compound (14)

[0044]

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Next, the radical polymerizable compound (B) used in the present invention will be described. The radical polymerizable compound (B) in the present invention means a compound having at least one radically polymerizable ethylenically unsaturated bond in a molecule. Further, each of them has a chemical form of a monomer, oligomer or polymer which is liquid or solid at normal temperature and normal pressure.

Examples of such a radical polymerizable compound (B) include acrylic acid, methacrylic acid, itaconic acid,
Unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, and maleic acid, and salts, esters, urethanes, acid amides and acid anhydrides thereof, and acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated poly Examples thereof include ethers, unsaturated polyamides, and unsaturated polyurethanes, but the present invention is not limited to these. Hereinafter, specific examples of the radical polymerizable compound (B) in the present invention will be described. Examples of acrylates: Examples of monofunctional alkyl acrylates: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate , Isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, benzyl acrylate. Examples of monofunctional hydroxy acrylates: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl Acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate. Examples of monofunctional halogen-containing acrylates: 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate , 1H, 1H, 2H,
2H-heptadecafluorodecyl acrylate, 2,6
-Dibromo-4-butylphenyl acrylate, 2,
4,6-tribromophenoxyethyl acrylate,
2,4,6-tribromophenol 3EO addition acrylate. Examples of monofunctional ether-containing acrylates: 2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate,
Methoxy dipropylene glycol acrylate, methoxy tripropylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy diethylene glycol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxy ethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol Acrylate, p-nonylphenoxyethyl acrylate, p-nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate. Examples of monofunctional carboxyl-containing acrylates: β-carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyl Oxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate. Examples of other monofunctional acrylates: N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate,
Trimethylsiloxyethyl acrylate, diphenyl-
2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified 2-acryloyloxyethyl acid phosphate. Examples of bifunctional acrylates: 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol #
400 diacrylate, polypropylene glycol # 7
00 diacrylate, neopentyl glycol diacrylate, neopentyl glycol PO modified diacrylate, neopentyl glycol hydroxypivalate diacrylate, caprolactone adduct diacrylate of hydroxypivalate neopentyl glycol ester, 1,6-hexanediol bis ( 2-hydroxy-3-acryloyloxypropyl) ether, 1,
9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO
Modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A
Diacrylate, bisphenol F diacrylate, E
O-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, EO-modified tetrabromobisphenol A diacrylate, tricyclodecane dimethylol diacrylate, isocyanuric acid EO-modified diacrylate. Examples of trifunctional acrylates: glycerin PO modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane PO modified triacrylate, isocyanuric acid EO modified triacrylate, isocyanuric acid EO modified ε-caprolactone modified Triacrylate, 1,3,5-triacryloylhexahydro-s
-Triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate. Examples of tetrafunctional or higher acrylates: pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate,
Tris (acryloyloxy) phosphate. Examples of methacrylates: Examples of monofunctional alkyl methacrylates: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate , Isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate. Examples of monofunctional hydroxymethacrylates include: 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl Methacrylate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate. Examples of monofunctional halogen-containing methacrylates: 2,2,2-
Trifluoroethyl methacrylate, 2,2,3,3-
Tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 1H, 1H, 5
H-octafluoropentyl methacrylate, 1H, 1
H, 2H, 2H-heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO
Additional methacrylate. Examples of monofunctional ether-containing methacrylates: 2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxy Tripropylene glycol methacrylate, methoxy polypropylene glycol methacrylate, ethoxydiethylene glycol methacrylate, 2
-Ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxypolyethylene glycol methacrylate, cresyl polyethylene glycol methacrylate, p-nonylphenoxyethyl methacrylate, p-
Nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate. Examples of monofunctional carboxyl-containing methacrylates: β-carboxyethyl methacrylate, monomethacryloyloxyethyl succinate, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate, 2-methacryloyl Oxypropyl hexahydrohydrogen phthalate, 2-methacryloyloxypropyl tetrahydrohydrogen phthalate. Examples of other monofunctional methacrylates: N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl Acid phosphate, caprolactone-modified-2-methacryloyloxyethyl acid phosphate. Examples of bifunctional methacrylates: 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 dimethacrylate, polyethylene glycol #
400 dimethacrylate, polyethylene glycol # 6
00 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, Neopentyl glycol hydroxypivalate dimethacrylate, caprolactone adduct of neopentyl glycol hydroxypivalate dimethacrylate, 1,6
-Hexanediol bis (2-hydroxy-3-methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, bisphenol A dimethacrylate , EO-modified bisphenol A dimethacrylate, PO
Modified bisphenol A dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO modified bisphenol F dimethacrylate,
PO-modified bisphenol F dimethacrylate, EO-modified tetrabromobisphenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO-modified dimethacrylate. Examples of trifunctional methacrylates: glycerin PO modified trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate,
Isocyanuric acid EO-modified ε-caprolactone-modified trimethacrylate, 1,3,5-trimethacryloylhexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate. Examples of tetrafunctional or higher methacrylates: pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, tris (methacryloyloxy) phosphate. Examples of arylates: allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate. Examples of acid amides: acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetone Methacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine. Examples of styrenes: styrene, p-hydroxystyrene,
p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt
-Butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene. Examples of other vinyl compounds: vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate,
Vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone and the like.

The above-mentioned radical polymerizable compound (B) can be easily obtained as a commercial product of the following manufacturer. For example, "Light Acrylate", "Light Ester", "Epoxy Ester", "Urethane Acrylate" and "Highly Functional Oligomers" series manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., "Shin Nakamura Chemical Co., Ltd." “NK Ester” and “NK Oligo” series, “Fancryl” series manufactured by Hitachi Chemical Co., Ltd., “Aronix M” series manufactured by Toagosei Chemical Co., Ltd., manufactured by Daihachi Chemical Co., Ltd. "Functional monomer" series,
“Special acrylic monomer” series manufactured by Osaka Organic Chemical Industry Co., Ltd., “Acryester” and “Diabeam Oligomer” series manufactured by Mitsubishi Rayon Co., Ltd., “Kayarad” manufactured by Nippon Kayaku Co., Ltd. "Kayamar"
Series, "Acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Shokubai Co., Ltd., "NICHIGO-UV purple light urethane acrylate oligomer" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Shin-Etsu Vinyl Acetate Co., Ltd.
And the "functional monomer" series manufactured by Kojin Co., Ltd.

The following cyclic compounds are also exemplified as the radical polymerizable compound (B). Example of a three-membered ring compound: Journal of Polymer Science Polymer Chemistry Edition (J.Po
lym.Sci.Polym.Chem.Ed.), Vol. 17, p. 3169 (1
997), described in Macromolecular Chemie Rapid Communication (Ma
kromol. Chem. Rapid Commun.), Vol. 5, p. 63 (19
1-phenyl-2-vinylcyclopropane described in Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Poly)
m. Chem. Ed.), Vol. 23, p. 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. E.
d.), Vol. 21, p. 4331 (1983).
Phenyl-3-vinyloxiranes, Chemical Society of Japan No. 50
2,3-Divinyloxiranes described in Proceedings of the Spring Meeting, p. 1564 (1985). Examples of cyclic ketene acetals: Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 20, 30
21 (1982) and Journal of Polymer Science Polymer Letter Edition (J.
Polym. Sci. Polym. Lett. Ed.), Volume 21, p. 373 (1
983), 2-methylene-1,3-dioxepane, polymer prepreprint (Polym. Preprint)
s), 34, 152 (1985), dioxolanes, Journal of Polymer Science.
Polymer Letter Edition (J.Polym.Sci.Polym.
Lett. Ed.), Volume 20, p. 361 (1982), Makromol. Chem., 183.
Vol. 1913 (1982) and Macromolecular Chem. 186, 1543.
2-methylene-4-phenyl- described on page 1985.
1,3-dioxepane, macromolecules (Macromol
ecules), Vol. 15, p. 1711 (1982), 4,7-dimethyl-2-methylene-1,3-dioxepane, polymer prepreprint (Polym. Preprint).
s), Vol. 34, p. 154 (1985), 5, 6
-Benzo-2-methylene-l, 3-diosepan.

Further, the radical polymerizable compound (B) is
Examples described in the following documents can also be given. For example, edited by Shinzo Yamashita et al., “Handbook of Crosslinking Agents”, (19
1981, Taiseisha) and Kato Kiyomi eds., "UV / EB Curing Handbook (Raw Materials)", (1985, Polymer Publishing Association), Radtech Study Group, "Applications and Markets of UV / EB Curing Technology" 79, (1989, CMC),
Edited by Kiyoshi Akamatsu, “New Technology for Photosensitive Resins”, (1987
(CMC), edited by Tsuyoshi Endo, "Refining Thermosetting Polymers" (1986, CMC), Eiichiro Takiyama, "Polyester Resin Handbook", (1988)
Year, Nikkan Kogyo Shimbun).

Further, the polymerizable composition of the present invention can be used by adding a carboxyl group-containing polymer (C) shown below. Here, the carboxyl group-containing polymer (C) is a copolymer of acrylic acid ester or methacrylic acid ester [hereinafter abbreviated as (meth) acrylic acid ester] and acrylic acid, (meth) acrylic acid ester and (meth) acrylic acid. ) Copolymers of acrylic acid and vinyl monomers copolymerizable therewith. These copolymers may be used alone or in combination of two or more.

Here, (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isovolyl Nil methacrylate and the like. Further, (meth) acrylic acid ester, (meth) acrylic acid and vinyl monomers copolymerizable therewith include tetrahydrfurfuryl acrylate,
Dimethylaminoethyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, tetrahydrfurfuryl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, 2,2 Examples thereof include 2-trifluoroethyl methacrylate, acrylamide, and styrene.

The radical polymerizable compound (B) of the present invention comprises
Only one kind may be used, or a mixture of two or more kinds at an arbitrary ratio may be used in order to improve desired characteristics. The polymerization initiator (A) of the present invention is used in an amount of 0.01 to 2 parts by weight per 100 parts by weight of the radically polymerizable compound (B).
It is preferably used in the range of 0 parts by weight.
More preferably, it is used in the range of 10 to 10 parts by weight. The carboxyl group-containing polymer (C) is used in an amount of from 20 to 500 based on 100 parts by weight of the radical polymerizable compound (B).
It is preferably used in the range of parts by weight, and more preferably in the range of 50 to 150 parts by weight.

The polymerizable composition of the present invention is used by mixing with a binder such as an organic polymer and coating it on a glass plate, an aluminum plate, another metal plate, or a polymer film such as polyethylene terephthalate or polyethylene. Is possible. Examples of the binder that can be used by mixing with the polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetal, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, Polymers such as polyvinyl esters, copolymers, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolak resin, phenol resin, Epoxy resin, alkyd resin and others, supervised by Kiyoshi Akamatsu, "New technology of photosensitive resin", (CMC, 1987) and "Chemical products of 10188", 657
To 767 (Kagaku Kogyo Nippo, 1988).

The polymerizable composition of the present invention can be used in combination with a sensitizer or another photopolymerization initiator for the purpose of further improving the sensitivity. Benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, and 4,4′-dimethylbenzophenone include sensitizers and other photopolymerization initiators that can be used in combination by mixing with the polymerizable composition of the present invention. , 4,4'-dimethoxybenzophenone, 4,4'-
Benzophenones such as bis (diethylamino) benzophenone, coumarin 1, coumarin 338, coumarin 102
And the like; ketocoumarins such as 3,3'-carbonylbis (7-diethylaminocoumarin); and Irgacure 651, Irgacure 184, and Darocure described in the Ciba Specialty Chemicals Photopolymerization Initiator General Catalog (issued in 1997). 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 36
9, Irgacure 1700, Irgacure 149,
Irgacure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, and Irgacure 261.

Further, Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 6
No. 1-9621 and the triazine derivatives described in JP-A-60-60104, U.S. Pat. No. 2,848,328, JP-B-36-22062, JP-B-37-13109,
JP-B-38-18015 and JP-B-45-961
Ortho-quinonediazides described in No. 0, JP-B-55-3
9162, JP-A-59-140203 and Macr.
omolecules, Vol. 10, p. 1307 (1977,
Various onium compounds including iodonium compounds described in American Chemical Society), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, and European Patent No. 12671.
No. 2, Journal of Imaging Science, Vol. 30, No. 1
Metal allene complexes described on page 74 (1986), JP-A-6
Titanocenes described in JP-A-1-151197;
127,550 and 2,4,5-triarylimidazole dimer described in JP-A-60-202037;
2,2′-bis (o-chlorophenyl) -4,4 ′,
5,5′-Tetraphenyl-1,1′-biimidazole, organic halogen compounds described in JP-A-59-107344, and the like can also be mentioned as photopolymerization initiators that can be used in combination.

The polymerizable composition of the present invention can 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-butyl catechol, phenothiazine and the like can be mentioned. These thermal polymerization inhibitors are used in an amount of 0.001 to 5 based on 100 parts by weight of the radical polymerizable compound (B).
It is preferably added in the range of 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, or a chain transfer catalyst 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, N-
Amines such as phenylglycine, triethanolamine and N, N-diethylaniline, U.S. Pat. No. 4,414,431
2, thiols described in JP-A-64-13144, disulfides described in JP-A-2-291561, thiones described in British Patent No. 3558322 and JP-A-64-17048, JP-A-2-291560. O-acylthiohydroxamate and N-alkoxypyridinethiones described in the above.

The polymerizable composition of the present invention may further contain, depending on the purpose, dyes, organic pigments, inorganic pigments, oxygen removing agents such as phosphine, phosphonate, phosphite, etc., reducing agents, antifoggants, anti-fading agents, antihalation agents. Agent, optical brightener,
Used by mixing with surfactants, colorants, plasticizers, flame retardants, antioxidants, dye precursors, ultraviolet absorbers, antifungal agents, antistatic agents, magnetic substances, organic solvents for dilution, etc. May be.

Therefore, various recording media such as photosensitive materials such as ink, printing plate material, photoresist, electrophotography, direct printing plate material, hologram material, and microcapsules, and adhesives are applied by coating on a substrate together with a binder and the like. , Adhesives, adhesives, sealants and various paints.

[0060]

The polymerization initiator (A) of the present invention acts very effectively as a radical polymerization initiator for the radically polymerizable compound (B), and its photoreaction mechanism is considered as follows. First, the thioxanthone moiety in the polymerization initiator (A) absorbs light to be in an excited state, so that an electron transfer reaction from a borate anion, which is a counter anion of the polymerization initiator (A), efficiently occurs. The resulting boranyl radical is decomposed to generate free radicals.
The free radicals generated here are considered to cause polymerization or crosslinking reaction of the radical polymerizable compound (B).

[0061]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the examples, “parts” means “parts by weight” unless otherwise specified. First, prior to the examples, synthesis examples of the above-described polymerization initiator (A) of the present invention will be described.

Synthesis Example 1 Synthesis of Compound (1) [2-Hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) propyl]
Dissolve 1.23 parts of trimethylammonium chloride in 50 parts of acetonitrile and, with stirring, add Lithium butylt
50 parts of an aqueous solution containing 1.00 part of riphenylborate
It was added dropwise at 25 ° C. over 0 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to give Compound (1)
1.47 parts were obtained.

Elemental analysis C ₄₁ H ₄₆ BNO ₃ S theoretical C, 76.50%; H, 7.20%; N, 2.18%; S, 4.98% found C, 76.61%; H, 7.41%; N, 2.20%; S, 5.01% Synthesis Example 2 Synthesis of Compound (2) Triethyl [2-hydroxy-3- (9-oxo-9H-thioxanthen-2-ylox)
y) propyl] ammonium chloride 1.37 parts are dissolved in 50 parts of acetonitrile, and while stirring, Lithium buty
50 parts of an aqueous solution containing 1.00 part of ltriphenylborate,
It was added dropwise at 25 ° C. over 10 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 1.74 parts of compound (2).

Elemental analysis C ₄₄ H ₅₂ BNO ₃ S Theoretical C, 77.06%; H, 7.64%; N, 2.04%; S, 4.68% Found C, 69.98%; H, 7.72%; N, 2.14%; S, 4.72% Synthesis Example 3 Synthesis of Compound (3) Tributyl [2-hydroxy-3- (9-oxo-9H-thioxanthen-2-ylox)
y) propyl] ammonium bromide 1.80 parts are dissolved in 50 parts of acetonitrile and, with stirring, Lithiumbutyltr
50 parts of an aqueous solution containing 1.00 part of iphenylborate
It was added dropwise at 25 ° C. over 0 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to give Compound (3)
2.1 parts were obtained.

Elemental analysis C ₅₀ H ₆₄ BNO ₃ S theoretical C, 78.00%; H, 8.38%; N, 1.82%; S, 4.16% found C, 78.12%; H, 8.51%; N, 1.93%; S, 4.23% Synthesis Example 4 Synthesis of Compound (4) Butyl [2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) pr
opyl] dimethylammonium chloride 1.40 parts are dissolved in 50 parts of acetonitrile, and while stirring, Lithium bu
50 parts of an aqueous solution containing 1.00 part of tyltriphenylborate was added dropwise at 25 ° C. over 10 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 1.61 parts of compound (4).

Elemental analysis C ₄₄ H ₅₂ BNO ₃ S Theoretical C, 77.06%; H, 7.64%; N, 2.04%; S, 4.68% Found C, 76.92%; H, 7.72%; N, 2.14%; S, 4.73% Synthesis Example 5 Synthesis of Compound (5) [3- (7-Chloro-9-oxo-9H-thioxanthen-2-yloxy) -2-hydro
Dissolve 1.35 parts of xypropyl] trimethylammonium chloride in 50 parts of acetonitrile and, with stirring, Lith
An aqueous solution 5 containing 1.00 parts of ium butyltriphenylborate
0 parts were added dropwise at 25 ° C. over 10 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 1.42 parts of compound (5).

Elemental analysis C ₄₁ H ₄₆ BNO ₃ S Theoretical C, 72.62%; H, 6.69%; N, 2.07%; S, 4.73% Found C, 72.72%; H, 6.81%; N, 2.13%; S, 4.81% Synthesis Example 6 Synthesis of Compound (6) [2-Hydroxy-3- (7-methyl-9-oxo-9H-thioxanthen-2-ylox
y) propyl] trimethylammonium chloride 1.28 parts are dissolved in 50 parts of acetonitrile and, with stirring, Lith
An aqueous solution 5 containing 1.00 parts of ium butyltriphenylborate
0 parts were added dropwise at 25 ° C. over 10 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 1.74 parts of compound (6).

Elemental analysis C ₄₂ H ₄₈ BNO ₃ S theoretical C, 76.70%; H, 7.36%; N, 2.13%; S, 4.88% found C, 76.78%; H, 7.41%; N, 2.19%; S, 4.91% Synthesis Example 7 Synthesis of Compound (7) [3- (7-Bromo-9-oxo-9H-thioxanthen-2-yloxy) -2-hydrox
Dissolve 1.50 parts of ypropyl] trimethylammonium chloride in 50 parts of acetonitrile and, with stirring,
Aqueous solution 50 containing 1.00 part of m butyltriphenylborate
The part was added dropwise at 25 ° C. over 10 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 1.37 parts of compound (7).

Elemental analysis C ₄₁ H ₄₅ BBrNO ₃ S theoretical C, 68.15%; H, 6.28%; N, 1.94%; S, 4.44% found C, 68.23%; H, 6.39%; N, 2.01%; S, 4.49% Synthesis Example 8 Synthesis of Compound (8) [2-Hydroxy-3- (7-methoxy-9-oxo-9H-thioxanthen-2-ylo
Dissolve 1.34 parts of xy) propyl] trimethylammonium chloride in 50 parts of acetonitrile and, with stirring, Lithium
An aqueous solution 5 containing 1.00 parts of ium butyltriphenylborate
0 parts were added dropwise at 25 ° C. over 10 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 1.78 parts of compound (8).

Elemental analysis C ₄₂ H ₄₈ BNO ₄ S Theoretical C, 74.88%; H, 7.18%; N, 2.08%; S, 4.76% Found C, 75.01%; H, 7.23%; N, 2.13%; S, 4.81% Synthesis Example 9 Synthesis of Compound (9) [2-Hydroxy-3- (4-methyl-9-oxo-9H-thioxanthen-2-ylox
y) propyl] trimethylammonium chloride 1.28 parts are dissolved in 50 parts of acetonitrile and, with stirring, Lith
An aqueous solution 5 containing 1.00 parts of ium butyltriphenylborate
0 parts were added dropwise at 25 ° C. over 10 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 1.61 parts of compound (9).

Elemental analysis C ₄₂ H ₄₈ BNO ₃ S Theoretical C, 76.70%; H, 7.36%; N, 2.13%; S, 4.88% Found C, 76.92%; H, 7.51%; N, 2.25%; S, 5.00% Synthesis Example 10 Synthesis of Compound (10) [3- (3,4-Dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -2-h
Dissolve 1.33 parts of ydroxypropyl] trimethylammonium chloride in 50 parts of acetonitrile and, with stirring,
50 parts of an aqueous solution containing 1.00 part of Lithium butyltriphenylborate was added dropwise at 25 ° C. over 10 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 1.62 parts of a compound (10).

Elemental analysis C ₄₃ H ₅₀ BNO ₃ S theoretical C, 76.88%; H, 7.50%; N, 2.09%; S, 4.77% found C, 76.92%; H, 7.62%; N, 2.14%; S, 4.81% Synthesis Example 11 Synthesis of Compound (11) [3- (5,7-Diethyl-9-oxo-9H-thioxanthen-2-yloxy) -2-hy
Dissolve 1.56 parts of droxypropyl] trimethylammonium bromide in 50 parts of acetonitrile.
50 parts of an aqueous solution containing 1.00 part of thium butyltriphenylborate was added dropwise at 25 ° C. over 10 minutes. The generated pale yellow crystals are filtered, washed with distilled water, and dried under reduced pressure.
1.58 parts of compound (11) were obtained.

Elemental analysis C ₄₅ H ₅₄ BNO ₃ S Theoretical C, 77.23%; H, 7.78%; N, 2.00%; S, 4.58% Found C, 77.43%; H, 7.83%; N, 2.09%; S, 4.62% Synthesis Example 12 Synthesis of Compound (12) [3- (5,7-Diethyl-4-methyl-9-oxo-9H-thioxanthen-2-yl
oxy) -2-hydroxypropyl] trimethylammonium bromide
61 parts were dissolved in 50 parts of acetonitrile, and 50 parts of an aqueous solution containing 1.00 part of Lithium butyltriphenylborate was added dropwise at 25 ° C. over 10 minutes with stirring. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 1.70 parts of compound (12).

Elemental analysis C ₄₆ H ₅₆ BNO ₃ S theoretical C, 77.40%; H, 7.91%; N, 1.96%; S, 4.49% found C, 77.54%; H, 8.01%; N, 2.03%; S, 4.54% Synthesis Example 13 Synthesis of Compound (13) [2-Hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) propyl]
Dissolve 1.64 parts of trimethylammonium chloride in 50 parts of acetonitrile and, with stirring, add Lithium butylt
50 parts of an aqueous solution containing 1.50 parts of ris (p-tolyl) borate was added dropwise at 25 ° C. over 10 minutes. The resulting pale yellow crystals were filtered, washed with distilled water, and dried under reduced pressure to obtain 2.37 parts of compound (13).

Elemental analysis C ₄₄ H ₅₂ BNO ₃ S Theoretical C, 77.06%; H, 7.64%; N, 2.04%; S, 4.68% Found C, 77.13%; H, 7.71%; N, 2.09%; S, 4.71% Synthesis Example 14 Synthesis of compound (14) [2-Hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) propyl]
Dissolve 1.64 parts of trimethylammonium chloride in 50 parts of acetonitrile and, with stirring, add Lithium butylt
50 parts of an aqueous solution containing 1.55 parts of ris (m-fluorophenyl) borate was added dropwise at 25 ° C. over 10 minutes. The generated pale yellow crystals are filtered, washed with distilled water, and dried under reduced pressure.
2.61 parts of compound (14) were obtained.

Elemental analysis C ₄₁ H ₄₆ BF ₃ NO ₃ S Theoretical C, 70.58%; H, 6.21%; N, 2.01%; S, 4.60% Found C, 70.65%; H, 6.35%; N, 2.11 %; S, 4.59% Example 1 Using a bar coater, a polymerizable composition comprising 3 parts of compound (1) as the polymerization initiator (A) and 100 parts of pentaerythritol triacrylate as the radical polymerizable compound (B) was used. To a thickness of about 10 μm on an aluminum plate,
UV irradiator (Metal halide lamp 3 manufactured by Toshiba Corporation)
When irradiated with a KW2 lamp at 120 W / cm, irradiation distance of 180 mm) at a conveyor speed of 30 m / min, the polymerizable composition was completely cured, and a tack-free cured film was obtained.

Examples 2 to 14 The same procedure as in Example 1 was conducted, except that the polymerization initiator (A) shown in Table 1 was used instead of 3 parts of the compound (1) in Example 1. Experiments were performed, and in each case, a tack-free cured film was obtained.

Table 1 Example Polymerization Initiator (A) Example Polymerization Initiator (A) ──────────────────────── 2 Compound (2) 9 Compound (9) 3 Compound (3) 10 Compound (10) 4 Compound (4) 11 Compound (11) 5 Compound (5) 12 Compound (12) 6 Compound (6) 13 Compound (13) 7 Compound (7) 14 Compound (14) 8 Compound (8)例 Comparative Examples 1 to 5 Instead of compound (1) in Example 1, compounds (15) to (19) which are known photopolymerization initiators are used. ) (Where Ph represents a phenyl group and Bu represents a butyl group), and a tack-free cured product was not obtained.

Compound (15)

[0080]

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Compound (16)

[0082]

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Compound (17)

[0084]

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Compound (18)

[0086]

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Compound (19)

[0088]

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Examples 15 to 30 The same procedures as in Example 1 were carried out except that the radical polymerizable compound (B) shown in Table 2 was used instead of 100 parts of pentaerythritol triacrylate in Example 1. Experiments were performed by operation, and in each case, a tack-free cured film was obtained.

Table 2 Example Radical polymerizable compound (B) ───────────────15 Trimethylol propyl triacrylate 16 2-Ethylhexyl acrylate 17 2-Hydroxyethyl acrylate 18 1,6-Hexane diol acrylate 19 Ethylene glycol acrylate 20 Polyphenylene alcohol Acrylates 21 Pentaerythritol acrylate 22 Pentaerythritol tetraacrylate 23 Dipentaerythritol hexaacrylate 24 2-Ethylhexyl methacrylate 25 Plastic methacrylate 26 1,6-Hexanediol methacrylate 27 Plastic ethylene methacrylate DOO 28 Torimechirorufu ° Ropa down trimethacrylate 29 Bu diallyl phthalate 30 triallyl trimellitate ─────────────────────────

[0091]

The polymerization initiator (A) of the present invention is effective as a polymerization initiator for the radically polymerizable compound (B), and the polymerizable composition comprising these has good physical properties upon irradiation with light. It is possible to obtain a cured product. Therefore,
The polymerizable composition of the present invention includes a molding resin, a casting resin, a sealing agent, a dental polymerization resin, an optical molding resin, a resist for a printed circuit board, a resist for a color filter, a dry film resist, a resist for microelectronics, and a printing plate. Resin, photosensitive ink jet, ink for printing (offset, gravure, silk screen), color proof for print proofing, paint, surface coating agent, adhesive, adhesive, release agent, hologram recording material, etc. Can be used for material.

Claims (1)

[Claims] 1. A polymerization initiator (A) represented by the general formula (1)
And a radical polymerizable compound (B). General formula (1) (However, R ¹ and R ⁴ are primary alkyl groups having 1 to 8 carbon atoms, R ² and R ³ are halogen groups, alkyl groups having 1 to 6 carbon atoms, alkoxyl groups having 1 to 6 carbon atoms, and Ar is aryl Group, p represents an integer of 0 to 3, and q represents an integer of 0 to 4.)