JPH06263809A - Liquid curable resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin composition having a shortened curing time by mixing a compound having at least one polymerizable ethylenic unsaturation with a polymerization initiator and at least one organophosphorus compound selected among a plurality of compounds represented by specified formulas.

CONSTITUTION: A urethane (meth)acrylate polymer is mixed with a reactive diluent as an ethylenically unsaturated compound such as N-vinylpyrrolidone, a 0.1-10 wt.%, based on the resin composition, heat polymerization initiator (e.g. benzoyl peroxide) and/or a photopolymerization initiator (e.g. benzophenone). Next, the obtained mixture is mixed with 0.1-10 wt.%, based on the resin composition, at least one organophosphorus compound represented by formula I (wherein R¹ is an alkyl, a cycloalkyl, an aryl or an aralkyl), formula II (wherein R¹ is an alkyl, an aryl or an aralkyl; R² and R⁴ are each H, an alkyl, an aryl or an aralkyl; and X is a halogen) or formula III (wherein R¹ is an alkyl, an aryl or an aralkyl; and R² to R⁴ are each H, an alkyl, an aryl or an aralkyl) to obtain a liquid curable resin composition having a viscosity of 200-20,000 cP at 25°C.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid curable resin composition having a high curing rate, excellent durability after curing and excellent adhesion to various substrates. Such a liquid curable resin composition is used for plastic, wood, ceramics, glass,
It is useful as a protective coating material such as paper, or as a photo-molding material, a three-dimensional solid molding material, a printing plate material, etc., and has a fast curing speed and excellent durability after curing, so it is suitable as an optical fiber coating material. is there.

[0002]

2. Description of the Related Art Normally, the surface of an optical fiber is coated with a resin for the purpose of protecting and reinforcing the optical fiber strand. The resin coating of such an optical fiber wire is performed immediately after the hot melt spinning of the glass fiber, and the coating structure of the optical fiber has a flexible primary coating layer on the surface of the optical fiber and a secondary coating layer on the outside thereof. A structure provided with is known.

The following characteristics are required for the coating material used for coating the resin on such an optical fiber wire. (1) Liquid at room temperature and high workability, (2) Fast curing and good productivity, (3) Little change in physical properties due to wide temperature change, (4) Heat resistance Excellent hydrolysis resistance, (5) little change in physical properties over time, and long-term reliability (storage stability),
(6) Excellent resistance to chemicals such as acids and alkalis, (7) Low hygroscopicity and water absorption, (8)
Excellent light resistance, (9) excellent oil resistance, (10) small amount of hydrogen gas that adversely affects the optical fiber, (11) excellent yellowing resistance (heat, light) By the way, in recent years, in the process of manufacturing an optical fiber cable, it has been required to reduce the time required for coating the surface of the optical fiber wire with a resin from the viewpoint of cost and productivity. As a method of shortening the time required to coat the surface of the optical fiber strand with a resin, a method of shortening the coating treatment time by improving manufacturing equipment, and a method of changing the composition of the liquid curable resin composition to shorten the curing time (higher There are two methods of increasing the curing speed). Among these, as a method of shortening the curing time of the liquid curable resin composition, a method of adding a larger amount of a polymerization initiator, a method of increasing the initiation efficiency by using a more active polymerization initiator, or a sensitizer A method of increasing the activity of the initiator by combining it with a polymerization initiator has been studied.

[0004]

However, since the polymerization initiator and the sensitizer are generally expensive, in terms of cost,
It has been difficult to mix a certain amount or more with the liquid curable resin composition. Therefore, a liquid curable resin composition that sufficiently satisfies the fast curability required for improving productivity has not been found.

The present invention has been made in view of the above-mentioned prior art, has a low viscosity at room temperature, is excellent in workability when coating the surface of an optical fiber element wire, and has long-term storage stability. Good, fast curing speed, low hydrogen gas generation, good UV resistance, heat resistance, light yellowing resistance, heat yellowing resistance, oil resistance, and adhesion to various substrates. An object of the present invention is to provide a liquid curable resin composition capable of forming an excellent coating film. In particular, the present invention provides a liquid curable resin composition for an optical fiber coating material, which exhibits appropriate adhesion to the optical fiber strand and can shorten the time required to coat the surface of the optical fiber strand. It is an object.

[0006]

That is, a liquid curable resin composition according to the present invention comprises [A] a compound having at least one ethylenically unsaturated bond having a polymerization ability,
[B] a polymerization initiator and [C] at least one organic phosphorus compound selected from the group consisting of compounds represented by the following formulas [I] to [III]:

[0007]

[Chemical 4]

(In the formula, R ¹ is an alkyl group which may have a substituent, a cycloalkyl group, an aryl group or an alkoxy group, and R ² and R ³ are each independently hydrogen or a substituent. An alkyl group which may have, a cycloalkyl group, an aryl group or an alkoxy group),

[0009]

[Chemical 5]

(In the formula, R ¹ is an alkyl group which may have a substituent, an aryl group or an aralkyl group, and R ² to
R ⁴ is each independently hydrogen, or an optionally substituted alkyl group, aryl group or aralkyl group, and X is halogen),

[0011]

[Chemical 6]

(In the formula, R ¹ is an alkyl group which may have a substituent, an aryl group or an aralkyl group, and R ² to
R ⁴ is independently hydrogen, or an optionally substituted alkyl group, aryl group, or aralkyl group).

Hereinafter, [A] a compound having at least one ethylenically unsaturated bond having polymerization ability, [B] a polymerization initiator, and [C] an organophosphorus compound which form the liquid curable resin composition of the present invention. Will be specifically described.

The compound [A] having at least one ethylenically unsaturated bond having polymerization ability used in the present invention is a polymer having at least one ethylenically unsaturated bond having polymerization ability, and a compound having polymerization ability. Examples thereof include monomers having at least one ethylenically unsaturated bond. The compound [A] having at least one ethylenically unsaturated bond having polymerization ability can be used alone or in combination of two or more kinds.

Examples of the polymer having at least one ethylenically unsaturated bond having a polymerization ability include urethane (meth) acrylate polymer, polyester (meth) acrylate, epoxy (meth) acrylate polymer, polyamide (meth) acrylate and (meth). Examples thereof include a siloxane polymer having an acryloyloxy group. These can be used alone or in combination of two or more.

The urethane (meth) acrylate polymer can be produced by reacting the polyol compound (a), the polyisocyanate compound (b) and the hydroxyl group-containing (meth) acrylate compound (c).

As the polyol compound (a), polyethylene polyol, polypropylene polyol, polytetramethylene polyol, polyheptamethylene polyol, polyhexamethylene polyol, polydecamethylene polyol, or two or more kinds of ion-polymerizable cyclic compounds are opened. Examples thereof include polyether polyols obtained by copolymerization.

Here, as the ionically polymerizable cyclic compound,
Ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl Methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether,
Examples include cyclic ethers such as glycidyl benzoate.

Specific combinations of the above-mentioned two or more kinds of ion-polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene. Examples thereof include a combination of oxide and ethylene oxide. The ring-opening copolymer of these ion-polymerizable cyclic compounds may be bonded randomly.

The above-mentioned polyether polyols are, for example, PTMG1000, PTMG2000 (all manufactured by Mitsubishi Kasei Co., Ltd.), PPG1000 and EXCENOL202.
0, EXCENOL 1020 (all manufactured by Asahi Ohrin Co., Ltd.),
PEG1000, Unisafe DC1100, Unisafe DC1800 (above manufactured by NOF Corporation), PPTG200
0, PPTG1000, PTG400, PTG650,
PTGL2000, PTGL4000 (above Hodogaya Chemical Co., Ltd.), Z-4441-1, PBG2000A, PBG
2000B, Z-3001-4, Z-3001-5, Z-3
It can also be obtained as a commercial product such as 001-9, Z-3001-15 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

As the polyol compound (a), the above ionic polymerizable cyclic compound, cyclic imines such as ethyleneimine, cyclic lactone acids such as β-propiolactone and glycolic acid lactide, or dimethylcyclopolysiloxanes. It is also possible to use a polyether diol obtained by ring-opening copolymerization of and.

In addition to the above polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, etc. can also be used, and these polyols can also be used in combination with the polyether polyols. The mode of polymerization of these constituent units is not particularly limited and may be random polymerization, block polymerization or graft polymerization.

Examples of polyester polyols include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol. , 3-methyl-
1,5-pentanediol, 1,9-nonanediol, 2-methyl
Polyester polyols obtained by reacting polyhydric alcohols such as -1,8-octanediol with polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid Mention may be made of, for example, Clapor P-2010, PMIP.
A, PKA-A, PKA-A2, PNA-200 (all manufactured by Kuraray Co., Ltd.) and the like are commercially available.

Examples of the polycarbonate polyol include 1,6-hexane polycarbonate and the like. DN-980, DN-981, DN-982, DN-
983 (Nippon Polyurethane Co., Ltd.), PC-8000
(Manufactured by PPG Company, USA) and the like.

Further, as polycaprolactone polyol, ε-caprolactone and, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, tetramethylene glycol, polytetramethylene glycol, 1,
Examples thereof include polycaprolactone diol obtained by reacting a polyol such as 2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol. These diols include Praxel 205, Praxel 205AL, Praxel 212, and Praxel 212A.
L, Praxel 220AL (all manufactured by Daicel) and the like are commercially available.

Many polyols not included in the above can also be used. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol,
1,4-cyclohexanedimethanol, bisphenol A ethylene oxide addition diol, bisphenol A butylene oxide addition diol, bisphenol F ethylene oxide addition diol, bisphenol F butylene oxide addition diol, hydrogenated bisphenol A ethylene oxide addition diol, Butylene oxide addition diol of hydrogenated bisphenol A, ethylene oxide addition diol of hydrogenated bisphenol F, butylene oxide addition diol of hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol, β-methyl-δ-valero Lactone,
Examples thereof include hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane terminal diol compound, and polydimethylsiloxane carbitol-modified polyol.

Besides the above-mentioned polyols, it is also possible to use diamines together with the polyols. As the diamines, ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4'- Examples include diamines such as diaminodiphenylmethane, diamines containing a hetero atom, and polyether diamines.

Among these polyols, PTMG100
0, PTMG2000 (all manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), PP
G1000, EXCENOL2020, EXCENOL
1020 (all manufactured by Asahi Ohrin Co., Ltd.), PEG1000, P
PTG2000, PPTG1000, PTG400, P
TG650, PTGL2000, PTGL4000 (above Hodogaya Chemical Co., Ltd.), Z-4441-1, PBG20
00A, PBG2000B, Z-3001-4, Z-3
001-5, Z-3001-9, Z-3001-15
(All manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Curapol P-2010,
PNA-2000 (all manufactured by Kuraray Co., Ltd.), DN-980,
DN-981, DN-982, DN-983 (all manufactured by Nippon Polyurethane Co., Ltd.), PLAXEL 205, PLAXEL 2
05AL, Praxel 212, Praxel 212AL,
Praxel 220, Praxel 220AL (all manufactured by Daicel), bisphenol A ethylene oxide addition diol, bisphenol F ethylene oxide addition diol, dicyclopentadiene dimethylol compound, tricyclodecane dimethanol, β-methyl-δ-
Valerolactone and the like are preferable.

The number average molecular weight of these polyols is preferably 200 to 10,000, and particularly preferably 500 to 8,000.
Examples of the polyisocyanate compound (b) include 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hydrogenated xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p- Phenylene diisocyanate, 3,3 '
-Dimethyl-4,4'-diphenylmethane diisocyanate,
4,4'-diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), 2, 2,4-trimethylhexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, bis (2-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate and the like, In particular, 2,4-tolylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,3-xylylene diisocyanate, hydrogenated xylylene diisocyanate, 4,4'- Diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate are preferred.

These polyisocyanate compounds (b)
Can be used alone or in combination of two or more. Hydroxyl group-containing (meth) acrylate compound (c)
As, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate,
1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate,
4-hydroxycyclohexyl (meth) acrylate, 1,
6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, and the following formula [IV]

[0031]

[Chemical 7]

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and n represents a number of 1 to 15, preferably 1 to 4.)
And a compound obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate with (meth) acrylic acid. You can

Of these, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth)
Acrylate and the like are preferred. These hydroxyl group-containing (meth) acrylate compounds (c) can be used alone or in combination of two or more.

The molecular weight of the urethane (meth) acrylate polymer is usually 500 to 20000, preferably 7
It is preferably in the range of 00 to 12000 (number average molecular weight).

A monomer having at least one ethylenically unsaturated bond having a polymerization ability (also referred to as a reactive diluent)
Examples include monofunctional compounds and polyfunctional compounds. Examples of the monofunctional compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl ( (Meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl ( (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , Isodecyl (meth) acrylate, undecyl (meth) acrylate,
Dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) Acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylate, methoxy polypropylene glycol (meth) acrylate,
Dicyclopentadiene (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, diacetone (meth) Acrylamide, isobutoxymethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N,
N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N- Vinyl ethers such as diethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, maleic acid esters, fumar Examples thereof include acid esters and compounds represented by the following formulas [V] to [VII].

[0036]

[Chemical 8]

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁸ represents a hydrogen atom or 1 to 1 carbon atoms.
2, preferably 1 to 9 alkyl groups, m is 0 to 1
2, preferably a number of 1-8. )

[0038]

[Chemical 9]

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁹ represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, and p represents 1 to 8, preferably 1 to 4 Indicates the number of.)

[0040]

[Chemical 10]

(Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁹ represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, p represents 1 to 8, preferably 1 to 4) The commercially available product is Aronix M11.
1, M113, M114, M117 (all manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD TC110S, R62
9, R644 (all manufactured by Nippon Kayaku Co., Ltd.), IBXA, and VISCOAT 3700 (all manufactured by Osaka Organic Chemical Co., Ltd.).

Examples of the polyfunctional compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth). ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2 -Hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol Diglycidyl ether (meth) acrylate added was epoxy (meth) acrylate, and triethylene glycol divinyl ether. Commercially available products include Copimer UV and S
A1002, SA2007 (all manufactured by Mitsubishi Petrochemical Co., Ltd.), Viscoat 700 (manufactured by Osaka Organic Chemical Company), KAYARADR
-604, DPCA-20, -30, -60, -120, H
X-620, D-310, D-330 (Nippon Kayaku Co., Ltd.), Aronix M-210, M-215, M-31
5, M-325 (all manufactured by Toagosei Chemical Industry Co., Ltd.) and the like.

As the polymerization initiator [B] used in the present invention, a radical polymerization initiator such as a thermal polymerization radical polymerization initiator or a photopolymerization radical initiator is usually used. Examples of the thermal polymerization radical polymerization initiator include peroxides and azo compounds, and specific examples include benzoyl peroxide, t-butyl-oxybenzoate,
Examples thereof include azobisisobutyronitrile.

As the photopolymerization radical initiator, 1-
Hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone,
Fluorenone, fluorene, 3-methylacetophenone, benzophenone, 4-chlorobenzophenone, 4,
4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-
Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [ 4- (methylthio) phenyl]
-2-morpholino-propan-1-one, 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide, commercially available IRUGACURE 184,65
1,500,907, CGI369, CG24-61
(These are made by Ciba Geigy), Lucirine LR87
28, Initiator 654 (all manufactured by BASF), Darocure 1116, 1173 (all manufactured by Merck), Yubecryl P36 (manufactured by UCB) and the like. These are used together with a photosensitizer as needed.

Among these, benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, thioxanthone, IRUGACURE 184,651,907, CG
I369, CG24-61 (all manufactured by Ciba Geigy),
Lucirine LR8728, Initiator6
54 (above manufactured by BASF), Darocure111
6,1173 (Merck)
(Manufactured by UCB) and the like are preferable.

These polymerization initiators [B] are optionally used together with a photosensitizer. As the photosensitizer, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, Ubecryl P102, 103, 104, manufactured by UCB
105 and the like.

These polymerization initiators and photosensitizers can be used alone or in combination of two or more. The polymerization initiator is preferably added in an amount of 0.1 to 10% by weight, preferably 0.3 to 6% by weight, based on the liquid curable resin composition of the present invention.

The liquid curable resin composition according to the present invention is a composition comprising [A] a compound having at least one ethylenically unsaturated bond having polymerization ability and [B] a polymerization initiator. Is blended with an organophosphorus compound selected from the group consisting of compounds represented by the following formulas [I] to [III].

[0049]

[Chemical 11]

In the above formula [I], R ¹ is an alkyl group which may have a substituent, a cycloalkyl group, an aryl group or an alkoxy group, and R ² and R ³ are each independently hydrogen, Alternatively, they are an alkyl group which may have a substituent, a cycloalkyl group, an aryl group and an alkoxy group.

Specific examples of the alkyl group include a methyl group, an ethyl group, a butyl group and the like. These are --P.
It may have a substituent such as (C ₆ H ₅ ) ₂ . Examples of the cycloalkyl group include a cyclohexyl group, and these cycloalkyl groups may have a substituent.

Examples of the aryl group include a phenyl group and a tolyl group, which may have a substituent such as an alkoxy group such as a methoxy group. A methoxy group etc. are mentioned as an alkoxy group, and these alkoxy groups may have a substituent.

Specific examples of the organophosphorus compound represented by the formula [I] include tris (methylphenyl) phosphine, tris (methoxyphenyl) phosphine, triphenylphosphine, tributylphosphine, tricyclohexylphosphine and methyl. Examples thereof include tertiary phosphine compounds such as diphenylphosphine and methoxydiphenylphosphine, secondary phosphine compounds such as butylphenylphosphine and diphenylphosphine, and primary phosphine compounds such as phenylphosphine.
Further, 1,2-bis (diphenylphosphino) ethane, bis (diphenylphosphino) methane and the like can be mentioned.

Of these, a tertiary phosphine compound is preferable, and specifically, triphenylphosphine, tris (methylphenyl) phosphine, tris (methoxyphenyl) phosphine, methyldiphenylphosphine, methoxydiphenylphosphine and the like are preferable,
Particularly, triphenylphosphine, methyldiphenylphosphine and methoxydiphenylphosphine are preferable.

[0055]

[Chemical 12]

In the above formula [II], R ¹ is an alkyl group which may have a substituent, an aryl group, an aralkyl group or the like, and R ^{2 to} R ⁴ are each independently hydrogen or a substituent. Examples thereof include an alkyl group which may have a group, an aryl group and an aralkyl group, and X is halogen.

Specific examples of the alkyl group include a methyl group, an ethyl group and a butyl group, and these alkyl groups may have a substituent. A phenyl group etc. are mentioned as an aryl group, and these aryl groups may have a substituent.

Examples of the aralkyl group include a benzyl group, and these aralkyl groups may have a substituent. Examples of halogen include chlorine and bromine.

Specific examples of the organophosphorus compound represented by the formula [II] include tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, methyltriphenylphosphonium bromide,
Examples thereof include ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide and benzyltriphenylphosphonium chloride. Among these, those derived from triarylphosphine are preferable, and tetraphenylphosphonium bromide, butyltriphenylphosphonium bromide, and benzyltriphenylphosphonium chloride are particularly preferable.

The organophosphorus compound represented by the formula [II] is easily obtained by a quaternization reaction of the organophosphorus compound represented by the formula [I] and an alkyl halide, and is used in the quaternization reaction. Examples of the halide include alkyl chloride and alkyl bromide, and are not particularly limited as long as they are compounds capable of forming a phosphonium salt.

[0061]

[Chemical 13]

In the above formula [III], R ¹ is an alkyl group, an aryl group or an aralkyl group which may have a substituent, and R ^{2 to} R ⁴ are each independently hydrogen or a substituent. An alkyl group which may have, an aryl group,
It is an aralkyl group.

Specific examples of the alkyl group include a methyl group, an ethyl group, a butyl group and an octyl group.
These alkyl groups may have a substituent. Examples of the aryl group include a phenyl group and a tolyl group, which may be substituted with halogen such as chlorine or -CN.

Examples of the aralkyl group include a benzyl group and the like, and these aralkyl groups may have a substituent. Specific examples of the organophosphorus compound represented by the formula [III] include tetraphenyldiphosphine dioxide, tetra (p-tolyl) diphosphine dioxide, and 1,2-di (p-chlorophenyl) -1. , 2-diphenyldiphosphine dioxide, 1,2-di (p-cyanophenyl) -1,2-diphenyldiphosphine dioxide,
Examples thereof include tetrabenzyl diphosphine dioxide and tetraoctyl diphosphine dioxide. Of these, tetraaryldiphosphine dioxide is preferable, and tetraphenyl diphosphine dioxide is particularly preferable.

The organophosphorus compound represented by the formula [III] is
It can be obtained by dimerization accompanied by oxidation of dialkylphosphinas chloride, and its production method is described in the literature (L.
D. Quin et al., J. Org. Chem., 31, 1206 (1966)). Further, in the formula [III], when R ¹ and R ³ and R ² and R ⁴ are the same, it can be obtained from one kind of dialkylphosphinas chloride, and R ¹ and R ³ and R 4 can be obtained.
^{When 2} and R ⁴ are different, they can be obtained from two kinds of dialkylphosphinas chlorides.

These [C] organophosphorus compounds may be used alone or in combination of two or more. Such a [C] organophosphorus compound is used for the purpose of promoting curing.
It is used by uniformly mixing or dissolving [A] a compound having at least one ethylenically unsaturated bond having polymerization ability and [B] a polymerization initiator. The [C] organophosphorus compound is preferably added in an amount of 0.1 to 10% by weight, preferably 0.3 to 6% by weight, based on the liquid curable resin composition. If the amount of the [C] organophosphorus compound added to the liquid curable resin composition is too large, the curing rate of the composition may decrease. On the other hand, if the compounding amount of the [C] organophosphorus compound is too small, the effect is insufficient.

The liquid curable resin composition of the present invention contains, as other additives, epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene block copolymer. Even if compounded, styrene / ethylene / butene / styrene block copolymer, styrene / isoprene / styrene block copolymer, petroleum resin, xylene resin, ketone resin, fluorine-based oligomer, silicone-based oligomer, polysulfide-based oligomer, etc. Good.

In the liquid curable resin composition of the present invention, various additives other than the above, for example, antioxidants, colorants, ultraviolet absorbers, light stabilizers, silane coupling agents,
If necessary, a thermal polymerization inhibitor, a leveling agent, a surfactant, a storage stabilizer, a plasticizer, a lubricant, a solvent, a filler, an antiaging agent, a wettability improving agent, a coating surface improving agent and the like may be added.

Commercially available antioxidants include I
rganox 1010, 1035, 1076, 122
2 (above manufactured by Ciba Geigy) and the like. Examples of the ultraviolet absorber include Tinuvin P, 234, 320,
326, 327, 328, 213 (all manufactured by Ciba Geigy), Sumisorb 110, 130, 140, 2
20, 250, 300, 320, 340, 350, 40
0 (all manufactured by Sumitomo Chemical Co., Ltd.) and the like. Examples of commercially available light stabilizers include Tinuvin 292, 144,
622LD (above Ciba Geigy) Sanor LS-7
70, 765, 292, 2626, 1114, 744
(Manufactured by Sankyo Kasei Kogyo Co., Ltd.) and the like, and as the silane coupling agent, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, commercially available products include SH6062, 6030 (manufactured by Toray Silicone Co., Ltd.), KBE903, 603, 403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
nightgene W, S, P, 3C, 6C, RD-G,
FR, AW (all manufactured by Sumitomo Chemical Co., Ltd.) and the like can be mentioned.

Further, to the liquid curable resin composition of the present invention, other radiation-curable polymers, reactive diluents and other additives may be added within a range that does not impair the effects of the composition.

The liquid curable resin composition of the present invention is cured by heating and / or irradiation with radiation. In the present invention, radiation means ionizing radiation such as infrared rays, visible rays, ultraviolet rays and X-rays, electron beams, α rays, β rays, γ rays.

The liquid curable resin composition of the present invention can be produced by mixing the above-mentioned components by a conventional method. The viscosity of the liquid curable resin composition of the present invention thus obtained is usually 200 to 20000 cp / 25 ° C, preferably 2000 to 15000 cp / 25 ° C.

[0073]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

In the following examples, "parts" means parts by weight.

[0075]

[Synthesis example of urethane acrylate]

[Synthesis of Urethane Acrylate [A-1]] To a reaction vessel equipped with a stirrer, manufactured by Toagosei Kagaku Kogyo Co., Ltd., trade name Aronix M113; 100 g, 2,4-tolylene diisocyanate; 70.2 g, dibutyltin dilaurate; 1 g and 2,6-di-t-butyl-methylphenol as a polymerization inhibitor;
0.3 g was charged. Copolymerized diol of ethylene oxide having a number average molecular weight of 4000 and 1,2-butylene oxide (ethylene oxide: 1,2-butylene oxide = 3: 7 (weight ratio) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name PBG
2000B); 1153.0 g was added while keeping the temperature at 40 to 50 ° C., and the mixture was reacted for 2 hours. Next, add 26.8 g of hydroxyethyl acrylate, and 50-60 ° C.
After continuing stirring for 5 hours, the reaction was terminated to obtain urethane acrylate [A-1] having a number average molecular weight of about 10800.

[Synthesis of Urethane Acrylate [A-2]]
In a reaction vessel equipped with a stirrer, isophorone diisocyanate; 158.2 g, a copolymer of ethylene oxide and 1,2-butylene oxide having a number average molecular weight of 2052 (ethylene oxide: 1,2-butylene oxide = 3: 7 (weight Ratio) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name PBG2000A);
1044.6 g and 2,6-di-t-butyl-methylphenol; 0.3 g as a polymerization inhibitor were charged. This was cooled to 15 ° C. in an ice-water bath, dibutyltin dilaurate (1 g) was added thereto to start the reaction, and the reaction was carried out for 2 hours while maintaining the temperature at 30 to 40 ° C. Next, 47.2 g of hydroxyethyl acrylate was added, and after stirring at 50 to 60 ° C. for 5 hours, the reaction was terminated to obtain urethane acrylate [A-2] having a number average molecular weight of about 6140.

[Synthesis of Urethane Acrylate [A-3]]
A reaction vessel equipped with a stirrer was charged with 170.0 g of isophorone diisocyanate, 1 g of dibutyltin dilaurate, and 0.3 g of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor. Next, 59.2 g of hydroxyethyl acrylate was added while controlling the temperature at 20 ° C. or lower. After the addition, the mixture was further stirred at 10 to 20 ° C. for 1 hour, and then tetrahydrofuran-propylene oxide copolymer diol having a number average molecular weight of 2000 (tetrahydrofuran: propylene oxide = 3: 7 (weight ratio) manufactured by Hodogaya Chemical Industry Co., Ltd., product Name PPTG2000);
1020.8 g was added keeping the temperature at 40-50 ° C. Then, after continuing stirring at 50 to 60 ° C. for 5 hours, the reaction was terminated to obtain a urethane acrylate [A-3] having a number average molecular weight of about 4900.

[Synthesis of Urethane Acrylate [A-4]]
A reaction vessel equipped with a stirrer was charged with 331.1 g of isophorone diisocyanate, 1 g of dibutyltin dilaurate and 1 g of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor. Next, 173.0 g of hydroxyethyl acrylate was added while controlling the temperature below 20 ° C. After the addition, the mixture was further stirred at 10 to 20 ° C. for 1 hour, and then polytetramethylene glycol having a number average molecular weight of 1000;
It was added while keeping at 0 ° C. Then 5 at 50-60 ° C
After continuing stirring for an hour, the reaction was terminated to obtain a urethane acrylate [A-4] having a number average molecular weight of about 1680.

[Synthesis of Urethane Acrylate [A-5]]
In a reaction vessel equipped with a stirrer, trade name IBXA manufactured by Osaka Organic Chemical Co., Ltd .; 100 g, 2,4-tolylene diisocyanate;
562.0 g, dibutyltin dilaurate; 1 g and, as a polymerization inhibitor, 2,6-di-t-butyl-4-methylphenol; 0.3 g were charged. Next, 374.7 g of hydroxyethyl acrylate was added while controlling the temperature at 20 ° C. or lower. After the addition, the mixture was further stirred at 10 to 20 ° C. for 1 hour, and then tricyclodecane dimethanol having a number average molecular weight of 194 (manufactured by Mitsubishi Petrochemical, trade name TCDD
M); 313.3 g was added keeping the temperature at 40-50 ° C. Then, after continuing stirring at 50 to 60 ° C. for 5 hours, the reaction was terminated to obtain a urethane acrylate [A-5] having a number average molecular weight of about 774.

[0080]

[Example of liquid composition]

[B-1] Mixing Example of Liquid Composition In a reaction vessel equipped with a stirrer, urethane acrylate [A-1]; 55 parts, Aronix M113; 30 parts as a reaction diluent, Kayarad TC110S (Nippon Kayaku Co., Ltd.) Manufactured); 8.
5 parts, vinylpyrrolidone; 5 parts, Irganox 1035 (manufactured by Ciba Geigy);
3 parts, Sumisorb 110 (manufactured by Sumitomo Chemical Co., Ltd.) as an ultraviolet absorber; 0.1 part, diethylamine; 0.1 part as a photosensitizer, and 1 part of a silane coupling agent (manufactured by Torre Silicone, trade name SH6062) Is stirred and mixed at 50 to 60 ° C., and the viscosity is 6700 cp / 2.
A transparent liquid composition [B-1] at 5 ° C was obtained.

[Example of [B-2] of liquid composition] In a reaction vessel equipped with a stirrer, urethane acrylate [A-2]; 55 parts, Aronix M113; 25 parts, isobornyl acrylate; 13.5 Parts, vinylpyrrolidone; 5 parts, Irganox 1035 (manufactured by Ciba Geigy);
3 parts, diethylamine; 0.1 part, and SH6062; 1 part were mixed with stirring at 50 to 60 ° C., and the viscosity was 3000 cp / 2.
A transparent liquid composition [B-2] at 5 ° C. was obtained.

[B-3] Mixing Example of Liquid Composition In a reaction vessel equipped with a stirrer, urethane acrylate [A-3]; 60.5 parts, Aronix M113; 37 parts, vinylpyrrolidone; 6.5 Part, Irganox 1035 (manufactured by Ciba Geigy);
3 parts, diethylamine; 0.1 part, and SH6062; 1 part were mixed with stirring at 50 to 60 ° C., and the viscosity was 2500 cp / 2.
A transparent liquid composition [B-3] at 5 ° C was obtained.

[B-4] Formulation example of liquid composition In a reaction vessel equipped with a stirrer, urethane acrylate [A-4]; 60 parts, tricyclodecane dimethanol diacrylate;
5 parts, isobornyl acrylate; 10 parts, N-vinylpyrrolidone; 10 parts, and Irganox 1035; 0.3 parts are stirred and mixed at 50 to 60 ° C., and the viscosity is 2000 cp / 2.
A transparent liquid composition [B-4] at 5 ° C was obtained.

[Compounding Example of Liquid Composition [B-5]] In a reaction vessel equipped with a stirrer, urethane acrylate [A-4]; 30 parts, urethane acrylate [A-5]; 25 parts, tricyclodecanediene Methanol diacrylate; 21.
5 parts, isobornyl acrylate; 15 parts, N-vinylpyrrolidone; 10 parts, and Irganox 1035; 0.3 parts are stirred and mixed at 50 to 60 ° C., and the viscosity is 8000 cp / 2.
A transparent liquid composition [B-5] at 5 ° C was obtained.

[0085]

Examples 1 to 9 and Comparative Examples 1 to 6 100 parts of each of the transparent liquid compositions [B-1] to [B-5] were blended with a predetermined amount of the polymerization initiator and the organic phosphorus compound shown in Table 1. Then, a liquid curable resin composition was obtained.

[0086]

[Test Example] Using the liquid curable resin composition obtained above, the effect of promoting curing was evaluated by the following method. The results are shown in Table 1. [Preparation of test piece] A liquid material was applied on a glass plate using an applicator bar having a thickness of 150 µm, and ultraviolet rays of 25 mJ / cm ² were irradiated in a nitrogen atmosphere to obtain a cured film. Then, peel the cured film from the glass plate,
The test piece was conditioned for 24 hours at 23 ° C. and 50% relative humidity.

[Measurement of Young's modulus (according to JIS K7113)] The Young's modulus of the test piece at 23 ° C. was measured by a tensile tester under the conditions of a pulling speed of 1 mm / min and a marked line distance of 25 mm.

[Gel Fraction] After the initial weight of the cured film was weighed (the initial weight is W ₀ ), it was extracted for 12 hours with methyl ethyl ketone as a solvent in a Soxhlet extractor.

Thereafter, the film is dried in a vacuum dryer at 50.
After drying at ℃ for 12 hours, it was left at room temperature for 1 hour, and then weighed (dry weight is W ₁ ). The gel fraction (%) was calculated from the following formula.

Gel fraction = (W ₁ / W ₀ ) × 100

[0091]

[Table 1]

[0092]

According to the present invention, a specific organic phosphorus compound is blended with a liquid curable resin composition containing a compound having at least one ethylenically unsaturated bond having a polymerization ability and a polymerization initiator. Therefore, the curing speed is high, the curing time can be shortened, and a liquid curable resin composition which gives an optical fiber coating material having desirable characteristics in a short time can be obtained.

Further, the composition of the present invention is not only used as an optical fiber coating material, but is also excellent in heat resistance, curability and adhesion, so that it can be used in various substrates such as metal, plastic, wood,
It is also useful as a pottery, glass coating material, optical molding material, three-dimensional solid molding material, and printing plate material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 175/16 PDZ 8620-4J G02B 6/44 301 A 7036-2K (72) Inventor Hideki Chiba Tokyo 2-11-24 Tsukiji, Chuo-ku, Japan Within Japan Synthetic Rubber Co., Ltd. (72) Atsushi Shioda Tokyo, 2-11-24 Tsukiji, Chuo-ku, Japan Synthetic Rubber Co., Ltd. (72) Etsuo Kubota Tokyo 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Japan Synthetic Rubber Co., Ltd. (72) Inventor Mitsuhiko Sakakibara 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A compound [A] having at least one ethylenically unsaturated bond having polymerization ability, a polymerization initiator [B], and a compound [C] represented by the following formulas [I] to [III]. A liquid curable resin composition comprising: at least one organic phosphorus compound selected from the group consisting of: (In the formula, R ¹ is an alkyl group which may have a substituent,
A cycloalkyl group, an aryl group, an alkoxy group,
R ² and R ³ are each independently hydrogen, or an optionally substituted alkyl group, cycloalkyl group, aryl group or alkoxy group), (In the formula, R ¹ is an alkyl group which may have a substituent,
An aryl group or an aralkyl group, R ^{2 to} R ⁴ are each independently hydrogen, or an alkyl group which may have a substituent, an aryl group or an aralkyl group, and X is a halogen); 3] (In the formula, R ¹ is an alkyl group which may have a substituent,
An aryl group and an aralkyl group, and R ^{2 to} R ⁴ are each independently hydrogen, or an alkyl group which may have a substituent, an aryl group, or an aralkyl group). 2. A liquid curable resin composition for an optical fiber coating material, which comprises the composition according to claim 1.