JP3324710B2 - Liquid curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable material useful as a protective coating material such as plastic, wood, ceramics, glass, paper, etc., an optical molding material, a three-dimensional molding material, a printing plate material, and an optical fiber coating material. Excellent durability, liquid curable resin composition with good adhesion to various substrates, especially,
The present invention relates to a liquid curable resin composition suitable as an optical fiber coating material because it has a low Young's modulus at room temperature, exhibits appropriate adhesion to glass fibers, has excellent durability, and can be cured at high speed.

[0002]

2. Description of the Related Art An optical fiber is provided with a resin coating for protecting and reinforcing the optical fiber immediately after hot-melt spinning of a glass fiber. This coating generally has a structure in which a flexible primary coating layer is provided on the surface of an optical fiber and a secondary coating layer is provided outside the primary coating layer.

The characteristics required of the optical fiber coating material include (1) a liquid state at normal temperature and high workability, (2) quick curing and good productivity, and (3)
Excellent in flexibility, (4) little change in physical properties due to a wide range of temperature changes, (5) excellent heat resistance and hydrolysis resistance, (6) little change in physical properties over time, long term Excellent reliability, (7) excellent resistance to chemicals such as acid and alkali, (8) low hygroscopicity and water absorption, (9) excellent light fastness,
(10) excellent oil resistance; and (11) excellent yellowing resistance (heat and light).

In order to satisfy the above requirements, various radiation-curable liquid coating materials have already been developed, including, for example, tetrahydrofuran-ethylene oxide ring-opening copolymer (JP-A-61-86450), tetrahydrofuran. -Propylene oxide ring-opening copolymer (JP-A-60-1)
81170) or a urethane acrylate containing a tetrahydrofuran-alkyltetrahydrofuran copolymer (JP-A-1-115964).

Problems to be Solved by the Invention

[0005] However, urethane acrylates using these polyether copolymers have a defect in either ultraviolet resistance or light yellowing resistance, and have not been sufficiently satisfactory as optical fiber coating materials.
Accordingly, an object of the present invention is to provide a liquid curable resin composition which has ultraviolet resistance and yellowing resistance and which satisfies the above-mentioned characteristics.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above circumstances, and as a result, reacted a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound and a polyol compound containing a specific structural unit. A liquid curable resin composition containing the obtained urethane (meth) acrylate polymer is synthesized, and has a low viscosity at room temperature.
Good workability when coating optical fiber, good photocurability, high-speed production of optical fiber is possible, cured material is rich in flexibility, UV resistance, heat resistance, light yellowing resistance, heat yellowing resistance The present invention was found to be excellent in oil resistance, low in the amount of hydrogen gas generated, and suitable in optical fiber, and suitable as an optical fiber coating material.

That is, the present invention provides the following compound (A):
(B) and (C)

[0008]

Embedded image (Wherein, R represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and n represents a number of 2 to 7 ) as a constituent unit. (B) Polyisocyanate compound (C Urethane (meth) acrylate polymer obtained by reacting a hydroxyl group-containing (meth) acrylate compound ,
And N-vinylpyrrolidone or N-vinylcaprolacter
The present invention provides a liquid curable resin composition characterized by containing a liquid as a constituent component. The polyol compound (A) used in the present invention needs to contain the structural units represented by the formulas (1) and (2).
Both structural units require that the terminal of the molecular chain to be bonded alternately be a hydroxyl group. The polyol having both structural units can be produced by subjecting a hydrocarbon-based polyol and a cyclic or acyclic carbonate to a carbonate exchange reaction by a known method.

Examples of the hydrocarbon polyol containing the structural unit represented by the formula (2) include a polyether polyol obtained by ring-opening polymerization of a tetrahydrofuran derivative which is an ionic polymerizable cyclic compound. Here, as the tetrahydrofuran derivative, tetrahydrofuran, 3-methyltetrahydrofuran, 3-ethyltetrahydrofuran, 3-n-propyltetrahydrofuran, 3-sec
-Propyltetrahydrofuran, 3-n-butyltetrahydrofuran, 3-t-butyltetrahydrofuran, 3
-Pentyltetrahydrofuran, and among these tetrahydrofuran derivatives, preferred are tetrahydrofuran, 3-methyltetrahydrofuran, 3-ethyltetrahydrofuran and 3-n-propyltetrahydrofuran.

The number of n in the formula (2) contained in the polyol compound (A) is from 1 to 20, preferably from 2 to 7
It is. If the number n of the formula (2) exceeds 20, the polyol compound (A) tends to crystallize at room temperature, which is not preferable in terms of workability. The preferred molecular weight of the polyol compound (A) is 200 to 10,000 in number average molecular weight, and more preferably 500 to 8,000. When the number average molecular weight of the polyol compound (A) is less than 200, Young's modulus of the cured product at ordinary temperature and low temperature increases, and transmission loss due to lateral pressure increases. On the other hand, when the number average molecular weight exceeds 10,000, the viscosity of the composition increases, and the coatability when coating the composition on an optical fiber is unfavorably deteriorated.

The polyol compound (A) may contain structural units other than the above structural units as long as the effects of the present invention are not impaired. Further, a polyol compound other than the polyol compound (A) constituting the urethane (meth) acrylate polymer used in the present invention can be used in combination.

Examples of the polyol compound that can be used in combination here include polyether polyols and polyester polyol compounds having no skeleton structure, polycarbonate polyols having a different structure from (A), polycaprolactone polyols, and other polyols. I can do it.

Examples of the polyether polyol having no skeletal structure include polyethylene polyol, polypropylene polyol, polytetramethylene polyol, polyheptamethylene polyol, polyhexamethylene polyol, polydecamethylene polyol, or two or more ionic polymerizable polymers. Examples include polyether polyols obtained by ring-opening copolymerization of a cyclic compound. Here, as the ion-polymerizable cyclic compound, ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2 or 3-methyltetrahydrofuran,
Dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether And cyclic ethers such as glycidyl benzoate. Further, a polyether obtained by ring-opening copolymerization of the ionic polymerizable cyclic compound and a cyclic imine such as ethyleneimine, a cyclic lactone acid such as p-propiolactone or glycolic lactide, or dimethylcyclopolysiloxanes. Diols can also be used. Specific combinations of the two or more 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 oxide and ethylene oxide, and the like can be given. The ring-opening copolymers of these ionic polymerizable cyclic compounds may be randomly bonded. These polyether polyols described so far include, for example, PTMG1000, PTM
G2000 (Mitsubishi Chemical Industries, Ltd.), PPG100
0, EXCENOL2020, EXCENOL1020
(All manufactured by Asahi Ohlin Co., Ltd.), PEG1000, Unisafe DC1100, Unisafe DC1800 (all manufactured by NOF Corporation), PPTG2000, PPTG1000, PTG
400, PTG650, PTGL2000, PTGL4
000 (all manufactured by Hodogaya Chemical Industry Co., Ltd.), Z-4441-
1, PBG2000A, PBG2000B, Z-300
1-4, Z-3001-5, Z-3001-9, Z-3
It can also be obtained as a commercial product such as 001-15 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

Examples of the polyester polyol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol. , 3-
Polyhydric alcohols such as methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, Examples thereof include polyester polyols obtained by reacting with polybasic acids such as sebacic acid. Commercial products include Krabol P-2010, PMIPA, PKA-A, and PKA-A
2. PNA-2000 (all manufactured by Kuraray Co., Ltd.) and the like can be obtained.

The polycarbonate polyol having a different structure from the compound (A) includes, for example, 1,6-hexane polycarbonate.
N-980, DN-981, DN-982, DN-98
3 (manufactured by Nippon Polyurethane Co., Ltd.), PC-8000 (manufactured by PPG, USA) and the like are available.

Further, as the polycaprolactone polyol, ε-caprolactone and, for example, ethylene glycol, polyethylene glycol, propylene glycol,
Polypropylene glycol, glycerin, tetramethylene glycol, polytetramethylene glycol, 1,2
-Polycaprolactone diol obtained by reacting polyols such as polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol. These diols are available in placcel 205, placcel 205AL, placcel 212, placcel 2
12AL, Plaxel 220, Plaxel 220AK
(Manufactured by Daicel Chemical Industries, Ltd.) and the like can be obtained as commercial products.

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, , 4-cyclohexanedimethanol, ethylene oxide added diol of bisphenol A, butylene oxide added diol of bisphenol A, ethylene oxide added diol of bisphenol F, butylene oxide added diol of bisphenol F, hydrogenated bisphenol A ethylene oxide added diol, water Butylene oxide-added diol of hydrogenated bisphenol A, ethylene oxide-added diol of hydrogenated bisphenol F, butylene oxide-added diol of hydrogenated bisphenol F, Dimethylol compounds of black cyclopentadiene, tricyclodecanedimethanol, hydroxy-terminated polybutadienes, hydroxy-terminated hydrogenated polybutadiene, castor oil modified polyol, terminal diol compound of polydimethylsiloxane, there is polydimethylsiloxane carbitol-modified polyol.

In addition to the above-mentioned polyol, it is also possible to use a diamine together with the polyol. Examples of the diamine include ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, and 4,4 ′. Diamines such as diaminodiphenylmethane, diamines containing a hetero atom, and polyether diamines.

Of these polyols, preferably, P
TMG1000, PTMG2000 (Mitsubishi Kasei Kogyo), PPG1000, EXCENOL2020, E
XCENOL1020 (all manufactured by Asahi Ohlin), PEG
1000, Unisafe DC1100, Unisafe DC1
800 (all manufactured by NOF Corporation), PPTG2000, PP
TG1000, PTG400, PTG650, PTGL
2000, PTGL4000 (all made by Hodogaya Chemical Industry Co., Ltd.), Z-4441-1, PBG2000A, PBG2
000B, Z-3001-4, Z-3001-5, Z-
3001-9, Z-3001-15 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Crabor P-2010, PMIPA, PKA
-A, PKA-A2, PNA-2000 (Kuraray Co., Ltd.), DN-980, DN-981, DN-982, D
N-983 (all made by Nippon Polyurethane), PC-80
00 (manufactured by U.S. PPG), Praxel 205, Praxel 205AL, Praxel 212, Praxel 212A
L, Praxel 220, Praxel 220AL (all manufactured by Daicel Chemical Industries, Ltd.), ethylene oxide addition diol of bisphenol A, ethylene oxide addition diol of bisphenol F, butylene oxide addition diol of bisphenol F, ethylene oxide addition diol of hydrogenated bisphenol A, Butylene oxide-added diol of hydrogenated bisphenol A, hydrogenated bisphenol F
Ethylene oxide-added diols, dimethylol compounds of dicyclopentadiene, and tricyclodecane dimethanol.

Particularly preferably, PTMG1000,
PTMG2000 (Mitsubishi Chemical Industries, Ltd.), PPG1
000, EXCENOL2020, EXCENOL10
20 (all manufactured by Asahi Ohlin Co., Ltd.), PEG1000, PPT
G2000, PPTG1000, PTG400, PTG
650, PTGL2000, PTGL4000 (all manufactured by Hodogaya Chemical Industry Co., Ltd.), Z-4441-1, PBG200
0A, PBG2000B, Z-3001-4, Z-30
01-5, Z-3001-9, Z-3001-15 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Clapol P-2010, PNA
-2000 (Kuraray Co., Ltd.), DN-980, DN-
981, DN-982, DN-983 (all manufactured by Nippon Polyurethane), Plaxel 205, Plaxel 205A
L, Praxel 212, Praxel 212AL, Praxel 220, Praxel 220AL (manufactured by Daicel Chemical Industries, Ltd.) bisphenol A ethylene oxide addition diol, bisphenol F ethylene oxide addition diol, dicyclopentadiene dimethylol compound, tricyclodecane dimethanol, β-methyl-δ-
Valerolactone and the like. The preferred molecular weight of these polyols is usually from 200 to 10,000, particularly preferably from 500 to 8,000 in number average molecular weight.

Examples of the polyisocyanate compound (B) used in the present invention 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, 4,
4′-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate),
2,2,4-trimethylhexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 2,2-
Bis (4-isocyanate) propane, lysine diisocyanate and the like are listed. In particular, 2,4-tolylene diisocyanate, isophorone diisocyanate, 2,4,4
-Trimethylhexamethylene diisocyanate, 1,3
-Xylylene diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate and the like are preferred. These polyisocyanate compounds (B) may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (meth) acrylate compound (C) include, 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-hydroxy (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono ( Meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate,
Pentaerythritol (meth) acrylate, dipentaerythritol penta (meth) acrylate, the following formula (3)

CH ₂ = C (R ¹ ) -COOCH ₂ CH _2- (OCOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) _m -OH (3)

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and m represents a number of 1 to 15, preferably 1 to 4. And glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether and glycidyl (meth) acrylate, and compounds obtained by addition reaction of (meth) acrylic acid. Can be. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like are particularly preferable.

The urethane (meth) acrylate polymer used in the present invention comprises the above-mentioned polyol compound (A),
It is produced by reacting a polyisocyanate compound (B) and a hydroxyl group-containing (meth) acrylate compound (C). Specifically, the reaction is carried out by reacting the isocyanate groups of the polyisocyanate compound (B) with the hydroxyl groups of the polyol compound (A) and the hydroxyl groups of the hydroxyl group-containing (meth) acrylate compound (C), respectively. This reaction is performed, for example, by the following method.

(1) A method in which a polyol compound (A) is charged and reacted with a polyisocyanate compound (B) and a hydroxyl group-containing (meth) acrylate compound (C). (2) A method in which a polyol compound (A) and a polyisocyanate compound (B) are reacted, and then a hydroxyl group-containing (meth) acrylate compound (C) is reacted. (3) A method in which a polyisocyanate compound (B) and a hydroxyl group-containing (meth) acrylate compound (C) are reacted, and then a polyol compound (A) is reacted. (4) The polyisocyanate compound (B) and the hydroxyl group-containing (meth) acrylate compound (C) are reacted, then the polyol compound (A) is reacted, and finally, the hydroxyl group-containing (meth) acrylate compound (C) is reacted again. Method.

The proportion of each of the polyol compound (A), the polyisocyanate compound (B) and the hydroxyl group-containing (meth) acrylate compound (C) is such that the ratio of the hydroxyl group contained in the polyol compound (A) is equivalent to 1 equivalent of the hydroxyl group. It is preferable that the isocyanate group contained in the isocyanate compound (B) be 1.1 to 3 equivalents, and the hydroxyl group of the (meth) acrylate compound (C) having a hydroxyl group be 0.1 to 1.5 equivalents.

In the above reaction, a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, and triethylenediamine-2-methyltriethylenediamine is usually used in a total amount of 100 parts by weight of the reactants. It is used in an amount of 0.01 to 1 part by weight based on part by weight. The reaction temperature is usually 10 to 90 ° C,
It is particularly preferable to carry out at 30 to 80 ° C. The molecular weight of the urethane (meth) acrylate polymer thus obtained is usually from 250 to 20,000, preferably from 500
１５15,000 (number average molecular weight). The content of these urethane (meth) acrylate polymers in the composition of the present invention is usually from 5 to 99%. However, the coatability when coating the optical fiber, the flexibility of the coating material after curing, and the long-term reliability In order to maintain the property, the content is preferably set to 20 to 90%.

The liquid curable resin composition of the present invention may further comprise, if necessary, other than the urethane (meth) acrylate polymer.
Other radiation-curable polymers, reactive diluents and other additives can be added as long as the effects of the composition of the present invention are not impaired.

The other radiation-curable polymers include urethane (meth) acrylates other than the urethane (meth) acrylate polymer, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, and (meth) acrylate. And siloxane polymers having an acryloyloxy group.

The reactive diluent includes a monofunctional compound and a polyfunctional compound. Examples of the monofunctional compound include 2-hydroxyethyl (meth) acrylate and 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, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy polypropylene glycol (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-diethyl (Meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and other vinyl ethers, maleic esters, and fumaric acid Examples thereof include esters and compounds represented by the following formulas (4) to (6).

[0032]

Embedded image

[In the formula, R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 6, preferably 2 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or 1 to 12 carbon atoms. ,
It preferably represents 1 to 9 alkyl groups, p is 0 to 12,
Preferably a number of 1 to 8 is shown. ]

[0034]

Embedded image

[0035] wherein, R ² is as defined above, R ⁵
Represents an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, and q represents a number of 1 to 8, preferably 1 to 4. ]

[0036]

Embedded image

As a commercially available product, Aronix M-10
2, M-111, M-113, M-114, M-117
(Toa Gosei Chemical Industry Co., Ltd.), KAYARAD TC
-110S, R-629, R-644 (all manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 3700, and IBXA (all manufactured by Osaka Organic Chemical Co., Ltd.).

Examples of the multifunctional compound include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. (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, epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A, triethylene glycol Divinyl ether and the like. Commercially available products include Yupimer UV, SA1002, SA2007 (Mitsubishi Yuka), Viscoat 700 (Osaka Organic Chemicals), KA
YARAD R-604, DPCA-20, -30,-
60, -120, HX-620, D-310, D-33
0 (Nippon Kayaku Co., Ltd.), Aronix M-210, M
-215, M-315, and M-325 (all manufactured by Toa Gosei Chemical Industry Co., Ltd.).

Of these reaction diluents, (meth) acrylate compounds are preferable, and their molecular weight is usually 2
It is in the range of about 00 to 3,000. Specific examples of particularly preferred (meth) acrylate compounds include phenoxyethyl acrylate, lauryl acrylate, and commercially available products Aronix M-102, M-111, M
-113, M-114, M-117 (all manufactured by Toa Gosei Chemical Industry Co., Ltd.), KAYARAD, TC-110S, R62
9, R644 (Nippon Kayaku Co., Ltd.) and IBXA (Osaka Organic Chemical Co., Ltd.). By using these (meth) acrylate-based compounds, the flexibility of the cured product is further improved, and especially the flexibility at low temperatures is also improved.

The curing rate of the composition obtained by using two or more of these (meth) acrylate compounds can be improved. These (meth) acrylate compounds are preferably blended in the composition of the present invention in an amount of 5 to 60% by weight, particularly 10 to 40% by weight. If the amount is less than 5% by weight, the Young's modulus at a low temperature after curing of the obtained composition increases, and the transmission loss tends to increase when applied to an optical fiber. If the amount exceeds 60% by weight, the curability of the composition decreases. Tend to.

Further, the reaction diluents N-vinylpyrrolidone and N-vinylcaprolactam are preferred compounds for improving the adhesion and curability of the resulting composition.
These are used in the composition in an amount of preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight. 20 used
If the amount is more than 10% by weight, the water absorption of the resulting composition after curing tends to be high, the water resistance and alkali resistance tend to decrease, and the flexibility at low temperatures tends to deteriorate.

The composition of the present invention can be cured by heat and / or radiation. Here, radiation means infrared rays, visible light rays, ultraviolet rays and X-rays, electron beams, α-rays, β-rays,
It means ionizing radiation such as gamma rays.

When the composition of the present invention is cured by heat,
Usually, a radical polymerization initiator is used. Examples of the radical polymerization initiator include peroxides and azo compounds. Specific examples thereof include benzoyl peroxide, t-butyl-oxybenzoate, and azobisisobutyi. Ronitrile and the like can be mentioned.

When the composition of the present invention is photocured, a photopolymerization initiator and, if necessary, a photosensitizer are further used. Examples of such a photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2
-Dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3
-Methylacetophenone, 4-chlorobenzophenone,
4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl)-
2-hydroxy-2-methylpropan-1-one, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
On, thioxanthone, diethylthioxanthone, 2-
Isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholino-propan-1-one, 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide, commercially available as IRGACURE 184, 651,
500, 907, CGI-369, CG24-61 (all manufactured by Ciba-Geigy), Lucirin LR872
8, Initiator 654 (all made by BASF),
Darocur 1116 and 1173 (all manufactured by Merck), Ubecryl P36 (UCB) and the like. Particularly preferred are benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, thioxanthone, IRGACURE184, 651, 907, and CGI.
369, CG24-61 (all manufactured by Ciba Geigy), L
ucirin LR8728, Initiator 65
4, Darocur 1116 (from BASF)
1173 (Merck), Juvecryl P36 (UC
B company). These polymerization initiators are preferably added to the composition in an amount of 0.1 to 10%. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate. , As commercial products Jubecryl P102, 103, 104, 105 (above UCB
And the like).

In the composition of the present invention, epoxy resin, polyamide, polyamide imide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene block copolymer may be added as necessary. A copolymer, a styrene / ethylene / butene / styrene block copolymer, a styrene / isoprene / styrene block copolymer, a petroleum resin, a xylene resin, a ketone resin, a fluorine-based oligomer, a silicone-based oligomer, a polysulfide-based oligomer, and the like can also be blended.

The composition of the present invention may further contain various additives other than those described above, for example, an antioxidant, a coloring agent, an ultraviolet absorber,
Requires light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wetting improvers, coating surface improvers, etc. Can be blended according to Here, commercially available antioxidants include Irganox 1010, 1
035, 1076, 1222 (all manufactured by Ciba Geigy)
And the like, and as the ultraviolet absorber, Tinuvin
P, 234, 320, 326, 327, 328, 21
3 (all manufactured by Ciba-Geigy), Sumisorb11
0, 130, 140, 220, 250, 300, 32
0, 340, 350, 400 (all manufactured by Sumitomo Chemical Co., Ltd.)
And commercially available light stabilizers include Tinuv
in292, 144, 622LD (all manufactured by Ciba Geigy) Sanol LS-770, 765, 292, 262
6, 1114, and 744 (manufactured by Sankyo Kasei Kogyo Co., Ltd.). Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, SH6062, 6030 as commercial products
(Manufactured by Toray Silicone Co., Ltd.), KBE903, 603,
403 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of commercially available antioxidants include Antigene W, S, R, and 3
C, 6C, RD-G, FR, AW (all manufactured by Sumitomo Chemical Co., Ltd.) and the like.

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 composition of the present invention thus obtained is
It is usually from 200 to 20,000 cp / 25 ° C, preferably from 1,500 to 10,000 cp / 25 ° C. In addition,
When the composition of the present invention is used as an optical fiber primary coating material, the Young's modulus after curing is 0.05 to 0.5 kg.
/ Mm ² , particularly preferably 0.06 to 0.35 kg / mm ^2, and the Young's modulus of such a cured product at −40 to 60 ° C. is usually 0.01 to 10 kg / mm ^2. In the range.

[0048]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following, parts mean parts by weight.

Urethane Acrylate Synthesis Example 1 In a reaction vessel equipped with a stirrer, 109.8 g of 2,4-tolylene diisocyanate, 1 g of dibutyltin dilaurate and 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor were placed. 0.3 g was charged. Next, 48.8 g of hydroxyethyl acrylate was added while controlling the temperature to 24 ° C. or lower. After the addition, stirring was further continued at 10-20 ° C for 1 hour, and then a diol compound (A) having a number average molecular weight of 2000 (formula (1) and a number average molecular weight of 250,
And 841.4 g of a compound wherein R is a hydrogen atom and a repeating unit represented by the formula (2):
It was added while maintaining at 0 ° C. Then at 50-60 ° C for 5
After stirring was continued for an hour, the reaction was terminated to obtain a urethane acrylate [A-1] having a number average molecular weight of about 4750.

Urethane acrylate synthesis example 2 In a reaction vessel equipped with a stirrer, 104.3 g of 2,4-tolylene diisocyanate, a diol compound (A) having a number average molecular weight of 2000 (formula (1) and a number average molecular weight of 750 856.0 g of a compound obtained by repeating a structural unit represented by the formula (2) wherein R is an ethyl group) and 0.3 g of 2,6-di-tert-butyl-methylphenol as a polymerization inhibitor. This was cooled to 15 ° C in an ice-water bath, and then 1 g of dibutyltin dilaurate was added to start the reaction. The reaction was carried out for 2 hours while maintaining the temperature at 30-40 ° C.
Next, 39.7 g of hydroxyethyl acrylate was added, and stirring was continued at 50-60 ° C. for 5 hours. Then, the reaction was terminated, and a urethane acrylate [A-2] having a number average molecular weight of about 5840 was obtained.

Urethane acrylate synthesis example 3 In a reaction vessel equipped with a stirrer, 100 g of Aronix M-113 (trade name, manufactured by Toagosei Chemical Industry Co., Ltd.), 124.7 g of isophorone diisocyanate, 1 g of dibutyltin dilaurate, and 2 g of 2,2 as a polymerization inhibitor. 0.3 g of 6-di-tert-butyl-methylphenol was charged. 842.7 g of a diol compound (A) having a number average molecular weight of 2000 (a compound obtained by repeating the formula (1) and a structural unit having a number average molecular weight of 140 and R represented by a hydrogen atom represented by the formula (2)) was heated at a temperature of 842.7 g. While maintaining the temperature at 40-50 ° C, the reaction mixture was added and reacted for 2 hours.
Next, 32.6 g of hydroxyethyl acrylate was added, and stirring was continued at 50-60 ° C. for 5 hours. Then, the reaction was terminated, and a urethane acrylate [A-3] having a number average molecular weight of about 7120 was obtained.

Urethane acrylate synthesis example 4 In a reaction vessel equipped with a stirrer, 233.1 g of 2,4-tolylene diisocyanate, 1 g of dibutyltin dilaurate and 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor were placed. 0.3 g was charged. Next, 250.6 g of hydroxyethyl acrylate was added while controlling the temperature to 20 ° C. or lower. After addition, add
After continuing stirring for a period of time, a diol compound (A) having a number average molecular weight of 1,000 (a compound obtained by repeating formula (1) and a structural unit represented by formula (2) in which the number average molecular weight is 250 and R is a methyl group). 516.8 g at a temperature of 40-50 ° C
While maintaining the temperature. Next, after continuing stirring at 50-60 ° C for 5 hours, the reaction was terminated, and a urethane acrylate [A-4] having a number average molecular weight of about 1850 was obtained.

Urethane Acrylate Comparative Synthesis Example 1 A reaction vessel equipped with a stirrer was charged with 109.8 g of 2,4-tolylene diisocyanate, 1 g of dibutyltin dilaurate and 2,6-di-tert-butyl-4-methyl as a polymerization inhibitor. 0.3 g of phenol was charged. Next, 48.8 g of hydroxyethyl acrylate was added while controlling the temperature to 20 ° C. or lower. After the addition, stirring was further continued at 10-20 ° C. for 1 hour, and then polypropylene glycol having a number average molecular weight of 2,000 (trade name: PPG20, manufactured by Asahi Ohlin Co., Ltd.)
00) 841.4 g was added while maintaining the temperature at 40-50 ° C. Next, after continuing stirring at 50-60 ° C for 5 hours, the reaction was terminated, and a urethane acrylate [B-1] having a number average molecular weight of about 4750 was obtained.

Urethane Acrylate Comparative Synthesis Example 2 A reaction vessel equipped with a stirrer was charged with 104.3 g of 2,4-tolylene diisocyanate, 1 g of dibutyltin dilaurate, and 0,2-di-tert-butyl-methylphenol as a polymerization inhibitor. .3 g was charged. This has a number average molecular weight of 200
Of polytetramethylene glycol (trade name: PTG2000, manufactured by Hodogaya Chemical Industry Co., Ltd.) at a temperature of 40-5.
The reaction was added for 2 hours while maintaining the temperature at 0 ° C. Then, 39.7 g of hydroxyethyl acrylate was added, and 50-
After continuing stirring at 60 ° C. for 5 hours, the reaction was terminated, and a urethane acrylate having a number average molecular weight of about 5840 [B-
2] was obtained.

Example 1 A reaction vessel equipped with a stirrer was charged with urethane acrylate [A
-1], 30 parts of Aronix M-113, K
AYARAD TC-110S (Nippon Kayaku) 7 parts,
5 parts of N-vinylpyrrolidone, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Irganox 1035 (manufactured by Ciba-Geigy) 0.3
Part, 0.1 part of diethylamine and a silane coupling agent (product name: SH6062, manufactured by Toray Silicone Co., Ltd.)
One part was stirred and mixed at 50-60 ° C, and the viscosity was 3500 cp.
/ 25 ° C. to obtain a transparent liquid composition.

[0056]

Example 2 In a reaction vessel equipped with a stirrer, urethane acrylate [A
-3], 60.5 parts, Aronix M-113 37
Part, N-vinylpyrrolidone 5 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 1.5
Part, Irganox 1035 (made by Ciba-Geigy) 0.3
Parts, 0.1 part of diethylamine and SH6062, 1
Parts were stirred and mixed at 50-60 ° C, and the viscosity was 7000 cp /
A transparent liquid composition at 25 ° C. was obtained.

Example 3 In a reaction vessel equipped with a stirrer, urethane acrylate [A
-4] 60 parts, tricyclodecane dimethanol diacrylate 20 parts, isobornyl acrylate 10 parts and N
10 parts of vinylpyrrolidone, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, I
0.3 parts of rganox1035 were stirred and mixed at 50-60 ° C to obtain a transparent liquid composition having a viscosity of 2500 cp / 25 ° C.

Comparative Example 1 A transparent liquid composition having a viscosity of 3000 cp / 25 ° C. was prepared in the same manner as in Example 1 except that 55 parts of urethane acrylate [B-1] was used instead of urethane acrylate [A-1]. Obtained.

Comparative Example 2 A transparent liquid composition having a viscosity of 11,000 cp / 25 ° C. was prepared in the same manner as in Example 1 except that 55 parts of urethane acrylate [B-2] was used instead of urethane acrylate [A-2]. Obtained.

Test Example 1 (Film Test) Using the liquid composition obtained above, test pieces were prepared as described below and evaluated as described below. Table 1 shows the results.

1. Preparation of test piece A liquid substance was applied on a glass plate using a 150 micron thick applicator bar, and then applied to the glass plate at 25 mJ / cm ² or 500 m
The cured film was obtained by irradiating ultraviolet rays of J / cm ² . Then
The cured film was peeled off from the glass plate, and the condition was adjusted at 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test piece.

2. Measurement of Young's modulus (according to JIS K7113) The Young's modulus of the test piece at 23 ° C. was measured at a tensile speed of 1 mm / min and a distance of 25 mm between the marked lines using a tensile tester.

3. After the gel fraction cured film was weighed initial weight (initial weight W ₀
And ), And extraction was performed for 12 hours using methyl ethyl ketone as a solvent in a Soxhlet extraction apparatus. Thereafter, the film was dried in a vacuum dryer at 50 ° C. for 12 hours, left at room temperature for 1 hour, and then weighed (dry weight W ₁
And ). The gel fraction was calculated from the following equation.

[0065]

(Equation 1)

4. The cured film by UV weathering 500 mJ / cm ² UVB-
The film was exposed for 200 hours with a QUV-accelerated weathering tester manufactured by Q-PANEL using a 313 lamp, and after taking out the film, the appearance of the film was observed, and then the gel fraction and weight change were measured.

A) Change in appearance The film was subjected to a weather resistance test, left at room temperature for 1 hour, and examined for yellowing.

B) Gel fraction The film was subjected to a weather resistance test, left to stand at room temperature for 1 hour, weighed (the initial weight was set to W ₀ ), and extracted with a Soxhlet extractor using methyl ethyl ketone as a solvent.
Extracted for 2 hours. Thereafter, the film was dried in a vacuum dryer at 50 ° C. for 12 hours, left at room temperature for 1 hour, and weighed (the dry weight is referred to as W ₁ ). The gel fraction was calculated from the following equation.

[0069]

(Equation 2)

C) Change in Weight After weighing the initial weight of the cured film with ultraviolet rays of 500 mJ / cm ² (the initial weight is W ₀ ), the film was subjected to a weather resistance test and left at room temperature for 1 hour. was weighed weight (dry weight and W _1.) weight change was calculated from the following equation.

[0071]

(Equation 3)

5. Seeding test The obtained liquid resin composition was stored at 5 ° C for one week, and the presence or absence of solid deposition from the liquid resin composition was observed.

[0073]

[Table 1]

[0074]

According to the present invention, the liquid curable resin composition of urethane acrylate using a polyol containing a specific group as a constituent unit has a high curing rate with a conventional liquid curable resin composition, Combines low Young's modulus and high gel fraction, and has excellent heat resistance, heat-resistant yellowing, and low hydrogen gas generation, as well as new UV resistance, light yellowing resistance, and work at low temperatures. This is a liquid curable resin composition that provides an optical fiber coating material having excellent properties. In addition, the composition of the present invention is not only an optical fiber coating material, but also has excellent heat resistance, weather resistance, heat yellowing resistance, weather yellowing resistance, curability, and adhesion.
It is also useful as a coating material for plastic, wood, ceramics, and glass, as well as a light molding material, a three-dimensional three-dimensional molding material, and a printing plate material.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Komiya 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Katsushi Igarashi 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-4-296315 (JP, A) JP-A-3 -273017 (JP, A) JP-A-63-165418 (JP, A) JP-A-2-11628 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18/00- 18/87 C08F 290/06 C09D 175/14-175/16

Claims (2)

(57) [Claims] 1. The following compounds (A), (B) and (C): (Wherein, R represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and n represents a number of 2 to 7 ) as a constituent unit. (B) Polyisocyanate compound (C A) a urethane (meth) acrylate polymer obtained by reacting a hydroxyl group-containing (meth) acrylate compound , and N-vinylpyrrolidone or N-vinylcap
A liquid curable resin composition comprising loractam as a constituent. 2. The liquid curable resin composition according to claim 1, wherein the polyol compound of the compound (A) has a number average molecular weight of 500 to 8,000.