JP3292326B2 - 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 liquid curable resin composition, and more particularly, to a liquid curable resin composition suitable as a material for binding optical fiber strands and optical fiber tapes having excellent slipperiness on the surface of the cured resin. About things.

[0002]

2. Description of the Related Art In order to put an optical fiber wire coated with a resin into practical use, conventionally, for example, four such wires are arranged on a plane, and these are tied with a binding material. It has been practiced to harden into a tape-like structure having a rectangular cross section.

[0003] The curable resin used for the binding material generally requires the following properties. (1) It is liquid at room temperature and has high workability. (2) Fast curing and good productivity. (3) Have sufficient strength and flexibility. (4) Physical property changes are small in a wide temperature range. (5) Excellent heat resistance and hydrolysis resistance. (6) Excellent resistance to acids, alkalis, and the like. (7) Low moisture absorption and water absorption. (8) Excellent light fastness. (9) Excellent oil resistance. (10) Do not generate hydrogen gas. (11) It has a proper adhesion to the substrate. (12) It can be easily separated from the base material if necessary.

Further, the curable resin is required to have good slipperiness on the surface of the cured resin. If the slippage of the tape core wire stored in the optical fiber cable is poor, when the cable is bent, stress concentrates on the tape core portion which is adhered to the cable without slipping, and light is transmitted at the stress concentration portion. This is because the loss is increased.

However, in general, the surface of a resin cured from a solution is always smooth, and a tape-shaped core wire using the same is easy to stick and is hard to slip. Therefore, conventionally, attempts have been made to prevent an increase in transmission loss by applying a powder or a liquid capable of imparting slipperiness to the surface of the tape core wire in a cable forming step or the like. However, there is a problem that the productivity of the product is remarkably reduced.

Therefore, there has been a demand for the development of a liquid curable resin composition having the above-mentioned various properties (1) to (12) and having excellent surface slipperiness.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned circumstances, and as a result, the following components (a) to
The present inventors have found that the resin composition containing (d) has various characteristics required for a binding material for an optical fiber and has particularly excellent surface slipperiness, thereby completing the present invention.

That is, the present invention provides the following component (a):
(B), (c) and (d); (a) a urethane acrylate or urethane methacrylate containing at least 10% by weight of an aromatic polyether-based urethane acrylate or urethane methacrylate;
10-70 wt%, (b) polyvinyl monomer containing 10 to 50 wt% reactive diluent 5-70 wt%, (c) a polymerization initiator
0.1 to 10% by weight , (d) stearyl (meth) acrylate 1 to 30 % by weight
% , An optical fiber binding material characterized by containing
To provide a liquid curable resin composition for use .

Hereinafter, in the present specification, “acrylate or methacrylate” is referred to as “(meth) acrylate”.
Called.

The aromatic polyether-based urethane (meth) acrylate of the component (a) used in the present invention is obtained, for example, by reacting an aromatic polyether polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound. Can be manufactured.

The above reaction is carried out, for example, by the following production methods 1-4: production method 1: a method in which an aromatic polyether polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate compound are charged at once and reacted. A method of reacting an aromatic polyether polyol compound and a polyisocyanate compound and then reacting a hydroxyl group-containing (meth) acrylate compound, Production method 3: reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, and then aromatic polyether polyol Method 4 for reacting the compound, Production method 4: reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, then reacting an aromatic polyether polyol compound, and finally reacting a hydroxyl group-containing (meth) acrylate compound In the reaction.

Examples of the aromatic polyether polyol compound used in the present invention include an alkylene oxide-added diol of bisphenol A, an alkylene oxide-added diol of bisphenol F, an alkylene oxide-added diol of hydroquinone, and an alkylene oxide-added diol of naphthoquinone. No. These aromatic polyether polyols are commercially available, for example, Uniol DA400, DA700; DA1
000, DB400 (all manufactured by NOF Corporation) and the like. Of these, in the present invention, the aromatic polyether polyol is preferably an alkylene oxide-added diol of bisphenols A and F,
Particularly preferred is an ethylene oxide-added diol of bisphenol A.

The number average molecular weight of the aromatic polyether polyol compound is preferably from 200 to 7,000, more preferably from 300 to 3,000. When the number average molecular weight of the aromatic polyether polyol compound is less than 200, the Young's modulus of the cured product at ordinary temperature and low temperature increases, and the transmission loss due to the increase in the side pressure of the optical fiber increases. On the other hand, if the number average molecular weight exceeds 7,000, the viscosity of the composition increases, and the coatability when coating the composition on optical fiber strands, tape cores, and other substrates is undesirably deteriorated. .

In addition to the polyol compound constituting the aromatic polyether-based urethane (meth) acrylate used in the present invention, a polyol compound other than the compound may be used in combination. That is, a urethane acrylate synthesized by using an aromatic polyether and another polyol in combination may be used, or a urethane acrylate using another polyol may be used in combination with the aromatic polyether-based urethane (meth) acrylate. Is also good.

Other polyols include aliphatic and alicyclic polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols and the like.

As the aliphatic polyether polyol,
At least one selected from ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, substituted tetrahydrofuran, oxetane, substituted oxetane, tetrahydrofuran, and oxebans
Examples include those obtained by ring-opening (co) polymerizing a kind of compound. Specific examples of these include polyethylene glycol, 1,2-polypropylene glycol,
1,3-polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, polyisobutylene glycol, copolymer polyol of propylene oxide and tetrahydrofuran, copolymer polyol of ethylene oxide and tetrahydrofuran, ethylene oxide and propylene oxide Copolymer polyol of tetrahydrofuran and 3-methyltetrahydrofuran, ethylene oxide and 1,
And copolymer polyols with 2-butylene oxide.

The alicyclic polyether polyols include:
Examples thereof include alkylene oxide-added diols of hydrogenated bisphenol A and alkylene oxide-added diols of hydrogenated bisphenol F.

Commercial products of these aliphatic and alicyclic polyether polyols include, for example, Unisafe DC110
0, Unisafe DC1800, Unisafe DCB110
0, Unisafe DCB1800, Uniall DA40
0, DA700, DA1000, DB400 (manufactured by NOF Corporation); PPTG4000, PPTG200
0, PPTG1000, PTG2000, PTG300
0, PTG650, PTGL2000, PTGL100
EXCENOL4 (from Hodogaya Chemical Industry Co., Ltd.)
020, EXCENOL3020, EXCENOL20
20, EXCENOL 1020 (Asahi Glass Co., Ltd.)
PBG3000, PBG2000, PBG100
And Z3001 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

Examples of the polyester diol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol,
6-hexanediol, neopentyl glycol, 1,
4-cyclohexanedimethanol, 3-methyl-1,5
Polyhydric alcohols such as pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and phthalic acid, isophthalic acid, terephthalic acid, maleic acid,
Polyester polyol obtained by reacting with a basic acid such as fumaric acid, adipic acid, sebacic acid, Kurapole P-2010, PMIPA, PKA-A manufactured by Kuraray Co., Ltd.
PKA-A2, PNA-2000 and the like.

Examples of the polycarbonate polyol include 1,6-hexane polycarbonate, DN-980, DN-981 and DN-9 manufactured by Nippon Polyurethane Co., Ltd.
82, DN-983, etc., manufactured by Daicel Chemical Industries, Ltd.
LACCEL-CD205, CD205HL, CD22
And PC-8000 manufactured by PPG in the United States. As the polycaprolactone polyol, for example, ε-caprolactone, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, Neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-
Polycaprolactone diol obtained by reacting with a divalent diol such as butanediol, PLACCEL-205, 205AL, 21 manufactured by Daicel Chemical Industries, Ltd.
2, 212AL, 220, 220AL and the like.

Other polyols that can be used in the present invention include ethylene glycol, propylene glycol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol, β-methyl
δ-valerolactone, hydroxy-terminated polybutadiene,
Hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane terminal diol compound, polydimethylsiloxane carbitol-modified polyol, and the like can be mentioned.

Among the above polyols used in the present invention, aliphatic polyether polyols are preferable, and polytetramethylene glycol and copolymerized diols of methyltetrahydrofuran and tetrahydrofuran are particularly preferable.

Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-
Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3 '
-Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate,
3,3'-dimethylphenylene diisocyanate, 4,
4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate),
2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6
-Isopropyl-1,3-phenyl diisocyanate,
Polyisocyanate compounds such as 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and tetramethyl xylylene diisocyanate; and 2,4-tolylene diisocyanate, isophorone diisocyanate, 2,2,4 -Trimethylhexamethylene diisocyanate and the like are preferred. These polyisocyanates may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (meth) acrylate compound include 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, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate, the following formula (1) or (2)

[0025]

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(Wherein, R ¹ represents a hydrogen atom or a methyl group, and n represents a number from 1 to 15).
Acrylate and the like. Furthermore, compounds obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid are also included. Among these hydroxyl group-containing (meth) acrylate compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like are preferable.

The proportion of each of the polyol compound, the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate compound is such that the isocyanate group contained in the polyisocyanate compound is 1.1 to 2 equivalents per 1 equivalent of the hydroxyl group contained in the polyol compound. It is preferable that the hydroxyl group of the (meth) acrylate compound having a hydroxyl group has 0.2 to 1.5 equivalents.

In the above reaction, usually, copper naphthenate,
Cobalt naphthenate, zinc naphthenate, dilaurate
-Butyltin, triethylamine, DABCO, methyl D
The reaction is carried out using a urethanization catalyst such as ABCO in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the reactants. The reaction temperature in this reaction is usually 10 to 90 ° C, particularly 3
It is preferable to carry out at 0 to 80 ° C.

The urethane (meth) acrylate which is the component (a) of the composition of the present invention thus obtained is an aromatic polyether-based urethane (meth) acrylate.
0% by weight (hereinafter simply referred to as "%") or more, preferably 50 to 90%, is incorporated in the composition of the present invention preferably in a range of 5 to 99%. In order to maintain coatability at the time of coating, flexibility of the coating material after curing, and long-term reliability, 10-7
It is particularly preferable to add 0%.

Examples of the polyvinyl monomer which is the component (b) of the present invention include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. ) Acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (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, and the like. Commercial products include Iupima UV, SA1
002, SA2007 (Mitsubishi Yuka Co., Ltd.), VISCOAT 700 (Osaka Organic Chemical Industry Co., Ltd.) KAYAR
ADR-604, DPCA-20, -30, -60,
-120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-
215, M-315, and M-325 (all manufactured by Toa Gosei Chemical Industry Co., Ltd.).

As the reactive diluent other than the polyvinyl monomer used in the present invention, for example, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate ) 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) acryl Over DOO, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (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, methoxypolypropylene glycol (meth) acrylate, dicyclopentadiene (meth) acrylate, Cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Rishikurodekaniru (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, diacetone (meth) acrylamide, iso-butoxymethyl (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, vinyl ethers such as hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether,
2-ethylhexyl vinyl ether and the following formula (3)
To (5).

[0032]

Embedded image

(Wherein, 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 carbon atom.
Represents an alkyl group of from 1 to 12, preferably from 1 to 9;
-12, preferably 1-8. )

[0034]

Embedded image

Wherein R ² is as defined above, R ⁵ is an alkylene group having 2 to 8, preferably 2 to ⁵ carbon atoms, and p is 1 to 8, preferably 1 to 4 Is shown.)

[0036]

Embedded image

(Wherein R ² , R ⁵ and p have the same meanings as described above, and R ⁶ represents a hydrogen atom or a methyl group.) As commercial products, Aronix M-111, M-113, M
-114, M-117 (Toa Gosei Chemical Industry Co., Ltd.)
KAYARAD TC110S, R629, R6
44 (Nippon Kayaku Co., Ltd.), VISCOAT 3700
(Manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The reactive diluent of the component (b) used in the present invention contains 10 to 50% of the polyvinyl monomer. The amount of the component (b) to be added to the composition of the present invention is preferably from 5 to 70%, particularly preferably from 15 to 60%.

Examples of the polymerization initiator of the component (c) used in the present invention include a thermal polymerization initiator and a photopolymerization initiator. As the thermal polymerization initiator, a radical polymerization initiator is usually used. Examples of the radical polymerization initiator include peroxides and azo compounds, and specific examples include benzoyl peroxide, t-butyl-oxybenzoate, and azobisisobutyronitrile.

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, -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-propane- 1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, IRGACURE184, 651,500, manufactured by Ciba-Geigy
907, CGI369, CG24-61, Lucirine LR8728 from BASF, Daroc from Merck
ur 1116 1173, Ubecryl P3 manufactured by UCB
6, Vikure 55 manufactured by Akzo Corporation, and the like.

It is preferable to add a photosensitizer to the photopolymerization initiator, if necessary. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, UCB manufactured by UCB, P102, 103,
104, 105 and the like.

These polymerization initiators and photosensitizers may be used alone or in combination of two or more. These polymerization initiators are added to the composition of the present invention in an amount of 0.1 to 10%.

When the composition of the present invention is cured by using both heat and ultraviolet light, the above-mentioned radical polymerization initiator and photopolymerization initiator can be used in combination.

[0044]

The amount of the component (d) to be added to the composition of the present invention is preferably 1 to 30%, particularly preferably 5 to 15%.

In the present invention, the above component (a),
In addition to (b), (c) and (d), a diluting solvent and / or an additive can be blended if necessary. As the diluting solvent and / or additive, for example, epoxy resin, polyamide, polyamideimide, polyurethane,
Polybutanediene, chloroprene, polyether, polyester, pentadiene derivative, SBS (styrene / butadiene / styrene block copolymer), and hydrogenated S
Examples include polymers such as EBS and SIS (styrene / isoprene / styrene block copolymer), petroleum resins, xylene resins, ketone resin fluorine oligomers, silicone oligomers, and polysulfide oligomers.

Further, various additives other than those described above, for example, antioxidants, coloring agents, ultraviolet absorbers, light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, An agent, a lubricant, a solvent, a filler, an antioxidant, a wettability improver, a coating surface improver, and the like can be blended as necessary. For example, as an antioxidant, I
rganox1010, 1035, 1076, 1222
(All manufactured by Ciba-Geigy), and as the ultraviolet absorber, Tinuvin P, 234, 320, 32
6,327,328,213,329 (manufactured by Ciba-Geigy), SEESORB 102,103,501,2
02,712 (all manufactured by Cipro Kasei Co., Ltd.) and the like, and as a light stabilizer, Tinuvin 292,14
4,622LD (all manufactured by Ciba-Geigy) SANOL LS
770, LS440 (manufactured by Sankyo) Sumisorb
TM-061 (manufactured by Sumitomo Chemical Co., Ltd.) and the like. Examples of the silane coupling agent are γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, SH6062, 6030 as commercial products
(Manufactured by Toray Silicone Co., Ltd.), KBE903, 60
3,403 (manufactured by Shin-Etsu Chemical Co., Ltd.).

In the present invention, the above components are added as necessary for the purpose of adjusting the viscosity of the composition of the present invention or imparting desired properties. The blending amount of the above components in the composition of the present invention is preferably 0.1 to 10%.

The composition of the present invention comprises the above component (a),
(B), (c) and (d), and if necessary, other than the diluting solvent and / or the additive, other radiation-curable polymers are added as long as the properties of the composition of the present invention are not impaired. can do. For example, the urethane (meta)
Other than the acrylate polymer, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, and a siloxane polymer having a (meth) acryloyloxy group may be used. These may be used alone or in combination of two or more.

The composition of the present invention is cured by heat and / or radiation. Here, radiation refers to ionizing radiation such as infrared, visible, ultraviolet and X-rays, electron beams, α-rays, β-rays, and γ-rays.

The viscosity of the composition of the present invention is usually from 200 to 2
0000 cp / 25 ° C., preferably 2,000 to 10,000
cp / 25 ° C. When compounded as a material for binding optical fiber strands or core wires, the Young's modulus after curing is 1
0 to 50 kg / mm ² is preferable, and 20 to 40 kg / mm ² is particularly preferable.

[0052]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the following, “parts” means “parts by weight”. Reference Example 1 (Synthesis example 1 of urethane acrylate) In a reaction vessel equipped with a stirrer, 348 g of 2,4-tolylene diisocyanate, 1 g of dibutyltin dilaurate, and 2,6-di-t-butyl-4-methylphenol 0 as a polymerization inhibitor were used. .2 g was charged. This was cooled to 10 ° C. in an ice-water bath, after which 232 g of hydroxyethyl acrylate was added while controlling the temperature to 20 ° C. or lower. After the addition, stirring was further continued for 1 hour at 10 to 20 ° C., and then a bisphenol A ethylene oxide adduct having a number average molecular weight of 700 (manufactured by NOF Corporation, Uniol DA)
700) was added while maintaining the temperature below 50 ° C. Subsequently, the reaction was terminated after continuing stirring at 50 to 60 ° C. for 5 hours, to obtain a urethane acrylate [A-1] having a number average molecular weight of 1280.

Reference Example 2 (urethane acrylate synthesis example 2) In a reaction vessel equipped with a stirrer, 1,776 g of 2,4-tolylene diisocyanate, 5 g of butyltin dilaurate, 2,6
1.5 g of -di-t-butyl-4-methylphenol and 1250 g of tricyclodecane dimethanol diacrylate (upimer UV-SA1002, manufactured by Mitsubishi Yuka Co., Ltd.) were charged. This was cooled in an ice water bath to 10 ° C., and 1184 g of hydroxyethyl acrylate was added thereto while controlling the temperature to 20 ° C. or lower. 10-20 after addition
After continuing stirring at 1 ° C. for 1 hour, 2041 g of a bisphenol A ethylene oxide adduct having a number average molecular weight of 400 (manufactured by NOF Corporation, Uniol DA400) was added while maintaining the temperature at 50 ° C. or lower. Then 50-60
After continuing stirring at 5 ° C. for 5 hours, the reaction was terminated to obtain a mixture of urethane acrylate having a number average molecular weight of about 980 and tricyclodecane dimethanol diacrylate at a weight ratio of 4: 1. The polyether urethane acrylate component in the obtained mixture is referred to as [A-2].

Reference Example 3 (urethane acrylate synthesis example 3) In a reaction vessel equipped with a stirrer, 674 g of 2,4-tolylene diisocyanate, 5 g of dibutyltin dilaurate and 2,6-di-t-butyl-4- as a polymerization inhibitor were placed. 1 g of methylphenol was charged. This was cooled to 10 ° C. in an ice water bath, and then hydroxyethyl acrylate 450
g was added while controlling the temperature below 20 ° C. After the addition, stirring was further continued at 10 to 20 ° C. for 1 hour, and then polytetramethylene glycol having a number average molecular weight of 2,000 (PTG2000, manufactured by Hodogaya Chemical Industry Co., Ltd.) 3879
g was added while keeping the temperature below 50 ° C. Then
After continuing stirring at 50 to 60 ° C. for 5 hours, the reaction was terminated, and a urethane acrylate [A-3] having a number average molecular weight of 2580 was obtained.

Reference Example 4 (Urethane acrylate synthesis example 4) In a reaction vessel equipped with a stirrer, 1648 g of 2,4-tolylene diisocyanate, 5 g of butyltin dilaurate, 2,6
1.5 g of -di-t-butyl-4-methylphenol and 1155 g of tricyclodecane dimethanol diacrylate (upimer SA1002, manufactured by Mitsubishi Yuka Co., Ltd.) were charged. This was cooled to 10 ° C. in an ice-water bath, and 2197 g of hydroxyethyl acrylate was added thereto while controlling the temperature to 50 ° C. or lower. 50-60 ° C after addition
After stirring for 5 hours while maintaining the temperature, the reaction was terminated. The obtained mixture was determined to be a 10: 3 weight ratio mixture of urethane acrylate and tricyclodecane dimethanol diacrylate obtained by reacting 2 moles of hydroxyethyl acrylate with 1 mole of tolylene diisocyanate by gel permeation chromatography. Confirmed by analysis. The urethane acrylate in the obtained mixture is referred to as [A-4].

Reference Example 5 (Comparative Synthesis Example 1 of Urethane Acrylate) Instead of polytetramethylene glycol, number average molecular weight was 2
Polycaprolactone urethane acrylate was produced in the same manner as in Synthesis Example 3 except that 000 polycaprolactone diol (PLACCEL220AL, manufactured by Daicel Chemical Industries, Ltd.) was used. Let the obtained polycaprolactone urethane acrylate be [B-1].

Example 1 In a reaction vessel equipped with a stirrer, urethane acrylate [A
-1], 27 parts of a mixture of urethane acrylate [A-2] and tricyclodecane dimethanol diacrylate, 17 parts of urethane acrylate [A-3], 7 parts of isobornyl acrylate, N-vinyl 8 parts of pyrrolidone, 3.1 parts of tricyclodecane dimethanol diacrylate, 4.2 parts of Aronix M-113, 8.5 parts of stearyl acrylate, Irgacure 18
4 2.5 parts, Irgacure 907 2.5 parts, I
rganox1035 0.3 part and 50-60 ° C
To obtain a transparent liquid composition having a viscosity of 3000 cp / 25 ° C.

Example 2 4.2 parts of Aronix M-113 and 8.5 parts of stearyl acrylate were replaced with 12.7 of stearyl acrylate.
A composition was prepared in the same manner as in Example 1 except that the composition was replaced with parts. The viscosity of the composition was 3100 cp / 25 ° C.

Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that urethane acrylate [A-1], [A-2] and [A-3] were replaced with urethane acrylate [B-1]. . The viscosity of the composition was 4500 cp / 25 ° C.

Comparative Example 2 12.7 parts of stearyl acrylate was added to Aronix M-
A composition was prepared in the same manner as in Example 2 except that 113 was replaced with 12.7 parts. The viscosity of the composition is 3800 cp /
25 ° C.

For each of the liquid compositions obtained as described above, test specimens were prepared as follows,
The measurement was performed for the items described above. Table 1 shows the results.

(Preparation of Test Specimen) A liquid substance was applied on a glass plate using an applicator bar having a thickness of 250 μm.
It was irradiated with ultraviolet rays of 0.1 J / cm ² and 1.0 J / cm ² to obtain a cured film. Next, 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.

(Measurement Method) Friction Force Measurement Using a HEIDON-14 type (manufactured by Shinto Kagaku Co., Ltd.) surface measuring machine flat indenter in accordance with ASTM D1849, the friction force (g) when both surfaces of the cured film were stuck together was measured. As a sample shape, a 1.0 J / cm ² cured film was used. Upper film (fixing surface); width 8 mm, length 100 mm Lower film (moving surface): width 10 cm, length 15 cm Contact area: 8 mm × 63.5 mm Lower film moving speed; 300 mm / min load; 10 g, 50 g, 100 g

2. Measurement of Young's modulus Using a tensile tester, measure the Young's modulus (kg / mm ² ) of the test piece at 23 ° C at a pulling speed of 1 mm / min and a distance between mark lines of 25 mm.
It measured on condition of.

3. The Young's modulus was calculated ratio of the cured film of the curing rate measuring the amount of ultraviolet irradiation 0.1 J / cm ² and 1.0 J / cm ^2. As the value of the Young's modulus ratio is closer to 1, the curing speed is determined to be higher.

[0066]

[Table 1]

As is clear from the results shown in Table 1, the composition of the present invention has a small frictional force, that is, excellent surface slipperiness, and has a high curing rate.

[0068]

The liquid curable resin composition of the present invention has a high curing speed and a cured surface having excellent slipperiness. Therefore, the liquid curable resin composition of the present invention can be used as a material for binding optical fibers and optical fiber ribbons. It is suitable. Furthermore, the present composition is a material useful as a protective coating material for various substrates, for example, metals, plastics, wood, ceramics, and glass, because of the above properties.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tohru Odaka 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Synthetic Rubber Co., Ltd. (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo No. Japan Synthetic Rubber Co., Ltd. (72) Inventor Katsutoshi Igarashi 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-2-47122 (JP, A) JP-A Heisei 3-199227 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 G02B 6/44

Claims (2)

(57) [Claims] 1. The following components (a), (b), (c) and (d): (a) urethane acrylate or urethane methacrylate containing at least 10% by weight of an aromatic polyether urethane acrylate or urethane methacrylate
10-70 wt%, (b) polyvinyl monomer containing 10 to 50 wt% reactive diluent 5-70 wt%, (c) a polymerization initiator
0.1 to 10% by weight , (d) stearyl (meth) acrylate 1 to 30 % by weight
% , And a liquid curable resin composition for an optical fiber binding material . 2. The polyvinyl monomer as component (b) is trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, or polyethylene glycol. Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate,
From the group consisting of tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate and epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A 1 to be chosen
The liquid curable resin composition according to claim 1, wherein the liquid curable resin composition is at least one kind.