JPH10204250A - Liquid curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, having a high curing rate, readily separable from a material to be bundled and suitable as a bundling material for a tape material by including a polyol polyurethane, a polyfunctional compound and a compound having an N-vinyl group therein. SOLUTION: This composition is produced by including (A) a polyol polyurethane having ethylenically unsaturated groups, (B) a polyfunctional compound having >=3 (meth)acryloyl groups [e.g. trimethylolpropane tri(meth)acrylate] and (C) a compound having an N-vinyl group in an amount so as to provide 0.25-2mol N-vinyl groups in the compound based on 1mol (meth)acryloyl groups in the whole composition (N-vinylpyrrolidone, etc.). The component A is produced by reacting, e.g. a polyol (polyethylene glycol, etc.) and a diisocyanate (2,4-tolylene diisocyanate, etc.) with a compound containing an ethylenically unsaturared group [2-hydroxyethyl (meth)acrylate, etc.].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a liquid curable resin composition. More specifically, because of its low viscosity, it has good applicability to tape materials, its curing speed is fast, and its elongation of its cured material is small, so it can give a cured product with excellent tearing properties. It relates to a suitable liquid curable resin composition.

[0002]

2. Description of the Related Art In the production of an optical fiber, a resin coating is applied for the purpose of protection and reinforcement immediately after hot-spinning a glass fiber. As this resin coating,
There is known a structure in which a flexible primary coating layer is first provided on the surface of an optical fiber, and a secondary coating layer having higher rigidity is provided outside the primary coating layer. In order to put these resin coated optical fiber wires into practical use, several
For example, it is known to form a so-called tape-structure core wire in which four or eight wires are arranged and covered with a binding material to form a tape-like structure having a rectangular cross section. Further, a method of further binding two or more core wires having a tape structure to form a multi-core core is also known. For example, a core material having a four-core tape structure is covered with two binding materials to form eight cores. . The resin composition used for these optical fiber coating applications is a resin material for forming the primary coating layer as a soft material, a resin composition for forming the secondary coating layer as a hard material, A binding material for bundling the strands to form a tape-structured core wire is called a tape material, and a binding material for further bundling the tape-structured core wire to form a multi-core is called a bundling material.

A curable resin used as a bundling material for such an optical fiber has a high curing speed, a low viscosity, a high coating speed on a tape material, a high productivity, and a sufficient cured product. High strength and flexibility, little change in physical properties over a wide temperature range, little change over time in physical properties, excellent long-term reliability, excellent chemical resistance to acids, alkalis, etc., moisture absorption, water absorption Characteristics such as low surface roughness and good surface smoothness and low coefficient of friction. As described above, the ability of the bundling material to be relatively easily peeled from the object to be bound and the ability to easily separate the object to be bound is often required not only for the optical fiber bundling material but also for various uses. For temporary or semi-permanent bundling, for example, when binding two structural materials together for temporary bonding to bond or weld, or when temporarily tying parts together until the product reaches the consumer Properties are often required.

[0004]

An object of the present invention is to provide a liquid curable resin composition. Another object of the present invention is to provide a liquid curable resin composition which has a high curing rate and a low viscosity and thus has good productivity, is easy to separate from a material to be tied and does not cause residue of the material to be tied at the time of separation. To provide things. Still other objects and advantages of the present invention will become apparent from the following description.

[0005]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) a polyol polyurethane having an ethylenically unsaturated group, and (B) three or more (meth) acryloyl groups. Polyfunctional compound and (C)
For 1 mol of (meth) acryloyl group in the whole composition,
This is achieved by a liquid curable resin composition containing a compound having an N-vinyl group at a ratio of 0.25 to 2 mol of the N-vinyl group in the compound. Hereinafter, the present invention will be described in detail, and the objects, advantages and effects of the present invention will be more apparent.

(A) Polio having an ethylenically unsaturated group
The polyurethane having an ethylenically unsaturated group (hereinafter, referred to as a component (A)), which is a component (A) used in the present invention, is obtained by reacting a polyol, a diisocyanate, and a compound containing an ethylenically unsaturated group. Can be manufactured. That is, it can be produced by reacting an isocyanate group of a diisocyanate with a compound containing a hydroxyl group and an ethylenically unsaturated group of a polyol, respectively. As the reaction method, for example, a method in which a polyol, a diisocyanate and an ethylenically unsaturated group-containing compound are charged and reacted at once; a method in which a polyol and a diisocyanate are reacted, and then a reaction in which an ethylenically unsaturated group-containing compound and a hydroxyl group-containing compound are reacted; A method of reacting a diisocyanate and an ethylenically unsaturated group-containing compound and then reacting a polyol; reacting a diisocyanate and an ethylenically unsaturated group-containing compound,
Then, a method of reacting a polyol, and finally reacting a compound containing an ethylenically unsaturated group, and the like can be mentioned.

The polyol used here includes, for example, aliphatic polyether diol, alicyclic polyether diol or aromatic polyether diol, polyester diol, polycarbonate diol, polycaprolactone diol and other polyols. These polyols can be used alone or in combination of two or more. The polymerization mode of each structural unit in these polyols is not particularly limited, and may be any of random polymerization, block polymerization, and graft polymerization.

Among these, aliphatic polyether diols include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and two or more ion-polymerizable cyclic compounds. Polyether diols obtained by subjecting compounds to ring-opening copolymerization are exemplified.

The above-mentioned ionic polymerizable cyclic compounds include, for example, 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 monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether And cyclic ethers such as glycidyl benzoate.

Examples of polyether diols obtained by ring-opening copolymerization of the above two or more ion-polymerizable cyclic compounds include binary copolymers and ternary copolymers. Specific examples thereof include: For example, a binary copolymer obtained from a combination of tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1-oxide and ethylene oxide; tetrahydrofuran, Ternary copolymers obtained from a combination of butene-1-oxide and ethylene oxide can be exemplified.

The above-mentioned ion-polymerizable cyclic compound is subjected to ring-opening copolymerization with a cyclic imine such as ethyleneimine; a cyclic lactone acid such as β-propiolactone and glycolic lactide; or dimethylcyclopolysiloxane. The polymer can also be used as a polyether diol.

Such aliphatic polyether diols include, for example, PTMG650, PTMG1000, PTMG20
00 (all manufactured by Mitsubishi Chemical Corporation), PPG400, PP
G1000, EXCENOL 720, 1020, 202
0 (manufactured by Asahi Ohrin Co., Ltd.), PEG1000, Unisafe DC1100, DC1800 (manufactured by NOF Corporation), PPTG2000, PPTG1000, P
TG400, PTGL2000 (all made by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, P
BG2000A, PBG2000B, EO / BO400
0, EO / BO2000 (Daiichi Kogyo Seiyaku Co., Ltd.)
) Can also be obtained as commercial products.

Examples of the alicyclic polyether diol include alkylene oxide-added diols of hydrogenated bisphenol A, alkylene oxide-added diols of hydrogenated bisphenol F, and alkylene oxide-added diols of 1,4-cyclohexanediol.

Examples of the aromatic polyether diol include alkylene oxide-added diols of bisphenol A such as polyoxyethylene bisphenol A ether.
Alkylene oxide-added diols of bisphenol F,
Examples thereof include alkylene oxide-added diols of hydroquinone, alkylene oxide-added diols of naphthohydroquinone, and alkylene oxide-added diols of anthrahydroquinone. Such aromatic polyether diols include, for example, Uniol DA400, DA700,
DA1000, DA4000 (Nippon Oil & Fats Co., Ltd.)
) Can also be obtained as commercial products.

Examples of the polyester diol include, for example, a polyester polyol obtained by reacting a polyhydric alcohol with a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and Methyl-1,5-pentanediol, 1,9-
Nonanediol, 2-methyl-1,8-octanediol and the like can be mentioned. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like. These polyester diols are Clapol P-201
0, PMIPA, PKA-A, PKA-A2, PNA-
It can be obtained as a commercial product such as 2000 (all manufactured by Kuraray Co., Ltd.).

As the polycarbonate diol, for example, polycarbonate of polytetrahydrofuran, 1,6
-Polycarbonates of hexanediol and the like. Commercial products include DN-980, 981, 982, 9
83 (all made by Nippon Polyurethane Co., Ltd.), PC-80
00 (manufactured by U.S. PPG), PC-THF-CD (BAS
F company).

As polycaprolactone diol, ε
-Polycaprolactone diol obtained by reacting caprolactone and diol. Examples of the diol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol,
6-hexanediol, neopentyl glycol, 1,
4-cyclohexanedimethanol, 1,4-butanediol and the like. These polycaprolactone diols are available from Praxel 205, 205AL, 212, 21
2AL, 220, 220AL (Daicel Corporation)
Available as commercial products.

Other polyols other than the above include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4- Cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecanedimethanol, pentacyclodecanedimethanol, β-methyl-
δ-valerolactone, hydroxy-terminated polybutadiene,
Hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, terminal diol compound of polydimethylsiloxane, polydimethylsiloxane carbitol-modified polyol, and the like.

The preferred molecular weight of the polyol used for producing the component (A) is a number average molecular weight in terms of polystyrene by gel permeation chromatography, preferably 50 to 15,000, more preferably 10 to 15,000.
0 to 12,000.

As the polyol, among these polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols and the like, polyether polyols are preferred because they give polyurethanes having particularly excellent durability and low-temperature properties.

The diisocyanate used for producing the component (A) includes, for example, 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, 4-diphenylpropane diisocyanate, lysine diisocyanate, Examples thereof include hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and tetramethyl xylylene diisocyanate. Of these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate) and the like are preferable. These diisocyanates can be used alone or in combination of two or more.

As the compound containing an ethylenically unsaturated group used for producing the component (A), for example, a (meth) acrylate containing a hydroxyl group is preferable. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
-Hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexane Diol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth)
Acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, the following formulas (1) and (2) CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ ( OCOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) _n OH (1) CH ₂ = C (R ¹ ) COOCH ₂ CH (OH) CH ₂ O (C ₆ H ₅ ) (2) In the formula, R ¹ represents a hydrogen atom or a methyl group;
(An integer of from 15 to 15). Among these hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like are particularly preferable. As the ethylenically unsaturated group-containing compound,
In addition, 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 can also be used. These ethylenically unsaturated group-containing compounds can be used alone or in combination of two or more.

When the component (A) is reacted with a polyol, a diisocyanate and an ethylenically unsaturated group-containing compound for production, the ratio of the isocyanate group in the diisocyanate to 1 mole of the hydroxyl group contained in the polyol is 1 mole. The ratio is preferably such that the hydroxyl group in the hydroxyl group-containing (meth) acrylate is 0.2 to 1.5 mol, and the isocyanate group in the diisocyanate is 1.0 to 1 mol per mol of the hydroxyl group contained in the polyol. 5 to 2 mol, when the hydroxyl group in the hydroxyl group-containing (meth) acrylate is 0.
A ratio which is 5 to 1.0 mol is particularly preferred.

In the above reaction, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7 It is preferable to use 0.01 to 1 part by weight of a urethanation catalyst such as -trimethyl-1,4-diazabicyclo [2.2.2] octane based on 100 parts by weight of the total amount of the reactants. The reaction is preferably carried out usually at 10 to 90 ° C, particularly preferably at 30 to 80 ° C.

The component (A) preferably has a number average molecular weight in terms of polystyrene of from 500 to 20,000. If the molecular weight is less than 500, the molecular weight between the cross-linking points is small, so that the flexibility of the cured product may be insufficient, and the shrinkage strain during curing may be large. If the molecular weight exceeds 20,000, the strength of the cured resin may be insufficient. The component (A) preferably accounts for 10 to 90% by weight of the composition of the present invention,
It is particularly preferred to account for 20 to 80% by weight.

(B) 3 or more (meth) acryloyl groups
Polyfunctional compound having (M) component (B) used in the composition of the present invention
Examples of the polyfunctional compound having three or more acryloyl groups (hereinafter, referred to as component (B)) include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylol propane tri. (Meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate,
Dipentaerythritol monohydroxypenta (meta)
Acrylate, tris (2- (meth) acryloxyethyl) isocyanurate and the like can be mentioned. (B)
The component is, for example, FA731A (Hitachi Chemical Industry Co., Ltd.)
Aronix M-315, M-350, M-36
0, M-405, M-450 (manufactured by Toagosei Co., Ltd.); K
AYARAD DPHA, D-310, D-320, D
-330, DPCA-20, DPCA-30, DPCA
-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.); Viscoat # 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Pho
tomer 4172, 4149 (manufactured by San Nopco Co., Ltd.)
Etc. can be obtained as a commercial product. Of these, Aronix M-450, Viscort # 400, P
photomer4149 and the like are preferable. In the composition of the present invention, the proportion of the component (B) is preferably from 3 to 75% by weight, and more preferably from 5 to 68% by weight.
When this proportion is less than 3%, the hardness of the cured product obtained from the composition is reduced and the rubber elasticity is enhanced. Therefore, when this composition is used for binding the core wire of a tape structure of an optical fiber, the two bundled fibers are used. In the operation of separating the structural core wire of the tape, the bundling material elongates, and the separating workability deteriorates. If the proportion of the component (B) exceeds 75%, the hardness of the cured product obtained from the composition becomes too high, so that the bundling material is less likely to break, and the obtained composition undergoes shrinkage during curing. Therefore, the adhesiveness to the core wire of the tape structure tends to be deteriorated.

(C) Compound Having an N-Vinyl Group The compound having an N-vinyl group (hereinafter, referred to as a component (C)), which is a component (C) used in the composition of the present invention, is, for example, N-vinyl. Pyrrolidone, N-vinylcaprolactam and the like. The proportion of the compound having an N-vinyl group is such that the (meth) acryloyl group in the entire composition is 1%.
The ratio is preferably such that the N-vinyl group in the compound is 0.25 to 2 mol per mol. If the ratio of the N-vinyl group to the (meth) acryloyl group in the composition is too large or too small, the ratio of the alternating copolymerization of the N-vinyl group and the (meth) acryloyl group decreases, so that the curing speed is reduced. It tends to decrease.

The liquid curable resin composition of the present invention may further contain urethane (meth) acrylate obtained by reacting 2 moles of a hydroxyl group-containing (meth) acrylate compound with 1 mole of diisocyanate. Examples of the urethane (meth) acrylate include a reaction product of hydroxyethyl (meth) acrylate and 2,5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane or hydroxyethyl (meth) acrylate and 2,2 6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane reactant, hydroxyethyl (meth) acrylate and 2,4-tolylene diisocyanate reactant, hydroxyethyl (meth) acrylate and isophorone diisocyanate Examples of the reactant include a reactant of hydroxypropyl (meth) acrylate and 2,4-tolylene diisocyanate, and a reactant of hydroxypropyl (meth) acrylate and isophorone diisocyanate. These urethane (meth) acrylates can be used in an amount of preferably not more than 30 parts by weight per 100 parts by weight of the total of the polyol polyurethane (A) having an ethylenically unsaturated group and the urethane (meth) acrylate.

The composition of the present invention cures upon heating and / or irradiation. The composition of the present invention usually contains a polymerization initiator. Examples of the polymerization initiator include a thermal polymerization initiator and a radiation polymerization initiator. Here, radiation means infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α
Rays, β rays, γ rays, etc.

When the composition of the present invention is cured by heat,
The composition of the present invention usually contains a radical polymerization initiator such as a peroxide or an azo compound. Specific examples of the radical polymerization initiator include, for example, benzoyl peroxide, t-
Butyl-oxybenzoate, azobisisobutyronitrile and the like.

When the composition of the present invention is cured by radiation, the composition of the present invention usually contains a radiation polymerization initiator. Here, as the radiation polymerization initiator, for example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone,
4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether,
Benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-
On, 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, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be mentioned. These polymerization initiators,
Irgacure 184, 369, 651, 500, 9
07, CGI1700, CGI1750, CGI185
0, CG24-61 (all made by Ciba Geigy); Luc
irinLR8728 (manufactured by BASF); Darocur
e1116, 1173 (all made by Merck); and commercially available products such as Juvecryl P36 (manufactured by UCB).

When the composition of the present invention is cured by using both heating and irradiation of radiation, the above-mentioned thermal polymerization initiator and radiation polymerization initiator can be used in combination. The polymerization initiator preferably accounts for 0.1 to 10% by weight, particularly 0.5 to 7% by weight, of the total composition.

Other Ingredients The composition of the present invention may contain, in addition to the above-mentioned components, a reactive diluent, other additives, and the like, as needed, as long as the properties of the composition of the present invention are not impaired. Can be. As the reactive diluent, a monomer having a (meth) acryloyl group or a vinyl group other than the above components (A), (B) and (C) can be used. Such monomers include monofunctional monomers and bifunctional monomers.

Examples of the monofunctional monomer include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate;

Benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acryloylmorpholine, 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, stearyl (meth) acrylate, isostearyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate,

Polyoxyethylene nonylphenyl ether acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, 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, acryloylmorpholine, the following formulas (3) to (5) CH ₂ = C (R ² ) COO (R ³ O) _m R ⁴ ... (3) [In the formula (3), R ² represents a hydrogen atom or a methyl group;
R ³ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms; R ⁴ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably 1 to 9; Is an integer of 1 to 8]

[0037]

Embedded image

[In the formula (4), R ² is the same as in the formula (3), R ⁵ is an alkylene group having 2 to 8, preferably 2 to ⁵ carbon atoms, p is 1 to 8, Preferably it is an integer of 1-4.

[0039]

Embedded image

[In the formula (5), R ² , R ⁵ and p have the same meanings as in the formula (4), and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 12, preferably 1 to 9 carbon atoms. (Meth) acryloyl group-containing monomers such as the compounds shown below]; and monomers having a vinyl group other than the N-vinyl group, such as hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether.

Commercial products of these monofunctional monomers include, for example, Aronix M-111, M-113 and M-113.
114, M-117 (all manufactured by Toagosei Co., Ltd.); KA
YARAD TC110S, R629, R644 (all manufactured by Nippon Kayaku Co., Ltd.); IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like. Of these, isobornyl (meth) acrylate and polyoxyethylene nonylphenyl ether acrylate are preferred.

The bifunctional monomers include, for example, 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, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A Di (meth) acrylate of alkylene oxide-added diol, di (meth) acrylate of alkylene oxide-added diol of hydrogenated bisphenol A,
(Meth) acryloyl group-containing monomers such as epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A; and vinyl group-containing monomers such as triethylene glycol divinyl ether.

Commercial products of these bifunctional monomers include, for example, Iupimer UV, SA1002 (manufactured by Mitsubishi Chemical Corporation); Viscoat 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); KAYARAD R-604, HX-62.
0 (all manufactured by Nippon Kayaku Co., Ltd.); Aronix M-21
0, M-215 (all manufactured by Toagosei Co., Ltd.) and the like. Among these, tricyclodecane dimethanol diacrylate and di (meth) acrylate of an alkylene oxide-added diol of bisphenol A are particularly preferred.

These reactive diluents can be used alone or in combination of two or more, and are usually mixed so as to account for 80% by weight or less, preferably 10 to 70% by weight in the composition of the present invention. I do. When the amount of the reaction diluent is within the above range, the coatability and the curing speed are appropriately maintained, and the cured product has an appropriate toughness and a low cure shrinkage.

Further, the composition of the present invention can contain an amine in order to suppress the generation of hydrogen gas which causes transmission loss of an optical fiber. Examples of such amines include diallylamine, diisopropylamine, diethylamine, diethylhexylamine and the like. Further, in addition to the above components, various additives such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, and coloring An agent, a solvent, a filler, an antioxidant, a wettability improver, a coating surface improver, and the like can be added as necessary.

Here, as the antioxidant, for example, Ir
ganox 1010, 1035, 1076, 1222
(Above, manufactured by Ciba Geigy), Antigen P, 3
C, FR, GA-80 (all manufactured by Sumitomo Chemical Co., Ltd.)
And the like. As the ultraviolet absorber, for example, Tin
uvin P, 234, 320, 326, 327, 32
8, 329, 213 (all made by Ciba Geigy), See
sorb102, 103, 501, 202, 712, 7
04 (all manufactured by Cipro Kasei). As the light stabilizer, for example, Tinuvin 292, 144, 6
22LD (all made by Ciba Geigy), Sanol LS77
0 (manufactured by Sankyo Chemical Industries, Ltd.), Sumisorb ™
-061 (manufactured by Sumitomo Chemical Co., Ltd.). Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and commercial products such as SH6062 and 6030
(The above are made by Toray Silicone Co., Ltd.), KBE903,
603, 403 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The viscosity of the composition of the present invention, as measured at 25 ° C., is usually preferably from 200 to 10,000 cp, particularly preferably from 1,000 to 8,000 cp.

The adhesive strength between the cured product of the composition according to the present invention and the tape material is preferably 5 to 200 g / cm. If the adhesive force with the tape material is too large, the binding material in the portion that needs to be peeled is difficult to peel off, and the workability tends to decrease, and if the adhesive force is too low, there is a possibility that it will peel off to the part that does not need to be peeled. .

[0049]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 In a reaction vessel equipped with a stirrer, EO / BO4000 having a number average molecular weight of 4125 as a diol (Daiichi Kogyo Seiyaku Co., Ltd.)
10408 g, 713 g of 2,4-tolylene diisocyanate, 2,6-di-t-butyl- as a polymerization inhibitor
2.8 g of 4-methylphenol and 0.1 g of phenothiazine
9 g were charged. After cooling this in an ice water bath to 10 ° C, 9.3 g of dibutyltin dilaurate was added at a temperature of 20 ° C.
It was added while controlling as follows. After addition, 10-2
After stirring at 0 ° C. for 1 hour and then at 50-60 ° C. for 1 hour, 366 g of 2-hydroxyethyl acrylate
Was added while maintaining the temperature below 60 ° C. further,
The mixture was stirred at 50-60 ° C for 5 hours to complete the reaction. Thus, 11500 g of a polyol polyurethane was obtained. To this, 3680 g of reaction diluent tricyclodecane dimethanol diacrylate, 1610 g of isobornyl acrylate, 3450 g of N-vinylcaprolactam,
As the component (B), 2300 g of pentaerythritol tetraacrylate, and a photopolymerization initiator Lucirin LR
872 (manufactured by BASF) 253 g and Irgacure
907 (manufactured by Ciba Geigy) and 230 g
The mixture was stirred at 5 to 55 ° C for 3 hours, and the composition 23023 of the present invention was stirred.
g was obtained.

Example 2 In a reaction vessel equipped with a stirrer, 1538 g of polyoxyethylene nonylphenyl ether acrylate, 780 g of 2,4-tolylene diisocyanate, 4.0 g of dibutyltin dilaurate, and 2,6-di-t as a polymerization inhibitor were used. 1.5 g of -butyl-4-methylphenol and 0.5 g of phenothiazine were charged. After cooling this to 10 ° C. in an ice water bath, 600 g of 2-hydroxyethyl acrylate was added,
The addition was carried out while keeping the temperature below 30 ° C. After the addition, the mixture was further stirred at 20 to 30 ° C. for 1 hour, and then 179 g of polyoxyethylene bisphenol-A ether and polytetramethylene glycol 28 having a number average molecular weight of 2,000
34 g were added keeping the temperature below 50 ° C. Next, after stirring at 50 to 60 ° C. for 5 hours, the reaction was terminated. In this way, the polyol polyurethane (74
5,937 g of a reactive diluent polyoxyethylene nonylphenyl ether acrylate (26% by weight). To this, 228 g of reactive diluent tricyclodecane dimethanol diacrylate, 2890 g of trimethylolpropaneethoxy triacrylate,
N-vinylpyrrolidone 1000 g, photopolymerization initiator Luc
150 g of irin LR872 (manufactured by BASF) and I
20 g of rgacure907 (manufactured by Ciba Geigy) was further added, and the mixture was stirred at 45 to 55 ° C. for 3 hours to obtain 10225 g of a composition of the present invention.

Comparative Example 1 A composition was obtained in the same manner as in Example 2 except that the component (B) (trimethylolpropaneethoxytriacrylate) was not added at all.

Comparative Example 2 A composition was obtained in the same manner as in Example 2 except that no component (C) (N-vinylpyrrolidone) was added.

<Evaluation of Liquid Curable Resin Composition> The viscosities of the compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured according to the following evaluation methods, and the curing speed and Young's modulus of the cured product were measured. , The breaking strength and the breaking elongation, and the adhesion to the tape material were measured. Table 1 shows the results. (Measurement of viscosity) Using a B-type viscometer manufactured by Tokyo Keiki, 25 ° C
Was measured. (Evaluation of Curing Rate of Cured Product) 1. Preparation of Test Specimen 12
5 μm thick, 0.1 mJ / c
m ² , 1.0 mJ / cm ² by irradiating ultraviolet rays (Oak Jet Printer HMW
312MX) and a cured film having a thickness of 50 μm was obtained. Next, the cured film was peeled off from the glass plate, and left for 24 hours in an atmosphere of 23 ° C. and a relative humidity of 50% was used as a test piece. 2. Measurement of Young's modulus A test piece was cut into a strip having a width of 6 mm.
The Young's modulus at 23 ° C. was measured according to (using Autograph AGS-1KND manufactured by Shimadzu Corporation). However, the tensile speed was 1 mm / min, and the Young's modulus was calculated from the tensile stress at 2.5% strain. 3. Calculation of Curing Speed The ratio of the Young's modulus of the film cured by irradiation with ultraviolet rays at 0.1 mJ / cm ² and the film cured by irradiation with 1.0 J / cm ² was calculated as the curing speed.

(Measurement of Strength and Elongation at Break of Cured Product) 1. Preparation of Test Specimen 30 pieces of the composition were placed on a glass plate using an applicator bar.
0 μm thickness and apply 1.0 J / cm ² under air atmosphere.
Irradiated with UV light to obtain a cured film having a thickness of 200 μm. Next, the cured film was peeled off from the glass plate, and left for 24 hours in an atmosphere of 23 ° C. and a relative humidity of 50% was used as a test piece. 2. Measurement of Elongation at Break A test piece was cut into a strip having a width of 6 mm, and the elongation at break at 23 ° C. was measured (Autograph AGS- manufactured by Shimadzu Corporation).
1KND). However, the pulling speed is 50 mm /
min and the distance between the marked lines was 25 mm. 3. Measurement of breaking strength A test piece was cut into a strip having a width of 6 mm, and the breaking strength at 23 ° C was measured (Autograph AGS- manufactured by Shimadzu Corporation).
1KND). However, the pulling speed is 50 mm /
min and the distance between the marked lines was 25 mm.

(Measurement of Adhesive Strength with Tape Material) 1. Preparation of Test Sample Using an applicator bar, an optical fiber coating material R3139 manufactured by Nippon Synthetic Rubber Co., Ltd. was 300 μm on a glass plate.
The coating was applied thickly and irradiated with ultraviolet rays at 0.5 J / cm ² under a nitrogen atmosphere to obtain a cured film having a thickness of 200 μm. Next, the cured film was peeled off from the glass plate and left for 24 hours in an atmosphere at 23 ° C. and a relative humidity of 50% to obtain a test piece. Each composition obtained in Examples and Comparative Examples was applied to one surface of this test piece with a spin coater (SPINNER 1H-2 manufactured by Mikasa Co., Ltd.), and irradiated with 0.1 J / cm ² ultraviolet rays in a nitrogen atmosphere. Thus, a sample having a two-layer structure in which the film thickness of the composition was 50 μm was obtained. 2. Measurement of Adhesion Force with Tape Material A sample was cut into 1 cm widths, and a peel tester (Shimadzu Autograph AGS-1KND (TYPE) manufactured by Shimadzu Corporation)
In (I) type), the adhesion was measured at a pulling speed of 50 mm / min.

[0057]

[Table 1]

[0058]

The liquid curable resin composition of the present invention has a high curing rate and a low viscosity, so that the productivity of optical fiber production is good, and the elongation of the cured product is small, so that the tearability is excellent. Due to these characteristics, the composition of the present invention is excellent as a bundling material and other various binding resins. A preferred embodiment of the present invention will be described as follows.

1. (A) Polyol polyurethane having an ethylenically unsaturated group, (B) a polyfunctional compound having three or more (meth) acrylate groups, and (C) 1 mole of an acryloyl group in the whole composition. On the other hand, the N-vinyl group of the N-vinyl compound is
-A liquid curable resin composition containing a compound having a vinyl group. 2. The composition according to the above 1, wherein (A) the polyol polyurethane having an ethylenically unsaturated group is obtained by reacting a polyol, a diisocyanate and a (meth) acrylate containing a hydroxyl group. 3. (B) The composition according to the above 1, wherein the polyfunctional compound having a (meth) acrylate group accounts for 3 to 75% by weight. 4. The composition according to the above 1, wherein the polymerization initiator is a radical polymerization initiator and / or a radiation initiator. 5. The viscosity of the composition is from 200 to 10.0 as measured at 25 ° C.
The composition of claim 1, wherein the composition is 00 cp.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI G02B 6/44 381 G02B 6/44 381 (72) Inventor Toshikazu Kikuchi 2-11-24 Tsukiji, Chuo-ku, Tokyo Nippon Gosei Rubber Co., Ltd. (72) Inventor Komiya All within Nihon Gosei Rubber Co., Ltd. 2- 11-24 Tsukiji, Chuo-ku, Tokyo (72) Inventor Takashi Ukaji 2- 11-24 Tsukiji Chuo-ku, Tokyo Nihon Gosei Rubber Co., Ltd. Inside

Claims (1)

[Claims] 1. (A) a polyol polyurethane having an ethylenically unsaturated group, (B) a polyfunctional compound having three or more (meth) acryloyl groups, and (C) a (meth) acryloyl group 1 in the entire composition. A liquid curable resin composition comprising a compound having an N-vinyl group in a ratio such that the N-vinyl group in the compound is 0.25 to 2 mol per mol.