JPH0674307B2 - Liquid curable resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a liquid curable resin composition, and particularly to a liquid curable resin composition suitable as a coating material for optical fibers.

[Conventional technology]

In the production of optical fibers, resin coating is applied immediately after hot melt spinning of glass fibers for the purpose of protection and reinforcement.

As this resin coating, a structure in which a flexible primary coating layer is first provided on the optical fiber surface and a secondary coating layer having high rigidity is provided on the outside thereof is well known.

As a material for the secondary coating layer, a material such as nylon 12 having a Young's modulus of about 200 kg / mm ² and high toughness was conventionally used, but recently, due to the diversification of the structure of the optical fiber cable, A material for the secondary coating layer having a rate of 10 to 60 kg / mm ^{2 at} room temperature has come to be used.

[Problems to be solved by the invention]

By the way, the material of the secondary coating layer of the optical fiber is in the practical temperature range, that is, −
It is desirable that the Young's modulus changes little with temperature in the range of 40 to 60 ° C.
The material of the secondary coating layer of 60 kg / mm ² has a problem that the temperature dependence of the Young's modulus is generally extremely large in the range of -40 to 60 ° C.

Therefore, an object of the present invention is to provide a liquid curable resin composition (hereinafter simply referred to as "composition") having a Young's modulus of 10 to 60 kg / mm ² and a small Young's modulus temperature dependence. To do.

[Means for solving problems]

According to the present invention, as a solution to the above problems, (a) the following general formula (I): (I) RO _m R′O _n —X— [wherein R is CH _{2 4} and R ′ is And -RO- and -R'O- may be bonded at random, and X is R or R '. Also, m and n
The respective average values of 9 <m <70, 0 ≦ n ≦ 40, m ≧ n
And 9 <m + n <80. ] A polymer obtained by adding a diol having a molecular chain represented by: to a diisocyanate compound and reacting the obtained reaction product with a (meth) acrylic compound having a hydroxyl group, (b) 2 in one molecule A liquid curable resin composition comprising a monomer containing a crosslinked alicyclic hydrocarbon compound having the above ethylenically unsaturated group and two or more aliphatic rings, and (c) a polymerization initiator.

In the present specification, the crosslinked alicyclic hydrocarbon compound is a compound having two or more aliphatic rings, and these aliphatic rings share carbon atoms forming a part of each other. Having a structure of

In the composition of the present invention, the polymer which is the component (a),
In association with the reaction of the (meth) acrylic compound, it has an ethylenically unsaturated group derived from it. Specific examples of such unsaturated groups include groups represented by the following general formulas (III) and (IV).

[In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ is
Ethylene, propylene, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, C ₂ -C _8, such as octamethylene group, preferably an alkylene group of C ₂ -C _3. ] Or [In the formula, R ₁ is the same as in the general formula (III). The polymer of the component (a) is related to the reaction with a diisocyanate compound in addition to the structure represented by the general formula (I) and the ethylenically unsaturated group derived from the (meth) acrylic compound described above. Urethane bond (-NHCOO
-) Is included. The number average molecular weight of the polymer is preferably 1000 to 7000, and particularly preferably 1500 to 5000. Further, the proportion of the structure of the general formula (I) in the polymer is preferably 50 to 98% by weight, particularly preferably 60 to 93% by weight, and 75 to 90% by weight.
Is most preferable.

If the number average molecular weight of the polymer is less than 1000, the temperature dependency of the Young's modulus of the cured product at −40 to 60 ° C. becomes large, and if it exceeds 7,000, the viscosity of the composition becomes high and it becomes difficult to handle. Further, when the ratio of the structure of the general formula (I) in the polymer is less than 50% by weight, the Young's modulus on the low temperature side is increased and the temperature dependence of the Young's modulus is increased.

As an example of the polymer as the component (a), an polymer having an ethylenically unsaturated group represented by the above general formula (III) or (IV) at least at one terminal and having the general formula (I) Has a structure represented by and optionally other structures, and these ethylenically unsaturated groups and structures are bonded via a urethane bond, and each structure has a urea bond (-NH- It may be bound by CO-NH-).

Examples of the other structure include the structures represented by the following general formulas (V) to (XI).

(V) R ₃ O ₁ R ₄ O _{m n} R ₃ − or R ₃ O ₁ R ₄ O _{m n} R ₄ − [In the formula, R ₃ and R ₄ are an ethylene group, a pentamethylene group, a hexamethylene group, or the like. C ₂ -C _6, preferably an alkylene group other than tetramethylene group and an isopropylene group of C ₂ -C _4, or different and the same, l and m are each 0 to 50, It is preferably an integer of 5 to 20 and must not be 0 at the same time, and n is an integer of 0 to 50, preferably 1 to 10] Or [In the formula, R ₃ and R ₄ are the same as those in the general formula (V), and R ₅
The structural formula _{-CH 2 -CH = CH-CH 2} -, - CH = CH-, CH _{2 2} , CH _{2 3} , CH _{2 4} , CH _{2 7} , CH _{2 8} , -C
Represents a C _{2 to} C ₈ divalent aliphatic, alicyclic or aromatic hydrocarbon group such as ≡C-, 1 and m are the same as those in the general formula (V), and p is 1 to 50, preferably an integer of 1-20] Or [In the formula, R ₂ is the same as in the general formula (III), and R ₆ , R ₇ , and R
₈ and R ₉ are each a hydrogen atom or a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a phenyl group, a cyclohexyl group or the like.
Alkyl C ₁ -C _8, aryl group or cycloalkyl group, preferably an alkyl group of C ₁ -C _3, or different, even the same, r and s are 1 to 50, preferably is an integer of 5-20, q is 1-20, preferably an integer of 5-20] (VIII) -R ₁₀ - wherein, R ₁₀ is an ethylene group, a propylene group, oxypropylene group , Tetramethylene group, hexamethylene group, phenylene group, cyclohexylene group, methylenebisphenylene group, methylenebiscyclohexylene group, or structural formula And C _{2 to} C ₁₃ aliphatic, alicyclic or aromatic divalent hydrocarbon groups and divalent halogenated hydrocarbon groups in which these are halogen-substituted. ] (In the formula, R ₁₁ is a C _{1 to} C ₈ alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a phenyl group, a cyclohexyl group, or an aryl group. Or a cycloalkyl group, preferably a C _{1 to} C ₃ alkyl group, R ₁₂ is represented by the general formula CR ₁₃ R ₁₄
an alkylene group represented by _w (wherein R ₁₃ and R ₁₄ are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group,
Pentyl group, a hexyl group, a heptyl group, an octyl group, a phenyl group, an alkyl group of C ₁ -C _8, such as a cyclohexyl group,
An aryl group or a cycloalkyl group, preferably a hydrogen atom or a C _{1 to} C ₃ alkyl group, may be the same or different. w is an integer of 1 to 20, preferably 1 to 6. ), A phenylene group, a cyclohexylene group, a methylenebisphenylene group, a methylenebiscyclohexylene group, or a paraphenylene group, and x is 1
It is an integer of ˜1000, preferably 20 to 100. ] [In the formula, R ₁₁ and R ₁₂ are the same as those in the general formula (IX),
y is 1 to 1000, preferably an integer of 30 to 130, z is 1 to 1
It is an integer of 0, preferably 2-5. ] [In the formula, Is 0.2 to 0.8, v is an integer of 5 to 200, and any double bond in the formula may be cleaved by hydrogenation].

In the present invention, the above-mentioned polymer of the component (a) is obtained by adding a diol having a molecular chain represented by the general formula (I) to a diisocyanate compound, and the obtained reaction product has a (meth) acryl having a hydroxyl group. It is important to produce by reacting a system compound. For example, if the means for adding the diisocyanate compound to the diol is adopted by changing the order of addition, the resulting composition will have an extremely high viscosity and the workability will be significantly reduced.

Specific examples of the method for producing the polymer of the component (a) are given below,
The reaction between the diol and the diisocyanate compound is carried out by adding the diol to the diisocyanate compound.

[Production Method 1] Acrylic or methacrylic compound having a hydroxyl group in the isocyanate group of a polymer having an isocyanate group and bonded by a urethane bond, which is obtained by reacting a diol having a structure of the general formula (I) with a diisocyanate compound. A method of introducing an ethylenically unsaturated group through a urethane bond by reacting a system compound.

[Production Method 2] A diol having a structure of general formula (I) or, in some cases, a combination of at least one selected from a diol having no structure of general formula (I) and a diamine, with a diisocyanate compound. The isocyanate group of the polymer having an isocyanate group obtained by the reaction and a urethane bond and optionally further bound by a urea bond is reacted with an acrylic or methacrylic compound having a hydroxyl group to form an ethylenic group through the urethane bond. A method of introducing an unsaturated group.

[Production Method 3] An isocyanate group of an adduct having an isocyanate group and an ethylenically unsaturated group obtained by reacting a diisocyanate compound with an acrylic or methacrylic compound having a hydroxyl group and bonded by a urethane bond is represented by the general formula By reacting a diol having the structure of (I) or, in some cases, a combination of at least one selected from the diol not having the structure of the general formula (I) and a diamine, a urethane bond and optionally Is a method of further binding via a urea bond.

[Production Method 4] A diol having a structure of the general formula (I) or, in some cases, a combination of at least one selected from a diol having no structure of the general formula (I) and a diamine is used as a diisocyanate compound. Through a urethane bond by reacting an acrylic or methacrylic compound having a hydroxyl group with a part of the isocyanate group of the polymer having an isocyanate group obtained by the reaction and having a urethane bond and optionally a urea bond. And a compound having the structure of general formula (VIII) in the molecule with the residual isocyanate group of the reaction product and containing two secondary amino groups (hereinafter referred to as "specific amine adduct") and Urethane bond by reacting with at least one compound selected from diamine Method of binding via a urea bond or N- substituted urea bond.

Examples of the diol having the structure of the general formula (I) used in the above method include polyether glycol represented by the following general formula (XII).

(XII) HORO _m R′O _n X—OH [wherein R is CH _{2 4} and R ′ is And -RO- and -R'O- may be bonded at random, and X is R or R '. Also, m and n
The respective average values of 9 <m <70, 0 ≦ n ≦ 40, m ≧ n
And 9 <m + n <80. This polyether glycol can be produced by a known method by ring-opening polymerization of tetramethylene oxide or tetramethylene oxide to which a required amount of propylene oxide is added, and PTMG2000 (Mitsubishi Kasei Co., Ltd. )), PTMG1000 (same), PPTG2000 (Hodogaya Chemical Co., Ltd.), PPTG4000 (same), etc.

Further, as the diol having no structure of the general formula (I),
Examples thereof include polyester diols, polyether diols, polycaprolactam diols, and polycarbonate diols other than the structure represented by the general formula (XII). Examples of the polyester diol include polyhydric compounds such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol and 1,4-cyclohexanedimethanol. Examples thereof include polyester diols obtained by reacting an alcohol with a polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid and sebacic acid. Examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol (excluding the structure represented by the general formula (XII))
Examples thereof include liquid polybutadiene having two hydroxyl groups in one molecule, and hydrogenated products of this compound.

Examples of the diamine include ethylenediamine, tetramethylenediamine, hexamethylenediamine, para-phenylenediamine, 4,4′-diaminodiphenylmethane, and other diamines; diamines containing a hetero atom; and polyetherdiamine.

As the diisocyanate compound, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-
Xylene diisocyanate, 1,4-xylene 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, hexamethylene diisocyanate, isophorone diisocyanate,
Examples thereof include dicyclohexylmethane diisocyanate and methylenebis (4-cyclohexylisocyanate).

Examples of the acrylic or methacrylic compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-Hydroxyoctyl (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin di (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate and the like can be mentioned.

Examples of the acrylic or methacrylic compound having a carboxyl group include acrylic acid and methacrylic acid.

The specific amine adduct is a diepoxy compound, an epoxy group of the compound and an equivalent amount or more of ammonia or a primary amine in the absence of a catalyst or in the presence of one or more compounds selected from water, alcohol, phenol and the like. , For example, by reacting at room temperature to 150 ° C.
Examples of the diepoxy compound here include glycidyl ethers of polyhydric phenols obtained by reacting polyhydric phenols such as bisphenol A, hydrogenated bisphenol A, catechol and resorcinol with epichlorohydrin; ethylene glycol, polyethylene glycol,
Polyhydric alcohol glycidyl ether obtained by reacting polyhydric alcohols such as propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol and epichlorohydrin, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, etc. Glycidyl ester of polybasic acid obtained by reacting polybasic acid with epichlorohydrin; Epoxy novolak resin obtained by reacting novolak type phenolic resin with epichlorohydrin; polyamines such as aniline and 4,4'-diaminodiphenylmethane Glycidylamine obtained by reacting with epichlorohydrin; vinylcyclohexene dioxide, dicyclopentadiene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Rubokishireto, bis (3,4
Alicyclic epoxy compounds such as epoxycyclohexylmethyl) phthalate; and epoxidized polybutadienes. Examples of primary amines include aliphatic amines such as ethylamine, propylamine, butylamine, and amylamine; aromatic amines such as aniline and benzylamine; alicyclic amines such as cyclopentylamine and cyclohexylamine; monoethanolamine;
Examples thereof include amino alcohols such as monoisopropanolamine. As the catalyst in the reaction, water and aliphatic alcohol, phenol, paratoluenesulfonic acid,
Organic acids such as salicylic acid, formic acid, oxalic acid and acetic acid can be exemplified.

Next, a preferred embodiment of the above production method 1 will be shown.

The amount of the diisocyanate compound used is about 1 mol per equivalent of the hydroxyl group of the diol having the structure of the general formula (I). In this reaction, a catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-butyltin laurate, triethylamine and the like is usually used in a total amount of 100 parts of the reactants.
The reaction is performed using 0.01 to 1.0 parts by weight based on parts by weight. The reaction temperature in this reaction is 30 to 80 ° C.

An acrylic or methacrylic compound having a hydroxyl group is reacted with the isocyanate group of the intermediate product thus obtained, and the amount of the acrylic or methacrylic compound having a hydroxyl group is such that the isocyanate group of the intermediate product is used. It is about 1 mol per 1 equivalent, and the reaction conditions are the same as the reaction conditions for producing the above-mentioned intermediate product.

Next, a preferred embodiment of the above production method 2 will be shown.

A diol having a structure of general formula (I) or optionally a diol having at least one selected from a diol not having the structure of general formula (I) and a diamine, and a hydroxyl group and optionally present amino. About 1 mol of the diisocyanate compound is used per equivalent of the groups, and the isocyanate group of the intermediate product obtained by reacting in the same manner as in the production method 1 is reacted with an acrylic or methacrylic compound having a hydroxyl group. The amount of the acrylic or methacrylic compound used is about 1 mol per 1 equivalent of the isocyanate group of the intermediate product, and the reaction conditions thereof are the same as those in the production method 1.

Next, a preferred embodiment of the above production method 3 will be shown.

About 1 mol of an acrylic or methacrylic compound having a hydroxyl group per 1 mol of a diisocyanate compound
A diol having the structure of the general formula (I) per 1 equivalent of isocyanate group of an intermediate product obtained by the reaction under the same reaction conditions as described above, or in some cases, the diol does not have the structure of the general formula (I). A combination of at least one selected from a diol and a diamine is used such that the sum of the hydroxyl groups and amino groups optionally present is about 1 equivalent, and the reaction is carried out under the same reaction conditions as in production method 1.

Next, a preferred embodiment of the above production method 4 will be shown.

In the reaction of the diisocyanate compound with a diol having the structure of the general formula (I) or optionally a combination of at least one selected from a diol not having the structure of the general formula (I) and a diamine,
The amount of the diol having the structure of the general formula (I) or the combination of at least one selected from the diol not having the structure of the general formula (I) and the diamine may be used with respect to 1 mol of the diisocyanate compound. , 0.1 to 0.9 mol, preferably 0.5 to 0.9 mol.
This reaction can be performed under the same reaction conditions as in production method 1. Next, 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight of an acrylic or methacrylic compound having a hydroxyl group is reacted with 100 parts by weight of the intermediate product obtained by this reaction. This reaction can also be carried out under the same reaction conditions as in production method 1. After the reaction, the reaction product is further reacted with at least one selected from a specific amine adduct and a diamine. The amount of the specific amine adduct or diamine is 0.2 to 20 parts by weight based on 100 parts by weight of the reaction product, The amount is preferably 0.4 to 10 parts by weight, and the reaction conditions are the same as in the production method 1.

In carrying out the above-mentioned production methods 1 to 4, to the extent that the product does not gel a polyol other than difunctional to diol, a polyamine other than difunctional to diamine, or a polyisocyanate compound other than difunctional to diisocyanate compound. Can be used in combination with
Diol, diamine or diisocyanate compound 100
It is 5 to 30 parts by weight with respect to parts by weight. As the polyol other than the bifunctional, for example, an addition product of glycerin and propylene oxide, glycerin, 1,2,3-
Pentanetriol, 1,2,3-butanetriol, tri (2-hydroxypolyoxypropyl) polysiloxane, polycaprolactone triol, polycaprolactone chitraol, liquid polybutadiene having more than 2 hydroxyl groups in one molecule, or this Examples thereof include hydrogenated compounds. Examples of non-bifunctional polyamines include diethylenetriamine, 1,2,3-triaminopropane, polyoxypropyleneamine, and the like, and examples of non-bifunctional polyisocyanate compounds include, for example, polymethylene polyphenyl isocyanate,
Examples thereof include triphenylmethane 4,4 ′, 4 ″ -triisocyanate.

The above-mentioned component (a) polymer is used in the composition of the present invention.
It is preferable to blend in the range of 0 to 80% by weight, particularly 30 to 70% by weight. When the proportion of the polymer is less than 20% by weight, the Young's modulus of the obtained cured product in the low temperature region (for example, around -40 ° C) becomes particularly high, and the temperature dependence of the Young's modulus becomes large. On the other hand, if it exceeds 80% by weight, the viscosity of the composition increases, and the handleability tends to deteriorate.

The monomer which is the component (b) used in the present invention includes a crosslinked alicyclic hydrocarbon compound having two or more ethylenically unsaturated groups in one molecule (hereinafter, simply referred to as "crosslinked alicyclic hydrocarbon"). Is included as an essential compound. Specific examples of the crosslinked alicyclic hydrocarbon include tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, dicyclopentadiene diacrylate, dicyclopentadiene dimethacrylate, dicyclopentadieneoxyethyl diacrylate, Cyclopentadieneoxyethyl dimethacrylate, etc. can be mentioned, and among them, preferable ones are
Examples thereof include tricyclodecane dimethanol diacrylate, and tricyclodecane dimethanol diacrylate includes tricyclo [5.2.1.0 ^2.6 ] decane-3,8-diyldimethylene diacrylate and tricyclo [5.2.1.0].
^2.6 ] decane-3,9-diyldimethylene diacrylate,
There are isomers such as tricyclo [5.2.1.0 ^2.6 ] decane-4,8-diyldimethylene diacrylate.

The monomer as the component (b) is, in addition to the above-mentioned cross-linked alicyclic hydrocarbon, optionally other monomer, in the curing rate of the composition of the present invention, the mechanical properties after curing, etc. Can be used together. As the monomer other than the above-mentioned cross-linked alicyclic hydrocarbon, both monofunctional compounds and polyfunctional compounds are used. When a cured product having a relatively low elastic modulus is desired, a monofunctional compound is mainly used, but the elastic modulus of the cured product can be adjusted by using a polyfunctional compound in an appropriate ratio. These monofunctional compounds and polyfunctional compounds are not particularly limited, and the following can be exemplified.

Monofunctional compounds: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, butoxyethyl acrylate, ethyldiethylene glycol acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenoxyethyl acrylate, dicyclopentadiene acrylate, polyethylene glycol acrylate Acrylic compounds such as polypropylene glycol acrylate, methyltriethylene glycol acrylate, diethylaminoethyl acrylate, 7-amino-3,7-dimethyloctyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polypropylene glycol methacrylate, diethyl acrylate Methacrylic compounds such as minoethylmethacrylate, vinylpyrrolidone, vinylphenol, acrylamide, vinyl acetate, vinyl ether, styrene.

Polyfunctional compounds: trimethylolpropane triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate , Trimethylolpropane trioxyethyl acrylate, trimethylolpropane trioxypropyl acrylate.

The amount of the cross-linked alicyclic hydrocarbon used as the component (b) is usually 5% by weight or more, and particularly preferably 10% by weight or more based on the total amount of the component (b). If the blending ratio of this cross-linked alicyclic hydrocarbon is less than 5% by weight of the total of the component (b), the Young's modulus in the high temperature range (for example, about 60 ° C.) of the obtained cured product becomes low, so that the temperature of the Young's modulus is low. Greater dependency.

Further, the total amount of use of all the monomers as the component (b) is preferably 20 to 80% by weight with respect to the composition of the present invention,
It is particularly preferably 30 to 70% by weight.

The polymerization initiator which is the component (c), depending on whether the composition of the present invention is intended for radiation curability or thermosetting,
Either a radiation polymerization initiator or a thermal polymerization initiator is appropriately used.

The type of radiation polymerization initiator used when producing the composition of the present invention as a radiation curable resin composition is not particularly limited, and various radiation polymerization initiators can be used. A compound can be illustrated.

2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4 , 4'-Diaminobenzophenone, Michler's ketone, benzoinpropyl ether, acetophenone diethyl ketal, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-
2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-
1-one, thioxanthone compounds and the like.

These radiation polymerization initiators may be used alone or in combination of two or more, and if necessary, a sensitizer (radiation polymerization accelerator) such as an amine compound may be used in combination.

The thermopolymerization initiator used when the composition of the present invention is produced as a thermosetting resin composition is not particularly limited, and various ones can be used, and examples thereof include peroxides and azo compounds. Examples thereof include benzoyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, and the like.

The amount of the polymerization initiator which is the component (c) in the composition of the present invention is usually 0.1 to 5% by weight, preferably 1 to 3% by weight.

In addition, additives such as an antiaging agent and a storage stabilizer may be added to the composition of the present invention, if necessary.

The viscosity of the composition of the present invention thus prepared is usually 1000 to 20000 cP / 25 ° C, preferably 20000 to 10000 cP / 25.
C., and the Young's modulus after curing is usually 10 to 60 kg / mm ² .

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

Example 1 A reaction vessel equipped with a stirrer was charged with 132 g of 2,4-tolylene diisocyanate, 1 g of dibutyltin dilaurate and 1 g of 2,6-di-t-butyl-4-methylphenol. To this, 618 g of polytetramethylene glycol having a number average molecular weight of 2000 (average degree of polymerization of 28) (PTMG2000, Mitsubishi Kasei Co., Ltd.) was added over 3 hours while controlling the internal temperature to 60 to 70 ° C.

After addition of polytetramethylene glycol, 60 more
Stirring was continued at ~ 70 ° C for about 1 hour. Then, set the internal temperature to 60 ~
2-Hydroxyethyl acrylate kept at 70 ℃
74 g was added over 1 hour to obtain a polymer represented by the following general formula, which is the component (a).

The polymer is hereinafter referred to as "polymer A". Then, to the resulting polymer A 48g, tricyclodecane dimethanol diacrylate 15g, formula (In the formula, the average value of n is 1.1 to 1.2) 11 g of diacrylate (hereinafter referred to as “diacrylate A”), 5 g of vinylpyrrolidone, 10 g of phenoxyacrylate, 8 g of trimethylolpropane trioxypropyltriacrylate, And 3 g of acetophenone diethyl ketal were mixed to prepare a desired composition.
The viscosity of the composition was 5200 cP / 25 ° C.

Example 2 A composition was prepared in the same manner as in Example 1 except that when the composition was prepared in Example 1, the amount of tricyclodecane dimethanol diacrylate used was changed to 25 g and phenoxyethyl acrylate was not used. did. The viscosity of the obtained composition was 8000 cP / 25 ° C.

Example 3 In a reaction vessel equipped with a stirrer, 216 g of 2,4-tolylene diisocyanate, 1 g of dibutyltin dilaurate, 2,6-di-t
1 g of -butyl-4-methylphenol was charged. To this, 620 g of polytetramethylene glycol having a number average molecular weight of 1000 (average degree of polymerization of 14) (PTMG1000 of Mitsubishi Kasei Kogyo Co., Ltd.) was added.
The internal temperature was controlled while being controlled at 60 to 70 ° C over time.

After addition of polytetramethylene glycol, 60 more
Stirring was continued at ~ 70 ° C for about 1 hour. Then, set the internal temperature to 60 ~
While maintaining the temperature at 70 ° C, 74 g of 2-hydroxyethyl acrylate was added over 1 hour to obtain a polymer represented by the following general formula, which is the component (a).

The polymer is hereinafter referred to as "polymer B".

Then 48 g of the polymer B obtained above, 15 g of tricyclodecane dimethanol diacrylate, 11 g of the same diacrylate A used in Example 1, 5 g of vinylpyrrolidone, 10 g of phenoxyethyl acrylate, 8 g of trimethylolpropaneoxypropyltriacrylate, And 3 g of acetophenone diethyl ketal were mixed to prepare a desired composition. The viscosity of the composition was 3600 cP / 25 ° C.

Comparative Example 1 A reactor equipped with a stirrer was charged with 277 g of 2,4-tolylene diisocyanate, 1 g of dibutyltin dilaurate and 1 g of 2,6-di-t-butyl-4-methylphenol. 518 g of polytetramethylene glycol (Terratan 650 manufactured by DuPont) having a number average molecular weight of 650 (average degree of polymerization of about 9)
Was added over 3 hours while controlling the internal temperature to 60 to 70 ° C.

After the addition was completed, stirring was continued at 60 to 70 ° C for about 1 hour.
Then, 185 g of 2-hydroxyethyl acrylate was added over 1 hour while maintaining the internal temperature at 60 to 70 ° C. The obtained polymer is hereinafter referred to as "polymer C".

A composition was prepared in the same manner as in Example 1 except that the polymer C was used instead of the polymer A when preparing the composition in Example 1. The viscosity of the composition was 2700 cP / 25 ° C.

Comparative Example 2 Except that polycaprolactone polyol having a number average molecular weight of 2000 (Placcel 220AL manufactured by Daicel Chemical Industries Ltd.) was used instead of polytetramethylene glycol having a number average molecular weight of 2000 when synthesizing the polymer in Example 1. ,
A polymer was synthesized in the same manner as in Example 1, and the obtained polymer is referred to as "polymer D". A composition was prepared in the same manner as in Example 1 except that the obtained polymer D was used instead of the polymer A. The viscosity of this composition was 9000 cP / 25 ° C.

Test Example Using the compositions obtained in the above Examples and Comparative Examples, test pieces were prepared as follows, and the following tests were conducted.

1. Preparation of test piece A glass plate was coated with the composition using an applicator having a thickness of 250 μm and irradiated with 1 J / cm ² (wavelength 350 nm) of ultraviolet rays to obtain a cured film. The cured film was peeled off from the glass plate and conditioned at 23 ° C. and 50% relative humidity for 24 hours to prepare a test piece.

2. Measurement of Young's modulus The Young's modulus of the test piece at −40 ° C., 23 ° C. and 60 ° C. was measured by a tensile tester with a constant temperature bath at a pulling speed of 1 mm / min and a marked line distance of 25 mm. The ratio of Young's modulus at -40 ° C to Young's modulus at 60 ° C was obtained as an index of the temperature dependence of Young's modulus. The results are shown in Table 1.

Comparative Example 3 After adding dibutyltin dilaurate, 2,6-di-t-butyl-4-methylphenol and polytetramethylene glycol in the same composition as in Example 1 except that the order of addition was changed (in particular, the internal temperature should be controlled). Without), 2,4-tolylene diisocyanate was added. After the addition was completed, stirring was continued for about 1 hour, and then 2-hydroxyethyl acrylate was added to obtain a polymer as the component (a).
Hereinafter, the intended composition was prepared in the same manner as in Example 1 using this polymer. The viscosity of this composition is 36000cP / 25 ℃
Met.

As can be understood from the fact that the viscosity of this composition is significantly higher than the viscosity of the compositions prepared in the respective examples, when the isocyanate compound is added to the diol and the reaction is carried out, the temperature suddenly rises rapidly. It is also recognized that a side reaction such that a hydroxyl group further reacts with the formed urethane bond occurs, resulting in a higher molecular weight and an increase in viscosity, and further gelation.

〔The invention's effect〕

The composition of the present invention, when prepared as a radiation curable composition, contains various radiations such as X-rays, electron beams, ultraviolet rays,
When it is cured by visible light and prepared as a thermosetting composition, it is cured by heating.

The composition of the present invention has a Young's modulus at room temperature of a cured product within the range of 10 to 60 kg / mm ² , and the temperature dependence of the Young's modulus is extremely high in the practical temperature range of -40 to 60 ° C. It is a small and excellent one.

Therefore, the composition of the present invention is excellent as a coating material for optical fibers, and also as a coating material for various base materials.

Front page continuation (72) Inventor Yoshio Matsumura 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Kazuo Fuse 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor T. Bishop Argon Quin Riverwood Drive, Illinois, USA 1720 (56) References JP-A-54-139700 (JP, A) JP-A-62-50315 (JP, A) JP 62-226841 (JP, A)

Claims (1)

[Claims] (A) The following general formula (I): (I) RO _m R'O _n -X- [wherein R is CH _{2 4} and R'is And -RO- and -R'O- may be bonded at random, and X is R or R '. Also, m and n
The respective average values of 9 <m <70, 0 ≦ n ≦ 40, m ≧ n
And 9 <m + n <80. ] A polymer obtained by adding a diol having a molecular chain represented by: to a diisocyanate compound and reacting the obtained reaction product with a (meth) acrylic compound having a hydroxyl group, (b) 2 in one molecule A liquid curable resin composition comprising a monomer containing a crosslinked alicyclic hydrocarbon compound having the above ethylenically unsaturated group and two or more aliphatic rings, and (c) a polymerization initiator.