JPS61185519A - Liquid curable resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION 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.

As coating materials for optical fibers, various radiation-curing types are used which are mainly composed of urethane prepolymers terminated with ethylenically unsaturated groups at both ends, and which contain monomer compounds and radiation polymerization initiators. Resin compositions are known. Incidentally, coating materials for optical fibers must have high tensile water resistance, hydrolysis resistance, and Young's modulus at high temperatures after curing.

Furthermore, performance such as good coating properties and high curing speed is required, but the conventional radiation-curable resin compositions are
None of them had these required characteristics in a well-balanced manner and was unsatisfactory.

In particular, conventional radiation-curable resin compositions all have low tensile water resistance and hydrolysis resistance, and when these properties are improved, other properties are impaired.

The purpose of the present invention is to solve the above-mentioned problems of the conventional coating materials for optical fibers. It is an object of the present invention to provide a liquid curable resin composition suitable as a coating material for optical fibers having excellent Young's modulus, coating properties, curing speed, etc.

According to the present invention, (A) a polymer having a structural unit represented by the general formula (1) (n is an integer of 2 to 90) and an ethylenically unsaturated group; ) A monomer compound containing an ethylenically unsaturated compound having a crosslinked alicyclic hydrocarbon group; and (C) a polymerization initiator.

Examples of the ethylenically unsaturated group possessed by the polymer that is component (A) of the composition of the present invention include the following general formula (■),
Unsaturated groups represented by (III) and (IV) can be mentioned.

(If) CH2=C(R1)- [wherein, R1 represents a hydrogen atom or a methyl group. 〕(
III) CH2:C(R)-C-0-R2-[
In the formula, R1 is the same as the general formula (I[), and R2 is
C2 to C8, preferably 02 to C3, such as ethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc.
represents an alkylene group. ] HC- C)12=C(R1)-C-0-CH3I ■ or [wherein R1 is the same as in general formula (II). ](A
The polymer of component ) has at least one structural unit represented by the above general formula (1) as an essential structural unit. In general formula (1), n represents an integer of 2 to 90, preferably 3 to 30, most preferably 3 to 10. When n exceeds 90, the viscosity of the polymer increases,
The coating properties of the resulting composition deteriorate.

The polymer of component (A) may have other structural units as necessary in addition to the structural unit represented by general formula (1) and the ethylenically unsaturated group.

An example of the polymer is the general formula (■).

A structural unit having at least one ethylenically unsaturated group represented by (m) or (IV) and represented by the above general formula (1) or a structural unit represented by the above general formula (1) and the following general formula It has one or more types of structural units represented by formulas (V) to (X[), and these general formulas (
1) - (The structural unit represented by One example is merging.

(■) -++R20++R40+-+R3n or H(R30+→R,Otsuga-)-R45n [In the formula, R3 and R4 are ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, etc. It represents an alkylene group of 02 to C6, preferably 02 to C3, which may be the same or different, and Q and m are each an integer of 0 to 50, preferably 5 to 20, and may not be 0 at the same time. n is an integer from 0 to 50, preferably from 1 to 10]
VI) or [wherein R3 and R4 are the same as in general formula (V), R5 is a carbonized divalent aliphatic, alicyclic or aromatic 02-C8 structural formula % etc. represents a hydrogen group, Q and m are the same as in general formula (V), and p is 1 to
50, preferably an integer from 1 to 20] (■)
-E-+R20) C-0+-Rz-Ir or [wherein, R2 is the same as in general formula (m), R6, R
7, R8 and R9 are a hydrogen atom or a 00 to C8 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, an aryl group or a cycloalkyl group, preferably a C to C alkyl group, which may be the same or different, r and S are integers of 1 to 50, preferably 5 to 20, and q is , an integer of 1 to 20, preferably 5 to 20](
■) Rro- [wherein RIG is an ethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, a methylenebisphenylene group, a methylenebiscyclohexylene group, a paraphenylene group, or a structural formula, etc. (IK) R11R11R11 [In the formula, R11 is a methyl group, an ethyl group, a propyl group,
01-C8 such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, phenyl group, cyclohexyl group, etc.
represents an alkyl group, aryl group or cycloalkyl group, preferably a C2-C3 alkyl group, and R12 is an alkylene group represented by the general formula -+cRtaRx4←- (where R13 and R14 are a hydrogen atom, a methyl group, an ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group.

It represents an 01-C8 alkyl group such as a phenyl group or a cyclohexyl group, an aryl group, or a cycloalkyl group, preferably a hydrogen atom or a C□-C3 alkyl group, and may be the same or different. W is an integer of 1 to 20, preferably 1 to 6. ).

It represents a phenylene group, a cyclohexylene group, a methylenebisphenylene group, a methylenebiscyclohexylene group, or a paraphenylene group, and X is an integer of 1 to 1000, preferably 20 to 100. ] (X) [In the formula, R11 and R12 are the same as in general formula (IK), y is an integer of 1 to 1000, preferably 30 to 130, and 2 is an integer of 1 to 10, preferably 2 to 5 It is.

](X[) I (wherein, □ is 0.2 to 0.8, and ■ is 5 to 200
au integer, and any double bond in the formula may be cleaved by hydrogenation).

The polymer of component (A) can contain structural units other than general formula (1) as described above, but the polymer of general formula (I)
The proportion of structural units in the polymer is 30% by weight or more, especially 4
It is preferably 0% by weight or more. If the structural unit of general formula (1) is less than 30% by weight, the resulting composition will have poor tensile water properties after curing.

Further, the number average molecular weight of the polymer is 600 to 20.0.
00, particularly preferably from 700 to 10,000.

If the molecular weight is less than 600, the resulting composition will have poor mechanical properties after curing, and if it exceeds 20,000, the resulting composition will have a high viscosity and a problem with coating properties.

Next, a method for producing the polymer as component (A) will be exemplified.

[Production method 1] An acrylic type or acrylic type having an isocyanate group obtained by reacting a diol having the structural unit of general formula (1) with a diisocyanate compound and having a hydroxyl group in the incyanate group of the polymer bonded by a urethane bond. A method of introducing ethylenically unsaturated groups through urethane bonds by reacting methacrylic compounds.

[Production method 2] A diisocyanate containing a diol having the structural unit of the general formula (1) or, in some cases, a combination of the diol with at least one selected from diols and diamines not having the structural unit of the general formula (1) By reacting an acrylic or methacrylic compound having a hydroxyl group with the isocyanate group of a polymer obtained by reacting with a compound, which has isocyanate groups and which are further bonded by urethane bonds and, in some cases, urea bonds, through urethane bonds. A method of introducing ethylenically unsaturated groups.

[Production method 3] The general formula is added to the isocyanate group of a polymer having an isocyanate group obtained by reacting a diisocyanate compound with an acrylic or methacrylic compound having a hydroxyl group and an ethylenically unsaturated group, which are bonded by a urethane bond. Urethane bonds and In some cases, a method of further bonding via a urea bond.

C11 Method 4] A diisocyanate containing a diol having a structural unit of general formula (1) or, in some cases, a combination of the diol with at least one selected from diols and diamines having no structural unit of general formula (I) Urethane is produced by reacting an acrylic or methacrylic compound having a hydroxyl group with a part of the incyanate group of a polymer which has isocyanate groups and is bonded by a urethane bond and, in some cases, a urea bond. The remaining isocyanate group of the reaction product is then bonded to a compound having a structural unit of the general formula (■) in the molecule and containing two secondary amino groups (hereinafter referred to as "specific amine adduct"). A method of bonding via a urethane bond, a urea bond, or an N-substituted urea bond by reacting with at least one compound selected from diamines and diamines.

[Manufacturing method 5] A diisocyanate containing a diol having the structural unit of general formula (1) or, in some cases, a combination of the diol with at least one selected from diols and diamines not having the structural unit of general formula (1) An acrylic type polymer having a carboxyl group, an epoxy group, or an acid halide group as a functional group of a polymer having two functional groups selected from a hydroxyl group, a primary amino group, and a secondary amino group obtained by reacting with a compound. Alternatively, a method of bonding via an ester bond or an amide bond by reacting with a methacrylic compound.

Examples of the diol having the structural unit of general formula (I) used in the above method include polycaprolactone diol represented by the following general formula (X[l).

(X[I) HO(C(CH2)50)nH [wherein, n is the same as in general formula (I)] and general formula (
Examples of diols not having the structural unit 1) include polyester diols, polyether diols, polycaprolactam diols, polycarbonate diols, and the like. Examples of polyester diols include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6
-hexanediol, neopentyl glycol, 1,4
- Polyester diols obtained by reacting polyhydric alcohols such as cyclohexane dimetatool with polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid. .

Examples of polyether diols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and further examples include liquid polybutadiene having two hydroxyl groups in one molecule or hydrogenated products of this compound.

Examples of the diamine include diamines such as ethylene diamine, tetramethylene diamine, hexamethylene diamine, para-phenylene diamine, and 4,4'-diaminodiphenylmethane; diamines containing heteroatoms; polyether diamines, and the like.

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, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), and the like.

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

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

Examples of the acrylic or methacrylic compound having an epoxy group include glycidyl ester of acrylic acid or methacrylic acid.

Acrylic acid chloride is an example of the acrylic or methacrylic compound having an acid halide group.

Examples include acrylic acid halides and methacrylic acid halides such as methacrylic acid chloride, acrylic acid bromide, and methacrylic acid bromide.

The specific amine adduct is produced by combining a jepoxy compound with ammonia or a primary amine in an amount equivalent to or more than the epoxy group of this compound in the absence of a catalyst or in the presence of one or more compounds selected from water, alcohol, phenol, etc. , for example, by reacting at room temperature to 150°C. Examples of the jepoxy compounds here include glycidyl ethers of polyhydric phenols obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, hydrogenated bisphenol A, bisphenol F, catechol, and resorcinol; ethylene glycol, polyethylene glycol, and propylene glycol; Glycidyl ether of polyhydric alcohol obtained by reacting polyhydric alcohol such as glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol with epichlorohydrin, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, etc. Glycidyl ester of a polybasic acid obtained by reacting a polybasic acid with epichlorohydrin; Epoxy novolac resin obtained by reacting a novolac type phenol resin with epichlorohydrin; Epichlorohydrin with a polyamine such as aniline, 4,4'-diaminodiphenylmethane, etc. Glycidylamine obtained by reacting with: vinylcyclohexene dioxide,
Alicyclic epoxy compounds such as dicyclopentadiene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis(3,4-epoxycyclohexylmethyl) phthalate; epoxidized polybutadienes can be mentioned. 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; amino alcohols such as monoethanolamine and monoisopropanolamine; Catalysts for the 0 reaction include water, aliphatic alcohols, phenol, para-toluenesulfonic acid, and salicylic acid. , formic acid,
Examples include organic acids such as oxalic acid and acetic acid.

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

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

The isocyanate group of the intermediate product obtained in this way is reacted with an acrylic or methacrylic compound having a hydroxyl group. The amount is about 1 mol per equivalent, and the reaction conditions are the same as those for producing the intermediate product described above.

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

A hydroxyl group of a diol having a structural unit of general formula (1), or a combination of at least one selected from diols and diamines that do not have a structural unit of general formula (1), and optionally present in the diol. Using about 1 mol of diisocyanate compound per 1 equivalent of the sum of amino groups to be reacted in the same manner as in Production Method 1, the isocyanate group of the intermediate product obtained 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 equivalent of the isocyanate group of the intermediate product, and the reaction conditions are the same as in Production Method 1.

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

Manufacturing method 1: About 1 mol of an acrylic or methacrylic compound having a hydroxyl group is added to 1 mol of the diisocyanate compound.
A diol having a structural unit of general formula (1) per equivalent of isocyanate group of the intermediate product obtained by reacting under the same reaction conditions, or in some cases, a diol having a structural unit of general formula (1) in the diol. The reaction is carried out under the same reaction conditions as in Production Method 1, using a combination of at least one selected from diols and diamines such that the sum of the hydroxyl groups and optionally present amino groups is about 1 equivalent.

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

Reaction of a diol having a structural unit of general formula (I) or, in some cases, a combination of the diol with at least one selected from diols and diamines not having a structural unit of general formula (1), and a diisocyanate compound. A diol having a structural unit of the general formula (1) per mol of the diisocyanate compound, or in some cases, the diol is combined with at least one selected from diols and diamines having no structural unit of the general formula (I). The amount used is 0.1 to 0.9 mol, preferably 0.5 to 0.9 mol. This reaction can be carried out under the same reaction conditions as in Production Method 1. First, 0.1 to 20 parts by weight of an acrylic or methacrylic compound having a hydroxyl group, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the intermediate product obtained by this reaction. is reacted in an amount of 0.2 to 10 parts by weight. 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 diamine, and the amount of the specific amine adduct or diamine used is 0.2 to 20 parts by weight per 100 parts by weight of the reaction product. parts, preferably 0.4 to 10 parts by weight, and the reaction conditions are the same as in Production Method 1.

Next, a preferred embodiment of the above production method 5 will be shown.

A diisocyanate per mole of a diol having a structural unit of general formula (1) or, in some cases, a combination of at least one selected from diols and diamines that do not have a structural unit of general formula (I). An intermediate product obtained by reacting 0.1 to 0.9 mol of the compound in the same manner as in Production Method 1 is reacted with an acrylic or methacrylic compound having a carboxyl group, an epoxy group, or an acid halide group, but the intermediate product 100 The amount of the acrylic or methacrylic compound used per part by weight is 0.
1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, and 0.01 parts by weight of a base such as pyridine or triethylamine or an acid such as sulfuric acid or para-toluenesulfonic acid as a catalyst per 100 parts by weight of the intermediate product. ~10 parts by weight used, 20
The reaction is carried out at ~120°C.

When carrying out the above production methods 1 to 5, it is necessary to use a polyol other than trifunctional for diol, a polyamine other than trifunctional for diamine, or a polyisocyanate compound other than trifunctional for diisocyanate compound to the extent that the product does not gel. It can be used in combination with
Diol, diamine or diisocyanate compound 10
The amount is 5 to 30 parts by weight relative to 0 parts by weight. Examples of polyols other than trifunctional include 1, for example, an addition product of glycerin and propylene oxide, glycerin, 1,
2.3-pentanetriol, 1,2゜3-butanetriol, tri(2-hydroxypolyoxyprobyl)polysiloxane, polycaprolactone triol, polycaprolactone tetraol, containing more than two hydroxyl groups in one molecule Examples include liquid polybutadiene and hydrogenated products of this compound. Examples of polyamines other than trifunctional include diethylenetriamine, 1.2.
Examples of polyisocyanate compounds other than trifunctional include 3-triaminopropane, polyoxypropylene amine, etc., and examples of polyisocyanate compounds other than trifunctional include polymethylene polyphenylisocyanate, triphenylmethane 4.4',4'-triisocyanate, etc. be able to.

The polymer component (A) described above is preferably blended into the composition of the present invention in an amount of 10 to 95% by weight, particularly 20 to 80% by weight.

The monomer compound as component (B) used in the present invention includes an ethylenically unsaturated compound having a crosslinked alicyclic hydrocarbon group (hereinafter abbreviated as "crosslinked ethylenically unsaturated compound").

Specific examples of the crosslinked alicyclic hydrocarbon group include isobornyl group, dicyclopentenyl group, and bornyl group. Examples of crosslinked ethylenically unsaturated compounds include acrylates, methacrylates, oxyethyl acrylates, and oxyethyl methacrylates of these crosslinked alicyclic hydrocarbon groups; specific examples include isobornyl acrylate, isobornyl methacrylate, Mention may be made of dicyclopentenyl acrylate, dicyclopentenyl methacrylate, bornyl acrylate, bornyl methacrylate, isobornyloxyethyl acrylate, isobornyloxyethyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate . Among these, preferred crosslinked ethylenically unsaturated compounds include isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, and dicyclopentenyl methacrylate.

In addition to the above-mentioned crosslinked ethylenically unsaturated compound, the monomer compound that is the component (B) is prepared by combining other 7-mer compounds as necessary depending on the curing speed of the composition, the mechanical properties after curing, etc. Can be used together as long as it does not. Other hexamer compounds that can be used in combination are compounds that have good compatibility with the crosslinked ethylenically unsaturated compound and have an ethylenically unsaturated group, and that improve the viscosity of the composition of the present invention and the mechanical properties of the cured product. Can be adjusted. As other monomer compounds, both monofunctional compounds and polyfunctional compounds can be used. When a cured product with a relatively low elastic modulus is desired, a monofunctional compound is mainly used, but the elastic modulus of the cured product can also be adjusted by using a polyfunctional compound in an appropriate proportion. These monofunctional compounds and polyfunctional compounds are not particularly limited, and the following can be exemplified.

Monofunctional compounds: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydro,
Furfuryl acrylate, butoxyethyl acrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate.

cyclohexyl acrylate, Phenoxyethyl acrylate.

Dicyclopentadiene acrylate.

Acrylic compounds such as polyethylene glycol acrylate, polypropylene glycol acrylate, methyltriethylene glycol acrylate, diethylaminoethyl acrylate, 7-amino-3,7-dimethyloctyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

Methacrylic compounds such as polypropylene glycol methacrylate and diethylaminoethyl methacrylate, vinylpyrrolidone, vinylphenol, acrylamide, vinyl acetate, vinyl ether, and styrene.

Polyfunctional compound Trimethylolpropane triacrylate.

Ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate.

1.6-hexanediol diacrylate, neopentyl glycol diacrylate.

polyester diacrylate, diallyl adipate, diallyl phthalate.

Triallylisocyanurate, a double-terminal acrylic acid adduct of bisphenol A glycidyl ether.

Among these, acrylates whose functional group is an acryloyl group are preferred from the viewpoint of curing speed and compatibility.

The proportion of the crosslinked ethylenically unsaturated compound in the monomer compound as component (B) is 2% by weight or more.

In particular, it is preferably 10% by weight or more; if this proportion is less than 2% by weight, the balance of the curing speed, mechanical properties after curing, tensile water properties, etc. of the composition will deteriorate.

Further, the total amount of the heptamer compound used as the component (B) is preferably 20 to 80% by weight, particularly preferably 30 to 60% by weight, based on the composition of the present invention.

As the polymerization initiator which is component (C), either a radiation polymerization initiator or a thermal polymerization initiator is used as appropriate depending on whether the composition of the present invention is intended to be radiation curable or thermosetting. do.

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. Specific examples include the following: Compounds can be exemplified.

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.

Benzoin propyl 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, etc.

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 thermal polymerization initiator used when producing the composition of the present invention as a thermosetting resin composition is also not particularly limited, and various types can be used, such as peroxides and azo compounds. Specific examples include benzoyl peroxide, 1-butylperoxybenzoate, azobisisobutyronitrile, and the like.

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

The viscosity of the composition of the invention thus prepared is usually 1,000 to 20,000 cp/25°C, preferably 2,000 to 10,000 cp/25°C.

EXAMPLES The present invention will now be explained in more detail 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 786 g of 4,4'-methylenebis(cyclohexyl isocyanate), 2 g of dibutyltin dilaurate, and 1 g of 2,6-di-t-butyl-4-methylphenol. To this, polycaprolactone diol (Plaxel 20 manufactured by Daicel Chemical Industries, Ltd.)
5AL) 1000g at internal temperature of 60~60 for 3 hours.
The mixture was added while controlling the temperature to 70°C. After addition,
Stirring was further continued at 60 to 70°C for about 1 hour. Thereafter, 232 g of 2-hydroxyethyl acrylate was added over 1 hour while keeping the internal temperature at 60 to 70°C. The obtained liquid polymer is referred to as Polymer A.

Next, 455 g of isobornyl acrylate and 1 portion of vinylpyrrolidone were added to 1000 g of the polymer A obtained above.
27g, trimethylolpropane triacrylate 18
The viscosity of the target composition obtained by mixing 1 g of acetophenone diethyl ketal and 18 g of benzophenone was 9.0 OOcp/25°C.

Example 2 In a reaction vessel equipped with a stirrer, 444 g of inphorone diisocyanate, dibutyltin dilaurate t, a g and 2 were added.
, 1 g of 6-di-t-butyl-4-methylphenol was charged. To this was added 2000 g of polycaprolactone diol (Plaxel 220AL manufactured by Daicel Chemical Industries, Ltd.) over a period of 3 hours while controlling the internal temperature at 60 to 70°C. After the addition is completed, the temperature is further increased at 60 to 70°C for about 1
Stirring was continued for an hour. Thereafter, 232 g of 2-hydroxyethyl acrylate was added over 1 hour while keeping the internal temperature at 60 to 70°C. The obtained liquid polymer is referred to as Polymer B.

Next, to 81,000 g of the polymer obtained above, 490 g of isobornyl acrylate, 181 g of epoxy diacrylate represented by the formula %, 90 g of trimethylolpropane triacrylate, 36 g of acetophenone diethyl ketal, and 18 g of benzophenone were added.
g were mixed to obtain the desired composition. The viscosity of the composition is 9
, 800 cp/25°C. Example 3 Example 1 except that dicyclopentenyl acrylate was used instead of isobornyl acrylate.
The desired composition was obtained in the same manner as above.

The viscosity of the composition was 9,0OOcp/25°C.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that 455 g of vinylpyrrolidone was used instead of isobornyl acrylate.

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

1. Preparation of test piece The composition was applied onto a glass plate using a 250 micron thick applicator, and 3.5 J/cd (wavelength: 350 nm)
) to obtain a cured film. Peel the cured film from the glass plate and heat it for 2 hours at 23℃ and 50% relative humidity.
The condition was adjusted for 4 hours and a test piece was prepared.

2. Measurement of water absorption The water absorption was measured using the above test piece according to JIS K7301. The results are shown in Table-1.

3. Measurement of curing speed Using an optical fiber drawing device equipped with an ultraviolet irradiation device (3.5 Kl output) manufactured by Oak Seisakusho Co., Ltd., the composition was applied to an optical fiber at 1 m/sec and 3 m/sec. It was drawn coated and cured at drawing speed.

The cured fiber coated with the composition was broken into an appropriate length and subjected to Soxhlet extraction (methyl ethyl ketone, 1
2 hours), the extracted residual rate was calculated from the weight before and after extraction, and the extracted residual rate at a drawing speed of 1 m/see was calculated as 100, and the extracted residual rate at a drawing speed of 3 tm/sec was calculated. , the curing speed was evaluated. The results are shown in Table-1.

4. Measurement of Young's modulus The Young's modulus of the test piece was measured at 23°C and 40°C using a tensile tester equipped with a constant temperature bath at a tensile rate of 1 mm/win.
Measurement was performed under the condition that the distance between the gauge lines was 25 mm, and the value at 40°C was determined with the value at 23°C as 1. The results are shown in Table-1.

Table-1 Water absorption rate (%) Curing rate material Young's modulus ratio-2 Example-11, 1930, 6 Example-2 0.9 92
0.6 Example-3 1.1 90
0.6 Comparative Example 1 3.5
93 0.7 [Effects of the Invention] When the liquid curable resin composition of the present invention is prepared as a radiation curable composition, it is cured by various radiations, such as X-rays, electron beams, ultraviolet rays, and visible light; When prepared as a thermosetting composition, it is cured by heating.

The liquid curable resin composition of the present invention has excellent coating properties, has a fast curing speed, and has tensile water properties of the cured product, which are the basic characteristics required for optical fiber coating materials.

It has excellent hydrolysis resistance and Young's modulus at high temperatures. Therefore, the liquid curable resin composition of the present invention is excellent as a coating material for optical fibers, and also as a coating material for various base materials.

Agent: Patent Attorney Shushi Iwamiya Written Amendment (Own Ship May 9, 1986 2, Title of Invention: Liquid Curable Resin Composition 3, Relationship with the Case of the Person Making the Amendment: Address of Patent Applicant: Chuo, Tokyo) Ward Tsukiji 2-11-24
Name (417) Japan Synthetic Rubber Co., Ltd.
(1 other person) Representative Hisashi Yoshimitsu 4, Agent 5, Date of amendment order Voluntary 6, Number of inventions increased by amendment 7, Subject of amendment Detailed explanation of the invention in the specification Section 8,
Contents of the amendment (1) The following sentence will be added next to "..." on page 6, line 9 of the specification.

F (In addition, when the structural unit of general formula (I) is bonded to another structural unit by a urethane bond or an ester bond, the terminal oxygen atom of the structural unit of general formula (I) is one of these bonds. ) J (2) r (V ) in the same book, page 6, lines 10 to 12.
-E-(R30)7(R40 piece R3 or ++R3037→R403-R4"), r (V) -+-(R3f)) □R, nominal r end R3
- or +-(-R30)7-(R, 0th floor→-R2-").

(3) Same book, page 15, lines 12 to 17 (for example, Lajiichi 1matsu) enter°0° (I-1-1■) °°0
[In the formula, n is the same as in general formula (I)]".

"For example, polycaprolactone diol can be mentioned." Correct.

Claims (1)

[Claims] (A) General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (n is an integer from 2 to 90) A polymer having a structural unit and an ethylenically unsaturated group; (B) Crosslinked A liquid curable resin composition comprising: a monomer compound containing an ethylenically unsaturated compound having an alicyclic hydrocarbon group; and (C) a polymerization initiator.