JPH11167202A - Liquid hardening resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid hardening resin compsn. which shows good coating property during fast wiredrawing process, which gives little odor and extremely little contamination to the lamp and which is suitable as a coating material for optical fibers by incorporating a hydroxyl group-contg. urethane (meth) acrylate having a specified structural unit. SOLUTION: This compsn. is a liquid hardening resin compsn. containing a hydroxyl group-contg. urethane(meth)acrylate having one structural unit expressed by the formula in the molecule. In the formula, R<1> is a hydrogen atom or methyl group and preferably a hydrogen atom, R<2> is a (m+1)-valent org. group and preferably selected from 1-20C chain, branched or cyclic hydrocarbon groups or oxygen or nitrogen-contg. org. groups, and (m) is an integer of 1 to 5 and preferably 1 to 3. The structural unit expressed by the formula is produced, for example, by reacting a hydroxyl group-contg. (meth)acrylate with a compd. having an isocyanate group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a liquid curable resin composition. More specifically, the present invention relates to a liquid curable resin composition suitable as a photocurable coating material suitably used for optical fiber coating.

[0002]

2. Description of the Related Art In the production of optical fibers, various resin coatings are applied for the purpose of protection and reinforcement immediately after hot melt spinning of glass fibers. In many cases, radiation-curable liquid resins are used. I have. The basic properties required for these optical fiber-coating materials include, for example, applicability, storage stability, curability, water resistance, chemical resistance,
Good light resistance and oil resistance, sufficient strength and flexibility, little change in physical properties with temperature change, little hydrogen gas generation, etc.

The following prior arts have been proposed to meet these required characteristics. JP-A-3-247671 discloses a technique aimed at improving the temperature dependence of the elastic modulus by defining the glass transition temperature of a resin, and JP-A-4-74735 discloses a method using a specific hydroxyl group-containing acrylate as a raw material. A technology aimed at reducing the temperature dependence of elasticity, water resistance, and the generation of hydrogen gas by using urethane acrylate. Japanese Patent Application Laid-Open No. 6-59452 discloses that a block copolymer polyether containing butylene oxide is used as a raw material. Technology aimed at reducing the temperature dependency of coatability, curability and elastic modulus and improving oil resistance by using urethane acrylate. Japanese Patent Application Laid-Open No. 7-69686 discloses the compounding of N-vinylamide monomer and vinyl ether monomer. And Japanese Patent Application No. Hei 8-46407 discloses a technique aimed at improving the curing speed. By wherein fat viscosity, techniques to reduce the shape change of the cured product is disclosed. The prior art described above is a material comprising a urethane acrylate having acrylate groups at both ends as a main component, a reactive diluent selected from low molecular monomers and a photopolymerization initiator, and a coating property adapted to high-speed drawing. It was necessary to mix a large amount of a reactive diluent in order to obtain the following.

[0004]

Although the above prior art provides some of the characteristics required for an optical fiber coating material, it can be said that it is not necessarily sufficient as a technique to cope with the recent increase in the production of optical fiber cables. Absent. In other words, as a result of the fact that high-speed drawing has been carried out for the purpose of increasing the productivity of optical fibers, in order to stably provide good optical fiber coating, not only the curing speed of the resin is high, but also the bus or element. In order to form a uniform and stable coating film with respect to the wire, good coating properties, low odor as a working environment, and low contamination of the lamp due to volatilization and adhesion of the monomer are required. Therefore, there is a need for a technique for solving these problems without blending a large amount of a reactive diluent as has been practiced in the prior art.

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 suitably used for coating an optical fiber. Still another object of the present invention is to provide a liquid curable resin composition which has good coatability at the time of high-speed drawing, has low odor, and is suitable as a coating material for optical fibers in which contamination of a lamp is extremely small. is there. Still other objects and advantages of the present invention will become apparent from the following description.

[0006]

According to the present invention, the above objects and advantages of the present invention are as follows:

[0007]

Embedded image

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an m + 1-valent organic group, and m is an integer of 1 to 5, and has one structural unit represented by the following formula: This is achieved by a liquid curable resin composition comprising a hydroxyl group-containing urethane (meth) acrylate.

The hydroxyl group-containing urethane (meth) acrylate used in the present invention has one structural unit represented by the above formula (1) in the molecule. In the formula (1), R ¹ is a hydrogen atom or a methyl group, preferably a hydrogen atom. R ² is an m + 1-valent organic group, preferably
To C20 chain, branched or cyclic hydrocarbons or organic groups containing oxygen and nitrogen. m is an integer of 1 to 5, preferably 1 to 3. The structural unit represented by the formula (1) is formed, for example, by reacting a hydroxyl group-containing (meth) acrylate with a compound having an isocyanate group.

The number of hydroxyl groups contained in the molecule of the hydroxyl group-containing urethane (meth) acrylate is one or more, preferably one to five, more preferably one to three, and particularly preferably one. If the number of hydroxyl groups exceeds 5, the water resistance of the cured product may decrease. The hydroxyl group-containing urethane (meth) acrylate used in the present invention is produced by reacting a polyol having two or more hydroxyl groups in a molecule, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate.

The number of hydroxyl groups in the hydroxyl group-containing (meth) acrylates is usually one per molecule. That is, it is produced by reacting an isocyanate group of the polyisocyanate with a hydroxyl group of the polyol and a hydroxyl group-containing (meth) acrylate, respectively. As a synthesis method, for example, 1) a method in which a polyol, a polyisocyanate and a hydroxyl group-containing (meth) acrylate are charged and reacted at once, 2) a polyol and a polyisocyanate are reacted, and then a hydroxyl group (meth) acrylate is reacted. Method 3) A method in which a polyisocyanate and a hydroxyl group-containing (meth) acrylate are reacted, and then a polyol is reacted.

Among these, as a method for obtaining a hydroxyl group-containing urethane (meth) acrylate according to the present invention with good yield, a compound having a structure in which isocyanate is left by reacting a polyisocyanate and a hydroxyl group-containing (meth) acrylate to once synthesize the compound. Then, a method 3) of reacting a polyol is preferable.

The polyol used here includes, for example, aliphatic, alicyclic or aromatic polyether diols, polyester diols, polycarbonate diols and polycaprolactone diols. These polyols can be used alone or in combination of two or more. As the polyol, a divalent or higher valent polyol synthesized by a reaction between a diol and a polyisocyanate can also be used. The polymerization mode of each structural unit in these polyols is not particularly limited,
Any of random polymerization, block polymerization, and graft polymerization may be used.

As the aliphatic polyether diol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol and two or more ion-polymerizable cyclic compounds are ring-opened. And polyether diols obtained by copolymerization.

Examples of the ionic polymerizable cyclic compound 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.

Specific examples of polyether diols obtained by ring-opening copolymerization of two or more of the above ion-polymerizable cyclic compounds include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran. And a binary copolymer obtained from a combination of tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1-oxide and ethylene oxide, and a terpolymer obtained from a combination of tetrahydrofuran, butene-1-oxide and ethylene oxide. be able to.

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 acid lactide; or dimethylcyclopolysiloxane. Polyether diols can also be used.

The above aliphatic polyether diols include, for example, PTMG650, PTMG1000, PTMG200
0 (Mitsubishi Chemical), PPG400, PPG100
0, EXCENOL 720, 1020, 2020 (all manufactured by Asahi Ohlin), PEG1000, Unisafe DC
1100, DC1800 (all made by NOF Corporation), PPT
G2000, PPTG1000, PTG400, PTG
L2000 (all made by Hodogaya Chemical Industry), Z-300
1-4, Z-3001-5, PBG2000A, PBG
2000B, EO / BO4000, EO / BO2000
(Above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

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, for example, an alkylene oxide-added diol of bisphenol A, an alkylene oxide-added diol of bisphenol F, an alkylene oxide-added diol of hydroquinone, an alkylene oxide-added diol of naphthohydroquinone, and an alkylene oxide of anthrahydroquinone. And addition diols. The aromatic polyether diol is, for example, Uniol DA400, D
It is also available as a commercial product such as A700, DA1000, DA4000 (all manufactured by NOF Corporation).

Examples of the polyester diol include a polyester diol 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,
-Methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and the like. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like.

Among the above-mentioned polyester diols, commercially available products include, for example, Clapol P-2010, P-101
0, L-2010, L-1010, A-2010, A-
1010, F-2020, F-1010, PMIPA-
2000, PKA-A, PNOA-2010, PNOA
-1010 (all made by Kuraray) and the like.

As the polycarbonate diol, for example, polycarbonate of polytetrahydrofuran, 1,6
-Hexanediol polycarbonate; and commercial products such as DN-980, 981, 982, 9
83 (all made of Nippon Polyurethane), PC-8000
(US PPG), PC-THF-CD (BASF)
And the like.

Examples of the polycaprolactone diol include polycaprolactone diol obtained by reacting ε-caprolactone with a diol. Examples of the diol used herein include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, , 4-cyclohexanedimethanol, 1,4-butanediol and the like. These polycaprolactone diols are available from Praxel 205,
205AL, 212, 212AL, 220, 220AL
(Manufactured by Daicel) and other commercially available 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,
And polydimethylsiloxane carbitol-modified polyol.

The preferred molecular weight of the polyol used for producing the hydroxyl group-containing urethane (meth) acrylate of the present invention is usually 3 as a number average molecular weight in terms of polystyrene.
00 to 15,000, preferably 500 to 12.0
00.

Among these polyols (polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols and the like), polyether polyols are preferred in view of durability and low-temperature characteristics.

Examples of the polyisocyanate used for producing the hydroxyl group-containing urethane (meth) acrylate of the present invention include 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4, 4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1.6
-Hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenyl Diisocyanates such as propane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, and lysine triisocyanate, triisocyanates which are triisocyanuric derivatives that are trimers of the above diisocyanates, poly Methylene polyphenyl polyisocyanate.

Of these, diisosonates, particularly 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and methylene bis (4-cyclohexyl isocyanate) are preferred. These polyisocyanates are
They can be used alone or in combination of two or more.

The hydroxyl group-containing (meth) used for producing the hydroxyl group-containing urethane (meth) acrylate of the present invention.
As the acrylates, (meth) acrylates containing one hydroxyl group bonded to the first carbon atom or the second carbon atom in the molecule are used.

Examples of (meth) acrylates containing a hydroxyl group bonded to the first carbon atom include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1.6 -Hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate, poly (.epsilon.-caprolactone) mono [2- (meth) acryloxyethyl] ester, .gamma.
Examples include hydroxyalkyl acrylates such as phenoxy-β-hydroxypropyl (meth) acrylate.

Examples of (meth) acrylates containing a hydroxyl group bonded to the second carbon atom include glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether and glycidyl (meth) acrylate, and (meth) acrylic acid. Can be mentioned.

Of these hydroxyl group-containing (meth) acrylates, hydroxyl group-containing acrylates bonded to the first carbon atom are preferable, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxypropyl (meth) acrylate. Hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate,
Pentaerythritol tri (meth) acrylate is particularly preferred. These hydroxyl group-containing (meth) acrylates can be used alone or in combination of two or more.

In the production of the hydroxyl group-containing urethane (meth) acrylate used in the present invention, the proportion of the polyol, polyisocyanate and hydroxyl group-containing (meth) acrylate used is usually such that the hydroxyl group-containing (meth) acrylate is based on 1 mol of the polyol. One mole of a polyisocyanate can be synthesized by reacting 2.0 equivalents as isocyanate group equivalents. However, the present invention can be carried out outside this range as long as the hydroxyl group-containing urethane (meth) acrylate of the present invention is formed. For example, the number of moles B of polyisocyanate, the number N of isocyanate groups per molecule of polyisocyanate, the number C of moles of polyol, and the number M of hydroxyl groups per molecule of polyol are based on A mole of hydroxyl group-containing (meth) acrylate. In this case, it can be synthesized within the range of the following formula (2). C × M ≧ (B × N) -A (2) The viscosity of the hydroxyl group-containing urethane (meth) acrylate is 2
The viscosity at 5 ° C. is 1,000 to 30,000 cps, preferably 1,000 to 20,000 cps, more preferably 10 to 20,000 cps.
00 to 10000 cps. Viscosity 30,000 cp
If it exceeds s, or if it is less than 1000 cps, the coatability of the composition at the time of high-speed drawing tends to deteriorate.

The content of the hydroxyl group-containing urethane (meth) acrylate in the composition is not particularly limited, but is preferably 5 to 80 parts by weight, more preferably 20 to 60 parts by weight, per 100 parts by weight of the composition. Parts by weight.
If the amount is less than 5 parts by weight, a sufficient effect on coatability may not be obtained, and if the amount exceeds 80 parts by weight, the mechanical properties may not be sufficient.

The composition of the present invention may further contain, as another component, urethane acrylate having an acrylate group introduced at both terminals, which is commonly used in the art.

As such a urethane (meth) acrylate, for example, a urethane acrylate known in the art obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyisocyanate and a polyol can be used. In the synthesis, after a reaction product of a hydroxyl group-containing (meth) acrylate and a polyisocyanate is synthesized in advance,
It can be carried out in the step of reacting the polyol.
Examples of the above-mentioned reaction products synthesized in advance include, for example, hydroxyethyl (meth) acrylate and 2,5 or 2,
6-bis (isocyanatomethyl) -bicyclo [2.2.
1] Heptane reaction product, hydroxyethyl (meth)
Reaction product of acrylate and 2,4-tolylene diisocyanate, reaction product of hydroxyethyl (meth) acrylate and isophorone diisocyanate, reaction product of hydroxypropyl (meth) acrylate and 2,4-tolylene diisocyanate, hydroxypropyl Examples include a reaction product of (meth) acrylate and isophorone diisocyanate. Among these, it is a reaction product of hydroxyethyl (meth) acrylate and 2,4-tolylene diisocyanate. It is preferable to mix bis (2-acryloxyethyl) 2,4-tolylene dicarbamate from the viewpoint of improving the mechanical strength of the cured product.
These urethane acrylates can be synthesized as a mixture at the same time as the hydroxyl group-containing urethane acrylate.

In the reaction for producing urethane (meth) acrylate from polyol, diisocyanate and hydroxyl group-containing (meth) acrylate, an acidic or basic catalyst can be added for the main purpose of shortening the reaction time. Examples of such a catalyst include metal salts such as copper naphthenate, cobalt naphthenate, zinc naphthenate, and di-n-butyltin laurate; triethylamine; 1,4-diazabicyclo [2.2.2] octane;
6,7-trimethyl-1,4-diazabicyclo [2.2.
2] There are basic compounds such as octane. The amount of the catalyst added is usually 0.01 to 100 parts by weight of the total amount of the reactants.
Use up to 1 part by weight. The reaction temperature is usually 10 to 90
C., preferably at 30-80.degree.

The hydroxyl group-containing urethane (meth) acrylate of the present invention has a number average molecular weight in terms of polystyrene of 500 to 500.
Preferably, it is 20,000. The molecular weight is 500
If the molecular weight is less than 20,000, the mechanical strength of the cured product may be insufficient.

The composition of the present invention is cured by heating and / or light irradiation. In the present invention, a polymerization initiator may be blended as necessary. Examples of such a polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. Here, light means infrared light, visible light, ultraviolet light, X-ray,
Electron beam, α-ray, β-ray, γ-ray and the like.

When the composition of the present invention is cured by heat,
Usually, a radical polymerization initiator such as a peroxide or an azo compound is used. As a specific radical polymerization initiator,
Examples include benzoyl peroxide, t-butyl-oxybenzoate, azobisisobutyronitrile, and the like.

When the composition of the present invention is cured by light, a photopolymerization initiator is used. Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, and 4-chloroacetate. Benzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone,
-Chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1
-One, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like.

These commercial products include Irgacur
e184, 369, 651, 500, 907, CGI1
700, CGI1750, CGI1850, CG24-
61 (all, manufactured by Ciba Specialty Chemicals); Lucirin LR8728 (manufactured by BASF); D
arocur 1116, 1173 (all manufactured by Ciba Specialty Chemicals); Jubecryl P36 (UC
B). Preferred examples include: I
rgacure 184, Irgacure 651, Ir
gacure907, Darocur1173, L
ucirin LR8728.

When the composition of the present invention is cured by using both heating and irradiation of radiation, the above-mentioned thermal polymerization initiator and photopolymerization 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.

The composition of the present invention may contain, if necessary, other than the above components, as long as the properties of the composition of the present invention are not impaired.
A reactive diluent can be included. The content can be used at 20 parts by weight or less per 100 parts by weight of the composition. If the amount exceeds 20 parts by weight, odor and volatility may increase, and the lamp may be contaminated during high-speed drawing. The preferred range is 5 to 15 parts by weight. As the reactive diluent, a monomer having no urethane bond and having at least one (meth) acryloyl group or vinyl group in the molecule is used. Such monomers include monofunctional monomers and two or more polyfunctional monomers.

The monofunctional monomers include, for example, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Alicyclic structure-containing (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,

Phenoxyethyl (meth) acrylate,
Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene 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, and the following formula (3)

Embedded image

Here, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkylene group having 2 to 6, preferably 2 to 4 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Wherein n is an integer of 0 to 12, and a polyether skeleton-containing (meth) acrylate represented by the formula:

N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylcarbazole, N-vinylsuccinimide, N-vinylphthalate, which are unsaturated monomers having a vinyl group substituted on the nitrogen atom Acid imide,

Also, hydroxybutyl vinyl ether,
Lauryl vinyl ether, cetyl vinyl ether, 2-
And vinyl ethers such as ethylhexyl vinyl ether.

Commercial products of these monofunctional monomers include, for example, Aronix M111, M113, M11
4, M117 (all manufactured by Toagosei); KAYARAD
TC110S, R629, R644 (all manufactured by Nippon Kayaku); IBXA (manufactured by Osaka Organic Chemical Industry) and the like. Of these, isobornyl (meth) acrylate,
Polyoxyethylene nonyl phenyl ether acrylate and N-vinyl pyrrolidone 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. Among these, preferred are 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Tricyclodecane dimethanol di (meth) acrylate.

The trifunctional or higher polyfunctional monomers include:
For example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth)
Acrylate, tris (2- (meth) acryloxyethyl) isocyanurate and the like can be mentioned. Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexaacrylate are preferred.

These polyfunctional monomers include, for example, FA
731A (manufactured by Hitachi Chemical); Aronix M-31
5, M-350, M-360, M-405, M-450
(Manufactured by Toa Gosei); KAYARAD DPHA, D-31
0, D-320, D-330, DPCA-20, DPC
A-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku); Viscort # 400 (manufactured by Osaka Organic Chemical Industry), Photomer 4172, 4149 (manufactured by San Nopco) and the like. These reactive diluents can be used alone or in combination of two or more as necessary.

In the present invention, a non-polymerizable additive other than the reactive diluent and the polymerization initiator, for example, an antioxidant,
It may contain an ultraviolet absorber, a light stabilizer, a silane coupling agent, and the like. Here, as the antioxidant, for example, Irganox 1010, 1035, 107
6, 1222 (all made by Ciba Specialty Chemicals), Antigene P, 3C, FR, GA-
80 (manufactured by Sumitomo Chemical). As the ultraviolet absorber, for example, Tinuvin P, 234, 320,
326, 327, 328, 329, 213 (all manufactured by Ciba Specialty Chemicals), Seesorb
102, 103, 501, 202, 712, and 704 (all manufactured by Cipro Kasei). As the light stabilizer, for example, Tinuvin 292, 144, 622L
D (all made by Ciba Specialty Chemicals),
Sanol LS770 (manufactured by Sankyo), Sumisorb T
M-061 (manufactured by Sumitomo Chemical). Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and commercially available products SH6062, 6030 (and above)
Toray Dow Corning Silicone), KBE903,
603 and 403 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

In the composition of the present invention, inorganic and organic fillers, coloring pigments, dyes, dispersing agents, slip agents, antistatic agents, leveling agents, etc. A sensitizer, an amine, and an organic solvent may be blended. The preferable range of the viscosity of the composition of the present invention prepared as described above is preferably 1000 to 25000 cps, more preferably 1500 to 15000 cps, particularly preferably 2000 to 12000 cps, as measured at 25 ° C.

[0058]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Production examples of the hydroxyl group-containing urethane (meth) acrylate of the present invention are shown below.

Production Example 1-1 185.1 g (1.06) of 2,4-tolylene diisocyanate (hereinafter abbreviated as TDI) was placed in a reaction vessel equipped with a stirrer.
0.13 g of 2,6-di-t-butyl-4-methylphenol (hereinafter abbreviated as thermal polymerization inhibitor 1),
And phenothiazine (hereinafter abbreviated as thermal polymerization inhibitor 2)
Was charged. After cooling this in an ice water bath to 10 ° C., dibutyltin dilaurate (hereinafter abbreviated as catalyst)
Was added, and hydroxyethyl acrylate (hereinafter abbreviated as HEA) 123.4 g (1.063 mol) was further added.
l) was added while controlling the temperature to 30 ° C or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and the number average molecular weight was 650.
691.5 g of polytetramethylene glycol (hereinafter, referred to as
(Abbreviated as PTMG650) (1.063 mol)
The mixture was stirred at a temperature of 60 ° C. for 3 hours to complete the reaction. Thus, HEA / TDI / PTMG650 = 1/1 /
Thus, 1000 g of a hydroxyl group-containing urethane acrylate (A) as a reaction product in a molar ratio was obtained. Its viscosity at 25 ° C. was 6,600 cps.

Production Example 1-2 135 g of TDI (0.7 g) was placed in a reaction vessel equipped with a stirrer.
75 mol), 0.13 g of thermal polymerization inhibitor 1 and 0.04 g of thermal polymerization inhibitor 2 were charged. After cooling this to 10 ° C. in an ice water bath, 0.44 g of a catalyst was added, and HEA was further added.
90.0 g (0.775 mol) was added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 775 g (0.775 mol) of PTMG1000 was added.
l) The mixture was stirred at a temperature of 60 ° C. for 3 hours to complete the reaction. Thus, HEA / TDI / PTMG100
Thus, 1000 g of a hydroxyl group-containing urethane acrylate (B) as a reaction product in a molar ratio of 0 = 1/1/1 was obtained. Its viscosity at 25 ° C. was 5,800 cps.

Production Example 1-3 In a reaction vessel equipped with a stirrer, 76.0 g (0.4 g) of TDI was added.
36 mol), 0.13 g of thermal polymerization inhibitor 1 and 0.04 g of thermal polymerization inhibitor 2 were charged. After cooling this to 10 ° C. in an ice water bath, 0.44 g of a catalyst was added, and HEA was further added.
50.7 g (0.436 mol) were added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 873.2 g (0.436 mol) of PTMG2000 was added.
l) The mixture was stirred at a temperature of 60 ° C. for 3 hours to complete the reaction. Thus, HEA / TDI / PTMG200
Thus, 1000 g of a hydroxyl group-containing urethane acrylate (C) as a reaction product in a molar ratio of 0 = 1/1/1 was obtained. Its viscosity at 25 ° C. was 13,500 cps.

Production Example 1-4 In a reaction vessel equipped with a stirrer, 240.7 g of TDI (1.
382 mol), 0.13 g of thermal polymerization inhibitor 1 and 0.04 g of thermal polymerization inhibitor 2 were charged. This was cooled to 10 ° C. in an ice-water bath, and 0.44 g of a catalyst was added.
160.5 g (1.382 mol) of A was added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 598.8 g of PTMG650 (0.921 m
ol), and the mixture was stirred at a temperature of 60 ° C. for 3 hours to complete the reaction. Thus, HEA / TDI / PTMG65
Thus, 1000 g of a hydroxyl group-containing urethane acrylate (D) as a reaction product in a molar ratio of 0 = 1.5 / 1.5 / 1 was obtained. Its viscosity at 25 ° C. was 29000 cps.

Production Example 1-5 In a reaction vessel equipped with a stirrer, 182.0 g of TDI (1.
045 mol), 0.13 g of thermal polymerization inhibitor 1 and 0.04 g of thermal polymerization inhibitor 2 were charged. This was cooled to 10 ° C. in an ice-water bath, and 0.44 g of a catalyst was added.
A121.3 g (1.045 mol) was added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 696.7 g (0.697) of PTMG1000 was added.
mol), and the mixture was stirred at a temperature of 60 ° C. for 3 hours to complete the reaction. Thus, HEA / TDI / PTMG1
Thus, 1000 g of a hydroxyl group-containing urethane acrylate (E) as a reaction product in a 000 = 1.5 / 1.5 / 1 molar ratio was obtained. Its viscosity measured at 25 ° C. is 21,000 cp.
s.

Production Example 1-6 In a reaction vessel equipped with a stirrer, 107.3 g of TDI (0.4 g) was added.
616 mol), 0.13 g of thermal polymerization inhibitor 1 and 0.04 g of thermal polymerization inhibitor 2 were charged. This was cooled to 10 ° C. in an ice-water bath, and 0.44 g of a catalyst was added.
A71.5 g (0.616 mol) was added while controlling the temperature to 30 ° C or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 821.2 g (0.411 m) of PTMG2000 was added.
ol), and the mixture was stirred at a temperature of 60 ° C. for 3 hours to complete the reaction. Thus, HEA / TDI / PTMG20
Thus, 1000 g of a hydroxyl group-containing urethane acrylate (F) as a reaction product in a molar ratio of 00 = 1.5 / 1.5 / 1 was obtained.
Its viscosity measured at 25 ° C. was 24000 cps.

Production Example 2-1 In a reaction vessel equipped with a stirrer, 185.1 g (1.0 mL) of TDI was added.
63 mol), 0.13 g of thermal polymerization inhibitor 1, and
0.04 g of thermal polymerization inhibitor 2 was charged. This was cooled to 10 ° C. in an ice-water bath, and then 0.88 g of a catalyst was added.
123.4 g (1.063 mol) of EA was added while controlling the temperature to 30 ° C. or lower. After addition, at 20-30 ° C
After stirring for 69 hours, 691.5 g of polypropylene glycol having a number average molecular weight of 650 (hereinafter abbreviated as PPG650) (1.
0.63 mol) and stirred at a temperature of 60 ° C. for 12 hours.
The reaction was terminated. Thus, HEA / TDI /
There was obtained 1000 g of a hydroxyl group-containing urethane acrylate (G) which was a reaction product having a PPG650 = 1/1/1 molar ratio. Its viscosity measured at 25 ° C. is 10900 cp
s.

Production Example 2-2 In a reaction vessel equipped with a stirrer, 135 g (0.7 g) of TDI was added.
75 mol), 0.13 g of thermal polymerization inhibitor 1 and 0.04 g of thermal polymerization inhibitor 2 were charged. This was cooled to 10 ° C. in an ice-water bath, and then 0.88 g of the catalyst was added.
90.0 g (0.775 mol) was added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 775 g (0.775 mol) of PPG1000 was added.
In addition, the mixture was stirred at a temperature of 60 ° C. for 12 hours to complete the reaction. Thus, HEA / TDI / PPG1000
= 1000 g of a hydroxyl group-containing urethane acrylate (H), which is a reaction product at a 1/1/1 molar ratio, was obtained. Its viscosity at 25 ° C. was 6,800 cps.

Production Example 2-3 In a reaction vessel equipped with a stirrer, 76.0 g (0.4 g) of TDI was added.
36 mol), 0.13 g of thermal polymerization inhibitor 1 and 0.04 g of thermal polymerization inhibitor 2 were charged. This was cooled to 10 ° C. in an ice-water bath, and then 0.88 g of the catalyst was added.
50.7 g (0.436 mol) were added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 873.2 g (0.436 mol) of PPG2000 was added.
1) The mixture was stirred at a temperature of 60 ° C. for 12 hours to complete the reaction. Thus, the HEA / TDI / PPG200
There was obtained 1000 g of a hydroxyl group-containing urethane acrylate (I) as a reaction product in a molar ratio of 0 = 1/1/1. Its viscosity at 25 ° C. was 2700 cps.

Production Example 2-4 In a reaction vessel equipped with a stirrer, 182.0 g of TDI (1.
045 mol), 0.13 g of thermal polymerization inhibitor 1 and 0.04 g of thermal polymerization inhibitor 2 were charged. This was cooled to 10 ° C. in an ice water bath, and then 0.88 g of the catalyst was added.
A121.3 g (1.045 mol) was added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 696.7 g (0.697 m) of PPG1000 was added.
ol), and the mixture was stirred at a temperature of 60 ° C. for 12 hours to complete the reaction. Thus, HEA / TDI / PPG10
Thus, 1000 g of a hydroxyl group-containing urethane acrylate (J) as a reaction product in a molar ratio of 00 = 1.5 / 1.5 / 1 was obtained.
Its viscosity at 25 ° C. was 27000 cps.

Production Example 2-5 In a reaction vessel equipped with a stirrer, 107.3 g of TDI (0.1 mL) was added.
616 mol), 0.13 g of thermal polymerization inhibitor 1 and 0.04 g of thermal polymerization inhibitor 2 were charged. This was cooled to 10 ° C. in an ice water bath, and then 0.88 g of the catalyst was added.
A71.5 g (0.616 mol) was added while controlling the temperature to 30 ° C or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 821.2 g (0.411 mol) of PPG2000 was added.
1) The mixture was stirred at a temperature of 60 ° C. for 12 hours to complete the reaction. Thus, the HEA / TDI / PPG200
Thus, 1000 g of a hydroxyl group-containing urethane acrylate (K) as a reaction product in a molar ratio of 0 = 1.5 / 1.5 / 1 was obtained. Its viscosity at 25 ° C. was 7100 cps.

Comparative Production Example 1-1 In a reaction vessel equipped with a stirrer, 283.1 g of TDI (1.
626 mol), 0.13 g of polymerization inhibitor 1 and 0.04 g of polymerization inhibitor 2 were charged. After cooling this to 10 ° C. in an ice water bath, 0.44 g of catalyst was added, and HE was added.
A 188.7 g (1.626 mol) of A was added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 528.2 g (0.813 m) of PTMG650 was added.
ol), and the mixture was stirred at a temperature of 60 ° C. for 3 hours to complete the reaction. Thus, HEA / TDI / PTMG65
1000 g of urethane acrylate (L) having both ends at a molar ratio of 0 = 2/2/1 was obtained. Its viscosity at 25 ° C. was 226000 cps.

Comparative Production Example 1-2 In a reaction vessel equipped with a stirrer, 220.1 g of TDI, 0.13 g of polymerization inhibitor 1 and 0.04 g of polymerization inhibitor 2
Was charged. After this was cooled to 10 ° C. in an ice-water bath, 0.44 g of the catalyst was added, and 146.7 g of HEA was further added while controlling the temperature to 30 ° C. or lower. After addition, 20-3
The mixture was stirred at 0 ° C for 1 hour, 633 g of PTMG1000 was added, and the mixture was stirred at a temperature of 60 ° C for 3 hours to complete the reaction. Thus, HEA / TDI / PTMG1000 = 2
/ 2/1 molar ratio urethane acrylate (M) 1 at both ends
000 g were obtained. Its viscosity measured at 25 ° C. is 6
It was 9000 cps.

Comparative Production Example 1-3 In a reaction vessel equipped with a stirrer, 135.0 g of TDI (0.
775 mol), 0.13 g of polymerization inhibitor 1 and 0.04 g of polymerization inhibitor 2 were charged. After cooling this to 10 ° C. in an ice water bath, 0.44 g of catalyst was added, and HE was added.
90.0 g (0.775 mol) of A was added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 775 g of PTMG2000 (0.388 mol) was added.
l) The mixture was stirred at a temperature of 60 ° C. for 3 hours to complete the reaction. Thus, HEA / TDI / PTMG200
1000 g of urethane acrylate (N) at both ends was obtained in a molar ratio of 0 = 2/2/1. Its viscosity at 25 ° C. was 59000 cps.

Comparative Production Example 2-1 283.1 g of TDI (1.
626 mol), 0.13 g of polymerization inhibitor 1 and 0.04 g of polymerization inhibitor 2 were charged. This was cooled to 10 ° C. in an ice-water bath, and then 0.88 g of the catalyst was added.
188.7 g (1.626 mol) were added while controlling the temperature to 30 ° C. or lower. After the addition, the mixture was stirred at 20 to 30 ° C. for 1 hour, and 528.2 g (0.813 mol) of PPG650 was added.
1) The mixture was stirred at a temperature of 60 ° C. for 12 hours to complete the reaction. Thus, HEA / TDI / PPG650
= 1000 g of urethane acrylate (O) at both ends at a molar ratio of 2/2/1. Its viscosity at 25 ° C. was 1168000 cps.

Comparative Production Example 2-2 In a reaction vessel equipped with a stirrer, 220.1 g of TDI, 0.13 g of polymerization inhibitor 1 and 0.04 g of polymerization inhibitor 2
Was charged. After this was cooled to 10 ° C. in an ice-water bath, 0.88 g of the catalyst was added, and 146.7 g of HEA was further added while controlling the temperature to 30 ° C. or lower. After addition, 20-3
Stir at 0 ° C. for 1 hour, add 633 g of PPG1000,
The mixture was stirred at a temperature of 60 ° C. for 12 hours to complete the reaction. Thus, HEA / TDI / PPG1000 = 2/2
/ 1 molar ratio urethane acrylate (P) at both ends 100
0 g was obtained. Its viscosity measured at 25 ° C. is 130
It was 400 cps.

Reference Production Example Synthesis of bis (2-acryloxyethyl) 2,4-tolylenedicarbamate (hereinafter abbreviated as HTH) In a reaction vessel equipped with a stirrer, 428 g of TDI, 0.13 g of polymerization inhibitor 1 and 0.13 g of polymerization inhibitor 1 were added. 0.04 g of the polymerization inhibitor 2 was charged. The mixture was cooled to 10 ° C in an ice-water bath, 0.44 g of the catalyst was added, and 571 g of HEA was further cooled to 30 ° C.
It was added while controlling as follows. After the addition, the mixture was stirred at 20 to 30 ° C for 1 hour, and then stirred at a temperature of 60 ° C for 3 hours to complete the reaction. In this way, 1000 g of the above urethane acrylate was obtained. Its viscosity at 25 ° C. was 1,000,000 cps or more.

Examples 1 to 11 and Comparative Examples 1 to 5 The resin compositions of Examples and Comparative Examples were prepared by mixing the components at a temperature of 60 ° C. Tables 1 and 2 show composition examples of the compositions of the examples and evaluation results. Table 3 shows the composition examples of the compositions of the comparative examples and the evaluation results.

Test Examples The production examples, examples, comparative production examples and evaluation methods in comparative examples of the present invention are shown below.

(Measurement of Viscosity) The viscosity was measured at 25 ° C. using a B-type viscometer manufactured by Tokyo Keiki.

(Evaluation of Coating Property of Composition) Using an optical fiber drawing apparatus (manufactured by Yoshida Kogyo), a liquid curable resin composition Desolite (registered trademark) R1055 made of Japan Synthetic Rubber was used as a primary coating material. The compositions of the examples or comparative examples of the present invention were used as the secondary coating materials.
The drawing conditions of the optical fiber were as follows. Quartz glass was used as the optical fiber. The diameter of the drawn bus bar after melting was adjusted to 125 μm, the fiber diameter when the primary coating material was applied was adjusted to 200 μm, and the diameter after applying the composition of the example of the present invention and the composition of the comparative example was 25 μm.
Adjusted to 0 μm. Optical fiber drawing speed is 800
m / min, and an ultraviolet irradiation device (O
A UV lamp manufactured by RC, SMX 3.5 kw) was used. The evaluation of the coating property at the time of the drawing test was performed by observing the surface state of the coated optical fiber after performing the long-distance drawing at the above speed with an optical microscope having a magnification of 30 times. If there is a ○, the coating is cut,
A case where a non-uniform portion was found was marked as x.

(Evaluation of Lamp Contamination) A lamp which was found to be contaminated by the lamp cover after a long operation was evaluated as x, and a lamp which was not abnormal was evaluated as ○.

(Evaluation of presence or absence of odor) The presence or absence of odor was evaluated by the presence or absence of odor from around the lamp during operation.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

Industrial Applicability The liquid curable resin composition of the present invention has good coatability during high-speed drawing, has low odor, and reduces lamp contamination, and is suitable as an optical fiber coating material. Things. A preferred embodiment of the present invention will be described as follows. 1. In the molecule, the following formula (1)

Embedded image Here, R ¹ is a hydrogen atom or a methyl group;
² is an m + 1-valent organic group, and m is an integer of 1 to 5. A liquid curable resin composition comprising a hydroxyl group-containing urethane (meth) acrylate having one structural unit represented by the following formula: Stuff. 2. 25 ° C of hydroxyl group-containing urethane (meth) acrylate
1. The viscosity of the above 1., wherein the viscosity is 1000 to 30000 cps.
3. The liquid curable resin composition according to item 1. 3. 25 ° C of hydroxyl group-containing urethane (meth) acrylate
2. The viscosity as described in 1. above, wherein the viscosity is 1000 to 25000 cps.
3. The liquid curable resin composition according to item 1. 4. 3 above. 3. A cured product of the liquid curable resin composition according to item 1.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI G02B 6/44 301 G02B 6/44 301A // C08G 18/67 C08G 18/67 (72) Inventor Yuichi Eriyama 2-chome Tsukiji, Chuo-ku, Tokyo No. 11-24 Inside Nippon Gosei Rubber Co., Ltd. (72) Inventor Kozen Zen 2-chome Tsukiji, Chuo-ku, Tokyo 11-24 Inside Nippon Gosei Rubber Co., Ltd. No. 11-24, Nippon Gosei Rubber Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the following formula (1): Here, R ¹ is a hydrogen atom or a methyl group;
² is an organic group having a valence of m + 1, and m is an integer of 1 to 5. A liquid curable resin composition comprising a hydroxyl group-containing urethane (meth) acrylate having one structural unit represented by the following formula: Stuff. 2. A cured product of the liquid curable resin composition according to claim 1.