JP2003226725A - Radiation curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation curable resin composition having a high gel fraction with a small amount of radiation exposure. <P>SOLUTION: This radiation curable resin composition comprises (A) a polyurea polyurethane (meth)acrylate oligomer of 10-90 wt.% having a molecular chain terminal structure represented by formula (1) (wherein, R<SP>1</SP>, R<SP>3</SP>aer each a methyl group or hydrogen, R<SP>2</SP>is a divalent organic group and R<SP>4</SP>, R<SP>5</SP>are each a divalent organic group), in which the oligomer is obtained by a urea and urethane bonding reaction between an addition reaction product of a polymer having an amino group at its both terminals and a compound having two (meth)acrylic groups, and a diisocyanate compound and a (meth)acrylate having a hydroxyl group, and (B) an ethylenic unsaturated compound of 90-10 wt.%. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a cured product which is cured by radiation and achieves a high gel fraction even with a low irradiation dose of radiation, and has a fast curing property, and is particularly preferably used for coating an optical fiber. Radiation-curable resin composition.

[0002]

2. Description of the Related Art Conventionally, various optical fibers for optical communication, such as quartz fiber, multi-component glass fiber, and plastic fiber, are known.
Among them, silica-based fibers have been widely used because of their light weight, good heat resistance, good non-inductivity, low loss, and large transmission capacity.

Although this silica-based optical fiber for optical communication has the above-mentioned characteristics, it is extremely thin and brittle, is easily broken by external factors, and causes an increase in transmission loss due to external stress. After primary coating with a soft primary or buffer coating material, this secondary layer is then secondary coated with a secondary or top coating material to protect the primary coating layer. It is being appreciated.

The properties required for this primary coating material are low Young's modulus and small temperature dependence in order to prevent microbend loss due to external stress or temperature change, and the light leaked from the glass fiber is It is required to have a sufficiently high refractive index so as not to be returned to the fiber.

On the other hand, the secondary coating material protects the soft primary coating layer from external force and finally improves the strength of the optical fiber, and has a high Young's modulus and a high Young's modulus even at high temperature. High elongation and high strength are required.

From the viewpoint of reliability, both of these coating materials have low water absorption, low hydrogen generation, and durability (heat resistance, heat resistance,
It is required to have characteristics such as good water resistance.

Further, in recent years, there has been a demand for cost reduction of optical fibers, and in order to reduce costs, improvement of productivity by increasing the drawing speed of optical fibers has been studied. Currently, as a coating material, an ultraviolet-curable liquid resin composition is used as disclosed in Japanese Patent Nos. 2811070 and 2525177, and these resins are cured and coated with ultraviolet rays. As the ratio becomes large, the irradiation amount of this ultraviolet ray to the resin becomes small, and the gel fraction of the coating resin decreases, which affects the fiber performance. That is, unreacted components increase, and these act on the interface between the coating material (primary coating material) and glass, or between the coating materials (primary coating material and secondary coating), and the optical fiber characteristics deteriorate due to peeling, etc. To do.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a radiation curable resin composition having a high gel fraction even with a small irradiation amount of radiation.

[0009]

Means for Solving the Problems and Modes for Carrying Out the Invention The inventors of the present invention have made extensive studies in order to achieve the above-mentioned object, and as a result, have hitherto been known a UV-curable coating composition for optical fibers. That is, in a resin composition containing (A) a polyurethane (meth) acrylate oligomer and (B) an ethylenically unsaturated compound, a polyurethane (meth) acrylate oligomer as a main component is added to the terminal obtained by the following method. By using an oligomer having two acrylic functional groups, it was found that a cured product having a high gel fraction can be obtained even with a low irradiation amount of radiation, and the present invention was completed.

That is, the present invention is (A) A compound having amino groups at both ends and two (meth) acrylic groups To the product obtained by the addition reaction with The diisocyanate compound and the (meth) acrylate having a hydroxyl group are used as urea The structure represented by the following formula (1) obtained by the retanization reaction has a molecular chain end. Polyurea polyurethane (meth) acrylate oligomer having edges                                                         10 to 90% by weight

[0011]

[Chemical 2]

(R ¹ and R ³ are methyl groups or hydrogen atoms, R ² is a divalent organic group, R ⁴ and R ⁵ are divalent organic groups) and (B) an ethylenically unsaturated compound 90 A radiation-curable resin composition containing 10 to 10% by weight and a resin composition for coating an optical fiber are provided.

The present invention will be described in more detail below.

(A): Polyurea polyurethane (meth)
Acrylate Oligomer The polyurea polyurethane (meth) acrylate oligomer, which is the first component of the radiation curable resin composition of the present invention, comprises (a) a polymer having amino groups at both ends and (b) two (meth). By a Michael addition reaction with a compound having an acryl group, a polymer having an acryl group and an amino group at the (c) end is obtained, and then this polymer, and (d) diisocyanate and (e) a (meth) acrylate compound having a hydroxyl group. It can be obtained by a urethanization reaction with. The weight average molecular weight of the polyurea polyurethane (meth) acrylate oligomer is, for example, 1,000 to 2
It can be selected from the range of about 10,000, preferably about 1,000 to 10,000.

(A) Polymer having amino groups at both ends As a polymer component having amino groups at both ends, for example,
For example, an alkylene oxide having an amino group at the end (for example,
For example, ethylene oxide, propylene oxide, butylene
Oxide, tetrahydrofuran, 3-methyltetrahydr
C such as lofran _2-5Homopolymerization of alkylene oxide)
Polyether such as polymer or copolymer, or at the end
The organopolysiloxane having an amino group may be mentioned.
It These polymers may be used alone or in combination of two or more.
it can.

The preferred polyether polyol is C
_Homo- or copolymers of _2-4 alkylene oxides, especially C _3-4 alkylene oxides (propylene oxide, butylene oxide, tetrahydrofuran) (propylene oxide,
Butylene oxide, copolymer with tetrahydrofuran)
Is mentioned. The weight average molecular weight of these polyethers can be selected from the range of about 200 to 10,000, for example.

Examples of commercially available products thereof include "Jeffermin D-40" manufactured by San Techno Chemical Co., Ltd.
0 "," Jeffermin D-2000 "," Jeffermin D-4000 "," Jeffermin ED-60 "
0 "," Jeffermin ED-900 "," Jeffermin ED-2001 "," Jeffermin T-300 "
0 ”,“ Jeffermin T-5000 ”and the like.

Further, as the organopolysiloxane,
"KF-8001", "KF-8012", "X-2" as dimethyl polysiloxane manufactured by Shin-Etsu Chemical Co., Ltd.
2-161B "," X-22-1660B-3 "and the like can be given as the methylphenyl polysiloxane.

(B) Compound having two (meth) acryl groups A compound having two (meth) acryl groups is
Having (meth) acrylic groups, specifically, 2,2-dimethyl-3-hydroxypropyl-2,
2-dimethyl-3-hydroxypropionate di (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, 1,
4-butanediol di (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, glycol di (meth) acrylate, neopentyl glycerin di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, ethylene oxide adduct of bisphenol A di (meth) acrylate, Di (meth) acrylate of propylene oxide adduct of bisphenol A, di (meth) acrylate of 2,2′-di (hydroxyethoxyphenyl) propane, di (meth) acrylate of tricyclodecane dimethylol, dicyclopentadiene di ( Examples thereof include (meth) acrylate, pentane di (meth) acrylate, and a (meth) acrylic acid adduct of 2,27-di (glycidyloxyphenyl) propane.

(C) Polymer Having Acrylic Group and Amino Group at Terminal The polymer having an acrylic group and amino group at the terminal is the above-mentioned polyether having amino group at the terminal (a) and (b) 2
It can be obtained by a Michael addition reaction with a compound having one (meth) acrylic group. As the reaction conditions, the proportion of the component (b) is 1.6 to 4.0 mol, preferably 2.0 to 3.0 mol, relative to 1 mol of the component (a), and if necessary, Various organic solvents that do not react with the amino group and the (meth) acrylic group may be used, for example, aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, aromatic hydrocarbons such as toluene and xylene, n-pentane, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, dichloromethane,
Examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrachloride, and ethanol and 2-propanol (isopropyl alcohol) are preferable as alcohols having an effect of promoting the reaction. The addition reaction conditions are not particularly limited, but the reaction temperature is 40 to 100 ° C., preferably 50 to
It is preferable to react at 80 ° C. for several hours.

Examples of the (d) diisocyanate diisocyanate component include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate and isophorone. Diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, transcyclohexane-1,4-
Diisocyanate, lysine diisocyanate, tetramethyl xylene diisocyanate, etc. are used. Among these, tolylene diisocyanate and isophorone diisocyanate are preferable in terms of synthesis.

(E) Hydroxyl group-containing (meth) acrylates Examples of the hydroxyl group-containing (meth) acrylates include hydroxyalkyl (meth) acrylates [eg, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, Hydroxyl-C _2-10 alkyl (meth) acrylates such as neopentyl glycol mono (meth) acrylate], 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4 -Hydroxycyclohexyl (meth) acrylate etc. are mentioned.

The polyureapolyurethane (meth) acrylate oligomer has the above-mentioned (c), (d) and (e).
It can be adjusted by reacting the components with urea and urethane, and the ratio of each component constituting the polyurea polyurethane (meth) acrylate oligomer is, for example,
With respect to 1 mol of the isocyanate group of diisocyanate,
Component (c) has an amino group of 0.5 to 1.2 mol, preferably about 0.8 to 1.1 mol, and component (e) has a hydroxyl group-containing (meth) acrylate of 0.8 to 1.5 mol. It is preferably about 0.9 to 1.2 mol.

Further, the reaction method of the above-mentioned components is not particularly limited, and the components may be mixed and reacted at once, and (d) diisocyanate and (c) component and (e) hydroxyl group-containing (meth) acrylate may be used. After reacting with one of the components, the other component may be reacted.

Examples of catalysts for these urethanization reactions include stanas octoate, dibutyltin diacetate, dibutyltin dilaurate, cobalt naphthenate,
Organometallic urethane-forming catalysts such as lead naphthenate and amine-based catalysts such as triethylamine, triethylenediamine and diazabicycloundecene can be used, but other known urethane-forming catalysts can also be used.

The composition of the present invention may contain a usual polyurethane (meth) acrylate obtained from a polyether polyol, a polyester polyol, an alkyl polyol, etc., in addition to the oligomer.

The polyurea polyurethane (meth) acrylate oligomer (A) thus obtained has a structure represented by the following formula (1) at both ends of the molecular chain.

[0028]

[Chemical 3]

(R ¹ and R ³ are a methyl group or a hydrogen atom, R
² is a divalent organic group, and R ⁴ and R ⁵ are divalent organic groups. )

Here, R ² is derived from the component (b). That is, in indicated by component (b) by the following formula ^{_{CH 2 = CR 1 -COO-R}} 2 -OCO-CR 1 = CH 2, a divalent organic group represented by R ^2.

R ⁴ is derived from the diisocyanate of the component (d). That is, it is a divalent organic group represented by R ⁴ in the component (d) represented by the following formula OCN-R ⁴ -NCO.

Furthermore, R ⁵ is derived from component (e), in the component (e) represented by the following formula ^{HO-R 5 -OCO-CR 3} = CH 2, a divalent organic group represented by R ⁵ is there.

(B) Ethylenically unsaturated compound As the ethylenically unsaturated compound of the component (B) used in the present invention, for example, N-vinylacetamide compounds,
Examples include compounds having a structure in which (meth) acrylic acid is bound to a compound containing an amino group or a hydroxyl group by an amidation reaction or an esterification reaction. For example, the following monofunctional, difunctional, and polyfunctional compounds should be used. You can

<Monofunctional Compound> Examples of the N-vinylacetamide compound include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, N-vinylformamide and the like, and compounds containing an amino group or a hydroxyl group. Examples of the compound having a structure in which (meth) acrylic acid is bound to meth by an amidation reaction or an esterification reaction include methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol. (Meth) acrylate,
Nonylphenoxy polypropylene glycol (meth) acrylate 3-chloro-2-hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, butoxy polyethylene glycol (meth)
Acrylate, alkyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, cumylphenol (meth) acrylate, cumylphenoxy polyethylene glycol (meth) Acrylate, cumylphenoxy polypropylene glycol (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentadiene (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl Phthalic acid,
3-acryloyloxyglycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
2-hydroxy-1- (meth) acryloxy-3- (meth) acryloxypropane, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly ε-caprolactone mono (meth) acrylate, dialkylaminoethyl ( (Meth) acrylate, glycidyl (meth) acrylate,
Mono [2- (meth) acryloyloxyethyl] acid phosphate, trichloroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth)
Acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentenyl (meth)
Acrylate, dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyloxy (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) ) Acrylate, morpholine (meth) acrylate and the like.

<Bifunctional compound> As the bifunctional compound, specifically, di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth ) Acrylate, 1,6-hexanediol di (meth) acrylate, glycol di (meth) acrylate, neopentyl glycerin di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate,
Di (meth) acrylate of ethylene oxide adduct of bisphenol A, di (meth) acrylate of propylene oxide adduct of bisphenol A, di (meth) of 2,2′-di (hydroxyethoxyphenyl) propane
Acrylate, di (meth) acrylate of tricyclodecane dimethylol, dicyclopentadiene di (meth) acrylate, pentane di (meth) acrylate, 2,2
An example is a (meth) acrylic acid adduct of 7-di (glycidyloxyphenyl) propane.

<Polyfunctional Compound> Examples of the polyfunctional compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tris (acryloxy) isocyanurate, tris (2-hydroxy) isocyanurate,
Examples include tri (meth) acrylate of tris (hydroxypropyl) isocyanurate, tri (meth) acrylate of isocyanurate, triallyl trimellitic acid, triallyl isocyanurate, and the like.

These ethylenically unsaturated compounds have the desired viscosity of the composition of the present invention and the physical properties of the cured product (Young's modulus,
Strength, elongation). Further, from the viewpoint of curability by radiation, it is preferable to include an N-vinyl compound such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide and the like.

These polyurea polyurethanes (meth)
The blending amount of the acrylate oligomer and the monoethylenically unsaturated compound is determined by the type of the (A) polyurea polyurethane (meth) acrylate oligomer component and the (B) component of the ethylenically unsaturated compound, the desired viscosity of the resin composition, or the curing thereof. Depending on the physical properties of the product, for example, the polyurethane (meth) acrylate oligomer of (A) is 10 to 90% by weight, preferably 20 to 90% by weight, based on the total weight of the components (A) and (B). %, More preferably 2
It is 0 to 80% by weight. The content of the ethylenically unsaturated compound as the component (B) is 90 to 10% by weight, preferably 8
It is 0 to 10% by weight, more preferably 60 to 20% by weight. Further, as the component (B), an N-vinyl compound is added in an amount of 3 to 2
It is preferable to contain 0% by weight, preferably 5 to 15% by weight.

Further, if necessary, a polymerization initiator may be added.

As the polymerization initiator, known ones can be used, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-2-phenylacetophenone, phenylacetophenone diethyl ketal, alkoxyacetophenone, benzyl. Methyl ketal, benzophenone and 3,3-dimethyl-4-
Benzophenone derivatives such as methoxybenzophenone, 4,4-dimethoxybenzophenone and 4,4-diaminobenzophenone, alkyl benzoyl benzoate, bis (4
-Dialkylaminophenyl) ketone, benzyl derivatives such as benzyl and benzylmethyl ketal, benzoin derivatives such as benzoyl and benzoin butylmethyl ketal, benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone, 2,4-diethylthioxanthone and Thioxanthone derivatives such as 2,4-dichlorothioxanthone, fluorene, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-
1- (morpholinophenyl) -butanone-1,2,4
6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4
Phosphine oxide derivatives such as 4-trimethylpentylphosphine oxide, benzoyl peroxide, organic peroxides such as t-butyl peroxide, cumene hydroperoxide, azobiscyanophosphoric acid, azobisbutyronitrile, azobis (2,4-dimethyl) Examples thereof include organic azo compounds such as valeronitrile and azobis- (2-aminopropane) hydrochloride.

These may be used alone or in combination of two or more. The compounding amount is not particularly limited as long as it satisfies the characteristics of the composition of the present invention, and is a curing effective amount, but is 0.1 to 10 per 100 parts by weight of the total of the components (A) and (B). It is preferable that the amount is, especially 0.5 to 5 parts by weight.

In addition to the above components, these resin compositions include, for example, antioxidants, stabilizers such as ultraviolet absorbers, organic solvents, plasticizers, surfactants, silane coupling agents, color pigments, organic or inorganic substances. Additives such as particles can be added as necessary within a range that does not impair the object of the present invention.

The viscosity of the resin composition of the present invention is usually 1,000 to 10,000 mPa · s (25
℃), especially 1,000 to 4,000 under high-speed manufacturing conditions
The range of mPa · s (25 ° C) is desirable.

Radiation used for curing includes infrared rays, visible rays, ultraviolet rays, X-rays, electron rays, α rays, β
There are ionizing radiation such as rays and gamma rays. The cured film obtained by irradiating these radiations preferably has a Young's modulus of 0.5 to 2.5 MPa as a primary coating material for optical fibers and 300 to 1,000 MPa as a secondary coating material. .

The liquid radiation-curable resin composition of the present invention comprises
Not only the optical fiber coating material, but also various applications such as a releasable coating material, a water-repellent coating material, a protective coating material, various inks, and paints.

[0046]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[Synthesis Example] (c) Combination of a polymer having an acrylic group and an amino group at the terminal
Adult Synthesis Example 1 Jeffamine D-4000 (amine equivalent weight =
2325, manufactured by San Techno Chemical Co., Ltd., polypropylene glycol having amino groups at both ends) 465 g
r, 2,4-di-tert-butylhydroxytoluene 0.2 gr, Kayarad R-684 (manufactured by Nippon Kayaku Co., Ltd., 2
Functional acrylic compound) 91.2 gr, ethanol 24
The mixture of 0 gr is reacted under a dry air at a temperature of 70 to 80 ° C. for 6 hours, and a predetermined amount of the peak of Kayarad R-684 is measured by GPC (HLC-8220, manufactured by Tosoh Corporation).
It was confirmed that the number had decreased. Then, ethanol was distilled off from the reaction mixture at a temperature of 80 to 90 ° C. under reduced pressure to give a polyether having an acryl group and an amino group at the end, in which one acrylic group of Kayarad R-684 was added to the end amino group. Obtained.

This polyether has the following structure at both ends.

[0049]

[Chemical 4]

[Synthesis Example 2] Jeffamine D-4000
(Amine equivalent = 2325, manufactured by San Techno Chemical Co., polypropylene glycol having an amino group at the end) 465 gr, dibutyltin dilaurate 0.23 g
Into a reaction vessel, 87 g of 2,4-tolylene diisocyanate was added dropwise so that the reaction temperature was kept at 40 ° C. or lower, and after the addition was completed, the reaction was carried out at 70 ° C. for 4 hours, and the number average molecular weight was 9300 having an amino group at the end. Of polypropylene glycol was obtained. Then, add 2,4-di-t to the reaction vessel.
ert-butyl hydroxytoluene 0.2 gr, light acrylate NP-A (neopentyl glycol diacrylate, manufactured by Kyoeisha Chemical Industry Co., Ltd.) 21.96 g
The mixture of r and 240 gr of ethanol was dried under dry air for 7
The reaction was carried out at a temperature of 0 to 80 ° C. for 6 hours, and GPC (HLC-
It was confirmed that the light acrylate NP-A peak at 8220, manufactured by Tosoh Corporation) disappeared. Then, the reaction mixture was distilled under reduced pressure at a temperature of 80 to 90 ° C. to distill off ethanol, and light acrylate NP was added to the terminal amino group.
A polyether having an acrylic group and an amino group at the terminal to which -A was added was obtained.

[0051]

[Chemical 5]

This polyether has the following structure at both ends.

[0053]

[Chemical 6]

(A) Poly having two acrylic groups at the end
Urea Polyurethane (meth) acrylate oligomer
Synthesis [Synthesis Example 3] Isobornyl acrylate (acrylic compound manufactured by Toa Gosei Co., Ltd.) 30.34 gr, 2,4-tolylene diisocyanate 15.46 gr, dibutyltin dilaurate 0.056 gr, 2,4-di-tert-butyl Hydroxytoluene (0.092 gr) was charged into the reaction vessel and cooled to about 10 ° C. 2-Hydroxyethyl acrylate 1 at a rate to keep it below 15 ° C under dry air
0.32 gr was added dropwise. Then, after reacting at room temperature for 2 hours, 0.096 gr of dibutyltin dilaurate was added, and the reaction product 247.24 obtained in Synthesis Example 1 was obtained.
gr was added dropwise so that the reaction temperature was kept at 40 ° C. or lower. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 6 hours to obtain a polyetherpolyureapolyurethane (meth) acrylate oligomer (designated as oligomer A) solution containing 10% by weight of isobornyl acrylate and having two acrylic groups at the terminals.

This polyether has the following structure at both ends.

[0056]

[Chemical 7]

[Synthesis Example 4] In Synthesis Example 3, 51.8 gr of Aronix M-113 (nonylphenol EO adduct acrylate, manufactured by Toagosei Co., Ltd.) and 2,4-tolylene diisocyanate were used instead of isobornyl acrylate. 46 gr, dibutyltin dilaurate 0.07
7 gr, 2,4-di-tert-butylhydroxytoluene 0.16 gr, 2-hydroxyethyl acrylate 10.32 gr, dibutyltin dilaurate 0.18 g
r, 440.4 gr of the reaction product obtained in Synthesis Example 2 above
Is reacted in the same manner as in Synthesis Example 3 to give Aronix M-113.
To obtain a solution of a polyether polyurea polyurethane (meth) acrylate oligomer (referred to as oligomer B) containing two acrylic groups at the end containing 10% by weight of.

This polyether has the following structure at both ends.

[0059]

[Chemical 8]

[Synthesis Example 5] Isoboronyl acrylate (acrylic compound manufactured by Toagosei Co., Ltd.) 45.11 gr, 2,
174 gr of 4-tolylene diisocyanate, 0.5 gr of dibutyltin dilaurate and 0.1 gr of 2,4-di-tert-butylhydroxytoluene were charged into a reaction vessel, and 232 gr of 2-hydroxyethyl acrylate was added dropwise at a rate of keeping at 40 ° C or lower. . 6 at 70 ° C after completion of dropping
10 hours by weight of isobornyl acrylate
A low molecular weight urethane diacrylate compound (diacrylate compound-E) solution having a number average molecular weight of 406 was obtained.

[Comparative Synthesis Example 1] In Synthesis Example 3, 59.56 gr of isobornyl acrylate (acrylic compound manufactured by Toagosei Co., Ltd.), 69.6 gr of 2,4-tolylene diisocyanate, and 0.18 g of dibutyltin dilaurate.
r, 2,4-di-tert-butylhydroxytoluene 0.18 gr, 2-hydroxyethyl acrylate 4
6.4 gr, dibutyltin dilaurate 0.42 gr,
PP20 instead of the reaction product obtained in Synthesis Example 1
00 (polypropylene glycol, hydroxyl value = 53.
3, manufactured by Sanyo Chemical Industries, Ltd.) Synthesis Example 3 from 420 gr
In the same manner as described above, but containing 10% by weight of isobornyl acrylate, a polyether polyurethane acrylate oligomer having one acrylic group at the end (Oligomer C
To obtain a solution. This oligomer has an acrylic group at the end at the same concentration as the oligomer A obtained in Synthesis Example 3.
It is an oligomer having a number.

This has the following structure at both ends.

[0063]

[Chemical 9]

[Comparative Synthesis Example 2] In Synthesis Example 3, Aronix M-113 was used in place of isoboronyl acrylate.
(Acrylic compound manufactured by Toagosei Co., Ltd.) 53.11 gr,
2,4-Tolylene diisocyanate 34.8 gr, dibutyltin dilaurate 0.11 gr, 2,4-di-te
rt-Butylhydroxytoluene 0.16 gr, 2-hydroxyethyl acrylate 23.2 gr, dibutyltin dilaurate 0.42 gr, PP4000 (polypropylene glycol, hydroxyl value = 26.7, Sanyo Kasei Co., Ltd.) 420 gr as in Synthesis Example 3 To obtain a solution of polyether polyurethane acrylate oligomer (referred to as oligomer D) having one acrylic group at the end and containing 10% by weight of Aronix M-113. This oligomer is an oligomer having one acrylic group at the terminal at almost the same concentration as the oligomer B obtained in Synthesis Example 4.

This has the following structure at both ends.

[0066]

[Chemical 10]

[Examples 1-2, Comparative Examples 1-2] As shown in Table 1, the oligomers synthesized above and the compound containing an ethylenically unsaturated group were mixed to give Examples 1-2 and Comparative Examples. 1
The radiation curable resin compositions of ~ 2 were prepared. The physical properties of this composition were measured as described below. <Evaluation Method> (1) Preparation of Cured Film 50 to 60 of the radiation curable resin composition was placed on a glass plate.
It was applied to a film thickness of μm, and irradiated with an ultraviolet ray and an electron beam accelerated at 100 Kv with irradiation energy and absorbed dose shown in Table 1 under nitrogen to obtain a cured film. (2) Measurement of Young's modulus After conditioning the cured film for 24 hours at 25 ° C. and 50% relative humidity, the distance between marked lines is 25 mm and the pulling speed is 1 mm / m.
The 2.5% tensile elastic modulus was measured under the condition of in. (3) Measurement of tensile strength and elongation at break After conditioning the cured film for 24 hours at 25 ° C. and 50% relative humidity, 25 mm between marked lines and 50 mm / pulling speed
It was measured under the condition of min. (4) Gel fraction Cured under each irradiation condition, the cured film was added to acetone 1
The film was subjected to immersion extraction for 6 hours, the film was dried under reduced pressure at 70 ° C. for 2 hours, and the weight was calculated before and after extraction.

[0068]

[Table 1]

[0069]

EFFECTS OF THE INVENTION According to the present invention, the liquid radiation-curable resin composition of the present invention containing a polyurea polyurethane (meth) acrylate oligomer having two acrylic groups at the ends is used to obtain a high gel fraction even at a low radiation dose. The cured product can be obtained, and the composition of the present invention is useful as a coating material for an optical fiber.

Continued front page    F-term (reference) 4J027 AB28 AC03 AC04 AG04 AG09                       AG13 AG14 AG23 AG24 AG27                       AG33 AG34 BA07 BA08 BA10                       BA11 BA13 BA15 BA16 BA19                       BA20 BA21 BA23 BA24 BA26                       BA28 BA29 CB10 CC04 CC05                       CC06 CC08 CD03                 4J034 FA02 FB01 FC01 FD03 FD04                       FE04 FE05 GA62 GA74 HA01                       HA07 HB12 HC03 HC09 HC12                       HC13 HC17 HC22 HC46 HC52                       HC61 HC64 HC67 HC71 HC73                       KA01 KB02 KC17 KC18 KC35                       KD02 KD12 KE02 LA23 LA33                       MA14 MA18 MA24 RA07                 4J038 FA011 FA012 FA111 FA112                       FA271 FA272 FA281 FA282                       MA14 NA11 PA17 PB08

Claims (4)

[Claims] 1. A diisocyanate compound and a (meth) acrylate having a hydroxyl group are added to a product obtained by the addition reaction of (A) a polymer having amino groups at both ends and a compound having two (meth) acrylic groups. Polyurea polyurethane (meth) acrylate oligomer having a structure represented by the following formula (1) at the molecular chain end, which is obtained by a urea-urethane reaction: 10 to 90% by weight (R ¹ and R ³ are methyl groups or hydrogen atoms, R ² is a divalent organic group, and R ⁴ and R ⁵ are divalent organic groups.) (B) Ethylenically unsaturated compound 90 to 10% by weight A radiation-curable resin composition containing: 2. The radiation curable resin composition according to claim 1, wherein the ethylenically unsaturated compound contains at least one N-vinyl compound. 3. The radiation curable resin composition according to claim 2, wherein the N-vinyl compound contains at least one selected from N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinylformamide. 4. The radiation curable resin composition according to claim 1, which is used for coating an optical fiber.