JPS6245613A - Di(meth)acrylic ester mixture, resin composition and coating agent - Google Patents

Abstract

PURPOSE:A resin composition which has a high curing rate, flexibility and a low water absorption and scarcely undergoes changes in film properties over a wide range of temperature, comprising a specified di(meth)acrylic ester mixture, a monoethylenically unsaturated monomer and a photopolymerization initiator. CONSTITUTION:A di(meth)acrylic ester mixture (A) is obtained by reacting 5mol of an adduct obtained by an addition reaction between 1mol of a carbonate diol of an average MW of 500-3,000 and 0.5-0.8mol of an organic diisocyanate (e.g., tolylene diisocyanate) at 40-100 deg.C in the presence of a catalyst (e.g., triethylamine) is reacted with 1.0-2.0mol of (meth)acrylic acid at 70-130 deg.C in the presence of an esterification catalyst (e.g., sulfuric acid) and a polymerization inhibitor (e.g., hydroquinone). 5-80wt% component A is mixed with 20-80wt% monoethylenically unsaturated monomer (B) [e.g., alkylphenylpolyethoxy (meth)acrylate] and 0-10wt% photopolymerization initiator (C) (e.g., benzil dimethyl ketal).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel di(meth)acrylic acid ester mixture, a resin composition containing the same, and a coating agent for optical glass fibers for light transmission.

(Prior Art) Since optical fibers have excellent information transmission performance and are relatively immune to external interference, their use has increased significantly in recent years, especially in the communications field.

Optical fibers are generally glass-broken because they are used in the telecommunications field. However, glass fibers are inherently brittle and are easily broken due to chemical agitation by water vapor, making them difficult to handle. Therefore, conventionally, optical glass fibers are
The surface is coated with resin. Conventionally, epoxy resins, urethane resins, etc. have been used as such resin coating materials, but they require a long time to harden, resulting in poor productivity.They also lack flexibility, which has the disadvantage of impairing transmission characteristics due to lateral pressure. There is. Recently, ultraviolet curable compositions containing urethane acrylate have been actively studied in order to improve the above-mentioned drawbacks, and ultraviolet curable compositions for optical glass fibers and methods for forming such coatings have been published, for example, in Japanese Patent Application Laid-Open No.
No. 223,638 and Japanese Unexamined Patent Publication No. 59-170154.

(Problems to be Solved and Attempted by the Invention) Currently used ultraviolet curable compositions have the advantage of fast curing speed and the ability to easily and accurately obtain desired properties, but they have high water absorption. Glass fibers are easily damaged by water, and when they harden and the temperature changes periodically from room temperature to -60'C to +80'C, the physical properties become significantly distorted, causing an increase in transmission loss. (It has the disadvantage that there is no

(Means for Solving the Problems) In order to solve the above problems, the inventors have conducted extensive research (
- As a result, we synthesized a new di(meth)acrylic ester mixture, and using this di(meth)acrylic ester mixture, the curing speed was fast, and the resin film obtained by curing was flexible and had a high water absorption rate. It is small, has little change in film properties over a wide temperature range from high to low temperatures, and has a low glass transition point.
The present invention has been completed by successfully providing a new resin composition suitable for coating optical glass fibers for light transmission. That is, the present invention provides (1) carbonate diol (average molecular weight 500 to
3000) and an organic diisocyanate.
meth)acrylic acid ester mixture.

(2) Carbonate diol (average molecular weight 500~
3000) and an organic diisocyanate.
A resin composition comprising a meth)acrylic acid ester mixture (3), a monoethylenically unsaturated monomer (formerly monoethylenically unsaturated monomer), and a photopolymerization initiator (C1) as an optional component.

(3) Carbonate diol (average molecular weight 500~
3000) and an organic diisocyanate.
1. A coating agent for optical glass fibers, comprising a first-generation meth)acrylic acid ester mixture, monoethylenically unsaturated heptamer-CBI, and a photopolymerization initiator. It is related to.

The di(meth)acrylic acid ester mixture of the present invention is, for example, carbonate diol (average molecular i 500 to 30
00) and an organic diisocyanate (can be obtained by reacting al with (meth)acrylic acid. di(meth)
An example of a specific method for producing an acrylic ester mixture is as follows. Preferably 1.0 to 2.0 mol of (meth)acrylic acid, particularly preferably 1.0 to 2.0 mol, particularly preferably 1.0 to 2.0 mol, of (meth)acrylic acid to 0.5 mol of the addition reaction product (al) obtained by the addition reaction of carbonate diol and organic diisocyanate.
0 to 1.5 mol, esterification catalyst (e.g., I)-toluenesulfonic acid, sulfuric acid, methanesulfonic acid, etc.) and polymerization inhibitor (e.g., methquinone, hydroquinone, phenothiazine, etc.) to (meth)acrylic acid. Preferably, 0.01 to 5 M% is added, preferably 70 to 5 M%.
A di(meth)acrylic acid ester mixture is obtained by heating to 130'C, dehydration, alkaline washing, water washing, and removing low boiling point substances.

The addition reaction product (al) used as a raw material for producing the di(meth)acrylic acid ester mixture can be obtained by the reaction of carbonate diol and organic diisocyanate.

Carbonate diol, which is a raw material for producing the addition reaction product (al), can be produced, for example, in the following manner. Namely, carbonate derivatives, such as diphenyl carbonate, bis-chlorophenyl carbonate, dinaphthyl carbonate, Phenyl-tolyl-carbonate, phenyl-chlorophenyl-carbonate,
Diaryl carbonates or dialkyl carbonates such as 2-tolyl-4-tolyl carbonate, dimethyl carbonate, diethyl carbonate and diols, such as 1,6-hexanediol, neopentyl glycol, 1,4-butanediol, 1 , 8-octanediol, 1,4-bis-(hydroxymethyl)-cyclohexane, 2-methylpropanediol, dipropylene glycol, dibutylene glycol or the above diol compounds, and oxalic acid, malonic acid, succinic acid, adipic acid. , azelaic acid, hexahydrophthalic acid, and other dicarboxylic acids, or epsilon-caprolactone, by a transesterification reaction with a polyester diol, etc., which is a reaction product of ε-caprolactone. It can also be produced by reacting phosgene with the diols mentioned above.

The carbonate diol obtained in this way is a monocarbonate diol having one carbonate structure in the molecule or a polycarbonate diol having two or more carbonate structures in the molecule, and can be easily obtained from the market. .

Example engineering ff, y' Sumofen 2o2oE (Sumitomo Bayer■
crack, average molecular weight 2000), DN 980 (made by Japan Polyurethane (produced by average molecular weight 2000), DN-98
1 (manufactured by Nippon Polyurethane ■, average molecular weight 1000), D
N-982 (Japan Polyurethane ■Kyu, average molecular weight 200
0), DN-98:3 (manufactured by Japan Polyurethane, average molecular weight 3000), etc. DN-982 and DN-983 are particularly preferred as raw materials for producing the addition reaction product (al).

DN-982 and DN-983 are carbonate diols obtained by transesterification of a diol obtained by addition reaction of ε-caprolactone to 1,6-hexanediol and a carbonate derivative.

In addition, typical organic diisocyanates used as raw materials include tolylene diisocyanate, 4,4-
Aromatic diisocyanates such as diphenylmethane diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, trine clodecane dimethyl diisocyanate, diisocyanates of hydrogenated bisphenol A reacted with hexamethylene diisocyanate (Japanese polyurethane diisocyanate, Coronate 2094
) and aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2-trimethylhexamethylene diisocyanate.

Isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and tolylene diisocyanate are particularly preferred as raw materials for producing the addition reaction product (al).

The addition reaction product (at) between carbonate diol and organic diisocyanate is produced, for example, as follows.

The reaction between carbonate diol and organic diisocyanate is preferably carried out at 40-100°C, particularly preferably at 60-90°C.
C. for a period of time sufficient to complete the reaction between the charged reactants. The amount of organic diisocyanate charged in the reaction is preferably about 0.5 mol to 0.8 mol, particularly preferably about 075 mol to 0.6 mol, per mol of carbonate diol charged. In order to shorten the reaction time, it is preferred to use an effective amount of catalyst;
The amount used is preferably 0.00] to 1.0% by weight, particularly preferably 0.00% to 1.0% by weight, based on the weight of the reaction mixture.
005-01% by weight.

Examples of catalysts include tertiary amines such as triethylamine,
Examples include organometallic compounds such as dibutyltin silaurylate and dibutyltinodiacetate, and tin chlorides.

The product obtained by the reaction, which is a mixture of the addition reaction product (al) of carbonate diol and organic diisocyanate, can be used as it is in the next reaction.

In the resin composition and coating agent of the present invention (5)
As a component, a diacrylic ester mixture is preferable to a dimethacrylic ester mixture.

In the resin composition and coating agent of the present invention (hereinafter referred to as composition), the di(meth)acrylic acid ester mixture is preferably used in an amount of 5 to 80% by weight, particularly 20% by weight. It is preferable to use it in a range of 70% by weight.

In the present invention, a monoethylenically unsaturated monomer (Bl) is used, but as the monoethylenically unsaturated monomer that can be used, various monoacrylates or methacrylates can be used, but the glass transition temperature of the homopolymer thereof is as low as possible. It is preferable to use phenyloxy (or alkylphenyloxy) polyethoxy (meth)acrylate, phenyloxy (or alkylphenyloxy) polyethoxy (meth)acrylate, phenyloxy (or alkylphenyloxy) ethoxy (meth)acrylate, and phenyloxy (or alkylphenyloxy) ethoxy (meth)acrylate. ) acrylate, phenyloxy (
or alkylphenyloxy)propoxy(meth)acrylate, polyethoxy(meth)acrylate of tetrahydrofurfuryl alcohol, (meth)acrylate of ε-caprolactone adduct of tetrahydrofurfuryl alcohol (Nippon Kayaku @ Nashi, KAYARAD TC-]
10S, KAYARADTC-120, etc.), ε-caprolactone-β-hydroxyethyl (meth)acrylate adduct (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-1)
, Plaxel FM-L$), carpitol acrylate, ε of photoethoxy or polypropoxy compounds of phenol derivatives described in Japanese Patent Application No. 59-151179
-(Meth)acrylate of caprolactone adduct, etc.

Among the monoethylenically unsaturated monomers, particularly preferred are ', alkylphenyl polyethoxy (meth)
ε of acrylate, tetrahydrofurfuryl alcohol
- (Meth)acrylate of caprolactone adduct (Nippon Kayaku ■KAYARAD TC-1] O8, KAY
ARAD TC-120 etc.) and patent application 1986-151
ε- of polyethoxy or polypropoquino compounds of phenol derivatives having the following structural formula described in 179
Examples include (meth)acrylates of caprolactone adducts.

(In the formula, R1 is a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, R2 and R3 are each a hydrogen atom or a methyl group, and the average value of m is a number from 1 to 10,
The average value of n is a number from 1 to ]0. ) This compound is obtained by reacting nibsilone caprolactone with a compound obtained by adding ethylene oxide or propylene oxide to a phenol derivative such as phenol or nonylphenol, and esterifying (meth)acrylic acid with balatoluenesulfonic acid, etc. It can be obtained by reaction at a temperature of 70 to 130'C in the presence of a catalyst and a polymerization inhibitor such as hydroquinone.

The amount of monoethylenically unsaturated monomer (Bl) used is preferably 20 to 80% by weight in the composition, particularly 30 to 60% by weight.
Preferably, it is % by weight.

The photopolymerization initiator (Cl) used in the present invention may be any known photopolymerization initiator, but it is required to have good storage stability after blending.

Examples of such photopolymerization initiators include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; Acetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 4-dodecyl-2-hydroxy-
Propiophenone series such as 2-methylpropiophenone, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone and anthraquinone series such as 2-ethylanthraquinone and 2-chloroanthraquinone;
Other examples include thioxanthone photopolymerization initiators. Particularly preferred are -hydroxycyclohexylphenyl ketone, benzyl dimethyl ketal and the like. These photopolymerization initiators (q may be used alone or in a mixture of two or more kinds in any proportion. The amount used is usually preferably 0 to 10% by weight of the resin composition, and the coating agent Of O, 1 to 10% by weight, particularly 1 to 5% by weight is preferred.

The composition of the present invention may further contain epoxy acrylate, polyester acrylate, polyurethane acrylate, for example, polyurethane acrylate of a polyol having an ether group, ester group, or carbonate group in the molecule, or a polymerizable monomer, such as polyethylene You can also use glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.

Further, if desired, a modifying resin and various additives may be added. Examples of the modifying resin include epoxy resin, polyurethane, polybutadiene, polyether, polyamideimide, silicone resin, and phenol resin. Examples of the additives include organosilicon compounds, surfactants, and polymerization inhibitors.

The resin composition of the present invention is useful for coating optical glass fibers, and can also be used as a wetting agent for laminated glass, a fiber treatment agent, and the like.

When coating an optical glass fiber with the coating agent for optical glass fiber of the present invention, a die coating method is suitable as a coating method. The optical glass fiber can be drawn at a very high speed of 3 to 7 m/sec.

When coating an optical glass fiber, the thickness of the coating with the coating agent of the present invention is not particularly limited, but is usually 2.
It is preferably about 0 to 300μ.

The coating agent of the present invention is easily cured by ultraviolet irradiation. The coating agent of the present invention can be cured by ultraviolet irradiation using a conventional method. For example, ultraviolet rays may be irradiated using a low-pressure or high-pressure mercury lamp, a xenon lamp, or the like.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. In addition,
Parts in the examples are parts by weight.

[Production example of addition reaction product (al) obtained by reaction of carbonate diol and organic diisocyanate]

Production Example 1 Carbonate diol (Japanese polyurethane hair m
, DN-983, OH value 112.21 parts 1gK OH/
g y melting point 5°C, average molecular weight approximately 1000) 1000 parts, 111.15 parts of inphorone diisocyanate, and 0.2 part of loobyltin dilaurate were charged at 75-85°C.
The mixture was heated to a temperature of 1.5%, and the reaction was allowed to proceed until the remaining amount of incyanate became 0.05% by weight or less.

The obtained reaction product (a-1) was a pale yellow liquid with a hydroxyl value of 5.
0.5111gKOf(/g, acid value 0.1mgKO
H/g.

Production Example 2 Into the same reactor as Production Example], carbonate diol (Japan Polyurethane ■g, DN-982, OH value s 6 m
gKOH/g, melting point 5℃, "F average molecular weight t approx. 2000
) 1000 parts, isophorone diisocyanate) 55.57
75 parts, and 0.2 parts of n-butyltin dilaurate.
Heated to ~85°C until the residual amount of incyanate was 0.05
The reaction was carried out until the amount was below % by weight. The obtained reaction product (a
-2) is a pale yellow liquid, hydroxyl value 26.5 ■KOH/g,
Acid value 0.07 qKOH/g Teatsuta.

Production Example 3゜Into the same reactor as Production Example 1, carbonate diol (manufactured by Nippon Polyurethane ■, DN-983, 08 value 112.2
111gKOH/g, melting point 5°C1 average molecular weight approximately 100
0) 1000 parts, 87 parts of tolylene diisocyanate, and 0.2 parts of n-butyltin dilaurate were charged, and 75 to 85
℃ and the remaining amount of isocyanate is 0.05% by weight.
Let it react until it becomes the following. The obtained reaction product (a-3
) was a pale yellow liquid with a hydroxyl value of 51.6 KOH/g and an acid value of 0.1 mgKOH/g.

Mold making example 4 In the same reactor as in production example, carbonate diol (Japan Polyurethane (Sakuma, DN-981, OHHl10) was added.
KOH/g, melting point 43°C, average molecular weight approximately 1000) 10
00 parts, hydrogenated bisphenol A] mol and 2 mol of hexamethylene diinocyanate (Japan Polyurethane @
Coronate 2094, NC016, 3%) 257.
6 parts, and 0.25 parts of loobyltin dilaurate.
Heat to 75-85°C until the remaining amount of isocyanate is 0.
The reaction was carried out until the concentration became 0.05% by weight or less. The obtained reaction product (a-4) was a white waxy substance with a hydroxyl value of 14.6 q
KOH/g, acid value o, 1 mgKOH/g.

Production Example 5 In the same reactor as Production Example], carbonate diol (manufactured by Sumitomo Bayer (M), Desmofene 2020E, 08 valence 56 Ut, OH/g, melting point 53°C, average molecular weight 200
0) 1000 parts, tricyclodecane dimethyl diisocyanate) 61.7 parts, and dilaurin flfln-butyltin 0.2 parts were charged and heated to 75 to 85°C until the remaining amount of incynate was 0.05 parts. The reaction was allowed to take place until the concentration of The obtained reaction product (a-5) was a white waxy substance with a hydroxyl value of 26.4 mgKOH/g and an acid value of 0.2 m
gKo H/g.

[Example of production of di(meth)acrylic acid ester mixture]

Production Example 6 Carbonate diol obtained in 22 reactors equipped with a stirrer, temperature control device, temperature control, and condenser
A reaction product of 1 mole of OH/g, melting point 5°C, average molecular weight approximately 1000) and 0.5 mole of isophorone diisocyanate (
a-'1) 900 parts, 70 parts of phosphoric acid, 3.5 parts of p-toluenesulfonic acid, 1 part of hydroquinone, 720 parts of benzene, and 80 parts of cyclohexane were charged and heated.
The produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator, and the solvent is returned to the reactor.

When 4.5 parts of water had been produced, the mixture was cooled. The reaction temperature is 8
The temperature was 2-86°C. The reaction mixture was dissolved in 2240 parts of benzene and 560 parts of cyclohexane.
Wash 3 times with 0 parts.

The solvent was distilled off under reduced pressure to obtain 8 parts of a pale yellow liquid. This material has the following properties.

Viscosity (25°C) 68500 cps Acid value 0.08 ■KO
H/g refractive index (20°G) 1.4750 The absorption frequency of the obtained product was measured by high-resolution nuclear magnetic resonance (NMR), and the results are shown below.

M Absorption frequency (Hz) 1 2605.468 2 2335.937 3 1958.984 Slow Absorption frequency (H2) 4 1935.546 5 1193.359 6 1160.156 7 1128.906 8 1017.578 9 964.843 10 5 ] 3.67] 11 480.468 12 431.670 13 384.765 14 37], 093 15 0.000 However, in the above measurement, tetramethylsilane was used as a reference substance and Hl, Cl3-H coupling was performed. Finally, the results showed the identification of the C13 D couple. Among the above absorptions, 5.6.7 indicates the absorption peak position of the solvent. N[l]5 indicates the peak position of tetramethylsilane.

, 1! ! Preparation Example 7゜Into the same reactor as Preparation Example 6, the carbonate diol obtained in Preparation Example 2 (Japan Polyurethane type DN-982, OH
Value: 56 KOH/g, melting point: 5°C, average molecular weight: approximately 2000
600 parts of reaction product (a-2) of 1 mol of ) and 0.5 mol of isophorone diisocyate, 24.6 parts of acrylic acid, p
-Toluex/l/1.2 parts of fonic acid, 0 hydroquinone
．． 5 parts, 320 parts of benzene, and 80 parts of cyclohexane, and the produced water was 5.5 parts. The reaction was carried out in the same manner as in Production Example 6 until the amount of The reaction temperature was 81-86°C. The reaction mixture was dissolved in 1200 parts of benzene and 300 parts of cyclohexane, and neutralized, washed, and solvent removed in the same manner as in Production Example 6 to obtain 529 parts of a pale yellow liquid. This material has the following properties.

Viscosity (40°G) 65000 cps
Acid value 0.07 mgK
OH/g refractive index (20°C) L4735 NMR, measurement results Absorption frequency (Hz) 1 2607, 421 2 2335.937 3 1193°359 4 1160.156 5 1128.906 6 1019.53] 7 964.84-3 8 5]3,67] 9 429.687 10 382.812 11 37], 093 12 0.000 Among the above absorptions, Nn 3.4.5 indicates the absorption peak position t of the solvent . 2 indicates the peak position of tetramethylsilane.

Production Example 8゜Into the same reactor as Production Example 6, the carbonate diol obtained in Production Example 3 (Japan Polyurethane (Autopsy DN-983, O
Hfi] 12.2 JT@KOH/g, melting point 5°C
, average molecular weight of about 1000) 1 mol and tolylene diisocyanate (a-3) 500 parts, acrylic acid 39.8 parts, p-) luene X sulfonic acid 2.0 parts, 1.0 part of hydroquinone, 320 parts of benzene, and 80 parts of cyclohexane were charged, and the reaction was carried out in the same manner as in Production Example 6 until the amount of water produced was 8.3 parts. The reaction mixture was dissolved in 960 parts of benzene and 240 parts of cyclohexane, and neutralized, washed, and solvent removed in the same manner as in Production Example 6 to obtain 445 parts of a pale yellow liquid. This material has the following properties.

Viscosity (25°G) 75000 cps
Acid value 0.03 ■KOH
/g refractive index (20°G) 1.483O Measurement results by N, M, H % Absorption frequency (Hz) 1 2605.468 2 2496.093 3 2341.796 4 2335.937 % Absorption frequency (Hz) 5 23 ]2.500 6 2060.546 7 2050.78] 8 ]958,984 9 ]933.593 10 1720, 703 1] ]68], 640 12 1193.359 13 1160.156 14 1128.906 15 1017.57 8 ]6 974,609 ]7 964,843 18 939.453 19 5]1 7]820 4
90.234 2] 429,687 22 382.8] 2 23 369, ]40 % Absorption frequency (Hz) 24 255.859 25 0.000 Of the above absorptions, NQ12, 13.14 determines the absorption peak position of the solvent. show. Near 25 indicates the peak position of tetramethy/I/silane.

Production Example 9゜Into the same reactor as Production Example 6, the carbonate diol obtained in Production Example 4 (Japan Polyurethane I/Tan DN-981, O
H value] ] OnvKOH/g, melting point 43°C, average molecular weight approximately 1000) 1 mol, hydrogenated bisphenol A] mol and hexamethylene diisocyanate 2 mol reaction product (manufactured by Nippon Polyurethane, Coronate 2094, NC016%
) 600 parts of reaction product (a-4) with 0.5 mol, 41.2 parts of acrylic acid, 2.0 parts of p-toluenesulfonic acid, No.1
0.5 parts of hydroquinone, 400 parts of benzene, and 100 parts of cyclohexane were charged, and the reaction was carried out in the same manner as in Production Example 6 until the amount of water produced was 8.6 parts. The reaction mixture was dissolved in 1,120 parts of benzene and 280 parts of cyclohexane, and neutralized, washed, and solvent removed in the same manner as in Production Example 6 to obtain 519 parts of a white waxy substance. This material has the following properties.

Viscosity (60℃) 35000 cps acid
Value 0.03 mgKOH
/ gRefractive index (20°C) 1.476O Measurement results by N, M, R % Absorption frequency (Hz) 1 2337.890 2 1958, 984 3 1191, 406 4 1158.203 5 1126.953 6 1019.53 ] 7 968, 750 8 615.234 9 451.17] 10 43], 6"40 11 396.484 M Absorption frequency (Hz) 12 382.812 13 0.000 Among the above absorptions, l'k 3.4 .5 indicates the absorption peak position of the solvent. 3 indicates the peak position of tetramethylsilane.

Production Example] 0° Into the same reactor as Production Example 6, the carbonate diol obtained in Production Example 5 (Sumitomo Bayer ■Shitsu, Dessoufen 2020) was added.
E, OH number 56 KOH/g, melting point 5:3°C1 average molecular weight approx. 2000) Reaction product (a-5) of 1 mol of tricyclodecane dimethyl diisocyanate) 600
parts, 24.4 parts of acrylic acid, 1 part of p-toluenesulfonic acid
, 2 parts, hydroquinone o, 5gL benzene 400 parts,
100 parts of cyclohexane was charged, and the reaction was carried out in the same manner as in Production Example 6 until the amount of produced water became 5.1 parts. The reaction mixture was dissolved in 1,440 parts of benzene and 360 parts of cyclohexane, and neutralized, washed, and solvent removed in the same manner as in Production Example 6 to obtain 504 parts of a white waxy substance. This material has the following properties.

Viscosity (60°G) 61500 cps Acid value 0.03 ■KOH/g
Refractive index (206C) 1.4725 Measurement results by N, M, R Slow absorption frequency (Hz) 1 2335.937 2 2333.984 3 1191.406 4 1158.203 5 1126.953 6 1041.015 7 1025.437 8 1017.578 9 998.046 10 966.796 11 429.687 12 380.859 13 0.000 Of the above absorptions, ffi 3, 4, 5. indicates the absorption peak position of the solvent. Number 13. indicates the peak position of tetramethylsilane.

[Example of production of monoacrylate of 2 moles of ε-caprolactone adduct of nonylphenol with 4 moles of ethylene oxide] Manufactured example] 1.2, 8 equipped with a stirrer, temperature control device, thermometer, and condenser
A reactor was charged with a compound having the following structure, 624 parts of CH2-0 sho H, 108 parts of acrylic acid, 16.8 parts of paratoluene sulfone, 1.0 part of hydroquinone, 560 parts of benzene, and 140 parts of cyclohexane and heated. is distilled and condensed together with the solvent, and only water is removed from the system in a separator, and the solvent is returned to the reactor. Cooling occurred when 18 parts of water had been produced. The reaction temperature was 80-87°C. Reaction mixture 1040 parts of benzene and 260 parts of cyclohexane
After neutralizing with 20% caustic soda aqueous solution, 20%
5 Wash 3 times with 500 parts of saline solution. The solvent was removed under reduced pressure to obtain 596 parts of a pale yellow liquid. This material has the following properties.

Specific gravity (25°C) 1.045 Viscosity (25°G) 68.8 cps Saponification value
248 qKOH/g Acid value 0.04 111gKO
H/g [Example of ultraviolet curable resin composition] Example 1゜50 parts of the diacrylic acid ester mixture obtained in Production Example 7, 50 parts of monoacrylate obtained by adding 7 moles of ethylene oxide to nonylphenol, and 1-hydroxycyclo Resin composition A was prepared by mixing 5 parts of xylphenyl ketone (Ciba Geigy, Irgacure 184) and 0.01 part of methylhydroquinone. Table 1 shows the properties of the resin composition and its cured product.

Example 2 70 parts of the diacrylic acid ester mixture obtained in Production Example 6, monoacrylate of 2 moles of ε-caprolactone added to nonylphenol with 4 moles of ethylene oxide)
30 parts of 1-hydroxycyclohexyl phenyl ketone and 0.01 part of methylhydroquinone were mixed;
Resin composition B was prepared. Table 1 shows the properties of the m-fat composition and its cured product.

Example 3: 40 parts of the diacrylic ester mixture obtained in Example 8, 0.5 mol of polypropylene glycol (molecular weight 2000) and 0.5 mol of polyester polyol (manufactured by Daicel Chemical Industries, Plaxel L-220AL, molecular weight approximately 2000). 75 moles and 1.5 moles of isophorone diisocyanate.
After reacting at ~80°C, then ε-caprolactone-
10 parts of polyurethane acrylate obtained by reacting 1.1 moles of β-hydroxyethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-2), 2 parts of ε-caprolactone obtained by adding 4 moles of ethylene oxide to nonylphenol 30 parts of adduct monoacrylate,
ε-caprolactone-β-hydroxyethyl acrylate (Daicel Chemical Industries, Ltd., Plaxel FA-2) 2
Resin composition C was prepared by mixing 0 parts of hydroxycyclohexyl phenyl ketone and 0.01 parts of methylhydroquinone. Table 1 shows the properties of the resin composition and its cured product.

Example 4゜25 parts of the diacrylic ester mixture obtained in Production Example 7, 3s parts of the diacrylic ester mixture obtained in Production Example 9, and a monoacrylate prepared by reacting 1 mol of ε-caprolactone with 1 mol of tetrahydrofurfuryl alcohol. (Nippon Kayaku (Kayarad TC-1) 08) 3
5 parts, 7ff-/xyethyl acrylate) 15 parts and 1
-5 parts of hydroxycyclohexylphenyl ketone and 0.01 part of methylhydroquinone were mixed to prepare a resin composition. Table 1 shows the properties of the resin composition and its cured product.

Example 5 30 parts of the diacrylate mixture obtained in Production Example 8, 20 parts of the sialylic acid ester mixture obtained in Production Example 0, and 2 moles of ε-caprolactone added to nonylphenol with 4 moles of ethylene oxide added. Monoacrylate of 30 parts of monoacrylate, 1 mole of tetrahydrofurfuryl alcohol and 1 mole of ε-caprolactone (Nippon Kayaku, KAYARADTC-11)
O8) 20 parts and 4-dodecyl-2-hydroxy-2-
Methylglobiofuenone (Merck ■, Glocure 9)
53) and 0.01 part of methylhydroquinone were mixed to prepare resin composition E. Table 1 shows the properties of the resin composition and its cured product.

Comparative Example For comparison, Desoto 950
And so. Table 1 shows the properties of the resin composition and its cured product.

Measurement of [Shore hardness A] in Table 1 above: Compositions A, B, C, D, E, and F were irradiated at a position of 8 crn below the light source with a high-pressure mercury lamp (2 lamp outputs) arranged in parallel. (-x y Hair x Heat 30 m/min A sheet with a thickness of 250 μm was prepared and measured using this sheet.

The measurement method was performed according to the method of JIS-Z2246.

Measurement of [Glass Transition Point]: A test piece was prepared under the same conditions as those used for the above-mentioned Shore hardness measurement. Using this, a viscoelastic spectrometer (Iwamoto Seisakusho ■ke)
Measured using

Measurement of [Young's modulus kg/cm2]: A test piece was prepared under the same conditions as those used for the measurement of Shore hardness A above. Using this, Young's modulus (
kg/cm2) was measured.

Measurement of [Water Absorption]: A test piece was prepared under the same conditions as those used for the above-mentioned measurement of shear hardness. Using this, soak it in pure water at 20°C for 24 hours before testing.
The subsequent weight was measured, and the increase in weight due to water absorption was expressed in %.

Example 6 A base material for optical glass fiber was heated to about 2000'C and spun into an optical glass fiber having an outer diameter of 25 microns at a speed of 5 m/sec. In the successive steps indicated by the arrows, each of the resin compositions A to E shown in Examples was applied to the optical glass fiber by a die coating method, and then cured by irradiation with ultraviolet rays using a 2KW high-pressure mercury lamp. In the obtained coated optical glass fiber, no change in transmission loss was observed up to -60°C when any of the resin compositions A to E was applied.

(Effects of the Invention) The resin composition and coating agent using the novel di(meth)acrylic acid ester mixture of the present invention have a fast curing speed, a flexible resin film, and a low glass transition point.
It has low water absorption and little change in film properties over a wide temperature range from high to low temperatures, making it suitable for coating optical glass fibers for light transmission.

Claims (3)

[Claims] (1) Carbonate diol (average molecular weight 500-30
A di(meth)acrylic acid ester mixture of an addition reaction product of 00) and an organic diisocyanate. (2) Carbonate diol (average molecular weight 500-30
00) and an organic diisocyanate, a di(meth)acrylic acid ester mixture (A), a monoethylenically unsaturated monomer (B), and a photopolymerization initiator (as an optional component)
A resin composition comprising C). (3) Carbonate diol (average molecular weight 500-30
00) and an organic diisocyanate, a di(meth)acrylic acid ester mixture (A), a monoethylenically unsaturated monomer (B), and a photopolymerization initiator (C). Coating agent.