JPH03215453A - (meth)acrylic acid ester, resin composition using the same, coating agent for heat-resistant optical fiber and their cured product - Google Patents

Abstract

NEW MATERIAL:The (meth)acrylic acid ester expressed by formula I (R is H or CH3). USE:A coating composition for heat-resistant optical fiber. It has high curing rate and gives a cured coating resin film exhibiting little change of physical properties such as elongation and Young's modulus even after leaving in a high-temperature environment. It has low absorption and is most suitable for light-transmission use. PREPARATION:The objective (meth)acrylic acid ester of formula I can be produced by reacting a fluorine compound of formula II with epichlorohydrin and reacting the resultant epoxide with (meth)acrylic acid.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel (meth)acrylic ester, a resin composition using the same, a coating agent for heat-resistant optical glass fibers, and a cured product thereof. In particular, it relates to a coating agent applied to protect the glass surface of optical fibers used at high temperatures.

BACKGROUND OF THE INVENTION Optical fibers have seen a significant increase in their use in recent years, especially in the communications field, because their information transmission performance is excellent and they are relatively immune to external interference.

Optical fibers are generally made of glass 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, optical glass fibers have traditionally been coated with resin on their surfaces. As such resin coating materials,
Conventionally, epoxy resins, urethane resins, and the like have been used, but they require a long time to cure, resulting in poor productivity.They also lack flexibility, resulting in poor transmission characteristics due to lateral pressure. Recently, ultraviolet curable compositions containing urethane acrylate have been extensively studied in order to improve the above-mentioned drawbacks, and methods for forming ultraviolet curable compositions for optical glass fibers and such coatings have been published, for example, in JP-A-58-223638.
No., JP-A-59-170154 and JP-A-59-1
No. 70155 proposes a UV curable coating composition.

(Problem to be Solved by the Invention) Currently used UV-curable coating compositions have the advantage of fast curing speed and the ability to easily and accurately obtain desired properties, but they cannot be used for long periods of time at high temperatures. , Young's modulus, elongation, strength, etc. of the cured product change significantly, and it cannot be used in applications that are constantly used at high temperatures, for example, as a coating agent for optical fibers used in missiles, nuclear reactors, etc.

(Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted extensive research and found that by using a novel (meth)acrylic acid , a novel material suitable for coating optical glass fibers for optical transmission, which shows little change in physical properties such as elongation and Young's modulus even when the resin film obtained by curing is left at high temperatures, and has low water absorption. The present invention has been completed by successfully providing a resin composition.

That is, the present invention provides: 1) General formula [I] 0 R 111 0 CH2 CH CHz-O CC=CPb
A (meth)acrylic ester represented by 0H (in formula [I], R is H or CH3).

2) The present invention relates to a resin composition, a heat-resistant optical fiber coating agent, and a cured product thereof, which are characterized by containing a (meth)acrylic acid ester represented by the general formula [I].

In the present invention, a (meth)acrylic acid ester represented by general formula [I] is used. The (meth)acrylic acid ester compound is obtained by reacting the epoxidized product obtained by reacting the fluorine compound of HO+cH2, CFz, CH2 side H with shrimp chlorohydrin, and (meth)acrylic acid. The reaction between the fluorine compound and epichlorohydrin can be carried out by a known method. For example, 1 mole of the above fluorine compound and 2 moles of shrimp chlorohydrin are heated at 40 to 100°C, preferably 40 to 70°C, in the presence of a small amount of catalyst (for example, boron trifluoride ethyl ether complex, etc.).
It can be obtained by reacting with In the reaction between an epoxide and acrylic acid or methacrylic acid, the ratio of acrylic acid or methacrylic acid used per 1 chemical equivalent of epoxy group in the epoxide is preferably 0.5 to 2.0 chemical equivalents, particularly preferably 0.5 to 2.0 chemical equivalents. 9 to 1.1 chemical equivalents. The reaction temperature is preferably 70 to 130°C, particularly 80 to 100°C. The reaction can be accelerated using a catalyst. Such catalysts are known catalysts such as triethylamine, penzyldimethylamamine, deutyltriethylammonium chloride, triphenylstibine, etc., and the amount used is 0.05 to 20% by weight based on the weight of the reaction solution. Preferably, particularly preferably 0. 1-5% by weight is used.

The amount of the (meth)acrylic acid ester used in the resin composition and heat-resistant optical fiber coating agent of the present invention is 20-100% by weight, particularly preferably 40-99% by weight.

The resin composition and heat-resistant optical fiber coating agent of the present invention (hereinafter both referred to as compositions) further contain epoxy acrylates [e.g., epoxy acrylate of bisphenol A type epoxy resin, epoxy acrylate of bisphenol F type epoxy resin, etc. 7 acrylate, gipoxy acrylate of phenoloxy resin, etc.] isobornyl acrylate, adamantyl acrylate, acrylate of tris(2-hydroxyethynole)incyanuric acid, t'), lfa-/l/propane triacrylate, Acrylates such as hydrogenated dicyclopentadiene acrylate and the like can be used. The amounts used are 00 to 80% by weight of the composition, and 60% by weight of the special VcO.
Power; preferred. Furthermore, various additives such as silane cutting agents, antioxidants, light stabilizers, and polymerization inhibitors can be added as necessary.

Methods for curing the composition of the present invention include curing methods using electron beams, ultraviolet rays, and heat, and curing with ultraviolet rays is preferred. When curing with ultraviolet light, it is necessary to use a photoinitiator.

The photopolymerization initiator may be any known photopolymerization initiator, but it is required to have good storage stability after blending. Examples of such photopolymerization initiators include 2-hydroxy-2-methylbropiofenone, benzyl dimethyl ketal, 1-hydroxy-hexyl phenyl ketone,
2, 4. 6-trimethylbenzoyldiphenoylsulfine oxide and the like. Preferred examples include 1-hydroxycyclohexylphenyl ketone. These photopolymerization initiators may be used alone or in combination of two or more in any proportion.

The amount used is usually preferably 00 to 10% by weight of the composition, particularly preferably 1 to 5% by weight. The composition of the present invention is useful for coating optical glass fibers, and can also be used for protective coatings on plastics, coatings on metals, various inks, adhesives, and the like.

When coating an optical glass fiber with the heat-resistant optical fiber coating agent of the present invention, a dice coating method is suitable as the coating method. When coating an optical glass fiber with the heat-resistant optical fiber coating agent of the present invention, an optical glass base material is drawn, and the heat-resistant optical fiber coating agent of the present invention is preferably coated on the optical glass base material in a 20 to 300μ thick layer. It is coated thickly and cured by UV irradiation. The composition of the present invention is easily cured by ultraviolet irradiation.

For example, ultraviolet rays may be irradiated using a low-pressure or high-pressure mercury lamp or a xenon lamp.

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

[Production example of (meth)acrylic acid ester (3) represented by general formula CI] Production example 1. HO4-CHZ product CF2 layer CH2 volume 47.2 parts of OHl was charged, heated to 50°C to melt it, then 025 parts of boron trifluoride ethyl ether was charged, and 92.5 parts of shrimp chlorohydrin was added in a stirring bowl. The reaction liquid temperature is 50-55
Drop while maintaining the temperature at °C.

After the addition is complete, stir at 50°C for 1 hour. Next, 136 parts of a 30% by weight aqueous sodium hydroxide solution was added to the reaction solution at a temperature of 50 to 55°C.
The mixture was added dropwise while maintaining the temperature, and after the addition was completed, the mixture was stirred at 50°C for 1 hour. Next, add 100 parts of water and heat at 50°C for 30 minutes.
Stir with water, let stand, and wash and separate the reaction solution with water. After repeating this water washing operation three times, unreacted shrimp chlorhydrin was evaporated and HO+CHz }F{ CF2X C
An epoxidized product of H2#OH was obtained. Next, 660 parts of the obtained epoxidized product, 134 parts of acrylic acid, 4. 0 parts and 0.40 parts of methoquinone were charged, and the reaction was carried out at 95°C to reach an acid value of 2.0 parts. 1 mgKOH/g
, viscosity (25°C) 1200 cps O)
Acrylic acid ester was obtained. The results of nuclear magnetic resonance (NMR) measurements of the obtained product are shown below.

Absorption frequency (Hz) 2501.953 2496.093 1976.562 1939.453 1925.781 1771.484 1707.031 1675.781 1191.406 1160.156 1128.904 1103.519 1082 .031 1062.500 104L 828 1033 .203 986.328 957.031 929.687 Ryo Absorption frequency (HZ) 20 828.125 21 '763.671 22 664.062 23 652.343 24 53:l 203 25 511 718 26 498.046 2 7 474.609 28 455.078 29 0. 000 The above measurement results were obtained by a proton decoupling method using tetramethylsilane as a reference substance and deuterium chloroform as a solvent.

Production example 2. 660 parts of the epoxide obtained in Production Example 1, 160 parts of methacrylic acid, 4.1 parts of triphenylstibine, and 0.41 parts of methoquinone were charged, and the reaction was carried out at 95°C until the acid value was 1.
．． 5 mgKOH/g, viscosity (25'C) 1225c
Absorption frequency (Hz) of PS methacrylate ester 2519.531 2044.921 1945.312 1939.453 1896.484 1876.953 1771.484 1210.937 1191.406 1160.156 1128.906 110 7.421 1083. 984 1064, 453 1050.781 1035- 156 988.281 Ryo Absorption frequency (Hz) 18 984.375 19 957.031 20 931.640 21 828.125 22 763.671 23 654.296 24 535.156 25 511. 718 26 496.093 27 474.609 28 455.078 29 275.390 30 0.000 [Production example of epoxy acrylate] Production example 3, Bisphenol A type epoxy resin with epoxy equivalent of 187 (manufactured by Shell Chemical ■, Ebicor} 828 ) 959 parts, acrylic acid 362 parts, dimethylbenzylamine 4.7 parts, methoquinone 0. 7 parts and reacted at 95°C for 15 hours until the acid value was 1. 5 mg KOH/H of epoxy acrylate was obtained.

Production example 4. 900 parts of bisphenol F type epoxy resin (manufactured by Shell Chemical ■, Epicote 8o7) with an epoxy equivalent of 169, 376 parts of acrylic acid, 4.6 parts of triphenylstibine, 0.0 parts of methoquinone. 6 parts was added and the reaction was carried out at 9o0C for 20 hours until the acid value was 2. 1 mgKOH/g x poquine acrylate was obtained.

[Example of resin composition]

Example 1. Resin composition a was prepared by mixing 97 parts of the acrylic ester obtained in Production Example 1 and 3 parts of 1-hydoxylphenyl (manufactured by Ciba Germany, Irgakia-184). .

Example 2. 57 parts and 40 parts of the acrylic ester obtained in Production Example 1,
A resin composition b was prepared by mixing 3 parts of 1-hydroxyhexyl phenyl ketone. Table 1 shows the properties of the cured product.

Example 3. 30 parts of acrylic acid ester (A) obtained in Production Example 1, 3 5 parts of methacrylic acid ester (A) obtained in Surface Preparation Example 2
parts, 42 parts of epoxy acrylate obtained in Production Example 3, 1-
A resin composition C was prepared by mixing 3 parts of hydroxyl phenyl. Table 1 shows the properties of the cured product.

Example 4. Resin composition d was prepared by mixing 5 parts of acrylic acid ester (A) obtained in Production Example 1, 4 parts of epoxy acrylate obtained in Production Example 4, and 3 parts of 1-hydroxyphenyl ester. . Table 1 shows the properties of the cured product.

Table 1 In Table 1 above, measurement of [Shore hardness D]: Compositions a, b, c, and d were irradiated with a high-pressure mercury lamp (lamp output 2 KW) at a position 8 cm below the light source arranged in parallel. (Conveyor speed 2
0 m/min) A sheet with a thickness of 250 μm was prepared and measured using this sheet. The measurement method is JIS-2 22
It was carried out according to the method of No. 46.

[Measurement of breaking strength: kg/mm2, breaking elongation: %, Young's modulus: kg/mm2): The test was performed using a sheet made under the same conditions as those used for the measurement of Shore hardness D above. I did it.

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

Example 5. Heating the base material for optical glass fiber to about 2000°C,
It was spun into an optical glass fiber with an outer diameter of 125 microns at a speed of 5 m/sec. In the next successive step, the resin compositions a% d of Examples 1 to 4 were coated by a die coating method and cured by irradiation with ultraviolet rays. No change in transmission loss was observed in the obtained coated optical glass fibers even when they were left at 150° C. for one month, regardless of whether they were coated with any of the resin compositions a% and d.

(Effects of the Invention) The resin composition and heat-resistant optical fiber coating agent of the present invention have a fast curing speed, and the cured resin film does not elongate or become young even when left at high temperatures for a long period of time. It exhibits small modulus changes and low coloration, and is therefore particularly suitable for coating optical glass fibers for light transmission applications used at high temperatures.

Claims (1)

[Claims] 1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula [I], R is H or CH_3.) (meth)acrylic acid ester represented by 2) A resin composition containing a (meth)acrylic acid ester (A) represented by the general formula [I] described in item 1. 3) A heat-resistant optical fiber coating agent containing a (meth)acrylic acid ester (A) represented by the general formula [I] described in item 1. 4) A cured product of the resin composition according to item 2 or the coating agent according to item 3.