JPH01224247A - (meth)acrylate and resin composition and coating agent for optical fiber using said (meth)acrylate - Google Patents

Abstract

PURPOSE:To obtain a resin composition having rapid curing rate, low refractive index, excellent flexibility and good bonding to a core and suitable as clad coating of optical transmission, by containing a specific (meth)acrylic acid ester. CONSTITUTION:1mol. compound expressed by formula I or formula II (n and m are 4-10; l is 1 or 2) is reacted with 1-5mol. (meth)acrylic acid in an organic solvent (e.g., benzene) in the presence of a catalyst (e.g., P- toluenesulfonic acid) and polymerization inhibitor at 70-150 deg.C to afford (meth) acrylic acid ester (A). Then 20-100wt.% component A is blended with (B) 0-80wt.% ethylenic unsaturated compound [e.g., polyurethane (meth)acrylate] and (C) 0-10wt.% photopolymerization initiator (e.g., 1-hydroxycyclohexyphenyl ketone) to provide the coating agent for optical fiber consisting of resin composition. Then clad material for optical transmission is coated with the above- mentioned coating agent having 10-300mu thickness.

Description

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

(Prior Art) Optical fibers can be divided into inorganic glass fibers and synthetic resin fibers such as poly(methyl methacrylate).

Both systems consist of a highly transparent core with a high refractive index and a cladding with a low refractive index. As craft materials, silicon-based compounds with low refractive indexes and polymers of fluorine-containing monomers such as polyfluoroalkyl acrylate have been proposed and implemented. ), and as a craft material, a polymer of fluorinated alkyl group-containing (meth)acrylate 7, a copolymer of fluorinated alkyl group-containing (meth)acrylate and other hexamers, or poly (tetrafluoroethylene) is used. ) A method using fluorine-containing polymers such as poly(vinylidene fluoride/tetrafluoroethylene) and poly(vinylidene fluoride/hexafluoropropylene) (JP-A-59-84203, JP-A-5
9-84204, JP-A No. 59-98116, JP-A No. 59-Sho.
-147011, JP-A-59-204002).

(Problems to be Solved by the Invention) In the method of forming a cladding portion using a fluorine-containing polymer, the thickness tends to become non-uniform because a high temperature melt or solution of the fluorine-containing polymer is coated.

Also, the adhesion between the core part and the craft part is not sufficient,
Since peeling between the eyebrows is likely to occur due to various external factors such as bending and temperature changes, there have been problems with durability and the like. or,
In production methods in which a melt or solution of a fluorine-containing polymer is applied, it takes a long time to harden the cladding part, and in the solution application method, it is particularly difficult to completely remove the solvent from the system. However, there were drawbacks in terms of productivity, safety, economy, etc.

(Means for Solving the Problems) In order to solve the above problems, the present inventors synthesized a novel (meth)acrylic acid ester as a result of intensive research.
Using this (meth)acrylic acid ester, we succeeded in providing a resin composition that has a fast curing speed, a low refractive index, and excellent adhesion to the core, and is suitable for the clamp coating material of FAIVA for optical transmission. Completed the invention.

That is, the present invention provides: l) general formula (I) (in formula (I), n represents an integer of 4 to IO) or general formula (n) CHtOH(n) (in formula (n), l is 1 or 2, and m is an integer of 4 to 1O.

2) A resin composition characterized by containing a (meth)acrylic acid ester which is a reaction product of general formula (I) or general formula (II) and (meth)acrylic acid.

3) It relates to an optical fiber coating agent characterized by containing a (meth)acrylic acid ester which is a reaction product of the general formula (2) or the general formula (n) and (meth)acrylic acid.

The (meth)acrylic ester of the present invention has the -S formula (+)
Alternatively, it can be produced by reacting the compound represented by general formula (II) with acrylic acid or methacrylic acid.

OH, C6Ft of the compound represented by the general formula (II), which is the raw material for the (meth)acrylic ester of the present invention.
sCHz CHz OCHz - When reacting the compound represented by the general formula (ri or (n) with acrylic acid or methacrylic acid, the reaction temperature is TO-15
It is preferable to use 1 to 5 mol of acrylic acid or methacrylic acid, particularly 2 to 5 mol, per 1 mol of the compound represented by general formula (+) or (II), which is preferably 0°C, particularly preferably 80 to 130°C. It is preferable to use 3 mol, and it is preferable to use an organic solvent such as benzene, toluene, cyclohexane, etc. as the reaction solvent. To prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor, such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, phenothiazine, etc.To accelerate the reaction, a catalyst such as sulfuric acid, P-
Preferably, toluenesulfonic acid, methanesulfonic acid, etc. are used.

Resin composition and optical fiber coating agent of the present invention (
(hereinafter all referred to as compositions), the (meth)acrylic acid ester is preferably used in the range of 20 to 100% by weight, particularly preferably in the range of 40 to 98% by weight.

In the composition of the present invention, various known ethylenically unsaturated compounds can be used as components other than this novel (meth)acrylic acid ester. Specific examples of ethylenically unsaturated compounds include polyurethane (meth)acrylates, such as
Polyurethane (meth)acrylate of polyether polyol with ether group in the molecule, polyurethane (meth)acrylate of carbonate polyol with carbonate group, polyurethane (meth)acrylate of polyester polyol with ester group, or ether group and ester group Epoxy (meth)acrylates, such as polyurethane (meth)acrylates that have both of the following in their molecules, polyurethane (meth)acrylates of polymer polyols, etc.
meth)acrylate, (meth)acrylate of bisphenol F epoxy resin, (meth)acrylate 1 of phenol novolac epoxy resin, bisphenol A
Polyester (meth)acrylates such as (meth)acrylates of urethane-modified epoxy resins, diol compounds (e.g. ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, l,5-bentanediol, l,6-hexanediol, etc.) ) and dibasic acids (e.g. succinic acid, adipic acid,
(meth)acrylates of polyester diols consisting of phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, etc.;
polycarbonate (meth)acrylate, such as (meth)acrylate of polycarbonate diol containing 1,6-hexanediol as a diol component, adamantyl (meth)acrylate, isobornyl (meth)acrylate, phenyloxyethyl (
meth)acrylate, nonylphenyloxyboribroboxy(meth)acrylate, trinotyrolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, fluorine-containing (meth)acrylate with the following structural formula, H-+CF, CF- )-t cH
t 0CCH-CHI, H6CF t CF kes C
Hz OCCH= CHt, Cy F +sCHz O
CCH" CHz, C, F, ffCH, CH, 0CCH
-CHt, C4F + s CHz CHz OC
CH= CHz, (CH5-hCF CHz
OCCH-CHz, CHI 婁 CHCOCt
H4-÷CF-1Ct Ha+CF-CF Out
C, H, 0CCH CH,, F3 Particularly preferred ethylenically unsaturated compounds include, for example, polyurethane acrylates of polymer polyols, fluorine-containing monoacrylates, and the like. The above-mentioned ethylenically unsaturated compounds may be used singly or in combination of two or more compounds in any proportion as required. The amount of the ethylenically unsaturated compound used in the composition is preferably 0 to 80% by weight, particularly preferably 0 to 60% by weight.

When the composition of the present invention is cured by ultraviolet rays, it is preferable to add a photopolymerization initiator, and any known photopolymerization initiator may be used as such a photopolymerization initiator. Good storage stability after blending is required. Examples of such photopolymerization initiators include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether, and benzoin isopropyl ether, 2,2-jethoxyacetophenone, 4°-phenoxy-2,2-dichloroacetophenone, and the like. acetophenone series, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4'-dodecyl-2-hydroxy-2-methylpropiophenone, etc. Examples include phenone type, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, anthraquinone type such as 2-ethylanthraquinone and 2-chloroanthraquinone, and thioxanthone type photopolymerization initiators. Particularly preferred are 1-hydroxycyclohexylphenyl ketone, benzol dimethyl ketal, and the like. These photopolymerization initiators may be used alone or in a mixture of two or more in any proportion, and the amount used is usually preferably 0 to 10% by weight, particularly 1 to 5% by weight of the composition. is preferable, and various additives such as a silane cuff pulling agent, an antioxidant, and a polymerization inhibitor can also be added to the composition of the present invention.

The coating agent for optical fiber according to the present invention can be applied to a base material by various methods known in the art, for example,
Examples include dice coating method and dipping method. In addition, as the optical transmission fiber core wire referred to in the present invention, quartz-based fibers, polymethyl methacrylate, polyethyl methacrylate, deuterated polymethyl methacrylate, polystyrene,
Examples include plastics such as polycarbonate. When forming the cladding portion of an optical transmission fiber, the thickness of the coating formed by the coating agent of the present invention is not particularly limited, but is usually preferably about 10 to 300 μm.

In the case of curing polymerization, it is preferable to use ultraviolet rays from a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a metal halide lamp as a light source, and it is preferable to irradiate in nitrogen gas to increase the curing efficiency.

The composition of the present invention can be used not only as a craft material for optical transmission fibers, but also as a coating agent for glass or transparent plastic, a sealant for LEDs, etc. by taking advantage of its low refractive index.

(Example) Hereinafter, the present invention will be concretely explained with reference to Examples.

Note that parts in the examples are parts by weight.

[Synthesis example of (meth)acrylic acid ester] Synthesis example 1 Compound of the following structural formula: 394 parts, acrylic acid, 173 parts, sulfuric acid, 5.7 parts, hydroquinone: 2
．． 0 parts and 500 parts of toluene were charged and heated, the produced water was distilled and condensed together with the solvent, only the water was removed from the system in a separator, and the solvent was returned to the reactor. When 36 parts of water was produced, it was cooled. The reaction mixture, whose reaction temperature was 113 to 120°C, was dissolved in 1500 parts of toluene, neutralized with a 20% aqueous sodium hydroxide solution, and then washed three times with 500 parts of a 20% saline solution. The solvent was distilled off under reduced pressure to obtain 452 parts of a pale yellow liquid. This material has the following properties.

Viscosity 400 (25℃, CPS)
Refractive index LaB5 (25°C) The results of high-resolution nuclear magnetic resonance (NMR) measurements of the obtained product are shown below.

No, Absorption frequency (Hz) 1 2546.875 2 2494.140 3 2488.2814
2478.5155
1984.3756
1972.6567
1957.0318
1925.7819 1
919.9211 0 17
42.1871 1 119
1.4061 2 1160
．． 1561 3 1126.
9531 4 1074.2
181 5 970.70
31 6 898.437
1 7 507.8121
8 486.3281
9 462.8902 0
- 60.5462 1
0.000 Note: The above measurements were carried out by the proton dicuff pulling method using tetramethylsilane as a reference substance and deuterated chloroform as a solvent.

Synthesis Example 2 494 parts of a compound with the following structural formula, 173 parts of acrylic acid, 10 parts of P-1 sulfonic acid,
Prepare 2.0 parts of hydroquinone and 550 parts of toluene,
The reaction was carried out in the same manner as in Synthesis Example 1 until the amount of water produced was 36 parts. The reaction mixture, whose reaction temperature was 115 to 120°C, was dissolved in 1500 parts of toluene, neutralized with a 20% aqueous sodium hydroxide solution, and then washed three times with 500 parts of a 20% aqueous NaCl solution. ? Agent 8 was distilled off under reduced pressure to obtain pale yellow liquid 5.
Obtained 48 copies. This material has the following properties.

Viscosity 750 (25℃, CPS) Refractive index
1.379 (25℃) NMR measurement result pJo, absorption frequency (Hz) 1
2544.921 2 2486.3283
2472.6564
2185.5465
1982.4216
1970.7037
1955.0?88
1923.8289
1917.9681 0 1
732.4211 1,
1617.1871 2
11B9.4531 3
1158.2031 4 1
125.0001 5 10
41.0151 6 96
8.7501 7 89
6.4841 8 50
7.8121 9 4B4
．． 3752 0 13.6
712 1 0.00
0 Synthesis Example 3 394 parts of a compound with the following structural formula, 206 parts of methacrylic acid, 5.7 parts of sulfuric acid, 2.0 parts of hydroquinone, and 500 parts of toluene were charged, and the same procedure as in Synthesis Example 1 was carried out until the amount of water produced was 36 parts. The reaction temperature at which the reaction was carried out was 115-120°C.

The reaction mixture was dissolved in 1500 parts of toluene, neutralized with 20% aqueous sodium hydroxide solution, and after distilling off the solvent, a pale yellow liquid 47.
I got 7 copies. This material has the following properties.

Viscosity 379 (25℃, CPS) Refractive index
1.382 (25℃) NMR measurement result No. Absorption frequency (H2) 1
2546.875 2 2494, 140 3 2488.280 4 2478.115 5 2046.8006
1984.3757
1972.6568
1957.0319 1
925.7801 0 191
9.9211 1 1742
．． 1851 2 1191.4
061 3 1160.156
1 4 1126.9531
5 1074.2181 6
970.7031 7
898.4371 8
507.8121 9
486.32520
462.891 2 1 277.3682
2 60.5452 3
0.000 Synthesis Example 4 Compound of the following structural formula: 474 parts Acrylic acid: 187 parts, Sulfuric acid: 5.6 parts, Hydrodonone: 2 parts
．． 0 parts and 550 parts of toluene were charged, and the reaction was carried out in the same manner as in Synthesis Example 1 until the amount of produced water reached 36 parts. The reaction temperature was 112 to 120°C. Add 1 part of toluene to the reaction mixture
The solution was dissolved in 500 parts, neutralized with a 20% caustic soda aqueous solution, and the solvent was distilled off to obtain 529 parts of a pale yellow liquid. This material has the following properties.

Viscosity 365 (25℃, CPS) Refractive index
1,379 (25°C) NMR measurement result NOo @number frequency (Hz) 1 2570.312 2 2564.453 3 2554.687 4 2494, 140 5 2490.234 6 2484.3757
1982.4218
1978.5159
1972.6561 0
1925.7811 1
1921.8751 2
1191.4061 3
1160.1561 4
1126.9531 5
1070.3121 6 1
054.6871 7 10
31.250] 8 10
03.9061 9 99
2.1872 0 982
．． 4212 1 949.2
182 2 937.50
02 3 898.437
2 4 527.3432
5 509.7652
6 0.000 Synthesis Example 5 439 parts of compound with the following structural formula c Ht -OH 187 parts of acrylic acid, 5.6 parts of sulfuric acid, 2 parts of hydroquinone
．． The reaction mixture was dissolved in 1500 parts of toluene. , neutralized with 20% caustic soda aqueous solution,
After distilling off the solvent, 476 parts of a pale yellow liquid was obtained. This material has the following properties.

Viscosity 300 (25℃, CPS) Refractive index
1.381 (25℃) NMR measurement result No. Absorption frequency (Hz) 1
2571.112 2 2565.392 3 2555.5914
2.546.8755
2495.1516
2491.2537
2485.4028
2478.5159
1982.4211 0
197B, 5151 1
1972.6561 2
1925.7811 3
1921.8751
4 1742.1?91
5 1191.406
1 6 1160.15
61 7 1126.9
531 8 1070.
3121 9 1054
．． 6872 0 103
1.2502 1 10
03.9062 2
993.2052 3
983.4382 4
950.2372 5
938.5312 6
899.4522 7
528.4112 8
510.8032 9
0.000 [Example of resin composition] Example 6 97 parts of acrylic ester obtained in Synthesis Example 1, 3 parts of 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy Co., Ltd., Irugaki Air-184) were mixed to prepare resin composition A. Table 1 shows the properties of the cured product.

Example 7 Resin composition B was prepared by mixing 82 parts of the acrylic ester obtained in Synthesis Example 2, 15 parts of the methacrylic ester obtained in Synthesis Example 3, and 3 parts of l-hydroxycyclohexylphenyl ketone. . Table 1 shows the properties of the cured product.

Example 8 10 parts of methacrylic ester obtained in Synthesis Example 4, 30 parts of acrylic ester obtained in Synthesis Example 5, structural formula H
(CFz CFt LCHz - 27 parts of acrylate having active CCH=CH, urethane acrylate [manufactured by Nippon Carbide Co., Ltd., 1 mole of Nicalite H-472 (acrylic polymer polyol) and 2 moles of isophorone diisocyanate were reacted, and then 2- Resin composition C was prepared by mixing 330 parts of urethane acrylate reacted with 2.05 moles of hydroxyethyl acrylate and 3 parts of 1-hydroxycyclohexylphenyl ketone.

Table 1 shows the properties of the cured product.

Table 1 In the above Table 1, (Shore hardness D) measurement: Compositions A, B, and C were irradiated with a metal halide lamp (lamp output, 2 KW) at a position 8 cm below the light source arranged in parallel. A 250 μm sheet was prepared and used for measurement.

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

(Young's modulus, kg/am") measurement: The test piece was prepared under the same conditions as those used for the Shore hardness measurement above. Using this, the Young's modulus was measured by changing the temperature. went.

(Refractive index) measurement: A test piece was prepared under the same conditions as those used for the Shore hardness measurement described above.

Using this, the refractive index was measured.

(Effects of the Invention) The resin composition and optical fiber coating agent using the novel (meth)acrylic ester of the present invention have a fast curing speed, and the resulting resin film has flexibility and a low curvature. It has excellent adhesion to the core and can be passed through the craft layer of optical fiber for light transmission.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In formula (I), n represents an integer from 4 to 10.) Or,
General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In formula (II), l is 1 or 2, and m is an integer from 4 to 10.) and (meth)acrylic acid (meth)acrylic acid ester, which is a reaction product with. 2. A resin composition containing the (meth)acrylic acid ester described in item 1. 3. An optical fiber coating agent containing the (meth)acrylic acid ester described in item 1.