JP2868188B2 - (Meth) acrylic acid ester, method for producing the same, resin composition using the same, coating agent for optical fiber, and cured product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel (meth) acrylic acid ester, a method for producing the same, a resin composition using the same, a coating agent for optical fibers for optical transmission, and a cured product thereof.

[0002]

2. Description of the Related Art Optical fibers are classified into inorganic glass type and synthetic resin type such as poly (methyl methacrylate). Both systems are highly transparent and have a high refractive index.
And a sheath (cladding) having a low refractive index. As the cladding material, a silicon-based compound having a low refractive index, a polymer of a fluorine-containing monomer such as polyfluoroalkyl acrylate, and the like have been conventionally proposed and implemented. For example, poly (methyl methacrylate) is used as a core material, and a polymer of a fluorinated alkyl group-containing (meth) acrylate, a copolymer of a fluorinated alkyl group-containing (meth) acrylate and another monomer is used as a cladding material, or And a method using a fluoropolymer such as poly (tetrafluoroethylene), poly (vinylidene fluoride / tetrafluoroethylene), and poly (vinylidene fluoride / hexafluoropropylene). (For example, Japanese Unexamined Patent Publication No.
-84203, JP-A-59-84204, JP-A-59-84204
98116, JP-A-59-147011, JP-A-59-14701
204002).

[0003]

In the method of forming the clad portion using a fluoropolymer, the thickness tends to be non-uniform because a high temperature fluoropolymer melt or solution is coated. Further, the adhesion between the core portion and the clad portion is not sufficient, and delamination is likely to occur due to various external factors, for example, bending and temperature change, so that there is a problem in durability and the like. In addition, in the production method of applying a melt or solution of a fluoropolymer, it takes a long time to cure the clad portion. In the case of the solution application method, particularly, it is necessary to completely remove the solvent out of the system. Therefore, there were drawbacks in productivity, safety, economy and the like.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have assiduously studied and developed a novel (meth) acrylic acid ester, and by using this, the curing speed is high, The present invention succeeded in providing a resin composition suitable for a clad material of an optical transmission fiber having a low refractive index and excellent adhesion to a core, and completed the present invention. That is, the present invention relates to: 1 General formula (1)

[0005]

Embedded image And / or general formula (2)

[0006]

Embedded image (Wherein, R ₁ is _{C n F 2n + 1 - (} - CH 2 -) a -, C n
F _{2n + 1} -(-CH _2- ) _a -O- or H-(-CF
₂ CF _2- ) _b -(-CH _2- ) _c -O- and R
₂ is H or CH ₃ , n is an integer of 1 to 10, a
Is 0, 1 or 2, b is an integer of 1 to 5, c is 0 or 1.
Is)

Aster (meth) acrylate which is a reaction product of a fluorine-containing (meth) acrylate represented by the formula (1) and (meth) acrylic acid. 2 General formula (3)

Embedded image (Wherein, R ₁ has the same meaning as described above) and fluorine represented by general formula (1) and / or general formula (2), which is a reaction product of (meth) acrylic acid. The (meth) acrylate according to claim 1, wherein the (meth) acrylic acid ester is reacted with (meth) acrylic acid.
A method for producing an acrylic ester. (3) A resin composition comprising the (meth) acrylic acid ester according to (1). (4) An optical fiber coating agent comprising the (meth) acrylic acid ester according to (1). 5. A cured product of the resin composition according to item 3. 6. A cured product of the coating agent for an optical fiber according to item 4. It is about.

The (meth) acrylic acid ester of the present invention comprises:
It can be obtained by reacting the fluorine-containing (meth) acrylate represented by the general formula (1) and / or the general formula (2) with (meth) acrylic acid. The fluorine-containing (meth) acrylate represented by the general formula (1) and / or the general formula (2) is obtained by mixing the fluorine-containing monoepoxy compound represented by the general formula (3) with (meth) acrylic acid. It can be obtained by reacting. Specific examples of the fluorine-containing acrylate represented by the general formula (1) include, for example,

[0009]

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[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

Embedded image And the like. Specific examples of the fluorine-containing acrylate represented by the general formula (2) include, for example,

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

Embedded image And the like.

Specific examples of the fluorine-containing monoepoxy compound represented by the general formula (3) include 3- (perfluoro-
n-butyl) -propenoxide, 3- (perfluoro-
n-hexyl) -propenoxide, 3- (perfluoro-n-octyl) -propenoxide, 1.1-dihydroperfluoro-n-octylglycidyl ether, 1.
1.2.2 2-tetrahydroperfluoro-n-octyl glycidyl ether, 2-hydroperfluoroethyl glycidyl ether,

[0026]

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[0027]

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And the like. In the reaction between the fluorine-containing monoepoxy compound and acrylic acid or methacrylic acid, the epoxy group 1
The use ratio of acrylic acid or methacrylic acid to the chemical equivalent is preferably from 1.0 to 5.0 chemical equivalent, particularly preferably from 1.0 to 2.0 chemical equivalent. Reaction temperature is 50
-200 ° C is preferred, and 70-120 ° C is particularly preferred. The reaction can be promoted using a catalyst. Such a catalyst is a known catalyst such as triethylamine, benzyldimethylamine, methyltriethylammonium chloride, tetraethylammonium chloride, triphenylstibine and the like, and its use amount is 0.001 to 5.0 wt% based on the reaction mixture. Is preferable, and especially 0.
01-3.0 wt% is preferable. Reaction time is 3-48
Time is preferred.

The product obtained by this reaction is usually a mixture of (meth) acrylates represented by the general formulas (1) and (2).

The reaction between the fluorine-containing (meth) acrylic acid ester represented by the general formula (1) and / or the general formula (2) and (meth) acrylic acid is carried out in a non-aqueous system such as benzene, toluene and chlorobenzene. The reaction is carried out in a solvent using a known dehydration condensation reaction catalyst such as sulfuric acid, paratoluenesulfonic acid, and methanesulfonic acid, while azeotropically removing generated water out of the reaction system. It is preferable to react 0.5 to 5.0 chemical equivalents of (meth) acrylic acid with respect to 1 chemical equivalent of the hydroxyl group of the fluorine-containing (meth) acrylate.
Particularly preferably, 0.8 to 1.5 chemical equivalents are reacted.

The reaction temperature is preferably from 80 to 150 ° C.
The amount of the dehydration-condensation catalyst used is usually preferably 0.5 to 10% based on the weight of the reaction mixture excluding the reaction solvent. The reaction time is preferably 3 to 24 hours. Further, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether and methylhydroquinone can be added to the reaction system to prevent polymerization.

The resulting reaction solution is thoroughly washed with an aqueous alkali solution such as sodium hydroxide or sodium carbonate in order to remove the catalyst and excess (meth) acrylic acid, and then the reaction solvent is sufficiently distilled off. (Meth) acrylate can be obtained.

In the resin composition of the present invention or the coating agent for optical fibers (hereinafter referred to as composition), various (meth) acrylates can be used as components other than the (meth) acrylate of the present invention. Specific examples thereof include polyurethane (meth) acrylate [for example, polyurethane (meth) acrylate of a polyether polyol having an ether group in the molecule, and polyurethane (meth) of a carbonate polyol having a carbonate group.
Polyurethane (meth) acrylate of polyester polyol having acrylate or ester group, polyurethane (meth) acrylate having both ether group and ester group in molecule, polyurethane (meth) acrylate of polymer polyol, etc.), epoxy (meth)
Acrylates (eg, (meth) acrylate of bisphenol A epoxy resin, (meth) acrylate of bisphenol F epoxy resin, (meth) acrylate of phenol novolak epoxy resin, (meth) acrylate of urethane-modified epoxy resin of bisphenol A), polyester (Meth) acrylate [e.g., a diol compound (e.g., ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1.5-pentanediol, 1.6-hexanediol, etc.) and a dibasic acid (e.g., succinic acid, adipine) Acid phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, etc.)
(Meth) acrylates of lactone-modified polyester diols comprising acrylates, diol compounds, dibasic acids and ε-caprolactone, etc.], polycarbonate (meth)
Acrylate [for example, (meth) of polycarbonate diol containing 1.6-hexanediol as a diol component
Acrylate etc.],

Adamantyl (meth) acrylate, isobornyl (meth) acrylate, phenyloxyethyl (meth) acrylate, nonylphenyloxypolypropoxy (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, the following structural formula Containing Fluorine-Containing (Meth) acrylates

[0035]

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[0036]

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[0037]

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A fluorine-containing acrylate represented by the general formula (1) (for example, each compound of the formula (4) and the formula (11)) A fluorine-containing acrylate represented by the general formula (2) (for example, Compounds of Formulas (12) to (19)

Formula (1) and / or Formula (2)
And a compound represented by an organic polyisocyanate (for example,
Urethane (meth) acrylate obtained by reacting hexamethylene diisocyanate, isophorone diisocyanate, toluylene diisocyanate, etc.).

These acrylates can be used alone or in a mixture of two or more at an arbitrary ratio, if necessary. The amount used is preferably in the range of 0 to 80% by weight in the composition of the present invention, and particularly preferably in the range of 0 to 60% by weight.

When the composition of the present invention is cured by ultraviolet rays, a photopolymerization initiator is used. Is preferred. The photopolymerization initiator may be any known photopolymerization initiator, but is required to have good storage stability after blending. Such photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-
Methyl pupopiophenone, benzyl dimethyl ketal and the like. Preferred are 1-hydroxycyclohexyl phenyl ketone and the like. These photopolymerization initiators may be used alone or in combination of two or more kinds at an arbitrary ratio. The amount used is usually from 0 to 0% of the composition.
10 wt% is preferable, and particularly 0.5 to 5 wt% is preferable.

The composition of the present invention may further contain various additives such as a silane coupling agent, an antioxidant, a polymerization inhibitor and a light stabilizer, if necessary. The composition of the present invention can be obtained by uniformly mixing the components. A cured product of the composition of the present invention can be obtained by ultraviolet irradiation in a conventional manner.

The method for applying the coating agent for an optical fiber according to the present invention to a substrate (optical transmission fiber core wire) includes various methods known in the art, such as a die coating method and a dipping method. Examples of the optical fiber core wire include quartz and plastics such as polystyrene and polycarbonate. When forming the clad portion of the optical transmission fiber, the thickness of the coating with the coating agent of the present invention is not particularly limited, but is usually 10 to 30.
About 0 microns is preferable. In the case of curing polymerization, it is preferable to use ultraviolet light using a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a metal halide lamp as a light source, and it is desirable to irradiate in a nitrogen gas in order to increase curing efficiency.

The composition of the present invention can be used not only as a cladding material of an optical transmission fiber but also as a coating agent for glass or plastics, a sealing agent for LEDs, etc. by utilizing its low refractive index.

[0045]

The present invention will be described below in more detail with reference to examples. Parts in the examples are parts by weight. Synthesis Examples of (Meth) acrylates Example 1 3- (Perfluoro-n-hexyl) -propenoxide 376. in a reactor equipped with a stirrer, water separator and thermometer.
0 parts, 86.5 parts of acrylic acid, 2.3 parts of tetramethylammonium chloride and 0.23 part of hydroquinone monomethyl ether were charged and reacted at 90 to 95 ° C. for 15 hours. The product is a mixture of two acrylates of formulas (5) and (13).

Next, 500 parts of toluene and 8 parts of acrylic acid
6.5 parts, 16.5 parts of sulfuric acid and 5.5 parts of hydroquinone were added, the temperature was raised again, and the reaction was carried out for 15 hours while expelling water out of the reaction system by azeotropic distillation. Reaction temperature is 107-11
At 3 ° C., the generated water was 12.3 ml. The reaction solution thus obtained was dissolved in 1000 parts of toluene, washed three times with a 10% aqueous sodium hydroxide solution and three times with a 20% saline solution, and then toluene was distilled off under reduced pressure to obtain 477.0 parts of a slightly yellow liquid. Obtained. This had a viscosity (25 ° C.) of 400 cps and a refractive index (25 ° C.) of 1.3810. The results of 13 C-nuclear magnetic resonance (NMR) measurement of this product are shown below. In the measurement, tetramethylsilane was used as a reference substance, and the solvent was deuterated chloroform, and the measurement was performed by a proton decoupling method.

[0047]

Example 2 1.1.2.2 2-tetrahydroperfluoro-n-octyl glycidyl ether Using 420.0 parts, the two formulas (8) and (16) were obtained in the same manner as in Example 1. A mixture of acrylic esters was obtained.

Further, 507.8 parts of a slightly yellow liquid were obtained through the same condensation reaction, alkali washing and solvent evaporation. This has the following properties. Viscosity (25 ° C.) 300 cps Refractive index (25 ° C.) 1.3920

[0050]

Example 3 Using 476.0 parts of 3- (perfluoro-n-octyl) -propenoxide, the same procedure as in Example 1 was carried out except that 476.0 parts of the above formula (6) were used.
And a mixture of two acrylates of the above formula (14).

Then, 500 parts of toluene, 8 parts of acrylic acid
6.5 parts, 38.5 parts of paratoluenesulfonic acid, and 5.5 parts of hydroquinone were added, and a condensation reaction was performed for 20 hours.
572.0 parts of a pale yellow liquid was obtained through alkali washing and solvent evaporation in the same manner as in Example 1. This has the following properties. Viscosity (25 ° C) 750 cps Refractive index (25 ° C) 1.3790

[0053]

Example 4 1.1-Dihydroperfluoro-n-octylglycidyl ether was used in the same manner as in Example 1 by using 456.0 parts of the two acrylates of the above formulas (7) and (15). A mixture was obtained.

Further, a condensation reaction, alkali washing and solvent evaporation were carried out in the same manner as in Example 3 to obtain 530.0 parts of a slightly yellow liquid. This has the following properties. Viscosity (25 ° C.) 365 cps Refractive index (25 ° C.) 1.3890

[0056]

Example 5 In Example 1, methacrylic acid 10 was used instead of acrylic acid.
A mixture of two methacrylates having the following structure was obtained in the same manner except that 3.2 parts were used.

[0058]

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[0059]

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Subsequently, 500 parts of toluene, 103.2 parts of methacrylic acid, 16.5 parts of sulfuric acid, and 5.5 of hydroquinone
And the condensation reaction was carried out for 15 hours. After performing alkali washing and distilling off the solvent in the same manner as in Example 1, a slightly yellow liquid 47 was obtained.
7.0 parts were obtained. This has the following properties. Viscosity (25 ° C) 380 cps Refractive index (25 ° C) 1.3850

[0061]

Example of resin composition Example 6 97 parts of the acrylate obtained in Example 1, 1-hydroxycyclohexylphenyl ketone (Ciba Geigy)
And Irgacure 184) were mixed to obtain a resin composition A of the present invention. The resin composition A was applied on a glass plate to a thickness of 200 μm, and then irradiated with ultraviolet rays of 500 mJ / cm 2 from a high-pressure mercury lamp under a nitrogen atmosphere to obtain a cured product. Table 1 shows the properties of the obtained cured product.

Example 7 82 parts of the acrylate obtained in Example 3, 15 parts of the methacrylate obtained in Example 5, and 3 parts of 1-hydroxycyclohexyl phenyl ketone were mixed, and the resin composition B of the present invention was mixed. I got Table 1 shows the properties of the cured product obtained in the same manner as in Example 6.

Example 8 30 parts of the acrylate obtained in Example 2, 10 parts of the acrylate obtained in Example 4, and 27 parts of the acrylate of the formula (22)

Urethane acrylate [Nippon Carbide
1 mol of Nicalite H-472 (acrylic polymer polyol) and 2 mol of isophorone diisocyanate.
5 parts of a reacted urethane acrylate] and 1 part of 1-hydroxycyclohexyl phenyl ketone were mixed to obtain a resin composition C of the present invention. Table 1 shows the properties of the cured product obtained in the same manner as in Example 6.

Example 9 60 parts of the acrylate obtained in Example 1, urethane acrylate [the compound of the above formula (5) and the compound of the above formula (1)
37 parts of urethane acrylate obtained by reacting 1 mol of the mixture of the compound of 3) with 0.5 mol of hexamethylene diisocyanate, and 3 parts of 1-hydroxycyclohexyl phenyl ketone were mixed to obtain a resin composition D of the present invention. Table 1 shows the properties of the cured product obtained in the same manner as in Example 6.
Shown in

Table 1 Resin Composition ABCD Hardness (Shore D) 55 50 41 60 Young's Modulus (kg / mm ² ) 60 ° C 7.0 3.0 2.0 4.0 40 ° C 15 10 7.2 15 23 ° C 25 20 10 40 Refraction 25 ° C 1.399 1.400 1.415 1.404 Water absorption% 0.3 0.4 0.2 0.2

The hardness (Shore D) was measured in consideration of the influence of the hardness value of the sample holder, and the JIS having a thickness of about 200 microns was used.
It carried out according to the method of Z2246. The Young's modulus was measured using a 200 micron cured product according to JIS K 711.
Performed according to the method of No. 3. The water absorption was measured according to the method of JIS K 7209 using a cured product of 200 microns.

[0069]

According to the present invention, the resin composition and the optical fiber coating agent using the novel (meth) acrylic ester of the present invention have a high curing speed, and the obtained resin film has flexibility and low refractive index. It has excellent adhesion to the core and is suitable for cladding layers of optical fibers for optical transmission.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification code FI G03F 7/004 511 G03F 7/004 511 7/027 502 7/027 502 (58) Investigated field (Int.Cl. ⁶ , DB Name) C07C 69/653 C07C 67/08 C08F 220/28 G02B 6/00 G03F 7/004-7/027 CA (STN) REGISTRY (STN) WPI / L (QUESTEL)

Claims (6)

(57) [Claims] 1. A compound of the general formula (1) And / or general formula (2) (Wherein, R ₁ is _{C n F 2n + 1 - (} - CH 2 -) a -, C n
F _{2n + 1} -(-CH _2- ) _a -O- or H-(-CF
_{2 CF 2 -) b - (} - CH 2 -) c -O- and and R ₂ is H or CH _3, n is an integer of from 1 to 10, a is 0,
(Meth) acrylic acid, which is a reaction product of (meth) acrylic acid and a fluorine-containing (meth) acrylate represented by 1 or 2, and b is an integer of 1 to 5, and c is 0 or 1. ester. 2. A compound of the general formula (3) (Wherein, R ₁ is claim 1 as defined shows a. And R ₁ indicated) with a compound represented by (meth) general formula according to claim 1 wherein the reaction product of acrylic acid (1) and / The method for producing a (meth) acrylic ester according to claim 1, wherein the fluorine-containing (meth) acrylic ester represented by the general formula (2) is reacted with (meth) acrylic acid. 3. A resin composition comprising the (meth) acrylic ester according to claim 1. 4. A coating agent for an optical fiber, comprising the (meth) acrylic ester according to claim 1. 5. A cured product of the resin composition according to claim 3. 6. A cured product of the coating agent for an optical fiber according to claim 4.