JP2868191B2 - Urethane (meth) acrylate, 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 urethane (meth) acrylate, 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) portion 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 Using fluoropolymers such as poly (tetrafluoroethylene), poly (vinylidene fluoride / tetrafluoroethylene), and poly (vinylidene fluoride / hexafluoropropylene) (JP-A-59-84203;
JP-A-59-84204, JP-A-59-98116, JP-A-59-147011, JP-A-59-204002.
It has been known.

[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 made intensive studies and have developed a novel urethane (meth) acrylate.
The present invention succeeded in providing a resin composition suitable for a cladding material of an optical transmission fiber having a high curing rate, a low refractive index, and excellent adhesion to a core. That is,
The present invention relates to 1 polyol (A) and organic polyisocyanate (B)
And 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 and R ₂ is H or CH _3, n is an integer of from 1 to 10, a is 0,
1 or 2, b is an integer of 1 to 5, c is 0 or 1)

A urethane (meth) acrylate obtained by reacting a fluorine-containing (meth) acrylate (C) represented by the formula: (2) A resin composition comprising the urethane (meth) acrylate according to (1). (3) A coating agent for optical fibers, comprising the urethane (meth) acrylate according to (1). 4. A cured product of the resin composition according to item 2. 5. A cured product of the coating agent for an optical fiber according to item 3. It is about.

[0008] The urethane (meth) acrylate of the present invention comprises a polyol (A) and an organic polyisocyanate (B).
And then reacting the fluorine-containing (meth) acrylate (C) represented by the general formula (1) and / or the general formula (2). Alternatively, the organic polyisocyanate (B) is reacted with the fluorine-containing (meth) acrylate (C) represented by the general formula (1) and / or the general formula (2), and then reacted with the polyol (A). Can also be obtained.

Specific examples of the polyol (A) include:
For example, ethylene glycol, propylene glycol,
1.4-butanediol, 1.5-pentanediol,
Neopentyl glycol, 1.6-hexanediol,
1.8-octanediol, glycerin, trimethylolpropane, alkyl polyols such as pentaerythritol, polyether polyols such as polyethylene glycol and polytetramethylene glycol, succinic acid, adipic acid, azelaic acid, sabacic acid, phthalic acid, tetrahydro ( Dibasic acids such as phthalic anhydride and hexahydro (phthalic anhydride), ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1.4-butanediol, 1.5-pentanediol, neopentyl glycol; Polyester polyol, poly-ε-caprolactone-modified polyol, polymethylvalerolactone-modified polyol obtained by reaction with a diol compound such as 6-hexanediol,
Polycarbonate polyols,

[0010]

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[0011]

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[0012]

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And the like. Specific examples of the organic polyisocyanate (B) include, for example, isophorone diisocyanate hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, trimethyl hexamethylene diisocyanate, a trimer of hexamethylene diisocyanate, and a trimethylolpropane adduct of hexamethylene diisocyanate. And the like. Specific examples of the fluorine-containing (meth) acrylate represented by the general formula (1) include, for example, compounds of the following structural formulas.

[0014]

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[0015]

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[0016]

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[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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Specific examples of the fluorine-containing (meth) acrylate represented by the general formula (2) include compounds having the following structural formulas.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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The fluorine-containing (meth) acrylic acid ester (C) 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 (22) with ( It can be obtained by reacting (meth) acrylic acid.

[0032]

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 n is 1
An integer of 10 to 10, a is 0, 1 or 2, b is an integer of 1 to 5, c is 0 or 1.)

Specific examples of the fluorine-containing monoepoxy compound represented by the general formula (22) include, for example, 3- (perfluoro-n-butyl) -propenoxide, 3- (perfluoro-n-hexyl) -propenoxide, 3- (perfluoro-n-octyl) -propenoxide, 1.1-
Dihydroperfluoro-n-octyl glycidyl ether, 1.1.2.2-tetrahydroperfluoro-n-
Octyl glycidyl ether, 2-hydroperfluoroethyl glycidyl ether,

[0034]

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[0035]

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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 0.9 to 5.0 chemical equivalent, particularly preferably from 0.9 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) acrylic esters represented by the general formulas (1) and (2). The (meth) acrylic acid ester thus obtained is once dissolved in a non-aqueous solvent such as toluene to remove an excess of (meth) acrylic acid or a catalyst if necessary. Well washed with an aqueous solution of Thereafter, when the solvent is sufficiently distilled off, a (meth) acrylic ester having higher purity can be obtained. Also, in some cases,
In some cases, it is purified by distillation under reduced pressure or fractionated into individual components for use.

The polyol (A) is reacted with the organic polyisocyanate (B), and then the above-mentioned general formula (1) and / or
Alternatively, in the method for producing a urethane (meth) acrylate of the present invention by reacting the compound represented by the general formula (2), the charged amount of the organic polyisocyanate per one chemical equivalent of the hydroxyl group of the polyol (A) is as follows: Groups 1.1-2.0 chemical equivalents are preferred, especially 1.2-2.
Zero chemical equivalents are preferred. The reaction temperature is preferably from 20 to 120C, particularly preferably from 50 to 90C. Next, 0.9 to 1.5 chemical equivalents, particularly preferably 1.0 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the isocyanate group of the compound having an isocyanate group at the terminal thus obtained is preferably used. And / or reacting the compound represented by the general formula (2). This reaction can be performed in the presence of a known catalyst such as a tertiary amine, dibutyltin dilaurate, or dioctyltin dilaurate to promote the reaction between the isocyanate group and the hydroxyl group. Reaction temperature is 30-9
0 ° C. is preferred.

The urethane of the present invention is obtained by first reacting the organic polyisocyanate (B) with the compound (C) represented by the general formula (1) and / or (2), and then reacting the polyol (A). In the method for producing (meth) acrylate, the general formula (1) and / or
Alternatively, the compound represented by the general formula (2) is preferably used in 0.1.
One to 0.5 chemical equivalents, particularly preferably 0.5 chemical equivalents, are reacted. The reaction temperature is preferably from 20 to 120C, particularly preferably from 50 to 90C. 0.95 to 1 chemical equivalent of residual isocyanate groups of the compound thus obtained
1.05 chemical equivalents, particularly preferably 1.0 chemical equivalent, of the polyol (A) having a hydroxyl group is reacted. This reaction can be performed in the presence of a known catalyst such as a tertiary amine, dibutyltin laurate, or dioctyltin dilaurate to promote the reaction between the isocyanate group and the hydroxyl group. The reaction temperature is preferably from 30 to 90C.

In the above two production methods, the reaction may be carried out without solvent or with a solvent such as acetone, methyl ethyl ketone, toluene or the like which is inert to the isocyanate group, or an acrylate ester used in the resin composition of the present invention described later. It can be carried out using as a reaction solvent.

The resin composition of the present invention or a coating agent for an optical fiber (hereinafter referred to as a composition) includes an acrylate ester other than the urethane (meth) acrylate of the present invention, for example,

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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The compound represented by the general formula (1), the compound represented by the general formula (2) and the like can be used. These acrylates are used in the composition of the present invention with respect to 100 parts by weight of the urethane (meth) acrylate of the present invention.
It is preferred to use from 10 to 900 parts by weight, particularly preferably from 50 to 500 parts by weight.

When the composition of the present invention is cured by ultraviolet rays, a photopolymerization initiator is used. The photopolymerization initiator may be any known photopolymerization initiator, but is required to have good storage stability after blending. Examples of such a photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, and benzyl dimethyl ketal. 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. Usually, the amount used is preferably from 0 to 10% by weight, particularly preferably from 0.5 to 5% by weight of the composition. Further, the composition of the present invention further comprises a silane coupling agent, if necessary,
Various additives such as an antioxidant, a polymerization inhibitor and a light stabilizer can also be added. The composition of the present invention can be obtained by uniformly mixing the components. Further, a cured product of the composition of the present invention can be obtained by irradiation with radiation by a conventional method.

The method for applying the coating agent for 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 the curing efficiency.

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

[0057]

The present invention will be described below in more detail with reference to examples. Parts in the examples are parts by weight. General formula (1)
Synthesis Example of Fluorine-Containing (Meth) acrylate Represented by General Formula (2) and / or Example 1 3- (perfluoro-n-hexyl) -propenoxide 376.0 parts, acrylic acid 86.5 parts , 2.3 parts of tetramethylammonium chloride and 0.23 part of hydroquinone monomethyl ether.
Allowed to react for hours. The obtained reaction solution was toluene 1500 m
and 15% aqueous sodium carbonate three times with 20%
After washing three times with sodium chloride solution, toluene was distilled off under reduced pressure to obtain 425.0 parts of a colorless liquid. Its refractive index at 20 ° C. was 1.3620. This is a mixture of two acrylates of the above formulas (7) and (15).

Example of synthesis of urethane (meth) acrylate Example 2 45.1 parts of 1.4-butanediol and 222.3 parts of isophorone diisocyanate were charged and reacted at 75 to 80 ° C. for 5 hours while heating and cooling. Was. Next, the mixture of the fluorine-containing acrylic acid ester obtained in Example 1 was 448.0.
The mixture was stirred at 75-80 ° C for 1 hour to uniformly dissolve, then cooled to 60 ° C, and 0.36 parts of di-n-butyltin dilaurate was added. 1 hour at 60-65 ° C, 8
The reaction was carried out at 0 to 85 ° C for 5 hours to obtain a colorless product. Its refractive index at 25 ° C. was 1.4345.

Example 3 262.6 parts of PLACSEL 205 (caprolactone polyol, manufactured by Daicel Chemical Industries, hydroxyl value 213.7) and 222.3 parts of isophorone diisocyanate were charged and reacted at 75 to 80 ° C. for 5 hours while heating and cooling. Then, it was cooled to room temperature. Next, 448.0 parts of the mixture of the fluorine-containing acrylate obtained in Example 1 and 0.46 part of di-n-butyltin dilaurate were charged, and 35 to 40 parts were charged.
Reaction was carried out at 3 ° C. for 3 hours and at 60-65 ° C. for 2 hours to obtain colorless products. Its refractive index at 25 ° C. was 1.44.
It was 50.

Example 4 59.0 parts of 1.6-hexanediol and 222.3 parts of isophorone diisocyanate were charged and reacted at 75 to 80 ° C. for 5 hours while heating and cooling. Next, the mixture of the fluorine-containing acrylic acid ester obtained in Example 1 was 448.0.
Then, the mixture was stirred at 75 to 80 ° C. for 1 hour to uniformly dissolve, then cooled to 60 ° C., and 0.34 part of di-n-butyltin dilaurate was added. 1 hour at 60-65 ° C,
The reaction was carried out at 80 to 85 ° C for 5 hours to obtain a colorless product. Its refractive index at 25 ° C. was 1.4340.

Example 5 Compound having the following structural formula

[0062]

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After 219.1 parts and 112.2 parts of hexamethylene diisocyanate were charged and reacted at 80 to 85 ° C. for 24 hours, 149.4 parts of the fluorine-containing acrylate obtained in Example 1 were treated with the above formula (31) Compound 480.7 of
And 0.30 part of di-n-butyltin dilaurate were charged and reacted at 80 to 85 ° C. for 10 hours to obtain a slightly yellow product. Its refractive index at 25 ° C. was 1.401.
It was 5.

Example 6 of Resin Composition Example 6 34.0 parts of the urethane acrylate obtained in Example 2, 29.0 parts of the compound of the formula (31), 34.0 parts of the compound of the formula (34), and 1 -Hydroxycyclohexyl phenyl ketone (3.0 parts) was mixed to prepare a resin composition (a). It exhibited the following properties: Refractive index (25 ° C.) 1.4130 Viscosity (25 ° C.) 1620 cps Further, after applying this resin composition a on a glass plate at a thickness of 200 μm, the resin composition a was coated with a high-pressure mercury lamp under a nitrogen atmosphere at 500
The cured product was obtained by irradiating ultraviolet rays of mJ / cm2. Table 1 shows the properties of the obtained cured product.

Example 7 A resin composition b was prepared by mixing 50.0 parts of the urethane acrylate obtained in Example 3, 47.0 parts of the compound of the above formula (34), and 3.0 parts of 1-hydroxycyclohexyl phenyl ketone. Was prepared. It exhibited the following properties: Refractive index (25 ° C.) 1.4330 Viscosity (25 ° C.) 2240 cps Table 1 shows the properties of the cured product obtained in the same manner as in Example 6.

Example 8 50.0 parts of the urethane acrylate obtained in Example 4, 47.0 parts of the acrylate obtained in Example 1, and 1-
3.0 parts of hydroxycyclohexyl phenyl ketone was mixed to prepare a resin composition c. It exhibited the following properties: Refractive index (25 ° C.) 1.4055 Viscosity (25 ° C.) 31900 cps Table 1 shows the properties of the cured product obtained in the same manner as in Example 6.

Example 9 A resin composition d was prepared by mixing 40.0 parts of the urethane acrylate obtained in Example 5, 57.0 parts of the compound of the formula (31), and 3 parts of 1-hydroxycyclohexyl phenyl ketone. did. It exhibited the following properties: Refractive index (25 ° C.) 1.3920 Viscosity (25 ° C.) 1030 cps Table 1 shows the properties of the cured product obtained in the same manner as in Example 6.

[0068]

[Table 1] Resin composition abcd Hardness (Shore D) 73 58 70 47 Young's modulus (kg / mm ² ) [25 ° C] 69 39 64 29 Breaking strength (kg / m ² ) [25 ° C] 4.4 3.1 2.9 1.8 Elongation at break (%) [25 ° C] 9.7 19.9 11.8 17.9 Water absorption (%) 0.2 0.2 0.2 0.3

The hardness (Shore D) was measured according to the method of JIS Z 2246 by stacking ten cured products having a thickness of about 200 μm in consideration of the influence of the hardness value of the sample holder. Measurements of Young's modulus, breaking strength and breaking elongation
Performed according to the method of S K 7113. The water absorption was measured according to the method of JIS K 7209. As is clear from Examples 6 to 9 and Table 1, the resin composition of the present invention has a high curing rate, and the cured product has a low refractive index, a low water absorption rate, a high hardness, a Young's modulus, a high breaking rate, and an acceptable rate. A resin film suitable for a cladding layer of a flexible optical fiber for optical transmission was obtained.

[0070]

The resin composition and the coating agent for optical fiber using the novel urethane (meth) acrylate of the present invention have a high curing speed, and the obtained resin film has flexibility and a low refractive index. Excellent adhesion to the core,
Suitable for cladding layer of optical fiber for optical transmission.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ identification code FI G02B 6/00 386 G02B 6/00 386 6/44 301 6/44 301A (56) References JP-A-4-321660 (JP, A) JP-A-59-182256 (JP, A) JP-A-2-135211 (JP, A) JP-A-4-93317 (JP, A) JP-A-1-242613 (JP, A) JP-A-1 JP-A-308420 (JP, A) JP-A-2-255711 (JP, A) JP-A-1-308414 (JP, A) JP-A-62-296508 (JP, A) JP-A-61-36374 (JP, A) JP-A-62-226841 (JP, A) JP-A-3-106915 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 18/00-18/87 C03C 25 / 00-25/06 C08F 290/00-290/14 C08F 299/00-299/08 C09D 1/00-201/10 G02B 6/00-6/54

Claims (5)

(57) [Claims] 1. A polyol (A), an organic polyisocyanate (B) and a compound represented by the general formula (1): ## STR1 ## And / or general formula (2) (Wherein, R ₁ is _{Cn 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,
1 or 2, and b is an integer of 1 to 5, and c is 0 or 1.) A urethane (meth) acrylate obtained by reacting with a fluorine-containing (meth) acrylate (C) represented by the following formula: 2. A resin composition comprising the urethane (meth) acrylate according to claim 1. 3. A coating agent for an optical fiber, comprising the urethane (meth) acrylate according to claim 1. 4. A cured product of the resin composition according to claim 2. 5. A cured product of the coating agent for an optical fiber according to claim 3.