JPH04321660A - Urethane (meth)acrylate and resin composition, coating agent for optical fiber and curing agent using the same monomer - Google Patents

Abstract

PURPOSE:To provide the subject new compound having a high curing speed and useful for a resin composition having a low refractive index, excellent in adhesion to a core and suitable for a clad material of a light transmission fiber. CONSTITUTION:A fluorine-containing (meth)acrylic acid ester of formula I [R1 is CnF2n+1-(-CH2-)a-, H-(-CF2CF2-)b-(-CH2-)c-O-, etc.; R2 is H or CH3; n is 1-10; a is 0-2; b is 1-5; c is 0 or 1] and/or formula II is reacted with an organic polyisocyanate (e.g. isophorone diisocyanate) in the presence of a catalyst (e.g. di-n-butyltin dilaurate), as necessary, at 10-100 deg.C for 1-24hr to obtain the subject compound. The reaction is carried out by using the organic polyisocyanate in an amount of 0.5-1.1 equivalent on isocyanate group base based on 1 equivalent hydroxyl group of the fluorine-containing (meth)acrylate.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD The present invention relates to a novel urethane (meth)acrylate, a resin composition using the same, a coating agent for optical fibers for light transmission, and a cured product thereof.

0002

2. Description of the Related 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 sheath (cladding) with a low refractive index. As the cladding material, silicon-based compounds having a low refractive index and polymers of fluorine-containing monomers such as polyfluoroalkyl acrylate have been proposed and put into practice. For example, poly(methyl methacrylate) is used as the core material, and the cladding material is a polymer of fluorinated alkyl group-containing (meth)acrylate, a copolymer of fluorinated alkyl group-containing (meth)acrylate and other monomers, or , a method using fluorine-containing polymers 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).

0003

Problems to be Solved by the Invention In the method of forming a cladding portion using a fluoropolymer, the thickness tends to be non-uniform because a high temperature melt or solution of the fluoropolymer is coated. Furthermore, the adhesion between the core portion and the cladding portion is insufficient, and delamination is likely to occur due to various external factors such as bending, temperature changes, etc., resulting in problems in durability and the like. In addition, in manufacturing methods that apply a melt or solution of a fluoropolymer, it takes a long time to harden the cladding part, and in the solution coating method, it is especially necessary to completely remove the solvent from the system. Therefore, there were drawbacks in terms of productivity, safety, economy, etc.

0004

[Means for Solving the Problems] In order to solve the above problems, the present inventors have developed a new urethane (meth)acrylate as a result of intensive research, and by using this,
The present invention has been completed by successfully providing a resin composition suitable for the cladding material of optical transmission fibers, which has a fast curing speed, a low refractive index, and excellent adhesion to the core. That is,
The present invention has the following features: 1 General formula (1)

[0005]

[Chemical formula 3] and/or general formula (2)

[0006]

[Chemical formula 4] (However, R1 is CnF2n+1-(-CH2-)
a −,Cn F2n+1−(−CH2 −)a −O
-, or H-(-CF2 CF2 -)b -(-C
H2 -)c -O- and R2 is H or CH3
, n is an integer from 1 to 10, a is 0, 1 or 2,
b is an integer from 1 to 5, c is 0 or 1)

Urethane (meth)acrylate is a reaction product of a fluorine-containing (meth)acrylic acid ester (A) represented by the following formula and an organic polyisocyanate (B). 2. A resin composition containing the urethane (meth)acrylate according to item 1. 3. An optical fiber coating agent containing the urethane (meth)acrylate according to item 1. 4. A cured product of the resin composition according to item 2. 5. A cured product of the coating agent for optical fibers according to item 3. It is related to.

The urethane (meth)acrylate of the present invention is a fluorine-containing (meth)acrylic ester (A) represented by the general formula (1) and/or the general formula (2).
and organic polyisocyanate (B). For example, the fluorine-containing (meth)acrylic acid ester (A) represented by the general formula (1) and/or the general formula (2) can be used with a fluorine-containing monoepoxy compound represented by the general formula (3) and (meth) It can be obtained by reacting acrylic acid.

[0009]

[C5] (However, R1 has the same meaning as above.)

0010
] 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-octyl glycidyl ether, 1,1,2,2
-tetrahydroperfluoro-n-octyl glycidyl ether, 2-hydroperfluoroethyl glycidyl ether,

[0011]

[C6]

0012

[C7]

[0013] etc. In the reaction of the fluorine-containing monoepoxy compound with acrylic acid or methacrylic acid, the epoxy group 1 of the fluorine-containing monoepoxy compound
The ratio of acrylic acid or methacrylic acid used relative to the chemical equivalent is preferably 0.9 to 5.0 chemical equivalent, particularly preferably 0.9 to 2.0 chemical equivalent. The reaction temperature is 50
-200 degreeC is preferable, and 70-120 degreeC is especially preferable. The reaction can be accelerated using a catalyst. Such catalysts are known catalysts such as triethylamine, benzyldimethylamine, methyltriethylammonium chloride, tetraethylammonium chloride, triphenylstibine, etc., and the amount used is 0.001 to 5.0 wt% based on the reaction mixture. is preferable, especially 0.0
1 to 3.0 wt% is preferable. The reaction time is preferably 3 to 48 hours.

The product obtained by this reaction is usually a mixture of (meth)acrylic acid esters represented by general formula (1) and general formula (2). The thus obtained (meth)acrylic acid ester is once dissolved in a non-aqueous solvent such as toluene to remove excess (meth)acrylic acid or catalyst, etc., and then dissolved in an alkali such as sodium hydroxide or sodium carbonate. Wash well with an aqueous solution of Thereafter, by sufficiently distilling off the solvent, a (meth)acrylic acid ester with higher purity can be obtained. In some cases, it may be purified by vacuum distillation or fractionated into its respective components for use.

Specific examples of the organic polyisocyanate (B) include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate trimer, and hexamethylene diisocyanate. Examples include trimethylolpropane adducts.

The reaction between the fluorine-containing (meth)acrylic acid ester (A) represented by the general formula (1) and/or the general formula (2) and the organic polyisocyanate (B) Hydroxyl group 1 of acid ester (A)
It is preferable to react 0.5 to 1.1 chemical equivalents of isocyanate groups of the organic polyisocyanate (B), particularly preferably 0.8 to 1.0 chemical equivalents, based on the chemical equivalents.

[0017] The reaction temperature is preferably 10 to 100°C. A catalyst such as di-n-butyltin dilaurate may also be used to accelerate the reaction. The amount of catalyst used is usually 10 to 1000 pp based on the weight of the reaction mixture.
m is preferred. The reaction time is preferably 1 to 24 hours. The resin composition or optical fiber coating agent (hereinafter referred to as composition) of the present invention includes the urethane (
Acrylic esters other than meth)acrylates, e.g.

[0018]

[Chemical formula 8]

[0019]

[Chemical formula 9]

[0020]

[Chemical formula 10]

[0021]

[Chemical formula 11]

[0022]

[Chemical formula 12]

[0023]

[Chemical formula 13]

[0024]

[Chemical formula 14]

[0025]

[Chemical formula 15]

[0026]

[Chemical formula 16]

[0027]

[Chemical formula 17]

[0028]

[Chemical formula 18]

Fluorine-containing acrylic ester represented by general formula (1) (for example,

[0030]

[Chemical formula 19]

[0031]

[C20]

[0032]

[C21]

[0033]

[C22]

[0034]

[C23]

[0035]

[C24]

[0036]

[C25]

[0037]

[C26]

Fluorine-containing acrylic ester represented by general formula (2) (for example,

[0039]

[C27]

[0040]

[C28]

[0041]

[C29]

[0042]

[C30]

[0043]

[Chemical formula 31]

[0044]

[C32]

[0045]

[Chemical formula 33]

[0046]

[C34]

[0047] etc. can be used. These acrylic esters are used in the composition of the present invention.
10 to 90 parts by weight of meth)acrylate
Preferably, 0 parts by weight are used, particularly preferably 5 parts by weight.
0 to 500 parts by weight are used.

When the composition of the present invention is cured by ultraviolet light, a photopolymerization initiator is used. 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 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, benzyl dimethyl ketal, and the like. Preferred examples include 1-hydroxycyclohexylphenyl ketone. These photopolymerization initiators may be used alone or in a mixture of two or more in any proportion. The amount used is usually preferably 0 to 10 wt% of the composition, particularly preferably 0.5 to 5 wt%.

[0049] Furthermore, various additives such as a silane coupling agent, an antioxidant, a polymerization inhibitor, and a light stabilizer may be added to the composition of the present invention, if necessary. The composition of the present invention can be obtained by uniformly mixing each component. Further, a cured product of the composition of the present invention can be obtained by irradiation with ultraviolet rays in a conventional manner.

Methods for applying the optical fiber coating agent of the present invention to the base (optical transmission fiber core wire) include various methods known in the art, such as die coating agent and dipping method. Examples of the optical fiber core wire include quartz-based materials and plastic-based materials such as polystyrene and polycarbonate. When forming the cladding part 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 10 to 30 mm.
Approximately 0 micron is preferable. 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 in order to improve the curing efficiency, irradiation is preferably performed in nitrogen gas.

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 sealant for LEDs, etc. by utilizing its low refractive index.

[0052]

[Examples] The present invention will be specifically explained below using examples. Note that parts in the examples are parts by weight. Synthesis Examples of Urethane (meth)acrylate Example 1 376.0 parts of 3-(perfluoro-n-hexyl)-propenoxide, 86.5 parts of acrylic acid, 2.3 parts of tetramethylammonium chloride, 0.0 parts of hydroquinone monomethyl ether. Prepare 23 parts and heat at 90-95℃ for 15 minutes.
Allowed time to react. The obtained reaction solution was mixed with 1500ml of toluene.
3 times with 15% sodium carbonate aqueous solution for 20
% saline solution three times, toluene was distilled off under reduced pressure to obtain 425.0 parts of a slightly yellow liquid. This is a mixture of two acrylic esters with the following structure.

[0053]

[C35]

[0054]

[C36]

224.0 parts of the acrylic ester mixture thus obtained, 37 parts of hexamethylene diisocyanate
．． 8 parts of hydroquinone monomethyl ether, 0.13 parts of di-n-butyltin dilaurate, and the reaction was carried out while maintaining the temperature at 35 to 40°C. The reaction was continued until completion as indicated by less than 0.1% free isocyanate groups, yielding a pale yellow liquid. This product has a viscosity (30℃) of 104P and a refractive index (25℃).
It was 1.3920. The structural formula of the product can be expressed as below.

[0056]

[C37]

Example 2 224.0 parts of the acrylic ester mixture obtained in Example 1, 54.5 parts of isophorone diisocyanate, 0.13 parts of hydroquinone monomethyl ether, and 0.13 parts of di-n-butyltin dilaurate were added. Preparation, temperature 35
The reaction was carried out while maintaining the temperature at ~40°C. The reaction was continued until completion as indicated by less than 0.1% free isocyanate groups, yielding a pale yellow liquid. This one has a viscosity (
50°C) 465P, and the refractive index (25°C) was 1.4041. The structural formula of the product can be expressed as below.

[0058]

[C38]

Example 3 457.6 parts of a mixture of two acrylic acid esters having the following structures were prepared in the same manner as in Example 1 using 420.0 parts of 1,1,2,2-tetrahydroperfluoro-n-octylglycidyl ether. I got it.

[0060]

[C39]

[0061]

[C40]

This acrylic acid ester mixture 246.0
1 part, 37.8 parts of hexamethylene diisocyanate, 0.13 parts of hydroquinone monomethyl ether, and 0.13 parts of di-n-butyltin dilaurate, and the temperature was raised to 35 parts.
The reaction was carried out while maintaining the temperature at ~40°C. The reaction was continued until completion as indicated by less than 0.1% free isocyanate groups, yielding a pale yellow liquid. This one has a viscosity (
The refractive index (25°C) was 1.3990. The structural formula of the product can be expressed as below.

[0063]

[C41]

Example 4 3-(Perfluoro-n-butyl)-propenoxide 2
Using 76.0 parts, 273.6 parts of a mixture of two acrylic esters having the following structure were obtained in the same manner as in Example 1.

[0065]

[C42]

[0066]

[C43]

This acrylic acid ester mixture 138.0
part, trimethylhexamethylene diisocyanate 47.
3 parts, 0.13 parts of hydroquinone monomethyl ether,
and 0.13 parts of di-n-butyltin dilaurate were charged, and the reaction was carried out while maintaining the temperature at 35 to 40°C. The reaction was continued until completion as indicated by less than 0.1% free isocyanate groups, yielding a pale yellow liquid. This product has a viscosity (30℃) of 183P and a refractive index (25℃).
It was 1.4105. The structural formula of the product can be expressed as below.

[0068]

[C44]

Example 5 In Example 1, methacrylic acid 103 was used instead of acrylic acid.
．． In the same manner except that 2 parts were used, 426.0 parts of a mixture of two methacrylic acid esters having the following structures were obtained.

[0070]

[C45]

[0071]

[C46]

This methacrylic acid ester mixture 231.
0 parts, 37.8 parts of hexamethylene diisocyanate, 0.13 parts of hydroquinone monomethyl ether, and 0.13 parts of di-n-butyltin dilaurate were charged, and the reaction was carried out while maintaining the temperature at 35 to 40°C. 0.1%
The reaction was continued until completion as indicated by the free isocyanate groups below. The reaction product was allowed to stand at room temperature overnight and crystallized. When this crystal was left in a dryer at 70° C. for 1 hour, it completely melted. The refractive index of this material (25
°C) was 1.3932. The structural formula of this is
It can be shown as below.

[0073]

[C47]

Examples of resin compositions Example 6 40 parts of the urethane acrylate obtained in Example 1, 60 parts of fluorine-containing acrylic acid ester having the following structure, and 3 parts of 1-hydroxycyclohexyl phenyl ketone were mixed,
A resin composition a was prepared. This resin composition a was applied to a thickness of 200 microns on a glass plate, and then irradiated with ultraviolet rays of 500 mJ/cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere to obtain a cured product. Table 1 shows the properties of the obtained cured product.

[0075]

[C48]

Example 7 75 parts of the urethane acrylate obtained in Example 2, 25 parts of fluorine-containing acrylic acid ester having the following structure, and 3 parts of 1-hydroxycyclohexyl phenyl ketone were mixed,
A resin composition b was prepared. Table 1 shows the properties of the cured product obtained in the same manner as in Example 6.

[0077]

[C49]

Example 8 80 parts of the urethane acrylate obtained in Example 3, 20 parts of fluorine-containing acrylic ester having the following structure, and 3 parts of 1-hydroxycyclohexyl phenyl ketone were mixed,
A resin composition c was prepared. Table 1 shows the properties of the cured product obtained in the same manner as in Example 6.

[0079]

[C50]

Example 9 50 parts of urethane acrylate obtained in Example 4, Example 5
20 parts of the urethane methacrylate obtained in Example 1, 30 parts of the acrylic acid ester mixture obtained in Example 1, and 3 parts of 1-hydroxycyclohexylphenyl ketone were mixed to prepare a resin composition d. Table 1 shows the properties of the cured product obtained in the same manner as in Example 6.

[0081]

Hardness (Shore D) is measured according to JIS Z
It was carried out according to the method of No. 2246. Young's modulus was measured with reference to the method of JIS K 7113. The water absorption rate was measured with reference to the method of JIS K 7209.

[0083]

Effects of the Invention The resin composition and optical fiber coating agent using the novel urethane (meth)acrylate of the present invention have a fast curing speed, and the resulting resin film has flexibility and a low curvature. Excellent adhesion to the core,
Suitable for the cladding layer of optical fibers for optical transmission.

Claims (5)

[Claims] Claim 1: General formula (1) [Formula 1] and/or General formula (2) [Formula 2] (However, R1 is Cn F2n+1-(-CH2 -)
a −,Cn F2n+1−(−CH2 −)a −O
-, or H-(-CF2 CF2 -)b -(-C
H2 -)c -O- and R2 is H or CH3
, n is an integer from 1 to 10, a is 0, 1 or 2,
urethane (which is a reaction product of a fluorine-containing (meth)acrylic ester (A) represented by b is an integer of 1 to 5, and c is 0 or 1) and an organic polyisocyanate (B)
Meta) acrylate. 2. A resin composition comprising the urethane (meth)acrylate according to claim 1. 3. An optical fiber coating agent 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 optical fiber coating agent according to claim 3.