JP2000044650A - New fluorine-containing urethane (meth)acrylate compound, resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound capable of forming an optical fiber clad having a low refractive index, excellent adhesion to an optical fiber core and an excellent mechanical strength at a large curing rate by reacting a specific fluorine-containing (meth)acrylate with a specified isocyanate compound. SOLUTION: This new fluorine-containing urethane (meth)acrylate compound is obtained by reacting (A) a compound of formula I [R1 is a group of the formula: CnF2n-1-(-CH2-)a [(n) is 1-10; (a) is 0-2], a group of the formula: CnF2n-1-(- CH2-)a-O, a group of the formula: CF3CF(CF3)Cn-3F(n-3)-(-CH2-)a, a group of the formula: CF3CF(CF3)Cn-3F2(n-3)-(-CH2-)a-O or a group of the formula: H-(-CF2 CF2-)b-(-CH2-)c-O [(b) is 1-5; (c) is 0 or 1]; R2 is H or CH3] or a compound of formula II with (B) 2-(meth)acryloyloxyethyl isocyanate. The component A can be obtained, for example, by reacting a compound of formula III with (meth)acrylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fluorine-containing urethane (meth) acrylate, a resin composition using the same, an optical fiber coating agent for light transmission, and a cured product thereof.

[0002]

2. Description of the Related Art Optical fibers are classified into inorganic glass such as quartz and synthetic resin such as poly (methyl methacrylate). Both material systems are composed of a high-refractive-index core having excellent transparency and a low-refractive-index sheath (cladding). As a clad material, a silicon-based compound having a lower refractive index than the conventional one (JP-A-58-30703)
However, this clad material has a drawback of insufficient mechanical strength. In contrast, in recent years,
As general properties, high heat resistance, chemical resistance, weather resistance,
It is noted that it has water repellency, oil repellency, surface lubricity, etc., and particularly has a low refractive index, and the use of fluorine compounds as optical fiber cladding materials has been activated. 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 A method using a fluorine-containing polymer such as poly (tetrafluoroethylene), poly (vinylidene fluoride / tetrafluoroethylene), and poly (vinylidene fluoride / hexafluoropropylene) is known (for example, Japanese Patent Application Laid-Open No. -842
03, JP-A-59-84204, JP-A-59-9811
6, JP-A-59-147011, JP-A-59-2040
02). Further, when an ultraviolet curable resin composition is used (for example, see JP-A-62-250047, JP-A-3-16
6206, JP-A-5-32749), the resin composition is excellent in mechanical strength because of a crosslinked structure by ultraviolet curing.
It also has the advantage of improving productivity.

[0003]

In a method of forming a clad material from a fluoropolymer, a method of coating a non-cured melt or solution of a fluoropolymer which is uncured at a high temperature, so that the thickness is not uniform. Easy to be. In addition, the adhesion between the core portion and the clad portion is not sufficient, and delamination is likely to occur due to various external factors such as bending and temperature change, and thus there is a problem in durability and the like. Also, in the production method of applying a melt or solution of a fluoropolymer, it takes a long time to cure the clad portion, and in the solution application method,
In particular, the need to completely remove the solvent outside the system, productivity,
There were drawbacks in safety, economy, etc. When a large amount of a monofunctional monomer is contained as a component constituting the resin composition, the mechanical strength may be somewhat insufficient depending on the application.

[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.
We have succeeded in developing a resin composition suitable for a cladding material of an optical transmission fiber having a high curing rate, a low refractive index, excellent adhesion to a core, and further improved mechanical strength. That is, the present invention provides:

[0005]

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And / or equation (2)

[0007]

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(Where R ₁ is C _n F _{2n + 1} -(-CH
_{2 -) a -, C n} F 2n + 1 - (- CH 2 -) a -O -, (CF
_{3) 2 CFC n-3 F} 2 (n-3) - (- CH 2 -) a -, (C
_{F 3) 2 CFC n -3 F} 2 (n-3) - (- CH 2 -) a -O-, or _{H - (- CF 2 CF 2} -) b - (- CH 2 -) c -O-
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, and c is 0 or 1. A urethane (meth) acrylate compound (B) obtained by reacting the contained (meth) acrylate (A) with 2- (meth) acryloyloxyethyl isocyanate.

(2) A resin composition comprising the urethane (meth) acrylate compound (B) described in (1). (3) The resin composition according to (2), further comprising a fluorine-containing urethane (meth) acrylate compound (E) other than the urethane (meth) acrylate compound (B) described in (1). (4) The fluorine-containing urethane (meth) acrylate compound (E) is a reaction product of the polyol (C), the organic polyisocyanate (D), and the fluorine-containing (meth) acrylate (A) described in (1). The resin composition of (3). (5) The resin composition according to any one of (2) to (4), which is used for coating an optical fiber. (6) A cured product of the resin composition according to any one of (2) to (5). (7) An article having a cured product of the resin composition according to (5). (8) The article according to (7), which is an optical product. (9) The article according to (8), wherein the optical product is an optical fiber. (10) A coating agent for optical fibers, comprising the urethane (meth) acrylate compound (B) according to (1). It is about.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The urethane (meth) acrylate compound (B) of the present invention comprises a fluorine-containing (meth) acrylate (A) represented by the above formula (1) and / or the above formula (2). It can be obtained by reacting with 2- (meth) acryloyloxyethyl isocyanate.

The fluorine-containing (meth) acrylate represented by the formula (1) includes, for example, 1- (meth)
Acryloyloxy-3-perfluoro-n-butyl-
2-propanol, 1- (meth) acryloyloxy-
3-perfluoro-n-hexyl-2-propanol,
1- (meth) acryloyloxy-3-perfluoro-
n-octyl-2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-decyl-2-propanol, 1- (meth) acryloyloxy-3-
(2-perfluoro-n-butyl) ethoxy-2-propanol, 1- (meth) acryloyloxy-3- (2
-Perfluoro-n-hexyl) ethoxy-2-propanol, 1- (meth) acryloyloxy-3- (2-
Perfluoro-n-octyl) ethoxy-2-propanol, 1- (meth) acryloyloxy-3- (2-perfluoro-n-decyl) ethoxy-2-propanol, 1- (meth) acryloyloxy-3- ( Perfluoro-3-methylbutyl) -2-propanol, 1-
(Meth) acryloyloxy-3- (perfluoro-5
-Methylhexyl) -2-propanol, 1- (meth)
Acryloyloxy-3- (perfluoro-7-methyloctyl) -2-propanol, 1- (meth) acryloyloxy-3- (perfluoro-9-methyldecyl)
-2-propanol, 1- (meth) acryloyloxy-3- (2,2,3,3-tetrafluoropropoxy)
-2-propanol, 1- (meth) acryloyloxy-3- (1H, 1H, 5H-octafluoropentyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (1H, 1H, 7H-dodeca Fluoroheptyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (1H, 1H, 9H-hexadecafluorononyloxy) -2-propanol and the like can be mentioned.

The fluorine-containing (meth) acrylate represented by the formula (2) includes, for example, 2- (meth) acryloyloxy-3-perfluoro-n-butyl-1-propanol, 2- ( (Meth) acryloyloxy-3-perfluoro-n-hexyl-1-propanol, 2- (meth) acryloyloxy-3-perfluoro-n-octyl-1-propanol, 2- (meth) acryloyloxy-3-per Fluoro-n-decyl-1
-Propanol, 2- (meth) acryloyloxy-3
-(2-perfluoro-n-butyl) ethoxy-1-propanol, 2- (meth) acryloyloxy-3-
(2-perfluoro-n-hexyl) ethoxy-1-propanol, 2- (meth) acryloyloxy-3-
(2-perfluoro-n-octyl) ethoxy-1-propanol, 2- (meth) acryloyloxy-3-
(2-perfluoro-n-decyl) ethoxy-1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-3-methylbutyl) -1-propanol,
2- (meth) acryloyloxy-3- (perfluoro-5-methylhexyl) -1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-7-methyloctyl) -1-propanol, 2- (Meth) acryloyloxy-3- (perfluoro-9-methyldecyl) -1-propanol, 2- (meth) acryloyloxy-3- (2,2,3,3-tetrafluoropropoxy) -1-propanol, 2 -(Meth) acryloyloxy-3- (1H, 1H, 5H-octafluoropentyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (1H, 1H, 7H-dodecafluoroheptyloxy) -1 -Propanol, 2- (meth) acryloyloxy-3- (1H, 1H, 9H-hexadecafluorononyl Carboxymethyl) -1-propanol, and the like.

The fluorine-containing (meth) acrylate (A) represented by the formula (1) and / or the formula (2) comprises a fluorine-containing monoepoxy compound represented by the formula (3) and (meth) acrylic acid Can be obtained by reacting

[0014]

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(However, R₁Is C_nF_{2n + 1}-(-CH
_Two−)_a-, C_nF_{2n + 1}-(-CH_Two−)_aO-, (CF_Three)
_TwoCFC_n-3F_{2 (n-3)}-(-CH_Two−)_a−, (CF_Three)_TwoC
FC_n-3F _{2 (n-3)}-(-CH_Two−)_a-O- or H-
(-CF_TwoCF_Two−)_b-(-CH_Two−)_c-O-,
n is an integer of 1 to 10, a is 0, 1 or 2, b is 1 to 5
And c is 0 or 1.)

Examples of the fluorine-containing monoepoxy compound represented by the formula (3) include 3-perfluoro-n-butyl-1,2-epoxypropane and 3-perfluoro-n
-Hexyl-1,2-epoxypropane, 3-perfluoro-n-octyl-1,2-epoxypropane, 3-
Perfluoro-n-decyl-1,2-epoxypropane, 3- (2-perfluoro-n-butyl) ethoxy-
1,2-epoxypropane, 3- (2-perfluoro-
n-hexyl) ethoxy-1,2-epoxypropane,
3- (2-perfluoro-n-octyl) ethoxy-
1,2-epoxypropane, 3- (2-perfluoro-
n-decyl) ethoxy-1,2-epoxypropane, 3
-(Perfluoro-3-methylbutyl) -1,2-epoxypropane, 3- (perfluoro-5-methylhexyl) -1,2-epoxypropane, 3- (perfluoro-7-methyloctyl) -1,1, 2-epoxypropane,
3- (perfluoro-9-methyldecyl) -1,2-epoxypropane, 3- (2,2,3,3-tetrafluoropropoxy) -1,2-epoxypropane, 3- (1
H, 1H, 5H-octafluoropentyloxy)-
1,2-epoxypropane, 3- (1H, 1H, 7H-
Dodecafluoroheptyloxy) -1,2-epoxypropane, 3- (1H, 1H, 9H-hexadecafluorononyloxy) -1,2-epoxypropane, and the like.

In order to synthesize the fluorine-containing (meth) acrylate (A) represented by the formula (1) and / or the formula (2), the fluorine-containing monoepoxy compound represented by the formula (3) and the acrylic In the reaction with the acid or methacrylic acid, the ratio of the charge of acrylic acid or methacrylic acid to 1 mol of the fluorine-containing monoepoxy compound is 0.90.
~ 3.00 mol, more preferably 1.00-3.0 mol.
1.50 mol. The reaction temperature at which acrylic acid or methacrylic acid is added to the fluorine-containing monoepoxy compound represented by the formula (3) is preferably from 50 to 150 ° C, more preferably from 70 to 100 ° C.

In order to further accelerate the reaction, a catalyst can be used. Examples of the catalyst that can be used at this time include amines such as triethylamine and benzyldimethylamine, triethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium. Quaternary ammonium salts such as chloride, trimethylphenylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetramethylammonium iodide, tetra-n-butylammonium iodide, triphenylphosphine, Bird
n-butylphosphine, tri-m-toluylphosphine, tricyclohexylphosphine, diphenylphosphinas chloride, 1,1-bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,4-bis (Diphenylphosphino) butane,
Organic phosphine compounds such as 1,5-bis (diphenylphosphino) pentane can be exemplified. The amount of the catalyst added is 0.001 to 5.0 based on the whole reaction mixture.
wt% is preferable, and more preferably 0.01 to 3.0 w
t%. The reaction time is preferably from 3 to 60 hours, more preferably from 8 to 24 hours.

The product obtained by this reaction is usually
It is a mixture of the (meth) acrylic acid esters represented by the 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. Sodium carbonate, potassium carbonate,
It is well washed with an aqueous alkali solution such as sodium hydrogen carbonate and potassium hydrogen carbonate. Thereafter, the residue is washed with water or a saline solution to remove the remaining alkali, and the solvent is sufficiently distilled off to obtain a fluorine-containing (meth) acrylate ester with higher purity. In some cases, it may be used after being purified or fractionated by distillation under reduced pressure.

The urethane (meth) acrylate compound (B) of the present invention is a fluorine-containing (meth) acrylate represented by the above formula (1) and / or the above formula (2) synthesized as described above. It can be obtained by reacting (A) with 2- (meth) acryloyloxyethyl isocyanate. In the method for synthesizing the urethane (meth) acrylate compound (B) at this time, the amount of 2- (meth) acryloyloxyethyl isocyanate charged is determined by the fluorine represented by the formula (1) and / or the formula (2). It is preferable to charge so as to be 0.80 to 1.20 mol with respect to 1 mol of the contained (meth) acrylate (A), and more preferably 0.98.
It is good to charge so that it may be -1.00 mol. In this reaction, the terminal hydroxyl group of the fluorine-containing (meth) acrylate (A) represented by the formula (1) and / or the formula (2) and the terminal isocyanate group of 2- (meth) acryloyloxyethyl isocyanate In order to accelerate the reaction, tertiary amines such as triethylamine and benzyldimethylamine, and dilaurates such as dibutyltin dilaurate and dioctyltin dilaurate can be used as a catalyst. The catalyst was added in an amount of 0.001 to 5.0 wt% based on the entire reaction mixture.
Is more preferable, and more preferably 0.01 to 1.1 wt%. The reaction time is preferably 1 to 10 hours. The reaction temperature is preferably from 30 to 100 ° C, more preferably from 40 to 100 ° C.
80 ° C.

In the above method for synthesizing the urethane (meth) acrylate compound (B), any of the reactions can be carried out without a solvent or a solvent such as acetone, methyl ethyl ketone, toluene, or xylene which is inert to an isocyanate group can be used as a reaction solvent. .

The resin composition of the present invention may further contain a fluorine-containing urethane (meth) acrylate compound (E) other than the urethane (meth) acrylate compound (B). The fluorine-containing urethane (meth) acrylate compound (E) sufficiently reacts the polyol (C) with the organic polyisocyanate (D), and then reacts with the fluorine-containing urethane (meth) acrylate represented by the formula (1) and / or the formula (2). It can be obtained by reacting a (meth) acrylate (A). Alternatively, the organic polyisocyanate (D) is first reacted with the fluorine-containing (meth) acrylate (A) represented by the formula (1) and / or the formula (2), and then the polyol (C) is reacted. Can also be obtained.

Examples of the polyol (C) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,4-butanediol and 1,5-pentane. Diol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8
-Low molecular weight diols such as octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, succinic acid, adipic acid , Azelaic acid, sebacic acid, phthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, dibasic acids such as 1,4-cyclohexanedicarboxylic acid and ethylene glycol, propylene glycol, diethylene glycol , Triethylene glycol, 1,4
Polyester polyol, poly-ε-caprolactone modified polyol, polymethyl valerolactone modified polyol, polycarbonate obtained by reaction with diols such as -butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc. Polyols and the like.

As the polyol (C), a fluorine-containing diol compound can be used. Examples of the fluorine-containing diol compound include 3-perfluoro-n
-Butyl-1,2-dihydroxypropane, 3-perfluoro-n-hexyl-1,2-dihydroxypropane, 3-perfluoro-n-octyl-1,2-dihydroxypropane, 3-perfluoro-n-decyl -1,
2-dihydroxypropane, 3- (2-perfluoro-
n-butyl) ethoxy-1,2-dihydroxypropane, 3- (2-perfluoro-n-hexyl) ethoxy-1,2-dihydroxypropane, 3- (2-perfluoro-n-octyl) ethoxy-1, 2-dihydroxypropane, 3- (2-perfluoro-n-decyl) ethoxy-1,2-dihydroxypropane, 3- (perfluoro-3-methylbutyl) -1,2-dihydroxypropane, 3- (perfluoro- 5-methylhexyl)-
1,2-dihydroxypropane, 3- (perfluoro-
7-methyloctyl) -1,2-dihydroxypropane, 3- (perfluoro-9-methyldecyl) -1,2
-Dihydroxypropane, 3- (2,2,3,3-tetrafluoropropoxy) -1,2-dihydroxypropane, 3- (1H, 1H, 5H-octafluoropentyloxy) -1,2-dihydroxypropane, -(1
H, 1H, 7H-dodecafluoroheptyloxy)-
1,2-dihydroxypropane, 3- (1H, 1H, 9
H-hexadecafluorononyloxy) -1,2-dihydroxypropane, 2,2,3,3-tetrafluoro-
1,4-butanediol, 3,3,4,4-tetrafluoro-1,6-hexanediol, 2,2,3,3
4,4,5,5-octafluoro-1,6-hexanediol, 3,3,4,4,5,5,6,6-octafluoro-1,8-octanediol, 2,2,3 3,
4,4,5,5,6,6,7,7-dodecafluoro-
1,8-octanediol, 2,2,3,3,4,4
5,5,6,6,7,7,8,8-tetradecafluoro-1,9-nonanediol, 2,2,3,3,4,4
5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol, 2,2,3
3,4,4,5,5,6,6,7,7,8,8,9,
9,10,10,11,11-icosafluoro-1,1
2-dodecanediol and the like.

As the organic polyisocyanate (D),
For example, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate,
Xylylene diisocyanate and the like can be mentioned.

The polyol (C) is reacted with the organic polyisocyanate (D), and then the fluorine-containing (meth) acrylate (A) represented by the above formula (1) and / or the above formula (2). In the method for obtaining the urethane (meth) acrylate compound (E) of the present invention, the charged amount of the organic polyisocyanate (D) per one chemical equivalent of the hydroxyl group of the polyol (C) is 1.10 to 2.00. It is preferably a chemical equivalent, more preferably from 1.60 to 2.00. The reaction temperature is preferably from 20 to 120 ° C, more preferably from 50 to 90 ° C. Next, 0.90 to 1.50 chemical equivalent, more preferably 1.00 to 1.05 chemical equivalent to 1 chemical equivalent of isocyanate group of the compound having an isocyanate group at the terminal thus obtained is preferably used. And / or reacting the fluorine-containing (meth) acrylate (A) represented by the formula (2).
This reaction can be carried out by adding a known catalyst to promote the reaction between the isocyanate group and the hydroxyl group. Examples of the catalyst used at this time include tertiary amines such as triethylamine and benzyldimethylamine, and dilaurate compounds such as dibutyltin dilaurate and dioctyltin dilaurate. The addition amount is 0.001 to 5.0 wt% based on the whole reaction mixture.
Is more preferable, and more preferably 0.01 to 1.1 wt%. The reaction time is preferably 1 to 10 hours. The reaction temperature is preferably from 30 to 100 ° C, more preferably from 60 to 90 ° C.
° C.

First, the organic polyisocyanate (D) is reacted with the fluorine-containing (meth) acrylate (A) represented by the formula (1) and / or the formula (2),
Next, in the method for obtaining the urethane (meth) acrylate compound (E) of the present invention by reacting the polyol (C), the formula (1) and / or The charged amount of the fluorine-containing (meth) acrylate (A) represented by the formula (2) is preferably 0.20 to 0.50 chemical equivalent, and more preferably 0.50 chemical equivalent. The reaction temperature is preferably from 20 to 120 ° C, more preferably from 50 to 90 ° C. 0.95 to 1.05 chemical equivalents, more preferably 1.1 to 1 chemical equivalent of residual isocyanate groups of the compound thus obtained.
The polyol (C) having 00 chemical equivalents of hydroxyl groups is reacted. In this reaction, a catalyst such as a tertiary amine such as triethylamine or benzyldimethylamine, or a dilaurate compound such as dibutyltin dilaurate or dioctyltin dilaurate is added to promote the reaction between the isocyanate group and the hydroxyl group. You can also do it. The addition amount is 0.001 to the entire reaction mixture.
~ 5.0 wt% is preferred, and more preferably 0.01 ~
1.1 wt%. The reaction time is preferably 1 to 10 hours. The reaction temperature is preferably from 30 to 100C, more preferably from 40 to 80C.

In each of the above two production methods, the reaction can be carried out without a solvent or with a solvent such as acetone, methyl ethyl ketone or toluene which is inert to isocyanate groups. Further, a fluorine-containing (meth) acrylate ester which can be used by being mixed with the resin composition of the present invention or a coating agent for optical fibers described later can be used as a reaction solvent.

The urethane (meth) acrylate compound (B) of the present invention may be used alone, or the urethane (meth) acrylate compound (B) and the fluorine-containing resin composition of the present invention may be used alone. The urethane (meth) acrylate compound (E) may be mixed and used. Furthermore, the urethane (meth) acrylate compound (B) and the fluorine-containing urethane (meth) acrylate compound (E) do not necessarily need to be single compounds, and may be used by mixing two or more compounds. When the urethane (meth) acrylate compound (B) and the fluorine-containing urethane (meth) acrylate compound (E) are used as a mixture, the mixing ratio thereof is urethane (meth) acrylate compound (B): fluorine-containing urethane in weight ratio. (Meth) acrylate compound (E) is preferably from 50:50 to 95: 5, more preferably from 70:30 to 90:10.

The resin composition of the present invention or the coating agent for an optical fiber includes the urethane (meth) acrylate compound (B) of the present invention and a fluorine-containing urethane (meth)
Fluorine-containing (meth) acrylates other than the acrylate compound (E) can be mixed and used. The fluorine-containing (meth) acrylic acid ester is used in the resin composition or the coating agent for optical fiber of the present invention.
The urethane (meth) acrylate compound (B) of the present invention,
Alternatively, 10 to 900 parts by weight based on 100 parts by weight of the entire mixture of the urethane (meth) acrylate compound (B) and the fluorine-containing urethane (meth) acrylate compound (E).
It is preferred to use parts by weight. Such fluorine-containing (meth) acrylates include, for example, 2,2,
2-trifluoroethyl (meth) acrylate, 2,
2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) Ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) Acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 2- (perfluoro-9-methyldecyl) ethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate 1,1H, 1H, 5H-octafluoropentyl (meth) acryle DOO, 1H, 1H, 7H- dodecafluoroheptyl (meth) acrylate, IH, 1
H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,2-trifluoro-1-trifluoromethylethyl (meth) acrylate, 2,2,3,3
4,4-hexafluorobutyl (meth) acrylate,
6- (perfluoroethyl) hexyl (meth) acrylate, 6- (perfluorobutyl) hexyl (meth) acrylate, 2-perfluoroethoxy-2,2,3,
3-tetrafluoropropyl (meth) acrylate,
1,2-bis [(meth) acryloyloxy] -3-
(Perfluoro-n-butyl) propane, 1,2-bis [(meth) acryloyloxy] -3- (perfluoro-n-hexyl) propane, 1,2-bis [(meth) acryloyloxy] -3- (Perfluoro-n-octyl) propane, 1,2-bis [(meth) acryloyloxy] -3- (perfluoro-n-decyl) propane,
1,2-bis [(meth) acryloyloxy] -3-
[(2-perfluoro-n-butyl) ethoxy] propane, 1,2-bis [(meth) acryloyloxy] -3
-[(2-perfluoro-n-hexyl) ethoxy] propane, 1,2-bis [(meth) acryloyloxy]
-3-[(2-perfluoro-n-octyl) ethoxy] propane, 1,2-bis [(meth) acryloyloxy] -3-[(2-perfluoro-n-decyl) ethoxy] propane, 2-bis [(meth) acryloyloxy] -3- (perfluoro-3-methylbutyl) propane, 1,2-bis [(meth) acryloyloxy]
-3- (Perfluoro-5-methylhexyl) propane, 1,2-bis [(meth) acryloyloxy] -3
-(Perfluoro-7-methyloctyl) propane,
1,2-bis [(meth) acryloyloxy] -3-
(Perfluoro-9-methyldecyl) propane, 1,2
-Bis [(meth) acryloyloxy] -3- (2,
2,3,3-tetrafluoropropoxy) propane,
1,2-bis [(meth) acryloyloxy] -3-
(1H, 1H, 5H-octafluoropentyloxy)
Propane, 1,2-bis [(meth) acryloyloxy] -3- (1H, 1H, 7H-dodecafluoroheptyloxy) propane, 1,2-bis [(meth) acryloyloxy] -3- (1H, 1H , 9H-hexadecafluorononyloxy) propane, 1,4-di (meth) acryloyloxy-2,2,3,3-tetrafluorobutane, 1,6-di (meth) acryloyloxy-3,
3,4,4-tetrafluorohexane, 1,6-di (meth) acryloyloxy-2,2,3,3,4,4
5,5-octafluorohexane, 1,8-di (meth)
Acryloyloxy-3,3,4,4,5,5,6,6
-Octafluorooctane, 1,8-di (meth) acryloyloxy-2,2,3,3,4,4,5,5,6
6,7,7-dodecafluorooctane, 1,9-di (meth) acryloyloxy-2,2,3,3,4,4
5,5,6,6,7,7,8,8-tetradecafluorononane, 1,10-di (meth) acryloyloxy-
2,2,3,3,4,4,5,5,6,6,7,7,
8,8,9,9-hexadecafluorodecane, 1,12
Di (meth) acryloyloxy-2,2,3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,11,11-icosafluorododecane and the like can be mentioned.

When the resin composition or the coating agent for optical fibers of the present invention is cured by irradiating ultraviolet rays or the like, a photopolymerization initiator is used. As the photopolymerization initiator, any known photopolymerization initiator may be used, but it is required to have good storage stability after blending. Examples of such a photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, benzyldimethylketal, and 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-
Propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, and the like. These photopolymerization initiators may be used alone or in combination of two or more kinds at an arbitrary ratio. If necessary, a photosensitizer such as an amine compound or a phosphorus compound may be added to further promote the polymerization. The amount of initiator added is
Usually, it is preferably 0.1 to 10.0 w%, more preferably 0.5 to 3.0 w%, based on the entire resin composition or the coating material for optical fibers of the present invention.

The resin composition or the coating material for optical fiber 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 resin composition or the coating material for optical fibers of the present invention can be obtained by uniformly mixing the above components. Also,
The cured product of the resin composition or the coating material for an optical fiber of the present invention can be obtained by irradiating active energy rays such as ultraviolet rays.

As a method of applying the resin composition according to the present invention to a substrate, for example, a method of directly applying with a brush coating, a bar coater, an applicator, a roll coater or a roller brush, an air spray or an airless spray coater, etc. Spray coating method, flow coating method (flow coating) using a shower coater or a curtain flow coater, dipping method, casting method, and spinner coating method. It is desirable that the above-mentioned coating method be appropriately used depending on the material, shape, application, and the like of the base material.

As a method for applying the resin composition according to the present invention to a substrate (for example, a core wire of an optical transmission fiber) as a coating material for an optical fiber, various methods known in the art, for example, the resin composition according to the present invention The optical fiber core wire is continuously immersed in a storage tank containing the resin, pulled up, and irradiated with active energy rays such as ultraviolet rays to form a partially cured clad, or optical transmission to a die capable of continuously supplying the resin composition of the present invention. A method in which the coating is continuously applied through a fiber core wire, and an active energy ray such as an ultraviolet ray is irradiated to cure and form the clad portion. When forming the cladding of the optical transmission fiber, the thickness of the coating of the coating material of the present invention is not particularly limited.
About 0 microns is preferable.

The core of the optical transmission fiber in the present invention includes quartz and plastics such as polymethyl methacrylate, deuterated polymethyl methacrylate, polyethyl methacrylate, polystyrene and polycarbonate.

As the light source used for curing by irradiating active energy rays such as ultraviolet rays, for example, a xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a high pressure mercury lamp for copying, a medium or high pressure mercury lamp, A high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam using a scanning or curtain type electron beam accelerating path can be used. In order to sufficiently perform curing, it is desirable to irradiate active energy rays such as ultraviolet rays in an inert gas atmosphere such as nitrogen gas.

The resin composition of the present invention can be used not only as a clad material of an optical transmission fiber, but also as a glass or plastic coating agent or an LED encapsulant utilizing its low refractive index. The article of the present invention has a cured product of the above resin composition. Examples of the article include optical products such as optical fibers.

[0038]

The present invention will be described below in more detail with reference to examples. Parts in Examples are parts by weight.

Formula (1) and / or Formula (2)
Synthesis Example of Fluorine-Containing (Meth) acrylate (A) Represented by Example 1 3- (2-perfluoro-n-hexyl) ethoxy-
1095.5 parts of 1,2-epoxypropane, 235.4 parts of acrylic acid, 5.5 parts of tetramethylammonium chloride, and 0.5 part of hydroquinone monomethyl ether were charged and stirred at 90 to 95 ° C. for 18 hours to be reacted. . Dissolve the obtained reaction solution in 2000 mL of toluene,
After washing twice with a 15% aqueous sodium carbonate solution and three times with a 20% aqueous sodium chloride solution, toluene was distilled off under reduced pressure to obtain 1264.3 parts of a colorless and transparent liquid. The refractive index of the obtained reaction product at 25 ° C. was 1.3714,
Was 180 cps. Further, the obtained reaction product is a mixture of the following structural formulas (4) and (5).

[0040]

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[0041]

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Example 2 1007.2 parts of 3-perfluoro-n-octyl-1,2-epoxypropane, 191.8 parts of acrylic acid, 5.1 parts of tetramethylammonium chloride and 0.5 part of hydroquinone monomethyl ether were used. Preparation, 90-95
The mixture was stirred at 21 ° C. for 21 hours to be reacted. The obtained reaction solution was dissolved in 2000 mL of toluene, washed twice with a 15% aqueous sodium carbonate solution and three times with a 20% aqueous sodium chloride solution, and then toluene was distilled off under reduced pressure. Two parts were obtained. The melting point of the obtained reaction product was 40 ° C., and the refractive index at 25 ° C. was 1.3524. The obtained reaction product is a mixture of the following structural formulas (6) and (7).

[0043]

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[0044]

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Synthesis Example of Urethane (meth) acrylate Compound (B) Example 3 500.3 parts of a fluorine-containing acrylate represented by the formulas (4) and (5), di-n-butyltin dilaurate: 3 parts were charged, and 153.7 parts of 2-methacryloyloxyethyl isocyanate was slowly charged at 50 ° C.
The reaction was carried out at ４60 ° C. for 4 hours.
Got a part. The refractive index of the obtained reaction product at 25 ° C. was 1.4048, and the viscosity at 25 ° C. was 830 cp.
s. The obtained reaction product is a mixture of the following structural formulas (8) and (9).

[0046]

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[0047]

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Example 4 Fluorine-containing acrylic acid ester 50 represented by the formulas (6) and (7) which had been heated and melted in advance
0.3 part, and 0.3 part of di-n-butyltin dilaurate were charged, and 141.6 parts of 2-methacryloyloxyethyl isocyanate was slowly charged.
The reaction was carried out for an hour to obtain 654.3 parts of a colorless transparent liquid. The refractive index of the obtained reaction product at 25 ° C. was 1.3922, and the viscosity at 25 ° C. was 2,830 cps.
Further, the obtained reaction product is a mixture of the following structural formulas (10) and (11).

[0049]

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[0050]

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Synthesis Example of Urethane (meth) acrylate Compound (E) Example 5 Trimethylhexamethylene diisocyanate 284.7
And 80.0 parts of 1,6-hexanediol, and reacted at 70 to 80 ° C. for 5 hours while heating and cooling. Next, the fluorinated acrylic ester mixture 666. represented by the formulas (4) and (5) obtained in Example 1 was used.
After charging 4 parts and stirring at 40 ° C. for 30 minutes to uniformly dissolve, 0.5 part of di-n-butyltin dilaurate was added, and the mixture was reacted at 40 to 50 ° C. for 1 hour while heating and cooling. The mixture was further heated and reacted at 70 to 80 ° C. for 3 hours to obtain a colorless, transparent and highly viscous product. Its refractive index at 25 ° C was 1.4295, and its viscosity at 25 ° C was 110,000 cps.

Example 6 222.3 parts of isophorone diisocyanate and 45.1 parts of 1,4-butanediol were charged and reacted at 70 to 80 ° C. for 3 hours while heating and cooling. Next, 492.6 parts of the fluorine-containing acrylate mixture represented by the formulas (4) and (5) obtained in Example 1 were charged,
After stirring at 40 ° C. for 30 minutes to uniformly dissolve, 0.4 parts of di-n-butyltin dilaurate is added, and the mixture is reacted at 40 to 50 ° C. for 1 hour while heating and cooling, and further heated to 70 ° C. The reaction was carried out at ８０80 ° C. for 3 hours to obtain a colorless, transparent and highly viscous product. Its refractive index at 25 ° C. was 1.4395, and its viscosity at 25 ° C. was 180,000 cp.
s.

Example of Resin Composition Example 7 1-Hydroxycyclohexyl phenyl ketone 1.0 was added to 100.0 parts of the mixture represented by the formulas (8) and (9) obtained in Example 3, A composition was prepared. Its refractive index at 25 ° C. was 1.4066,
The viscosity at 属 C was 750 cps. This resin composition was applied on a glass plate to a thickness of 200 μm, and then irradiated with ultraviolet rays at a radiation intensity of 500 mJ / cm ² under a nitrogen atmosphere with a high-pressure mercury lamp to obtain a cured product. Table 1 shows the properties of the obtained cured product.

Example 8 A resin composition was prepared by blending 100.0 parts of the mixture represented by the formulas (10) and (11) obtained in Example 4 with 1-hydroxycyclohexylphenyl ketone 1.0. Its refractive index at 25 ° C. is 1.4404,
The viscosity at 25 ° C. was 2760 cps. Also,
Table 1 shows the properties of the cured product obtained in the same manner as in Example 7.

Example 9 80.0 parts of the mixture represented by the formulas (8) and (9) obtained in Example 3 and the urethane acrylate 2 obtained in Example 5
0.0 parts and 1.0 of 1-hydroxycyclohexyl phenyl ketone were blended to prepare a resin composition. Its refractive index at 25 ° C. was 1.4113 and 2
The viscosity at 5 ° C. was 2260 cps. Table 1 shows the properties of the cured product obtained in the same manner as in Example 7.

Example 10 90.0 parts of the mixture represented by the formulas (8) and (9) obtained in Example 3 and the urethane acrylate 1 obtained in Example 6
0.0 parts and 1.0 of 1-hydroxycyclohexyl phenyl ketone were blended to prepare a resin composition. Its refractive index at 25 ° C. was 1.4102 and 2
The viscosity at 5 ° C. was 2730 cps. Table 1 shows the properties of the cured product obtained in the same manner as in Example 7.

[0057]

Table 1 Example 7 8 9 10 Refractive index (25 ° C.) 1.4275 1.4145 1.4303 1.4291 Hardness (Shore D) 65 57 43 47 Young's modulus (kg / mm ² ) 43 36 23 27 Strength at break (kg / m) ² ) 4.1 3.4 1.8 2.3 Elongation at break (%) 10.3 11.4 19.7 17.2 Water absorption (%) 0.3 0.2 0.2 0.2

The hardness (Shore D) was measured for a cured product having a thickness of about 200 μm by taking into account the influence of the hardness of the sample holder.
The sheets were stacked and performed according to the method of JIS Z 2246. Measurements of Young's modulus, strength at break, and elongation at break
Performed according to the method of S K 7209.

[0059]

As is clear from Examples 7 to 10 and Table 1, the resin composition of the present invention can be cured by irradiating active energy rays such as ultraviolet rays, and the cured product has a hardness. , Young's modulus, strength at break, high flexibility and low water absorption. Further, since the cured product of the resin composition of the present invention has a low refractive index, it can be applied to a cladding layer of an optical fiber for optical transmission.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 6/00 386 G02B 6/00 386 6/44 301 6/44 301A F-term (Reference) 2H050 AB42Y AB44Y AB50Y AC03 4G060 AC02 AC07 AC12 CB09 4J027 AG03 AG04 AG12 AG13 AG14 AG23 AG24 AG26 AG34 AJ08 BA01 BA07 CB10 CC05 CD03 CD08 4J034 BA05 CA04 CB03 CB07 CC03 CC08 CD04 CD12 DA01 DB03 DB04 DB07 DF02 DF11 DF12 DF12 DF12 DF16 DF20 DF12 DF16 DF12 DF16 DF12 DF16 DF20 DF12 DF16 DF20 DF20 HA04 HA18 HB12 HC03 HC09 HC12 HC17 HC22 HC46 HC52 HC61 HC64 HC67 HC71 HC73 JA01 JA14 KA01 KB02 KB04 KC17 KD02 KD03 KD08 KD12 KE02 LA23 LA33 RA07 RA13 4J038 FA281 FA282 GA12 PB08

Claims (10)

[Claims] (1) Formula (1)And / or formula (2)(However, R₁Is C_nF_{2n + 1}-(-CH_Two−)_a-, C_nF
_{2n + 1}-(-CH_Two−)_a-O-, CF_ThreeCF (CF_Three) C
_n-3F_{2 (n-3)})-(-CH_Two−)_a-, CF_ThreeCF (C
F_Three) C_n-3F_{2 (n-3)})-(-CH_Two−)_a-O-, or
H-(-CF_TwoCF_Two−) _b-(-CH_Two−)_c-O- (this
Here, n is an integer of 1 to 10, a is 0, 1 or 2, and b is
An integer of 1 to 5, c is 0 or 1);_TwoIs
H or CH_ThreeIt is. ) Containing fluorine represented by
(T) Acrylate (A) and 2- (meth) acrylo
To react with yloxyethyl isocyanate
Urethane (meth) acrylate compound obtained
(B) 2. A resin composition comprising the urethane (meth) acrylate compound (B) according to claim 1. 3. The resin composition according to claim 2, further comprising a fluorine-containing urethane (meth) acrylate compound (E) other than the urethane (meth) acrylate compound (B) according to claim 1. 4. A reaction product of a polyol (C), an organic polyisocyanate (D) and a fluorine-containing (meth) acrylate (A) according to claim 1, wherein the fluorine-containing urethane (meth) acrylate compound (E) is The resin composition according to claim 3, which is 5. The resin composition according to claim 2, which is for coating an optical fiber. 6. A cured product of the resin composition according to any one of claims 2 to 5. 7. An article having a cured product of the resin composition according to claim 6. 8. The article according to claim 7, which is an optical product. 9. The article of claim 8, wherein the optical product is an optical fiber. 10. A coating agent for optical fibers, comprising the urethane (meth) acrylate compound (B) according to claim 1.