JP2002128816A - Low refractive index resin composition containing urethane (meth)acrylate compound having fluorine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition quickly curable by irradiation with an active energy beam such as ultraviolet rays, and giving a cured product having high hardness, Young's modulus and break strength, flexibility, low refractive index and good clarity, and being used mainly for an optical fiber clad for transmittance. SOLUTION: The resin composition is composed of a fluorine-containing urethan (meth)acrylate compound which is obtained from a reaction of a 2-(meth)acryloyloxyethyl isocyanate with a 3 or more C fluorine-containing 1,2-diol compound and a fluorine-containing urethan (meth)acrylate compound which is obtained from reactions of a diisocyanate compound with a 3 or more C 1,2-diol compound and the diisocyanate with a fluorine-containing (meth) acrylate compound with one hydroxy group in its structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing urethane compound (meth) acrylate compound, a low-refractive-index resin composition containing the same, an optical fiber coating agent 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 polymethyl 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 that of the prior art (JP-A-58-30703) has been known, but this clad material has a drawback of insufficient mechanical strength. On the other hand, in recent years, fluorine compounds have high general heat resistance, chemical resistance, weather resistance, water repellency, oil repellency, surface lubricity, etc. Has become active as an optical fiber cladding material. For example, polymethyl 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, or polytetramethyl methacrylate is used as a cladding material. Methods using fluoropolymers such as fluoroethylene, poly (vinylidene fluoride / tetrafluoroethylene), and poly (vinylidene fluoride / hexafluoropropylene) are known (for example, JP-A-59-84203, JP-A-59-84203). Showa 5
9-84204, JP-A-59-98116, JP-A-59-98116
-147011, JP-A-59-204002). Also,
When an ultraviolet curable resin composition is used (for example, JP-A-62-250047, JP-A-3-166206, and JP-A-5-32749), the resin composition has excellent mechanical strength due to a cross-linked structure formed 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 make. In addition, the adhesion between the core portion and the cladding portion is not sufficient, and delamination is likely to occur due to various external factors, such as bending and temperature change. Further, 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 case of the solution application method, in particular, it is necessary to completely remove the solvent outside the system. ,
There were drawbacks in productivity, safety, economy, etc.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have assiduously studied and developed a urethane (meth) acrylate containing a fluorine atom. We have succeeded in developing a resin composition suitable for an optical fiber cladding material, which is fast, has a low refractive index, has excellent adhesion to a core material, and has further improved mechanical strength. That is, the present invention relates to [1] Formula (1)

[0005]

Embedded image

(Where R ₁ is C _n F _{2n + 1-} (CH ₂ )
_{a -, C n F 2n +} 1 - (CH 2) a -O-, CF 3 CF (C
F ₃ ) C _n-1 F _{2 (n-1)} -(CH ₂ ) _a- , CF ₃ CF (C
F ₃ ) C _n-1 F _{2 ( n-1)} -(CH ₂ ) _a -O-, H- (CF ₂
CF ₂ ) _b- (CH ₂ ) _a -or H- (CF ₂ CF ₂ ) _b-
(CH ₂ ) _a —O— (where n is an integer from 1 to 12,
a is an integer from 0 to 2, and b is an integer from 1 to 4. ). )) And a fluorine-containing urethane (meth) acrylate compound (B) obtained by reacting 2- (meth) acryloyloxyethyl isocyanate with a fluorine-containing diol compound (A) and formula (1). Fluorine-containing diol compound (A), diisocyanate compound (C) and formula (2)

[0007]

Embedded image

And / or equation (3)

[0009]

Embedded image

(Where R ₂ is C _m F _{2m + 1-} (CH ₂ )
_{d -, C m F 2m +} 1 - (CH 2) d -O-, CF 3 CF (C
F ₃ ) C _m-1 F _{2 (m-1)} -(CH ₂ ) _d- , CF ₃ CF (C
F ₃ ) C _m-1 F _{2 ( m-1)} -(CH ₂ ) _d -O-, H- (CF _{2
CF 2) e - (CH 2} ) d - or _{H- (CF 2 CF 2) e} -
(CH ₂ ) _d —O— (where m is an integer of 1 to 12,
d is an integer from 0 to 2, and e is an integer from 1 to 4. ) And R ₃ is H or CH ₃ . ) Containing a fluorine-containing urethane (meth) acrylate compound (E) obtained by reacting a fluorine-containing (meth) acrylate compound (D) having one hydroxyl group in the structure represented by Resin composition, [2]
Equation (4)

[0011]

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(Where R ₄ is a hydrogen atom or a methyl group, X is a linear or branched C ₁ -C ₁₂ alkyl group, CH _3- (O (CH ₂ ) _k- ) _l- , CH ₃ H ₂ −
_{(O (CH 2) k)} l -, C j F 2j + 1 - (CH 2) f -, CF
₃ CF (CF ₃ ) C _j-1 F _{2 (j-1)} -(CH ₂ ) _f -or H
_{- (CF 2 CF 2) g} - (CH 2) f - ( wherein, k is 2
An integer of 4, g and l are integers of 1 to 4, j is an integer of 1 to 10, and f is 1 or 2. ). A) a monofunctional (meth) acrylate compound (F) and / or formula (5)

[0013]

Embedded image

(Where R ₅ is a hydrogen atom or a methyl group, and Y is C ₁ -C ₁₂ which may be linear or branched)
An alkyl group of —CH ₂ (CH ₂ OCH ₂ ) _h CH ₂ —,
CH ₂ (CF ₂ OCF ₂ ) _h CH ₂ —, —CH ₂ — (CF ₂ ) _{i
-CH 2 -, - CH 2 CH} 2 - (CF 2) i -CH 2 CH 2 -
(Where h is an integer of 1 to 4 and i is an integer of 2 to 10). The resin composition according to [1], which comprises a bifunctional (meth) acrylate compound (G) represented by the formula (1), and [3] a photopolymerization initiator (H). [1] or [2], [4] The resin composition according to any one of [1] to [3], which is a coating agent for an optical fiber, [5] [1] ] To a cured product of the resin composition according to any one of [4] to [4].

[0015]

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

Specific examples of the fluorine-containing diol compound (A) represented by the above formula (1) include, for example, 3-trifluoromethyl-1,2-propanediol, 3-perfluoroethyl-1,2- Propanediol, 3-perfluoro-n-propyl-1,2-propanediol, 3
-Perfluoro-n-butyl-1,2-propanediol, 3-perfluoro-n-hexyl-1,2-propanediol, 3-perfluoro-n-octyl-1,2
-Propanediol, 3-perfluoro-n-decyl-
1,2-propanediol, 3-perfluoro-n-dodecyl-1,2-propanediol, 4-trifluoromethyl-1,2-butanediol, 4-perfluoroethyl-1,2-butanediol, -Perfluoro-n
-Propyl-1,2-butanediol, 4-perfluoro-n-butyl-1,2-butanediol, 4-perfluoro-n-hexyl-1,2-butanediol, 4-
Perfluoro-n-octyl-1,2-butanediol, 4-perfluoro-n-decyl-1,2-butanediol, 4-perfluoro-n-dodecyl-1,2-butanediol, 5-trifluoro Methyl-1,2-pentanediol, 5-perfluoroethyl-1,2-pentanediol, 5-perfluoro-n-propyl-1,
2-pentanediol, 5-perfluoro-n-butyl-1,2-pentanediol, 5-perfluoro-n-
Hexyl-1,2-pentanediol, 5-perfluoro-n-octyl-1,2-pentanediol, 5-perfluoro-n-decyl-1,2-pentanediol,
5-perfluoro-n-dodecyl-1,2-pentanediol, 3-trifluoromethyloxy-1,2-propanediol, 3-perfluoroethyloxy-1,2
-Propanediol, 3-perfluoro-n-butyloxy-1,2-propanediol, 3-perfluoro-
n-hexyloxy-1,2-propanediol, 3-
Perfluoro-n-octyloxy-1,2-propanediol, 3-perfluoro-n-decyloxy-1,
2-propanediol, 3-perfluoro-n-dodecyloxy-1,2-propanediol, 3-trifluoromethylmethyloxy-1,2-propanediol,
-Perfluoroethylmethyloxy-1,2-propanediol, 3-perfluoro-n-butylmethyloxy-1,2-propanediol, 3-perfluoro-n-
Hexylmethyloxy-1,2-propanediol, 3
-Perfluoro-n-octylmethyloxy-1,2-
Propanediol, 3-perfluoro-n-decylmethyloxy-1,2-propanediol, 3-perfluoro-n-dodecylmethyloxy-1,2-propanediol, 3- (2-trifluoromethyl) ethyloxy-
1,2-propanediol, 3- (2-perfluoroethyl) ethyloxy-1,2-propanediol, 3-
(2-perfluoro-n-butyl) ethyloxy-1,
2-propanediol, 3- (2-perfluoro-n-
Hexyl) ethyloxy-1,2-propanediol,
3- (2-perfluoro-n-octyl) ethyloxy-1,2-propanediol, 3- (2-perfluoro-n-decyl) ethyloxy-1,2-propanediol, 3- (2-perfluoro- n-dodecyl) ethyloxy-1,2-propanediol, 3- (perfluoro-3-methylbutyl) -1,2-propanediol,
-(Perfluoro-5-methylhexyl) -1,2-propanediol, 3- (perfluoro-7-methyloctyl) -1,2-propanediol, 3- (perfluoro-9-methyldecyl) -1,1, 2-propanediol,
4- (perfluoro-3-methylbutyl) -1,2-butanediol, 4- (perfluoro-5-methylhexyl) -1,2-butanediol, 4- (perfluoro-
7-methyloctyl) -1,2-butanediol, 4-
(Perfluoro-9-methyldecyl) -1,2-butanediol, 5- (perfluoro-3-methylbutyl)-
1,2-pentanediol, 5- (perfluoro-5-
Methylhexyl) -1,2-pentanediol, 5-
(Perfluoro-7-methyloctyl) -1,2-pentanediol, 3- (perfluoro-3-methylbutyloxy) -1,2-propanediol, 3- (perfluoro-5-methylhexyloxy)- 1,2-propanediol, 3- (perfluoro-7-methyloctyloxy) -1,2-propanediol, 3- (perfluoro-3-methylbutyl) methyloxy-1,2-propanediol, 3- ( Perfluoro-5-methylhexyl) methyloxy-1,2-propanediol, 3-
(Perfluoro-7-methyloctyl) methyloxy-
1,2-propanediol, 3- (2- (perfluoro-3-methylbutyl) ethyloxy) -1,2-propanediol, 3- (2- (perfluoro-5-methylhexyl) ethyloxy) -1,2 -Propanediol,
3- (2- (perfluoro-7-methyloctyl) ethyloxy) -1,2-propanediol, 3- (1,
1,2,2-tetrafluoroethyl) -1,2-propanediol, 3- (4H-octafluorobutyl)-
1,2-propanediol, 3- (6H-dodecafluorohexyl) -1,2-propanediol, 3- (8H
-Hexadecafluorooctyl) -1,2-propanediol, 4- (1,1,2,2-tetrafluoroethyl) -1,2-butanediol, 4- (4H-octafluorobutyl) -1,2 -Butanediol, 4- (6H
-Dodecafluorohexyl) -1,2-butanediol, 4- (8H-hexadecafluorooctyl) -1,
2-butanediol, 5- (1,1,2,2-tetrafluoroethyl) -1,2-pentanediol, 5- (4
H-octafluorobutyl) -1,2-pentanediol, 5- (6H-dodecafluorohexyl) -1,2-
Pentanediol, 5- (8H-hexadecafluorooctyl) -1,2-pentanediol, 3- (1,1,
2,2-tetrafluoroethyloxy) -1,2-propanediol, 3- (4H-octafluorobutyloxy) -1,2-propanediol, 3- (6H-dodecafluorohexyloxy) -1,2- Propanediol, 3- (8H-hexadecafluorooctyloxy)
-1,2-propanediol, 3- (2,2,3,3-
Tetrafluoropropyloxy) -1,2-propanediol, 3- (1H, 1H, 5H-octafluoropentyloxy) -1,2-propanediol, 3- (1
H, 1H, 7H-dodecafluoroheptyloxy)-
1,2-propanediol, 3- (1H, 1H, 9H-
Hexadecafluorononyloxy) -1,2-propanediol, 3- (3,3,4,4-tetrafluorobutyloxy) -1,2-propanediol, 3- (1H,
1H, 2H, 2H, 6H-octafluorohexyloxy) -1,2-propanediol, 3- (1H, 1H,
2H, 2H, 8H-dodecafluorooctyloxy)-
1,2-propanediol, 3- (1H, 1H, 2H,
2H, 10H-hexadecafluorodecyloxy)-
1,2-propanediol and the like can be mentioned.

The fluorine-containing urethane (meth) acrylate compound (B) of the present invention comprises the above-mentioned fluorine-containing diol compound (A) represented by the formula (1) and 2- (meth) acryloyloxyethyl isocyanate. Can be obtained by reacting In the method of synthesizing the fluorine-containing urethane (meth) acrylate compound (B) at this time, the amount of 2- (meth) acryloyloxyethyl isocyanate charged is the fluorine-containing diol compound (A) represented by the formula (1). It is preferable to charge so as to be 1.60 to 2.40 moles, more preferably 1.96 to 2.00 moles, relative to 1.00 mole. This reaction is carried out according to the above formula (1)
In order to promote the reaction between the terminal hydroxyl group of the fluorine-containing diol compound (A) represented by and the terminal isocyanate group of 2- (meth) acryloyloxyethyl isocyanate, for example, tertiary amines such as triethylamine and benzyldimethylamine; Dilaurate compounds such as dibutyltin dilaurate and dioctyltin dilaurate can be used as catalysts. The amount of the catalyst to be added is determined by the fluorine-containing diol compound (A) represented by the formula (1).
The amount is preferably 0.001 to 5.0 w%, more preferably 0.01 to 1.1 w%, based on the whole charged amount of and 2- (meth) acryloyloxyethyl isocyanate. The reaction time is preferably from 0.5 to 10 hours, more preferably from 2 to 4 hours. The reaction temperature is 30 to 12
0 ° C is preferable, and more preferably 40 to 80 ° C.

In the method for producing the fluorine-containing urethane (meth) acrylate compound (B), when the fluorine-containing diol compound (A) represented by the formula (1) is a liquid, the reaction does not use a solvent. Can be done with However, when the fluorine-containing diol compound (A) represented by the formula (1) is waxy or solid, the reaction can be carried out using a solvent inert to the isocyanate group. Specific examples of the solvent that is inert to the isocyanate group used at this time include, for example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and aromatic hydrocarbon compounds such as toluene, xylene, and ethylbenzene. Can be.

The resin composition of the present invention further contains a fluorine-containing urethane (meth) acrylate compound (E) having a structure other than the fluorine-containing urethane (meth) acrylate compound (B). The fluorine-containing urethane (meth) acrylate compound (E) sufficiently reacts the fluorine-containing diol compound (A) represented by the formula (1) with the diisocyanate compound (C), and then reacts with the formula (2) and / or It can be obtained by reacting a fluorine-containing (meth) acrylate compound (D) having one hydroxyl group in the structure represented by the formula (3).

Specific examples of the diisocyanate compound (C) used for producing the fluorine-containing urethane (meth) acrylate compound (E) include, for example, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), and trimethylhexadiene. Examples thereof include methylene diisocyanate, 4,4-diphenylmethane diisocyanate, and xylylene diisocyanate.

Specific examples of the fluorine-containing (meth) acrylate compound (D) having one hydroxyl group in the structure represented by the formula (2) include, for example, 1- (meth) acryloyloxy-3-tri Fluoromethyl-2-propanol, 1- (meth) acryloyloxy-3-perfluoroethyl-2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-propyl-2-propanol, 1- (meta ) 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- - propanol, 1- (meth) acryloyloxy-3-perfluoro -n- dodecyl -
2-propanol, 1- (meth) acryloyloxy-
4-trifluoromethyl-2-butanol, 1- (meth) acryloyloxy-4-perfluoroethyl-2
-Butanol, 1- (meth) acryloyloxy-4-
Perfluoro-n-propyl-2-butanol, 1-
(Meth) acryloyloxy-4-perfluoro-n-
Butyl-2-butanol, 1- (meth) acryloyloxy-4-perfluoro-n-hexyl-2-butanol, 1- (meth) acryloyloxy-4-perfluoro-n-octyl-2-butanol, 1- (Meth) acryloyloxy-4-perfluoro-n-decyl-2-
Butanol, 1- (meth) acryloyloxy-4-perfluoro-n-dodecyl-2-butanol, 1- (meth) acryloyloxy-5-trifluoromethyl-2
-Pentanol, 1- (meth) acryloyloxy-5
-Perfluoroethyl-2-pentanol, 1- (meth) acryloyloxy-5-perfluoro-n-propyl-2-pentanol, 1- (meth) acryloyloxy-5-perfluoro-n-butyl-2 -Pentanol, 1- (meth) acryloyloxy-5-perfluoro-n-hexyl-2-pentanol, 1- (meth) acryloyloxy-5-perfluoro-n-octyl-
2-pentanol, 1- (meth) acryloyloxy-
5-perfluoro-n-decyl-2-pentanol, 1
-(Meth) acryloyloxy-5-perfluoro-n
-Dodecyl-2-pentanol, 1- (meth) acryloyloxy-3-trifluoromethyloxy-2-propanol, 1- (meth) acryloyloxy-3-perfluoroethyloxy-2-propanol, 1- (meth) ) Acryloyloxy-3-perfluoro-n-butyloxy-2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-hexyloxy-2
-Propanol, 1- (meth) acryloyloxy-3
-Perfluoro-n-octyloxy-2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-decyloxy-2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-dodecyl Oxy-2-propanol, 1- (meth) acryloyloxy-3-trifluoromethylmethyloxy-2
-Propanol, 1- (meth) acryloyloxy-3
-Perfluoroethylmethyloxy-2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-butylmethyloxy-2-propanol, 1-
(Meth) acryloyloxy-3-perfluoro-n-
Hexylmethyloxy-2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-octylmethyloxy-2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-decylmethyloxy- 2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-dodecylmethyloxy-2-propanol, 1- (meth) acryloyloxy-3- (2-trifluoromethyl) ethyloxy-2
-Propanol, 1- (meth) acryloyloxy-3
-(2-perfluoroethyl) ethyloxy-2-propanol, 1- (meth) acryloyloxy-3- (2
-Perfluoro-n-butyl) ethyloxy-2-propanol, 1- (meth) acryloyloxy-3- (2
-Perfluoro-n-hexyl) ethyloxy-2-propanol, 1- (meth) acryloyloxy-3-
(2-perfluoro-n-octyl) ethyloxy-2
-Propanol, 1- (meth) acryloyloxy-3
-(2-perfluoro-n-decyl) ethyloxy-2
-Propanol, 1- (meth) acryloyloxy-3
-(2-perfluoro-n-dodecyl) ethyloxy-
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-4- (perfluoro-3-methylbutyl) -2-butanol, 1- (meth) acryloyloxy-4- (perfluoro-5-methylhexyl) -2-
Butanol, 1- (meth) acryloyloxy-4-
(Perfluoro-7-methyloctyl) -2-butanol, 1- (meth) acryloyloxy-4- (perfluoro-9-methyldecyl) -2-butanol, 1- (meth) acryloyloxy-5- (perfluoro -3-methylbutyl) -2-pentanol, 1- (meth) acryloyloxy-5- (perfluoro-5-methylhexyl) -2-pentanol, 1- (meth) acryloyloxy-5- (perfluoro- 7-methyloctyl) -2
-Pentanol, 1- (meth) acryloyloxy-3
-(Perfluoro-3-methylbutyloxy) -2-propanol, 1- (meth) acryloyloxy-3-
(Perfluoro-5-methylhexyloxy) -2-propanol, 1- (meth) acryloyloxy-3-
(Perfluoro-7-methyloctyloxy) -2-propanol, 1- (meth) acryloyloxy-3-
(Perfluoro-3-methylbutyl) methyloxy-2
-Propanol, 1- (meth) acryloyloxy-3
-(Perfluoro-5-methylhexyl) methyloxy-2-propanol, 1- (meth) acryloyloxy-3- (perfluoro-7-methyloctyl) methyloxy-2-propanol, 1- (meth) acryloyloxy -3- (2- (Perfluoro-3-methylbutyl)
Ethyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (2- (perfluoro-5-methylhexyl) ethyloxy) -2-propanol, 1-
(Meth) acryloyloxy-3- (2- (perfluoro-7-methyloctyl) ethyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (1,
1,2,2-tetrafluoroethyl) -2-propanol, 1- (meth) acryloyloxy-3- (4H-octafluorobutyl) -2-propanol, 1- (meth) acryloyloxy-3- (6H- Dodecafluorohexyl) -2-propanol, 1- (meth) acryloyloxy-3- (8H-hexadecafluorooctyl) -2-propanol, 1- (meth) acryloyloxy-4- (1,1,2,2 -Tetrafluoroethyl)
-2-butanol, 1- (meth) acryloyloxy-
4- (4H-octafluorobutyl) -2-butanol, 1- (meth) acryloyloxy-4- (6H-dodecafluorohexyl) -2-butanol, 1- (meth) acryloyloxy-4- (8H-hexa Decafluorooctyl) -2-butanol, 1- (meth) acryloyloxy-5- (1,1,2,2-tetrafluoroethyl) -2-pentanol, 1- (meth) acryloyloxy-5- (4H -Octafluorobutyl) -2-
Pentanol, 1- (meth) acryloyloxy-5-
(6H-dodecafluorohexyl) -2-pentanol, 1- (meth) acryloyloxy-5- (8H-hexadecafluorooctyl) -2-pentanol, 1-
(Meth) acryloyloxy-3- (1,1,2,2-
Tetrafluoroethyloxy) -2-propanol, 1
-(Meth) acryloyloxy-3- (4H-octafluorobutyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (6H-dodecafluorohexyloxy) -2-propanol, 1- (meth) Acryloyloxy-3- (8H-hexadecafluorooctyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (2,2,3,3-tetrafluoropropyloxy) -2-propanol, 1- (Meta)
Acryloyloxy-3- (1H, 1H, 5H-octafluoropentyloxy) -2-propanol, 1-
(Meth) acryloyloxy-3- (1H, 1H, 7H
-Dodecafluoroheptyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (1H, 1
H, 9H-hexadecafluorononyloxy) -2-propanol, 1- (meth) acryloyloxy-3-
(3,3,4,4-tetrafluorobutyloxy) -2
-Propanol, 1- (meth) acryloyloxy-3
-(1H, 1H, 2H, 2H, 6H-octafluorohexyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (1H, 1H, 2H, 2H, 8H
-Dodecafluorooctyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (1H, 1
H, 2H, 2H, 10H-hexadecafluorodecyloxy) -2-propanol and the like.

Further, specific examples of the fluorine-containing (meth) acrylate compound (A) represented by the above formula (3) include:
For example, 2- (meth) acryloyloxy-3-trifluoromethyl-1-propanol, 2- (meth) acryloyloxy-3-perfluoroethyl-1-propanol, 2- (meth) acryloyloxy-3-perfluoro -N-propyl-1-propanol, 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-perfluoro-n-decyl-1-propanol, 2- (meth) acryloyloxy-3-perfluoro-n-dodecyl-1-propanol, 2-
(Meth) acryloyloxy-4-trifluoromethyl-1-butanol, 2- (meth) acryloyloxy-
4-perfluoroethyl-1-butanol, 2- (meth) acryloyloxy-4-perfluoro-n-propyl-1-butanol, 2- (meth) acryloyloxy-4-perfluoro-n-butyl-1- Butanol,
2- (meth) acryloyloxy-4-perfluoro-
n-hexyl-1-butanol, 2- (meth) acryloyloxy-4-perfluoro-n-octyl-1-butanol, 2- (meth) acryloyloxy-4-perfluoro-n-decyl-1-butanol, 2- (meta)
Acryloyloxy-4-perfluoro-n-dodecyl-1-butanol, 2- (meth) acryloyloxy-
5-trifluoromethyl-1-pentanol, 2- (meth) acryloyloxy-5-perfluoroethyl-1
-Pentanol, 2- (meth) acryloyloxy-5
-Perfluoro-n-propyl-1-pentanol, 2
-(Meth) acryloyloxy-5-perfluoro-n
-Butyl-1-pentanol, 2- (meth) acryloyloxy-5-perfluoro-n-hexyl-1-pentanol, 2- (meth) acryloyloxy-5-perfluoro-n-octyl-1-pen Tertanol, 2- (meth) acryloyloxy-5-perfluoro-n-decyl-1-pentanol, 2- (meth) acryloyloxy-5-perfluoro-n-dodecyl-1-pentanol, 2- (meth) ) Acryloyloxy-3-trifluoromethyloxy-1-propanol, 2- (meth) acryloyloxy-3-perfluoroethyloxy-1-
Propanol, 2- (meth) acryloyloxy-3-
Perfluoro-n-butyloxy-1-propanol,
2- (meth) acryloyloxy-3-perfluoro-
n-hexyloxy-1-propanol, 2- (meth)
Acryloyloxy-3-perfluoro-n-octyloxy-1-propanol, 2- (meth) acryloyloxy-3-perfluoro-n-decyloxy-1-propanol, 2- (meth) acryloyloxy-3-perfluoro -N-dodecyloxy-1-propanol,
2- (meth) acryloyloxy-3-trifluoromethylmethyloxy-1-propanol, 2- (meth) acryloyloxy-3-perfluoroethylmethyloxy-1-propanol, 2- (meth) acryloyloxy-3- Perfluoro-n-butylmethyloxy-1-
Propanol, 2- (meth) acryloyloxy-3-
Perfluoro-n-hexylmethyloxy-1-propanol, 2- (meth) acryloyloxy-3-perfluoro-n-octylmethyloxy-1-propanol, 2- (meth) acryloyloxy-3-perfluoro-n -Decylmethyloxy-1-propanol, 2-
(Meth) acryloyloxy-3-perfluoro-n-
Dodecylmethyloxy-1-propanol, 2- (meth) acryloyloxy-3- (2-trifluoromethyl) ethyloxy-1-propanol, 2- (meth) acryloyloxy-3- (2-perfluoroethyl) ethyloxy- 1-propanol, 2- (meth) acryloyloxy-3- (2-perfluoro-n-butyl) ethyloxy-1-propanol, 2- (meth) acryloyloxy-3- (2-perfluoro-n-hexyl)
Ethyloxy-1-propanol, 2- (meth) acryloyloxy-3- (2-perfluoro-n-octyl) ethyloxy-1-propanol, 2- (meth) acryloyloxy-3- (2-perfluoro-n- Decyl) ethyloxy-1-propanol, 2- (meth) acryloyloxy-3- (2-perfluoro-n-dodecyl) ethyloxy-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-4- (perfluoro-3-methylbutyl) -1-butanol, 2- (meth) acryloyloxy-4- (perfluoro- 5-methylhexyl) -1-butanol, 2- (meth) acryloyloxy-4- (perfluoro-7-methyloctyl) -1-butanol, 2- (meth) acryloyloxy-4- (perfluoro-9- Methyldecyl) -1-butanol, 2- (meth) acryloyloxy-5- (perfluoro-3-methylbutyl) -1-pentanol,
2- (meth) acryloyloxy-5- (perfluoro-5-methylhexyl) -1-pentanol, 2- (meth) acryloyloxy-5- (perfluoro-7-methyloctyl) -1-pentanol, 2- (meth) acryloyloxy-3- (perfluoro-3-methylbutyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-5-methylhexyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-7-methyloctyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-3-methylbutyl) methyloxy-1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-5-methylhexyl)
Methyloxy-1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-7-methyloctyl) methyloxy-1-propanol, 2- (meth) acryloyloxy-3- (2- (perfluoro- 3-methylbutyl) ethyloxy) -1-propanol, 2-
(Meth) acryloyloxy-3- (2- (perfluoro-5-methylhexyl) ethyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (2-
(Perfluoro-7-methyloctyl) ethyloxy)
-1-propanol, 2- (meth) acryloyloxy-3- (1,1,2,2-tetrafluoroethyl) -1
-Propanol, 2- (meth) acryloyloxy-3
-(4H-octafluorobutyl) -1-propanol, 2- (meth) acryloyloxy-3- (6H-dodecafluorohexyl) -1-propanol, 2- (meth) acryloyloxy-3- (8H-hexadeca (Fluorooctyl) -1-propanol, 2- (meth) acryloyloxy-4- (1,1,2,2-tetrafluoroethyl) -1-butanol, 2- (meth) acryloyloxy-4- (4H-octa) Fluorobutyl) -1-
Butanol, 2- (meth) acryloyloxy-4-
(6H-dodecafluorohexyl) -1-butanol,
2- (meth) acryloyloxy-4- (8H-hexadecafluorooctyl) -1-butanol, 2- (meth) acryloyloxy-5- (1,1,2,2-tetrafluoroethyl) -1-pen Tanol, 2- (meta)
Acryloyloxy-5- (4H-octafluorobutyl) -1-pentanol, 2- (meth) acryloyloxy-5- (6H-dodecafluorohexyl) -1-pentanol, 2- (meth) acryloyloxy-5 −
(8H-hexadecafluorooctyl) -1-pentanol, 2- (meth) acryloyloxy-3- (1,
1,2,2-tetrafluoroethyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (4
H-octafluorobutyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (6H-dodecafluorohexyloxy) -1-propanol, 2
-(Meth) acryloyloxy-3- (8H-hexadecafluorooctyloxy) -1-propanol, 2-
(Meth) acryloyloxy-3- (2,2,3,3-
Tetrafluoropropyloxy) -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-hexadecafluorononyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (3,3,4,4-tetrafluorobutyloxy) -1-propanol, 2- ( (Meth) acryloyloxy-3- (1H, 1H, 2H, 2H, 6H-octafluorohexyloxy) -1-propanol, 2-
(Meth) acryloyloxy-3- (1H, 1H, 2
H, 2H, 8H-dodecafluorooctyloxy) -1
-Propanol, 2- (meth) acryloyloxy-3
-(1H, 1H, 2H, 2H, 10H-hexadecafluorodecyloxy) -1-propanol and the like.

Formula (2) and / or Formula (3)
The fluorine-containing (meth) acrylate compound (D) having one hydroxyl group in the structure represented by is obtained by reacting the fluorine-containing monoepoxy compound represented by the formula (6) with (meth) acrylic acid. be able to.

[0024]

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(R ₂ has the same meaning as described above)

Examples of the fluorine-containing monoepoxy compound represented by the formula (6) 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-perfluoro-n-dodecyl-1,2-epoxypropane, 3-trifluoromethyloxy-1,2-
Epoxy propane, 3-perfluoroethyloxy-
1,2-epoxypropane, 3-perfluoro-n-butyloxy-1,2-epoxypropane, 3-perfluoro-n-hexyloxy-1,2-epoxypropane, 3-perfluoro-n-octyloxy- 1,2-
Epoxypropane, 3-perfluoro-n-decyloxy-1,2-epoxypropane, 3-perfluoro-n
-Dodecyloxy-1,2-epoxypropane, 3-trifluoromethylmethyloxy-1,2-epoxypropane, 3-perfluoroethylmethyloxy-1,2-
Epoxypropane, 3-perfluoro-n-butylmethyloxy-1,2-epoxypropane, 3-perfluoro-n-hexylmethyloxy-1,2-epoxypropane, 3-perfluoro-n-octylmethyloxy-
1,2-epoxypropane, 3-perfluoro-n-decylmethyloxy-1,2-epoxypropane, 3-perfluoro-n-dodecylmethyloxy-1,2-epoxypropane, 3- (2-trifluoro Methyl) ethyloxy-1,2-epoxypropane, 3- (2-perfluoroethyl) ethyloxy-1,2-epoxypropane, 3- (2-perfluoro-n-butyl) ethyloxy-1,2-epoxypropane, 3- (2-perfluoro-n-hexyl) ethyloxy-1,2-epoxypropane, 3- (2-perfluoro-n-octyl) ethyloxy-1,2-epoxypropane, 3- (2-perfluoro- n-decyl) ethyloxy-1,2-epoxypropane, 3- (2-perfluoro-n-dodecyl)
Ethyloxy-1,2-epoxypropane, 3- (perfluoro-3-methylbutyl) -1,2-epoxypropane, 3- (perfluoro-5-methylhexyl)-
1,2-epoxypropane, 3- (perfluoro-7-
Methyloctyl) -1,2-epoxypropane, 3-
(Perfluoro-9-methyldecyl) -1,2-epoxypropane, 3- (perfluoro-3-methylbutyloxy) -1,2-epoxypropane, 3- (perfluoro-5-methylhexyloxy) -1 , 2-epoxypropane, 3- (perfluoro-7-methyloctyloxy) -1,2-epoxypropane, 3- (perfluoro-3-methylbutyl) methyloxy-1,2-epoxypropane, 3- (per Fluoro-5-methylhexyl)
Methyloxy-1,2-epoxypropane, 3- (perfluoro-7-methyloctyl) methyloxy-1,2
-Epoxypropane, 3- (2- (perfluoro-3-
Methylbutyl) ethyloxy) -1,2-epoxypropane, 3- (2- (perfluoro-5-methylhexyl) ethyloxy) -1,2-epoxypropane, 3-
(2- (perfluoro-7-methyloctyl) ethyloxy) -1,2-epoxypropane, 3- (1,1,
2,2-tetrafluoroethyl) -1,2-epoxypropane, 3- (4H-octafluorobutyl) -1,2
-Epoxypropane, 3- (6H-dodecafluorohexyl) -1,2-epoxypropane, 3- (8H-hexadecafluorooctyl) -1,2-epoxypropane, 3- (1,1,2,2- Tetrafluoroethyloxy) -1,2-epoxypropane, 3- (4H-octafluorobutyloxy) -1,2-epoxypropane,
3- (6H-dodecafluorohexyloxy) -1,2
-Epoxypropane, 3- (8H-hexadecafluorooctyloxy) -1,2-epoxypropane, 3-
(2,2,3,3-tetrafluoropropyloxy)-
1,2-epoxypropane, 3- (1H, 1H, 5H-
Octafluoropentyloxy) -1,2-epoxypropane, 3- (1H, 1H, 7H-dodecafluoroheptyloxy) -1,2-epoxypropane, 3- (1
H, 1H, 9H-hexadecafluorononyloxy)-
1,2-epoxypropane, 3- (3,3,4,4-tetrafluorobutyloxy) -1,2-epoxypropane, 3- (1H, 1H, 2H, 2H, 6H-octafluorohexyloxy)- 1,2-epoxypropane, 3
-(1H, 1H, 2H, 2H, 8H-dodecafluorooctyloxy) -1,2-epoxypropane, 3- (1
H, 1H, 2H, 2H, 10H-hexadecafluorodecyloxy) -1,2-epoxypropane.

Formula (2) and / or Formula (3)
In order to produce a fluorine-containing (meth) acrylate compound (D) having one hydroxyl group in the structure represented by
In the reaction between the fluorine-containing monoepoxy compound represented by the formula (6) and (meth) acrylic acid, the ratio of the charged amount of (meth) acrylic acid to 1.00 mol of the fluorine-containing monoepoxy compound is 0.90 to 3%. 0.000 mol is preferable, and 1.00 to 1.50 mol is more preferable. The reaction temperature for adding (meth) acrylic acid to the fluorine-containing monoepoxy compound represented by the formula (6) is 50 to 15
0 ° C is preferable, and more preferably 70 to 100 ° C.

A catalyst can be used to promote the reaction. The catalyst that can be used at this time includes
For example, triethylamine, amines such as benzyldimethylamine, triethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, trimethylphenylammonium bromide,
Tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetramethylammonium iodide,
Quaternary ammonium salts such as tetraethylammonium iodide, tetra-n-butylammonium iodide, triphenylphosphine, tri-n-butylphosphine, tri-m-tolylphosphine, tricyclohexylphosphine, diphenylphosphinas chloride,
1,1-bis (diphenylphosphino) methane, 1,2
And organic phosphine compounds such as -bis (diphenylphosphino) ethane, 1,4-bis (diphenylphosphino) butane, and 1,5-bis (diphenylphosphino) pentane. The amount of the catalyst added is preferably 0.001 to 5.0 w%, more preferably 0.01 to 3.0 w%, based on the entire reaction mixture. The reaction time is preferably from 3 to 60 hours, more preferably from 8 to 25 hours.

The product obtained by this reaction is usually
In the structures represented by the formulas (2) and (3), 1
It becomes a mixture of the fluorine-containing (meth) acrylate compound (D) having two hydroxyl groups. The fluorine-containing (meth) acrylate compound (D) thus obtained is temporarily dissolved in a non-aqueous solvent such as toluene to remove excess (meth) acrylic acid or a catalyst if necessary, and then sodium carbonate, carbonate It is often washed with an alkaline aqueous solution of potassium, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like. Thereafter, the residue is washed with water or a saline solution to remove the remaining alkali, and the solvent is sufficiently distilled off, whereby a fluorine-containing (meth) acrylate compound represented by the above formulas (2) and (3) having higher purity is obtained. (D) is obtained. In some cases, it may be used after being purified or fractionated by distillation under reduced pressure.

The fluorine-containing urethane (meth) acrylate compound (E) used in the present invention is obtained by sufficiently reacting the fluorine-containing diol compound (A) represented by the formula (1) with the diisocyanate compound (C). It can be obtained by reacting a fluorine-containing (meth) acrylate compound (D) having one hydroxyl group in the structure represented by the formula (2) and / or the formula (3). In this case, the charge amount of the diisocyanate compound (C) per one chemical equivalent of the hydroxyl group of the fluorine-containing diol compound (A) represented by the formula (1) is 1.10 to 2.00 chemical equivalents of isocyanate groups. Is particularly preferable, and it is more preferable that it is 1.60 to 2.00 chemical equivalent. The reaction temperature is preferably from 20 to 120C, more preferably from 40 to 80C. Next, the thus-obtained compound having an isocyanate group at the terminal is added to a fluorine-containing (meth) compound having one hydroxyl group in the structure represented by the formula (2) and / or the formula (3). The acrylate compound (D) is reacted. The (meth) acrylate compound (D) having one hydroxyl group in the structure represented by the formula (2) and / or the formula (3) is obtained by converting the compound represented by the formula (1)
Is preferably 0.90 to 1.1 equivalent to 1 chemical equivalent of isocyanate group of a compound having a terminal isocyanate group obtained by reacting a diisocyanate compound (C) with a fluorine-containing diol compound (A) represented by
The reaction is preferably carried out by charging 50 chemical equivalents, more preferably 1.00 to 1.02 chemical equivalents. In this reaction, a known catalyst can be added 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 preferably 0.001 to 5.0 w%, more preferably 0.01 to 1.1 w%, based on the whole reaction mixture. The reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours. Reaction temperature is 20
To 100 ° C, more preferably 40 to 80 ° C.

In the above production method, the reaction can usually be carried out without a solvent. However, when the fluorine-containing diol compound (A) represented by the formula (1) is waxy or solid, the reaction can be carried out using a solvent inert to the isocyanate group. Specific examples of the solvent that is inert to the isocyanate group used at this time include, for example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and aromatic hydrocarbon compounds such as toluene, xylene, and ethylbenzene. Can be. Further, a monofunctional (meth) acrylate compound (H) represented by the formula (4) and / or a compound represented by the formula (5), which can be used as a mixture with the resin composition of the present invention or a coating agent for an optical fiber described below. The resulting bifunctional (meth) acrylate compound (I) can be used as a reaction solvent.

The resin composition or the coating agent for optical fiber of the present invention comprises a fluorine-containing urethane (meth) acrylate compound (B) and a fluorine-containing urethane (meth)
It may be used as it is as a mixture of the acrylate compound (E). Further, the fluorine-containing urethane (meth) acrylate compound (B) and the fluorine-containing urethane (meth) acrylate compound (E) are not necessarily required to be a single compound, but may be used by mixing two or more compounds. May be. When mixing the fluorine-containing urethane (meth) acrylate compound (B) and the fluorine-containing urethane (meth) acrylate compound (E),
The compounding ratio of these is fluorine-containing urethane (meth) acrylate compound (B): fluorine-containing urethane (meth) acrylate compound (E) = 30: 70-9 by weight ratio.
The ratio is preferably 9: 1, more preferably 60: 4.
0 to 90:10.

The resin composition or the coating agent for optical fibers of the present invention comprises a mixture of a fluorine-containing urethane (meth) acrylate compound (B) and a fluorine-containing urethane (meth) acrylate compound (E), The monofunctional (meth) acrylate compound (F) represented and / or the bifunctional (meth) acrylate compound (G) represented by the formula (5) are mixed for the purpose of adjusting viscosity, refractive index, and the like. Can be used. Specific examples of the monofunctional (meth) acrylate compound (F) represented by the formula (4) used herein include, for example, methyl (meth)
Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl methacrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, Isohexyl (meth) acrylate, n-heptyl (meth) acrylate, isoheptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, Lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) Acrylate, 3- (3-methoxypropoxy) propyl (meth) acrylate, 4- (4
-Methoxybutoxy) butyl (meth) acrylate, 2
-(2- (2-methoxyethoxy) ethoxy) ethyl (meth) acrylate, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate ,
3-ethoxypropyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 3- (3-ethoxypropoxy) propyl (meth) acrylate, 4
-(4-ethoxybutoxy) butyl (meth) acrylate, 2- (2- (2-ethoxyethoxy) ethoxy) ethyl (meth) acrylate, 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) Ethyl (meth)
Acrylate, 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, 1H, 1H, 5H
Octafluoropentyl (meth) acrylate, 1
H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 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 and the like can be mentioned.

Specific examples of the bifunctional (meth) acrylate compound (G) represented by the formula (5) include, for example, ethylene glycol di (meth) acrylate,
3-propylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, 1,8
-Octanediol di (meth) acrylate, 1,9-
Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 3-methyl-
1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,
2,4-trimethyl-1,6 hexanediol di (meth) acrylate, 2,4,4-trimethyl-1,6-
Hexanediol (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 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 , 3,3,4,4,5,5,6,6,6
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
4,5,5,6,6,7,7,8,8,9,9,10,
Examples thereof include 10,11,11-icosafluorododecane and a compound represented by the following formula or the like.

[0035]

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The monofunctional (meth) acrylate compound (F) represented by the formula (4) and the bifunctional (meth) acrylate compound (G) represented by the formula (5) exemplified above have one of them. One kind may be used alone, and the monofunctional (meth) acrylate compound (F) represented by the formula (4) and the bifunctional (meth) acrylate compound (G) represented by the formula (5) are respectively used. You may mix and use several types. Note that the monofunctional (meth) acrylate compound (F) represented by the formula (4) and the bifunctional (meth) acrylate compound (G) represented by the formula (5) may be mixed at any ratio. I do not care. Further, a monofunctional (meth) acrylate compound (F) represented by the formula (4) and a mixture of the fluorine-containing urethane (meth) acrylate compound (B) and the fluorine-containing urethane (meth) acrylate compound (E) according to the present invention, and And / or the proportion of the bifunctional (meth) acrylate compound (G) represented by the formula (5) is a mixture of the fluorine-containing urethane (meth) acrylate compound (B) and the fluorine-containing urethane (meth) acrylate compound (E). The total amount of the monofunctional (meth) acrylate compound (F) represented by the formula (4) and / or the bifunctional (meth) acrylate compound (G) represented by the formula (5) is based on 100 parts by weight of the whole. It is preferably from 5 to 900 parts by weight, more preferably from 10 to 120 parts by weight.

When the resin composition or the coating agent for an optical fiber of the present invention is cured by irradiating active energy rays such as ultraviolet rays, a photopolymerization initiator (H) is used. As the photopolymerization initiator (H) used in the present invention, any known photopolymerization initiator may be used, but it is required to have good storage stability after blending. Specific examples of such a photopolymerization initiator (H) include, for example, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, benzyldimethylketal, 4-
(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4
-Thiomethylphenyl) propan-1-one and the like. One type of these photopolymerization initiators (H) may be used, or two or more types may be mixed and used at an arbitrary ratio. The amount of the photopolymerization initiator (H) to be added is usually preferably 0.1 to 10.0% by weight, more preferably 0.5% by weight, based on the entire resin composition of the present invention or the coating agent for optical fibers. ~ 5.0 w%.

The resin composition of the present invention or the coating agent for an optical fiber may optionally contain additives such as a silane coupling agent, an antioxidant, a polymerization inhibitor and a light stabilizer. The resin composition or the coating agent for optical fibers of the present invention can be obtained by uniformly mixing the above components.

The resin composition according to the present invention is generally used by coating it on a substrate. In this case, specific examples of the substrate used include, for example, glasses such as quartz glass, metals such as copper and aluminum, polymethyl methacrylate, deuterated polymethyl methacrylate, polyethyl methacrylate, polystyrene, polycarbonate, ABS Plastics such as resin can be exemplified. Examples of the method of applying the resin composition according to the present invention to a substrate include, for example, brush coating, a bar coater, an applicator, a method of directly applying with a roll coater or a roller brush, an air spray or an airless spray coater, or the like. Spray coating, flow coating using a shower coater or curtain flow coater (flow coating), dipping, casting, spinner coating, and the like can be used. 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 of applying the composition according to the present invention to a substrate (for example, a core wire for an optical transmission fiber) as a coating agent for an optical fiber, various methods known in the art, for example, a resin composition according to the present invention The optical fiber core wire is continuously immersed and pulled up in a storage tank containing the resin, and a method for curing and forming the clad portion by irradiating active energy rays such as ultraviolet rays, or a method for continuously supplying the resin composition of the present invention to a die capable of continuously supplying the resin composition. A method in which the coating is continuously applied through a transmission fiber core wire, and an active energy ray such as ultraviolet rays is irradiated to cure and form the clad portion. When curing and forming the clad portion of the optical transmission fiber, the thickness of the coating film of the present invention is not particularly limited, but usually,
It is preferably about 5 to 300 microns.

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

The light source used for curing the resin composition of the present invention or the coating agent for optical fibers by irradiating with an active energy ray such as ultraviolet rays may be, for example, a xenon lamp, a carbon arc, a germicidal lamp, or a fluorescent lamp for ultraviolet rays. A high-pressure mercury lamp for copying, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam by a scanning or curtain-type electron beam accelerating path can be used. Also, in order to fully cure,
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 cladding material for optical transmission fibers, but also as a coating material for glass or plastics, a sealing agent for LEDs, a lens, etc. It can also be used as an antifouling paint, a UV adhesive for optical articles, and the like.

[0044]

The present invention will be described below in more detail with reference to examples. The present invention is not limited at all by the following examples. Parts in the examples are parts by weight.

[Synthesis Example of Fluorine-Containing Urethane (meth) acrylate Compound (B)] Example 1 A 500 mL separable flask was charged with 3- (2-perfluoro-n-hexyl) ethyloxy-1,2-propanediol 250 Then, 0.3 parts of dibutyltin dilaurate is added, and the mixture is stirred at 40 ° C. To this solution, 177.0 parts of 2-methacryloyloxyethyl isocyanate is added dropwise at 40 to 50 ° C. over 1 hour and 30 minutes while paying attention to heat generation. After dropping, it is 40 ~
The mixture was stirred at 50 ° C for 1 hour and further at 70 to 80 ° C for 3 hours to obtain a colorless transparent liquid product. NC of this thing
The O value is 0.01% by weight or less, the refractive index at 25 ° C is 1.4210, and the viscosity at 25 ° C is 1240.
mPa · s.

[Synthesis Example of Fluorine-Containing (Meth) acrylate Compound (D) Represented by the Formula (2) and / or the Formula (3)] Example 2 -N-butyl-1,2-epoxypropane 502.4 g, acrylic acid 174.2 g, tetramethylammonium chloride 2.6 g, hydroquinone monomethyl ether
0.3 g was charged and stirred at 90 to 95 ° C. for 24 hours to react. The obtained reaction solution is dissolved in 1,000 mL of toluene, washed twice with a 15% by weight aqueous sodium carbonate solution and three times with a 15% by weight aqueous sodium chloride solution, and then toluene is distilled off under reduced pressure. liquid
615.5 g was obtained (yield 97.2%). The refractive index of the obtained reaction product at 25 ° C. was 1.3711,
The viscosity at ° C was 48 mPa · s. The obtained reaction product is a mixture of the following structural formulas (7) and (8).

[0047]

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[0048]

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[Synthesis Example of Fluorine-Containing Urethane (meth) acrylate Compound (E)] Example 3 In a 500 mL separable flask, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-
170.0 g of a 1: 1 mixture by weight of trimethylhexamethylene diisocyanate was added, and 8
Warmed to 0 ° C. Then, 3- (2-perfluoro-
177.1 g of n-hexyl) ethyloxy-1,2-propanediol was added dropwise at 80 to 90 ° C. while paying attention to heat generation. After the addition, the reaction was allowed to proceed for 3 hours. When the NCO value of the product obtained here was measured, it was 9.80 watts.
%Met. Next, 243.6 g of the fluorine-containing acrylate compound represented by the formulas (7) and (8) obtained in Example 2 was placed in a 1 L separable flask, and 0.3 g of dibutyltin dilaurate was added thereto. Stirred at ° C. The reaction solution obtained by reacting with this solution earlier 300.
0 g was slowly added dropwise over 1 hour while paying attention to heat generation. After the dropwise addition, the temperature was raised to 80 ° C and the mixture was stirred at 80 to 90 ° C for 3 hours to obtain a colorless, transparent, and highly viscous liquid product. The NCO value was 0.01 w% or less, the refractive index at 25 ° C was 1.4023, and the viscosity at 25 ° C was 20 Pa · s or more.

[Examples of resin composition] Example 4 80.0 parts of the product obtained in Example 1, 20.0 parts of the product obtained in Example 3, and 1-hydroxycyclohexyl phenyl ketone 1.0 Was blended to prepare a resin composition. Its refractive index at 25 ° C. is 1.4193.
And the viscosity at 25 ° C. was 2680 mPa · s. This resin composition is placed on a glass plate at 150 to 200 μm.
m was applied by a bar coater and irradiated with ultraviolet light at a radiation intensity of 500 mJ / cm2 from a high-pressure mercury lamp under a nitrogen atmosphere to obtain a cured product. Table 1 shows the physical properties of the obtained cured product.

Example 5 70.0 parts of the product obtained in Example 1, 20.0 parts of the product obtained in Example 3, 1,8-diacryloyloxy-
A resin composition was prepared by mixing 10.0 parts of 3,3,4,4,5,5,6,6-octafluorooctane and 1.0 of 1-hydroxycyclohexylphenyl ketone. Its refractive index at 25 ° C was 1.4178, and its viscosity at 25 ° C was 1480 mPa · s. Table 1 shows the physical properties of the cured product obtained in the same manner as in Example 4.

Example 6 70.0 parts of the product obtained in Example 1, 20.0 parts of the product obtained in Example 3, 10.0 parts of 1,9-nonanediol diacrylate and 1-hydroxycyclohexylphenyl Ketone 1.0 was blended to prepare a resin composition. Its refractive index at 25 ° C. was 1.4230, and its viscosity at 25 ° C. was 1,720 mPa · s. Table 1 shows the physical properties of the cured product obtained in the same manner as in Example 4.

Example 7 60.0 parts of the product obtained in Example 1, 20.0 parts of the product obtained in Example 3, 1,8-diacryloyloxy-
3,3,4,4,5,5,6,6-octafluorooctane 10.0 parts, 1,9-nonanediol diacrylate 10.0 parts and 1-hydroxycyclohexyl phenyl ketone 1.0 A resin composition was prepared. Its refractive index at 25 ° C was 1.4215, and its viscosity at 25 ° C was 1150 mPa · s. Table 1 shows the physical properties of the cured product obtained in the same manner as in Example 4.

Table 1 Example 4 5 6 7 Refractive index (25 ° C.) * 1 1.4350 1.4364 1.4404 1.4407 Hardness (Shore D) * 2 45 50 48 55 Young's modulus (kg / mm ² ) * 3 28 32 31 35 Breaking point Strength (kg / mm ² ) * 3 2.6 2.8 2.7 3.2 Elongation at break (%) * 3 11.0 10.3 10.5 9.8 Transparency * 4 ○ ○ ○ ○ Antifouling property * 5 ○ ○ ○ ○

Note) * 1 Refractive index: Measured by Abbe refractometer 1T. * 2 Hardness (Shore D): Ten cured products having a thickness of 150 to 200 μm were piled up, and the measurement was performed according to the method of JIS Z 2246. * 3 Young's modulus, breaking strength, breaking elongation: JIS K7
Performed according to the method of No. 113. * 4 Transparency: A cured product having a thickness of 150 to 200 μm was observed, and the presence or absence of a whitened portion was confirmed.・ ・ ・: There is no whitened portion in the cured product. * 5 Antifouling property: Ten lines having a line width of 2 mm were drawn on the surface of the cured product with black oil-based magic ink, and the surface was wiped off with gauze impregnated with methanol, and the state where the magic ink remained was observed.・ ・ ・: No trace of the magic ink line remains on the surface of the cured product.

[0056]

As apparent from Examples 4 to 7 and Table 1, the resin composition of the present invention can be rapidly cured by irradiating active energy rays such as ultraviolet rays. Has high hardness, Young's modulus, strength at break, and flexibility. Further, the cured product of the resin composition of the present invention has a low refractive index and excellent transparency, so that it can be applied to a cladding layer of an optical fiber for optical transmission. Furthermore, since it has excellent antifouling properties, it can be applied as a coating agent for various articles.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 175/16 4J100 175/16 G02B 6/44 301A G02B 6/44 301 C03C 25/02 B F-term (reference) 2H050 AB44Y 4G060 AA03 AA18 AC07 AC12 AC15 AC16 AC17 AD22 AD24 AD26 AD43 AD44 AD53 CB05 CB09 CB22 CB33 CB38 4J011 QA03 QA04 QA13 QA32 QA33 QB24 SA01 SA21 SA51 UA01 BA03 FA02 BA09 FA03 GA12 JA33 JB39 JC02 KA03 NA11 NA12 NA17 PA17 PB08 PC03 4J100 AL08P AL08Q BA02P BA02Q BA03P BA03Q BA34P BA34Q BB11P BB11Q CA04 FA03 JA35

Claims (5)

[Claims] (1) Formula (1) (Wherein, R ₁ is _{C n F 2n + 1 - (} CH 2) a -, C n F 2n + 1
_{- (CH 2) a -O-,} CF 3 CF (CF 3) C n-1 F
_{2 (n-1) - (} CH 2) a -, CF 3 CF (CF 3) C n-1 F 2 (
_{n-1) - (CH 2} ) a -O-, H- (CF 2 CF 2) b - (C
H _{2) a} - or _{H- (CF 2 CF 2) b} - (CH 2) a -O
-(Where n is an integer from 1 to 12, a is an integer from 0 to 2 and b is an integer from 1 to 4). )) And a fluorine-containing urethane (meth) acrylate compound (B) obtained by reacting 2- (meth) acryloyloxyethyl isocyanate with a fluorine-containing diol compound (A) and formula (1). Fluorine-containing diol compound (A), diisocyanate compound (C) and formula (2) And / or formula (3) (Wherein, R ₂ is _{C m F 2m + 1 - (} CH 2) d -, C m F 2m + 1
_{- (CH 2) d -O-,} CF 3 CF (CF 3) C m-1 F
_{2 (m-1) - (} CH 2) d -, CF 3 CF (CF 3) C m-1 F 2 (
_{m-1) - (CH 2} ) d -O-, H- (CF 2 CF 2) e - (C
H _{2) d} - or _{H- (CF 2 CF 2) e} - (CH 2) d -O
- (. Here, m is an integer of up to 1 to 12, d is up to 0-2 integer, e is an integer from 1 to 4) and, R ₃
Is H or CH ₃ . ) Containing a fluorine-containing urethane (meth) acrylate compound (E) obtained by reacting a fluorine-containing (meth) acrylate compound (D) having one hydroxyl group in the structure represented by Resin composition. (2) Formula (4) (Where R ₄ is a hydrogen atom or a methyl group, X is a linear or branched C ₁ -C ₁₂ alkyl group, CH <sub>3
- (O (CH 2) k</sub> -) l -, CH 3 H 2 - (O (C
_{H 2) k) l -,} C j F 2j + 1 - (CH 2) f -, CF 3 CF
(CF ₃ ) C _j-1 F _{2 (j-1)} -(CH ₂ ) _f -or H- (C
F ₂ CF ₂ ) _g- (CH ₂ ) _f- (where k is an integer of 2 to 4, g and l are integers of 1 to 4, j is an integer of 1 to 10, and f is 1 or 2 ). A) a monofunctional (meth) acrylate compound (F) and / or a compound of formula (5) (Wherein, R ₅ is a hydrogen atom or a methyl group, Y represents a linear or branched C ₁ may be -C _{12 alkyl, -CH 2 (CH 2 OCH 2} ) h CH 2 -, - CH ₂ (CF
_{2 OCF 2) h CH 2 -} , - CH 2 - (CF 2) i -CH 2 -,
_{-CH 2 CH 2 - (CF 2} ) i -CH 2 CH 2 - ( wherein, h
Is an integer of 1 to 4, and i is an integer of 2 to 10. ). The resin composition according to claim 1, further comprising a bifunctional (meth) acrylate compound (G) represented by the following formula: 3. The resin composition according to claim 1, further comprising a photopolymerization initiator (H). 4. The resin composition according to claim 1, wherein the resin composition is used for a coating agent for an optical fiber. 5. A cured product of the resin composition according to any one of claims 1 to 4.