JP2002194031A - Low refractive index resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which is quickly capable of curing by irradiating active energy rays such as ultraviolet rays to produce a cured product having excellent mechanical strength, flexibility, low refractive index and excellent transparency and which can be mainly applied to the cladding layers of light transmitting optical fibers. SOLUTION: A bifunctional fluorine-containing urethane(meth)acrylate compound and a bifunctional (meth)acrylate monomer which is capable of dissolving uniformly in the compound are compounded and all components of the resin composition are constituted by a bifunctional (meth)acrylate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low refractive index resin composition containing a fluorine-containing urethane compound (meth) acrylate compound and a bifunctional (meth) acrylate compound, an optical fiber coating agent, and a cured product thereof. is there.

[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. Further, 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 conducted intensive studies, and as a result, have found that all difunctional fluorine-containing urethane (meth) acrylates and (meth)
Developed a low refractive index resin composition composed of acrylate monomer, and by using this, a resin composition suitable for optical fiber cladding materials that has a high curing speed, low refractive index, and further improved mechanical strength I succeeded in developing things. That is, the present invention relates to [1] Formula (1)

[0005]

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And / or equation (2)

[0007]

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(However, R₁Is C_mF_{2m + 1}− (CH_Two)
_a-, C_mF_{2m + 1}− (CH_Two)_a-O-, CF_ThreeCF (C
F_Three) C_nF_2n− (CH_Two)_a-, CF_ThreeCF (CF_Three) C_n
F_2n− (CH _Two)_a-O-, H- (CF_TwoCF_Two)_b− (C
H_Two)_a-Or H- (CF_TwoCF_Two)_b− (CH_Two)_a-O
-(Where m is an integer from 1 to 12 and n is 0 to 10
, A is an integer from 0 to 2 and b is an integer from 1 to 4.
Is a number. ) And R_TwoIs H or CH_ThreeIt is. )so
Expressed fluorine-containing (meth) acrylate compound (A)
With the diisocyanate compound (B)
-Containing urethane (meth) acrylate obtained by
Compound (C) and Formula (3)

[0009]

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(Where X is a linear or branched C ₁ -C ₁₂ alkyl group,-(YO) _h -Y-,-
CH ₂ — (CF ₂ ) _i —CH ₂ —, —CH ₂ CH ₂ — (C
F ₂ ) _i —CH ₂ CH ₂ — or —CH ₂ (CF ₂ OCF ₂ ) _j
CH ₂ — (where h is an integer of 1 to 3, i is an integer of 2 to 10, j is an integer of 1 to 4, Y is an ethylene group or a propylene group), and R ₃ is a hydrogen atom Or a methyl group. A) a resin composition comprising a bifunctional (meth) acrylate compound (D) represented by
[2] reacting a diol compound (E), a diisocyanate compound (B) and a fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) according to [1]. The resin composition according to [1], which contains a fluorine-containing urethane (meth) acrylate compound (F) obtained by (1), and [3] a photopolymerization initiator (G). The resin composition according to [1] or [2], wherein the content of [4] the photopolymerization initiator (G) is such that the fluorine-containing urethane (meth) acrylate compound (C) and the bifunctional (meth) acrylate compound (D Or a fluorine-containing urethane (meth) acrylate compound (C), a fluorine-containing urethane (meth) acrylate compound (F) and a bifunctional (meth) acrylate compound (D) Characterized in that it is a 0.5～5.0W% relative to the total weight of the mixture (1) to the resin composition according to any one of [3], [5]
The resin composition according to any one of [1] to [4], which has a refractive index at 25 ° C. of 1.47 or less, and [6] an optical fiber coating agent for [1]. ] The present invention relates to the resin composition according to any one of [1] to [5], and [7] a cured product of the resin composition according to any one of [1] to [6].

[0011]

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

Specific examples of the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) include, for example, 1- (meth) acryloyloxy-3-trifluoromethyl-2-propanol and 1- (meth) acryloyloxy-3-trifluoromethyl-2-propanol. (Meth) acryloyloxy-3-perfluoroethyl-2-propanol, 1- (meth) acryloyloxy-3-perfluoro-n-propyl-2-propanol, 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-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-dodecyloxy-2-propanol,
1- (meth) acryloyloxy-3- (2,2,2-
Trifluoroethyloxy) -2-propanol, 1-
(Meth) acryloyloxy-3- (perfluoroethyl) methyloxy-2-propanol, 1- (meth) acryloyloxy-3- (perfluoro-n-butyl)
Methyloxy-2-propanol, 1- (meth) acryloyloxy-3- (perfluoro-n-hexyl) methyloxy-2-propanol, 1- (meth) acryloyloxy-3- (perfluoro-n-octyl) Methyloxy-2-propanol, 1- (meth) acryloyloxy-3- (perfluoro-n-decyl) methyloxy-2-propanol, 1- (meth) acryloyloxy-3- (perfluoro-n-dodecyl) Methyloxy-2-propanol, 1- (meth) acryloyloxy-3- (3,3,3-trifluoropropyloxy)
-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-1-methylethyl) -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- (perfluoro-11-methyldodecyl)-
2-propanol, 1- (meth) acryloyloxy-
4- (perfluoro-1-methylethyl) -2-butanol, 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-1-methylethyloxy) -2-propanol, 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-9-methyldecyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (perfluoro-11-methyldodecyloxy) -2-propanol, 1- (meth) Acryloyloxy-3- (perfluoro-3-methylbutyl) methyloxy-2-propa , 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
-(1,1,2,2,3,3,4,4-octafluorobutyl) -2-propanol, 1- (meth) acryloyloxy-3- (1,1,2,2,3,3,3 4,4,4
5,5,6,6-dodecafluorohexyl) -2-propanol, 1- (meth) acryloyloxy-3-
(1,1,2,2,3,3,4,4,5,5,6,6
7,7,8,8-Hexadecafluorooctyl) -2-
Propanol, 1- (meth) acryloyloxy-4-
(1,1,2,2-tetrafluoroethyl) -2-butanol, 1- (meth) acryloyloxy-4- (1,
1,2,2,3,3,4,4-octafluorobutyl)
-2-butanol, 1- (meth) acryloyloxy-
4- (1,1,2,2,3,3,4,4,5,5,6,
6-dodecafluorohexyl) -2-butanol, 1-
(Meth) acryloyloxy-4- (1,1,2,2,
3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctyl) -2-butanol, 1-
(Meth) acryloyloxy-5- (1,1,2,2-
Tetrafluoroethyl) -2-pentanol, 1- (meth) acryloyloxy-5- (1,1,2,2,3,
3,4,4-octafluorobutyl) -2-pentanol, 1- (meth) acryloyloxy-5- (1,1,
2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl) -2-pentanol, 1- (meth) acryloyloxy-5- (1,1,2,2,3 , 3,4
4,5,5,6,6,7,7,8,8-hexadecafluorooctyl) -2-pentanol, 1- (meth) acryloyloxy-3- (1,1,2,2-tetrafluoro Ethyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (1,1,2,2,3,3,
4,4-octafluorobutyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (1,
1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyloxy) -2-propanol, 1-
(Meth) acryloyloxy-3- (1,1,2,2,
3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (2,2,
3,3-tetrafluoropropyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (2,
2,3,3,4,4,5,5-octafluoropentyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (2,2,3,3,4,4,5,5 ,
6,6,7,7-dodecafluoroheptyloxy) -2
-Propanol, 1- (meth) acryloyloxy-3
− (2,2,3,3,4,4,5,5,6,6,7,
7,8,8,9,9-hexadecafluorononyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (3,3,4,4-tetrafluorobutyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (3,3,4,4,5,5,6,6-octafluorohexyloxy) -2-propanol, 1-
(Meth) acryloyloxy-3- (3,3,4,4,
5,5,6,6,7,7,8,8-dodecafluorooctyloxy) -2-propanol, 1- (meth) acryloyloxy-3- (3,3,4,4,5,5,6 ,
6,7,7,8,8,9,9,10,10-hexadecafluorodecyloxy) -2-propanol and the like.

Further, specific examples of the fluorine-containing (meth) acrylate compound (A) represented by the formula (2) 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- (2,2,2-
Trifluoroethyloxy) -1-propanol, 2-
(Meth) acryloyloxy-3- (perfluoroethyl) methyloxy-1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-n-butyl)
Methyloxy-1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-n-hexyl) methyloxy-1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-n-octyl) Methyloxy-1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-n-decyl) methyloxy-1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-n-dodecyl) Methyloxy-1-propanol, 2- (meth) acryloyloxy-3- (3,3,3-trifluoropropyloxy)
-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-1-methylethyl) -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- (perfluoro-11-methyldodecyl)-
1-propanol, 2- (meth) acryloyloxy-
4- (perfluoro-1-methylethyl) -1-butanol, 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-1-methylethyloxy) -1-propanol, 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-9-methyldecyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (perfluoro-11-methyldodecyloxy) -1-propanol, 2- (meth) Acryloyloxy-3- (perfluoro-3-methylbutyl) methyloxy-1-propa 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
-(1,1,2,2,3,3,4,4-octafluorobutyl) -1-propanol, 2- (meth) acryloyloxy-3- (1,1,2,2,3,3,3 4,4,4
5,5,6,6-dodecafluorohexyl) -1-propanol, 2- (meth) acryloyloxy-3-
(1,1,2,2,3,3,4,4,5,5,6,6
7,7,8,8-Hexadecafluorooctyl) -1-
Propanol, 2- (meth) acryloyloxy-4-
(1,1,2,2-tetrafluoroethyl) -1-butanol, 2- (meth) acryloyloxy-4- (1,
1,2,2,3,3,4,4-octafluorobutyl)
-1-butanol, 2- (meth) acryloyloxy-
4- (1,1,2,2,3,3,4,4,5,5,6,
6-dodecafluorohexyl) -1-butanol, 2-
(Meth) acryloyloxy-4- (1,1,2,2,
3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctyl) -1-butanol, 2-
(Meth) acryloyloxy-5- (1,1,2,2-
Tetrafluoroethyl) -1-pentanol, 2- (meth) acryloyloxy-5- (1,1,2,2,3,
3,4,4-octafluorobutyl) -1-pentanol, 2- (meth) acryloyloxy-5- (1,1,
2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl) -1-pentanol, 2- (meth) acryloyloxy-5- (1,1,2,2,3 , 3,4
4,5,5,6,6,7,7,8,8-hexadecafluorooctyl) -1-pentanol, 2- (meth) acryloyloxy-3- (1,1,2,2-tetrafluoro Ethyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (1,1,2,2,3,3,
4,4-octafluorobutyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (1,
1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyloxy) -1-propanol, 2-
(Meth) acryloyloxy-3- (1,1,2,2,
3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (2,2,
3,3-tetrafluoropropyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (2,
2,3,3,4,4,5,5-octafluoropentyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (2,2,3,3,4,4,5,5 ,
6,6,7,7-dodecafluoroheptyloxy) -1
-Propanol, 2- (meth) acryloyloxy-3
− (2,2,3,3,4,4,5,5,6,6,7,
7,8,8,9,9-hexadecafluorononyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (3,3,4,4-tetrafluorobutyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (3,3,4,4,5,5,6,6-octafluorohexyloxy) -1-propanol, 2-
(Meth) acryloyloxy-3- (3,3,4,4,
5,5,6,6,7,7,8,8-dodecafluorooctyloxy) -1-propanol, 2- (meth) acryloyloxy-3- (3,3,4,4,5,5,6 ,
6,7,7,8,8,9,9,10,10-hexadecafluorodecyloxy) -1-propanol and the like.

The fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) is obtained by combining the fluorine-containing monoepoxy compound represented by the formula (4) with (meth) acrylic acid. It can be obtained by reacting.

[0015]

Embedded image

(However, R ₁ represents the same as above.)

As the fluorine-containing monoepoxy compound represented by the formula (4), for example, 3-trifluoromethyl-
1,2-epoxypropane, 3-perfluoroethyl-
1,2-epoxypropane, 3-perfluoro-n-propyl-1,2-epoxypropane, 3-perfluoro-n-butyl-1,2-epoxypropane, 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, 4-trifluoromethyl-1,2
-Epoxybutane, 4-perfluoroethyl-1,2-
Epoxybutane, 4-perfluoro-n-propyl-
1,2-epoxybutane, 4-perfluoro-n-butyl-1,2-epoxybutane, 4-perfluoro-n-
Hexyl-1,2-epoxybutane, 4-perfluoro-n-octyl-1,2-epoxybutane, 4-perfluoro-n-decyl-1,2-epoxybutane, 4-perfluoro-n-dodecyl- 1,2-epoxybutane,
5-trifluoromethyl-1,2-epoxypentane,
5-perfluoroethyl-1,2-epoxypentane,
5-perfluoro-n-propyl-1,2-epoxypentane, 5-perfluoro-n-butyl-1,2-epoxypentane, 5-perfluoro-n-hexyl-1,
2-epoxypentane, 5-perfluoro-n-octyl-1,2-epoxypentane, 5-perfluoro-n
-Decyl-1,2-epoxypentane, 5-perfluoro-n-dodecyl-1,2-epoxypentane, 3-trifluoromethyloxy-1,2-epoxypropane,
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- (2,2,2-trifluoroethyloxy) -1,2-epoxypropane, 3-
(Perfluoroethyl) methyloxy-1,2-epoxypropane, 3- (perfluoro-n-butyl) methyloxy-1,2-epoxypropane, 3- (perfluoro-n-hexyl) methyloxy-1, 2-epoxypropane, 3- (perfluoro-n-octyl) methyloxy-1,2-epoxypropane, 3- (perfluoro-n-decyl) methyloxy-1,2-epoxypropane, 3- (perfluoro -N-dodecyl) methyloxy-1,2-epoxypropane, 3- (3,3,3-trifluoropropyloxy) -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-1-methylethyl) -1,2-epoxypropane, 3- (perfluoro-3-methylbutyl) -1,2-epoxypropane,
-(Perfluoro-5-methylhexyl) -1,2-epoxypropane, 3- (perfluoro-7-methyloctyl) -1,2-epoxypropane, 3- (perfluoro-9-methyldecyl) -1,1, 2-epoxypropane,
3- (perfluoro-11-methyldodecyl) -1,2
-Epoxypropane, 4- (perfluoro-1-methylethyl) -1,2-epoxybutane, 4- (perfluoro-3-methylbutyl) -1,2-epoxybutane,
-(Perfluoro-5-methylhexyl) -1,2-epoxybutane, 4- (perfluoro-7-methyloctyl) -1,2-epoxybutane, 4- (perfluoro-
9-methyldecyl) -1,2-epoxybutane, 5-
(Perfluoro-3-methylbutyl) -1,2-epoxypentane, 5- (perfluoro-5-methylhexyl) -1,2-epoxypentane, 5- (perfluoro-7-methyloctyl) -1,2 -Epoxypentane,
3- (perfluoro-1-methylethyloxy) -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-9-methyldecyloxy) -1,2-
Epoxypropane, 3- (perfluoro-11-methyldodecyloxy) -1,2-epoxypropane, 3-
(Perfluoro-3-methylbutyl) methyloxy-
1,2-epoxypropane, 3- (perfluoro-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,
-(1,1,2,2-tetrafluoroethyl) -1,2
-Epoxypropane, 3- (1,1,2,2,3,3
4,4-octafluorobutyl) -1,2-epoxypropane, 3- (1,1,2,2,3,3,4,4,5,
5,6,6-dodecafluorohexyl) -1,2-epoxypropane, 3- (1,1,2,2,3,3,4,
4,5,5,6,6,7,7,8,8-hexadecafluorooctyl) -1,2-epoxypropane, 4-
(1,1,2,2-tetrafluoroethyl) -1,2-
Epoxybutane, 4- (1,1,2,2,3,3,4,
4-octafluorobutyl) -1,2-epoxybutane, 4- (1,1,2,2,3,3,4,4,5,5,
6,6-dodecafluorohexyl) -1,2-epoxybutane, 4- (1,1,2,2,3,3,4,4,5,
5,6,6,7,7,8,8-hexadecafluorooctyl) -1,2-epoxybutane, 5- (1,1,2,2
2-tetrafluoroethyl) -1,2-epoxypentane, 5- (1,1,2,2,3,3,4,4-octafluorobutyl) -1,2-epoxypentane, 5-
(1,1,2,2,3,3,4,4,5,5,6,6-
Dodecafluorohexyl) -1,2-epoxypentane, 5- (1,1,2,2,3,3,4,4,5,5,5)
6,6,7,7,8,8-hexadecafluorooctyl) -1,2-epoxypentane, 3- (1,1,2,2
2-tetrafluoroethyloxy) -1,2-epoxypropane, 3- (1,1,2,2,3,3,4,4-octafluorobutyloxy) -1,2-epoxypropane, 3- ( 1,1,2,2,3,3,4,4,5,5
6,6-dodecafluorohexyloxy) -1,2-epoxypropane, 3- (1,1,2,2,3,3,4,
4,5,5,6,6,7,7,8,8-hexadecafluorooctyloxy) -1,2-epoxypropane,
-(2,2,3,3-tetrafluoropropyloxy)
-1,2-epoxypropane, 3- (2,2,3,3,
4,4,5,5-octafluoropentyloxy)-
1,2-epoxypropane, 3- (2,2,3,3,
4,4,5,5,6,6,7,7-dodecafluoroheptyloxy) -1,2-epoxypropane, 3- (2,
2,3,3,4,4,5,5,6,6,7,7,8,
8,9,9-hexadecafluorononyloxy) -1,
2-epoxypropane, 3- (3,3,4,4-tetrafluorobutyloxy) -1,2-epoxypropane,
3- (3,3,4,4,5,5,6,6-octafluorohexyloxy) -1,2-epoxypropane,
(3,3,4,4,5,5,6,6,7,7,8,8-
Dodecafluorooctyloxy) -1,2-epoxypropane, 3- (3,3,4,4,5,5,6,6,7,
7,8,8,9,9,10,10-hexadecafluorodecyloxy) -1,2-epoxypropane.

In order to synthesize the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2), the fluorine-containing monoepoxy compound represented by the formula (4) and (meth) ) In the reaction with acrylic acid, the ratio of the charged amount of (meth) acrylic acid to 1.00 mol of the fluorine-containing monoepoxy compound is preferably 0.90 to 3.00 mol, more preferably 1.00 to 1.50. Is a mole. The reaction temperature for adding (meth) acrylic acid to the fluorine-containing monoepoxy compound represented by the formula (4) is 50
To 150 ° C, more preferably 70 to 100 ° C
It is.

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
It becomes a mixture of the fluorine-containing (meth) acrylate compounds represented by the formulas (1) and (2). The fluorine-containing (meth) acrylate compound thus obtained is once dissolved in a non-aqueous solvent such as toluene to remove excess (meth) acrylic acid or a catalyst if necessary.
Sodium carbonate, potassium carbonate, sodium bicarbonate,
Washed well with an aqueous alkali solution such as 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, whereby a fluorine-containing (meth) acrylate compound represented by the above formulas (1) and (2) having higher purity is obtained. (A) 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 (C) used in the present invention is represented by the above formula (1) and / or the formula (2) synthesized or commercially available as described above. It can be obtained by reacting a fluorine-containing (meth) acrylate compound (A) with a diisocyanate compound (B). Specific examples of the diisocyanate compound (B) used when synthesizing the fluorine-containing urethane (meth) acrylate compound (C) include, for example, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), and trimethylhexamethylene diisocyanate. , 4,4-diphenylmethane diisocyanate, xylylene diisocyanate and the like.

In the method for synthesizing the fluorine-containing urethane (meth) acrylate compound (C), the charged amount of the diisocyanate compound (B) is controlled by the fluorine-containing (meth) compound represented by the above formulas (1) and (2). It is preferable to charge the acrylate compound (A) so as to be 0.90 to 1.05 mol with respect to 2.00 mol, more preferably 0.1 to 1.0 mol.
It is good to charge so that it may be 98-1.00 mol. This reaction is carried out according to the formula (1) and / or the formula (2).
In order to promote the reaction between the terminal hydroxyl group of the fluorine-containing (meth) acrylate compound (A) and the terminal isocyanate group of the diisocyanate compound (B) represented by
Dilaurate compounds such as secondary amines, dibutyltin dilaurate and dioctyltin dilaurate can be used as catalysts. The amount of the catalyst to be added is preferably 0.001 to 5.0 w%, more preferably 0.01 to 1 w%, based on the whole reaction mixture. The catalyst is a fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) in advance.
And the mixture of the fluorine-containing (meth) acrylate compound (A) and the diisocyanate compound (B) represented by the above formula (1) and / or the above formula (2) with caution against heat generation. It may be used while being added. The reaction time is preferably 1 to 10 hours. The reaction temperature is 30
To 100 ° C, more preferably 40 to 80 ° C.

In the method for synthesizing the fluorine-containing urethane (meth) acrylate compound (C), the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) is usually used. For liquids,
The reaction can be performed without using a solvent. However,
When the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) is waxy or solid, a solvent inert to an isocyanate group is used as a reaction solvent. To perform the reaction.
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 bifunctional (meth) acrylate compound (D) represented by the formula (3), which can be used by mixing with the resin composition of the present invention described later, can also be used as a reaction solvent.

In the resin composition of the present invention, in addition to the above-mentioned fluorine-containing urethane (meth) acrylate compound (C),
Further, a fluorine-containing urethane (meth) acrylate compound (F) can be contained. The fluorine-containing urethane (meth) acrylate compound (F) sufficiently reacts the diol compound (E) with the diisocyanate compound (B), and then reacts with the fluorine-containing urethane (meth) acrylate represented by the formula (1) and / or the formula (2). (Meth) acrylate compound (A)
Can be obtained by reacting

Specific examples of the diol compound (E) used when synthesizing the fluorine-containing urethane (meth) acrylate compound (F) include, for example, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,
4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-
Methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,
Low molecular weight diols such as 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,
A dibasic acid such as 1,4-cyclohexanedicarboxylic acid;
Polyester polyols obtained by reaction with diols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol;
Poly-ε-caprolactone-modified polyols, polymethylvalerolactone-modified polyols, polycarbonate polyols and the like can be mentioned.

As the diol compound (E), a fluorine-containing diol compound can also be used. Examples of the fluorine-containing diol compound include 3-perfluoro-n-butyl-1,2-dihydroxypropane,
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) ethyloxy-1,2-dihydroxypropane, 3- (2-perfluoro-n-hexyl) ethyloxy-1,2-dihydroxypropane, -(2
-Perfluoro-n-octyl) ethyloxy-1,2
-Dihydroxypropane, 3- (2-perfluoro-n
-Decyl) ethyloxy-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-tetrafluoropropyloxy) -1,2
-Dihydroxypropane, 3- (2,2,3,3,4,
4,5,5-octafluoropentyloxy) -1,2
-Dihydroxypropane, 3- (2,2,3,3,4,
4,5,5,6,6,7,7-dodecafluoroheptyloxy) -1,2-dihydroxypropane, 3- (2,
2,3,3,4,4,5,5,6,6,7,7,8,
8,9,9-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, 2,2,3,3,4,4,5,5-octafluoro-1,8-octanediol, 3, 3,
4,4,5,5,6,6-octafluoro-1,8-octanediol, 2,2,3,3,4,4,5,5,5
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-1,1
0-decanediol, 2,2,3,3,4,4,5
5,6,6,7,7,8,8,9,9,10,10,1
1,11-icosafluoro-1,12-dodecanediol and the like can be mentioned.

The diol compound (E) and the diisocyanate compound (B) are sufficiently reacted, and then the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) is reacted. In the method of obtaining a fluorine-containing urethane (meth) acrylate compound (F), the charged amount of the diisocyanate compound (B) per one chemical equivalent of the hydroxyl group of the diol compound (E) is 1.10 to 2.00 chemical isocyanate groups. It is preferably an equivalent, more preferably 1.60 to 2.00 chemical equivalent. Reaction temperature is 20-12
0 ° C is preferable, and more preferably 40 to 80 ° C.
Next, the thus obtained compound having an isocyanate group at the terminal is reacted with the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2). The fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) is a terminal isocyanate compound obtained by reacting a diol compound (E) with a diisocyanate compound (B). Isocyanate group 1 of a compound having a group
The reaction is preferably carried out by charging 0.90 to 1.10 chemical equivalents, more preferably 1.00 to 1.02 chemical equivalents, relative to the 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% based on the entire reaction mixture,
More preferably, it is 0.01 to 1.1 w%. The reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours. The reaction temperature is preferably from 20 to 100C, more preferably from 40 to 80C.

In the above production method, the reaction can usually be carried out without a solvent. However, in some cases, such as when the reaction product of the diol compound (E) and the diisocyanate compound (B) is in a wax form, the isocyanate group The reaction can be carried out using an inert solvent. 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 bifunctional (meth) acrylate compound (D) represented by the formula (3), which can be used by mixing with the resin composition of the present invention described later, can also be used as a reaction solvent.

In the resin composition or the coating agent for optical fiber of the present invention, the fluorine-containing urethane (meth) acrylate compound (C) synthesized in the present invention and the above formula (3)
Or a mixture of a bifunctional (meth) acrylate compound (D) represented by the following formula or a mixture of a fluorine-containing urethane (meth) acrylate compound (C) and a fluorine-containing urethane (meth) acrylate compound (F) The bifunctional (meth) acrylate compound (D) represented by the formula (3) is mixed and used. Specific examples of the bifunctional (meth) acrylate compound (D) represented by the formula (3) used at this time include, for example, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate 1,3-propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol 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 (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, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-di (meth) acryloyloxy-2,2,3,3-tetrafluorobutane , 1,6
Di (meth) acryloyloxy-2,2,3,3
4,4,5,5-octafluorohexane, 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,
8,9,9,10,10,11,11-icosafluorododecane, 1,6-di (meth) acryloyloxy-
3,3,4,4-tetrafluorohexane, 1,8-di (meth) acryloyloxy-3,3,4,4,5
5,6,6-octafluorooctane, 1,10-di (meth) acryloyloxy-3,3,4,4,5
5,6,6,7,7,8,8-dodecafluorodecane,
1,12-di (meth) acryloyloxy-3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10-hexadecafluorododecane, 1,14-di (meth) acryloyloxy-3,3,4,4,5
5,6,6,7,7,8,8,9,9,10,10,1
Examples thereof include 1,11,12,12-icosafluorotetradecane and a compound represented by the following formula (5).

[0030]

Embedded image

(Where j is an integer of 1 to 4; R ₃
Represents a hydrogen atom or a methyl group. )

In the resin composition or the coating agent for optical fiber of the present invention, when the fluorine-containing urethane (meth) acrylate compound (C) and the fluorine-containing urethane (meth) acrylate compound (F) are used in combination, The ratio by weight is fluorine-containing urethane (meth) acrylate compound (C): fluorine-containing urethane (meth) acrylate compound (F) = 5: 95 to 9
The ratio is preferably 5: 5, more preferably 50: 5.
0 to 90:10. Further, the above formula (3) used by mixing with a fluorine-containing urethane (meth) acrylate compound (C) or a mixture of a fluorine-containing urethane (meth) acrylate compound (C) and a fluorine-containing urethane (meth) acrylate compound (F) The blending ratio of the bifunctional (meth) acrylate compound (D) represented by the formula is a fluorine-containing urethane (meth) acrylate compound (C) or a fluorine-containing urethane (meth) acrylate compound (C) and a fluorine-containing urethane ( Mixture of (meth) acrylate compound (F): bifunctional (meth) acrylate compound (D) = 99: 1 to 10:90, preferably 95: 5 to 50:50.

In the resin composition or the coating agent for optical fiber of the present invention, the fluorine-containing urethane (meth) acrylate compound (C) and the fluorine-containing urethane (meth) acrylate compound (F) are not necessarily required to be a single compound. Alternatively, two or more compounds may be used in combination. Also, the bifunctional (meth) acrylate compound (D) represented by the formula (3) need not be limited to one kind, and two or more kinds can be used in combination.

When the resin composition or the coating agent for optical fiber of the present invention is cured by irradiating active energy rays such as ultraviolet rays, a photopolymerization initiator is used. As the photopolymerization initiator, any known photopolymerization initiator may be used, but it is required that storage stability after blending is good. 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, but may be used as a mixture of two or more kinds at an arbitrary ratio. The amount of the photopolymerization initiator to be added is generally preferably 0.1 to 10.0 w% based on the whole resin composition of the present invention or the coating agent for an optical fiber,
More preferably, it is 0.5 to 5.0 w%.

The resin composition of the present invention or the coating agent for an optical fiber may contain additives such as a silane coupling agent, an antioxidant, a polymerization inhibitor and a light stabilizer, if necessary. 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 used, for example, by applying it to a substrate usually used for an optical fiber.
As a method of applying, for example, brush coating, a bar coater, an applicator, a method of directly applying by a roll coater or a roller brush, a spray coating method using an air spray or an airless spray coating machine,
A flow coating method (flow coating) using a shower coater or a curtain flow coater or the like, an immersion method, a casting method, a spinner coating method, or 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.

The composition of the present invention can be used as a coating agent for an optical fiber and applied to a substrate (for example, a core wire for an optical transmission fiber) to form a clad portion thereof. As a method of coating, various methods known in the art, for example, the optical fiber core wire is continuously immersed in a storage tank containing the resin composition according to the present invention, pulled up, and irradiated with active energy rays such as ultraviolet rays to form a clad. A method of curing and forming a portion, or a method of continuously applying a core capable of continuously supplying the resin composition of the present invention through an optical transmission fiber core wire and irradiating active energy rays such as ultraviolet rays to cure and form a clad portion. Can be 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.

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

The light source used for curing the resin composition of the present invention or the coating agent for optical fibers by irradiating active energy rays such as ultraviolet rays, for example, a xenon lamp, a carbon arc, a germicidal lamp, and 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 for cladding materials of optical transmission fibers, but also for glass or plastic coating agents, sealing agents for LEDs, castings such as lenses, and surfaces utilizing the low refractive index. It can also be used as an antifouling paint, a UV adhesive for optical articles, and the like.

[0041]

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.

Formula (1) and / or Formula (2)
Example 1: Synthesis of 3- (2-perfluoro-n-hexyl) ethoxy-1,2-epoxypropane 1095.5 g, acrylic acid 235.4 g , 5.5 g of tetramethylammonium chloride and 0.5 g of hydroquinone monomethyl ether were stirred and reacted at 90 to 95 ° C. for 24 hours. The obtained reaction solution was dissolved in 2000 mL of toluene, washed twice with a 10% by weight aqueous solution of sodium carbonate and three times with a 15% by weight aqueous solution of sodium chloride, and then distilled off under reduced pressure and filtered to obtain a colorless and transparent solution. Liquid 1
264.3 g were obtained (yield 98.5%). The refractive index of the obtained reaction product at 25 ° C. was 1.3714,
The viscosity at ° C was 180 mPa · s. 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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Example 2: 1007.2 g of 3-perfluoro-n-octyl-1,2-epoxypropane, 191.8 g of acrylic acid, 5.1 g of tetramethylammonium chloride, 0.5 of hydroquinone monomethyl ether
g was charged and stirred at 90 to 95 ° C. for 20 hours to be reacted. Dissolve the obtained reaction solution in 2000 mL of toluene,
After washing twice with a 10% by weight aqueous solution of sodium carbonate and three times with a 15% by weight aqueous solution of sodium chloride, the toluene is distilled off under reduced pressure and filtered to obtain a colorless and transparent liquid 115.
6.2 g were obtained (99.7% yield). When the obtained reaction product was cooled to 25 ° C., it became a waxy white solid. 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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Synthesis Example of Fluorine-Containing Urethane (Meth) acrylate Compound (C) Example 3 In a 2 L separable flask, the formula (6) obtained in Example 1 was added.
Then, 1000.0 g of the fluorine-containing acrylate compound represented by (7) was added, 0.6 g of dibutyltin dilaurate was added, and the mixture was stirred at 40 ° C. 2,
209.4 g of a 1: 1 mixture of 2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate in 1: 1 parts by weight was added dropwise at 40 to 50 ° C. over 1 hour while paying attention to heat generation. After the addition, the mixture was stirred at 40 to 50 ° C. for 3 hours,
The mixture was stirred at ８０80 ° C. for 1 hour to obtain a colorless, transparent and highly viscous liquid product. The NCO value was 0.1 w% or less, and the refractive index at 25 ° C. was 1.4030.

Example 4 A 2 L separable flask was previously heated to 40 to 50 ° C.
Formulas (8) and (9) obtained in Example 2 melted in
The fluorine-containing acrylate compound represented by 1200.
0 g, 0.7 g of dibutyltin dilaurate was added, and the mixture was stirred at 40 ° C. 230.1 g of a 1: 1 mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate in 1: 1 by weight was added to this solution while paying attention to heat generation.
It was added dropwise at ５０50 ° C. over 1 hour. After dropping, 4
The mixture was stirred at 0 to 50 ° C. for 3 hours and further at 60 to 70 ° C. for 1 hour to obtain a colorless, transparent and highly viscous liquid product. Its NCO value was 0.1% by weight or less, and its refractive index at 25 ° C. was 1.3910.

Synthesis Example of Fluorine-Containing Urethane (meth) acrylate Compound (F) Example 5 In a 500 mL separable flask, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-
210.4 g of a 1: 1 mixture by weight of trimethylhexamethylene diisocyanate was added, and stirred.
Warmed to ° C. Next, 59.1 g of 3-methyl-1,5-pentanediol was added dropwise at 80 to 100 ° C. while paying attention to heat generation. After the addition, the reaction was allowed to proceed for 3 hours. The NCO value of the product obtained here was measured.
It was 5 w%. Next, in a 1L separable flask,
370.5 g of the fluorine-containing acrylate compound represented by the formulas (6) and (7) obtained in Example 1 was added, 0.3 g of dibutyltin dilaurate was added, and the mixture was stirred at 45 ° C. To this solution, 2,2,4-trimethylhexamethylene diisocyanate obtained by the reaction
200.0 g of a reaction product of a 1: 1 mixture of trimethylhexamethylene diisocyanate and 3-methyl-1,5-pentanediol in 1 part by weight was slowly added dropwise over 1 hour while paying attention to heat generation. Stirring at 3 ° C. for 3 hours gave a colorless, transparent and highly viscous liquid product. The NCO value was 0.1 w% or less, and the refractive index at 25 ° C. was 1.4284.

Example 6 In a 500 mL separable flask, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-
210.4 g of a 1: 1 mixture by weight of trimethylhexamethylene diisocyanate was added, and stirred.
Warmed to ° C. Then, 1,4-butanediol 45.
1 g 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 16.3 w%.
Next, 429.6 g of the fluorine-containing acrylate compound represented by the formulas (8) and (9) 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. In this solution,
200.0 g of a reaction product of 1,4-butanediol and a 1: 1 mixture of 1,2 by weight of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate obtained by the above reaction was added. The mixture was slowly added dropwise over 1 hour while paying attention to heat generation, and after the addition, the mixture was stirred at 80 to 90 ° C. for 3 hours to obtain a colorless, transparent and highly viscous liquid product. Its NCO value was 0.1% by weight or less, and the refractive index at 25 ° C. was 1.4177.

Example 7 of Resin Composition Example 7 1,8-Nonanediol diacrylate 1 was added to 84.9 g of the fluorine-containing urethane acrylate compound obtained in Example 3.
5.0 g and 1.1 g of 1-hydroxycyclohexylphenyl ketone were blended and stirred at 60 ° C. to prepare a transparent and uniform resin composition. Its refractive index at 25 ° C. was 1.4149, and its viscosity at 25 ° C. was 11
00 mPa · s. This resin composition was coated on a glass plate with a bar coater so as to have a thickness of 150 to 200 μm, and was applied with a high pressure mercury lamp under a nitrogen atmosphere at 600 mJ /.
Ultraviolet rays were irradiated at an irradiation intensity of cm ² to obtain a cured product. Table 1 shows the physical properties of the obtained cured product.

Example 8 To 70.0 g of the fluorine-containing urethane acrylate compound obtained in Example 4, 1,8-diacryloyloxy-3,
30.0 g of 3,4,4,5,5,6,6-octafluorooctane and 1.0 g of 1-hydroxycyclohexylphenyl ketone were blended and stirred at 60 ° C. to prepare a transparent and uniform resin composition. . Its refractive index at 25 ° C. was 1.3967, and its viscosity at 25 ° C. was 1
It was 540 mPa · s. This resin composition was used in Example 7
A cured product was obtained in the same manner as described above. Table 1 shows the physical properties of the obtained cured product.

Example 9 60.3 g of the fluorine-containing urethane acrylate compound obtained in Example 3, 25.1 g of the fluorine-containing urethane acrylate compound obtained in Example 5, 15.3 g of 1,9-nonanediol diacrylate and 1- 1.0 g of hydroxycyclohexyl phenyl ketone was blended and stirred at 60 ° C. to prepare a transparent and uniform resin composition. 25 of this one
The refractive index at ° C. was 1.4194, and the viscosity at 25 ° C. was 1070 mPa · s. This resin composition was applied in the same manner as in Example 7 to obtain a cured product. Table 1 shows the physical properties of the obtained cured product.

Example 10 40.3 g of the fluorine-containing urethane acrylate compound obtained in Example 4, 25.3 g of the fluorine-containing urethane acrylate compound obtained in Example 6, 1,8-diacryloyloxy-3,3,4, 35.4 g of 4,5,5,6,6-octafluorooctane and 1.0 g of 1-hydroxycyclohexylphenyl ketone were blended and stirred at 60 ° C to prepare a transparent and uniform resin composition. 25 ℃
Was 1.4038 and the viscosity at 25 ° C. was 1760 mPa · s. This resin composition was applied in the same manner as in Example 7 to obtain a cured product. Table 1 shows the physical properties of the obtained cured product.

Table 1 Example 7 8 9 10 Refractive index (25 ° C.) * 1 1.4318 1.4126 1.4360 1.4213 Young's modulus (MPa) * 2 328 350 287 296 Strength at break (MPa) * 2 14.2 17.7 11.2 12.2 Elongation at break (%) * 2 8.0 7.1 14.7 12.8 Transparency * 3 ○ ○ ○ ○

Note) * 1 Refractive index: Measured by Abbe refractometer 1T. * 2 Young's modulus, breaking strength, breaking elongation: JIS K7
Performed according to the method of No. 113. * 3 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.

[0058]

As is clear from Examples 7 to 10 and Table 1, the resin composition of the present invention is irradiated with active energy rays such as ultraviolet rays since all the constituents are bifunctional (meth) acrylate compounds. The cured product has excellent mechanical strength and is flexible since it contains a urethane (meth) acrylate compound. Further, since the cured product of the resin composition of the present invention contains fluorine and has a low refractive index and excellent transparency, it can be applied to a cladding layer of an optical fiber for optical transmission.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G02B 6/00 391 G02B 6/00 391 F term (Reference) 2H050 AA11 AA13 AB43Y AB43Z BB07Q 4J011 AC04 QA04 QA12 QA14 QA32 QB24 SA01 SA06 SA16 SA51 SA78 UA01 VA01 VA05 WA03 4J027 AG12 AG22 AG34 BA19 BA20 BA21 CB10 CC05 CD03 4J034 BA08 CA02 CA04 CC03 CD12 DA01 DF14 DG02 FA02 HA07 HC03 HC12 HC17 HC22 KD11 KD12 KD17 RA13PJBBC18BC18BC18BBC FA03

Claims (7)

[Claims] (1) Formula (1)And / or formula (2)(However, R₁Is C_mF_{2m + 1}− (CH_Two)_a-, C_mF_{2m + 1}
− (CH_Two)_a-O-, CF_ThreeCF (CF_Three) C_nF_2n−
(CH_Two)_a-, CF_ThreeCF (CF_Three) C_nF_2n− (CH _Two)
_a-O-, H- (CF_TwoCF_Two)_b− (CH_Two)_a-Or H
− (CF_TwoCF_Two)_b− (CH_Two)_a-O- (where m is
An integer from 1 to 12, n is an integer from 0 to 10, a is 0
B is an integer of 1 to 4; )
R_TwoIs H or CH_ThreeIt is. Containing fluorine represented by)
Diisocyanate to (meth) acrylate compound (A)
The fluorine compound obtained by reacting the compound (B)
A boron-containing urethane (meth) acrylate compound (C);
Formula (3)(Where X is a linear or branched C₁~ C
₁₂An alkyl group of-(YO)_h-Y-, -CH_Two− (C
F_Two)_i-CH_Two-, -CH_TwoCH_Two− (CF_Two)_i-CH_TwoC
H_Two-Or -CH_Two(CF_TwoOCF_Two)_jCH_Two-(Here
Where h is an integer of 1 to 3, i is an integer of 2 to 10, j is 1 to
And Y is an ethylene group or a propylene group.
You. ) And R_ThreeIs a hydrogen atom or a methyl group
You. ) Bifunctional (meth) acrylate compound represented by
A resin composition containing (D). 2. A reaction between a diol compound (E), a diisocyanate compound (B) and a fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or (2) according to claim 1. The resin composition according to claim 1, further comprising a fluorine-containing urethane (meth) acrylate compound (F) obtained by the above-described method. 3. The resin composition according to claim 1, further comprising a photopolymerization initiator (G). 4. A photopolymerization initiator (G) containing a mixture of a fluorine-containing urethane (meth) acrylate compound (C) and a bifunctional (meth) acrylate compound (D), or a fluorine-containing urethane (meth) acrylate It is 0.5 to 5.0 w% based on the total weight of the mixture of the compound (C), the fluorine-containing urethane (meth) acrylate compound (F) and the bifunctional (meth) acrylate compound (D). The resin composition according to claim 1. 5. The resin composition according to claim 1, wherein the resin composition has a refractive index at 25 ° C. of 1.47 or less. 6. The resin composition according to claim 1, wherein the resin composition is used as a coating agent for an optical fiber. 7. A cured product of the resin composition according to claim 1.