JP2002308829A - Fluorine-containing ester compound, low refractive index resin composition containing the same and cured matter thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a resin composition containing (2-trifluoromethyl) acrylate compound capable of being rapidly cured by the irradiation with active energy beam such as ultraviolet rays or the like to form cured matter excellent in mechanical strengths, having flexibility and a low refractive index and excellent in transparency and antistaining properties. SOLUTION: 2-Trifluoromethylacrylic acid and a fluorine-containing diol compound are subjected to esterification reaction to synthesize a (2- trifluoromethyl) acrylate compound which is, in turn, mixed with a fluorine- containing urethane (meth)acrylate compound and a photopolymerization initiator to produce a low refractive index resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for synthesizing a di (2-trifluoromethyl) acrylate compound, further obtaining the di (2-trifluoromethyl) acrylate compound and a fluorine-containing urethane (meth) acrylate compound. The present invention relates to a low-refractive-index resin composition and a cured product thereof, which are mainly used for optical applications, and especially for optical fiber coating agents.

[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. In recent years,
Materials having a lower refractive index than ever have been required. As a clad material, a urethane (meth) acrylate containing a fluorine atom may be blended with the resin composition in order to give the cured product some flexibility (for example, JP-A-4-321660, JP-A-5-231). 3
2749). In the case of synthesizing a urethane (meth) acrylate containing a fluorine atom, a (meth) acrylate compound having a hydroxyl group in the structure is reacted with a diisocyanate compound, or the diol compound is charged so that the diisocyanate compound is increased in a molar ratio. Reaction to synthesize a compound having isocyanate groups remaining at both ends, and this compound has a hydroxyl group in the structure (meth)
It can be obtained by a method such as reacting an acrylate compound. The urethane (meth) acrylate containing a fluorine atom synthesized in this way is usually diluted by blending a (meth) acrylate monomer as a reactive diluent and adjusting the viscosity to an appropriate viscosity as a coating agent. used. In addition, in order to obtain a resin composition having a low refractive index, a fluorine atom is contained as a reactive diluent (meth)
Use acrylate monomers. However, it contains a fluorine atom used as a reactive diluent (meth)
To lower the refractive index of the acrylate monomer, use (meth)
There is a method of increasing the fluorine content of alcohols to be reacted with acrylic acid, but instead of (meth) acrylic acid, 2
-By using trifluoromethylacrylic acid as a raw material, it is possible to further lower the refractive index of the reactive diluent. In addition, when a large amount of a mono (2-trifluoromethyl) acrylate compound is contained as a component constituting the resin composition, the mechanical strength may be slightly insufficient depending on the application, so that the reaction with 2-trifluoromethylacrylic acid may occur. By using a diol as the fluorine-containing alcohol to be used and using a di (2-trifluoromethyl) acrylate compound obtained by the esterification reaction as a reactive diluent, the curing speed is higher and the mechanical strength is improved. It becomes possible to obtain a refractive index resin composition.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and found that 2- (trifluoromethylacrylic acid) and a fluorine-containing diol compound undergo an esterification reaction to form di (2-trimethyl acrylate). Fluoromethyl) acrylate compound was synthesized, and the obtained di (2-trifluoromethyl) acrylate compound was converted to fluorine-containing urethane (meth).
By blending with an acrylate compound, a resin composition having a low refractive index before and after curing, a high curing rate, excellent adhesion to a core material, and excellent mechanical strength was successfully developed. That is, the present invention relates to [1] Formula (1)

[0005]

Embedded image

(Where X is -CH2CH2- (CF2) n
—CH 2 CH 2 — (where n is an integer of 2 to 10). A) a di (2-trifluoromethyl) acrylate compound (A), [2] a di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1) described in [1], , Equation (2)

[0007]

Embedded image

And / or equation (3)

[0009]

Embedded image

(Where R1 is CmF2m + 1- (CH2) h
-, CmF2m + 1- (CH2) h-O-, CF3CF (CF
3)-(CF2) l- (CH2) h-, CF3CF (CF3)
-(CF2) l- (CH2) h-O-, H- (CF2CF2)
i- (CH2) h- or H- (CF2CF2) i- (CH
2) h-O- (where m is an integer of 1 to 12, l is 0 to 1)
Integer of 0, h is an integer of 0 to 2, and i is an integer of 1 to 4. ) And R2 is H or CH3. A resin composition comprising a fluorine-containing urethane (meth) acrylate compound (D) obtained by reacting a diisocyanate compound (C) with a fluorine-containing (meth) acrylate compound (B) represented by the following formula: , [3]
Diol compound (E) and diisocyanate compound (C)
And a fluorine-containing urethane (meth) acrylate compound (F) obtained by reacting the fluorine-containing (meth) acrylate compound (B) represented by the formula (2) and / or the formula (3) according to [2]. [4] The resin composition according to [2] or [3], which further comprises [4] a photopolymerization initiator (G), [5] Curing by irradiation with active energy rays [2] to [4]
[6] The resin composition according to any one of [2] to [5], wherein [6] the application is a coating agent for an optical fiber, [7]. A cured product of the resin composition according to any one of [2] to [6].

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The above formula (1) used in the present invention
The di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1) can be obtained by reacting 2-trifluoromethylacrylic acid with a fluorine-containing diol compound. Specific examples of the fluorine-containing diol compound used herein include, for example, 3,3,4,4-tetrafluoro-1,6-hexanediol, 3,3,3
4,4,5,5-hexafluoro-1,7-heptanediol, 3,3,4,4,5,5,6,6-octafluoro-1,8-octanediol, 3,3,4 4,
5,5,6,6,7,7-decafluoro-1,9-nonanediol, 3,3,4,4,5,5,6,6,7,
7,8,8-dodecafluoro-1,10-decanediol, 3,3,4,4,5,5,6,6,7,7,8,
8,9,9,10,10-hexadecafluoro-1,1
2-dodecanediol, 3,3,4,4,5,5,6
6,7,7,8,8,9,9,10,10,11,1
Examples thereof include 1,12,12-icosafluoro-1,14-tetradecanediol.

Specific examples of the di (2-trifluoromethyl) acrylate compound (A) represented by the above formula (1) include, for example, 1,6-di (2-trifluoromethyl) acryloyloxy-3, 3,4,4-tetrafluorohexane, 1,7-di (2-trifluoromethyl) acryloyloxy-3,3,4,4,5,5-hexafluoroheptane, 1,8-di (2-tri Fluoromethyl) acryloyloxy-3,3,4,4,5,5,6,6-
Octafluorooctane, 1,9-di (2-trifluoromethyl) acryloyloxy-3,3,4,4,5
5,6,6,7,7-decafluorononane, 1,10-
Di (2-trifluoromethyl) acryloyloxy-
3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorodecane, 1,12-di (2-trifluoromethyl) acryloyloxy-3,3,4,4 , 5
5,6,6,7,7,8,8,9,9,10,10-hexadecafluorododecane, 1,14-di (2-trifluoromethyl) acryloyloxy-3,3,4,4
5,5,6,6,7,7,8,8,9,9,10,1
0,11,11,12,12-icosafluorotetradecane and the like can be mentioned.

The di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1) can be obtained by reacting 2-trifluoromethylacrylic acid with a fluorine-containing diol compound. When synthesizing the di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1), the amount of 2-trifluoromethylacrylic acid charged is stoichiometric with respect to the amount of fluorine-containing diol compound charged. Stoichiometric ratio or more, but it is usually 2 to the charged amount of the fluorine-containing diol compound used.
The charged amount of trifluoromethylacrylic acid is 2.
It is preferably set to 0 to 4.0, more preferably 2.4.
３3.0. The di (2-) represented by the above formula (1)
The esterification reaction for synthesizing the (trifluoromethyl) acrylate compound (A) can be accelerated by using an acid catalyst and removing water generated by the reaction. Here, specific examples of the acid catalyst used for the esterification reaction include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like. The amount of the acid catalyst used in the esterification reaction was 1 to 2 trifluoromethylacrylic acid.
The amount is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight. Further, water generated by the esterification reaction is removed by previously charging an azeotropic solvent with water that does not participate in the reaction and causing the water to azeotropically evaporate. Specific examples of the azeotropic solvent that can be used here include, for example, n-hexane, isohexane, n-hexane.
Aliphatic hydrocarbons such as heptane, isoheptane, n-octane, isooctane, etc., toluene, o-xylene,
Examples thereof include aromatic hydrocarbons such as m-xylene, p-xylene, and ethylbenzene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Usually, the amount of the azeotropic solvent to be charged is preferably 5 to 70% by weight of the reaction mixture. The reaction temperature may be in the range of 60 to 130 ° C, but is generally preferably 80 to 120 ° C from the viewpoint of shortening the reaction time and preventing polymerization during the reaction.

When synthesizing the di (2-trifluoromethyl) acrylate compound (A) represented by the above formula (1), the reaction is preferably carried out while blowing air in order to prevent polymerization during the reaction. For the same purpose, a polymerization inhibitor may be added simultaneously with the charging of the raw materials. Specific examples of the polymerization inhibitor used at this time include, for example, hydroquinone, methylhydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, α-nitroso-β-naphthol, p-benzoquinone, Phenothiazine and the like can be mentioned. Usually, the amount of the polymerization inhibitor used is preferably 0.01 to 1% by weight based on the whole reaction mixture.

The di (2-) represented by the above formula (1) of the present invention.
The (trifluoromethyl) acrylate compound (A) is once dissolved in a non-aqueous solvent such as toluene in order to remove excess 2-trifluoromethylacrylic acid and a catalyst.
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 di (2-trifluoromethyl) represented by the above formula (1) having higher purity is obtained.
An acrylate compound (A) is obtained.

The resin composition or the coating agent for optical fiber of the present invention comprises a di (2-trifluoromethyl) acrylate compound (A) represented by the above formula (1) and the above formula (2) and / or the above formula (2). It can be obtained by blending a fluorine-containing urethane (meth) acrylate compound (D) obtained by reacting a diisocyanate compound (C) with the fluorine-containing (meth) acrylate compound (B) represented by (3).

Specific examples of the fluorine-containing (meth) acrylate compound (B) represented by the formula (2) 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 (B) 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- (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 (B) represented by the formula (2) and / or the formula (3) is obtained by combining the fluorine-containing monoepoxy compound represented by the formula (4) with (meth) acrylic acid. It can be obtained by reacting.

[0020]

Embedded image

(Where R1 is CmF2m + 1- (CH2) h
-, CmF2m + 1- (CH2) h-O-, CF3CF (CF
3)-(CF2) l- (CH2) h-, CF3CF (CF3)
-(CF2) l- (CH2) h-O-, H- (CF2CF2)
i- (CH2) h- or H- (CF2CF2) i- (CH
2) h-O- (where m is an integer of 1 to 12, l is 0 to 1)
Integer of 0, h is an integer of 0 to 2, and i is an integer of 1 to 4. ). )

Examples of the fluorine-containing monoepoxy compound represented by the formula (4) include 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 (B) represented by the formula (2) and / or the formula (3), the fluorine-containing monoepoxy compound represented by the formula (4) ) 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 may 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-toluylphosphine, 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 (2) and (3). 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. After that, the residue is washed with water or a saline solution to remove the remaining alkali, and the solvent is sufficiently distilled off. (B) 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 (D) used in the present invention is represented by the above formula (2) and / or the above formula (3) synthesized or commercially available as described above. It can be obtained by reacting a fluorine-containing (meth) acrylate compound (B) with a diisocyanate compound (C). Specific examples of the diisocyanate compound (C) used when synthesizing the fluorine-containing urethane (meth) acrylate compound (D) 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 (D), the charged amount of the diisocyanate compound (C) is determined based on the fluorine-containing compound represented by the formula (2) and / or the formula (3). 0.90 to 1.0.1 mol of meth) acrylate compound (B) per 2.00 mol.
Preferably, it is charged so as to be 0.5 mol, and more preferably, it is charged so as to be 0.98 to 1.00 mol. This reaction promotes the reaction between the terminal hydroxyl group of the fluorine-containing (meth) acrylate compound (B) represented by the formula (2) and / or the formula (3) and the terminal isocyanate group of the diisocyanate compound (C). For example, tertiary amines such as triethylamine and benzyldimethylamine, dibutyltin dilaurate,
A dilaurate compound such as dioctyltin dilaurate can be used as a catalyst. The amount of catalyst added is
It is preferably 0.001 to 5.0% by weight, more preferably 0.01 to 1% by weight, based on the whole reaction mixture. The catalyst may be used by being mixed in advance with the fluorine-containing (meth) acrylate compound (B) represented by the formula (2) and / or the formula (3).
And / or may be added to a mixture of the fluorine-containing (meth) acrylate compound (B) and the diisocyanate compound (C) represented by the formula (3) while paying attention to heat generation. The reaction time is preferably 1 to 10 hours. The reaction temperature is preferably from 30 to 100 ° C, more preferably from 40 to 100 ° C.
８０80 ° C.

In the method for synthesizing the fluorine-containing urethane (meth) acrylate compound (D), the fluorine-containing (meth) acrylate compound (B) represented by the formula (2) and / or the formula (3) is usually used. For liquids,
The reaction can be performed without using a solvent. However,
When the fluorine-containing (meth) acrylate compound (B) represented by the formula (2) and / or the formula (3) 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 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, the di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1), which is used by being mixed with the resin composition of the present invention or the coating agent for an optical fiber, may be used as a reaction solvent.

The resin composition or the coating agent for optical fiber of the present invention comprises the di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1) and the formula (2) and / or the formula (2). It can be obtained by blending a fluorine-containing urethane (meth) acrylate compound (D) obtained by reacting a diisocyanate compound (C) with a fluorine-containing (meth) acrylate compound (B) represented by 3), Di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1)
The fluorine-containing urethane (meth) acrylate compound (D) does not necessarily need to be a single compound, and may be used as a mixture of two or more compounds. Further, a di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1) and a fluorine-containing urethane (meth) acrylate compound (D)
May be mixed at any compounding ratio in order to obtain a desired refractive index, viscosity, etc., but preferably, the di (2-trifluoromethyl) acrylate compound represented by the formula (1) in a weight ratio ( A): Fluorine-containing urethane (meta)
The acrylate compound (D) is preferably in the range of 80:20 to 20:80.

The resin composition or the coating agent for optical fiber of the present invention may further contain a fluorine-containing urethane (meth) acrylate compound (F) in addition to the fluorine-containing urethane (meth) acrylate compound (D). it can. The fluorine-containing urethane (meth) acrylate compound (F) sufficiently reacts the diol compound (E) with the diisocyanate compound (C), and then contains the fluorine-containing compound represented by the formula (2) and / or the formula (3). It can be obtained by reacting a (meth) acrylate compound (B).

Specific examples of the diol compound (E) used for 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 and 2,4-diethyl-1,5-pentanediol; polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; succinic acid, adipic acid and azelaic acid , Sebacic acid, phthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-
Dibasic acids such as cyclohexanedicarboxylic acid and diols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol Polyester-polyols obtained by the reaction with
-Caprolactone-modified polyols, polymethylvalerolactone-modified polyols, polycarbonate polyols and the like.

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) ethoxy-1,2-dihydroxypropane, 3- (2-perfluoro-n-hexyl) ethoxy-1,2-dihydroxypropane, -(2-perfluoro-n-octyl) ethoxy-1,2-dihydroxypropane, 3- (2-perfluoro-n-decyl) ethoxy-1,2-dihydroxypropane, 3- (perfluoro-3-methylbutyl) ) -1,2-Dihydroxypropane, 3- (perfluoro-5-methylhexyl)-
1,2-dihydroxypropane, 3- (perfluoro-
7-methyloctyl) -1,2-dihydroxypropane, 3- (perfluoro-9-methyldecyl) -1,2
-Dihydroxypropane, 3- (2,2,3,3-tetrafluoropropoxy) -1,2-dihydroxypropane, 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,
3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol, 2,2,3,3
4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1,9-nonanediol, 2,2,3,3
4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol, 2,
2,3,3,4,4,5,5,6,6,7,7,8,
8, 9, 9, 10, 10, 11, 11-icosafluoro-1,12-dodecanediol and the like.

The diol compound (E) is sufficiently reacted with the diisocyanate compound (C), and then the fluorine-containing (meth) acrylate compound (B) represented by the formula (2) and / or the formula (3) is reacted. In the method for obtaining a fluorine-containing urethane (meth) acrylate compound (F), the charged amount of the diisocyanate compound (C) per one chemical equivalent of the hydroxyl group of the diol compound (E) is 1.10 to 2.00 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 a terminal is reacted with the fluorine-containing (meth) acrylate compound (B) represented by the formula (2) and / or the formula (3). The fluorine-containing (meth) acrylate compound (B) represented by the formula (2) and / or the formula (3) is a terminal isocyanate compound obtained by reacting a diisocyanate compound (C) with a diol compound (E). Isocyanate group 1 of a compound having a hydroxyl 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-mentioned production method, the reaction can usually be carried out without a solvent. In some cases, for example, when the reaction product of the diol compound (E) and the diisocyanate compound (C) is in a wax form, the isocyanate group The reaction can be carried out using an inert solvent. Specific examples of the solvent 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, the di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1), which is used by being mixed with the resin composition of the present invention or the coating agent for an optical fiber, may 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)
The acrylate compound (D) and the fluorine-containing urethane (meth) acrylate compound (F) do not necessarily need to be single compounds, and may be used as a mixture of two or more compounds. When the fluorine-containing urethane (meth) acrylate compound (D) and the fluorine-containing urethane (meth) acrylate compound (F) are mixed, their mixing ratio is fluorine-containing urethane (meth) acrylate compound (D): fluorine-containing Urethane (meth) acrylate compound (F) = 30: 70-9
The ratio is preferably 9: 1, more preferably 50: 5.
0 to 95: 5. Further, in the resin composition or the coating agent for optical fiber of the present invention, the formula (1)
The mixture of the di (2-trifluoromethyl) acrylate compound (A), the fluorine-containing urethane (meth) acrylate compound (D) and the fluorine-containing urethane (meth) acrylate compound (F) represented by the following formulas has a desired refractive index and viscosity. Any mixing ratio may be used in order to obtain the same, but it is preferable that the di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1) and the fluorine-containing urethane (meth) ) The mixture of the acrylate compound (D) and the fluorine-containing urethane (meth) acrylate compound (F) may be in the range of 90:10 to 20:80.

When the resin composition or the coating agent for an optical fiber of the present invention is cured by irradiation with active energy rays such as ultraviolet rays, a photopolymerization initiator (G) is used. As the photopolymerization initiator (G) 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 (G) 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 (G) may be used, or two or more types may be mixed and used at an arbitrary ratio. The amount of the photopolymerization initiator (G) to be added is usually preferably 0.1 to 10.0% by weight, more preferably 0.5% by weight, based on the whole 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 after being applied to 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 for coating the substrate (for example, a core wire for an optical fiber) with the resin composition of the present invention as a cladding material for an optical fiber, various methods known in the art, for example, the resin composition of the present invention is used. A method of continuously immersing the optical fiber core wire in a storage tank and pulling it up, irradiating active energy rays such as ultraviolet rays to cure and form the clad portion, or continuously passing the optical fiber core wire through a die capable of continuously supplying the resin composition of the present invention. A method of applying and irradiating active energy rays such as ultraviolet rays to cure and form the clad portion may be used. When the clad portion of the optical fiber is formed by curing, the thickness of the film made of the resin composition of the present invention is not particularly limited, but is usually preferably about 5 to 300 microns.

The core of the optical fiber in the present invention includes, for example, 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 active energy rays such as ultraviolet rays to light is, 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 as a cladding material for optical fibers, but also as a coating material for glass or plastics, a sealing agent for LEDs, a casting material such as a lens, and a surface antifouling utilizing its low refractive index. It can also be used as a hydrophilic paint, a UV adhesive for optical articles, and the like.

[0043]

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.

Synthesis Example of Di (2-trifluoromethyl) acrylate Compound (A) Represented by Formula (1) Example 1: 3,3,4,4,5,5,6,6-octafluoro 100.4 g of -1,8-octanediol, 2-
118.7 g of trifluoromethylacrylic acid, 2.4 g of hydroquinone, 160 mL of toluene, 3.7 g of sulfuric acid
Was charged into a 1 L four-necked flask equipped with a stirrer, a thermometer, a water separator with a condenser and an air blowing tube, and stirred at 109 to 118 ° C. for 5 hours while blowing air.
A dehydration condensation reaction was performed. After the reaction, 320 mL of toluene was added to the obtained reaction solution, and the mixture was washed once with a 25 w% aqueous sodium hydroxide solution and three times with a 15 w% aqueous sodium chloride solution. , 137.9 g of a colorless and transparent liquid (yield 74.6)
%). The obtained reaction product was a compound represented by the following formula (5), and had a refractive index at 25 ° C. of 1.377.
2, the viscosity at 25 ° C was 76 mPa · s, and the specific gravity at 25 ° C was 1.545. The analysis data of the obtained compound are shown below.

[0045]

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(A) Mass * 1: m / e = 534 (B) 1H-NMR * 2: 2.47 to 2.62 ppm 4H 4.53 to 4.57 ppm 4H 6.50 ppm 2H 6.77 ppm 2H

* 1: Mass is an abbreviation for mass spectrum. * 2: 1H-NMR is CDCl3 solvent tetramethylsilane standard.

Formula (2) and / or Formula (3)
Example 2: Synthesis of 3- (2-perfluoro-n-hexyl) ethoxy-1,2-epoxypropane 1100 in a 2 L separable flask. 0 g, 236.0 g of acrylic acid,
5.5 g of tetramethylammonium chloride and 0.5 g of hydroquinone monomethyl ether were charged, and 90-
The mixture was stirred at 95 ° C. for 24 hours to be reacted. 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. 1276.4 g of a liquid was obtained (yield 99.0%). The refractive index of the obtained reaction product at 25 ° C was 1.3713, and the viscosity at 25 ° C was 180 m.
Pa · s. The obtained reaction product is a mixture of the following structural formulas (6) and (7).

[0049]

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[0050]

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Synthesis Example of Fluorine-Containing Urethane (meth) acrylate Compound (D) Example 3 A 1-L separable flask was charged with the fluorine-containing acrylate compound represented by the formulas (6) and (7) obtained in Example 2 Was added, and 0.4 g of dibutyltin dilaurate was added, followed by stirring at 40 ° C. To this solution, 128.2 g of a 1: 1 mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate at 1: 1 by weight was added at 40 to 50 ° C. for 1 hour while paying attention to heat generation. And dropped.
After the dropwise addition, the mixture was stirred at 40 to 50 ° C for 3 hours, and further stirred at 70 to 80 ° C for 1 hour to obtain a colorless, transparent, highly viscous liquid product. The NCO value was 0.1 w% or less, and the refractive index at 25 ° C. was 1.4403.

Synthesis Example of Fluorine-Containing Urethane (Meth) acrylate Compound (F) Example 4: In a 500 mL separable flask, 2
210.4 g of a 1: 1 mixture by weight of 2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate was added, and the mixture was heated to 80 ° C. with stirring. Then 3-methyl-1,
59.1 g of 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. When the NCO value of the product obtained here was measured, it was 15.7 w%. Next, 375.4 g of the fluorine-containing acrylate compound represented by the formulas (6) and (7) obtained in Example 1 was placed in a 1 L separable flask, and 0.3 g of dibutyltin dilaurate was added thereto.
Stirred at 5 ° C. To this solution was added the 2,
200.0 g of a reaction product of a mixture of 2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate in a ratio of 1: 1 by weight and 3-methyl-1,5-pentanediol was observed while generating heat. While slowly dropping over 1 hour, and after dropping, 80-9
After stirring at 0 ° C. for 3 hours, a colorless, transparent, highly viscous liquid product was obtained. The NCO value of this is 0.1 w% or less,
The refractive index at 25 ° C. was 1.4282.

Example of resin composition Example 5 40.0 g of the di (2-trifluoromethyl) acrylate compound obtained in Example 1, 60.0 g of the fluorine-containing urethane acrylate compound obtained in Example 3, and 1-hydroxy 1.0 g of cyclohexyl phenyl ketone
The mixture was stirred at 0 ° C. to prepare a transparent and uniform resin composition. Its refractive index at 25 ° C. is 1.3950,
The viscosity at 25 ° C. is 940 mPa · s. This resin composition is coated on a glass plate with a bar coater so as to have a thickness of 150 to 200 μm, and is irradiated with ultraviolet rays at a radiation intensity of 1000 mJ / cm ^{2 by} a high-pressure mercury lamp under a nitrogen atmosphere to cure the cured product. Obtained. Table 1 shows the physical properties of the obtained cured product.

Example 6 40.0 g of the di (2-trifluoromethyl) acrylate compound obtained in Example 1, 40.0 g of the fluorine-containing urethane acrylate compound obtained in Example 3, and the fluorine-containing urethane obtained in Example 4 Acrylate compound 20.0 g and 1-hydroxycyclohexyl phenyl ketone 1.0 g
Was stirred at 60 ° C. to prepare a transparent and uniform resin composition. Its refractive index at 25 ° C. was 1.39.
89, and the viscosity at 25 ° C. was 890 mPa · s. This resin composition was applied in the same manner as in Example 5 to obtain a cured product. Table 1 shows the physical properties of the obtained cured product.

Table 1 Example 56 Refractive index (25 ° C.) * 1 1.4115 1.4139 Young's modulus (MPa) * 2 329 236 Strength at break (MPa) * 2 14.9 8.7 Elongation at break (%) * 2 8.4 14.7 Transparency * 3 ○ ○ Antifouling property * 4 ○ ○

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. * 4 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.

[0057]

As is clear from Examples 5 and 6, and Table 1, the resin composition of the present invention uses 2-trifluoromethylacrylic acid as a raw material instead of (meth) acrylic acid. Esterification reaction of trifluoromethylacrylic acid and a fluorine-containing diol compound to give di (2-
It can be prepared by synthesizing a (trifluoromethyl) acrylate compound, blending the obtained di (2-trifluoromethyl) acrylate compound with a fluorine-containing urethane (meth) acrylate compound, and adding a photopolymerization initiator. . Further, the resin composition obtained in the present invention,
It is possible to quickly cure by irradiating active energy rays such as ultraviolet rays, and the cured product has excellent mechanical strength,
Since it contains a urethane (meth) acrylate compound, it is flexible, and has a low refractive index and excellent transparency, so that it can be applied to cladding materials of optical fibers for optical transmission. Furthermore, since it has excellent antifouling properties, it can be applied as a coating agent for various articles.

Continued on front page F-term (reference) 4H006 AA01 AB46 AB48 BM10 BM71 4J027 AG02 AG09 AG12 AG13 AG14 AG15 AG23 AG24 AG27 BA19 CB10 CC05 CD03 CD04 4J034 BA02 CA02 CB01 FA02 FB01 FC01 FE08 HA01 HC03 HC12 HC17 HC22 HC46 HC52 HC53 HC53 HC61 KA01 KC17 KD02 KD12 QB08 RA13 4J100 AL66Q AL71P BA38Q BB10P BB18P CA04 FA03 JA32 JA33 JA35

Claims (7)

[Claims] (1) Formula (1) (Where X is -CH2CH2- (CF2) n-CH2CH2
-(Where n is an integer of 2 to 10). )
And a di (2-trifluoromethyl) acrylate compound (A). 2. A di (2-trifluoromethyl) acrylate compound (A) represented by the formula (1) according to claim 1.
And formula (2) And / or formula (3) (However, R1 is CmF2m + 1- (CH2) h-, CmF2m + 1
-(CH2) h-O-, CF3CF (CF3)-(CF2) l
-(CH2) h-, CF3CF (CF3)-(CF2) l-
(CH2) h-O-, H- (CF2CF2) i- (CH2) h
-Or H- (CF2CF2) i- (CH2) h-O- (where m is an integer of 1 to 12, l is an integer of 0 to 10, h is an integer of 0 to 2 and i is an integer of 1 to 4 An integer.) And R
2 is H or CH3. A resin composition comprising a fluorine-containing urethane (meth) acrylate compound (D) obtained by reacting a diisocyanate compound (C) with a fluorine-containing (meth) acrylate compound (B) represented by the following formula: . 3. A reaction between a diol compound (E), a diisocyanate compound (C) and a fluorine-containing (meth) acrylate compound (B) represented by the formula (2) and / or (3) according to claim 2. The resin composition according to claim 2, further comprising a fluorine-containing urethane (meth) acrylate compound (F) obtained by the reaction. 4. The resin composition according to claim 2, further comprising a photopolymerization initiator (G). 5. The resin composition according to claim 2, wherein the resin composition is cured by irradiation with an active energy ray. 6. The resin composition according to claim 2, wherein the resin composition is used as a coating agent for an optical fiber. 7. A cured product of the resin composition according to any one of claims 2 to 6.