JP2002363219A - Resin component having low refractive index and cured product of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To synthesize a fluorine-containing urethane (meth)acrylate compound through a process comprising reaction of a triisocyanate compound with a fluorine-containing alcohol compound, and to develop a resin composition able to cure quickly with radiation of actinic energy rays such as ultraviolet rays to cause a hardened product having flexibility without losing mechanical strength, low in refractive index, excellent in transparency and applicable mainly to a clad layer of an optical fiber for optical communication by using the compound. SOLUTION: The fluorine-containing urethane (meth)acrylate compound is synthesized by reacting a triisocyanate compound with a fluorine-containing (meth)acrylate compound having hydroxy group in the structure and a fluorine- containing monool compound. The resin composition contains the obtained fluorine-containing urethane (meth)acrylate compound, a fluorine-containing mono functional (meth)acrylate compound and a photoinitiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fluorine-containing urethane (meth) acrylate compound obtained by reacting a fluorine-containing (meth) acrylate compound having one hydroxyl group with a triisocyanate compound and a fluorine-containing primary alcohol compound. Low refractive index resin composition, low refractive index resin composition containing the obtained fluorine-containing urethane (meth) acrylate compound and fluorine-containing monofunctional (meth) acrylate compound, coating agent for optical fiber, and cured product thereof It is about.

[0002]

2. Description of the Related Art Optical fibers are classified into inorganic glass such as quartz and synthetic resin such as polymethacrylate. 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, which have high heat resistance, chemical resistance, weather resistance, water repellency, oil repellency, and surface lubricity as general properties, and are particularly noted for having a low refractive index Use as an optical fiber cladding material has been active. For example, a polymer of a fluorinated alkyl group-containing (meth) acrylate compound, a polymer of a fluorinated alkyl group-containing (meth) acrylate compound with another monomer as a cladding material using a polymethacrylate compound as a core material A method using a copolymer or a fluorine-containing polymer such as polytetrafluoroethylene, poly (vinylidene fluoride-tetrafluoroethylene), or poly (vinylidene fluoride-hexafluoropropylene) is known (for example, 59-84203, JP-A-59-84204, JP-A-59-98116, JP-A-59-147011, and JP-A-59-204002). In addition, when a fluorine-containing compound is used as an ultraviolet-curable resin composition, the low-refractive-index resin composition has excellent mechanical strength due to a cross-linked structure by ultraviolet curing,
It also has the advantage that the productivity is improved (for example, Japanese Patent Application Laid-Open Nos.
6206, JP-A-5-32749).

[0003]

In the method of forming a clad material from a fluoropolymer, the clad material is coated with a non-cured melt or solution of the fluoropolymer at a high temperature, so that the thickness is not uniform. Prone. In addition, the adhesion between the core portion and the clad portion is not sufficient, and various external factors such as bending and temperature change easily cause delamination,
There is a problem with durability. 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 are drawbacks in productivity, safety, economy, etc. As a clad material, a urethane (meth) acrylate compound containing a fluorine atom may be blended with the resin composition in order to give the cured product some flexibility.
-321660, JP-A-5-32749). In the case of synthesizing a urethane (meth) acrylate compound containing a fluorine atom, a (meth) acrylate compound having one hydroxyl group in the structure may be reacted with a diisocyanate compound, or the molar ratio of the diisocyanate compound to the diol compound may be increased. , A compound having isocyanate groups remaining at both ends is synthesized, and a (meth) acrylate compound having one hydroxyl group in the structure is reacted with the compound to obtain a compound.
The fluorine atom-containing urethane (meth) acrylate compound thus synthesized is usually diluted with a (meth) acrylate monomer as a reactive diluent and adjusted to an appropriate viscosity as a coating agent. Used. In recent years, a material having a lower refractive index than ever has been required. Until now, when synthesizing a urethane (meth) acrylate compound containing a fluorine atom, the isocyanate compound usually used as a raw material is a diisocyanate compound. As a means for further lowering the refractive index of the urethane (meth) acrylate compound containing a fluorine atom, a fluorine-containing (meth) acrylate compound having one hydroxyl group in the structure and a fluorine-containing monoalcohol compound are blended, and this mixture is mixed with diisocyanate. Fluorine-containing urethane (meth) reacted with a compound
An acrylate compound was synthesized, and a low-refractive-index resin composition using the obtained fluorine-containing urethane (meth) acrylate compound was prepared. A cured film obtained by curing the low-refractive-index resin composition was a fluorine-containing resin. As the blending ratio of the contained monoalcohol compound increases, the mechanical strength tends to become insufficient.

[0004]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and as a result, have found that a hydroxyl group is contained in the structure.
The fluorine-containing (meth) acrylate compound having the same number as that described above and the triisocyanate compound represented by the formula (3) are reacted in advance, and the remaining isocyanate groups of the obtained reaction product are reacted with an equivalent amount of the fluorine-containing monoalcohol compound. Or, conversely, the fluorine-containing monoalcohol compound is reacted in advance with the triisocyanate compound represented by the formula (3), and the remaining isocyanate groups of the obtained reaction product have one hydroxyl group in the equivalent structure. A fluorine-containing urethane (meth) acrylate compound is synthesized by reacting a fluorine-containing (meth) acrylate compound having the same, and by using this compound, the refractive index of the cured product before curing is low, the curing speed is high, and the mechanical strength is high. And succeeded in developing a low refractive index resin composition having excellent low refractive index. That is, the present invention relates to [1] Formula (1)

[0005]

Embedded image

And / or equation (2)

[0007]

Embedded image

Wherein R ₁ is H or CH ₃ , and X is C _m F _{2m + 1-} (CH ₂ ) _a- , C _{mF 2m + 1-} (CH ₂ ) _a -O
_{-, CF 3 CF (CF 3} ) C n F 2n - (CH 2) a -, CF 3
_{CF (CF 3) C n F} 2n - (CH 2) a -O-, H- (CF
_{2 CF 2) b - (CH} 2) a - or _{H- (CF 2 CF 2) b} -
(CH ₂ ) _a —O (where m is an integer of 1 to 12, n is 0)
An integer of 10 to 10, a is an integer of 0 to 2, and b is an integer of 1 to 4. ). A) a fluorine-containing (meth) acrylate compound (A) represented by the formula (3):

[0009]

Embedded image

A triisocyanate compound represented by the formula:
The molar ratio of the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) and the isocyanate group of the triisocyanate represented by the formula (3) is 1.00: 3.00. To 2.99: 3.00 in advance, and the remaining isocyanate groups of the obtained reactant were added to the formula (4)

[0011]

Embedded image

(Where Y is H, F or CF ₃ CF (C
F ₃ ), h is an integer of 1 to 12, and i is 1 or 2. However, when Y is CF ₃ CF (CF ₃ ), h represents an integer of 0 to 10. A resin composition comprising a fluorine-containing urethane (meth) acrylate compound (C) obtained by reacting a fluorine-containing alcohol compound (B) represented by
[2] A fluorine-containing alcohol compound represented by the formula (4) and a triisocyanate compound represented by the formula (3) and a fluorine-containing alcohol compound represented by the formula (4) (B) and the isocyanate group of the triisocyanate represented by the formula (3) are in a molar ratio of 0.01: 3.0.
0 to 2.00: 3.00 in advance, and reacting the remaining isocyanate groups of the obtained reactant with a fluorine-containing compound represented by the formula (1) and / or (2) A) a resin composition containing a fluorine-containing urethane (meth) acrylate compound (C ′) obtained by reacting an acrylate compound (A), [3] a formula (5)

[0013]

Embedded image

(Wherein R_TwoIs H or CH_Three3 and Z
Is H, F or CF_ThreeCF (CF_Three), And j is 1 to 6.
And k represents an integer of 1 to 12. Where Z
Is CF _ThreeCF (CF_Three), J is 1 or 2
And k represents an integer of 0 to 10. ) Monofunctional
It is characterized in that it contains a (meth) acrylate compound (D).
The resin composition according to [1] or [2],
[4] It is characterized by containing a photopolymerization initiator (E).
The resin composition according to any one of [1] to [3].
Object, [5] Use is an optical article
The resin composition according to any one of [1] to [4].
Object, [6] Use is coating agent for optical fiber
The resin composition according to any one of [1] to [5].
The product according to any one of [7] [1] to [6]
A cured product of a resin composition.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing urethane (meth) acrylate compound (C) used in the present invention is a fluorine-containing (meth) acrylate compound represented by the above formula (1) and / or the above formula (2) ( A) is preliminarily reacted with the triisocyanate compound represented by the formula (3), and a fluorine-containing alcohol compound (B) represented by the formula (4) in an amount equivalent to the remaining isocyanate group of the obtained reaction product. And, conversely, a fluorine-containing urethane (meth) acrylate compound (C ′)
Is obtained by previously reacting the fluorine-containing alcohol compound (B) represented by the formula (4) with the triisocyanate compound represented by the formula (3), and an equivalent amount of the remaining isocyanate group of the obtained reaction product. It can be obtained by reacting the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2).

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-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 -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-per Fluoro-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-4- (perfluoro-11-methyldodecyl) -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-propanol, 1- (meth) acryloyloxy-3- (perfluoro-5-methylhexyl) methyl Oxy-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- (1,1,2,2,3,3,4 , 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-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- (meth) acryloyloxy-4-perfluoro-n-dodecyl-1-butanol, 2- (meta)
Acryloyloxy-5-trifluoromethyl-1-pentanol, 2- (meth) acryloyloxy-5-perfluoroethyl-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-pentanol, 2- (meth) acryloyloxy-5-perfluoro-n-decyl-1-pentanol, 2- (meth) acryloyloxy-5-perfluoro-n-dodecyl-1-pen Tanol, 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-4- (perfluoro-11-methyldodecyl) -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-propanol, 2- (meth) acryloyloxy-3- (perfluoro-5-methylhexyl) methyl Oxy-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- (1,1,2,2,3,3,4 , 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.

Formula (1) and / or Formula (2)
Can be obtained by reacting a fluorine-containing monoepoxy compound represented by the formula (6) with (meth) acrylic acid.

[0019]

Embedded image

Here, X represents the same as those of the above formulas (1) and (2).

Examples of the fluorine-containing monoepoxy compound represented by the formula (6) include 3-trifluoromethyl-1,2-epoxypropane, 3-perfluoroethyl-1,2-epoxypropane, 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-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-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, 3- (perfluoro-5-methylhexyl) -1,2-epoxypropane, 3- (perfluoro-7-methyloctyl)
-1,2-epoxypropane, 3- (perfluoro-9
-Methyldecyl) -1,2-epoxypropane, 3-
(Perfluoro-11-methyldodecyl) -1,2-epoxypropane, 4- (perfluoro-1-methylethyl) -1,2-epoxybutane, 4- (perfluoro-
3-methylbutyl) -1,2-epoxybutane, 4-
(Perfluoro-5-methylhexyl) -1,2-epoxybutane, 4- (perfluoro-7-methyloctyl) -1,2-epoxybutane, 4- (perfluoro-
9-methyldecyl) -1,2-epoxybutane, 4-
(Perfluoro-11-methyldodecyl) -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-epoxy propane, 3-
(2- (perfluoro-3-methylbutyl) ethyloxy) -1,2-epoxypropane, 3- (2- (perfluoro-5-methylhexyl) ethyloxy) -1,2
-Epoxypropane, 3- (2- (perfluoro-7-
Methyloctyl) ethyloxy) -1,2-epoxypropane, 3- (1,1,2,2-tetrafluoroethyl) -1,2-epoxypropane, 3- (1,1,2,2
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, 1- (meth) acryloyloxy-4- (1, 1,
2,2-tetrafluoroethyl) -2-butanol, 1
-(Meth) acryloyloxy-4- (1,1,2,2
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, 5- (1,
1,2,2-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,
5,6,6,7,7,8,8-hexadecafluorooctyl) -1,2-epoxypentane, 3- (1,1,
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, 3- (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-
(2,2,3,3,4,4,5,5,6,6,7,7,7,
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- (3,3,4,4,5,5,6,6,7,7,8,
8-Dodecafluorooctyloxy) -1,2-epoxypropane, 3- (3,3,4,4,5,5,6,6,6)
7,7,8,8,9,9,10,10-hexadecafluorodecyloxy) -1,2-epoxypropane.

Formula (1) and / or Formula (2)
In order to synthesize the fluorine-containing (meth) acrylate compound (A) represented by the formula, in the reaction between the fluorine-containing monoepoxy compound represented by the formula (6) and (meth) acrylic acid, the fluorine-containing monoepoxy compound The ratio of the charged amount of (meth) acrylic acid to 1.00 mol is 0.9
0 to 3.00 mol is preferable, and 1.00 is more preferable.
１．５1.50 mol. The reaction temperature at which (meth) acrylic acid is added to the fluorine-containing monoepoxy compound represented by the formula (6) is preferably from 50 to 150C, more preferably from 70 to 100C.

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-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 15 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. After that, the residue is washed with water or a saline solution to remove the remaining alkali, and the solvent is sufficiently distilled off. (A) is obtained. In some cases, it may be used after being purified or fractionated by distillation under reduced pressure.

In the present invention, the fluorine-containing urethane (meth)
In order to synthesize the acrylate compound (C), the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) and the triisocyanate represented by the formula (3) The compound is reacted in advance, and the remaining isocyanate group of the obtained reaction product is reacted with an equivalent amount of the fluorine-containing alcohol compound (B) represented by the formula (4), or a fluorine-containing urethane (meth) acrylate compound In order to synthesize (C ′), the fluorine-containing alcohol compound (B) represented by the above formula (4) and the triisocyanate compound represented by the above formula (3) are reacted in advance, and An equivalent amount of the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) is reacted with the remaining isocyanate group. Respond. The fluorine-containing urethane (meth) acrylate compound (C) or the fluorine-containing alcohol compound (B) represented by the formula (4) used when synthesizing the fluorine-containing urethane (meth) acrylate compound (C ′) used here (B) Examples of the above) include, for example, 2,2-difluoroethanol, 2,2,2
3,3-tetrafluoropropanol, 2,2,3
3,4,4-hexafluorobutanol, 2,2,3
3,4,4,5,5-octafluoropentanol,
2,2,3,3,4,4,5,5,6,6-decafluorohexanol, 2,2,3,3,4,4,5,5,5
6,6,7,7,8,8-tetradecafluorooctanol, 2,2,3,3,4,4,5,5,6,6,7,
7,8,8,9,9,10,10-octadecafluorodecanol, 2,2,3,3,4,4,5,5,6
6,7,7,8,8,9,9,10,10,11,1
1,12,12-docosadecafluorododecanol,
3,3-difluoropropanol, 3,3,4,4-tetrafluorobutanol, 3,3,4,4,5,5
6,6-octafluorohexanol, 3,3,4
4,5,5,6,6,7,7,8,8,9,9,10,
10,11,11,12,12-icosafluorododecanol, 3,3,4,4,5,5,6,6,7,7,
8, 8, 9, 9, 10, 10, 11, 11, 12, 1
2,13,13,14,14-tetracosafluorotetradecanol, 2,2,2-trifluoroethanol,
2,2,3,3,3-pentafluoropropanol, 1
H, 1H-perfluoro-1-butanol, 1H, 1H
-Perfluoro-1-hexanol, 1H, 1H-perfluoro-1-octanol, 1H, 1H-perfluoro-1-decanol, 1H, 1H-perfluoro-1-
Dodecanol, 3,3,3-trifluoropropanol, 3,3,4,4,4-pentafluorobutanol,
2- (perfluoro-n-butyl) ethanol, 2-
(Perfluoro-n-hexyl) ethanol, 2- (perfluoro-n-octyl) ethanol, 2- (perfluoro-n-decyl) ethanol, 2- (perfluoro-n-dodecyl) ethanol, 1H, 1H- Perfluoro-1-isopropanol, 1H, 1H-perfluoro-1-isobutanol, 1H, 1H-perfluoro-1
-Isohexanol, 1H, 1H-perfluoro-1-
Isooctanol, 1H, 1H-perfluoro-1-isodecanol, 1H, 1H-perfluoro-1-isododecanol, 2- (perfluoroisopropyl) ethanol, 2- (perfluoro-2-methylpropyl) ethanol, 2 -(Perfluoro-3-methylbutyl) ethanol, 2- (perfluoro-5-methylhexyl) ethanol, 2- (perfluoro-7-methyloctyl)
Ethanol, 2- (perfluoro-9-methyldecyl)
Examples thereof include ethanol and 2- (perfluoro-11-methyldodecyl) ethanol.

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), which is synthesized as described above or is commercially available. Containing fluorine (meta)
The acrylate compound (A) is reacted in advance with the triisocyanate compound represented by the formula (3), and an equivalent of the remaining isocyanate group of the obtained reaction product is the fluorine-containing alcohol compound represented by the formula (4). (B), and the fluorine-containing urethane (meth) acrylate compound (C ′)
The fluorine-containing alcohol compound (B) represented by the formula (4) is reacted in advance with the triisocyanate compound represented by the formula (3), and the remaining isocyanate group of the obtained reactant is reacted with the compound represented by the formula (1). ) And / or a fluorine-containing (meth) acrylate compound (A) represented by the formula (2). The triisocyanate compound represented by the formula (3) can be obtained on the market.

The fluorine-containing urethane (meth) acrylate compound (C) is obtained by combining the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) with the formula (3). A method in which a triisocyanate compound represented by the formula (4) is reacted in advance with an isocyanate group remaining in the obtained reaction product, and an equivalent amount of the fluorine-containing alcohol compound (B) represented by the formula (4) is reacted. The amount of the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) with respect to the triisocyanate compound represented by the formula (3) is determined by the formula (1) and / or Or equation (2)
The molar ratio of the fluorine-containing (meth) acrylate compound (A) represented by the formula (A) and the isocyanate group of the triisocyanate represented by the formula (3) is 1.00: 3.00 to 2.9.
The ratio is preferably 9: 3.00, more preferably 1.50: 3.00 to 2.00: 3.00. Further, when the remaining isocyanate group of the obtained reaction product is caused to undergo the fluorine-containing alcohol compound (B) represented by the formula (4), the formula (4) is added to 1.00 mol of the remaining isocyanate group. ) The fluorine-containing alcohol compound (B) represented by
It is preferably charged at a rate of 1.05 mol, and more preferably at a rate of 1.00 to 1.02 mol.

Further, the fluorine-containing urethane (meth) acrylate compound (C ′) is prepared by combining the fluorine-containing alcohol compound (B) represented by the formula (4) and the triisocyanate compound represented by the formula (3) in advance. And reacting the remaining isocyanate group of the obtained reactant with the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2). Is the amount of the fluorine-containing alcohol compound (B) represented by the formula (3) with respect to the triisocyanate compound represented by the formula (4). ) And the isocyanate group of the triisocyanate represented by the formula (3) in a molar ratio of 0.01: 3.00 to 2.00: 3.0.
0, more preferably 1.0.
It is preferable to charge at a ratio of 0: 3.00 to 1.50: 3.00. Further, when the remaining isocyanate group of the obtained reactant is reacted with the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2), Group 1.00
Formula (1) and / or Formula (2) based on moles
It is preferable to charge the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) at a ratio of 0.95 to 1.10 mol, more preferably at a ratio of 1.00 to 1.02 mol.

When the fluorine-containing urethane (meth) acrylate compound (C) or the fluorine-containing urethane (meth) acrylate compound (C ') is synthesized,
The isocyanate group of the triisocyanate compound represented by the formula (3), the hydroxyl group of the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) and the formula ( In order to promote the reaction with the fluorine-containing alcohol compound (B) hydroxyl group represented by 4), for example, tertiary amines such as triethylamine and benzyldimethylamine, and dilaurates such as dibutyltin dilaurate and dioctyltin dilaurate Compounds can be used as catalysts. The catalyst comprises a fluorine-containing urethane (meth) acrylate compound (C) represented by the formula (1) and / or the fluorine-containing (meth) acrylate compound (A) represented by the formula (2) and the formula (3). When the triisocyanate compound to be obtained is preliminarily reacted and the remaining isocyanate group of the obtained reaction product is reacted with an equivalent amount of the fluorine-containing alcohol compound (B) represented by the formula (4), It may be used by mixing with the triisocyanate compound represented by the formula (3),
Alternatively, it may be added to a mixture of the fluorine-containing (meth) acrylate compound (A) represented by the formula (2) and the triisocyanate compound represented by the formula (3) while paying attention to heat generation. Further, after reacting the triisocyanate compound represented by the formula (3) with the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2), it remains. When the fluorine-containing alcohol compound (B) represented by the formula (4) is reacted with the isocyanate group, a catalyst is added before the fluorine-containing alcohol compound (B) represented by the formula (4) is charged. Alternatively, after charging the fluorine-containing alcohol compound (B) represented by the formula (4), the catalyst may be added while paying attention to heat generation. Also,
The fluorine-containing urethane (meth) acrylate compound (C ′) is obtained by previously reacting the fluorine-containing alcohol compound (B) represented by the formula (4) with the triisocyanate compound represented by the formula (3). The above formula (1) and / or
Alternatively, in the case of a method obtained by reacting the fluorine-containing (meth) acrylate compound (A) represented by the formula (2), the method is used by mixing with the triisocyanate compound represented by the formula (3) in advance. And a fluorine-containing alcohol compound (B) represented by the above formula (4)
And a mixture of the triisocyanate compound represented by the above formula (3) while paying attention to heat generation. Further, after reacting the fluorine-containing alcohol compound (B) represented by the formula (4) with the triisocyanate compound represented by the formula (3), the remaining isocyanate group is treated with the formula (1) and / or When reacting the reaction of the fluorine-containing (meth) acrylate compound (A) represented by the formula (2), the fluorine-containing (meth) compound represented by the formula (1) and / or the formula (2) is previously used. ) A catalyst may be added before charging the acrylate compound (A), and the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2)
And then add the catalyst while paying attention to heat generation. The amount of catalyst added is 0.0
It is preferably from 0.01 to 5.0 w%, more preferably from 0.01 to 1 w%. The reaction time is preferably 1 to 10 hours. The reaction temperature is preferably 30 to 100 ° C,
More preferably, it is 60 to 90 ° C.

The fluorine-containing urethane (meth) acrylate compound (C) or the fluorine-containing urethane (meth)
In the method for synthesizing the acrylate compound (C ′), usually, the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) and the formula (4) When the fluorine-containing alcohol compound (B) is a liquid, the reaction can be carried out without using a solvent. However, the fluorine-containing (meth) acrylate compound (A) represented by the formula (1) and / or the formula (2) and the fluorine-containing alcohol compound (B) represented by the formula (4) are wax-like. Alternatively, in the case of a solid, the reaction can be carried out using a solvent inert to the isocyanate group of the triisocyanate compound represented by the formula (3) as a reaction 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, a monofunctional (meth) acrylate compound (D) represented by the above formula (5), which can be used by being mixed with the resin composition of the present invention or a coating agent for optical fibers described later, can also be used as a reaction solvent.

The fluorine-containing urethane (meth) acrylate compound (C) or the fluorine-containing urethane (meth) acrylate compound (C ') used as the resin composition of the present invention or the coating agent for an optical fiber need not be a single compound. Instead, two or more compounds may be synthesized and used as a mixture. A mixture of two or more fluorine-containing (meth) acrylate compounds (A) represented by the formula (1) and / or the formula (2);
And / or reacting two or more types of the fluorine-containing alcohol compound (B) represented by the formula (4) with the triisocyanate compound represented by the formula (3) to form a fluorine-containing urethane (meth) acrylate compound ( C) or a fluorine-containing urethane (meth) acrylate compound (C ′) may be synthesized and used. The fluorine-containing urethane (meth) acrylate compound (C) or the fluorine-containing urethane (meth) acrylate compound (C ′)
It is preferable to synthesize either one in the process,
Fluorine-containing urethane (meth) acrylate compound (C)
Alternatively, one of the fluorine-containing urethane (meth) acrylate compounds (C ′) is synthesized in advance, and this is added to the fluorine-containing urethane (meth) acrylate compound (C ′) or the fluorine-containing urethane (meth) acrylate compound (C ′), respectively. ) Can be used as a mixture.

The resin composition or the coating agent for optical fiber of the present invention is obtained by adding the fluorine-containing urethane (meth) acrylate compound (C) or the fluorine-containing urethane (meth) acrylate compound (C ′) synthesized in the present invention to the above formula (C ′). The monofunctional (meth) acrylate compound (D) represented by 5) can be mixed and used for the purpose of adjusting viscosity, refractive index and the like. Equation (5) used here
Specific examples of the monofunctional (meth) acrylate compound (D) represented by (2) include, for example, 2,2-difluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, , 2,3,3
4,4-hexafluorobutyl (meth) acrylate,
2,2,3,3,4,4,5,5,6,6-decafluorohexyl (meth) acrylate, 2,2,3,3
4,4,5,5,6,6,7,7,8,8-tetradecafluorooctyl (meth) acrylate, 2,2,3
3,4,4,5,5,6,6,7,7,8,8,9,
9,10,10-octadecafluorodecyl (meth) acrylate, 2,2,3,3,4,4,5,5,6
6,7,7,8,8,9,9,10,10,11,1
1,12,12-docosafluorododecyl (meth) acrylate, 3,3,4,4-tetrafluorobutyl (meth) acrylate, 5,5,6,6-tetrafluorohexyl (meth) acrylate, 7,7, 8,8-tetrafluorooctyl (meth) acrylate, 2,2,2-
Trifluoroethyl (meth) acrylate, 2,2
3,3,3-pentafluoropropyl (meth) acrylate, 1H, 1H-perfluoro-n-butyl (meth)
Acrylate, 1H, 1H-perfluoro-n-hexyl (meth) acrylate, 1H, 1H-perfluoro-
n-octyl (meth) acrylate, 1H, 1H-perfluoro-n-decyl (meth) acrylate, 1H, 1
H-perfluoro-n-dodecyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, 3,3,4,4,4-pentafluorobutyl (meth) acrylate, 2- (perfluoro -N-butyl) ethyl (meth) acrylate, 2- (perfluoro-n-hexyl) ethyl (meth) acrylate, 2-
(Perfluoro-n-octyl) ethyl (meth) acrylate, 2- (perfluoro-n-decyl) ethyl (meth) acrylate, 2- (perfluoro-n-dodecyl) ethyl (meth) acrylate, 3- (per Fluoro-n-butyl) propyl (meth) acrylate, 4-
(Perfluoro-n-butyl) butyl (meth) acrylate, 6- (perfluoro-n-butyl) hexyl (meth) acrylate, 6- (perfluoro-n-hexyl) hexyl (meth) acrylate, 1H, 1H- Perfluoro-1-isopropyl (meth) acrylate, 1
H, 1H-perfluoro-1-isobutyl (meth) acrylate, 1H, 1H-perfluoro-1-isohexyl (meth) acrylate, 1H, 1H-perfluoro-
1-isooctyl (meth) acrylate, 1H, 1H-
Perfluoro-1-isodecyl (meth) acrylate,
1H, 1H-perfluoro-1-isododecyl (meth)
Acrylate, 2- (perfluoroisopropyl) ethyl (meth) acrylate, 2- (perfluoro-2-methylpropyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (Perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-
Methyloctyl) ethyl (meth) acrylate, 2-
Examples thereof include (perfluoro-9-methyldecyl) ethyl (meth) acrylate and 2- (perfluoro-11-methyldodecyl) ethyl (meth) acrylate.

The monofunctional (meth) acrylate compound (D) represented by the formula (5) exemplified above may be used alone or in combination of several kinds. Further, the monofunctional (meth) acrylate compound (D) represented by the formula (5) with respect to the fluorine-containing urethane (meth) acrylate compound (C) or the fluorine-containing urethane (meth) acrylate compound (C ′) of the present invention. The use ratio is 20 to 200 parts by weight based on 100 parts by weight of the fluorine-containing urethane (meth) acrylate compound (C) or the fluorine-containing urethane (meth) acrylate compound (C ′).
0 parts by weight, more preferably 50 to 50 parts by weight.
300 parts by weight.

When the resin composition or the coating agent for optical fiber of the present invention is cured by irradiation with active energy rays such as ultraviolet rays, a photopolymerization initiator (E) is used. As the photopolymerization initiator (E) 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 (E) 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 kind of these photopolymerization initiators (E) may be used, or two or more kinds thereof may be used by mixing at an arbitrary ratio. The amount of the photopolymerization initiator (E) to be added is usually preferably 0.1 to 10.0% by weight, more preferably 0.5% by weight, based on the entire resin composition of the present invention or the coating agent for optical fibers. ~ 5.0 w%.

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

The resin composition according to the present invention is generally used 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 applying the composition according to the present invention to a substrate (for example, a core wire for an optical transmission fiber) as a coating agent for an optical fiber, various methods known in the art, for example, a resin composition according to the present invention The optical fiber core wire is continuously immersed in a storage tank containing the resin, pulled up, and irradiated with active energy rays such as ultraviolet rays to cure and form the clad portion. A method in which the coating is continuously applied through a transmission fiber core wire, and an active energy ray such as ultraviolet rays is irradiated to cure and form the clad portion. When the clad portion of the optical transmission fiber is formed by curing, the thickness of the film formed by the coating agent of the present invention is not particularly limited.
It is preferably about 5 to 300 microns.

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

The light source used for curing the resin composition or the coating agent for optical fibers of the present invention by irradiating active energy rays such as ultraviolet rays, for example, includes 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 a clad material of an optical transmission fiber, but also for a coating material such as a glass or plastic coating agent, an LED encapsulant, a lens or the like utilizing the low refractive index. It can also be used for antifouling paints, UV adhesives 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.

Formula (1) and / or Formula (2)
Synthesis Example of Fluorine-Containing (Meth) acrylate Compound (A) Represented by: Example 1: 500.0 g of 3- (2-perfluoro-n-octyl) ethoxy-1,2-epoxypropane and 87.0 g of acrylic acid , 2.5 g of tetramethylammonium chloride, 0.3 of hydroquinone monomethyl ether
g, and the mixture was stirred at 95 to 100 ° C. for 20 hours to be reacted. The obtained reaction solution is dissolved in 1000 mL of toluene, washed twice with a 10% by weight aqueous sodium carbonate solution and three times with a 15% by weight aqueous sodium chloride solution, and then toluene is distilled off under reduced pressure. Liquid 56
5.0 g was obtained (yield 99.2%). The resulting reactant is a liquid at 40 ° C, but is a colorless to pale yellow soft wax at 25 ° C. The obtained reaction product is a mixture of the following structural formulas (7) and (8).

[0043]

Embedded image

[0044]

Embedded image

Example of Synthesis of Fluorine-Containing Urethane (meth) acrylate Compound (C) Example 2: 2-mL was placed in a separable flask of 200 mL.
(Perfluoro-n-octyl) ethyl acrylate 6
0.9 g and 8.5 g of a triisocyanate compound represented by the formula (4): 2-isocyanatoethyl-2,6-diisocyanatocaproate (trade name: LTI, manufactured by Kyowa Hakko Kogyo Co., Ltd.) Further, 0.03 g of dibutyltin dilaurate was added, and the mixture was stirred at 40 ° C.
In this solution, 37.9 g of the fluorine-containing acrylate compound represented by the formulas (7) and (8) obtained in Example 1 was previously melted at 40 to 50 ° C.
Add slowly in a temperature range of
After stirring at 時間 50 ° C. for 1 hour,
After stirring for an hour, the mixture was directly cooled to 40 ° C. To this reaction solution, 14.7 g of 2- (perfluoro-n-octyl) ethanol, which had been finely pulverized in advance, was added not to exceed 50 ° C. while paying attention to heat generation. After adding 2- (perfluoro-n-octyl) ethanol, the mixture was stirred at 40 to 50 ° C. for 3 hours, and further heated to 6
The mixture was stirred at 0 to 70 ° C. for 1 hour to obtain a colorless to pale yellow transparent viscous liquid reaction mixture. The NCO value of this product was measured to be 0.1% by weight or less, the refractive index at 25 ° C was 1.3614, and the viscosity at 25 ° C was 8%.
It was 20 mPa · s. The refractive index of 2- (perfluoro-n-octyl) ethyl acrylate used as a reactive diluent also as a solvent at 25 ° C. was 1.
Since it was 3352, the refractive index of the fluorine-containing urethane acrylate compound obtained in this example at 25 ° C.
It is estimated to be 1.3875.

Synthesis Example of Fluorine-Containing Urethane (Meth) acrylate Compound (C ′) Example 3
(Perfluoro-n-octyl) ethyl acrylate 6
0.9 g and 8.5 g of 2-isocyanatoethyl-2,6-diisocyanatocaproate, and 0.03 g of dibutyltin dilaurate were added.
With stirring. To this solution, 2- (perfluoro-n-octyl) ethanol 1
4.7 g were added not to exceed 50 ° C., paying attention to the exotherm. After adding 2- (perfluoro-n-octyl) ethanol, the mixture was stirred at 40 to 50 ° C. for 1 hour,
After further raising the temperature and stirring at 60 to 70 ° C. for 1 hour, 40
Cooled to ° C. Into this reaction solution, 37.9 g of the fluorine-containing acrylate compound represented by the formulas (7) and (8) obtained in Example 1 was previously melted at 40 to 50 ° C and slowly added while paying attention to heat generation. ~ 50
After stirring at 3 ° C. for 3 hours, the mixture was further stirred at 60 to 70 ° C. for 1 hour to obtain a colorless to pale yellow transparent viscous liquid reaction mixture. When the NCO value of this product was measured, it was 0.1
w% or less, and the refractive index at 25 ° C. is 1.3617.
And the viscosity at 25 ° C. was 830 mPa · s. In addition, 2 used as a reactive diluent also as a solvent
Since the refractive index of-(perfluoro-n-octyl) ethyl acrylate at 25 ° C was 1.3352,
The refractive index of the fluorine-containing urethane acrylate compound obtained in this example at 25 ° C. is estimated to be 1.3881.

Example of resin composition Example 4: 50.0 g of the reaction product obtained in Example 2
0.5 g of hydroxycyclohexyl phenyl ketone was blended and dissolved by heating at 40 to 50 ° C. for 1 hour to prepare a photocurable resin composition. Its refractive index at 25 ° C was 1.3638, and its viscosity at 25 ° C was 760 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 coated with a high-pressure mercury lamp under a nitrogen atmosphere at 1000 μm.
Ultraviolet rays were irradiated at an irradiation intensity of mJ / cm ² to obtain a cured product. Table 1 shows the physical properties of the obtained cured product.

Example 5: Reaction product 5 obtained in Example 3
A photocurable resin composition was prepared by mixing 0.5 g of 1-hydroxycyclohexylphenyl ketone with 0.0 g and heating and dissolving at 40 to 50 ° C. for 1 hour. Its refractive index at 25 ° C. was 1.3641,
Was 770 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.

Table 1 Example 34 Refractive index (25 ° C) * 1 1.3792 1.3793 Young's modulus (MPa) * 2 162 169 Strength at break (MPa) * 2 10.1 10.3 Elongation at break (%) * 2 16.5 16.3 Water absorption (%) * 3 0.2 0.2 Transparency * 4 ○ ○ Antifouling property * 5 ○ ○

Note) * 1 Refractive index: Measured by Abbe refractometer 1T. * 2 Young's modulus, breaking strength, elongation at break: JIS K
It measured according to the method of 7113. * 3 Water absorption: Measured according to the method of JIS K 7209. * 4 Transparency: A cured product having a thickness of 150 to 200 μm was observed, and the presence or absence of a whitened portion was confirmed.・ ・ ・: There is no whitened portion in the cured product. * 5 Antifouling property: Ten lines having a line width of 2 mm were drawn with black oil-based magic ink on the surface of the cured product, and the surface was wiped off with gauze soaked with methanol to observe the state where the magic ink remained.・ ・ ・: No trace of the magic ink line remains on the surface of the cured product.

[0051]

As is clear from Examples 4 and 5 and Table 1, the resin composition of the present invention can be rapidly cured by irradiating active energy rays such as ultraviolet rays. It has good flexibility without deteriorating mechanical strength. The cured product of the resin composition of the present invention contains a fluorine-containing urethane (meth) acrylate compound using a triisocyanate compound as a raw material, and further contains a fluorine-containing urethane (meta) compound using a triisocyanate compound as a raw material. ) Since the fluorine-containing alcohol compound is reacted with the acrylate compound and bonded, the fluorine-containing urethane (meth) acrylate compound has a high fluorine content, so that the refractive index is lower and the transparency is excellent, so that light transmission is achieved. It can be applied to the cladding layer of the optical fiber. Furthermore, since it has excellent antifouling properties, it can be applied as a coating agent for various articles.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H050 AB44Y AB47Y AB50Y 4J027 AG12 AG28 CB10 CC04 CC05 CD03 CD04 CD05 4J034 BA02 BA03 CA02 CB01 CC01 CC02 CD06 FA02 FB01 FD01 HA01 HA08 HA11 HB12 HC01 JA02 JA21 KA01 KB02 KB04 QC07 AL08P AL66P AL67P BA34P BB12P BB13P BB17P BB18P JA32 JA35

Claims (7)

[Claims] (1) Formula (1) And / or formula (2) (Wherein R ₁ is H or CH ₃ , and X is C _m F _{2m + 1} −
_{(CH 2) a -, C} m F 2m + 1 - (CH 2) a -O-, CF 3 C
_{F (CF 3) C n F} 2n - (CH 2) a -, CF 3 CF (C
_{F 3) C n F 2n -} (CH 2) a -O-, H- (CF 2 CF 2)
_b - (CH _{2) a} - or _{H- (CF 2 CF 2) b} - (C
H ₂ ) _a —O— (where m is an integer of 1 to 12, and n is 0 to 0)
An integer of 10, a is an integer of 0 to 2, and b is an integer of 1 to 4. ). ) And a fluorine-containing (meth) acrylate compound (A) represented by the formula (3): The triisocyanate compound represented by the formula (1) and / or the fluorine-containing (meth) acrylate compound (A) represented by the formula (2) and the isocyanate group of the triisocyanate represented by the formula (3) 1.00: 3.
The reaction is carried out in advance so as to give a ratio of 00 to 2.99: 3.00, and the remaining isocyanate groups of the obtained reaction product are added with the formula (4). Wherein Y is H, F or CF ₃ CF (CF ₃ );
h is an integer of 1 to 12, and i is 1 or 2. However, when Y is CF ₃ CF (CF ₃ ), h is 0 to
Represents an integer of 10. A resin composition containing a fluorine-containing urethane (meth) acrylate compound (C) obtained by reacting a fluorine-containing alcohol compound (B) represented by the formula (1). 2. The fluorine-containing alcohol compound (B) represented by the formula (4) according to claim 1 and the triisocyanate compound represented by the formula (3) are combined with a fluorine-containing alcohol compound represented by the formula (4). The molar ratio of the alcohol compound (B) and the isocyanate group of the triisocyanate represented by the formula (3) is 0.0
1: 3.0 to 2.00: 3.00 is reacted in advance, and the remaining isocyanate groups of the obtained reaction product are represented by the formula (1) and / or the formula (2). A resin composition containing a fluorine-containing urethane (meth) acrylate compound (C ′) obtained by reacting a fluorine-containing (meth) acrylate compound (A). (3) Formula (5) (Wherein, R ₂ is H or CH ₃ , Z is H, F or CF ₃ CF (CF ₃ ), j is an integer of 1 to 6,
k represents an integer of 1 to 12. Where Z is CF ₃ CF
In the case of (CF ₃ ), j is 1 or 2, and k represents an integer of 0 to 10. The resin composition according to claim 1, further comprising a monofunctional (meth) acrylate compound (D) represented by the formula: 4. The resin composition according to claim 1, further comprising a photopolymerization initiator (E). 5. The resin composition according to claim 1, wherein the resin composition is used for an optical article. 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 any one of claims 1 to 6.