JPH01223107A - Curable composition - Google Patents

Abstract

PURPOSE:To provide the title composition, capable of immediately crosslinking and curing by irradiation of active energy rays such as electron beams or by heating, and suitable for forming cladds for optical fibers, comprising, as the main components, a specified fluorine-containing polymerizable unsaturated resin and fluorine-containing unsaturated monomer. CONSTITUTION:The objective curable copolymer composition comprising, as the essential components, a resin with polymerizable double bonds (pref., having 5,100-31,000 number-average molecular weight) obtained by introducing polymerizable double bond-containing groups into a polymer composed of, as the monomer components, a fluoroalkyl (meth)acrylate of formula I (R is CH3 or H; X is F or H; m is 1 or 2; n is 1-12) [e.g., 1H,1H,3H-tetrafluoropropyl (meth)acrylate] and fluorine-containing di(meth)acrylate of formula II (p is 1-12) (e.g., compound of formula III or IV).

Description

[Detailed description of the invention] Industrial applications The present invention relates to novel curable compositions.

Conventional technology and its challenges Optical fiber technology has developed significantly in recent years, and has been widely used in communication, control,
It has been put into practical use in a wide range of fields such as various optical applied measurements. Examples of this technology include a system that converts various signals into optical signals, transmits them through optical fibers, converts the transmitted optical signals into target signals, and receives the signals.

The tip fiber consists of a core at the center and a cladding at the periphery. The core usually has a refractive index of about 1.43 to 1.60, is made of stretched glass such as quartz glass, or a plastic fiber such as polymethyl methacrylate, and has a thickness of about 5 to 1000 μm. Often. The cladding is formed around the core and has a thickness of about 3 to 1
It is a transparent coating layer with a refractive index lower than that of the core of about 00μ.

Optical signals propagate through the core while undergoing repeated total reflection at the interface between the core and cladding. At this time, in order to efficiently transmit long distances without leaking the optical signals to the outside and causing loss, The material forming the cladding is required to have various properties as described below.

(1) It has a lower refractive index than the core.

(2) Good adhesion to the core.

(3) Good flexibility and bendability.

(4) No crystallinity.

(5) Avoid absorbing light as much as possible.

(6) No thermal decomposition or thermal shrinkage.

(7) Changes in physical properties due to temperature are small.

(8) Excellent water and oil resistance.

(9) Excellent curability and strength.

Conventionally, as a material for forming the cladding, for example, silicone resin, fluorine-containing resin, quartz glass containing boron, fluorine, etc. have been used. However, these materials
None of them have sufficient performance. That is, silicone resin has the disadvantage that it has a high refractive index, tends to shrink due to thermal decomposition, has large changes in physical properties with respect to temperature, and is inferior in hardenability and strength. In addition, as a fluorine-containing resin,
It is known to use non-crosslinked thermoplastic resins such as a copolymer of vinylidene fluoride and tetrafluoroethylene (Japanese Patent Publication No. 53-21660) or a fluoroalkyl methacrylate polymer (Japanese Patent Publication No. 43-8978). However, since the former has residual crystallinity, light is scattered at the interface between the core and cladding, reducing transmission performance, while the latter has insufficient adhesion with the core, flexibility, and bendability. However, they each have the drawback of large changes in physical properties due to temperature. In addition, quartz glass containing boron, fluorine, etc. has the disadvantage that it does not have sufficient flexibility and bendability, and it is also extremely expensive.
It is expensive and economically undesirable.

In addition to the above, it is known to use active energy ray-curable resins containing fluorine-containing polymers having no polymerizable double bonds and fluorine-based monomers (Japanese Unexamined Patent Publication No. 62-1999
643), the cured product obtained by irradiating the resin with active energy rays does not chemically bond the fluorine-containing polymer and the polymer derived from the fluorine monomer, so the phase of both polymers is The drawbacks remain that the solubility is insufficient and the transmission loss changes greatly with temperature. Furthermore, the fluorine-based polymer has a number average molecular weight of 600,000 or more in order to give it a particle size that can be applied to optical transmission fibers. If too much is used, the viscosity of the system increases, making it difficult to apply, or it is not compatible with fluorine-based monomers and may separate during storage, or it may not be possible to obtain curing properties with excellent cold and heat resistance. There is.

Means for Solving the Problems The present inventor conducted extensive research in order to develop a cladding material that eliminates the above-described deficiencies of conventional cladding materials and satisfactorily satisfies all of the above-mentioned required performances. As a result, a composition containing a specific fluorine-containing polymerizable unsaturated resin and a specific fluorine-containing unsaturated monomer is rapidly crosslinked and cured by irradiation with active energy rays such as ultraviolet rays or electron beams, or by heat. However, they have discovered that the cured product satisfactorily achieves the above-mentioned required performance, and have completed the present invention.

That is, the present invention is based on (a) the general formula [wherein R represents a methyl group or a hydrogen atom, and X represents a fluorine atom or a hydrogen atom, respectively]; m is 1 or 2, n is 1 to 12
indicates an integer. ] A polymerizable double bond-containing resin obtained by introducing a polymerizable double bond-containing group into a polymer having a fluoroalkyl (meth)acrylate as a monomer component represented by (b) general formula % formula % [ In the formula, R and m have the same meanings as above, and p is 1 to 1
Indicates an integer of 2. ] It concerns on the curable composition which has the fluorine-containing di(meth)acrylate represented by these as an essential component.

In the present invention, the polymerizable double bond-containing resin used in component (A) is a polymer containing a fluoroalkyl (meth)acrylate represented by general formula (I) as a monomer, and This is achieved by introducing the . The resin is usually reacted with the functional group to form a copolymer containing the monomer of general formula (I) and a vinyl monomer containing a functional group for introducing a polymerizable double bond as a comonomer. A polymerizable double bond is introduced into the side chain by reacting a compound containing a functional group and a polymerizable double bond.

Examples of vinyl monomers containing a functional group for introducing the polymerizable double bond include epoxy group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, carboxyl group-containing vinyl monomers, and isocyanate group-containing vinyl monomers. Examples include vinyl monomers.

In addition, as a compound containing a functional group and a polymerizable double bond that reacts with the functional group, a compound that reacts with the vinyl monomer by an ester bond forming reaction, a urethane bond forming reaction, etc. is used. It is preferable to use one selected from the following. For example, when introducing a polymerizable double bond by an ester bond forming reaction, when an epoxy group-containing vinyl monomer or a hydroxyl group-containing vinyl monomer is used as the functional group-containing comonomer of the copolymer, the copolymer It is preferable to use a carboxyl group-containing vinyl monomer as the compound to be reacted in the coalescence, and conversely, when a carboxyl group-containing vinyl monomer is used as the comonomer, an epoxy group-containing vinyl monomer is used as the compound to be reacted. Alternatively, it is preferable to use a vinyl monomer containing a hydroxyl group. For example, when introducing a polymerizable double bond by a urethane bond forming reaction, when a hydroxyl group-containing vinyl monomer is used as the comonomer, a hydroxyl group-containing vinyl monomer is used as the compound to be reacted, and a polyisocyanate compound is used. or a vinyl monomer containing an isocyanate group may be used as the compound to be reacted, and when a vinyl monomer containing an isocyanate group is used as the comonomer, a vinyl monomer containing a hydroxyl group may be used as the compound to be reacted. You can use quantities.

In the present invention, n in the fluoroalkyl (meth)acrylate of the above general formula used in component (a) is 2 to
Particularly preferred is an integer of 8.

Preferred specific examples of the fluoroalkyl (meth)acrylate of the above general formula include IH, 11,3H-tetrafluoropropyl (meth)acrylate) (n=2),
IH, IH, 5H-octafluoropentyl (meth)acrylate (n=4), IH, IH-)lysosylfluorohebutyl (meth)acrylate (n=6), I
Among these, particularly preferred are IH, IH, 5H,
-Octafluoropentyl (meth)acrylate, IH
, 1) 1.2M, 2H-hebutadecafluorodecyl (meth)acrylate.

Examples of the epoxy group-containing vinyl monomer include glycidyl (meth)acrylate and methylglycidyl (meth)acrylate.

Preferred examples of the hydroxyl group-containing vinyl monomer include acrylic monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and caprolactone-modified (meth)acrylate.

Examples of carboxyl group-containing vinyl monomers include (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylmaleic acid, and 2-(meth)acryloyloxyethyl phthalate. Examples include unsaturated basic acids such as acids, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and β-carboxyethyl (meth)acrylate.

In addition, as the isocyanate group-containing vinyl monomer, for example, isocyanate ethyl (meth)acrylate, m-
Examples include isopropenyl-α,α'-dimethylbenzyl isocyanate, a product obtained by adding approximately equal moles of the above-mentioned hydroxyl group-containing vinyl monomer and a polyisocyanate compound through a urethane bond, and the like.

Here, the polyisocyanate compound is a compound having two or more isocyanate groups in one molecule,
For example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4°4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2°6)-diisocyanate, 1.3- (Isocyanate methyl)cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octa Examples include decylene diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, triphenylmethane triisocyanate, naphthylene diisocyanate, and among these, tolylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, and the like are particularly preferred.

The copolymer used as a polymer for introducing a polymerizable double bond in component (A) is a vinyl containing a monomer of general formula (I) and a functional group for introducing a polymerizable double bond. Although it is necessary to use a monomer as a comonomer,
Furthermore, other monomers other than these may be used in combination as necessary. Other monomers include, for example, esterified products of (meth)acrylic acid and monohydric alcohol (1 to 24 carbon atoms), hydroxyalkyl (2 to 8 carbon atoms) esters of (meth)acrylic acid, styrene and its Examples include derivatives, (meth)acrylonitrile, vinyl acetate, vinyl chloride, etc., and one or more of these types can be used.

The above-mentioned "copolymer" is produced by solution polymerization of at least one monomer of general formula (I) and at least one vinyl monomer containing a functional group for introducing a polymerizable double bond. It can be obtained by copolymerizing by a conventional method such as suspension polymerization.The ratio of these two components is determined based on the total weight of the two components, from the viewpoint of curability and refractive index of the composition of the present invention.
0 to 97% by weight, especially 70 to 95% by weight, the latter being 50 to 3% by weight
% by weight, especially 30-5% by weight is preferred. Also,
When using other monomers as necessary, it is appropriate to use them in a proportion of 100 parts by weight or less based on the total of 100 parts by weight of both of the above components. The number average molecular weight of these copolymers is preferably in the range of about 3,000 to 50,000, particularly about 5,000 to 30,000.

Component (a) used in the present invention is a compound containing a functional group that reacts with the functional group and a polymerizable double bond, which is reacted with the functional group contained in the above copolymer to form an ester bond, and a urethane bond. It can be obtained by introducing a polymerizable double bond into the copolymer by addition through a formation reaction or the like. The amount of addition is not particularly limited, but the degree of unsaturation (the number of equivalents of polymerizable double bonds per number average molecular weight of 1000) of the addition reaction product is 0.2 to 3.0, particularly 0.3 to 2.0. It is preferable to set the amount within the range. The number average molecular weight of the resin of component (a) obtained by introducing a polymerizable double bond is:
Approximately 3,100 to 62,000, particularly approximately 5,100 to 3,100
The range is preferably about 0. Number average molecular weight is approximately 3
If the number average molecular weight is less than 100, cold and heat resistance, weather resistance, etc. will deteriorate, while if the number average molecular weight is greater than 62,000, the compatibility with component (b) will deteriorate and it will be easy to separate, or the copolymerizability with component (b) will deteriorate. If the cured product deteriorates in refractive index, transmission loss, and surface tension, it is not suitable.

Preferred specific examples of the polymerizable double bond-containing resin used as component (a) include the following.

(A) Polymerization obtained by esterifying a carboxyl group-containing vinyl monomer to a copolymer containing the monomer of general formula (I) and an epoxy group-containing vinyl monomer or a hydroxyl group-containing vinyl monomer as a comonomer. Resin containing double bonds.

(B) Polymerization obtained by esterifying an epoxy group-containing vinyl monomer or a hydroxyl group-containing vinyl monomer to a copolymer containing the monomer of general formula (I) and a carboxyl group-containing vinyl monomer as a comonomer. Resin containing double bonds.

(C) A polymerizable doublet formed by urethanizing a hydroxyl group-containing vinyl monomer via a polyisocyanate compound to a copolymer containing the monomer of general formula (I) and a hydroxyl group-containing vinyl monomer as a comonomer. Bond-containing resin.

(D) A polymerizable double bond-containing resin obtained by urethanizing an isocyanate group-containing vinyl monomer into a copolymer containing the monomer of general formula (I) and a hydroxyl group-containing vinyl monomer as a comonomer.

(E) A polymerizable double bond-containing resin obtained by urethanizing a hydroxyl group-containing vinyl monomer into a copolymer containing the monomer of general formula CI) and an isocyanate group-containing vinyl monomer as comonomers.

In the ester bond forming reaction when producing the resins (A) and (B) above, the ratio of the copolymer and the compound to be reacted is in the range of about 0.3 to 1 mole per mole of the former functional group. It is preferable that

Further, the resin (C) above is preferably produced, for example, in the following manner. ■A polyisocyanate compound is added to the hydroxyl group in an approximately equimolar ratio per mole of hydroxyl group in the above copolymer through a urethane bond, and then a hydroxyl group-containing vinyl monomer is added to the isocyanate group in the adduct. A polymerizable double bond-containing group is introduced into the copolymer by adding a hydroxyl group in the polymer via a urethane bond. ■An adduct is prepared in advance by reacting equimolar amounts of a polyisocyanate compound and a vinyl monomer containing a hydroxyl group to form a urethane bond, and then the isocyanate group in the adduct is reacted with the hydroxyl group in the above copolymer to form a urethane bond. By reacting, a polymerizable double bond-containing group is introduced into the copolymer. The ratio of the copolymer to the adduct at this time is preferably in the range of about 0.3 to 1 mole of the adduct per mole of hydroxyl group in the copolymer.

In addition, in the production of the resin (D) above, for example, the isocyanate group-containing vinyl monomer is added to the isocyanate group-containing vinyl monomer at a ratio of about 0.3 to 1 mole per 1 mole of hydroxyl group in the copolymer. It is preferable to introduce polymerizable double bonds into the above copolymer by adding a polymer via a urethane bond.

In addition, in the production of the resin (E) above, for example, about 0.3 to 1 mole of a hydroxyl group-containing vinyl monomer is added to the isocyanate group contained in the above copolymer via a urethane bond per 1 mole of isocyanate group. It is preferable to introduce polymerizable double bonds into the above-mentioned copolymer. It has the function of lowering the refractive index of a cured product (for example, a cured film) and maintaining the physical strength of the cured product together with the following component (b). Furthermore, when the content of polymerizable double bonds is increased within the range of the degree of unsaturation mentioned above, the molecular weight between crosslinks decreases, and the hardness of the cured product can be increased.

In the present invention, fluorine-containing di(meth) used in component (b)
Acrylates are general acrylates that have polymerizable double bonds at both ends of the molecule that undergo a radical copolymerization reaction with the polymerizable double bonds of component (a) by generating radicals when exposed to active energy rays such as ultraviolet rays or electron beams or heat. It is a compound represented by formula (n).

Specific examples of the compound represented by general formula (n) include the following.

CH2-CCOOCHCl2-CC00CH2CF2C
F2CF2CHH Cl2-CC00CH2CF2CF2CF2CH,0O
CC-CH2CH, CH3 CH2-CCOOCH2CF2 CF2CF2CH20
0CC-CH2HCH.

CH2-CCOOCH2(CF2 CF2)2 CH2
00CC-CH2HH Cl2-CCOOCH2(CF2 CF2)2 CH2
00CC-CH2CH3CH3 CH2-CCOOCH2(CF2 CF2)2 CH2
00CC-CH2HCHa CH2-CCOOCH2(CF2 CF2)a CH2
00CC=CH2HH Cl2-CCOOCH2(CF2 CF2)a CH2
00CC-CH2CH3CHa CH2”CCOOCH2(CF2 CF2)6 CH2
00CC-CH2CHs
CH3CH2 intestinal CCOOC2Ha (CF
CF2)a C2H400C■CH2CHs
CFs CH3 general formula (n)
These compounds can be used alone or in combination of two or more.

The composition of the present invention is obtained by mixing the above-mentioned (a) component and (b) component, and the composition ratio of these two components is based on the total weight of the two components. 5-95
Approximately 20-80% by weight, component (b) 95-80% by weight
It is preferably about 5% by weight, particularly 80 to 20% by weight. In the present invention, used as a reactive diluent (oral)
If the proportion of the components is more than 95% by weight, the mechanical properties of the cured product tend to deteriorate, while if it is less than 5% by weight, the viscosity becomes high and coating becomes difficult, which is not preferable.

The fluorine-containing di(meth)acrylate of component (B) has a low viscosity in itself, so it can reduce the viscosity of the composition, and the radicals formed by the polymerizable double bond between component (B) and component (A) can reduce the viscosity of the composition. The reaction is easily carried out, and a cured product having excellent compatibility between component (b) and component (a) can be formed. In addition, since the component (B) has polymerizable double bonds at both ends of the molecule, the crosslinking reaction of the component (B) and itself takes place, resulting in a cured product with excellent physical strength, hardness, etc. Form. Furthermore, since component (b) contains fluorine atoms in its molecules, it forms a cured product with low surface tension and low refractive index.

In the present invention, in addition to the components (a) and (b), polyester (meth)acrylate resin, ethylenically unsaturated group-containing epoxy resin, ethylenically unsaturated group-containing polyurethane resin, ethylenically unsaturated group-containing acrylic resin, Polymerizable double bond-containing resins such as ethylenically unsaturated group-containing silicone resins, esterified products of (meth)acrylic acid and monohydric alcohol (carbon number 1 to 24), hydroxyalkyl (carbon number) of (meth)acrylic acid 2-8) Esters, styrene and its derivatives, (meth)acrylonitrile, vinyl acetate, vinyl chloride, (meth)acrylic acid and polyhydric alcohols (
products obtained by reacting (meth)acrylic acid with adducts of polyhydric alcohols and ethylene oxide or propylene oxide, products obtained by reacting adducts of polyhydric alcohols with ε-caprolactone (meth) ) A product obtained by reacting acrylic acid, a phosphorus-containing polymerizable unsaturated monomer, a fluoroalkyl compound represented by the general formula (,I)
It can be used by adding compounds such as polymerizable double bond-containing monomers such as meth)acrylate. Of these compounds,
Fluoroalkyl (meth) represented by general formula (I')
It is preferable to use acrylate, and in that case, the amount used is approximately 200 parts by weight or less, preferably 100 parts by weight or less, per 100 parts by weight of the mixture of components (a) and (b). In addition, when using other compounds, the amount used is a mixture of component (a) and component (b).
It is appropriate that the amount is about 50 parts by weight or less, preferably 20 parts by weight or less from the viewpoint of compatibility.

Furthermore, in addition to the above-mentioned compounds, coloring pigments, extender pigments, dyes, organic or inorganic fillers, etc. may be added and used. When the composition of the present invention is used as a heat-polymerizable composition, the proportions of the pigments, dyes, and fillers to be added are not particularly limited, and can generally be added in the range of about 0 to 70% by weight.
Further, when used as an active energy ray-curable type, it can be added in an amount of usually 0 to 20% by weight to the extent that it does not interfere with curability.

The thus obtained curable composition of the present invention undergoes a crosslinking reaction and is cured by irradiation with active energy rays such as ultraviolet rays and electron beams or by heat. ...When the composition of the present invention is cured by irradiation with ultraviolet rays, it is preferable to add a photopolymerization initiator to the composition in advance. Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether,
Benzoin n-butyl ether, benzyl, benzophenone, p-methylbenzophenone, diacetyl, eosin, thionin, Michler's ketone, acetophenone, 2-
Chlorothioxanthone, anthraquinone, chloroanthraquinone, 2-methylanthraquinone, α-hydroxyisobutylphenone, p-isopropyl-α-hydroxyisobutylphenone, α,α′-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexyl Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, methylbenzoinformate,
2-Methyl-1-[4-(methylthio)phenyl]-2
- Morpholinopropene, dichlorothioxanthone, diisopropylthioxanthone, phenyl disulfide -
Examples include 2-nitrosofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, and tetramethylthiuram disulfide, and one type or a combination of two or more of these can be used.

The amount of the photopolymerization initiator to be used is generally 0.1 to 10 parts by weight per 100 parts in total of components (a) and (b). Furthermore, for the purpose of promoting the photocrosslinking reaction by the photopolymerization initiator, a photopolymerization accelerator can be used in combination with the initiator. Examples include tertiary amines, alkyl phosphines represented by triphenylphosphine, and thiols represented by β-thioglycol.

Examples of irradiation sources for curing by ultraviolet irradiation include mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arcs, metal halide lamps, sunlight, and the like. The atmosphere in which ultraviolet rays are irradiated is preferably air or an inert gas. Moreover, when the atmosphere to be irradiated is air, it is particularly preferable to use a high-pressure mercury lamp as the irradiation source. The amount of ultraviolet rays irradiated is not particularly limited, but is usually 10 to 2000 m.
It is appropriate to set it to about J/(to)2.

Examples of electron beam accelerators used for curing by electron beam irradiation include Cockcroft type, Cockcroft-Walton type, resonant transformer type, transformer type, insulated core transformer type, Dynamidron type, linear filament type, and broadband type. Examples include beam type, area beam type, cathode electronic type, and high frequency type. Further, the irradiation of electron beams is not limited as long as the dose necessary to cure the composition is given, but
-Generally about 0.5-20M at about 100-2000KeV
irradiate with a dose of rad. The atmosphere in which the electron beam is irradiated is
Preferably it is an inert gas.

Further, when curing by heat, it is preferable to add a thermal polymerization catalyst to the composition. Thermal polymerization catalysts include azo catalysts such as azobisisobutyronitrile, organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, and lauroyl peroxide, and cobalt naphthenate and naphthene as polymerization promoters for organic peroxides. Some contain manganese acid, dimethylaniline, phenylphosphonic acid, vanadyl acetylacetate, etc. The amount of thermal polymerization catalyst used is usually 0.1 to 10 parts by weight per 100 parts by weight of components (a) and (b), and the amount of polymerization accelerator used is the same <0.1 parts. ~5 parts by weight is preferable. Further, the heat curing conditions are usually room temperature to about 100°C.

Effects of the Invention The curable composition of the present invention is particularly suitable for forming the cladding of optical fibers. It is completely satisfying. That is, for example, a core made of quartz glass or the like drawn into a thread shape is coated with the composition of the present invention by a method known per se such as line drawing or dip coating, and then irradiated with active energy rays such as ultraviolet rays or electron beams. When heated, the coating is quickly crosslinked and cured, so that a cladding can be easily formed, and thus a high-performance optical fiber can be obtained.

This cladding fully satisfies all of the above-mentioned required performances. In particular, in the composition of the present invention, the fluorine atom content can be adjusted to about 25 to 60% by weight, and thereby the refractive index can be adjusted in the range of about 1.45 to 1.36, so it is easy to obtain a low refractive index. , and therefore more light can be transmitted. In addition, it is hard and has excellent flexibility and bendability, and its physical properties change little due to temperature, so it has characteristics such as improved fixation of the core. Flexibility and bendability are particularly excellent when a composition containing urethane bonds is used. In addition, since an optical fiber with a large NA (numerical aperture, defined by the formula Q, where N1 indicates the refractive index of the core and N2 indicates the refractive index of the cladding) can be obtained, the acceptance angle becomes large. , more light can be introduced into the optical fiber. Therefore, when used in light guides for lighting, decoration, etc., the output light becomes stronger, and the screen of image fibers for endoscopes etc. can be brightened, and when used for communication, the signal strength increases and the light on the input side and light receiving side increases. The exchange loss between electricity and electricity is reduced, and low-cost replacement elements can be used as replacement elements.

Therefore, an optical fiber having a cladding made of the composition of the present invention can be suitably used in various optical fiber technologies such as communications, image guides, light guides, optical fiber-based measurement, and the like.

Furthermore, since the composition of the present invention has properties of low surface tension and low refractive index, it can be used in water repellents, surface conditioning agents, anti-reflection coatings, piezoelectric elements, UV resists, EB resists, ion exchange membranes, etc. can do. Furthermore, the composition of the present invention has good weather resistance and can be used as an exterior paint.

EXAMPLES Next, the present invention will be explained in more detail with reference to production examples of component (a), examples, and comparative examples. In each example, parts and percentages are in principle based on weight.

Production Example 1 60 parts of methyl isobutyl ketone and 60 parts of meta-xylene hexafluoride were placed in a four-bottle flask (A)-I;
After putting in the heat and raising the temperature to 110℃,
170 parts of H,2H,2H-hebutadecafluorodecyl acrylate, 30 parts of glycidyl methacrylate and t-
6 parts of butylperoxy-2-ethylhexanoate was added dropwise over 3 hours using a dropping funnel, and the mixture was aged for 1 hour. Next, 1 part of t-butylperoxy-2-ethylhexanoate and 13 parts of methyl isobutyl ketone were added dropwise over 1 hour and aged for 7 hours to obtain a number average molecular weight of about 150.
A copolymer of No. 00 was obtained. In this, 0.1 hydroquinone
1 part of triethylamine and 16 parts of acrylic acid and kept at 110°C for 5 hours, the number average molecular weight was about 1.
6000. A noacryloyl group-containing resin with a degree of unsaturation of 1.0 was obtained. This resin solution was dried under reduced pressure at 40° C. to remove the solvent, resulting in a resin with a solid content of 100%.

Production Example 2 (A)-II: In the same manner as (A)-I, IHlIH,
A copolymer consisting of 190 parts of 5H-octafluoropentyl acrylate and 1 part of glycidyl methacrylate plus 6 parts of acrylic acid has a number average molecular weight of about 16,000.
An acryloyl group-containing resin with an unsaturation degree of 0.4 was synthesized.

This was similarly made into a resin with a solid content of 100%.

Production Example 3 (A)-III; In the same manner as (A)-I, IHlIH
, 21,2H-heptadecafluorodecyl acrylate, 80 parts of IH, IH, 5H-octafluoropentyl acrylate, and 40 parts of glycidyl methacrylate to which 20 parts of acrylic acid was added. An acryloyl group-containing resin with a saturation degree of 1.3 was synthesized. This was similarly made into a resin with a solid content of 100%.

Production Example 4 (A)-IV: 60 parts of methyl isobutyl ketone and 60 parts of meta-xylene hexafluoride were placed in a 2J2 four-bottle flask, and the temperature was raised to 110'C.
1. 170 parts of IH,2H,2H-hebutadecafluorodecyl acrylate, 20 parts of acrylic acid, and 6 parts of t-butylperoxy-2-ethylhexanoate were added dropwise over 3 hours using a dropping funnel, and aged for 1 hour. did.

Next, 1 part of t-butyl peroxy-2-ethylhexanoate and 13 parts of methyl isobutyl ketone were added dropwise over 1 hour, and aged for 7 hours to obtain a number average molecular weight of 1400.
A copolymer of 0 was obtained.

To this, 0.1 part of hydroquinone, 1 part of triethylamine
110 parts and 35 parts of glycidyl methacrylate were added.
By keeping it at ℃ for 5 hours, the number average molecular weight was 15,000.
, an acryloyl group-containing resin with an unsaturation degree of 1.1 was obtained. This resin solution was dried under reduced pressure at 40° C. to remove the solvent, resulting in a resin with a solid content of 100%.

Production Example 5 (A)-V; In the same manner as (A)-1V, IHlIH,
A copolymer consisting of 190 parts of 5H-octafluoropentyl acrylate and 7.5 parts of methacrylic acid to which 10 parts of glycidyl methacrylate was added, resulting in a number average molecular weight of 17.
000, an acryloyl group-containing resin with a degree of unsaturation of 0.4 was synthesized.

This was similarly made into a resin with a solid content of 100%.

Production Example 6 (A)-VIA In the same manner as (A)-IV, IHllH
, 80 parts of glycidyl methacrylate was added to a copolymer consisting of 80 parts of 2H,21-heptadecafluorodecyl acrylate, 80 parts of IH,IH,5H-octafluoropentyl acrylate, and 20 parts of acrylic acid, with a number average molecular weight of 19,000; An acryloyl group-containing resin with an unsaturation degree of 1.3 was synthesized. Similarly, the solid content is 100%
made of resin.

Production Example 7 (A)-■; In the same manner as (A)-IV, IHlIH
, 2H, 2H-hebutadecafluorodecyl acrylate and 20 parts of acrylic acid.
-32 parts of hydroxyethyl methacrylate and 1)-)
By adding 2 parts of luenesulfonic acid and maintaining the mixture at 120° C. for 3 hours, an acryloyl group-containing resin having a number average molecular weight of 14,500 and a degree of unsaturation of 1.0 was synthesized. This was similarly made into a resin with a solid content of 100%.

Production Example 8 (A)-■; 60 parts of methyl isobutyl ketone and 60 parts of meta-xylene hexafluoride in a 2ρ four-bottle flask.
of IH and I after increasing the temperature to 110℃.
170 parts of H,2H,2B-heptadecafluorodecyl acrylate, 10 parts of 2-hydroxyethyl methacrylate
1 part and 6 parts of t-butylperoxy-2-ethylhexanoate were added dropwise over 3 hours using a dropping funnel, and the mixture was aged for 1 hour. Then 1 part of t-butyl peroxy-2-ethylhexanoate and 1 part of methyl isobutyl ketone
was added dropwise over 1 hour and aged for 7 hours to obtain a copolymer with a number average molecular weight of 15,000. To this, 22 parts of an adduct obtained by reacting 1 mole of 2-hydroxyethyl acrylate per 1 mole of tolylene diisocyanate and 0.1 part of hydroquinone were added, and the mixture was reacted at 100°C for 3 hours to achieve a number average molecular weight of 16,500. , unsaturation level 0
．． 38 acryloyl group-containing resins were obtained. This resin solution was dried under reduced pressure at 40°C to remove the solvent and the solid content was 100%.
made of resin.

Production Example 9 (A)-1X; In the same manner as (A)-■, IH9IH,
A copolymer consisting of 150 parts of 3H-tetrafluoropropyl acrylate and 30 parts of 2-hydroxyethyl methacrylate was reacted with 77 parts of an equimolar adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate to obtain a number average molecular weight of 21,500, An acryloyl group-containing resin with an unsaturation degree of 1.0 was synthesized. This was similarly made into a resin with a solid content of 100%.

Production example 10 (A)-X; IH in the same manner as (A)-■.

IH, 5H-octafluoropentyl acrylate) 16
0 parts and 60 parts of an equimolar adduct of isophorone diisocyanate and 2-hydroxyethyl methacrylate were reacted with 20 parts of 2-hydroxyethyl acrylate to form a copolymer with a number average molecular weight of about 12,000 and a degree of unsaturation of 0.
．． 71 acryloyl group-containing resins were synthesized.

This was similarly made into a resin with a solid content of 100%.

Examples 1 to 10 and Comparative Examples 1 to 9 Curable compositions of Examples and Comparative Examples were obtained by mixing the components shown in Table 1.

The comparative resins used in each comparative example are as follows.

Comparative Resin-■ This is a resin with a number average molecular weight of 16,000 obtained by replacing the same amount of glycidyl methacrylate with methyl methacrylate in (a)--2 above and omitting the addition reaction of acrylic acid.

Comparative resin - ■ Obtained by producing in the same manner as (i)-I except that IH, IH, 2H, 2H-hebutadecafluorodecyl acrylate in (i)-I was replaced with 2-ethylhexyl acrylate. The number average molecular weight was approximately 15,000, and the degree of unsaturation was 1.
0 resin.

Comparative Resin - (1) A resin with a number average molecular weight of about 15,000 obtained by replacing acrylic acid with butyl methacrylate in (a)-IV above and omitting the addition reaction of glycidyl methacrylate.

Comparative resin - ■ Obtained in the same manner as (A)-1V except that IH, IH, 2H, 2H-heptadecafluorodecyl acrylate in (A)-IV was replaced with 2-ethylhexyl acrylate. It is a resin with a number average molecular weight of about 16,500 and a degree of unsaturation of 1.1.

Comparative Resin - (1) This is a resin with a number average molecular weight of about 16,000 obtained by replacing 2-hydroxyethyl acrylate with ethyl acrylate in (a) - (1) and omitting the subsequent reaction of the adduct.

Comparative resin - ■ Obtained by manufacturing in the same manner as in (i)-■ except that IH, IH, 2H, 2H-heptadecafluorodecyl acrylate in (i)-■ was replaced with 2-ethylhexyl acrylate. Number average molecular weight approximately 16,500, degree of unsaturation 0.
38 resin.

All numerical values in Table 1 above indicate parts. In addition, in Table 1, "Glocure 11734" is a photopolymerization initiator made by Merck & Co., Ltd. and whose active ingredient is α-hydroxyisobutylacetophenone. "Irgacure 651" is a 2,2-dimethoxy- This is a photopolymerization initiator containing 2-phenylacetophenone as an active ingredient.

Next, each of the curable compositions obtained in Examples and Comparative Examples was applied to a quartz glass with a diameter of 200 μm (20° C. using a sodium D wire).
A core with a refractive index of 1.458) was line-painted using a die coater to the thickness listed in Table 2, and cured by irradiating it with the amount of ultraviolet rays listed in Table 2 using a high-pressure mercury lamp. A cladding was formed to obtain an optical fiber.

The refractive index and NA of the cladding, as well as the transmission loss after the i-period and the cold/heat resistance test, were measured for the obtained fiber. The test methods for the refractive index, transmission loss, and cold/heat resistance test of the cladding are as follows.

Refractive index of 0 cladding: Place the sample on a glass plate at approximately 50 μm.
The film was coated to a thickness of 1,000 ml, cured by UV irradiation, and then made into a free film and measured using an Atsube refractometer. NA was calculated using this result.

0 transmission loss: An optical fiber that is slightly longer than IKm is used, and the light from the laser diode is transmitted through the input element at one end, and the output optical power (P o
) was measured, a portion of IKm was cut from the output end to the input end, and the output optical power at that point was defined as the input optical power (Pi) from the cut section to the output end, and was determined by the following formula.

a=-(10/L) ・10g1o (Po/P L
) Here, α represents the transmission loss (dB/■), and L represents the length of the optical fiber (Km).

0 Cold and heat resistance test: -30℃ for 12 hours, then +80℃
One cycle is to leave it for 12 hours, and this is 20 hours.
This was done by repeating the cycle.

The test results are shown in Table 2.

For Comparative Examples 2.5 and 8 in Table 2 above, no ultraviolet irradiation was performed, and the test was conducted on those that were dried at 50° C. for 30 minutes.

Table 2 shows that the optical fiber whose cladding is formed using the curable composition of the present invention has a large NA, so the signal strength is large, the transmission loss is very small, and the transmission loss after the cold and heat resistance test is extremely low. It is clear that long-distance transmission can be carried out efficiently because of the small amount, and it is clear that it has excellent performance.

Example 11 100 parts of the compound represented by the formula % and 5 parts of 1,6-hexanediol diacrylate were mixed and dissolved in 100 parts of the resin of (A)-IV, and 10 parts of titanium dioxide was mixed and dissolved.
A white enamel was obtained by mixing and dispersing 0 parts. This paint was applied to an acrylic plate to a thickness of 50 μm, and the paint was cured and dried by irradiation with an electron beam of 5 Mrad. This coating film was subjected to an accelerated weather resistance test using a sunshine weather meter for 8,000 hours. The gloss retention rate was 92%, and almost no discoloration was observed, showing very good results.

Example 12 A resin varnish consisting of 100 parts of the resin of (a)-■, 80 parts of the compound represented by the formula %, and 20 parts of IH, IH, 5H-octylfluoropentyl methacrylate was applied to a polyethylene terephthalate film with a thickness of 25 μm. The film was coated to a film thickness of 3 μm and cured by irradiation with an electron beam (5 Mrad).

The sunlight transmittance of this film was 92%, and in the case of polyethylene terephthalate alone, it was 85%.

Example 13 100 parts of the compound represented by the formula % is mixed and dissolved in 100 parts of the resin of (A)-11, 100 parts of titanium dioxide is mixed and dispersed to form a white enamel, and 6 parts of lauroyl peroxide and naphthene are mixed and dissolved. A paint was obtained by adding 2 parts of cobalt acid. Apply this paint to a slate board to a thickness of 5
The coating was applied to a thickness of 0 μm and left at 30° C. for one day to harden and dry the coating. The water repellency of this coating film was extremely good.

Example 14 (A) A resin varnish consisting of 100 parts of -1X resin and 100 parts of a compound represented by formula 0%,
6 parts of Darocure-1173 was added and mixed to obtain an ultraviolet curable fluorine paint. This paint was coated with acrylonitrile-butadiene-styrene resin (hereinafter referred to as ABS) and two
Painted to 0μm and 200m with high pressure mercury lamp.
It was cured by irradiating with J/cm2 ultraviolet rays. As a result of adhering ice to this and measuring the adhesion force, the adhesion force was 1.1 kg/
C■2 had good releasability. When ice was attached to ABS, the removability was 4.2 kg/cm2, which was not very good.

(that's all)

Claims (1)

[Claims] [1] (A) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R represents a methyl group or a hydrogen atom, and X represents a fluorine atom or a hydrogen atom, respectively. . m is 1 or 2, n is 1 to 12
indicates an integer. ] A polymerizable double bond-containing resin obtained by introducing a polymerizable double bond-containing group into a polymer containing fluoroalkyl (meth)acrylate as a monomer component represented by (b) General formula ▲ Numerical formula, chemical formula , tables, etc.▼(II) [In the formula, R and m have the same meanings as above, and p is 1 to 1
Indicates an integer of 2. ] A curable composition containing a fluorine-containing di(meth)acrylate represented by the following as an essential component.