JPH089586B2 - Bifunctional acrylate compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel difunctional acrylate compound, a process for producing the same and use thereof. More specifically, it relates to a novel difunctional acrylate compound represented by the following general formula (I), which is industrially useful as a cross-linking agent, a process for producing the same, and uses thereof.

(The symbols in the formulas have the same meanings as described below.) [Prior Art] Various polyfunctional acrylate compounds have been conventionally known. For example, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol-A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and the like are commonly used. It is used as a crosslinking agent or as a raw material for various synthetic resins.

[Problems to be Solved by the Invention] However, when attempting to polymerize the above-mentioned polyfunctional monomer, oxygen is remarkably inhibited, so that the portion in contact with air is hard to cure, and as a crosslinking agent. When used, the higher the crosslink density, the harder it becomes, but on the other hand, it becomes brittle.

[Means for Solving the Problems] As a result of earnest studies, the inventors of the present invention have found that a novel oxygen-resistant polymer is not easily affected by polymerization inhibition by oxygen, and when used as a cross-linking agent, the cross-linking density is increased to increase hardness and prevent brittleness. It came to obtain a bifunctional acrylate compound.

This compound is particularly useful as a cross-linking agent,
It can be used as a raw material for paints, adhesives, various coating agents, molding resins and the like.

Specific examples of the compound (I) of the present invention include those shown in Table 1 below.

[Production Method] According to the present invention, the compound (I) of the present invention has the general formula (I)
I) (In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, and k and l each independently represent 0 or
Alternatively, it represents an integer of 1 to 4. ) 2,2-bis (4'-hydroxyphenyl) hexafluoropropane or an alkylene glycol ether thereof represented by the general formula (III) And / or general formula (IV) (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and m and n are each independently 2
Or represents an integer of 3. However, when R ₁ = R ₂ , m ≠
The condition is that R ₁ ≠ R ₂ when n and m = n. ) It can manufacture by reacting with the isocyanate alkyl (meth) acrylate shown by these.

More specifically explaining the manufacturing method, for example,
2,2-bis (4'-hydroxyphenyl) hexafluoropropane represented by the general formula (II) or a (poly) alkyl glycol ether thereof and an amount corresponding to the -OH group of the compound of the general formula (II), Alternatively, a slight excess amount of an isocyanate alkyl (meth) acrylate (a compound represented by the general formula (III) and / or a general formula (IV)) is reacted with or without a solvent to give a corresponding urethane compound (I). Can be obtained.

When synthesizing the urethane compound (I) in which R ₁ ≠ R ₂ and / or m ≠ n, the compound of the general formula (II) and the compound of the general formula (III) are first reacted to Except for the unsymmetrical compound (II) and the symmetrical compound (I),
Then, the compound of the general formula (IV) is reacted in an amount corresponding to the remaining OH group or a slight excess amount thereof.
In this case, the amount of the compound of the general formula (III) to be reacted first may be an amount corresponding to 1/2 of the OH group of the compound (II), but it may be reduced by about 30% or conversely. The reaction makes the next separation easier. That is, in a solvent that is immiscible with water, 130% of compound (II) and its OH group
% With compound (III), then O
The H group was extracted with water as a Na salt, then neutralized with an acid, and then extracted with an organic solvent to remove water. After removing water, an amount corresponding to the remaining OH group or a slight excess amount of the compound (IV ) React with.

In the production method of the present invention, since the product is a solid at room temperature, dichloromethane, chloride-based compounds such as dichloroethane, benzene, aromatic hydrocarbons such as toluene,
It is convenient for taking out the product to carry out the reaction in a solvent inert to the isocyanate.

At this time, a catalyst is preferably used in order to allow the reaction to proceed promptly. The catalyst may be a tin compound such as dibutyltin dilaurate or dibutyltin diacetate, or a tertiary amine such as DABCO (1,4-diazabicyclo [2.2.
2] Octane) etc. are used.

The amount of the catalyst used varies depending on the amount of hydrolyzable chlorine in the isocyanate, but 0.1 to 1.5% by weight of the isocyanate (meth) acrylate is suitable. In addition, in order to prevent polymerization during the reaction process, BHT is used as a polymerization inhibitor.
(2,6-di-tert-butyl-4-hydroxytoluene)
Alternatively, it is desirable to use phenothiazine.

An appropriate amount of the polymerization inhibitor is about 200 to 2000 ppm of isocyanate alkyl (meth) acrylate. This reaction is a reaction with extremely high selectivity and does not require equipment such as an esterification reaction for removing the produced water. Therefore, the target product (I) can be industrially easily obtained in a high yield. You can

The bifunctional acrylate compound (I) thus obtained can be used as it is as a raw material for polymerization. If necessary, it may be dissolved in a solvent such as dichloromethane and washed with alkaline water and / or water. It can also be used.

Further, the product obtained in the form of a solution can be made to have a high purity by precipitating it by washing with water and then evaporating to dryness or by replacing the solvent with a base solvent.

[Use] The novel difunctional acrylate compound represented by the general formula (I) according to the present invention can be polymerized alone to produce a resin excellent in strength, gloss and transparency, but is reactively diluted. It may be copolymerized with another monomer as an agent, and exhibits excellent properties even when a small amount of the compound of the present invention is used as a crosslinking agent.

Specifically, surface treatment agents such as paints, inks, coating materials, fiber treatment agents, paper processing agents and various other coating materials, inks, adhesives, sealing agents, optical materials, dental materials, medical materials, photoresists, photographs. It can be used as a raw material for materials, electrical insulating materials, molding resins, and the like.

Type and composition of comonomer The type of comonomer copolymerized with the compound of the present invention varies depending on the field of application, and all copolymerizable monomers can be used, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as decyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Cyclohexyl, isobornyl (meth) acrylate,
(Meth) acrylate cycloalkane esters such as norbornyl (meth) acrylate, adamantyl (meth) acrylate, hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, diethylene glycol ester (meth) acrylic acid, polyethylene glycol ester (meth) acrylic acid, dipropylene glycol ester (meth) acrylic acid , Hydroxyalkyl esters or polyether polyol esters of (meth) acrylic acid such as (meth) acrylic acid polypropylene glycol ester, benzyl (meth) acrylate, phenethyl (meth) acrylate, phenoxyethyl (meth) acrylate ,
Contains an aromatic ring such as (meth) acrylic acid phenoxydiethylene glycol ester, (meth) acrylic acid-2-hydroxy-3-phenoxyprohillic ester, (meth) acrylic acid benzoyloxy ester, (meth) acrylic acid cinnamyl (meth ) Acrylic esters,
Tetrahydrofurfuryl (meth) acrylate, (meth)
(Meth) acrylic acid esters containing a cyclic ether group such as glycidyl acrylate, (meth) acrylic acid-
2-aziridinyl ethyl ester, (meth) acrylic acid-2-isocyanatoethyl ester, (meth) acrylic acid-N, N-dimethyl (or diethyl) aminoethyl ester, (meth) acrylic acid-N-hydroxyethyl Nitrogen-containing (meth) acrylic acid esters such as aminoethyl ester, (meth) acrylic acid-2,2,2-trifluoroethyl ester, (meth) acrylic acid-1,1,2,2-
Tetrahydroperfluorooctyl ester, (meth)
Acrylic acid-1,1,2,2-tetrahydroperfluorodecyl ester (meth) acrylic acid-1,1,2,2-tetrahydroperfluorododecyl ester, (meth) acrylic acid-1,1-dihydroperfluorooctyl ester (Meth) acrylic acid fluoroalkyl esters such as esters, (meth) acrylic acid-1,1-dihydroperfluorodecyl ester, (meth) acrylic acid-1,1, -dihydroperfluorododecyl ester, (meth) Acryloyloxyethyl phosphate, (meth) acrylic acid esters containing an ester moiety of an inorganic acid such as (meth) acrylic acid sulfopropyl ester, (meth) acrylic acid trimethoxy (or ethoxy) silylpropyl ester,
Silicon-containing esters of (meth) acrylic acid such as (meth) acrylic acid polydimethylsiloxanylpropyl ester, (meth) acrylonitrile, and (meth) other than (meth) acrylic acid ester such as (meth) acrylic amide
Acrylic compound, styrene, (o-, m-, or p-)
Examples thereof include vinyl compounds such as vinyltoluene, N-vinylpyrrolidone, N-vinylcarbazole, methyl vinyl ketone, ethyl vinyl ketone, vinyl acetate, vinyl chloride and vinylidene chloride. In addition to such a monomer containing only one C = C double bond, ethylene glycol di (meth) acrylate, butanediol di (meth)
Acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate,
Monomers having a plurality of C = C double bonds such as tris (meth) acryloyloxyethyl isocyanurate and divinylbenzene can also be used.

Further, upon copolymerization, not only the above-mentioned monomers but also those partially preliminarily polymerized such as methacrylic resin syrup can be used.

The use amount of the compound of the present invention varies depending on the use, but it is used in the range of 0.5 to 100% by weight based on the whole polymer (composition).

Polymerization Method Various types of polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization are possible.

From the viewpoint of radical generation method, peroxides such as benzoyl peroxide, hydroperoxides such as cumyl hydroperoxide, persulfates, inorganic systems such as hydrogen peroxide, azobisisobutyronitrile (AIBN) A polymerization method using such an azo-based polymerization initiator, a photopolymerization method, a radiation polymerization method such as an electron beam polymerization method, or the like is adopted.

When a polymerization initiator is used, its addition amount is about 0.01 to 10% by weight, preferably 0.05 to 5% by weight based on the whole polymerization components. If it is less than 0.01% by weight, it will be difficult to cure it sufficiently, and if it is more than 10% by weight, the molecular weight of the polymer will be low and no effect can be expected. The initiators may be used alone, but in some cases, a plurality of initiators may be used in combination (eg, azobis-based and peroxide-based).

The initiator is usually dissolved in a solvent or a monomer and charged into the reactor before charging the raw materials, but it is also possible to add 5 to 10% of the initial charge over several times in order to complete the polymerization. is there.

In the case of photopolymerization, it is common to add an initiator (photosensitizer), and various commercially available photoinitiators can be used, but α, β-diketones, benzoyls (benzoin, 2-methylbenzoin, etc.) and its alkyl ethers (benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, etc.), phenyl isopropyl ketone and those with various substituents, special ketones such as benzophenone, Michler's ketone, etc. Is a typical example. Further, these may be used in combination with a small amount of a sensitization aid such as amine.

The polymerization temperature and time are appropriately selected depending on the type of initiator to be used, the desired properties of the polymer, etc., but generally, the slower the polymerization at a low temperature, the higher the molecular weight of the polymer tends to be obtained.

 The use of the present invention will be described in detail below.

The compound of the present invention can be used, for example, as a crosslinking agent to prepare a polymer composition useful for various applications.

In particular, the features of the compound of the present invention as a crosslinking agent are as follows.

When used as a cross-linking agent, the elongation property does not deteriorate even if the cross-linking density is increased to increase the hardness.

When a commonly used crosslinking agent such as neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, or bisphenol-A-di (meth) acrylate is used, the amount of the crosslinking agent should be increased. There is a problem that when the hardness is increased, the elongation property becomes poor and the composition becomes brittle. However, when the compound of the general formula (I) is used as a cross-linking agent in place of these, the hardness can be improved without sacrificing the elongation property. Can be raised.

 Less likely to be affected by polymerization inhibition by oxygen.

In the case of methacrylic acid-based cross-linking agents, which are often used in the past, it is difficult to cure the part in contact with air, for example, it takes a long time for the surface to harden, or it is necessary to put it in a mold and cure it to obtain a molded product. However, if the compound of the general formula (I) is used as a cross-linking agent, the edge portion in contact with air will not be cured. It is difficult and can be cured in a relatively short time.

Specific Application Examples Hereinafter, application examples of the present invention will be specifically described individually.

(1) Paints The compounds of the present invention are solvent-based paints, paints for marine structures, and UV.
It can be used for various paints such as curable paints.

(B) Solvent-based paints have the following prescriptions (parts in the following prescriptions represent polymerized parts) Methyl methacrylate 37 parts Styrene 37 parts Ethyl methacrylate 15 parts Compound No. 1 (Table 1 Reference) 4 parts Hydroxyethyl acrylate 7 parts Benzoyl peroxide 1.5 parts The above mixture is added dropwise to 80 parts of xylene kept at 105 to 110 ° C over 2 hours while stirring.

After 1 hour, add 0.1 part of benzoyl peroxide and add 2
When 0.1 part of benzoyl peroxide is added again after a lapse of time and reacted, an acrylic resin which forms a coating film excellent in gloss, abrasion resistance and impact resistance is obtained.

(B) The following prescription is an example used in paints for marine structures.

Hydroxyethyl methacrylate 38.5 parts Titanium white 27 parts Hydroxyethyl methacrylate 38.5 parts Compound No. 1 0.2 parts Cobalt naphthenate 0.1 parts tert-Butyl peroctanate 0.3 parts Add a mixture and mix well to give a viscous syrup Is obtained.

For example, when this is applied to a hull and cured at 20 to 30 ° C., the living body does not adhere even in water for a long time, and the resistance of water is further reduced.

As described above, the compound of the present invention can be used in a coating material that is cured with a peroxide, but it is in the field of photocurable coating material that the characteristics can be more exerted.

(C) Photocurable paints are used in various applications such as underground and top coats for vacuum deposition processing, overprint varnishes, paints for woodwork, clear coats for PVC tiles, hard coats for plastics, and enamel for canned cans. .

Overprint varnish of oil-based ink is used to prevent mutual adhesion so that it can be stacked without spray powder and to improve abrasion resistance.For example, alkyd resin in the presence of benzene, toluene sulfonic acid An ultraviolet-curing varnish obtained by mixing a small amount of the compound of general formula (I) with an acrylic-modified alkyd resin obtained by allowing acrylic acid to act as a catalyst is applied by a roll coater or the like.

For woodworking, it is used as a filling agent and a hard coat agent. Polyether polyol such as polyethylene glycol or polypropylene glycol or acrylic polyol such as polyhydroxyethyl methacrylate and diisocyanate (toluylene diisocyanate, methylene diphenyl isocyanate, xylylene diisocyanate, isophorone diisocyanate, hydrogenation Methylenediphenyl diisocyanate, 1,3
-Or 1,4-bisisocyanatomethylcyclohexane etc.) is reacted with 2-hydroxyethylene acrylate to give urethane acrylate, which is then reacted with 1,6-hexanediol diacrylate, neopentyl glycol diacrylate. A mixture of diacrylates such as acrylate and tetraethylene glycol diacrylate and a compound of the general formula (I) is applied and cured by ultraviolet rays. When the compound of the general formula (I) is used, the surface hardness is increased and the impact resistance is also improved.

The clear coat for PVC tile is used to impart stain resistance, scratch resistance, burn resistance, solvent resistance, and to make it a maintenance free type that does not require waxing. A clear coating agent obtained by mixing furyl acrylate and the compound of the general formula (1) is used.

Hard coats for plastics are used to increase the surface hardness of plastics, especially methacrylic resins and polycarbonate resins, and improve scratch resistance. For example, pentaerythritol tetraacrylate 60 parts, compound No. 1 20 parts, N- A mixture of 20 parts of vinylpyrrolidone has excellent wear resistance, impact resistance and transparency.

For food cans, it can be used as a white enamel as a base coat on the outside of the can and as an overcoat after offset printing.

Vacuum deposition processing of plastic moldings such as cosmetic container caps, home appliance parts, automobile headlights, and decorative glasses has become widely used recently.
In this case, when the compound of the general formula (I) is used for the UV-curable coating material used as the undercoat and overcoat, it is possible to obtain a coating surface having excellent specularity, surface hardness and adhesion.

As a typical example of the ultraviolet curable coating material, the following are prescription examples for white enamel for food cans and for vacuum deposition processing.

[White enamel for food cans] Dipentaerythritol hexaacrylate 8.5 parts Compound No. 1 16.9 parts Methacryloyloxyethyl isocyanate and methyl ethyl ketoxime adduct 21.7 parts Titanium white 52.2 parts Isoamyl dimethylaminobenzoate 1.3 parts Benzophenone 1.3 parts Above The composition is applied on a steel sheet to a film thickness of 20 to 30 μm, left at room temperature for 2 hours to evaporate the solvent, and then cured with ultraviolet rays to form an underground layer. UV-curable ink is printed thereon by offset printing, a thermosetting acrylic varnish is overcoated in the final finishing step, and cured at 190 ° C. for 2 minutes.

[Plastic for vacuum deposition processing] Urethane acrylate ^* 16 parts Pentaerythritol tetraacrylate 30 parts Compound No. 19 parts Dimethoxyphenylacetone 5 parts Mixed alcohol solvent ^** 30 parts *) Polyester polyol with molecular weight = 1000, OH number = 500 Of 2-methacryloyloxyethyl methacrylate.

**) Mixed alcohol consisting of 50% methyl alcohol, 25% isopropyl alcohol, and 25% n-butyl alcohol.

An ultraviolet curable coating consisting of the above mixture is applied to the surface of a plastic molded product to cure it, a metal is vapor-deposited on it, and an ultraviolet curable coating is applied on top of it to cure the surface and it is vapor deposited. The peeling of the surface is prevented.

(2) Ink In the ink field, in addition to offset printing ink, foam printing ink, gravure printing ink,
It is used for special ink such as solder resist ink, painting ink for ceramics, and desensitizing ink for non-carbon paper.

(A) Ink for offset printing An alkyd resin is treated with acrylic acid to obtain an acrylic modified alkyd resin, to which dipentaerythritol hexaacrylate and the compound of the general formula (I) are added as a cross-linking agent to prepare an ink having a fast photocuring speed. Can be made.

(B) Solder resist ink As the solder resist ink, a mixture of bisphenol type epoxy acrylate, novolac type epoxy acrylate and the like with a small amount of the compound of the general formula (I) is used.

(C) Painting ink for ceramics The transfer paper for painting of ceramics is the one in which a pattern ink layer and a cover coat layer are screen-printed on a backing paper, and the general formula (I ) Compounds are utilized. A low molecular weight polyester is mainly used for the pattern ink, and the compound of the general formula (I) and other (meth) acrylic acid esters are used in combination. A combination of a (meth) acrylic acid ester copolymer, 2-hydroxyethyl methacrylate, and a compound of the general formula (I) is used for the ink for cover coat. In particular, the ink for cover coat using the compound of the general formula (I) has a good decomposability upon firing, and has a beautiful finish without cracks or flying patterns.

(D) Desensitizing ink A composition comprising a quaternary ammonium salt, urethane acryl, a compound of the general formula (I), titanium white, etc. as a desensitizing ink used for the purpose of preventing color development of carbonless pressure-sensitive copying paper. Is available.

As specific examples of application in the ink field, the following are formulation examples of offset printing ink, painting cover coat ink, and desensitizing ink.

[Ink for offset printing] Fatty acid-modified alkyd resin ^* 78.0 parts Acrylic acid 12.3 parts Benzene 9.0 parts p-Toluenesulfonic acid 0.6 parts Hydroquinone 0.1 parts *) A mixture composed of linseed oil fatty acid, trimethylolpropane and phthalic anhydride Is heated to reflux while removing water to obtain an acrylic modified alkyd resin. The resulting composition 10
A binder for ink is obtained by adding 6 parts of Compound No. 1 and 4 parts of dipentaerythritol hexaacrylate to 0 part.

[Coating ink for painting] Methyl methacrylate / methyl acrylate / butyl acrylate copolymer (MW = 70000) 35 parts 2-hydroxyethyl methacrylate 50 parts Compound No. 1 5 parts Benzoin butyl ether 10 parts A UV-curable ink with good degradability.

A pattern is printed on a paper coated with a dextrin solution with an ultraviolet curable ink and cured, and then the above composition is printed as a cover coat on the paper and cured by ultraviolet rays to obtain a transfer paper.

When the design of this transfer paper is transferred to a pottery and fired at 850 ° C, the cover coat layer disappears and a beautiful painting without cracks and pattern jumps can be made.

[Desensitizing ink] A product obtained by reacting methacryloyloxyethyl isocyanate with epoxidized soybean oil treated with acrylic acid.
41 parts Polypropylene glycol diacrylate 28 parts Compound No. 1 5 parts Titanium white 22 parts 2,4-Diethylthioxanthone 2 parts p-Dimethylaminobenzoic acid ethyl ester 2 parts The composition of When a coating film is formed by ultraviolet curing, color development is prevented even in the area where pressure is applied.

(3) Adhesives In recent years, what is called a second-generation adhesive has come to the spotlight. This adhesive is composed of an acrylic monomer, a catalyst, and an elastomer, and graft polymerization with the elastomer occurs during the polymerization of the monomer to form a cured product in which the acrylic polymer and the elastomer are chemically bonded.

When the compound of the general formula (I) is used as one component of this second generation adhesive, an adhesive layer having excellent peeling and impact strength can be obtained. For example, methyl methacrylate, general formula (I)
The mixture of the compound of 1., chlorosulfonated polyethylene, and a reaction initiator is applied on one side to be adhered, the reducing accelerator is applied on the other side, and both sides are lightly rubbed to adhere to each other for a short time. Harden.

In addition, it is also used as one component of the main component of a microcapsule type acrylic adhesive. For example, polymers of methyl methacrylate, triethylene glycol dimethacrylate, compounds of general formula (I), N, N-dimethyl-p-
By mixing microcapsules containing a solution of a polymerization initiator with a mixture of toluidine, a one-pack type microcapsule type acrylic resin is obtained.

 It is also used as an ultraviolet curable adhesive.

For example, a tackifier is added to a copolymer of ethyl acrylate and butyl acrylate and diluted with toluene so that the solid content is 46%. To this, 20% of diacrylate of adipic acid-1,6-hexanediol polyester having OH value = 500, 10% of compound of general formula (I) and 0.8% of benzophenone are added to obtain a UV-curable adhesive. This is applied to a polyester film and dried. The obtained pressure-sensitive adhesive film is attached to the glass surface, and when ultraviolet rays are irradiated from the opposite side of the glass surface or from the back surface of the polyester film, the pressure-sensitive adhesive layer is cured and fixed to the glass surface. This technology can also be applied to coating by transfer of metal plates and art paper.

As a specific example of the adhesive-related material, the formulation agent for the second-generation adhesive is shown below.

(A) Methyl methacrylate 45 parts Compound No. 1 8 parts Addition product of ethylene glycol 1 mol and methacryloyloxyethyl isocyanate 2 mol 5 parts Chlorosulfonated polyethylene 40 parts Cumene hydroperoxide 2 parts (b) N, N -Dimethylaniline 2 parts Cobalt naphthenate 1 part Toluene 97 parts Apply the main component of composition (a) on one side of the adhesive surface, apply the primer of composition (b) on the other side, and rub them lightly to adhere. Then, it cures in 5 to 6 minutes.
However, to completely cure and display the original strength, 1
It takes time.

(4) Photoresist [Solder resist] Orthocresol novolac type epoxy resin (epoxy equivalent = 230) 58 parts Methyl ethyl ketone 42 parts Acrylic acid 38.5 parts Benzyltrimethylammonium chloride 4 parts p-Methoxyphenol 1.5 parts Methyl ethyl ketone 10 parts of a solution having a composition of 56 parts was added at 60 ° C., heated to 80 ° C. and reacted for 15 hours, and further 2-methacryloyloxyethyl isocyanate 41 parts dibutyltin dilaurate 0.15 parts methyl ethyl ketone 26 parts Compound No. 1 33 21 parts of a solution of parts composition are added dropwise over 3 hours. 5 in a row
After stirring for 0.5 hour, 0.5 part of methyl alcohol is added thereto and the reaction is continued for 1 hour.

73 parts of the composition obtained, 2,4-diethylthioxanthone
1.3 parts, benzoic acid isobutyl ester 1.7 parts, diameter 1.5μ
When 24 parts of talc powder are mixed and mixed well, a photosensitive resin composition is obtained.

When this photosensitive resin composition is applied to a copper-clad laminate, dried to form a photosensitive layer, and exposed and developed through a negative mask, a solder mask having good dimensional accuracy and thermal shock resistance can be obtained.

[Dry film for printed wiring] Methyl methacrylate / acrylonitrile / glycidyl methacrylate copolymer 11 parts Methyl methacrylic acid / 2-hydroxyethyl acrylate copolymer 5 parts Compound No.1 3 parts tert-Butylanthraquinone 1.2 parts 2,2 ' -Methylene-bis (4-ethyl-6-tert-butylphenol) 0.3 part Ethyl violet dye 0.025 part Methyl ethyl ketone 79.5 parts A composition obtained by applying the composition on a polyethylene terephthalate transparent film and drying it, and then coating the surface with copper. Stick to epoxy / fiberglass board. Light is irradiated through the image film having a transparent conductive pattern and an opaque background to cure the conductive portion. The polyethylene terephthalate transparent film is peeled off, the uncured portion is washed off, and the ferric chloride solution is used for etching. Finally, the resist is removed to obtain a printed wiring board.

(5) Printing plate material When a printing plate material using an ultraviolet curable resin is used, it is more widely used because it is easier to systematize the plate making process than when a lead plate or a rubber plate is used.

Examples of these printing plates include flat plates, letterpress plates, screen printing plates and flexographic printing plates.

Examples of the use of the compound of the general formula (I) in a waterless plate include an unsaturated polyester, a compound of the general formula (I), ethylene glycol dimethacrylate, and an adhesive comprising a photoinitiator (such as benzophenone) on an aluminum plate. A transparent polypropylene film coated with a silicone rubber layer having a thickness of 5 μm is adhered thereto. When a positive film is placed on a polypropylene film and exposed to light, the adhesive cures and the silicone rubber layer is fixed. When the silicone rubber is swollen and rubbed with a developing solution, only the part exposed to the light remains and an ink repellent layer is formed.

Similarly, the screen printing plate also has the poval and general formula (I).
The solution comprising the compound of (1), photoinitiator, methanol and water is applied to a screen and dried, and then exposed through a positive film and then the uncured portion is washed away.

In the case of using for convex, a mixture of a soluble polymer such as bovar, a compound of the general formula (I), a photoinitiator, a thermal polymerization inhibitor (p-methoxyphenol, etc.), etc. is formed on the base film at a constant thickness. And exposed through a negative film, and then rinsed on the uncured portion to prepare a printing plate.

As a specific example of application to a printing plate, a prescription example used for convex printing is shown below.

Poval (saponification degree 85, average degree of polymerization 500) 34.6 parts 2-hydroxyethyl methacrylate 34.6 parts Compound No. 1 2.1 parts Benzoin butyl ether 0.9 parts p-Methoxyphenol 0.1 parts Rose Bengal 5% aqueous solution 0.2 parts Water 27.5 parts The liquid mixture is rolled on a polyester film to form a photosensitive layer having a certain thickness, laminated on a metal plate, heated and dried to form a plate. After the exposure, washing with water, development, and heating to cure the image gives a relief printing plate.

(6) Optical materials In the field of optical materials, they are used as materials for lenses, core materials for optical fibers, sheath materials (coating agents), mirror materials and the like.

(B) When the compound of the present invention is used for the plastic of the material for the lens, it has characteristics such as high hardness, no brittleness during demolding, good adhesion to the glass mold, and good impact resistance. You can get a good material and make a thin and lightweight lens.

Specific examples of the lens material include, for example, the compound of the general formula (I), trimethylolpropane triacrylate, and bis (2-hydroxyethyl) sulfide.
A composition having a compound having 2 moles of methacryloyloxyethyl isocyanate and a photoinitiator is poured into a glass mold and photocured to obtain a lens having the above characteristics.

As a material for contact lenses, a copolymer of hydroxyalkyl (meth) acrylate is generally used. However, since this alone generally lacks strength, a polyfunctional monomer is usually used as a crosslinking agent.

Examples of polyfunctional monomers for cross-linking agents include neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6 hexane glycol di (meth) acrylate.
Acrylate, trimethylolpropane tri (meth) acrylate and the like are generally used.

However, these conventional cross-linking agents usually have a poor elongation when the amount used is increased to increase the strength.

As an alternative cross-linking agent, a compound of the invention of formula (I) and a compound of formula (VI) (In the formula, R ₅ and R ₆ each independently represent a hydrogen atom or a methyl group.) When a curable composition containing a hydroxyalkyl (meth) acrylate represented by the formula is used, the strength is increased without deteriorating the elongation property. be able to.

The curable composition may contain, in addition to the compound of formula (I) and the hydroxyalkyl (meth) acrylate represented by formula (VI), another monomer having a carbon-carbon double bond. As the monomer having this double bond, various substances such as methyl methacrylate, butyl acrylate, ethylhexyl acrylate, acrylonitrile, perfluoroalkyl (meth) acrylate, and styrene can be used, and an appropriate one can be selected depending on the application.

The weight ratio of the hydroxyalkyl (meth) acrylate represented by the formula (VI) to the compound of the formula (I) in the present invention is 300: 1 to 4: 1, and particularly preferably 100: 1 to 10 :.
1 is good. If the amount of the compound of the formula (I) is too small, sufficient strength cannot be obtained. On the other hand, if the amount of the compound of the formula (I) is too small, the resulting resin becomes too hard and the formula (I Since the compound (1) is relatively expensive, it is not applicable economically.

(B) As a core material of an optical fiber, if the compound of the present invention is added as a cross-linking agent to methyl methacrylate (or a mixture of this and another acrylic monomer such as ethyl acrylate), a mechanical property is obtained. Excellent fibers are obtained.

(C) Coating agent for optical fibers The coating agent for optical fibers containing the compound of the present invention as a comonomer exhibits excellent durability and abrasion resistance.

Optical fibers used as a medium for optical transmission are generally fragile and easily scratched, so that the surface is conventionally coated with a coating resin, for example, an epoxy resin, a urethane resin, or a silicone resin. Since curing takes a long time, there are problems that (a) productivity is low and (b) curing failure is likely to occur.

In recent years, it has been considered to use an ultraviolet curable resin such as epoxy acrylate or urethane acrylate instead of these, but there is a general tendency that elongation is insufficient when the number of crosslinking points is increased to increase the strength.

On the other hand, when a mixture of the compound (I) of the present invention, another vinyl-polymerizable monomer and a polymerization initiator is applied to the surface of the optical fiber and then heated or irradiated with an ultraviolet ray or an electron beam, The resulting cured product has good adhesion to optical fibers and is excellent in toughness, satisfying both elongation and tensile strength and mechanical strength such as tensile modulus. become.

Examples of the other vinyl polymer monomer copolymerized with the compound represented by the formula (I) include (meth) acrylates such as methyl methacrylate, butyl acrylate and ethoxyethyl acrylate, styrene,
Examples thereof include N-vinylpyrrolidone and vinylcaprolactam.

The proportion of the compound of formula (I) and the other vinyl polymer monomer used is 2-40 mol% of the former, preferably 5-25%, and the latter is
It is 98-60%, preferably 95-75%.

Further, the compound represented by the formula (I) has a low refractive index of light because it contains fluorine, and in this respect as well, it is preferable as a coating material for optical fibers, but since the refractive index is further lowered, the following formula (V) (In the formula, R ₇ represents hydrogen base paper or a methyl group, and r is 0.
Or 1 and p represents an even number of 6-10. ) A 2-perfluoroalkylethyl (meth) acrylate or a fluorine-containing monomer such as an addition reaction product of 2-perfluoroalkylethanol and 2-isocyanatoethyl (meth) acrylate in a total amount of 10 to
60% by weight can be used.

In the optical fiber coating material of the present invention, in addition to these components, if necessary, various modifying resins (for example, polyester resin, polyamide resin, polyether resin, silicone resin, polyurethane resin, etc.) and surfactants are added. Agents may be added, and the overall viscosity is 1,000 to 10,000 m.
It is desirable to adjust to the range of Pa · s.

(7) Photographic materials In the field of photographic materials, when the compound of the present invention is used as a component of a coating material, it is possible to obtain a base paper for photographic paper which has excellent "folding strength" and which is generally incompatible with little "fog formation". .

 The prescription example is shown below.

Addition product of polybutadiene with OH at both ends and 2-mol of 2-methacryloyloxyethyl isocyanate 2 parts 21 parts Compound No.1 11 parts Urethane acrylate ^* 11 parts Polyester diacrylate ^** 30 parts Titanium white 27 parts *) PEG- 400 reacted with excess 1,3-bis (isocyanatomethyl) cyclohexane and acrylic modified with 2-hydroxyethyl acrylate **) Both ends of adipic acid and propylene glycol polyester with a molecular weight of 1000 and an OH value of 500 Is applied to one side of a photographic base paper at a thickness of 30 g / m ² and is irradiated with an electron beam of 0.5 Mrad to cure to obtain a base paper for photographic paper.

(8) Fiber treatment agent Copolymers containing acrylic acid ester as a main component have been widely used in the field of fiber coating agents. In this case, a copolymer containing a small amount of a copolymer component having a functional group such as a carboxyl group, an OH group, an epoxy group, and a methylol group is used. It is crosslinked by reacting with a nato compound or the like. However, since the crosslinkable composition containing each of these components has a very short pot life, it has the inconvenience of having to be prepared immediately before use (two-component type). Various one-part crosslinkable compositions have been devised to solve this problem, and the compound of the present invention is used as a component of this one-part crosslinkable composition.

 The prescription example is shown below.

Ethyl acrylate 39 parts 2-Hydroxyethyl acrylate 1 part Toluene 60 parts To the mixture, 0.004 parts of n-dodecyl mercaptan as a polymerization degree control agent and 0.04 parts of azobisisobutyronitrile as a polymerization initiator were added, and the system was replaced with nitrogen. After that, 80-90 ℃
It was polymerized for 6 hours. 1.2 parts of 2-methacryloyloxyethyl isocyanate and 0.01 part of dibutyltin dilaurate were added to the obtained copolymer solution, and the mixture was reacted at 70 ° C. for 3 hours. To 88 parts of this reaction product solution, 10 parts of Compound No. 1, 2 parts of benzoin ethyl ether, and 0.02 part of p-methoxyphenol were added to obtain a photocrosslinkable coating agent.

This coating agent is stable unless exposed to light and has excellent wash resistance even after being cured.

(9) Medical Material The compound of the general formula (I) can be used as a pressure-sensitive adhesive tape for treatment in which an adhesive tape containing a therapeutic agent is applied to the skin to gradually absorb the agent from the skin.

 The prescription example is shown below.

(A) 2-Hydroxyethyl methacrylate 130 parts Compound No. 1 0.65 parts Azobisisobutyronitrile 0.05 parts Ethyl acetate 40 parts The composition is polymerized for 60 hours while stirring at 50 ° C. Since the viscosity increases, ethyl acetate is added at any time, and azobisisobutyronitrile is added twice by 0.1 part each. Then, the temperature is raised and the reaction is carried out under reflux for 8 hours to complete the polymerization. The final polymer concentration is 18%.

(B) 2-Ethylhexyl acrylate 40 parts Butyl acrylate 100 parts Azobisisobutyronitrile 0.08 parts Ethyl acetate 30 parts The composition is polymerized in the same manner as in (a) (however, the final polymer concentration is 30%. Adjust the amount of ethyl acetate so that.

The polymer solutions of (a) and (b) are mixed at a ratio of 3: 2, a skin-penetrating agent is added to this and applied to a polyethylene terephthalate film, and a silicone release paper is attached onto it to give a therapeutic feel. A pressure-sensitive adhesive tape is obtained.

(10) Dental material As a dental material, it is used as a restorative material, a filling material, a coating agent, an adhesive agent and the like.

(A) For the repair agent, for example, the compound of the general formula (1), ethylene glycol dimethacrylate, is 3: 1 to 1: 3.
7 parts of fine powder of borosilicate glass is mixed with 3 parts of the mixture. Benzoyl peroxide as a polymerization catalyst
Addition of a combination of tertiary amines (such as N, N-dimethyl-p-toluidine) causes polymerization within minutes.

(B) As an example of use as a filler, a photoinitiator and a thermal polymerization inhibitor are added to a mixture of the compound of the general formula (1) and triethylene glycol dimethacrylate, and a silane coupling agent (3-methacryloyloxy) is added. Mix with silica powder or glass powder surface-treated with (such as propyltrimethoxysilane) to form a paste. Fill this in the hole,
It can be cured by irradiation with a dental lamp.

(C) Coating agent Plastic dentures are becoming more widely used because they are easier to manufacture and cheaper than ceramic dentures, but polymethylmethacrylate and polycarbonate resins are being widely adopted. The denture made of etc. is inferior in surface gloss and hardness to the one made of ceramics, so there is a problem in terms of aesthetics and usability. In order to compensate for this, a coating composition containing polyfunctional (meth) acrylate as a main component is applied onto the denture and cured to form a coating film having excellent gloss and hardness on the surface.

However, it has been difficult to say that the conventional ones are sufficiently satisfactory in terms of surface hardness, adhesion to a base material, wear resistance and the like.

Mixtures of a compound of formula (I) according to the invention and methacrylic acid esters, and 0.001 per 100 parts by weight of the mixture.
The curable composition containing 40 to 40 parts by weight of a photopolymerization initiator is suitable for dental surface coating, and a denture coating agent having excellent adhesion and strength can be obtained.

That is, the bifunctional monomer represented by the formula (1) is cross-linked and cured by light to give a polymer having excellent hardness and elongation, and usually has good photo-curing even in the presence of oxygen having polymerization-inhibiting curing. Shows sex.

Here, as the methacrylic acid ester, methyl methacrylate is a typical one, and in addition, ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl methacrylate and the like are used. It is also possible to use these methacrylic acid esters in the state of methacrylic resin syrup obtained by polymerizing 30 to 40% in advance.

As the photopolymerization initiator, a normal photopolymerization initiator is used, but one that reacts with visible light is particularly preferable, for example,
Α-diketones such as acetylbenzoyl, ketocoumarins, benzoin ethers, or a combination thereof with an aromatic mercaptocarboxylic acid such as p-mercaptobenzoic acid or mercaptodiphenylcarboxylic acid is used.

As light for irradiating to cure the curable composition of the present invention, light having a wavelength of 330 to 800 nm emitted from a halogen lamp, a xenon lamp, a mercury lamp, or a fluorescent lamp can be used.

(D) For the dental adhesive, 2-hydroxyethyl methacrylate, the compound of the general formula (I), 2-methacryloyloxyethyl phenyl acid phosphate, neopentyl glycol dimethacrylate, a polymerization inhibitor, a redox polymerization initiator ( For example, benzoyl peroxide)
Silica powder or glass powder surface-treated with a silane coupling agent (such as 3-methacryloyloxypropyltrimethoxysilane), a redox polymerization accelerator (such as N, N-diethanol-p-toluidine). Na 3
(A primary amine) and sodium benzenesulfinate are mixed together just before use.

Next, a formulation example of a dental coating agent will be shown as a specific example of application to a dental material.

Compound No.1 30 parts Methyl methacrylate resin syrup with a degree of polymerization of 35% 70 parts Acetylbenzoyl 5 parts Mercaptodiphenylcarboxylic acid 5 parts A coating composition consisting of 5 parts is applied to a plastic denture and cured by irradiation with light using a dental lamp. By doing so, a coating film having excellent surface hardness, adhesion to a substrate, abrasion resistance, and gloss is formed.

(11) Molding material The compound of the general formula (I) can be used as a comonomer for various molding resins or can be used for modifying molding resins.

(A) Modification of vinyl chloride resin Vinyl chloride resin is one of the most widely used resins because it has excellent mechanical properties and chemical resistance, but it has problems with impact resistance and processability. Therefore, various modifiers are used. As one of them, SBR graft polymerized with methyl methacrylate and styrene is used. By adding a small amount of the compound of the general formula (I) as a cross-linking agent, transparency, impact resistance, weather resistance and processability are obtained. Can be given.

That is, first, butadiene, styrene, and general formula (I)
Copolymerize the compound of (about 8: 2: 0.05 by weight ratio), and add a mixture of styrene, methyl methacrylate, the compound of general formula (I) (about 1: 1: 0.01), and a polymerization initiator. Further polymerize with vigorous stirring. The obtained resin and vinyl chloride resin are mixed, roll-kneaded and pressed to obtain a modified vinyl chloride resin.

(B) Vulcanization of synthetic rubber When a compound of the general formula (I) is used for crosslinking acrylonitrile butadiene rubber, ethylene propylene dienta-polymer rubber, acrylic rubber, chloroprene rubber, etc., improvement in corrosion resistance, aging resistance, hardness, resistance The chemical properties are improved.

(C) Others Generally, it shows excellent mechanical properties when used as a crosslinking agent for vinyl polymers.

(12) Electrical Insulation Material Conventionally, for impregnation insulation treatment of coil parts, etc., a thermosetting resin having radical polymerization property such as unsaturated polyester resin or 1,2-polybutadiene resin is diluted with vinyl monomer such as styrene, Electrically insulating varnishes containing redox catalysts are generally used, but curing is likely to be hindered in the presence of air, and surface tackiness is slowly lost at low temperatures, so it is necessary to cure at high temperatures for a long time. It was

By using the compound of the general formula (I), it is possible to obtain an insulating material having good curability in air and excellent insulating properties and mechanical properties.

 The following is a prescription example of the electrical insulating varnish.

Petroleum resin (Nippon Petrochemical Co., Ltd., OH value = 81) 30.1 parts 2-methacryloyloxyethyl isocyanate 6.9 parts BHT 0.015 parts Dibutyltin dilaurate 0.01 parts reacted with a compound of the general formula (I) 6 parts Styrene monomer 55 parts Trimethylolpropane trimethacrylate 2 parts tert-Butylperbenzoate 2 parts 6% Cobalt naphthenate solution 0.5 parts BHT 0.05 parts Add to make a varnish.

[Examples] Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. In addition,
In the following examples, parts are based on weight.

Example 1 168 parts of 2,2-bis (4min-hydroxyphenyl) hexafluoropropane, 162.6 parts of 2-isocyanatoethyl methacrylate (containing 200 ppm of BHT), and 0.17 parts of DABCO were placed in a glass reactor equipped with a stirrer. Charge, raise to 80 ℃
After stirring for 25 minutes while maintaining the temperature at 80 to 90 ° C, a yellowish brown oily product was obtained. This is dichloromethane 300m
Dissolve in l and once with 300 ml of 1N sodium hydroxide solution, water
After washing twice with 300 ml, the dichloromethane was removed by evaporation, and the product corresponding to compound No. 1 (formula (I): R ₁ = R ₂ = CH ₃ , m = n = 2, k = 0) was obtained. ) White semitransparent crystals (298 parts) were obtained.

The infrared absorption spectrum and nuclear magnetic resonance spectrum of this product are shown in FIGS. 1 and 2, respectively.

Example 2 148 parts of 2-isocyanatoethyl acrylate instead of 2-isocyanatoethyl methacrylate, BHT0.15
The same experiment as in Example 1 was carried out except that the parts were used.
The product corresponding to No. 2 (formula (I): R ₁ = R ₂ = H, m = n)
= 2, k = l = 0) 288 parts were obtained.

Example 3 The same experiment as in Example 1 was carried out except that 177 parts of 2-isocyanatopropyl methacrylate and 0.2 part of phenothiazine were used in place of 2-isocyanatoethyl methacrylate, and the product corresponding to compound No. 3 (formula (I):
R ₁ = R ₂ = CH ₃ , m = n = 3, k = 1 = 0) 299 parts were obtained.

Example 4 below 2,2-bis (4'-hydroxyphenyl) represented by
Hexafluoropropane propylene glycol ether 168.7 parts, toluene 300 ml, dibutyltin dilaurate
0.22 parts and 0.11 part of BHT were charged into a glass reactor equipped with a stirrer and a dropping funnel, and heated to 80 ° C.
110.3 parts of isocyanate ethyl methacrylate was added dropwise over 30 minutes. After completion of dropping, at 80 ° C, absorption of isocyanate is no longer observed in the IR spectrum (about 2 hours)
Stirring was continued.

After completion of the reaction, the product corresponding to the compound No. 4 (formula (I): R ₁ = R ₂ = CH ₃ , R ₃ was removed by evaporating toluene under reduced pressure.
= R ₄ = CH ₃ , m = n = 2, k = 2, l = 1) 279 parts were obtained.

Example 5 below 2,2-bis (4'-hydroxyphenyl) represented by
Hexafluoropropane tetraethylene glycol ether 82.6 parts, 2-isocyanatoethyl methacrylate
37.8 parts, dibutyltin dilaurate 0.08 parts, and BHT
Charge 0.04 parts into a glass reactor equipped with a stirrer, stir well in an oil bath heated to 60 ° C, and the temperature will reach 83 ° C in about 10 minutes.
Rose to.

After that, the temperature began to drop, so the temperature of the oil bath was set to 80 ° C., and stirring was continued for about 1.5 hours until the absorption of isocyanate in the IR spectrum disappeared. As a result, compound No. 5
(Corresponding to formula (I): R ₁ = R ₂ = CH ₃ , R ₃ = R ₄ =
120.5 parts of an oily substance which is considered to be H, m = n = 2, k = l = 4) was obtained.

Reference Example 1 9.9 parts of methyl methacrylate (MMA), 0.1 part of the compound obtained in Example 1 (Compound No. 1) and 0.05 part of α, α-diethoxyacetophenone were placed in a 25 ml round bottom flask and placed in a liquid nitrogen bath. Vacuum pump for 5 minutes. Next, the temperature was returned to room temperature and then returned to normal pressure with nitrogen. Do this operation 5
After repeating this operation repeatedly, the contents were put in a mold made of quartz glass in a dry box purged with nitrogen, covered with a lid, and irradiated with an infrared lamp to cure. Similarly, an experiment was conducted in which the MMA was 9.8 parts and 9.7 parts and the product of Example 1 was 0.2 parts and 0.3 parts, respectively, to obtain a cured product. An indirect tensile test was performed to examine the strength and brittleness of the obtained cured product (apparatus: Autograph IS-500 manufactured by Shimadzu Corporation). The results are shown in Fig. 3 (in the figure,
△ represents tensile strength, and ○ represents proportionality limit. ), The proportional limit does not change much with the addition amount.

Comparative Example 1 The same experiment as in Reference Example 1 was conducted except that 2,2-bis (4'-methacryloyloxyphenyl) hexafluoropropane was used in place of the product obtained in Example 1. The results are shown in Fig. 3 (in the figure, ▲ represents tensile strength, and ● represents proportional limit).

Reference Example 2 The product obtained in Example 5 (Compound No. 5) was dissolved in toluene to give a 50% solution, to which 2.5% by weight of α, α-diethoxyacetophenone was added and coated on a glass plate. When irradiated with a 2KW UV irradiation lamp, the irradiation dose was 600
Cured at mJ / cm ² .

Comparative Example 2 The same experiment as in Reference Example 2 was performed, except that neopentyl glycol diacrylate was used instead of the product obtained in Example 5. Irradiated with 3000 mJ / cm ^{2 of} ultraviolet rays,
Did not cure.

Reference Example 3 Compound No. 1 15 parts, 1,1,2,2-tetrahydroperfluorodecyl acrylate 55 parts, n-butyl acrylate 30
Part, benzophenone 3 parts, diethylaminoethanol 1
Part of the mixture was spin-coated on a glass plate and cured using a high pressure mercury lamp (80 w / cm), and then cured at an irradiation dose of about 300 mJ / cm ² . The tensile strength of the cured film is 450 kgf / cm ² ,
The elongation (proportional limit) was 10%.

Comparative Example 3 The same experiment as in Reference Example 3 was carried out except that hexafluorobisphenol-A dimethacrylate was used instead of Compound No. 1. As a result, not cured by irradiation dose 300 mJ / cm ^2, and finally cured at an irradiation of about 1,000 mJ / cm ^2.

Reference Example 4 The coating material prepared in Reference Example 3 was applied to fibers of a methyl methacrylate / ethyl acrylate (87:13) copolymer having a diameter of 0.05 mm and cured using a high pressure mercury lamp. The sheath-core filament exhibited excellent durability and abrasion resistance, and the light transmission rate was 70% per 50 cm.

Reference Example 5 Compound No. 2 (Formula (I): R ₁ = R ₂ = H, m = n = 2, k = l =
0) A coating material mixture consisting of 30 parts, 10 parts of N-vinylpyrrolidone, 60 parts of PEG-200 acrylic acid ester, 3 parts of benzophenone and 1 part of ethylaminoethanol was added to a coating having a diameter of 125 μm.
It was applied to the surface of the optical fiber (glass) and cured using a high pressure mercury lamp.

The optical transmission loss was compared between the state in which the obtained optical fiber coating was wound around a drum having a diameter of 30 cm by a bobbin and the state before winding, but no increase in the transmission loss was observed even in the state of bobbin winding. An optical fiber coating was sandwiched between two sheets of # 150 sandpaper, and an increase in transmission loss was examined with a load applied, but no increase was observed.

Comparative Example 4 An experiment similar to that of Reference Example 5 was performed using the coating material prepared in Comparative Example 3, but in any measurement, a remarkable increase in optical transmission loss was observed.

Reference Example 6 A composition consisting of 30 parts of compound No. 1, 70 parts of methyl methacrylate, 5 parts of acetylbenzoyl, and 5 parts of mercaptodiphenylcarboxylic acid was applied to a polymethylmethacrylate denture, and a mercury lamp was used at a distance of 3 mm for 50 seconds. Irradiated. The performance of the resulting cured coating film is shown in Table 2.

Reference Example 7 A composition comprising 30 parts of Compound No. 1, 70 parts of methyl methacrylate resin syrup having a degree of polymerization of 35%, 5 parts of acetylbenzoyl, and 5 parts of mercaptodiphenylcarboxylic acid was applied to a polycarbonate denture to give Reference Example 6 and Similarly, light was applied. The performance of the obtained cured coating film properties is shown in Table 2.

Comparative Example 5 The same experiment as in Reference Example 6 was conducted except that methyl methacrylate was used instead of the compound No. 1. The performance of the obtained cured coating film properties is shown in Table 2.

Comparative Example 6 The same experiment as in Reference Example 6 was performed except that neopentyl glycol dimethacrylate was used instead of compound No. 1. The performance of the obtained cured coating property is shown in Table 2.

Reference Example 8 Two tempered glass plates (200 x 200 x 5 mm) were framed with a soft vinyl chloride resin tube and fixed with a clasp to a thickness of 3 mm, to which 95 parts of 2-hydroxyethylmethacrylate, compound No.1 5 parts, azobisisobutyronitrile
0.05 part of the mixture was gently poured in, taking care that no air bubbles entered. Then hang it in a water bath with the inlet up and
Polymerization was carried out at a rate of 1 ° C./hour from 0 ° C. to 100 ° C., and further, at 100 ° C. for 30 hours. The retained metal was removed, and cold water was flown on both sides of the glass plate to release the polymer. When the tensile strength and the elongation of the obtained polymer were measured, the tensile strength was 42.5 kgf / cm ² and the elongation was 180.3%.

Reference Example 9 80 parts of 2-hydrothiethyl methacrylate, 17 parts of 2-hydroxypropyl methacrylate, 3 parts of Compound No. 1 and 0.05 part of azobisisobutyronitrile were mixed and polymerized in the same manner as in Reference Example 8 to obtain When the tensile strength and elongation of the obtained polymer were measured, the tensile strength was 32.5 kgf / cm ² ,
The elongation was 200.8%.

Reference Example 10 2-hydroxyethyl acrylate 99 parts, compound No. 1
1 part and 0.05 part of azobisisobutyronitrile were mixed, and the same experiment as in Reference Example 9 was performed. The tensile strength and elongation of the obtained polymer were 21.3 kgf / cm ² and 185.1%, respectively.

Reference Example 11 80 parts of 2-hydroxyethyl methacrylate, 20 parts of n-butyl acrylate, 3 parts of Compound No. 1 and 0.05 part of azobisisobutyronitrile were mixed, and the same experiment as in Reference Example 8 was conducted. The tensile strength and elongation of the obtained polymer are 2 respectively.
It was 8.3 kgf / cm ² and 209.7%.

Comparative Example 7 The same experiment as in Reference Example 8 was performed except that neopentyl dimethacrylate was used instead of Compound No. 1. The tensile strength and elongation of the obtained polymer are respectively 15.0 kgf / c
m ² was 120.5%.

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum of a reaction product of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane and 2-isocyanatoethyl methacrylate at a ratio of 1: 2,
FIG. 2 also shows a nuclear magnetic resonance spectrum. FIG. 3 shows the result of the tensile test.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C09D 4/02 PDW 11/10 PTY C09J 4/02 JBK D06M 13/428 G03C 1/79 G03F 7/027 502 H01B 3/44 C

Claims (2)

[Claims] 1. A general formula (I) (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, m and n each independently represent 2 or 3, and k and l are independently each other. Represents 0 or an integer of 1 to 4). 2. General formula (II) (Wherein R ₃ , R ₄ , k and l have the same meanings as described in claim 1) and 2,2-bis (4′-hydroxyphenyl) hexafluoropropane or an alkylene glycol ether thereof. General formula (III) And / or general formula (IV) (In the formula, R ₁ , R ₂ , m and n have the same meanings as described in claim 1.) An isocyanate alkyl (meth) acrylate represented by the following formula (I) ) (Each symbol in the formulas has the same meaning as described above.) A method for producing a bifunctional acrylate compound represented by the formula: