JPH08183816A - Curable resin composition - Google Patents

Abstract

PURPOSE: To produce a curable resin composition suitable for producing a resin having a high refractive index, low in water absorptivity and specific gravity, and excellent in curability. CONSTITUTION: This curable composition comprises 100 to 5wt.% vinyl oligomer represented by the formula (wherein R<1> , R<2> , R<3> , and R<4> , which are the same or different, each represent a hydrogen atom, a halogen atom, or 1-6C alkyl group; and n is an integer of 0 to 10) and 0 to 95wt.% compound copolymerizable with the above vinyl oligomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, and more specifically to an optical material such as a plastic lens for spectacles, a Fresnel lens, a lenticular lens, an optical disc substrate, a plastic optical fiber, a prism sheet for LCD, a light guide plate and the like. The present invention relates to a curable resin composition that is extremely useful as a coating material, an adhesive, and a sealing material, particularly as an optical material.

[0002]

2. Description of the Related Art Organic optical materials have been widely used in recent years as various materials because they are lighter in weight and easier to handle than glass and the like. As such resins for organic optical materials, polystyrene resins, polymethyl methacrylate resins, polycarbonate resins, diethylene glycol diallyl carbonate resins and the like have been widely used.

However, such conventional resins for organic optical materials have the drawbacks of low refractive index, large birefringence and high dispersibility and are inferior in heat resistance and impact resistance, so that they are not always satisfactory. There wasn't. In particular, diethylene glycol diallyl carbonate resin (CR-39), which is used as a lens material, has a low refractive index of 1.50. Therefore, when it is used as a lens, the edge thickness and center thickness become large, and the lens appearance However, there is a drawback in that the weight becomes worse and the weight increases.

In order to solve these drawbacks, various methods have been mainly studied for improving the refractive index. For example, Japanese Patent Publication No. 5-4404 discloses a resin in which halogen is introduced into an aromatic ring. However, the resin obtained by this technique has a high specific gravity of 1.37, although it has a large refractive index of 1.60, and is not satisfactory in terms of the lightness of the lens, which is a characteristic of plastic lenses.

Japanese Patent Publication No. 15249/1992 and Japanese Patent Laid-Open No.
0-199016 discloses a technique for obtaining a resin by polymerizing an isocyanate compound and a polythiol. However, although this resin also has a large refractive index of 1.60, it has a specific gravity of 1.30 or more, a relatively low polymerization temperature, and a high polymerization rate, which makes it difficult to control heat during polymerization. It had the drawback of large distortion.

[0006]

In view of the above situation, the present invention provides a curable resin composition suitable for producing a resin having low water absorption, low specific gravity, excellent curability and a high refractive index. It is intended to be provided.

[0007]

The gist of the first invention is as follows.
The curable resin composition comprises 100 to 5% by weight of a vinyl oligomer represented by the following general formula (I) and 0 to 95% by weight of a compound copolymerizable with the vinyl oligomer.

[0008]

Embedded image

In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each is a hydrogen atom, a halogen atom or a carbon number of 1 to 6.
Represents an alkyl group. n represents an integer of 0-10. Examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ in the vinyl oligomer represented by the above general formula (I) include chlorine, bromine, iodine and the like, having 1 to 6 carbon atoms.
As the alkyl group of, a linear or branched alkyl group,
For example, methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, pentyl, hexyl and the like can be mentioned. Preferably, R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, and n is 0.

The vinyl oligomer represented by the general formula (I) is not particularly limited, and examples thereof include the followings. Bis (4-vinylthiophenyl) sulfide Bis (3-methyl-4-vinylthiophenyl) sulfide Bis (3,5-dimethyl-4-vinylthiophenyl) sulfide Bis (2,3,5,6-tetramethyl- 4-vinylthiophenyl) sulfide bis (3-hexyl-4-vinylthiophenyl) sulfide bis (3,5-dihexyl-4-vinylthiophenyl)
Sulfide Bis (3-chloro-4-vinylthiophenyl) Sulfide Bis (3,5-dichloro-4-vinylthiophenyl) Sulfide Bis (2,3,5,6-tetrachloro-4-vinylthiophenyl) Sulfide Bis (3-Bromo-4-vinylthiophenyl) sulfide Bis (3,5-dibromo-4-vinylthiophenyl) sulfide Bis (2,3,5,6-tetrabromo-4-vinylthiophenyl) sulfide Among these, bis (4-Vinylthiophenyl) sulfide, bis (3-methyl-4-vinylthiophenyl) sulfide and bis (3,5-dimethyl-4-vinylthiophenyl) sulfide are preferred.

The method for producing the above vinyl oligomer is not particularly limited. For example, a dithiol compound represented by the following general formula (III) is reacted with dihaloethane and then dehalogenated in a polar solvent such as dimethylsulfoxide. How to use hydrogen chloride (Жypнaл Opгaничecкoй
Xимии, т. 28, вып. 9 1905, 19
92) and the like.

[0012]

[Chemical 4]

In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above. In this case, compounds having different numbers of n in the general formula (I) can be obtained by changing the reaction conditions such as the amount of dihaloethane used and the charging method. The vinyl oligomer represented by the general formula (I) can also be obtained by a method of reacting a mercaptan compound and vinyl halide in the presence of a base (JP-A-3-2875752).

The compound copolymerizable with the vinyl oligomer represented by the above general formula (I) is not particularly limited, and examples thereof include a vinyl group-containing monomer, an epoxy group-containing monomer, an epoxy group-containing oligomer, and a thiol. Examples thereof include a monomer having a group. These may be used alone or in combination of two or more. Further, not only a monofunctional compound but also a polyfunctional compound can be selected according to the purpose of use.

As the above-mentioned vinyl group-containing monomer,
For example, the following may be mentioned. Aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, bromostyrene, chloromethylstyrene, methoxystyrene, butylthiostyrene, divinylbenzene; cyclohexene, 4-vinylcyclohexene, 1,5-cycloocta Alicyclic vinyl compounds such as diene and 5-vinylcyclo [2,2,1] hept-2-ene.

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, chlorophenyl ( (Meth) acrylate, bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, cyanophenyl ( Data) acrylate, chloromethyl (meth) acrylate, bromoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate, N, N-
Monofunctional (meth) acrylates such as dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and (meth) acrylic acid.

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, tripropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylics, polyols such as pentaerythritol tetra (meth) acrylate, unsaturated fatty acids such as poly (meth) acrylate, and derivatives thereof.

Ethyl vinyl ether, n-propyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, isoamyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, n-octadecyl vinyl ether, dodecyl vinyl ether, propenyl ether propylene carbonate, ethylene glycol. Monovinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether,
Diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, butanediol monovinyl ether, butanediol divinyl ether, hexanediol monovinyl ether, hexanediol divinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanol divinyl ether, phenyl vinyl ether Vinyl ether compounds such as.

Ethyl vinyl sulfide, n-propyl vinyl sulfide, isobutyl vinyl sulfide, ter
t-butyl vinyl sulfide, n-amyl vinyl sulfide, isoamyl vinyl sulfide, cyclohexyl vinyl sulfide, 2-ethylhexyl vinyl sulfide, n-octadecyl vinyl sulfide, dodecyl vinyl sulfide, propenyl sulfide propylene carbonate, ethylene glycol monovinyl sulfide, ethylene glycol divinyl sulfide. , Diethylene glycol monovinyl sulfide, diethylene glycol divinyl sulfide, triethylene glycol monovinyl sulfide, triethylene glycol divinyl sulfide, butanediol monovinyl sulfide, butanediol divinyl sulfide, hexanediol monovinyl sulfide, hexanediol divinyl sulfide, cyclohexane dimeta Over mono vinyl sulfide, cyclohexanedimethanol divinyl sulfide, vinyl sulfide compounds such as phenyl vinyl sulfide.

The monomer having the epoxy group and the oligomer having the epoxy group are not particularly limited, and examples thereof include the followings. Allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, sec-butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether,
Monofunctional glycidyl ethers such as 2-methyloctyl glycidyl ether.

1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene Polyfunctional glycidyl ethers such as glycol diglycidyl ether.

Glycidyl esters such as glycidyl (meth) acrylate, diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate and dimethyldiglycidyl hexahydrophthalate. Bisphenol A, bisphenol F, brominated bisphenol A, biphenol, tetramethylbiphenol, resorcin, hydroquinone, dihydroxynaphthalene, bisphenol novolac resin, phenol novolac resin, cresol novolac resin, dicyclopentadiene phenol resin, terpene phenol resin, naphthol novolac resin, etc. Glycidyl ethers.

3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate,
3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, allylcyclohexene dioxide,
3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4- Epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethyl Alicyclic epoxy resin compounds such as siloxane.

The monomer having the thiol group is not particularly limited, and examples thereof include the followings. 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,2
-Cyclohexanedithiol, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, butanedithiol bisthioglycolate, butanedithiol bisthiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate , Aliphatic polythiols such as pentaerythritol tetrathioglycolate and pentaerythritol tetrathiopropionate.

Aliphatic sulfides such as bis (2-mercaptoethyl) sulfide, bis (3-mercaptopropyl) sulfide, bis (4-mercaptobutyl) sulfide and bis (8-mercaptooctyl) sulfide.
Aromatic dithiols such as 1,2-benzenedithiol, 4-methyl-1,2-benzenedithiol, 4-butyl-1,2-benzenedithiol and 4-chloro-1,2-benzenedithiol.

The content of the vinyl oligomer in the curable resin composition of the present invention is 100 to 5% by weight.
When the content of the vinyl oligomer is less than 5% by weight, the resin obtained by curing has a low refractive index. It is preferably 100 to 10% by weight. When the content of the vinyl oligomer in the curable resin composition of the present invention is 100% by weight, the curable resin composition of the present invention is composed of the vinyl oligomer alone. Even in this case, the effects of the present invention can be sufficiently exerted.

Examples of constitutions of the curable resin composition of the present invention include, for example, the vinyl oligomer and vinyl compound, the vinyl oligomer and unsaturated fatty acid derivative, the vinyl oligomer and epoxy group-containing monomer or oligomer, and the vinyl oligomer. And unsaturated fatty acid derivatives and vinyl compounds, and the above-mentioned vinyl oligomers and unsaturated fatty acid derivatives and polythiols.

The curable resin composition of the present invention can be cured by heat, light or the like by a usual method. When the compound copolymerizable with the vinyl oligomer is a vinyl group-containing monomer or a thiol group-containing monomer other than vinyl ethers, a radical polymerization initiator can be used as the polymerization initiator.

The polymerization initiator used in the case of the above heat curing is not particularly limited and includes, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, 2,2. Azo compounds such as ′ -azobis (2,4-dimethylvaleronitrile); ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide; benzoyl peroxide, 2,4
Examples thereof include diacyl peroxide such as dichlorobenzoyl peroxide.

The polymerization initiator used in the case of the above photo-curing is not particularly limited, and for example, p-isopropyl-
α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 4′-methylthio-2,2-dimethyl-2-morpholinoacetophenone, benzoin isobutyl ether, 2-chlorothioxanthone, 2, 4,6-
Examples thereof include trimethylbenzoyldiphenylphosphine oxide.

When the compound copolymerizable with the vinyl oligomer is a vinyl ether, a vinyl sulfide, an epoxy group-containing monomer, an epoxy group-containing oligomer, etc., a cationic polymerization initiator may be used as the polymerization initiator. it can. The polymerization initiator used in the case of the thermosetting is not particularly limited, and for example, boron trifluoride / diethyl ether complex, boron trifluoride / amine complex, aluminum chloride, titanium tetrachloride, tin tetrachloride,
Lewis acids such as iron (III) chloride and zinc chloride; ammonium salts, sulfonium salts, oxonium salts, phosphonium salts and the like can be mentioned. The polymerization initiator used in the case of the photo-curing is not particularly limited, and examples thereof include an aromatic sulfonium salt, an aromatic iodonium salt, an aromatic diazonium salt, and an aromatic phosphonium salt.

In the above polymerization, if necessary, a light stabilizer, an ultraviolet absorber, an antioxidant, a coloring inhibitor, a polymerization inhibitor, a release agent, an antifoaming agent, a bluing agent, a fluorescent dye, etc. are added. Agents may be added as appropriate.

In the above polymerization, the polymerization temperature and the polymerization time cannot be unconditionally specified because they vary depending on the composition of the curable resin composition of the present invention, the intended use, the type of polymerization initiator used and the amount thereof used. The polymerization temperature in thermosetting is preferably 0 to 200 ° C., more preferably 2
It is 0 to 150 ° C. The polymerization time is preferably 10 minutes to 50 hours, more preferably 1 to 24 hours.

The light used for the photocuring is preferably ultraviolet light, and examples of the light source include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp and the like. The irradiation time depends on the light source used,
Since it varies depending on the type and amount of the polymerization initiator, it cannot be specified unconditionally, but it is preferably 1 minute to 24 hours, more preferably 5 minutes to 10 hours. Irradiation temperature is 0-10
0 degreeC is preferable, More preferably, it is 20-50 degreeC.

The second curable resin composition of the present invention comprises an epoxy oligomer 100 represented by the following general formula (II):
5% by weight and 0 to 95% by weight of a compound copolymerizable with the epoxy oligomer.

[0036]

Embedded image

In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each is a hydrogen atom, a halogen atom or a carbon number of 1 to 6.
Represents an alkyl group. m represents an integer of 0-10. R in the vinyl oligomer represented by the above general formula (II)
Examples of the halogen atom represented by ⁵ , R ⁶ , R ⁷ and R ⁸ include chlorine, bromine, iodine and the like, and the alkyl group having 1 to 6 carbon atoms is a linear or branched alkyl group. Examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, pentyl, hexyl and the like. Preferably R ⁵ , R ⁶ , R ⁷ and R
^{All 8} are hydrogen atoms, and m is 0.

The epoxy oligomer represented by the general formula (II) is not particularly limited, and examples thereof include the following. Bis [4- (2,3-epoxypropylthio) phenyl] sulfide Bis [4- (2,3-epoxypropylthio) -3-methylphenyl] sulfide Bis [4- (2,3-epoxypropylthio)- 3,5
-Dimethylphenyl] sulfide Bis [4- (2,3-epoxypropylthio) -2,
3,5,6-Tetramethylphenyl] sulfide

Bis [4- (2,3-epoxypropylthio) -3-hexylphenyl] sulfide Bis [4- (2,3-epoxypropylthio) -3,5
-Dihexylphenyl] sulfide bis [4- (2,3-epoxypropylthio) -3-chlorophenyl] sulfide bis [4- (2,3-epoxypropylthio) -3,5
-Dichlorophenyl] sulfide bis [4- (2,3-epoxypropylthio) -2,
3,5,6-Tetrachlorophenyl] sulfide bis [4- (2,3-epoxypropylthio) -3-bromophenyl] sulfide bis [4- (2,3-epoxypropylthio) -3,5
-Dibromophenyl] sulfide bis [4- (2,3-epoxypropylthio) -2,
3,5,6-Tetrabromophenyl] sulfide, among them, bis [4- (2,3-epoxypropylthio) phenyl] sulfide, bis [4- (2,3-epoxypropylthio) -3-methylphenyl] Sulfide, bis [4- (2,3-epoxypropylthio)-
3,5-Dimethylphenyl] sulfide is preferred.

The method for producing the above-mentioned epoxy oligomer is not particularly limited. For example, a method in which an epihalohydrin is added to a dithiol compound represented by the following general formula (IV) and then a ring-closing reaction is carried out (J. Appl. Poly.
Sci ,. 39, 1623 (1990), U.S. Pat. No. 2,731,437) and the like.

[0041]

[Chemical 6]

In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as defined above. The compound copolymerizable with the epoxy oligomer is not particularly limited, and examples thereof include a monomer having an epoxy group, an oligomer having an epoxy group, a monomer having a vinyl ether group, a monomer having a vinyl sulfide group, and a monomer having a thiol group. Can be mentioned. Not only monofunctional compounds but also polyfunctional compounds can be selected according to the purpose of use. Moreover, these compounds can be used individually or in combination of 2 or more types.

The monomer having the epoxy group and the oligomer having the epoxy group are not particularly limited, and examples thereof include those mentioned above. The vinyl ether group-containing monomer is not particularly limited, and examples thereof include the vinyl ether compounds described above. The monomer having a vinyl sulfide group is not particularly limited, and examples thereof include the vinyl sulfide compounds described above. The monomer having the thiol group is not particularly limited,
For example, those mentioned above can be mentioned.

The content of the epoxy oligomer in the curable resin composition of the second invention is 100 to 5% by weight.
Is. When the content of the epoxy oligomer is less than 5% by weight, the refractive index of the resin obtained by curing becomes low. It is preferably 100 to 10% by weight. When the content of the epoxy oligomer in the second curable resin composition of the present invention is 100% by weight, the curable resin composition of the present invention is composed of the epoxy oligomer alone. Even in this case, the effects of the present invention can be sufficiently exerted.

Examples of the constitution of the curable resin composition of the second invention include, for example, the above epoxy oligomer and a monomer having an epoxy group, the above epoxy oligomer and an oligomer having an epoxy group, the above epoxy oligomer and a vinyl ether group. Examples thereof include a monomer, a monomer having an epoxy oligomer and a vinyl sulfide group, a monomer having an epoxy oligomer and a thiol group, a monomer having an epoxy oligomer and a vinyl sulfide group, and a monomer or an oligomer having an epoxy group.

The curable resin composition of the second invention can be cured by heat, light or the like by a usual method. When the compound copolymerizable with the epoxy oligomer is an epoxy group-containing monomer, an epoxy group-containing oligomer, a vinyl ether group-containing monomer, or a vinyl sulfide group-containing monomer, a cationic polymerization initiator can be used. . The cationic polymerization initiator is the same as the cationic polymerization initiator described above in the description of the vinyl oligomer in the first aspect of the invention.
When the compound copolymerizable with the epoxy oligomer is a monomer having a thiol group, a curing accelerator can be used. Examples of the curing accelerator include tertiary amines such as triethylamine, hexamethylenetetramine, and tetramethylguanidine; imidazoles such as 2-ethyl-4-methylimidazole and 2,4-diethylimidazole; dioctyltin dilaurate; Examples thereof include metal salts such as tin octylate.

In the present invention, the vinyl oligomer represented by the above general formula (I) or the above general formula (II), the epoxy oligomer, and a compound copolymerizable therewith are mixed and cured, It is possible to obtain a curable resin composition whose refractive index, specific gravity, water absorption, etc. can be easily adjusted according to the purpose of use and the like. Further, the above general formula (I)
To obtain a curable resin composition having features such as high refractive index, low specific gravity and low water absorption even when the vinyl oligomer represented by the formula (1) and the epoxy oligomer represented by the general formula (II) are individually cured. You can

[0048]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 Preparation of vinyl oligomer In a 5 L four-necked flask, 250 g of bis (4-mercaptophenyl) sulfide and 1,2-dichloroethane 20 were added.
00g and tetrabutylammonium bromide 8g were put, and while keeping at 30 ° C, 30% potassium hydroxide aqueous solution 4
10 g was dropped. After reacting at 30 ° C. for 2 hours, water 2
00 g was added and the crystals were collected by filtration. After drying, the crystals were placed in a 5 L brown four-necked flask, 2,000 g of dimethyl sulfoxide was added, and the crystals were kept at 30 ° C. or lower to 50
% Potassium hydroxide aqueous solution 320g was dripped. After reacting for 2 hours, 2000 g of water was added to separate the organic layer.
After washing this organic layer with water, R ¹ in the general formula (I),
260 g of bis (4-vinylthiophenyl) sulfide in which R ² , R ³ and R ⁴ are hydrogen atoms was obtained. It was a colorless and transparent liquid, and its refractive index was n ²⁵ _D = 1.695. Vinyl oligomers represented by the general formula (I) in which R ¹ , R ² , R ³ and R ⁴ are different were obtained by the same method.

Example 1 A mixture of 16 g of bis (4-vinylthiophenyl) sulfide obtained in Reference Example 1 and 4 g of styrene was added to 2,2'-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator. ) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) 0.0
4 g (0.2% by weight) was dissolved to obtain a curable resin composition. This curable resin composition has a diameter of 5 cm and a thickness of 0.3.
The mixture was poured into a glass mold of cm, heated at 40 ° C. for 5 hours, heated to 80 ° C. over 7 hours, kept at 80 ° C. for 3 hours, and then demolded. This was washed with methylene chloride and then annealed at 100 ° C. for 1 hour. The resulting curable resin was uniform and colorless and transparent. Each physical property was evaluated by the following methods and shown in Table 1.

(1) Refractive index: 25 using an Abbe refractometer (4T type manufactured by Atago Co., Ltd.)
The refractive index at ° C was measured. (2) Specific gravity It was measured according to JIS K 6911. (3) Total light transmittance Using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., model NDH-300A), the total light transmittance of a flat plate having a thickness of 3 mm was measured. (4) Boiling water absorption rate Measured according to JIS K 6911.

Examples 2 to 9 and Comparative Example 1 A curable resin was prepared in the same manner as in Example 1 except that the component compositions shown in Table 1 were used, and the respective physical properties were evaluated and shown in Table 1. .

Example 10 A mixture of 15 g (0.050 mol) of bis (4-vinylthiophenyl) sulfide obtained in Reference Example 1 and 5 g of styrene was added to 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF). Lucillin T
0.6 g (3% by weight) of PO) was dissolved to obtain a curable resin composition. This curable resin composition was poured into a quartz glass mold having a diameter of 5 cm and a thickness of 0.3 cm, irradiated with a high pressure mercury lamp at 40 ° C. for 1 hour, and then demolded. This was washed with methylene chloride and then annealed at 100 ° C. for 1 hour. The resulting curable resin was uniform and colorless and transparent. Each physical property was evaluated by the above methods, and Table 1
It was shown to.

In Table 1, BMA is n-butyl methacrylate, AMA is allyl methacrylate and DEDM.
Is diethylene glycol dimethacrylate, DMD
S is bis (2-mercaptoethyl) sulfide, M
Y-790 is a bisphenol A type epoxy resin (manufactured by Ciba Geigy) and V-65 is 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries).
SI-H40 is a cationic polymerization initiator (manufactured by Sanshin Chemical Co., Ltd., San-Aid SI-H40), and Lucillin TPO is
It represents 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF).

[0055]

[Table 1]

Reference Example 2 Preparation of Epoxy Oligomer In a 1 L four-necked flask, 100 g of bis (4-mercaptophenyl) sulfide and 150 epichlorohydrin were added.
g, 300 g of dioxane were added and 1 was kept at 10 ℃.
20 g of 0% aqueous potassium hydroxide solution was added dropwise. After reacting at 20 ° C. for 2 hours, the temperature was raised to 60 ° C. and 90 g of a 45% aqueous sodium hydroxide solution was added dropwise. After reacting for 12 hours at 60 ° C., water and toluene were added to separate the layers. After the organic layer is neutralized and washed with water, the solvent is distilled off, and bis (2,3) in which R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms in the general formula (II).
-Epoxypropylthiophenyl) sulfide 140 g
I got It is a colorless transparent liquid with a refractive index of n ²⁵ _D.
= 1.669. Epoxy oligomers represented by the general formula (II) in which R ⁵ , R ⁶ , R ⁷ and R ⁸ were different were obtained by the same method.

Example 11 A mixture of 16 g of bis [4- (2,3-epoxypropylthio) phenyl] sulfide obtained in Reference Example 2 and 4 g of epoxy resin (CY-177) was added to a cationic polymerization initiator (San Aid SI). -60) 0.4 g was dissolved to obtain a curable resin composition. This curable resin composition has a diameter of 5c
m, pour into a 0.3 cm thick glass mold, and 130 ℃
After heating at 20 ° C. for 20 hours, the mold was removed. The resulting curable resin was uniform and colorless and transparent. Each physical property was evaluated by the methods described above and is shown in Table 2.

Examples 12 to 18 and Comparative Example 2 A curable resin was prepared in the same manner as in Example 11 except that the component compositions shown in Table 2 were used, and its physical properties were evaluated.
It was shown to. In Table 2, CY177 is an alicyclic epoxy resin (main component: bis (4,5-epoxy-2-methylcyclohexylmethyl) adipate, manufactured by Ciba Geigy)
CY179 is an alicyclic epoxy resin (main component: 3,4-
Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Ciba Geigy),
MPS is bis (4-mercaptophenyl) sulfide, SI-60 is a cationic polymerization initiator (San-Aid SI-60 manufactured by Sanshin Chemical Co., Ltd.), and EMI is 2-ethyl-4-methylimidazole. Represent

[0059]

[Table 2]

[0060]

EFFECT OF THE INVENTION The curable resin composition of the present invention, having the above-mentioned constitution, has not only excellent curability and high refractive index, but also excellent physical properties such as low water absorption and low specific gravity. Since it has specific properties, it is particularly useful as an optical material, and also extremely useful as a paint, an adhesive, a sealing material and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08G 59/40 NKH 65/26 NQN 75/14 NTY 81/00 NUS (72) Inventor Suzuki Michio Hyogo 1 346, Miyanishi, Harima-cho, Kako-gun, Sumitomo Seika Chemicals Co., Ltd. 1st Research Laboratory (72) Inventor, Kazuo Sakiyama 1st, Irifune-cho, Shimaki-ku, Himeji City, Hyogo Prefecture

Claims (6)

[Claims] 1. A curable composition comprising 100 to 5% by weight of a vinyl oligomer represented by the following general formula (I) and 0 to 95% by weight of a compound copolymerizable with the vinyl oligomer. Resin composition. Embedded image In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different,
It represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0-10. 2. The curable resin composition according to claim 1, wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms. 3. The compound copolymerizable with the vinyl oligomer is at least selected from the group consisting of a monomer having a vinyl group, a monomer having an epoxy group, an oligomer having an epoxy group, and a monomer having a thiol group. The curable resin composition according to claim 1, which is one kind. 4. A curable composition comprising 100 to 5% by weight of an epoxy oligomer represented by the following general formula (II) and 0 to 95% by weight of a compound copolymerizable with the epoxy oligomer. Resin composition. Embedded image In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different,
It represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer of 0-10. ^5. The curable resin composition according to claim 4, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms. 6. A compound copolymerizable with the epoxy oligomer is selected from monomers having an epoxy group, oligomers having an epoxy group, monomers having a vinyl ether group, monomers having a vinyl sulfide group, and monomers having a thiol group. The curable resin composition according to claim 4, which is at least one selected from the group consisting of: