JP2003176332A - Heterocycle-containing compound and composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound and a composition suitably used for adhesives, coatings and resin molded products and a cured product of the composition suitably used for optical members. <P>SOLUTION: This heterocycle-containing compound is represented by general formula (I). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a compound containing a heterocycle in the molecule, a composition containing the compound, and a cured product obtained by curing the composition. Specifically, it relates to a compound, a composition, and a cured product that are preferably used for an adhesive, a coating agent, a resin molded product, and the like, and an optical member.

[0002]

2. Description of the Related Art In recent years, optical elements such as lenses are required to have complicated shapes such as element shapes and element surface shapes. Since the resin material can be molded by various molding methods, there is an advantage that an element having a relatively complicated shape can be easily molded. Further, the resin material is lighter in weight than glass, has toughness, and is hard to break. On the other hand, for example, when an optical element, specifically, a lens is created, even if the lens has the same focal length, if it is manufactured by using a material having a high refractive index, the lens can be made thin, and the weight and the optical path can be reduced. There is an advantage that the degree of freedom of design is improved.

[0003]

However, since the chemical structure of the resin material is restricted, there is usually a problem that the refractive index is not so high. Therefore, it has been proposed to obtain a resin material having a high refractive index by introducing an aromatic ring, a halogen atom, or a sulfur atom into the structure.
(See Japanese Patent Publication No. 4-30947 and Japanese Patent Publication No. 6-76370). But,
Further, a resin material having a high refractive index is required.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors in order to obtain a resin material having a high refractive index and having light and thermosetting properties, the specific novel heterocycle-containing compound has a high They have found that they have a refractive index, and have reached the present invention. That is, the gist of the present invention lies in the heterocycle-containing compound represented by the following general formula (I).

[0005]

[Chemical 2]

(In the formula, R ^{1 to} R ⁴ are independently carbon numbers.
Represents 1 to 10 hydrocarbon groups. X ^{1 to} X ⁸ are independently O
Or represents S. Y ¹ and Y ² are each independently O or
Represents S. Z ¹ and Z ² are each independently S, --SO _2- ,
Represents -S-S- or -CO-. m, n, p, and q each independently represent an integer of 0 to 10. r represents an integer of 0 to 10. The benzene ring in the formula may have a substituent. However, Z ¹
= Z ² = S, p = q = r = 0, and X ⁵ = X ⁸ = S and Z ¹ = Z ² = −SO ₂
-And except for Y ¹ = Y ² = O. )

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The heterocycle-containing compound of the present invention is represented by the above general formula (I).

R ^{1 to} R ⁴ are hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. The hydrocarbon group is composed of carbon atoms and hydrogen atoms, and is not particularly limited as long as it is a divalent group having 1 to 10 constituent carbon atoms. Specifically, a methylene group, an ethylene group, a 1,3-propylene group, a 1,1-propylene group,
1,2-propylene group, 1,4-butylene group, 1,1-
Butylene group, 1,2-butylene group, 1,3-butylene group, 1,5-pentylene group, 1,1-pentylene group,
1,2-pentylene group, 1,3-pentylene group, 1,4
-Pentylene group, 1,6-hexylene group, 1,1-hexylene group, 1,2-hexylene group, 1,3-hexylene group, 1,4-hexylene group, 1,5-hexylene group Base,
1,7-heptylene group, 1,8-octylene group, 1,6
-(2-ethyl) hexylene group, 1,9-nonylene group,
A chain aliphatic hydrocarbon group such as a 1,10-decylene group;
4-cyclohexylene group, 1,3-cyclohexylene group, cycloaliphatic hydrocarbon group such as 1,2-cyclohexylene group; 1,4-phenylene group, 1,3-phenylene group,
1,4-phenylene group, 1,4-xylylene group, 1,3
-Aromatic hydrocarbon groups such as a xylylene group and a 1,2-xylylene group. Preferably an aliphatic hydrocarbon group,
Particularly preferably linear aliphatic hydrocarbon, more preferably methylene group, ethylene group, 1,3-propylene group, 1,
A linear chain aliphatic hydrocarbon group having 1 to 6 carbon atoms such as 4-butylene group, 1,5-pentylene group, 1,6-hexylene group is used.

X ^{1 to} X ⁸ each independently represent O or S. X ² , X ³ , X ⁶ and X ⁷ preferably represent S. Y ¹
And Y ² are each independently O or S, preferably S
Represents

Z ¹ and Z ² are each independently S, --SO
_2- , -S-S- or -CO-, preferably S or -SO ₂
Represents-. m, n, p, and q each independently represent an integer of 0 to 10, preferably 0 to 5. r is 0 to 10, preferably 0
Represents an integer of 5.

The benzene ring in the above formula may have a substituent. The substituent is not particularly limited, but may be methyl group, ethyl group, n-propyl group, i-
Propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like having 1 to 10 carbon atoms. C5-C10 cycloaliphatic hydrocarbon groups such as chain aliphatic hydrocarbon groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, and cyclooctyl groups, phenyl groups, xylyl groups, naphthyl groups, benzyl groups, phenethyl groups Aromatic hydrocarbon groups having 6 to 10 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group Group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, and other alkoxy groups having 1 to 10 carbon atoms, fluorine atom, chlorine atom, bromine atom, iodine A halogen atom such as an atom is preferable, and an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom are more preferable.

However, in the general formula (I), Z ¹ = Z ² =
Compound with S, p = q = r = 0, and X ⁵ = X ⁸ = S and Z ¹ = Z ² = −SO ₂ −
And compounds with Y ¹ = Y ² = O are excluded. The heterocycle-containing compound of the present invention can lower the curing temperature and increase the curing rate as compared with the epoxy compound by containing sulfur or the like as a hetero atom of Y ¹ and Y ² .

The method for producing the heterocycle-containing compound of the present invention is not particularly limited as long as it is a method by which the desired compound can be synthesized. The compound in which Y ¹ and Y ² are O is synthesized, for example, as follows. (1) A method of obtaining a compound such as (II) by reacting dihydroxydiphenyl sulfone with epichlorohydrin in the presence of a base. Epichlorohydrin is usually 2 to 2 relative to dihydroxyphenyl sulfone.
It is used in an amount of 0 mol times, preferably 4 to 10 mol times.
As the base, sodium hydroxide, potassium hydroxide and the like are preferably used. During the reaction, a solvent is optionally used, but when a solvent is used, an alcohol solvent such as toluene, dimethylformamide, dimethylsulfoxide, and isopropyl alcohol is preferably used.
The solvent may be used alone or in combination of two or more kinds. The reaction temperature is generally -20 to 200 ° C, preferably 0 to 150.
It is in the range of ° C. After the reaction is completed, the reaction product is washed with water, and then the solvent and residual epichlorohydrin are distilled off to obtain the desired product.

[0014]

[Chemical 3]

[Chemical 4]

(2) Dichlorodiphenyl sulfone is reacted with mercaptoethanol in the presence of a base to synthesize a dihydroxy compound, which is reacted with epichlorohydrin to obtain a compound such as (III). As the base, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, sodium hydride or the like can be used. The solvent is used as necessary, but toluene, xylene, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like are used.

A compound in which Y ¹ and / or Y ² is S is
For example, a method for converting a known oxirane ring using a sulfurizing agent into a thiirane ring by using a compound in which a heteroatom of a three-membered ring is an oxygen atom (hereinafter abbreviated as “corresponding epoxy compound”) as a raw material in a heterocycle-containing compound Is synthesized by. Examples of the sulfurizing agent include thioureas and thiocyanates, and preferably thiourea and potassium thiocyanate are used. For example, JM Charleswort
h, J. Polym. Sci. Polym. Phys., 17, 329 (1979).
A method using thiourea described in etz et al, J. Org. Chem., 26, 3467 (1961) is described. The corresponding epoxy compound can be obtained by the above methods (1) and (2).

The composition containing the heterocycle-containing compound represented by the general formula (I) of the present invention is a curable composition which can be polymerized and cured by light, heat or the like, and has the general formula (I).
In addition to the heterocycle-containing compound represented by the formula (1), a compound selected from a compound having a functional group capable of reacting with the compound represented by the general formula (I) and a radically polymerizable compound is usually contained. Further, the composition of the present invention preferably contains a curing aid in addition to this. Examples of the curing aid include photoinitiators and curing agents. The content of the compound represented by the general formula (I) in the composition of the present invention is
It is usually 1 to 100% by weight, preferably 20 to 100% by weight, based on the curable composition.

The compound having a functional group capable of reacting with the heterocycle-containing compound represented by the general formula (I) includes (i)
A cationically polymerizable compound, (ii) anionically polymerizable compound and the like are preferably used. In addition, hydroxyl group,
Compounds having functional groups such as mercapto group, carboxyl group, amino group, isocyanate group and thioisocyanate group, cyclic carbonate, cyclic thiocarbonate,
Examples thereof include cyclic ethers and cyclic thioethers. The amount of the compound having a functional group capable of reacting with the heterocycle-containing compound represented by the general formula (I) is usually 0 to 95% by weight, preferably 0 to 80% by weight, based on the curable composition. is there. By mixing with a compound having a functional group capable of reacting with the heterocycle-containing compound represented by the general formula (I),
There is an advantage that the viscosity and the refractive index can be adjusted.

The term (i) cationically polymerizable compound means a compound having a cationically polymerizable functional group, and examples thereof include vinyl ethers, allyl compounds, epoxy compounds, cyclic ethers such as oxetanes, thiirane ring-containing compounds, and thietanes. And cyclic thioethers, carbonates, thiocarbonates and the like.

(Ii) Anionically polymerizable compound means a compound having anionically polymerizable functional group, for example, vinyl ether, allyl compound, epoxy compound, cyclic ethers such as oxetanes, thiirane ring-containing compounds, and thietanes. And cyclic thioethers, carbonates, thiocarbonates and the like.

The radical-polymerizable compound is a compound having at least one radical-polymerizable ethylenically unsaturated bond in the molecule, and refers to a compound which can be polymerized by a radical reaction. The number of ethylenically unsaturated bonds in the radical-polymerizable unsaturated bond-containing compound is not particularly limited, but usually 1 to 2
The number is 0, preferably 2 to 20, more preferably 2 to 10. Specifically, styrene or its derivatives; vinyl compounds such as vinyl esters and vinyl ethers;
(Meth) acrylates, etc. are mentioned. The addition amount of the radically polymerizable compound is usually 0 to 95% by weight, preferably 0 to 80% by weight, based on the curable composition. By mixing the radically polymerizable compound, it becomes possible to adjust the viscosity, the refractive index, and the stepwise curing.

Examples of styrene and its derivatives include styrene, indene, p-methylstyrene, α-methylstyrene, p-methoxystyrene and p-tert-styrene.
Examples include butoxystyrene, p-chloromethylstyrene, p-acetoxystyrene, divinylbenzene and the like. Examples of vinyl esters include vinyl acetate,
Vinyl propionate, vinyl butyrate, vinyl caproate,
Examples thereof include vinyl cinnamate.

The vinyl ethers include ethyl vinyl ether, n-propyl vinyl ether, butyl vinyl ether, ethylene glycol monovinyl ether, butanediol divinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, 4,
4-bis (vinyloxyethyloxy) biphenyl, 1,4-bis (vinyloxyethyloxy) benzene, 4,4-bis (vinyloxyethyloxy) diphenyl sulfide, 4,4-bis (vinyloxyethyloxy) diphenyl Sulfone, ethyl vinyl sulfide, n-propyl vinyl sulfide,
Cyclohexyl vinyl sulfide, ethylene glycol monovinyl sulfide, ethylene glycol divinyl sulfide, diethylene glycol divinyl sulfide,
Examples include phenyl vinyl sulfide.

As the vinyl compound, in addition to these, N
-Vinylpyrrolidone, N-acryloylmorpholine,
N-vinylcaprolactone, N-vinylpiperidine, N-
Also included are compounds such as vinylformamide, vinylnorbornene, vinylmethacrylate and the like.

Examples of the (meth) acrylates include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, sulfur-containing (meth) acrylates, and halogen-containing methacrylates.

As the monofunctional (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, 2
-Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) Acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, n-butoxyethyl (meth) Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,4,4,4 -Hexa Rorobuchiru (meth)
Acrylate, perfluorooctylethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4
-Hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 2-hydroxy -3-phenoxypropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid, 2-
(Meth) acryloyloxyethyl succinic acid, 2- (meth)
Examples thereof include acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and 2- (meth) acryloyloxyethyl acid phosphate.

As the polyfunctional (meth) acrylates,
1,3-propanediol di (meth) acrylate, 1,3-butane
Tandiol di (meth) acrylate, 1,4-butanedio
(Meth) acrylate, 1,6-hexanediol di
(Meth) acrylate, 1,9-nonanediol di (meth)
Acrylate, ethylene glycol di (meth) acrylate
, Polyethylene glycol di (meth) acrylate
G, propylene glycol di (meth) acrylate,
Lipropylene glycol di (meth) acrylate, neo
Pentyl glycol di (meth) acrylate, trimethyl
Roll propane tri (meth) acrylate, pentaery
Thritol di (meth) acrylate, pentaerythritol
Tri (meth) acrylate, pentaerythritol
Tetra (meth) acrylate, dipentaerythritol
Hexa (meth) acrylate, glycerin di (meth) a
Acrylate, 2-hydroxy-3- (meth) acryloyloxy
Cypropyl (meth) acrylate, bis (oxymethyi)
Le) tricyclo [5.2.0^2,6] Decan = di (meth) acryl
Bis (oxymethyl) pentacyclo [6.5.1.1^3,6.
0^{2, 7}.0^9,13] Pentadecane = di (meth) acrylate, etc.
Is mentioned.

Examples of the sulfur-containing methacrylate compound include (bis2- (meth) acryloyloxyethylthio)
Ethane, 1,1,1-tris ((meth) acryloylthiomethyl) ethane, 4,4-dimercaptodiphenyldi (meth) acrylate, 4,4'-bis (β- (meth) acryloyloxyethylthio) diphenyl Sulfone, p-bis (β- (meth) acryloyloxyethylthio) xylylene, m-bis (β- (meth) acryloyloxyethylthio) xylylene, p-bis- (β- (meth) acryloyloxyethyloxyethylthio ) Xylylene, m-bis- (β- (meth) acryloyloxyethyloxyethylthio) xylylene α, α-bis (β- (meth) acryloyloxyethylthio) -2,3,5,6-tetrachloro-p -Examples include xylylene.

Examples of the allyl compound include diallyl succinate, diallyl phthalate, diethyl allyl malonate, p-bis (β-allyloxyethylthio) xylylene and p-bis (β-allylthioethylthio) xylylene. Can be mentioned.

Examples of the photoinitiator used in the present invention include photobase generators, photoacid generators and photoradical generators. The photobase generator is a compound that produces a base upon irradiation with active energy rays such as visible light, ultraviolet rays, and electron beams. Examples of the photobase generator include a nonionic photobase generator and an ionic photobase generator. Examples of the nonionic photobase generator include oximes and carbamic acid esters, and examples of the ionic photobase generator include ammonium salts. The photobase generator may be used alone or in combination of two or more kinds. The synthesis methods are shown below, but the synthesis methods are not limited thereto.

The oximes include O-phenylacetylacetophenone oxime, O-benzoylacetophenone oxime, O, O'-succinyl diacetophenone oxime, O, O'-glutanyl diacetophenone oxime, O, O'-pivaloyl. Acetophenone oxime,
Dimethyl glyoxime diethyl carbonate, biacetyl monoxime ethyl carbonate, acetone oxime ethyl carbonate, benzophenone oxime ethyl carbonate, biacetyl monooxime phenyl urethane,
Biacetyl monooxime phenyl ester, biacetyl monooxime acetyl ester, acetone oxime phenyl ester, benzophenone oxime phenyl ester, benzophenone ester acetyl ester, 2,3
-Butanedione-O-methacryloyl oxime, 2,3
-Butanedione-O-vinylbenzoyl oxime, 2-
Propanone-O-methacryloyl oxime and the like can be mentioned. These include those that can also be radical initiators.

As a method for producing these photobase generators of oximes, known methods can be used, for example, the reaction can be carried out by reacting an acid chloride with an oxime as a raw material. Specifically, for example, Sung Il Hong. Et al,
It can be produced according to the method described in J. Polym. Sci., Polym. Chem. Ed., 12, 2553 (1974).

Carbamate esters are synthesized from nitrobenzyl alcohols and carbonyldiimidazoles, nitrobenzyl alcohols and isocyanates, benzoins and isocyanates, and the like. Examples of compounds synthesized from nitrobenzyl alcohols and carbonyldiimidazoles include N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, N- (4-nitrobenzyl). Oxycarbonyl) imidazole, N-
(4-chloro-2-nitrobenzyloxycarbonyl)
Imidazole, N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole, N- (4,5-dimethyl-2-nitrobenzyloxycarbonyl) imidazole, N- (2-nitrobenzyloxycarbonyl)-
2-Methylimidazole, N- (3-nitrobenzyloxycarbonyl) -2-methylimidazole, N- (4
-Nitrobenzyloxycarbonyl) -2-methylimidazole, N- (4-chloro-2-nitrobenzyloxycarbonyl) -2-methylimidazole, N- (5-
Methyl-2-nitrobenzyloxycarbonyl) -2-
Methylimidazole, N- (4,5-dimethyl-2-nitrobenzyloxycarbonyl) -2-methylimidazole, N- (2-methyl-2-phenylpropyl) -N
-Cyclohexylamine and the like. Examples of compounds synthesized from nitrobenzyl alcohols and isocyanate include cyclohexylcarbamic acid-2.
-Nitrobenzyl ester, cyclohexylcarbamic acid-3-nitrobenzyl ester, cyclohexylcarbamic acid-4-nitrobenzyl ester, cyclohexylcarbamic acid-4-chloro-2-nitrobenzyl ester, cyclohexylcarbamic acid-5-methyl-2-
Examples thereof include nitrobenzyl ester and cyclohexylcarbamic acid-4,5-dimethoxy-2-nitrobenzyl ester. Examples thereof include cyclohexylcarbamic acid-1-methyl-1-phenylethyl ether, cyclohexylcarbamic acid benzohydryl ester, and the like synthesized from benzyl alcohols and isocyanate. Examples of compounds synthesized from benzoins and isocyanates include cyclohexylcarbamic acid-2-oxo-1,2-diphenylethyl ester and cyclohexylcarbamic acid-2- (3,5-dimethoxyphenyl).
2-oxo-1-phenylethyl ester, cyclohexylcarbamic acid-1,2-bis (3,5-dimethoxyphenyl) -2-oxo-ethyl ester and the like can be mentioned.

Examples of the isocyanate include aliphatic isocyanate and aromatic isocyanate. Examples of the aliphatic isocyanate include methyl isocyanate, chloromethyl isocyanate, ethyl isocyanate, 2-bromoethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, t-butyl isocyanate, pentyl isocyanate, heptyl isocyanate, ethyl isocyanate acetate, octadecyl. Isocyanate, allyl isocyanate, cyclohexyl isocyanate, trichloromethyl isocyanate, chlorosulfonyl isocyanate, 3-isocyanate propyldimethylchlorosilane, octyl isocyanate, 3-iodopropyl isocyanate,
Hexyl isocyanate, methyl isocyanate chloroformate, tetrahydro-2-pyranyl isocyanate, undecyl isocyanate, ethyl-3-isocyanate propionate, ethyl-2-isocyanate-3-methylbutyrate, cyclopropyl isocyanate, hexamethylene diisocyanate, Dicyclohexamethane-4,4-diisocyanate, 1,12-dicyclocyanate dodecane, trimethylhexamethylenediamine disocyanate, tetraisocyanate silane, butoxysilane triisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate,
1,5-diisocyanate-2-methylpentane, 1,
4-diisocyanate butane, 1,3-bis (isocyanatomethyl) cyclohexane, methane diisocyanate, trimethyl-1,6-diisocyanate hexane,
Examples include 1,8-diisocyanate octane and dimeryl diisocyanate.

As the aromatic isocyanate, for example,
Phenyl isocyanate, 2-fluorophenyl isocyanate, 2,5-difluorophenyl isocyanate, 2-chloroisocyanate, 2,3-dichlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, 2-methoxyphenyl isocyanate, 2,
4-dimethoxyphenyl isocyanate, 2,5-dimethoxyphenyl isocyanate, 2-trifluorophenyl isocyanate, 2,5-dimethylphenyl isocyanate, 3-bromoisocyanate, 3-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 3-trifluoro Phenyl isocyanate,
4-bromophenyl isocyanate, 4-fluorophenyl isocyanate, 4-methoxyphenyl isocyanate, p-tolyl isocyanate, p-toluenesulfonyl isocyanate, benzoyl isocyanate, 1
-Phenylethyl isocyanate, 1-naphthyl isocyanate, 1- (1-naphthyl) ethyl isocyanate, 2-nitrophenyl isocyanate, benzenesulfonyl isocyanate, benzyl isocyanate, 4
-Chlorobenzylsulfonyl isocyanate, 3,5
-Bis (trifluoromethyl) phenyl isocyanate, 2,4,6-tribromophenyl isocyanate,
2,5-difluorophenyl isocyanate, methyl-2-isocyanate benzoate, 2,3-dimethylphenyl isocyanate, 2-ethyl-5-ethylphenyl isocyanate, 5-chloro-2,4-dimethoxyphenyl isocyanate, 3- (methylthio) phenyl Isocyanate, ethyl-3-isocyanate benzoate, 3-acetylphenyl isocyanate, 4-iodophenyl isocyanate, 4-methyl-3-nitrophenyl isocyanate, triphenylmethyl isocyanate, 4-cyanophenyl isocyanate, phenethyl isocyanate, dimethyl-5-isocyanate Isophthalate, phenyl isocyanate formate, 2-biphenylyl isocyanate, 3-isopropenyl-
α, α-dimethylbenzyl isocyanate, triphenylsilyl isocyanate, 3,5-dimethylisoxazole-4-isocyanate, 1-adamantyl isocyanate, PMPI, 4- (6-methyl-2-benzothiazoyl) phenyl isocyanate, 3 -Methylbenzyl isocyanate, 9H-fluoren-9-yl-isocyanate, tolylene-2,6-diisocyanate, tolylene-2,4-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4-chloro-6 -Methyl-1,3-phenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-bitrylene-
4,4'-biphenylene diisocyanate, 4,4 '
-Diisocyanate-3,3'-dimethyldiphenylmethane, α, α-dimethyl-α, 4-phenethyldiisocyanate, 4-bromo-6-methyl-1,3-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene-2 , 5-diisocyanate, 4,4′-methylenebis (2-chlorophenylisocyanate), 1,5-naphthalene diisocyanate,
Methylidine tri-p-phenylene triisocyanate, 3,3'-dichlorodiphenyl-4,4'-diisocyanate, 2-fluoro-1,3-diisocyanatebenzene, 1-chloromethyl-2,4-diisocyanatebenzene, 4,4 ' -Methylenebis (2,6-diethylphenyl) isocyanate, 2,2-bis (4-isocyanatephenyl) hexafluoropropane, 4,
4'-oxybis (phenylisocyanate), 2,
4,6-trimethyl-1,3-phenylene diisocyanate, tris (p-isocyanatophenyl) amine,
α, 4-tolylene diisocyanate, m-xylylene diisocyanate, 1,3-bis (2-isocyanate-
2-propyl) benzene and the like can be mentioned.

As a method for producing these carbamic acid ester photobase generators, known methods can be used.
Specifically, for example, Nishikubo, T. et al, Polym. J.,
26 (7), 864 (1994), Nishikubo, T. et al, Polym. J.,
29 (5), 450 (1997) J. Chem. Soc. Perkin Trans. 1,
It can be produced according to the method described in 2429 (1997).

As ammonium salts, salts of iododiphenylethane and triethylamine, salts of α-bromophenacyls and triethylenediamine, α-
A salt consisting of bromonaphthyls and triethylenediamine,
Hexaamine cobalt tetraphenyl boron salt and the like can be mentioned.

As a method for producing these ammonium salt photobase generators, known methods can be used, for example, α
It can be synthesized by reacting triethylenediamine with -bromophenacyls or α-bromonaphthyls as a raw material. Specifically, for example, Tachi, H. et al,
It can be manufactured according to the method described in J. Photopolym. Sci. Technol., 12, 313 (1999).

The photo-acid generator is a compound which produces an acid upon irradiation with active energy rays such as visible light, ultraviolet rays and electron rays. Examples of the photoacid generator include those represented by the general formula (I
V) and other iron-arene complex compounds, aromatic diazonium salts, aromatic iodonium salts such as general formulas (V) to (VIII), aromatic sulfonium salts such as general formulas (IX) to (XIII), pyridinium salts, Examples thereof include ammonium salts and aromatic silanol / aluminum complexes. The photoacid generator may be used alone or in combination of two or more.

[0040]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

The photoradical generator may be any compound that generates a radical upon irradiation with active energy rays such as visible light, ultraviolet rays, and electron beams, and is generally known as a photoinitiator for radically polymerizable monomers. Things are used. Examples of the photo radical generator include (bis)
Acylphosphine oxide and its esters, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, 2-benzyl-2-N, N-dimethylamino-1-
(4-morpholinophenyl) -1-butanone, aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds and the like. Preferably, a benzophenone derivative, a phosphine oxide derivative, and thioxanthones are used.

As the (bis) acylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2, 6-dichlorobenzoylphenylphosphine oxide, 2,6
-Dimethytoxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4
4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like can be mentioned.

Examples of acetophenone compounds include acetophenone, methoxyacetophenone and 1-phenyl-2.
-Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- On and the like.

Examples of the benzophenone compound include benzophenone, 4-phenylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3'-dimethyl-4-methoxybenzophenone and diphenoxybenzophenone.

Examples of the benzoin ether compounds include benzoin ethyl ether and benzoin propyl ether. Examples of the ketal derivative compound include benzyl dimethyl ketal. Examples of the thioxanthone compound include 2-chlorothioxanthone and 2,4-
Examples thereof include dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and isopropylthioxanthone. The photo radical generators may be used alone or in combination of two or more.

These photo-acid generators, photo-base generators, photo-radical generators and other initiators may be used alone or in combination of a plurality of types depending on the intended use. Preferably, each is used alone, a combination of a photobase generator and a photoradical generator, a combination of a photoacid generator and a photoradical generator, and the like. Considering the stability and workability of the composition, N- (2-nitrobenzyloxy) carbonylimidazole, 1-hydroxycyclohexyl phenyl ketone, which is mildly decomposed by visible light and rapidly decomposed by ultraviolet rays or infrared rays, 1 It is preferable to use -hydroxy-2-methyl-1-phenylpropan-1-one or the like.

The photoinitiator is preferably added when the curable resin composition is cured using active energy rays. When the photoinitiator is used, the amount of the photoinitiator added may be in a range such that the curable composition is well cured and a cured product is obtained. Specifically, the photoinitiator is added to 100 parts by weight of the total amount of one or more compounds selected from the compound represented by the general formula (I), the compound having a functional group capable of reacting with the compound and the radical polymerizable compound. Total amount is normal
0.001 parts by weight or more, preferably 0.05 parts by weight or more,
It is usually 10 parts by weight or less, preferably 5 parts by weight or less. If the amount of the initiator added is too small, the composition cannot be sufficiently cured.On the other hand, if the amount added is too large, the physical properties of the cured product may be adversely affected, such as reduced mechanical strength. There is.

Examples of the curing agent used in the present invention include so-called curing agents such as amines, quaternary ammonium salts, phosphines, organic acids, Lewis acids, peroxides and azo compounds. As amines, primary amines,
Examples thereof include primary polyamine, secondary amine, secondary polyamine, tertiary amine, tertiary polyamine, amidines and imidazoles.

As the primary amine, ethylamine, n-
Propylamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, t
ert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine,
Laurylamine, mistyrylamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol,
3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylhexyloxy) propylamine,
Examples thereof include aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine and furfurylamine.

As the primary polyamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5- Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis (3
-Aminopropyl) ether, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy) -2,2'-dimethylpropane, aminoethylethanolamine, 1,2-, 1 , 3- or 1, 4
-Bisaminocyclohexane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1,3-bisaminoethylcyclohexane, 1,4
-Bisaminoethylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, 2-aminopiperidine, 4-
Aminopiperidine, 2-aminomethylpiperidine, 4-
Aminomethylpiperidine, 2-aminoethylpiperidine, 4-aminoethylpiperidine, N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, isophoronediamine, menthanediamine, 1,4- Bisaminopropylpiperazine, o-, m-, or p-phenylenediamine, 2,4-tolylenediamine, 2,6
-Tolylenediamine, 2,4-toluenediamine, m-
Aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine, 4-
Methoxy-6-methyl-m-phenylenediamine, m
-Or p-xylylenediamine, 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane,
2,2- (4,4'-diaminodiphenyl) propane,
4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminoditolyl sulfone, methylenebis (o-chloroaniline),
3,9-bis (3-aminopropyl) 2,4,8,10
-Tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, Examples thereof include N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine and bis (3,4-diaminophenyl) sulfone.

As the secondary amine, diethylamine, dipropylamine, di-n-butylamine, di-sec-
Butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine,
Octylamine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-picoline, 2,4-, 2,
Examples thereof include 6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole and morpholine.

As the secondary polyamine, N, N'-dimethylethylenediamine, N, N'-dimethyl-1,2-
Diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,2-diaminobutane, N, N'-dimethyl-1,3-diaminobutane, N, N'- Dimethyl-1,4-diaminobutane,
N, N'-dimethyl-1,5-diaminopentane, N,
N'-dimethyl-1,6-diaminohexane, N, N '
-Dimethyl-1,7-diaminoheptane, N, N'-diethylethylenediamine, N, N'-diethyl-1,2
-Diaminopropane, N, N'-diethyl-1,3-diaminopropane, N, N'-diethyl-1,2-diaminobutane, N, N'-diethyl-1,3-diaminobutane, N, N ' -Diethyl-1,4-diaminobutane,
N, N'-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,
6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4 -Di- (4-piperidyl) butane, tetramethylguanidine and the like can be mentioned.

As the tertiary amine, trimethylamine,
Triethylamine, tri-n-propylamine, tri-
iso-propylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, tri-n-butylamine, tri-iso-butylamine, tri-sec-butylamine, tri-pentylamine, tri-3-. Pentylamine, tri-n-hexylamine,
Tri-n-octylamine, tri-2-ethylhexylamine, tri-dodecylamine, tri-laurylamine, dicyclohexylethylamine, cyclohexyldiethylamine, tri-cyclohexylamine, N, N-
Dimethylhexylamine, N-methyldihexylamine, N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, N-ethyldiethanolamine, triethanolamine, Ribenzylamine, N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-
Dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, 2- (N, N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N,
Examples thereof include N-diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy) -4-methyl-1,3,2-dioxabornane.

As the tertiary polyamine, tetramethylethylenediamine, pyrazine, N, N'-dimethylpiperazine, N, N'-bis ((2-hydroxy) propyl)
Piperazine, hexamethylenetetramine, N, N,
N ', N'-tetramethyl-1,3-butanamine, 2
-Dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N)
-Dimethylaminomethyl) phenol, heptamethylisobiguanide and the like.

Amidines include 1,8-diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo. (5,4,0) Undecen-
7,1,4-diazabicyclo (2,2,2) octane and the like can be mentioned.

Examples of the imidazoles include imidazole,
N-methylimidazole, 2-methylimidazole, 4
-Methylimidazole, N-ethylimidazole, 2-
Ethylimidazole, 4-ethylimidazole, N-butylimidazole, 2-butylimidazole, N-undecylimidazole, 2-undecylimidazole, N
-Phenyl imidazole, 2-phenyl imidazole,
N-benzyl imidazole, 2-benzyl imidazole, 1-benzyl-2-methyl imidazole, N-
(2'-Cyanoethyl) -2-methylimidazole, N
-(2'-cyanoethyl) -2-undecylimidazole, N- (2'-cyanoethyl) -2-phenylimidazole, 3,3-bis- (2-ethyl-4-methylimidazolyl) methane, alkylimidazole and isocyanate Examples thereof include an addition product of nouric acid and a condensation product of alkylimidazole and formaldehyde.

Examples of the quaternary ammonium salts include tetramethylammonium chloride, tetra-n-butylammonium hexafluorophosphite and trimethylbenzylammonium chloride.

Examples of the phosphines are trimethylphosphine, triethylphosphine, tri-iso-propylphosphine, tri-n-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine and tricyclohexyl. Phosphine, triphenylphosphine, tribenzylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (diethylamino) phosphine, tris (4-methylphenyl) ) Phosphine, dimethylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, chlorodiphenyl Osufin, and the like.

As the curing agent, amines,
Quaternary ammonium salts or phosphines, particularly preferably, secondary monoamines, tertiary monoamines, tertiary polyamines, imidazoles, amidines, quaternary ammonium salts or phosphines are used. These curing agents may be used alone or in combination of two or more.

When the curing agent is added, the amount of the curing agent added may be in the range such that the composition of the present invention is well cured and a cured product is obtained. Specifically, the curing agent is added to 100 parts by weight of the compound represented by the general formula (I), and one or more compounds selected from the compound having a functional group capable of reacting with the compound and the radical-polymerizable compound. The total amount is usually 0.001 parts by weight or more, preferably 0.05 parts by weight or more, and usually 10 parts by weight or less, preferably 5 parts by weight or less. If the amount of the initiator added is too small, the composition cannot be sufficiently cured.On the other hand, if the amount added is too large, the physical properties of the cured product may be adversely affected, such as reduced mechanical strength. There is.

There is a compound in which an initiator or a curing agent has a catalytic action of an acid or a base generated by a stimulus such as light and / or heat and further produces an acid or a base to increase the generation efficiency of the acid or the base. This compound includes a photobase generator and a photoacid generator which exhibit such a phenomenon. Examples of such a compound include p-toluenesulfonic acid esters and carbamic acid esters. 2, 4, 6
-Tris [2- (p-toluenesulfonyloxy) ethyl] -1,3,5-trioxirane, 3-phenyl-
3,3′-ethylenedioxy-1-propyl p-toluenesulfonate, 3-phenyl-3,3′-ethylenedioxy-1-propylmesitylenesulfonate, 2-phenyl-2-propyl-2-methyl-2 ( Hydroxymethyl) -3-ketobutanoate, t-butyl-2-methyl-2 ((p-toluenesulfonyloxy) methyl)-
3-ketobutanoate, 1- (9-fluorenylmethoxycarbonyl) piperidine, 1,3-bis [(2-nitrobenzyl) -oxycarbonyl-4-piperidyl] propanone, cyclohexylcarbamic acid-2-oxo-
1,2-diphenylethyl ester, cyclohexylcarbamic acid-2- (3,5-dimethoxyphenyl) -2
-Oxo-1-phenylethyl ester, cyclohexylcarbamic acid-1,2-bis (3,5-dimethoxyphenyl) -2-oxo-ethyl ester and the like can be mentioned. Such a compound can be added, if necessary, within a range in which the catalyst is not deactivated by the antagonism of an acid or a base.

In the composition of the present invention, in addition to the above, known polymerization inhibitors, antioxidants, ultraviolet absorbers, photosensitizers, chain transfer agents, solvents, etc. You may add various additives, such as a mold release agent, a plasticizer, a processing agent, a softness and shape retention imparting agent, and a filler. The stability of the composition can be improved by adding a polymerization inhibitor, an antioxidant and an ultraviolet absorber. Further, the curing can be efficiently performed by adding the photosensitizer and the chain transfer agent.

The solvent is not particularly limited as long as it is a type in which the essential components can be dissolved. Specifically, aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as hexane, ethers such as ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, Examples thereof include alcohols such as isopropyl alcohol. By adding a solvent, the viscosity of the composition of the present invention can be adjusted. Examples of the plasticizer include dibutyl phthalate and d4 silicone.

As the flexibility and shape-retaining agent, for example, polyvinyl butyral, acrylic polymer, polyphenylene ether, polyether sulfone, polysulfone, triacetyl cellulose (TAC) and the like can be used. If a release agent, a plasticizer, a treating agent, a flexibility and a shape-retaining agent are added in excess, the glass transition temperature of the cured product tends to decrease and the relative dielectric constant tends to increase.
The addition amount of these is usually selected from the range of 0 to 20 g per 100 g of the composition containing the compound represented by the general formula (I) of the present invention. As the filler, for example, silica,
Examples thereof include fillers such as alumina and calcium carbonate, metal particles such as copper, silver and gold, and fibrous substances.

The composition of the present invention is obtained by mixing the compound of the general formula (I), the compound having a functional group capable of reacting with the compound, the radically polymerizable compound, the curing aid and, if necessary, an additive. be able to. The composition of the present invention can be shaped into an appropriate shape and then cured to obtain a cured product. Examples of the method of curing the composition of the present invention include a method of curing by adding a curing agent, a method of curing by heating, and a method of curing by irradiating light. In the case of the method of adding a hardening agent and hardening, hardening can be normally performed above 50 ° C and below 200 ° C.

In the case of curing by heating, it is usually 5
It is usually 0.5 to 36 at a temperature of 0 ° C. or higher, preferably 100 ° C. or higher, usually 200 ° C. or lower, preferably 180 ° C. or lower.
Hold for hours. In the case of a method of curing by irradiating with light, the wavelength of light does not have to be a single wavelength, but depends on the characteristics of the photoinitiator used, and the wavelength at which the decomposition of the photoinitiator efficiently occurs. The active energy ray containing is selected. Specifically, visible light, ultraviolet light, near infrared light, far infrared light, electron beam, and the like can be used, and ultraviolet light emitted from a high pressure mercury lamp, a low pressure mercury lamp, a metal halogen lamp, or the like is preferable. These curing methods may be used alone or in combination. Examples of the combined use include a method of performing a heat treatment after performing light irradiation, a method of combining a method of curing with a curing agent and a method of light irradiation, and the like.

The method of shaping the composition of the present invention includes:
Examples thereof include a method of molding using a mold and a method of coating on a substrate. As a method of molding using a mold, after injecting the composition of the present invention into the molding die, curing by the method described above, and removing the mold, a molded article made of the composition of the present invention can be obtained. it can. When molding is performed using a mold and curing is performed by photo-curing, the composition of the present invention is injected into a mold having a portion transparent to energy rays, and the energy rays are irradiated from the transparent side of the molding die. Irradiate and cure,
A molded body can be obtained. By molding using a mold, it is possible to obtain a molded product in which the surface shape of the mold is transferred. At this time, if the composition of the present invention that is liquid at the time of molding is used,
Precision molding can be performed. The molded product thus obtained has a refractive index of usually 1.5 or more, preferably 1.6.
As described above, it can be used as an optical component such as a lens, a prism, a waveguide, and a substrate.

As a method of coating the composition on the substrate, a layer formed of a cured product obtained by curing the composition of the invention by coating the composition of the invention on the substrate, followed by drying and curing. It is possible to obtain a laminated body including the base material layer. In the method of coating and molding on a substrate, the substrate may be an inorganic material such as glass or copper foil, or an organic material such as a polyethylene terephthalate (PET) film, a polycarbonate sheet or a TAC film. The composition of the present invention is usually applied to a substrate so as to have a thickness of 1 μm to 2 mm. After the composition of the present invention is applied to a substrate, it is usually dried by ventilation to evaporate the solvent in the composition, heated and dried, and then cured by the method described above. By this method, a laminate having a layer obtained by curing the composition of the present invention on the substrate is obtained.

After coating the composition of the present invention on a substrate, it is partially irradiated with active energy rays to regioselectively cure any part of the layer comprising the composition of the present invention. be able to. As a method of selecting the position to be hardened, a mask is applied so that the active energy rays do not reach only the portion that is not desired to be hardened, or only the portion where the active energy ray having a high energy density and a narrow width, such as a laser, is desired to be hardened. The method of irradiation may be mentioned. The uncured portion which is not irradiated with the active energy ray can be removed by a solvent, and thus can be used as a photoresist. The solvent is not particularly limited as long as it can dissolve the components that form the uncured composition layer. Specifically, aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as hexane,
Examples thereof include ethers such as ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and alcohols such as isopropyl alcohol.

Applications of the composition of the present invention include coating agents, adhesives, sealing materials for the purpose of antireflection and protection, or raw materials for moldings such as parts, sheets, laminates and composite materials. Can be mentioned. Further, the use of the cured product obtained by curing the composition of the present invention, optical components such as lenses, prisms, waveguides, substrates, laminated materials,
The use as a material for composite materials and electronic parts is exemplified. In particular, the obtained cured product can be used for optical components such as lenses and waveguides, and their adhesives, sealants, etc., by utilizing the properties such as transparency and high refractivity. In addition, the method of selectively curing the portion irradiated with the active energy ray and removing the uncured portion with a solvent may be used as a photoresist or the like.

[0071]

The cured product of the composition containing the compound of the present invention can be suitably used as a material for optical parts such as lenses, prisms, waveguides, substrates, laminated materials, composite materials and electronic parts.

[0072]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. Example 1 A four-necked flask equipped with a stirrer was charged with 80 g of 4,4′-diphenyldihydroxysulfone (manufactured by Wako Pure Chemical Industries, Ltd.), and epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.) 41
5 g, isopropyl alcohol (Wako Pure Chemical Industries, Ltd.) 162 g
Was added and heated to 40 ° C. to dissolve. 20% here
An aqueous sodium hydroxide solution (sodium hydroxide (Wako Pure Chemical Industries, Ltd.) 28 g, distilled water 115 g) was added dropwise, and the mixture was stirred for 90 minutes while heating at 65 ° C. Distilled water was added to the obtained reaction solution to separate the organic phase. After the organic phase was washed twice with distilled water, 700 g of methanol was added and stirred for 1 hour to give a white powder 7
I got 8 g. The structure of the obtained white powder was as follows.

[0073]

[Chemical 15]

[0074] The chemical shifts of the proton NMR (ppm): 2.7-3.0 (methylene hydrogens of the oxirane ring) 3.2-3.4 (oxirane ring methine _{hydrogen) 3.8-4.4 (-C H 2 CH (} O) CH 2) 6.9-7.9 (Hydrogen of aromatic ring)

Example 2 In a 300 ml four-necked flask equipped with a stirrer, Example 1
15 g of the epoxy compound of 4,4′-dihydroxydiphenyl sulfone obtained in step 5 and 165 g of methyl ethyl ketone were added, and the mixture was heated to reflux and dissolved. To this, 7.57 g of thiourea (manufactured by Wako Pure Chemical Industries) and 66 g of methanol were added, and the mixture was refluxed for 5.5 hours. Then, distilled water was added to the reaction solution to separate the organic phase. The organic phase was washed with distilled water three times, and then the solvent was distilled off under reduced pressure to obtain 13.1 g of a white solid. The structure of the obtained white powder was as follows.

[0076]

[Chemical 16] Chemical shifts of the proton NMR (ppm): 2.2-2.7 (thiirane methylene hydrogens of the ring) 3.2-3.3 (thiirane ring methine _{hydrogen) 3.9-4.3 (-C H 2 CH (} S) CH 2) 6.9-8.0 ( aromatic ring Hydrogen)

Example 3 50 g of 4,4'-bis (2-hydroxyethylthio) diphenylsulfone (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in an eggplant flask containing a stir bar, and epichlorohydr was added thereto. Phosphorus (manufactured by Tokyo Chemical Industry Co., Ltd.) 250 g and dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.) 250 g were added and dissolved at room temperature.
A 40% aqueous potassium hydroxide solution (53.5 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 36 g of distilled water) was added dropwise in an ice bath, and the mixture was stirred for 60 minutes while gradually returning to room temperature. Distilled water and toluene were added to the obtained reaction solution to separate the organic phase. The organic phase was washed with warm water (60 ° C.) three times, and then the solvent and epichlorohydrin were distilled off under reduced pressure to obtain 67 g of a pale yellow viscous liquid.
The structure of the obtained viscous liquid was as follows.

[0078]

[Chemical 17] Chemical shifts of the proton NMR (ppm): 2.5-2.8 (oxirane ring methylene hydrogen) 3.0-3.2 (oxirane ring methine _{hydrogen) (-SC H 2 CH 2 O-} ) 3.3-3.4 (-C H 2 CH (O _{) CH 2) 3.6-3.9 (-C H} 2 CH (O) CH 2) (-SCH 2 C H 2 O-) 7.2-7.8 ( hydrogen of an aromatic ring)

Example 4 Example 3 was placed in a 300 ml four-necked flask equipped with a stirrer.
67 g of the epoxy compound of 4,4'-bis (2-hydroxyethylthio) diphenylsulfone obtained in 1. and 100 g of toluene
Was added and dissolved. 24.6 g of thiourea (manufactured by Wako Pure Chemical Industries) and 100 ml of methanol were added thereto and refluxed for 5 hours. Distilled water was added to the obtained reaction solution to separate the organic phase. The organic phase was washed 5 times with distilled water and the solvent was distilled off under reduced pressure to obtain 62.5 g of a pale yellow viscous liquid. The structure of the obtained viscous liquid was as follows.

[0080]

[Chemical 18] Chemical shifts of the proton NMR (ppm): 2.1-2.6 (thiirane methylene hydrogens of the ring) 2.9-3.1 (thiirane ring methine _{hydrogen) 3.1-3.3 (-C H 2 CH (} S) CH 2) (-SC H 2 CH ₂ O-) 3.5-3.8 (methylene hydrogens of glycidyl _{group) (-SCH 2 C H 2 O} ) 7.3-7.9 ( hydrogen of an aromatic ring)

Example 5 20 g of the compound obtained in Example 4 and ADEKA Optomer SP-1
70 m (made by Asahi Denka Kogyo Co., Ltd., photo-acid generator) is mixed with 0.4 g, and 2 m
20 mW / m, cast between glass plates with m-thick spacers
A total of 25 J / cm ² of UV light was irradiated from both sides with a cm ² high-pressure mercury lamp. 50 ℃, 80 ℃, 100 ℃ without removing the mold
After heating for 1 hour each, the mold was removed to obtain a cured product.
The obtained cured product had a refractive index of 1.67 and a thermal decomposition initiation temperature by TG / DTA of 265.5 ° C. (in N ₂ ).

Example 6 20 g of the compound obtained in Example 4 and ADEKA Optomer SP-1
50 mm (made by Asahi Denka Kogyo Co., Ltd., photo-acid generator) was mixed with 0.8 g, and 1 mm
Cast between glass plates with thick spacers, 20 mW / cm
It was irradiated with UV light of 25 J / cm ² in ² high pressure mercury lamp. After heating at 80 ° C. and 140 ° C. for 1 hour without removing the mold, the mold was removed to obtain a cured product. The refractive index of each of the obtained cured products was 1.66.

Example 7 In Example 6, 0.8 g of ADEKA OPTOMER SP-150 (manufactured by Asahi Denka Kogyo Co., Ltd., photo-acid generator) was added to ADEKA OPTOMER SP-170.
(Photoacid generator manufactured by Asahi Denka Co., Ltd.) The same procedure as in Example 6 was repeated except that the amount was changed to 0.8 g. The refractive index of the obtained cured product was 1.66.

Example 8 In Example 6, 0.8 g of Adekaoptomer SP-150 (manufactured by Asahi Denka Kogyo Co., Ltd., a photoacid generator) and 0.2 g of N- (2-nitrobenzyloxycarbonyl) imidazole (photobase generator) were used. g
The same procedure as in Example 6 was carried out except that N- (2-nitrobenzyloxycarbonyl), which is a photobase generator
Imidazole is available from Polymer Journal, Vol.26, No.7, p.
It was prepared according to the method described in p. 864-867 (1994). The refractive index of the obtained cured product was 1.67.

Example 9 In Example 6, 0.8 g of Adeka optomer SP-150 (manufactured by Asahi Denka Co., Ltd., a photoacid generator) was added to N- (4-chloro-2-nitrobenzyloxycarbonyl) imidazole (photobase). (Generator) The procedure of Example 6 was repeated except that the amount was changed to 0.2 g.
N- (4-chloro-2-nitrobenzyloxycarbonyl) imidazole, which is a photobase generator, is
It was produced according to the method described in Journal, Vol.29, No.5, pp. 450-456 (1997). The refractive index of the obtained cured product is 1.67.
Met.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 1/04 G02B 1/04 (72) Inventor Yasuaki Miki 8-3-1, Ami-cho, Inashiki-gun, Ibaraki No. Mitsubishi Chemical Co., Ltd. F-term (reference) 4J030 BA05 BA09 BA41 BA42 BA43 BA48 BA49 BB03 BB07 BC36 BD01 BD22 BG02 BG03 BG25 4J036 AB18 AD21 CA28 CA30 CC01 CD10 DC04 DC05 DC16 DC26 DC40 DD07 EA01 GA02 EA03 EA04 FA10 FA12 GA01 GA02 GA02 GA06 GA02 GA02 JA07 JA08 JA15 4J040 DB031 DB032 DD051 DD052 DE021 DE022 DE041 DE042 DF041 DF042 DF051 DF052 DJ011 DJ012 EC001 EC002 EC261 EC262 EE021 EE022 EJ011 EJ012 EJ021 EJ022 EJ031 EJ16 GA13 GA13 GA15 GA07 GA14 GA05 GA07 GA07 GA14

Claims (11)

[Claims] 1. A heterocycle-containing compound represented by the following general formula (I): [Chemical 1] (In the formula, R ^{1 to} R ⁴ each independently represent a hydrocarbon group having 1 to 10 carbon atoms. X ^{1 to} X ⁸ each independently represent O or S. Y ¹ and Y ² are each independently Represents O or S. Z ¹
And Z ² each independently represent S, —SO ₂ —, —S—S— or —CO—. m, n, p, and q are 0 to 10 independently.
Represents the integer. r represents an integer of 0 to 10. The benzene ring in the formula may have a substituent. However, Z ¹ = Z ² = S, p = q = r
= 0 and X ⁵ = X ⁸ = S and Z ¹ = Z ² = −SO ₂ − and Y ¹ = Y ² =
Except for O. ) 2. A composition comprising a heterocycle-containing compound represented by the general formula (I). 3. The composition according to claim 2, comprising one or more compounds selected from a compound having a functional group capable of reacting with the compound represented by the general formula (I) and a radically polymerizable compound. And the composition. 4. A polymerizable composition according to claim 3, which further comprises a curing aid. 5. The composition according to claim 4, wherein the curing aid is a compound selected from a photoinitiator and a curing agent. 6. A cured product obtained by polymerizing and curing the composition according to any one of claims 2 to 5. 7. A sealing material comprising the composition according to claim 2. 8. An adhesive comprising the composition according to claim 2. 9. An optical member comprising the cured product according to claim 6. 10. A laminate having a layer made of the cured product according to claim 6 and a base material layer. 11. A method for producing a cured product, which comprises curing the curable composition according to any one of claims 2 to 5 in a mold.