JP5412760B2 - New metal-containing compounds - Google Patents

Description

    The present invention relates to a novel compound having a polymerizable epithio group, which is a raw material of an optical material having a high refractive index, and the use of a cured product obtained by polymerizing the compound as an optical material. This optical material is useful for optical products such as plastic lenses, prisms, optical fibers, optical adhesives, optical material substrates, optical films, optical filters, optical performance improving coating films, information recording substrates and the like.

    A compound having an epithio group and a metal has been proposed with the aim of developing a high refractive index material, but the refractive index was low (see Patent Documents 1 and 2). In addition, 1,4,6,9-tetrathia-5-germa [4.4] nona-2,7-diene and bis (mercaptomethyl) -1,4,6,9-tetrathia-5-germer-spiro [ 4.4] Copolymerization of nonane and homopolymerization of tetrakis (epithiopropylthio) tin have been proposed (see Patent Documents 3, 4, 5, and 6), but there was a problem of coloring.

Japanese Patent No. 3400406 Japanese Patent No. 3705993 JP 2007-269648 A JP 2007-269649 A JP 2007-271744 A JP 2006-169190 A

    An object of the present invention is to provide a novel compound and composition capable of providing an optical product having a high refractive index and a color tone that can be practically used.

    As a result of intensive studies to solve the problems of the present invention, the present inventor has found that the compound represented by the general formula (1)

（式中、Ｍ_１およびＭ_２はそれぞれ独立に錫（Ｓｎ），ゲルマニウム（Ｇｅ）または鉛（Ｐｂ）を表し、
Ｂは硫黄(Ｓ)または酸素(Ｏ)を表し、
Ｐは０〜２を表し、
Ａ_１は下記一般式（２）のエピチオ基を表す。
Ｒ_１〜Ｒ_４はＣ１〜Ｃ４の炭化水素基を表す。）

(Wherein M ₁ and M ₂ each independently represent tin (Sn), germanium (Ge) or lead (Pb);
B represents sulfur (S) or oxygen (O);
P represents 0-2,
A ₁ represents an epithio group of the following general formula (2).
R _{1 to} R ₄ each represent a C1 to C4 hydrocarbon group. )

（式中、ｎは０または１を表す。）
で表される新規なエピチオ化合物、およびこれら化合物の少なくとも一つ含む組成物を重合硬化して得られる硬化物から高屈折率を有し、色調が実用可能な光学製品を提供できることを見出し本発明に至った。

(In the formula, n represents 0 or 1.)
It has been found that an optical product having a high refractive index and a practical color tone can be provided from a cured product obtained by polymerizing and curing a novel epithio compound represented by formula (1) and a composition containing at least one of these compounds. It came to.

    With the composition containing at least one compound represented by the general formula (1), it is possible to obtain a resin optical material having a high refractive index and a practical color tone.

    In the compound represented by the following general formula (1) of the present invention, two or more epithio groups are bonded to a skeleton containing a metal double nucleus selected from tin (Sn), germanium (Ge), or lead (Pb). It is characterized by this.

    Examples of the compound represented by the general formula (1) include compounds represented by the following chemical formulas (1-1) to (1-12), but are not limited thereto.

    The compound represented by the general formula (1) is preferably a compound of the chemical formula (1-1), (1-2), (1-3) or (1-4).

M ₁ and M ₂ in the general formula (1) are selected from Sn, Ge or Pb, preferably Sn or Ge, and more preferably Sn.

    The compound of the general formula (1) can be produced by the following reaction formula (1) using a thiol compound and a metal halide compound as raw materials.

（式中、Ｍ_１およびＭ_２はそれぞれ独立に錫（Ｓｎ），ゲルマニウム（Ｇｅ）または鉛（Ｐｂ）を表し、
Ｘは塩素(Ｃｌ)，臭素(Ｂｒ)，またはヨウ素(Ｉ)を表し、
Ｂは硫黄(Ｓ)または酸素(Ｏ)を表し、
Ｐは０〜２を表し、
Ｒ_１〜Ｒ_４はＣ１〜Ｃ４の炭化水素基を表す。
Ａ_１は下記一般式（４）の含エピチオ基を表す。）

(Wherein M ₁ and M ₂ each independently represent tin (Sn), germanium (Ge) or lead (Pb);
X represents chlorine (Cl), bromine (Br), or iodine (I);
B represents sulfur (S) or oxygen (O);
P represents 0-2,
R _{1 to} R ₄ each represent a C1 to C4 hydrocarbon group.
A ₁ represents an epithio group containing the following general formula (4). )

（式中、ｎは０または１を表す。）

(In the formula, n represents 0 or 1.)

    The amount of the metal halide compound and thiol compound used in the reaction formula (1) is usually 1 to 5 moles of thiol compound per mole of metal halide compound, preferably 1.5 to 3 moles, more preferably 1 .8 to 2.2 moles.

    Reaction formula (1) is carried out by heating or cooling the metal halide compound and the thiol compound simultaneously or in any order in the presence or absence of a solvent and in the presence or absence of a base. Further, after the reaction, washing, extraction, evaporation of solvent and impurities, dehydration, drying, filtration and purification (extraction, chromatographic separation, distillation, recrystallization) and the like may be performed in any order as necessary.

    The solvent used in the reaction formula (1) is not particularly limited, but ether solvents such as diethyl ether, tetrahydrofuran and diethylene glycol dimethyl ether, chlorine-containing solvents such as methylene chloride, chloroform, chlorobenzene and dichlorobenzene, petroleum Hydrocarbon solvents such as ether, hexane, benzene, toluene, xylene and mesitylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, N, N-dimethyl Examples include aprotic polar solvents such as formamide, N, N-dimethylacetamide, and dimethyl sulfoxide, and water.

    In reaction formula (1), it is preferable to use a base as a scavenger for the generated hydrogen halide in order to carry out the reaction efficiently. The base is not particularly limited, but is triethylamine, trimethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, diethylamine, diisopropylamine, ethylamine, n-propylamine, i-propylamine, sec. -Butylamine, pyridine, pyrrolidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, sodium hydrogen carbonate, NaOH, KOH and the like.

    The reaction temperature in the reaction formula (1) is usually in the range of -78 ° C to 200 ° C, preferably -78 ° C to 100 ° C. More preferably, it is -78 degreeC-50 degreeC.

    The reaction time in the reaction formula (1) is usually 1 minute to 100 hours, although it is affected by the raw material, base, reaction temperature and the like. Preferably, there are 5 minutes to 50 hours, more preferably 10 minutes to 10 hours.

    The composition of the present invention containing at least one compound represented by the general formula (1) can be polymerized by heating in the presence or absence of a curing catalyst to produce a resin. When a curing catalyst is used during polymerization, the curing catalyst includes amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, mineral acids and mineral acids. Half-esters, Lewis acids, organic acids, silicic acids, peroxides, azo compounds, condensates of aldehydes and amine compounds, guanidines, thioureas, thiazoles, sulfenamides, Examples include thiurams, dithiocarbamates, xanthates, and acidic phosphates.

    First, examples of the curing catalyst for polymerizing and curing the composition of the present invention containing at least one compound represented by the general formula (1) are shown. It is not limited. These may be used alone or in combination of two or more. The addition amount of the catalyst used in the present invention is 0.0001 to 10.0 parts by weight, preferably 0 with respect to 100 parts by weight of the composition containing at least one compound represented by the general formula (1). .0005 to 5.0 parts by weight.

    The composition of the present invention containing at least one compound represented by the general formula (1) has a color tone, oxidation resistance, weather resistance, etc., improved color tone, tensile strength, bending strength, tilt strength, impact resistance, etc. A compound that can react with a part or all of the composition components for the purpose of improving various performances such as improving the mechanical strength, improving the refractive index, improving the heat resistance, improving the dyeability, and improving the appearance such as cloudiness and striae. It is also possible to add and cure polymerization. In this case, a polymerization curing catalyst is separately added as necessary for this reaction. Further, prior to the main polymerization of the composition of the present invention, preliminary reaction may be performed with the performance improvers excluding the composition of the present invention or with the performance improver and the composition of the present invention. Examples of the performance improver include a thiol compound for improving the color tone, a thiol compound, an isocyanate compound, an isothiocyanate compound for improving the mechanical strength, and a sulfur atom for improving the refractive index. Examples include inorganic compounds, sulfur-containing metal compounds, and inorganic compounds having a selenium atom. Heat resistance improvement includes thiol compounds and isocyanate compounds, and dyeability improvement includes carboxylic acids, mercaptocarboxylic acids, hydroxycarboxylic acids, amides. 1,3-diketones, 1,3-dicarboxylic acids, 3-ketocarboxylic acids and esters thereof, and compounds having unsaturated groups, thiol compounds, isocyanate compounds, etc. Etc. In addition, alcohols containing phenols, carboxylic acid anhydrides, polybutene having a functional group at one end, and the like can also be added as performance improvers. These compounds can be added within a range in which there is no problem until necessary physical properties are obtained.

    Specific examples of thiol compounds as performance improvers include mercaptans, thiophenols, and mercaptans having unsaturated groups such as vinyl, aromatic vinyl, methacryl, acryl, and allyl, and thiophenols. Etc. Specific examples are shown below.

    Examples of mercaptans include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, allyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl. Mercaptan, n-tetradecyl mercaptan, n-hexadecyl mercaptan, n-octadecyl mercaptan, cyclohexyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, tert-nonyl mercaptan, tert-dodecyl mercaptan, benzyl mercaptan, 4-chlorobenzyl mercaptan, methylthio Glycolate, ethylthioglycolate, n-butylthioglycolate, n-octylthioglycolate Methyl (3-mercaptopropionate), ethyl (3-mercaptopropionate), 3-methoxybutyl (3-mercaptopropionate), n-butyl (3-mercaptopropionate), 2-ethylhexyl (3 -Ercaptopropionate), n-octyl (3-mercaptopropionate), 2-mercaptoethanol, 3-mercaptopropanol, 2-mercaptopropanol, 2-hydroxypropyl mercaptan, 2-phenyl-2-mercaptoethanol, Examples include 2-phenyl-2-hydroxyethyl mercaptan, 3-mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol, and mercaptomethylthiirane.

    Examples of mercaptans include mercaptans: methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1, 2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide, 1,2-bis (2-mercaptoethylthio) ethane, 1,5 -Dimercapto-3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2- Mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 2- (2mer Ptoethylthio) -1,3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1,1,1-tris (mercaptomethyl) propane, tetrakis (mercaptomethyl) methane, ethylene Glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate) , Trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptocetate), pentaerythritol tetrakis (3-mercaptopropionate) 1,1-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 1,3-bis (mercapto) Methyl) cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1- Thiane, 2,5-bis (2-mercaptoethyl) -1-thiane, 1,4-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) ether, 2,2-bis (4-mercaptophenyl) propane, bis (4 Mercaptomethylphenyl) sulfide, bis (4-mercaptomethylphenyl) ether, 2,2-bis (4-mercaptomethylphenyl) propane, 1,4-dimercapto-2,3-dithiabutane, 2,5-dimercapto-1, 3,4-thiadiazole, 3,4-thiophenedithiol, 1,2-dimercapto-3-propanol, 1,3-dimercapto-2-propanol, glyceryl dithioglycolate, 1,2,6,7-tetramercapto-4 -Thia-heptane, 1,2-epithio-6,7-dimercapto-4-thia-heptane, 3,11-bis (4-mercapto-2-thiabutyl) -1,4,7,9,12,15- Hexathia-8-stana-spiro [7.7] pentadecane, tetrakis (4-mercapto-1,3-dithiabutyl) Tin, tetrakis (mercaptomethyldithianylmethylthio) tin, bis (mercaptomethyl) -1,4,6,9-tetrathia-5-germer-spiro [4.4] nonane and the like and dimers to 20-mers thereof Can be mentioned.

    Examples of thiophenols include thiophenol, 4-tert-butylthiophenol, 2-methylthiophenol, 3-methylthiophenol, 4-methylthiophenol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, Examples thereof include thiophenols such as 1,4-dimercaptobenzene, 2-hydroxythiophenol, 3-hydroxythiophenol, and 4-hydroxythiophenol.

Specific examples of mercaptans and thiophenols having an unsaturated group are shown below.
Examples of mercaptans having an unsaturated group include allyl mercaptan, 2-vinylbenzyl mercaptan, 3-vinylbenzyl mercaptan, 4-vinylbenzyl mercaptan, and examples of thiophenols having an unsaturated group include 2-vinylthio. Phenol, 3-vinylthiophenol, 4-vinylthiophenol and the like can be mentioned.

    Illustrative examples of the performance improver isocyanate compounds include monoisocyanates, polyisocyanates and dimers of these polyisocyanates by a burette-type reaction, cyclized trimers of these polyisocyanates and There are adducts of these polyisocyanates and alcohols or thiols.

    Examples of monoisocyanates include methyl isocyanate, ethyl isocyanate, propyl isocyanate, iso-propyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, octyl isocyanate, dodecyl isocyanate, cyclohexyl Isocyanate, phenyl isocyanate, toluyl isocyanate and the like.

    Examples of polyisocyanates include diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, Isophorone diisocyanate, 2,6-bis (isocyanatomethyl) decahydronaphthalene, lysine triisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-tolidine diisocyanate, 4,4′-diphenylmethane diisocyanate, Diphenyl ether diisocyanate, 3- (2′-isocyanatocyclohexyl) propyl isocyanate, tris (pheny Isocyanate) thiophosphate, isopropylidenebis (cyclohexyl isocyanate), 2,2′-bis (4-isocyanatophenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 4,4 ′, 4 ″- Triisocyanate-2,5-dimethoxyphenylamine, 3,3′-dimethoxybenzidine-4,4′-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diisocyanatobiphenyl, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, dicyclohexylmethane-4,4′-diisocyanate, 1,1′-methylenebis (4-isocyanatobenzene), 1,1′-methylenebis (3-methyl- 4- Socyanatobenzene), m-xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1 -Isocyanate-1-methylethyl) benzene, 1,3-bis (2-isocyanato-2-propyl) benzene, 2,6-bis (isocyanatomethyl) naphthalene, 1,5-naphthalene diisocyanate, bis (isocyanate methyl) Tetrahydrodicyclopentadiene, bis (isocyanatemethyl) dicyclopentadiene, bis (isocyanatemethyl) tetrahydrothiophene, bis (isocyanatemethyl) thiophene, 2,5-diisocyanatemethylnorbornene, bis (isocyanatemethyl) A) adamantane, 3,4-diisocyanate selenophane, 2,6-diisocyanate-9-selenabicyclononane, bis (isocyanatomethyl) selenophan, 3,4-diisocyanate-2,5-diselenolan, dimer acid diisocyanate, 1, 3,5-tri (1-isocyanatohexyl) isocyanuric acid, bis (isocyanatomethyl) -1,4-dithiane, 2,5-bis (4-isocyanato-2-thiabutyl) -1,4-dithiane, 2,5-bis (3-isocyanatomethyl-4-isocyanato-2-thiabutyl) -1,4-dithiane, 2,5-bis (3-isocyanato-2-thiapropyl) -1,4-dithiane, 1,3,5-triisocyanatocyclohexane, 1,3,5-tris (isocyanatomethyl) cyclohexane Sun, bis (isocyanatomethyl) bicyclo [2.2.1] heptane, bis (isocyanatomethylthio) methane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2,3-tris (isocyanatoethyl) Thio) propane, 1,2,3-tris (isocyanatemethylthio) propane, 1,1,6,6-tetrakis (isocyanatemethyl) -2,5-dithiahexane, 1,1,5,5-tetrakis (isocyanatemethyl) -2,4-dithiapentane, 1,2-bis (isocyanatomethylthio) ethane, 1,5-diisocyanate-3-isocyanatomethyl-2,4-dithiapentane, 1,5-diisocyanate-3-isocyanatomethyl-2,4- Dithiapentane, tetraisocyanatogermany , Tetra (isocyanatoethylthio) germanium, isocyanatomethyl (triisocyanato) germanium, 3-isocyanatopropyl (triisocyanato) germanium, tri (vinylthio) isocyanatogermanium, di (vinylthio) diisocyanatogermanium, Examples thereof include vinylthiotriisocyanato germanium.

    As an isothiocyanate compound, the compound etc. which changed all or one part of the isocyanate group in the isocyanate compound described above into the isothiocyanate group can be mention | raise | lifted.

    Examples of inorganic compounds having sulfur atoms as performance improvers include elemental sulfur, hydrogen sulfide, carbon disulfide, carbon selenosulfide, ammonium sulfide, sulfur dioxide, sulfur trioxide, and other sulfur oxides, thiocarbonates, sulfuric acid and Its salts, hydrogen sulfide, sulfite, hyposulfite, persulfate, thiocyanate, thiosulfate, halides such as sulfur dichloride, thionyl chloride, thiophosgene, boron sulfide, nitrogen sulfide, silicon sulfide, phosphorus sulfide Arsenic sulfide, selenium sulfide, metal sulfide, metal hydrosulfide and the like.

    For example, 1,4,7,9,12,15-hexathia-8-stana-spiro [7.7] pentadecane, 1,4,7,9,12,15 -Hexathia-8-zirconium-spiro [7.7] pentadecane, tetrakis (dithiolanylmethylthio) tin, tetrakis (dithiolanylmethylthio) zirconium, tetrakis (dithianylmethylthio) tin, tetrakis (dithianylmethylthio) zirconium, tetrakis (N-butylthia) tin, tetrakis (n-butylthia) zirconium, 2,2-dimethyl-2-stana-1,3,6-trithiacyclooctane, 2,2-di (n-butyl) -2-stana -1,3,6-trithiacyclooctane, 2,2-di (phenyl) -2-stana-1,3,6-trithiaci Rookutan and the like.

    Specific examples of the inorganic compound having a selenium atom as a performance improver include selenium, hydrogen selenide, selenium dioxide, and carbon diselenide, except for selenosulfide and selenium sulfide, which are mentioned as specific examples of inorganic compounds containing a sulfur atom. Selenium oxides such as ammonium selenide and selenium dioxide, selenate and its salts, selenite and its salts, hydrogen selenate, selenosulfuric acid and its salts, selenopyrosulfuric acid and its salts, selenium tetrabromide, oxychloride Examples thereof include halides such as selenium, selenocyanate, boron selenide, phosphorus selenide, arsenic selenide, metal selenide and the like.

    Examples of performance improver carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, methyl mercaptopropionate, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, cyclohexane Carboxylic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, thiodipropionic acid, dithiodipropion An acid etc. can be mention | raise | lifted.

    Examples of the performance improving agent mercaptocarboxylic acids include thioglycolic acid, 2-thiopropionic acid, 3-thiopropionic acid, thiolactic acid, mercaptosuccinic acid, thiomalic acid, N- (2-mercaptopropionyl) glycine, 2- Examples thereof include mercaptobenzoic acid, 2-mercaptonicotinic acid, 3,3-dithioisobutyric acid, dithioglycolic acid, dithiopropionic acid and the like.

    Examples of the performance improving agent hydroxycarboxylic acids include hydroxyacetic acid, α-hydroxypropionic acid, β-hydroxypropionic acid, α-hydroxybutyric acid, β-hydroxyacetic acid, γ-hydroxybutyric acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid and the like.

    Examples of performance improver amides include formamide, N-methylformamide, acetamide, N-methylacetamide, phthalamide, isophthalamide, terephthalamide, benzamide, toluamide, 4-hydroxybenzamide, 3-hydroxybenzamide and the like. Can do.

    Examples of the performance improver 1,3-diketone include acetylacetone, cyclohexane-1,3,5-trione and the like, and examples of the performance improver 1,3-dicarboxylic acid and esters thereof include malonic acid, 2 Examples thereof include methylmalonic acid and the like and mono- and diesters thereof, and examples of the performance improving agent 3-ketocarboxylic acid and esters thereof include acetoacetic acid and esters thereof.

    Examples of the compound having an unsaturated group of the performance improver include alcohols, phenols, mercaptans, thiophenols, mercapto alcohols, carboxylic acids, and amides.

    Examples of alcohols having an unsaturated group include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 1, 3-dimethacryloxy-2-propanol, 1,3-diacryloxy-2-propanol, 1-acryloxy-3-methacryloxy-2-propanol, pentaerythritol trimethacrylate, pentaerythritol triacrylate, bis (2,2,2-trimethylol) Ethyl) ether pentamethacrylate, bis (2,2,2-trimethylolethyl) ether pentaacrylate, trimethylolpropane dimethacrylate, trimethyl Tyrolpropane diacrylate, allyl alcohol, crotyl alcohol, methyl vinyl carbinol, cinnamyl alcohol, 4-vinylbenzyl alcohol, 3-vinylbenzyl alcohol, 2- (4-vinylbenzylthio) ethanol, 2- (3-vinyl Benzylthio) ethanol, 1,3-bis (4-vinylbenzylthio) -2-propanol, 1,3-bis (3-vinylbenzylthio) -2-propanol, 2,3-bis (4-vinylbenzylthio) ) -1-propanol, 2,3-bis (3-vinylbenzylthio) -1-propanol, 3-phenoxy-2-hydroxypropyl acrylate, 2-hydroxyethyl isocyanurate bis (acrylate), 2-hydroxyethyl isocyanurate Bis (methacrylate), 2 Monohydroxy such as hydroxyethyl cyanurate bis (acrylate), 2-hydroxyethyl cyanurate bis (methacrylate), 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyne-3ol, propargyl alcohol, etc. Compounds such as pentaerythritol dimethacrylate, pentaerythritol diacrylate, pentaerythritol monomethacrylate, pentaerythritol monoacrylate, trimethylolpropane monomethacrylate, trimethylolpropane monoacrylate, 2-hydroxyethyl isocyanurate mono (acrylate), 2- Hydroxyethyl isocyanurate mono (methacrylate), 2-hydroxyethyl cyanurate mono (acrylate), 2-hydroxyethylsia Examples thereof include polyhydroxy compounds such as rate mono (methacrylate), and epoxy compounds described later such as 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane and acrylic acid or methacrylic acid. The unsaturated polyhydroxy compound produced | generated by addition reaction of these can be mention | raise | lifted.

    Examples of phenols having an unsaturated group include 2-vinylphenol, 3-vinylphenol, 4-vinylphenol and the like, and mercaptoalcohols having an unsaturated group include 2- (4-vinylbenzyl). Examples include thio) -2-mercaptoethanol, 2- (3-vinylbenzylthio) -2-mercaptoethanol, and the like.

    Examples of carboxylic acids having an unsaturated group include acrylic acid, methacrylic acid, crotonic acid, monohydroxyethyl acrylate phthalate, maleic acid, fumaric acid, monoallyl phthalate ester, and cinnamic acid. Examples of the amide having a group include α, β-unsaturated carboxylic acid amides such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and fumaric acid, and N-vinylformamide.

    Epoxy compounds of performance improvers include phenolic epoxy compounds, alcoholic epoxy compounds, glycidyl ester epoxy compounds, amine epoxy compounds, alicyclic epoxy compounds, epoxy compounds produced by epoxidation of unsaturated compounds, etc. I can give you.

    Examples of phenolic epoxy compounds include hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, bisphenol sulfide, halogenated bisphenol A, condensation of epihalohydrin with a polyphenolic compound such as bisphenol A and novolac resin. And phenolic epoxy compounds produced by the above method.

    Examples of alcohol-based epoxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexane. Diol, neopentyl glycol, glycerin, trimethylolpropane trimethacrylate, pentaerythritol, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A Alcohol-based epoxy produced by condensation of polyhalogen compound such as ethylene oxide adduct, bisphenol A / propylene oxide adduct and epihalohydrin Compounds, and the like.

    Examples of glycidyl ester epoxy compounds include adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, Hexahydroterephthalic acid, het acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, polyvalent carboxylic acid compounds such as naphthalene dicarboxylic acid, diphenyldicarboxylic acid and epihalohydrin The glycidyl ester type epoxy compound manufactured by condensation of these is mention | raise | lifted.

    Examples of amine-based epoxy compounds include 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, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1, 3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4 -Diaminodiphenylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, m- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, m- or p-xylylenediamine, 1,5- Alternatively, it is produced by condensation of a primary diamine such as 2,6-naphthalenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2- (4,4′-diaminodiphenyl) propane and epihalohydrin. Examples include amine-based epoxy compounds, 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- The (4-piperidyl) - propane, 1,4-di - (4-piperidyl) - amine based epoxy compounds produced by the condensation of 2 diamine and an epihalohydrin, such as butane may be mentioned.

    Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexane, 3,4-epoxycyclohexanecarboxylate, vinylcyclhexanehexane, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3. , 4-epoxycyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) adipate and the like.

    Examples of epoxy compounds produced by epoxidation of unsaturated compounds include epoxy compounds produced by epoxidation of unsaturated compounds such as cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, and vinylcyclohexene epoxide. .

    Moreover, the urethane type epoxy compound etc. which are manufactured from the above-mentioned polyhydric alcohol, a phenol compound, diisocyanate, glycidol, etc. can be mention | raise | lifted.

    Specific examples of the performance-improving epithio compounds include epithio compounds obtained by epithiolation of some or all of the epoxy groups of the epoxy compounds described above, 1,2-epithio-6,7-dimercapto-4 -Thia-heptane, mercaptomethylthiirane.

      These performance improvers may be used singly or in combination of two or more, and are added in an amount of 0.001 part by weight based on 100 parts by weight of the composition of the present invention containing at least one compound represented by the general formula (1). It can be used at 001 to 100 parts by weight.

    The composition of the present invention includes not only these performance improvers, but also oligomers of the compound of the general formula (1), and solvents, bases, acids, etc. used in the synthesis of the compound of the general formula (1). Cleaning agents, unreacted raw materials or by-products may be included as long as they do not cause a problem.

    When the composition of the present invention containing at least one compound represented by the general formula (1) is polymerized and cured to obtain an optical material, known antioxidants, ultraviolet absorbers, yellowing inhibitors, bluing agents, pigments Of course, it is possible to further improve the practicality of the resulting material by adding additives such as a polymerization modifier, a viscosity modifier, a release agent, and an adhesive.

    The amount of these additives to be added is adjusted depending on the composition and the type of performance improver used, but from 0.0000001 to 100 parts of the composition of the present invention containing at least one compound represented by the general formula (1). Used in 20 parts.

    An optical material obtained by polymerizing and curing the composition of the present invention containing at least one compound represented by the general formula (1) is mixed with a performance improver and an additive as desired, and then mixed with glass. After pouring into a metal mold and heating, the polymerization and curing reaction proceeds, and then the mold is removed from the mold. The present composition and additive are preliminarily partly or wholly added at -78 to 200 ° C for 1 minute to 100 hours with or without stirring in the presence or absence of a catalyst before casting. It is also possible to prepare the composition after the reaction and perform casting.

    In mixing the composition of the present invention containing at least one compound represented by the general formula (1), the performance improver, and the additive, the set temperature and the time required for this are basically sufficiently mixed. However, excessive heating / heating and an unnecessarily long treatment time may cause an undesirable reaction between the composition of the present invention, performance improver, additive, etc., and further increase the viscosity. This is not suitable because inconveniences such as making the casting operation difficult occur. Performing degassing under reduced pressure before, during or after mixing the composition, performance improver, and additive of the present invention is a preferable method from the viewpoint of preventing the generation of bubbles during the subsequent cast polymerization curing. It is. The degree of decompression at this time is about 0.1 mmHg to 700 mmHg, and preferably 10 mmHg to 300 mmHg. Furthermore, it is preferable to filter and remove impurities and the like with a microfilter having a pore diameter of about 0.1 to 5 [mu] m at the time of injection into the mold, from the viewpoint of further improving the quality of the optical material of the present invention.

    The curing time is 0.1 to 200 hours, usually 1 to 100 hours, and the curing temperature is −10 to 160 ° C., usually −10 to 140 ° C. The polymerization can be carried out at a predetermined polymerization temperature for a predetermined time, by raising the temperature from 0.1 ° C. to 100 ° C./h, lowering the temperature by 0.1 ° C. to 100 ° C./h, and combinations thereof. In addition, after the curing is completed, annealing the material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing the distortion of the optical material of the present invention. Furthermore, if necessary, dyeing, hard coating, impact-resistant coating, antireflection, antifogging surface treatment, antifouling surface treatment, and the like can be performed.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Moreover, the physical property measuring method is shown below.
Mass spectrum measurement: Measured by electrolytic desorption method using JMS-700 manufactured by JEOL.
¹ H-NMR: Measured using a JEOL NMR apparatus LA-500.
Refractive index: Atago Abbe refractometer NAR-4T was used, and the refractive index at the D line was measured at 25 ° C.
Appearance: A cured product having a thickness of φ30 × 2.5 mm is visually observed.

Example 1
1,3-Dichloro-1,1,3,3-tetra of known literature (Davies et al, J. Chem. Soc. (C), 1970, 2035) was added to a flask equipped with a stirrer, a thermometer and a nitrogen introduction tube. Methyl distanathiane (chemical formula (5)) 0.05 mol, dehydrated diethyl ether 500 mL, mercaptomethyl thiirane (chemical formula (6)) 0.1 mol were charged, and the liquid temperature in the flask was adjusted to 10 ° C. Thereto, 0.1 mol of triethylamine was dropped in 30 minutes while keeping the liquid temperature in the flask at 10 ° C., and then reacted at 10 ° C. for 2 hours. After the reaction, triethylamine hydrochloride produced as a by-product was filtered off, the filtrate was washed with 0.2N-phosphoric acid aqueous solution and then with water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent diethyl ether was removed. The product was obtained. 13.5 g (yield 50%) of the compound was obtained by liquid chromatography using the product as a styrene divinylbenzene copolymer stationary phase and a chloroform mobile phase.

The analysis result for structure determination of the compound obtained above is shown.

Elemental analysis;
Theoretical value (%) of compound of formula (1-1) (C, H, S) = (22.2, 4.1, 29.7)
Analytical value (%) of the compound obtained above (C, H, S) = (23.0, 4.0, 29.0)
Mass spectral analysis;
Theoretical molecular weight of the compound of formula (1-1): 540
Molecular weight analysis of the compound obtained above: 540
¹ H-NMR (ppm): 0.87 (CH ₃ —Sn, 12H), 2.27 (m, 2H),
2.58 (m, 2H), 2.59 (m, 2H), 3.05 (m, 2H), 3.09 (m, 2H)

From the above results, the obtained compound was determined to be the compound of formula (1-1).

Example 2
100 parts by weight of the compound (formula (1-1)) obtained in Example 1 and 0.1 part by weight of tetrabutylphosphonium bromide were mixed and degassed under reduced pressure to obtain a polymerization composition. This composition is poured into a 2.5 mm thick mold composed of two glass plates and a rubber ring, heated at 50 ° C. for 8 hours, and then constant from 50 ° C. to 100 ° C. over 10 hours. The temperature was raised, and finally, the mixture was heated at 100 ° C. for 2 hours to be cured by polymerization. After cooling to 50 ° C., the mold was released from the mold to obtain a cured product. Table 1 shows the refractive index and appearance of the obtained cured product.

Example 3, Example 4 and Example 5
Example 2 was repeated except that the composition shown in Table 1 was used instead of the compound of formula (1-1). Table 1 shows the refractive index and appearance of the cured product.

Comparative Example 1
Instead of the compound of formula (1-1), 0.032 part of dicyclohexylmethylamine instead of 0.1 part by weight of tetrabutylphosphonium bromide as a composition and polymerization catalyst shown in Table 1 is mixed, defoamed by reduced pressure, and polymerized. A composition was obtained. The composition is poured into a 2.5 mm thick mold composed of two glass plates and a rubber ring and heated at 60 ° C. for 10 hours, then at 90 ° C. for 5 hours, and further at 110 ° C. for 3 hours. And polymerized and cured. After cooling to 50 ° C., the mold was released from the mold to obtain a cured product. Table 1 shows the refractive index and appearance of the cured product.

Comparative Example 2
Instead of 0.1 parts by weight of tetrabutylphosphonium bromide as a composition and polymerization catalyst shown in Table 1 instead of the compound of formula (1-1), 0.33 part of N, N-dimethylcyclohexylamine was mixed and reduced in pressure. Defoamed to obtain a polymerization composition. This composition was poured into a mold having a thickness of 2.5 mm composed of two glass plates and a rubber ring, and the temperature was raised from 30 ° C. to 120 ° C. over 20 hours to be polymerized and cured. After cooling to 50 ° C., the mold was released from the mold to obtain a cured product. Table 1 shows the refractive index and appearance of the cured product.

Claims (5)

Compound represented by general formula (1)

(Wherein M ₁ and M ₂ each independently represent tin (Sn), germanium (Ge) or lead (Pb);
B represents sulfur (S) or oxygen (O);
P represents 0-2,
A ₁ represents an epithio group of the following general formula (2).
R _{1 to} R ₄ each represent a C1 to C4 hydrocarbon group. )

(In the formula, n represents 0 or 1.) The compound according to claim _{1, wherein} M _{1 and} M ₂ in the general formula (1) are tin (Sn).     The composition containing the compound represented by General formula (1).     A cured product obtained by polymerizing and curing the composition according to claim 3.     An optical material obtained by polymerizing and curing the composition according to claim 3.