JP4673814B2 - Polythiourethane polymerization catalyst, polymerizable composition containing the same, optical material obtained therefrom, and method for producing the same - Google Patents

Description

  The present invention relates to a polymerizable composition that gives a polythiourethane resin, an optical material obtained therefrom, and a method for producing the same. The polythiourethane resin obtained by the present invention is used for optical materials such as plastic lenses, prisms, optical fibers, information recording substrates, filters, and light emitting diodes, and is particularly preferably used as a plastic lens material for spectacles.

  In recent years, harmony with the global environment and environmental burden reduction have become major issues in industry, and the development of environmentally friendly products and technologies is being accelerated. There are also movements in the technical field of the present invention, and in particular, organotin catalysts that are widely used as catalysts for polythiourethane resins are problematic because of their high toxicity and environmental hormones. The regulations on the use of organotin compounds are being strengthened mainly in developed countries. In the eyeglass lens industry using polythiourethane resin, there is a demand for the development of a catalyst that replaces the organotin catalyst.

As a result of intensive studies, the present inventors have found several catalysts that can replace the organotin catalysts conventionally used as catalysts for polythiourethane resins (Patent Documents 1, 2, and 3). Effective catalysts with metal compounds have not been found. Moreover, as an internal mold release agent used for a polythiourethane resin-based plastic lens, a phosphoric acid ester composition is common (Patent Documents 4, 5, and 6), but a composition constituting the phosphoric acid ester composition. In some cases, problems may arise in the resin obtained and the workability. The phosphate ester composition is composed of various phosphate esters having different numbers of functional groups such as monoesters and diesters, and the number of carbons constituting the ester. When the composition ratio is high, the resulting resin may become cloudy and may not be suitable as a transparent resin for optics, and when the composition ratio of the monoester is high, the solubility in the monomer deteriorates and the dissolution time becomes long, When it gets worse, insoluble matter may be deposited. The present invention does not contain an organic tin compound conventionally used as a catalyst for a polythiourethane resin, and is suitably used as an optical transparent resin without requiring the addition of a conventional internal mold release agent. It is providing the polymeric composition from which a polythiourethane resin is obtained.
Japanese Patent Application No. 2006-044214 Japanese Patent Application No. 2006-046213 Japanese Patent Application No. 2006-053665 Japanese Laid-Open Patent Publication No. 1-163012 Japanese Patent Laid-Open No. 3-281313 Japanese Patent Laid-Open No. 3-287461

  The present inventors have intensively studied to solve the above problems. As a result, it was found that tin-free sulfonic acid showed catalytic activity, but at the same time it also revealed a mold release action. In a polythiourethane resin-based plastic lens, it is not known that sulfonic acid exhibits releasability, which is a surprising discovery. However, since the activity is too high with sulfonic acid alone, a side reaction with the polymerizable composition proceeds, and a partly opaque solid precipitates on the resulting resin, which may not be suitable for optical materials that require transparency. there were. However, by using an amine compound in combination, it is possible to prevent generation of opaque solids in the resulting resin, and to satisfy a polythio which can be satisfied as an optical transparent resin without requiring the addition of a conventional internal mold release agent. The inventors have found a polymerizable composition from which a urethane resin can be obtained, and have completed the present invention.

That is, the present invention
[1] From the amine compound represented by the general formula (1) and the sulfonic acid represented by the general formula (2), wherein the molar ratio of the sulfonic acid group to the amino group is 1.05 to 10. It relates to a polymerization catalyst for polythiourethane optical materials.

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group having 1 to 8 carbon atoms. R ¹ , R ² and R ³ are bonded to each other. A ring may be formed.)

(In the formula, n represents an integer of 1 or 2, and R ⁴ represents a monovalent or higher linear aliphatic, branched aliphatic, cycloaliphatic and aromatic organic residue which may contain a hydroxyl group or an amino group. Is shown.)

Hereinafter, [2] to [ 11 ] are each one of preferred embodiments of the present invention.
[2] The amine compound represented by the general formula (1) is triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine or triisobutylamine, Polymerization catalyst.
[3] The polymerization catalyst according to [1] or [2], wherein the sulfonic acid represented by the general formula (2) is an alkylsulfonic acid.
[4] The polymerization catalyst according to [1] or [2], wherein the sulfonic acid represented by the general formula (2) is methanesulfonic acid, toluenesulfonic acid or dodecylbenzenesulfonic acid.
[5] The polymerization catalyst according to any one of [1] to [4], one or more isocyanates selected from a polyisocyanate compound, a polyisothiocyanate compound, and a polyisothiocyanate compound having an isocyanato group; A polymerizable composition for a polythiourethane-based optical material containing one or more thiols selected from polythiol compounds.

[6] Isocyanate is m-xylylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) -bicyclo- [2 2.1] -one or more compounds selected from the group consisting of heptane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane and hexamethylene diisocyanate Thiols are 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-di Mercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1, 11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis Selected from the group consisting of (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithietane The polymerizable composition according to [5], wherein the polymerizable composition is one or more compounds.
[7] The addition amount of the sulfonic acid represented by the general formula (2) is 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the total of isocyanates and thiols. [5] Or the polymerizable composition as described in [6].
[8] A molded article comprising a polythiourethane resin obtained by curing the polymerizable composition according to any one of [5] to [7].
[9] An optical material comprising a polythiourethane resin obtained by curing the polymerizable composition according to any one of [5] to [7].
[10] A plastic lens comprising a polythiourethane resin obtained by curing the polymerizable composition according to any one of [5] to [7].
[11] A method for producing a molded article comprising a polythiourethane resin, which comprises subjecting the polymerizable composition according to any one of [5] to [7] to cast polymerization.

  According to the present invention, a polythiourethane resin that does not contain an organotin compound that is generally considered to be highly toxic and does not require the addition of a conventional internal mold release agent, is suitably used as an optical transparent resin. The polymerizable composition obtained was found. Such polythiourethane-based polymerizable compositions are used in the field of resins such as plastic lenses, prisms, optical fibers, information recording substrates, filters, light emitting diodes, and other optical materials that require high refractive index and high transparency, particularly glasses. It is preferably used in the field of plastic lens materials.

Hereinafter, the present invention will be described in detail.
A polythiol comprising an amine compound represented by general formula (1) and a sulfonic acid represented by general formula (2), wherein the molar ratio of sulfonic acid groups to amino groups is 1.05 to 10 The present invention relates to a polymerization catalyst for urethane optical materials.

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a monovalent or higher-valent linear aliphatic, branched aliphatic, cycloaliphatic and aromatic group which may contain a hydroxyl group or an amino group) Represents an organic residue, R ¹ , R ² and R ³ may be bonded to each other to form a ring.)

(In the formula, n represents an integer of 1 or 2, and R ⁴ represents a monovalent or higher linear aliphatic, branched aliphatic, cycloaliphatic and aromatic organic residue which may contain a hydroxyl group or an amino group. Is shown.)
R ¹ , R ² , R ^{3 in} the general formula (1) and R ⁴ in the general formula (2) are, for example, a hydrogen atom and methane, ethane, propane, butane, pentane, hexane, heptane, octane. , A monovalent organic residue derived from a linear aliphatic compound such as nonane, decane, undecane, dodecane, tetradecane, hexadecane, ethylene, propylene, 1-butene, 2-butene, butadiene, and the like, and

  2-methylpropane, 2-methylbutane, 2-methylpentane, 3-methylpentane, 3-ethylpentane, 2-methylhexane, 3-methylhexane, 3-ethylhexane, 2-methylheptane, 3-methylheptane 4-methylheptane, 3-ethylheptane, 4-ethylheptane, 4-propylheptane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 3-ethyloctane, 4-ethyloctane, Derived from branched aliphatic compounds such as 4-propyloctane, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 2-methyl-butadiene and 2,3-dimethylbutadiene A monovalent or higher valent organic residue, and

  Cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, norbornane , A monovalent or higher-valent organic residue derived from a cyclic aliphatic compound such as 2,3-dimethylnorbornane, 2,5-dimethylnorbornane, 2,6-dimethylnorbornane, bis (4-methylcyclohexyl) methane, and

  A monovalent or higher-valent organic residue derived from an aromatic compound such as benzene, toluene, o-xylene, m-xylene, p-xylene, naphthalene, biphenyl, anthracene, perylene, styrene, ethylbenzene, and

  One or more organic residues derived from alcohol compounds such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and the like, and

  Ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, ter-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, myristylamine, 3-pentylamine, 2-ethylhexyl A monovalent or higher-valent organic residue derived from a primary amine compound such as an amine or 1,2-dimethylhexylamine;

  Diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, methyl A monovalent organic residue derived from a secondary amine compound such as hexylamine, and

Triethylamine, tributylamine, trihexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, triethanolamine A monovalent or higher-valent organic residue derived from a tertiary amine compound such as N-ethyldiethanolamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, tribenzylamine, N-methyldibenzylamine, etc. However, it is not limited only to these exemplary compounds. R ¹ , R ² and R ³ may be bonded to form a ring.

R ¹ , R ² and R ³ are more preferably an alkyl group having 1 to 8 carbon atoms and a hydroxyalkyl group having 1 to 8 carbon atoms.
More preferably, R ⁴ is an alkyl group.

  Specific examples of the amine compound of the present invention include, for example, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, ter-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, lauryl. Amine, myristylamine, 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine, aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine, 2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline, Benzylamine, phenethylamine, 2,3-, or 4-methylbenzylamine, o-, m-, or p-methylaniline, o-, m-, or p-ethylamine Phosphorus, aminomorpholine, naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine, aminopyridine, aminophenol, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, methoxyethylamine, 2 -(2-aminoethoxy) ethanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-isobutoxypropylamine, 2,2-diethoxyethylamine and the like ,

  Ethylenediamine, 1,2-, or 1,3-diaminopropane, 1,2-, 1,3-, or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7 -Diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4 -Or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-, or 4,4 '-Diaminodiphenylsulfone, 2,7-diaminofluorene, 1,5-, 1,8-, or 2,3-diaminonaphthalene 2,3-, 2,6-, or 3,4-diaminopyridine, 2,4-, or 2,6-diaminotoluene, m-, or p-xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1 , 3- or 1,4-diaminomethylcyclohexane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylmorpholine, N- Primary amine compounds such as aminopropylmorpholine and derivatives thereof, and

  Diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, methyl Hexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N -Ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine and the like, and

  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-1,5-diaminopentane, N, N′-diethyl-1,6-diaminohexane, N, N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, Secondary amine compounds such as 1,4-di- (4-piperidyl) butane and tetramethylguanidine and derivatives thereof;

  Triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tripentylamine, trihexylamine, trioctylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N , N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, tribenzyl Ruamine, N-methyldibenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylbutylamine, N-methyldicyclohexylamine, N-ethyl Dicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, quinoline, N, N-dimethylaniline, N, N-diethylaniline, α-, β-, or γ-picoline, 2,2′-bipyridyl, 1 , 4-dimethylpiperazine, dicyandiamide, tetramethylethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo- [5,4,0] -7-undecene, 2,4,6-tris (N, N-dimethylaminomethyl) Although tertiary amine compounds, such as a phenol, and its derivative (s) can be mentioned, it is not limited only to these exemplary compounds.

Of these exemplified compounds, tertiary amines are preferred, and triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tripentylamine, trihexylamine, trioctylamine, N, N -Dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N-methyldicyclohexyl More preferred are amines, N-ethyldicyclohexylamine, and 1,8-diazabicyclo- [5,4,0] -7-undecene. More preferred are triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, and triisobutylamine.
These amine compounds can be used alone or in combination of two or more.

  Specific examples of the sulfonic acid of the present invention include, for example, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, Examples include decane sulfonic acid, undecane sulfonic acid, dodecane sulfonic acid, tetradecane sulfonic acid, hexadecane sulfonic acid, benzene sulfonic acid, toluene sulfonic acid, dodecyl benzene sulfonic acid and the like, and examples thereof. It is not limited to only compounds.

  Among these exemplary compounds, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and dodecylbenzenesulfonic acid are preferable, and methanesulfonic acid, toluenesulfonic acid, and dodecylbenzenesulfonic acid are more preferable. These sulfonic acids can be used alone or in combination of two or more.

  In the present invention, the ratio of the amine compound and sulfonic acid used is such that the molar ratio of the sulfonic acid group to the amino group is in the range of 1.05 to 10, preferably in the range of 1.10 to 5.0. A range of 20 to 4.0 is more preferred.

  The amount of sulfonic acid used is one or two or more isocyanates selected from polyisocyanate compounds, polyisothiocyanate compounds, polyisothiocyanate compounds having an isocyanate group, and one or two or more thiols selected from polythiol compounds. In the range of 0.05 to 0.5 parts by weight, preferably in the range of 0.07 to 0.3 parts by weight, more preferably in the range of 0.07 to 0.2 parts by weight. preferable. The usage-amount of an amine compound and a sulfonic acid is suitably determined by the kind of catalyst, the monomer to be used, the kind and usage-amount of an additive, and the shape of a molding.

  The method for adding the catalyst to the monomers is not particularly limited, and the amine compound and the sulfonic acid may be appropriately added to the monomers and resin modifiers used, or the amine compound and the sulfonic acid. After obtaining the above mixture, it may be added to the monomers and the resin modifier.

  For example, a method in which an amine compound and a sulfonic acid are separately added, or a mixture of an amine compound and a sulfonic acid is added to a resin modifier such as isocyanates, thiols, or alcohol compounds, or isocyanates and thiols. Examples include a method of adding to a mixture or a mixture of resin modifiers such as isocyanates and alcohol compounds, or a method of adding to a mixture of resin modifiers such as isocyanates, thiols and alcohol compounds. The preparation procedure differs depending on the types and amounts of monomers, catalysts, resin modifiers, and other additives, so they are not limited to a single one. Considering the solubility, operability, safety, convenience, etc. of the catalyst Thus, it is appropriately selected.

  The polythiourethane resin of the present invention is a polyisocyanate compound, a polyisothiocyanate compound, one or two or more isocyanates selected from polyisocyanate compounds having an isocyanate group, and one or two or more types selected from polythiol compounds. Mainly thiols. In addition, a resin modifier can be added for the purpose of adjusting the optical properties of the resin obtained, adjusting various physical properties such as impact resistance and specific gravity, and adjusting the handling property of the monomer.

  The polyisocyanate compound relating to the present invention includes hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4 4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis An aliphatic polyisocyanate compound such as (isocyanatoethyl) ether, and

  Isophorone diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, Dicyclohexyldimethylmethane isocyanate, 2,2-dimethyldicyclohexylmethane isocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2 , 2,1] -heptane, 3,8-bis (isocyanatomethyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) trisi Alicyclic polyisocyanate compounds such as clodecane, 4,9-bis (isocyanatomethyl) tricyclodecane, and

  o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ′, α′-tetramethylxylylene diisocyanate, Bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate , Trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl Isocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4, Aromatic polyisocyanate compounds such as 4-diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4-diisocyanate, and

  Bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatopropyl) disulfide, bis ( Isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, etc. A sulfurized aliphatic polyisocyanate compound, and

  Diphenyl sulfide-2,4-diisocyanate, diphenyl sulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4-isocyanatomethylbenzene) sulfide, 4,4- Methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide-5,5-diisocyanate, 3 , 3-Dimethyldiphenyl disulfide-6,6-diisocyanate, 4,4-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate 4,4 sulfur-containing aromatic polyisocyanate compounds such as dimethoxy diphenyl disulfide-3,3-diisocyanate and,

  2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, 3,4-bis ( Isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4, And sulfur-containing heterocyclic polyisocyanate compounds such as 5-bis (isocyanato-methyl) -1,3-dithiolane and 4,5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolane. However, it is not limited only to these exemplary compounds. Halogen-substituted products such as chlorine-substituted products and bromine-substituted products of these compounds, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, biurets Modified products, dimerization or trimerization reaction products, and the like can also be used. These polyisocyanate compounds can be used alone or in combination of two or more.

  Examples of the polyisothiocyanate compound according to the present invention include hexamethylene diisothiocyanate, 2,2-dimethylpentane diisothiocyanate, 2,2,4-trimethylhexane diisothiocyanate, butene diisothiocyanate, and 1,3-butadiene-1. , 4-diisothiocyanate, 2,4,4-trimethylhexamethylene diisothiocyanate, 1,6,11-undecatriisothiocyanate, 1,3,6-hexamethylene triisothiocyanate, 1,8-diisothiocyanate Aliphatic polyisothiocyanate compounds such as -4-isothiocyanate methyloctane, bis (isothiocyanatoethyl) carbonate, bis (isothiocyanatoethyl) ether, and

  Isophorone diisothiocyanate, 1,2-bis (isothiocyanatomethyl) cyclohexane, 1,3-bis (isothiocyanatomethyl) cyclohexane, 1,4-bis (isothiocyanatomethyl) cyclohexane, dicyclohexylmethane diisothiocyanate, Cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, dicyclohexyldimethylmethane isothiocyanate, 2,2-dimethyldicyclohexylmethane isothiocyanate, 2,5-bis (isothiocyanatomethyl) bicyclo- [2,2,1] -heptane, 2,6-bis (isothiocyanatomethyl) bicyclo- [2,2,1] -heptane, 3,8-bis (isothiocyanatomethyl) tricyclodecane, 3,9-bis (isothiocyanatomethyl) trisi Cycloaliphatic polyisothiocyanate compounds such as chlorodecane, 4,8-bis (isothiocyanatomethyl) tricyclodecane, 4,9-bis (isothiocyanatomethyl) tricyclodecane,

  o-xylylene diisothiocyanate, m-xylylene diisothiocyanate, p-xylylene diisothiocyanate, bis (isothiocyanatoethyl) benzene, bis (isothiocyanatopropyl) benzene, α, α, α ', α'-tetra Methylxylylene diisothiocyanate, bis (isothiocyanatobutyl) benzene, bis (isothiocyanatomethyl) naphthalene, bis (isothiocyanatomethyl) diphenyl ether, phenylene diisothiocyanate, tolylene dithiocyanate, ethylphenylene diisothiocyanate, isopropyl Phenylene diisothiocyanate, dimethylphenylene diisothiocyanate, diethylphenylene diisothiocyanate, diisopropylphenylene diisothiocyanate, Zentri isothiocyanate, benzene triisothiocyanate, biphenyl diisothiocyanate, toluidine diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, 3,3-dimethyldiphenylmethane-4,4-diisothiocyanate, bibenzyl-4,4- Diisothiocyanate, bis (isothiocyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisothiocyanate, phenylisothiocyanatoethyl isocyanate, hexahydrobenzene diisothiocyanate, hexahydrodiphenylmethane-4,4- Aromatic polyisothiocyanate compounds such as diisothiocyanate, and

  Bis (isothiocyanatoethyl) sulfide, bis (isothiocyanatopropyl) sulfide, bis (isothiocyanatohexyl) sulfide, bis (isothiocyanatomethyl) sulfone, bis (isothiocyanatomethyl) disulfide, bis (isothiocyanato) Propyl) disulfide, bis (isothiocyanatomethylthio) methane, bis (isothiocyanatoethylthio) methane, bis (isothiocyanatoethylthio) ethane, bis (isothiocyanatomethylthio) ethane, 1,5-diisothiocyanato-2 -Sulfur-containing aliphatic polyisothiocyanate compounds such as isothiocyanatomethyl-3-thiapentane, and

  Diphenyl sulfide-2,4-diisothiocyanate, diphenyl sulfide-4,4-diisothiocyanate, 3,3-dimethoxy-4,4-diisothiocyanatodibenzylthioether, bis (4-isothiocyanatomethylbenzene) sulfide 4,4-methoxybenzenethioethylene glycol-3,3-diisothiocyanate, diphenyl disulfide-4,4-diisothiocyanate, 2,2-dimethyldiphenyl disulfide-5,5-diisothiocyanate, 3,3- Dimethyldiphenyl disulfide-5,5-diisothiocyanate, 3,3-dimethyldiphenyl disulfide-6,6-diisothiocyanate, 4,4-dimethyldiphenyl disulfide-5,5-diisothiocyanate, 3,3-dimethoxydi Feni Disulfide-4,4-diisothiocyanate, 4,4-sulfur-containing aromatic such as dimethoxy diphenyl disulfide-3,3-diisothiocyanate polyisothiocyanate compounds and,

  2,5-diisothiocyanatothiophene, 2,5-bis (isothiocyanatomethyl) thiophene, 2,5-diisothiocyanatotetrahydrothiophene, 2,5-bis (isothiocyanatomethyl) tetrahydrothiophene, 3, 4-bis (isothiocyanatomethyl) tetrahydrothiophene, 2,5-diisothiocyanato-1,4-dithiane, 2,5-bis (isothiocyanatomethyl) -1,4-dithiane, 4,5-dithiane Isothiocyanato-1,3-dithiolane, 4,5-bis (isothiocyanatomethyl) -1,3-dithiolane, 4,5-bis (isothiocyanatomethyl) -2-methyl-1,3-dithiolane, etc. The sulfur-containing heterocyclic polyisothiocyanate compound can be exemplified, but is not limited to these exemplified compounds. Halogen-substituted products such as chlorine-substituted products and bromine-substituted products of these compounds, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, biurets Modified products, dimerization or trimerization reaction products, and the like can also be used. These polyisothiocyanate compounds can be used alone or in combination of two or more.

  Among these exemplary compounds, m-xylylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) -bicyclo- [2 2.1] -heptane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, and hexamethylene diisocyanate are more preferable.

  Examples of polythiol compounds related to the present invention include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4- Butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2, 2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, 1,2- Dimercaptopropyl methyl ether, 2,3-dimercaptopropyl Chirueteru, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, tetrakis aliphatic such as (mercaptomethyl) methane polythiol compound and,

  2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto -1-propanol (3-mercaptopropionate), 3-mercapto-1,2-propanediol di (2-mercaptoacetate), 3-mercapto-1,2-propanediol di (3-mercaptopropionate) , Diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2- Mercaptoa Tate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethanetris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), Pentaerythritol tetrakis (3-mercaptopropionate), glycerin tris (2-mercaptoacetate), glycerin tris (3-mercaptopropionate), 1,4-cyclohexanediol bis (2-mercaptoacetate), 1,4- An aliphatic polythiol compound containing an ester bond such as cyclohexanediol bis (3-mercaptopropionate), and

  1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethyleneoxy) Benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercap Benzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1, 3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2,4-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris ( Mercaptoethyleneoxy) benzene, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5-to (Mercaptoethyleneoxy) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2, 2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7 -Naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1,2,3,4-tetramercaptobenzene 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2, 3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (Mercaptomethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercapto) Ethyleneethylene) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2, , 5-Tetrakis (mercaptoethyleneoxy) benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-dichlorobenzene-1,3- Dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, 2,3,4,6-tetrachloro-1,5- Aromatic polythiol compounds such as bis (mercaptomethyl) benzene, and

  2-methylamino-4,6-dithiol sym-triazine, 2-ethylamino-4,6-dithiol sym-triazine, 2-amino-4,6-dithiol sym-triazine, 2-morpholino-4,6-dithiol sym-triazine, 2-cyclohexylamino-4,6-dithiol sym-triazine, 2-methoxy-4,6-dithiol sym-triazine, 2-phenoxy-4,6-dithiol sym-triazine, 2-thiobenzeneoxy- Examples include heterocyclic polythiol compounds such as 4,6-dithiol sym-triazine and 2-thiobutyloxy-4,6-dithiol sym-triazine, and halogen-substituted compounds thereof, but are limited to these exemplified compounds. Is not to be done. Further, halogen-substituted products such as chlorine-substituted products and bromine-substituted products may be used. These polythiol compounds can be used alone or in combination of two or more.

  Examples of polythiol compounds having one or more sulfide bonds in one molecule include bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, and bis (mercaptopropyl). Sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethyl) Thio) ethane, 1,2-bis (3-mercaptopropylthio) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3 -Mercaptopropylthio) propane, 1 2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 4-mercaptomethyl-1, 8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3, 6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane Tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptop) Pills) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-aliphatic and di-mercaptomethyl-2,5-dimethyl-1,4-dithiane polythiol compound and,

  These esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide Bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis ( 3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3 Mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropinate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3- Mercaptopropionate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester) ), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 4,4-dithiodibuty Acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithiodiglycolic acid bis (2, 3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid bis (2,3-dimercaptopropyl ester) and other aliphatic polythiols containing an ester bond;

Heterocyclic polythiol compounds such as 3,4-thiophenedithiol and bismuthiol, and
1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiacyclohexane, 1, 1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 2- (4,5-dimercapto-2-thiapentyl) -1,3-dithiacyclopentane, 2,5-bis (4,4-bis (mercaptomethylthio) -2-thiabutyl) -1,4-dithiane, 2, 2-bis (mercaptomethylthio) -1,3-propanedithiol, 3-mercaptomethylthio-1,7-dimercapto-2 6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 2- (2, 2-bis (mercaptodimethylthio) ethyl) -1,3-dithietane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3 7-dithianonane, tris (2,2-bis (mercaptomethylthio) ethyl) methane, tris (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, tetrakis (2,2-bis (mercaptomethylthio) ethyl) Methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5 9,11-tetrakis (mercaptomethylthio) -1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis (mercaptomethylthio) -1,19 Dimercapto-2,6,8,12,14,18-hexathiononadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1 , 17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis (mercaptomethylthio) -1,11-dimercapto-2,5,7,10- Tetrathiaundecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-dimercapto-2,5,7,10,12, 15-hexathiahexadecane, 8- [bis (mercaptomethylthio) methyl] -3,4,12,13-tetrakis (mercaptomethylthio) -1,15-dimercapto-2,5,7,9,11,14-hexa Thiapentadecane, 4,6-bis [3,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio] -1,3-dithiane, 4- [3,5-bis (mercaptomethylthio) ) -7-mercapto-2,6-dithiaheptylthio] -6-mercaptomethylthio-1,3-dithiane, 1,1-bis [4- (6-mercaptomethylthio) -1,3-dithianethio] -1 , 3-bis (mercaptomethylthio) propane, 1- [4- (6-mercaptomethylthio) -1,3-dithianethio] -3- [2,2-bis ( Lucaptomethylthio) ethyl] -7,9-bis (mercaptomethylthio) -2,4,6,10-tetrathiaundecane, 1,5-bis [4- (6-mercaptomethylthio) -1,3-dithianethio] -3- [2- (1,3-dithietanyl)] methyl-2,4-dithiapentane, 4,6-bis {3- [2- (1,3-dithietanyl)] methyl-5-mercapto-2,4 -Dithiapentylthio} -1,3-dithiane, 4,6-bis [4- (6-mercaptomethylthio) -1,3-dithianethio] -6- [4- (6-mercaptomethylthio) -1,3 -Dithianethio] -1,3-dithiane, 3- [2- (1,3-dithietanyl)] methyl-7,9-bis (mercaptomethylthio) -1,11-dimercapto-2,4,6,10-teto Thiaundecane, 9- [2- (1,3-dithietanyl)] methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16- Hexathiaheptadecane, 3- [2- (1,3-dithietanyl)] methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,4,6,10,12, 16-hexathiaheptadecane, 3,7-bis [2- (1,3-dithietanyl)] methyl-1.9-dimercapto-2,4,6,8-tetrathianonane, 4- [3,4, 8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecyl] -5-mercaptomethylthio-1,3-dithiolane, 4,5-bis [3,4- Bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio] -1,3-dithiolane, 4- [3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexyl Thio] -5-mercaptomethylthio-1,3-dithiolane, 4- [3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl] -5-mercaptomethylthio-1,3-dithiolane, 2- {bis [3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio] methyl} -1,3-dithietane, 2 -[3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio] mercaptomethylthiomethyl-1,3-dithieta 2- [3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecylthio] mercaptomethylthiomethyl-1,3-dithietane, 2- [3 -Bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl] mercaptomethylthiomethyl-1,3-dithietane, 4,5-bis {1- [2- (1,3-dithietanyl)]-3-mercapto-2-thiapropylthio} -1,3-dithiolane, 4- {1- [2- (1,3-dithietanyl)]-3-mercapto- 2-thiapropylthio} -5- [1,2-bis (mercaptomethylthio) -4-mercapto-3-thiabutylthio] -1,3-dithiolane, 2- {bis [4- ( -Mercaptomethylthio-1,3-dithiolanyl) thio] methyl} -1,3-dithietane, 4- [4- (5-mercaptomethylthio-1,3-dithiolanyl) thio] -5- {1- [2- ( 1,3-dithietanyl)]-3-mercapto-2-thiapropylthio} -1,3-dithiolane, and polythiol compounds having a dithioacetal or dithioketal skeleton such as oligomers thereof, and

  Tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane, bis [4,4-bis (mercaptomethylthio) -1,3 -Dithiabutyl]-(mercaptomethylthio) methane, tris [4,4-bis (mercaptomethylthio) -1,3-dithiabutyl] methane, 2,4,6-tris (mercaptomethylthio) -1,3,5-trithia Cyclohexane, 2,4-bis (mercaptomethylthio) -1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis (mercaptomethylthio) -2-thiapropane, bis (mercaptomethyl) methylthio-1,3 , 5-trithiacyclohexane, tris [(4-mercaptomethyl-2,5-di Acyclohexyl-1-yl) methylthio] methane, 2,4-bis (mercaptomethylthio) -1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane, 2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4 -Mercaptomethyl-2- (1,3-dimercapto-2-propylthio) -1,3-dithiacyclopentane, tris [2,2-bis (mercaptomethylthio) -2-thiapropyl] methane, tris [4,4 -Bis (mercaptomethylthio) -3-thiabutyl] methane, 2,4,6-tris [3,3-bis (mercaptomethylthio) -2- Apropyl] -1,3,5-trithiacyclohexane, tetrakis [3,3-bis (mercaptomethylthio) -2-thiapropyl] methane, and polythiol compounds having an ortho trithioformate skeleton such as oligomers thereof. Although it can, it is not limited only to these exemplary compounds. Further, halogen-substituted products such as chlorine-substituted products and bromine-substituted products may be used. These polythiol compounds having a sulfide bond can be used alone or in combination of two or more.

  Examples of the thiol compound having a hydroxyl group include 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 5-mercaptopentanol, 6-mercaptohexanol, 7-mercaptoheptanol, 8-mercaptooctanol, 5-mercapto- Although 3-thiapentanol etc. can be mentioned, it is not limited only to these exemplary compounds. These thiol compounds having a hydroxyl group can be used alone or in combination of two or more.

  Among these exemplary compounds, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7 Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis (3 -Mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3 -Dithian, 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithietane is more preferred .

  Examples of the resin modifier relating to the present invention include olefin compounds including alcohol compounds, epoxy resins, organic acids and anhydrides thereof, (meth) acrylate compounds, and the like.

  Examples of alcohol compounds that can be added as a resin modifier include diethylene glycol, triethylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1 , 7 heptanediol, 1,8-octanediol, thiodiethanol, dithiodiethanol, thiodipropanol, dithiodipropanol, and oligomers thereof, but are not limited to these exemplified compounds. These alcohol compounds can be used alone or in combination of two or more.

  Examples of the epoxy resin that can be added as a resin modifier include phenolic epoxy compounds obtained by condensation reaction of polyphenol compounds such as bisphenol A glycidyl ether and epihalohydrin compounds, and hydrogenated bisphenol A glycidyl ether. Alcohol-based epoxy compounds obtained by condensation of polyhydric alcohol compounds and epihalohydrin compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-hexahydrophthalic acid diglycidyl ester, etc. Glycidyl ester epoxy compounds obtained by condensation of polyvalent organic acid compounds and epihalohydrin compounds, and amine epoxys obtained by condensation of primary and secondary diamine compounds with epihalohydrin compounds Shi compounds and can be exemplified aliphatic polyhydric epoxy compounds such as vinylcyclohexene diepoxide, but is not limited only to these exemplified compounds. These epoxy resins can be used alone or in combination of two or more.

  Organic acids that can be added as resin modifiers and their anhydrides include thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Examples include methyltetrahydrophthalic anhydride, methylnorbornenoic anhydride, methylnalbornanoic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Absent. These organic acids and their anhydrides can be used alone or in combination of two or more.

  Examples of olefin compounds that can be added as a resin modifier include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, and glycidyl acrylate. Glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene Recall diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate Bisphenol A dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxyethoxyphenyl) Propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F diacrylate Tacrylate, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1-bis (4-methacryloxydiethoxyphenyl) methane, dimethyloltricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetra Chlorate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithioldi (Meth) acrylate compounds such as acrylate, xylylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, and

  Allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, and

  Examples include vinyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, and 3,9-divinylspirobi (m-dioxane), but are not limited to these exemplified compounds. . These olefin compounds can be used alone or in combination of two or more.

  In the present invention, the use ratio of raw materials including isocyanates and thiols used as raw materials, and alcohol compounds that are resin modifiers is usually the functional group molar ratio of (NCO + NCS) / (SH + OH). , 0.5 to 3.0, preferably 0.6 to 2.0, and more preferably 0.8 to 1.2.

  The temperature for preparing a polymerizable composition by mixing isocyanates, thiols, catalysts, and other additives is usually 25 ° C. or lower. From the viewpoint of the pot life of the composition, it may be preferable to lower the temperature further. However, if the solubility of the catalyst or additive in the monomer is not good, it can be heated in advance and dissolved in the isocyanate or thiol monomer or monomer mixture.

Examples of the method for producing the polythiourethane resin of the present invention include cast polymerization, that is, the polymerizable composition according to the present invention is injected between molding molds held by a gasket or a tape. At this time, depending on the physical properties required of the plastic lens to be obtained, it is often preferable to perform a defoaming treatment under reduced pressure, a filtration treatment such as pressurization or reduced pressure, and the like.
The polymerization conditions are not limited because the conditions vary greatly depending on the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc., but it takes approximately 1-50 hours at a temperature of -50 to 150 ° C. Done. Depending on the case, it is preferable to hold or gradually raise the temperature in a temperature range of 10 to 150 ° C. and cure in 1 to 25 hours.

  About the obtained polythiourethane resin, you may perform processes, such as annealing, as needed. The treatment temperature is usually 50 to 150 ° C, preferably 90 to 140 ° C, and more preferably 100 to 130 ° C.

  When molding the polythiourethane resin of the present invention, a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an anti-coloring agent, an oil-soluble dye, as in known molding methods, depending on the purpose. Various additives such as fillers and adhesion improvers may be added.

  The polythiourethane resin of the present invention can be obtained as molded articles having various shapes by changing the mold during the casting polymerization, and various kinds of optical resins such as spectacle lenses, camera lenses, and light emitting diodes (LEDs). It can be used for applications. In particular, it is suitable for optical materials and optical elements such as spectacle lenses, camera lenses, and light emitting diodes.

  The plastic lens using the polythiourethane resin of the present invention may be used with a coating layer on one side or both sides as required. Examples of the coating layer include a primer layer, a hard coat layer, an antireflection film layer, an antifogging coat film layer, an antifouling layer, and a water repellent layer. Each of these coating layers may be used alone, or a plurality of coating layers may be used in multiple layers. When a coating layer is applied to both sides, a similar coating layer or a different coating layer may be applied to each surface.

  Each of these coating layers is an ultraviolet absorber for the purpose of protecting the lens and eyes from ultraviolet rays, an infrared absorber for the purpose of protecting the eyes from infrared rays, a light stabilizer, an antioxidant, and a lens for the purpose of improving the weather resistance of the lens. For the purpose of enhancing fashionability, dyes and pigments, photochromic dyes and photochromic pigments, antistatic agents, and other known additives for enhancing the performance of the lens may be used in combination. For the layer to be coated by coating, various leveling agents for the purpose of improving coating properties may be used.

  The primer layer is usually formed between a hard coat layer described later and the optical lens. The primer layer is a coating layer for the purpose of improving the adhesion between the hard coat layer formed thereon and the lens, and in some cases, the impact resistance can also be improved.

  Any material can be used for the primer layer as long as it has high adhesion to the obtained optical lens, but usually it is mainly composed of urethane resin, epoxy resin, polyester resin, melanin resin, and polyvinyl acetal. A primer composition or the like is used. The primer composition may use an appropriate solvent that does not affect the lens for the purpose of adjusting the viscosity of the composition. Of course, you may use it without a solvent.

  The primer composition can be formed by either a coating method or a dry method. When using a coating method, a primer layer is formed by solidifying after applying to a lens by a known coating method such as spin coating or dip coating. When performing by a dry method, it forms by well-known dry methods, such as CVD method and a vacuum evaporation method. When forming the primer layer, the surface of the lens may be subjected to a pretreatment such as an alkali treatment, a plasma treatment, or an ultraviolet treatment as necessary for the purpose of improving adhesion.

  The hard coat layer is a coating layer for the purpose of imparting functions such as scratch resistance, abrasion resistance, moisture resistance, warm water resistance, heat resistance, and weather resistance to the lens surface.

  The hard coat layer is generally composed of an organic silicon compound having a curing property and an element selected from the element group of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti. A hard coat composition containing at least one kind of fine particles composed of one or more kinds of oxide fine particles and / or a composite oxide of two or more elements selected from these element groups is used.

  In addition to the above components, the hard coat composition includes at least amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, perchloric acid salts, acids, metal chlorides and polyfunctional epoxy compounds. It is preferable to include any of them. An appropriate solvent that does not affect the lens may be used in the hard coat composition. Of course, you may use it without a solvent.

  The hard coat layer is usually formed by applying a hard coat composition by a known application method such as spin coating or dip coating, followed by curing. Examples of the curing method include thermal curing, a curing method by irradiation with energy rays such as ultraviolet rays and visible rays, and the like. In order to suppress the occurrence of interference fringes, the refractive index of the hard coat layer is preferably in the range of ± 0.1 in the difference in refractive index from the lens.

The antireflection layer is usually formed on the hard coat layer as necessary. There are inorganic and organic antireflection layers. In the case of inorganic systems, inorganic oxides such as SiO ₂ and TiO ₂ are used, and vacuum deposition, sputtering, ion plating, ion beam assist, and CVD are used. It is formed by the dry method. In the case of an organic type, it is formed by a wet method using a composition containing an organosilicon compound and silica-based fine particles having internal cavities.

The antireflection layer has a single layer and a multilayer, and when used in a single layer, the refractive index is preferably at least 0.1 lower than the refractive index of the hard coat layer. In order to effectively exhibit the antireflection function, a multilayer antireflection film is preferably used. In that case, a low refractive index film and a high refractive index film are alternately laminated. Also in this case, the difference in refractive index between the low refractive index film and the high refractive index film is preferably 0.1 or more. Examples of the high refractive index film include ZnO, TiO ₂ , CeO ₂ , Sb ₂ O ₅ , SnO ₂ , ZrO ₂ , and Ta ₂ O _5, and examples of the low refractive index film include an SiO ₂ film. .

  On the antireflection film layer, an antifogging coating film layer, a contamination prevention layer, and a water repellent layer may be formed as necessary. As a method for forming the antifogging coat layer, the antifouling layer, and the water repellent layer, there is no particular limitation on the treatment method, treatment material, and the like as long as the antireflection function is not adversely affected. A coating treatment method, an antifouling treatment method, a water repellent treatment method, and a material can be used. For example, in the anti-fogging coat and anti-fouling treatment method, a method of covering the surface with a surfactant, a method of adding a hydrophilic film to the surface to make it water-absorbing, a method of covering the surface with fine irregularities and increasing water absorption, Examples thereof include a method of absorbing water using photocatalytic activity and a method of preventing water droplet adhesion by applying a super water-repellent treatment. Further, in the water repellent treatment method, a method of forming a water repellent treatment layer by vapor deposition or sputtering of a fluorine-containing silane compound or the like, or a method of forming a water repellent treatment layer by coating after dissolving the fluorine-containing silane compound in a solvent Etc.

  The plastic lens using the polythiourethane resin of the present invention may be dyed using a dye according to the purpose for the purpose of imparting fashionability or photochromic properties.

Although the lens can be dyed by a known dyeing method, it is usually carried out by the following method.
(1) A method of immersing a lens in a dyeing solution, (2) A method of coating using a coating agent containing a dye, or a method of providing a dyeable coating layer and dyeing the coating layer, (3) Raw material monomer (4) A method in which a sublimable dye is heated and sublimated.

  In the method (1), generally, a lens fabric finished with a predetermined optical surface is immersed (dyeing step) in a dyeing solution in which a dye to be used is dissolved or uniformly dispersed, and then as required. In this method, the lens is heated to fix the dye (annealing step after dyeing). The pigment used in the dyeing process is not particularly limited as long as it is a known pigment, but usually an oil-soluble dye or a disperse dye is used. The solvent used in the dyeing process is not particularly limited as long as the dye used is soluble or can be uniformly dispersed. In this dyeing process, a surfactant for dispersing the dye in the dyeing solution or a carrier for promoting dyeing may be added as necessary. In the dyeing step, a dyeing bath is prepared by dispersing a dye and an optionally added surfactant in water or a mixture of water and an organic solvent, and an optical lens is immersed in the dyeing bath, and a predetermined temperature is set. And dye for a predetermined time. Although the dyeing temperature and time vary depending on the desired color density, it is usually from 120 ° C. or less to several minutes to several tens of hours, and the dye concentration in the dye bath is 0.01 to 10% by weight. Moreover, when dyeing is difficult, you may carry out under pressure. The post-dyeing annealing step performed as necessary is a step of performing heat treatment on the dyed lens fabric. The heat treatment is performed by removing water remaining on the surface of the lens fabric dyed in the dyeing process with a solvent or air-drying the solvent, and then, for example, in a furnace such as an infrared heating furnace in an atmospheric atmosphere or a resistance heating furnace. Let it stay for a predetermined time. In the post-dyeing annealing step, color loss of the dyed lens fabric is prevented (color loss prevention treatment), and moisture that has penetrated into the lens fabric during dyeing is removed.

  In the method (2), the dyed coating layer is applied to the lens surface by applying an organic coating liquid in which the pigment is dispersed or dissolved to the plastic lens, and then curing it, instead of directly dyeing the plastic lens material. This is a method of forming, or a method of (1) after forming a dyeable coating layer on the surface of a plastic lens, that is, a method of dyeing by immersing a plastic lens in a dyeing solution and heating.

  The method (3) is a method in which a dye is previously dissolved in a raw material monomer for a plastic lens and then polymerized. The dye to be used is not particularly limited as long as it can be uniformly dissolved in the raw material monomer or dispersed so as not to impair the optical properties.

  The method (4) includes (a) a method of dyeing a tape plastic lens by sublimating a solid sublimable dye, and (b) a substrate formed by applying a solution containing the sublimable dye is opposed to the plastic lens in a non-contact state. And a method of dyeing by heating the substrate and the lens, and (c) a method of dyeing by heating after transferring a transfer layer composed of a colored layer containing a sublimable dye and an adhesive layer to a plastic lens. Yes, the optical lens of the present invention may be dyed by any method. The dye to be used is not particularly limited as long as it has a sublimation property.

  Hereinafter, the present invention will be specifically described by way of examples. Release properties, resin transparency, and lens performance tests (refractive index, Abbe number, heat resistance) were evaluated by the following test methods.

  Releasability: When the lens is released from the molding mold, “×” (poor release property) indicates that the lens was not released at all, or a part of the lens was missing or the molding mold was cracked. For those that did not have any such problems, it was rated as “◯” (good releasability).

Transparency of resin: The obtained resin was irradiated on a projector in a dark place, and the presence or absence of cloudiness of the lens and the presence of an opaque substance was visually determined. A lens having no fogging or opaque material was marked with ○ (with transparency), and a lens with x (without transparency).
Refractive index (ne), Abbe number (νe): Measured at 20 ° C. using a Purfrich refractometer.
Heat resistance: The glass transition temperature (Tg) (° C.) in the TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10 ° C./min) was defined as heat resistance.

  0.035 g (500 ppm based on the total weight of the polymerizable composition) of an ultraviolet absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) was mixed and dissolved in 36.4 g of m-xylylene diisocyanate at 20 ° C. 4-mercaptomethyl-1 in which 0.035 g of triethylamine (500 ppm based on the total weight of the polymerizable composition) and 0.070 g of methanesulfonic acid (1000 ppm based on the total weight of the polymerizable composition) were mixed with this solution. , 8-dimercapto-3,6-dithiaoctane 33.6 g was added. The mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. The releasability from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The obtained resin was transparent and had a refractive index (ne) of 1.665, an Abbe number (νe) of 32, and a heat resistance (Tg) of 89 ° C., which was suitable as an optical transparent resin. The evaluation results are shown in [Table 1].

  0.035 g (500 ppm based on the total weight of the polymerizable composition) of an ultraviolet absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) was mixed and dissolved in 36.4 g of m-xylylene diisocyanate at 20 ° C. To this solution, 0.035 g of triethylamine (500 ppm based on the total weight of the polymerizable composition) and 0.140 g of dodecylbenzenesulfonic acid (2000 ppm based on the total weight of the polymerizable composition) were mixed, and 4-mercaptomethyl- 33.6 g of 1,8-dimercapto-3,6-dithiaoctane was added. The mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. The releasability from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The obtained resin was transparent and had a refractive index (ne) of 1.665, an Abbe number (νe) of 32, and a heat resistance (Tg) of 88 ° C., and was suitable as an optical transparent resin. The evaluation results are shown in [Table 1].

  0.035 g (500 ppm based on the total weight of the polymerizable composition) of an ultraviolet absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) was mixed and dissolved in 36.4 g of m-xylylene diisocyanate at 20 ° C. In this solution, 0.007 g of triethylamine (100 ppm with respect to the total weight of the polymerizable composition), 0.140 g of dodecylbenzenesulfonic acid (2000 ppm with respect to the total weight of the polymerizable composition), 0.014 g of methanesulfonic acid (polymerizable) 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (33.6 g) mixed with 200 ppm of the total weight of the composition was added. The mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. The releasability from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The obtained resin was transparent and had a refractive index (ne) of 1.665, an Abbe number (νe) of 32, and a heat resistance (Tg) of 88 ° C., and was suitable as an optical transparent resin. The evaluation results are shown in [Table 1].

  0.035 g (500 ppm based on the total weight of the polymerizable composition) of an ultraviolet absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) was mixed and dissolved in 36.4 g of m-xylylene diisocyanate at 20 ° C. To this solution, 0.056 g of tri-n-butylamine (800 ppm based on the total weight of the polymerizable composition) and 0.112 g of methanesulfonic acid (1600 ppm based on the total weight of the polymerizable composition) were mixed. Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (33.6 g) was added. The mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. The releasability from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The obtained resin was transparent and had a refractive index (ne) of 1.665, an Abbe number (νe) of 32, and a heat resistance (Tg) of 89 ° C., which was suitable as an optical transparent resin. The evaluation results are shown in [Table 1].

  A mixture of 2,5-bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane and 2,6-bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane35. To 35 g, 0.035 g (500 ppm based on the total weight of the polymerizable composition) of an ultraviolet absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) was mixed and dissolved at 20 ° C. In this solution, 0.063 g of triethylamine (900 ppm with respect to the total weight of the polymerizable composition), 0.056 g of methanesulfonic acid (800 ppm with respect to the total weight of the polymerizable composition), and 0.161 g (polymerizable) of dodecylbenzenesulfonic acid. Add 17.9 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 16.7 g of pentaerythritol tetrakis (3-mercaptopropionate) mixed with 2300 ppm relative to the total weight of the composition did. The mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. The releasability from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The obtained resin was transparent and had a refractive index (ne) of 1.598, an Abbe number (νe) of 41, a heat resistance (Tg) of 122 ° C., and was suitable as an optical transparent resin. The evaluation results are shown in [Table 1].

  0.035 g (500 ppm based on the total weight of the polymerizable composition) of an ultraviolet absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) was mixed and dissolved in 35.5 g of m-xylylene diisocyanate at 20 ° C. 5,7-dimercapto in which 0.049 g of triethylamine (700 ppm with respect to the total weight of the polymerizable composition) and 0.098 g of methanesulfonic acid (1400 ppm with respect to the total weight of the polymerizable composition) were mixed with this solution. Methyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,8-dimercaptomethyl- 34.5 g of a mixture with 1,11-dimercapto-3,6,9-trithiaundecane was added. This mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. The releasability from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The obtained resin was transparent and had a refractive index (ne) of 1.668, an Abbe number (νe) of 32, a heat resistance (Tg) of 106 ° C., and was suitable as an optical transparent resin. The evaluation results are shown in [Table 1].

  A mixture of 2,5-bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane and 2,6-bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane38. To 35 g, 0.035 g (500 ppm based on the total weight of the polymerizable composition) of UV absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) was mixed and dissolved at 20 ° C. In this solution, 0.063 g of triethylamine (900 ppm with respect to the total weight of the polymerizable composition), 0.084 g of methanesulfonic acid (1200 ppm with respect to the total weight of the polymerizable composition), and 0.161 g (polymerizable) of dodecylbenzenesulfonic acid. 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane 32.0 g mixed with 2300 ppm) was added. The mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. The releasability from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The obtained resin was transparent and had a refractive index (ne) of 1.623, an Abbe number (νe) of 39, and a heat resistance (Tg) of 119 ° C., which was suitable as an optical transparent resin. The evaluation results are shown in [Table 1].

[Comparative Example 1]
36.4 g of m-xylylene diisocyanate, 0.0105 g of di-n-butyltin dichloride (150 ppm with respect to the total weight of the polymerizable composition), 0.070 g of an internal mold release agent (STEPAN, trade name, ZEREC UN) 1000 ppm with respect to the total weight of the polymerizable composition) and 0.035 g (500 ppm with respect to the total weight of the polymerizable composition) of UV absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) were mixed and dissolved at 20 ° C. To this solution, 33.6 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was added. The mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. The releasability from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The obtained resin was transparent and had a refractive index (ne) of 1.665, an Abbe number (νe) of 32, and a heat resistance (Tg) of 89 ° C., which was suitable as an optical transparent resin. However, organotin compounds that are generally considered to be highly toxic, resins obtained by the composition of the composition, and phosphate ester internal mold release agents that may cause problems in workability are used. The evaluation results are shown in [Table 1].

[Comparative Example 2]
36.4 g of m-xylylene diisocyanate, 0.0105 g of di-n-butyltin dichloride (150 ppm with respect to the total weight of the polymerizable composition), 0.21 g of internal mold release agent (STEPAN, trade name, ZEREC UN) 3000 ppm) with respect to the total weight of the polymerizable composition) and 0.035 g (500 ppm with respect to the total weight of the polymerizable composition) of UV absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) were mixed and dissolved at 20 ° C. To this solution, 33.6 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was added. The mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. The releasability from the mold was good. However, by increasing the amount of the phosphoric ester internal release agent, white turbidity was seen in the resin, which was not suitable as an optical transparent resin. The evaluation results are shown in [Table 1].

[Comparative Example 3]
0.035 g (500 ppm based on the total weight of the polymerizable composition) of an ultraviolet absorber (Kyodo Pharmaceutical Co., Ltd., trade name Biosorb 583) was mixed and dissolved in 36.4 g of m-xylylene diisocyanate at 20 ° C. To this solution was added 33.6 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane mixed with 0.070 g of methanesulfonic acid (1000 ppm based on the total weight of the polymerizable composition). The mixed solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over 21 hours. After completion of the polymerization, the mold was taken out from the oven. Although the releasability from the mold was good, an opaque solid was precipitated in the obtained resin, which was not suitable as an optical transparent resin. The evaluation results are shown in [Table 1].

  From the above results, the polymerizable composition of the present invention does not contain an organotin compound conventionally used as a catalyst for a polythiourethane resin, and does not require the addition of a conventional internal mold release agent, A polythiourethane resin suitably used as an optical transparent resin is obtained.

  According to the present invention, the polythiourethane which is suitably used as a transparent resin for optical use, which does not contain an organic tin compound conventionally used as a catalyst for a polythiourethane resin and does not require the addition of a conventional internal mold release agent. The present invention finds a polymerizable composition from which a urethane resin can be obtained, and contributes to providing a suitable material in the field of eyeglass lenses.

  The polythiourethane resin obtained by the present invention is used for optical materials such as plastic lenses, prisms, optical fibers, information recording substrates, filters, and light emitting diodes, and is particularly preferably used as a plastic lens material for spectacles.

Claims (11)

A polythiol comprising an amine compound represented by general formula (1) and a sulfonic acid represented by general formula (2), wherein the molar ratio of sulfonic acid groups to amino groups is 1.05 to 10 Polymerization catalyst for urethane optical materials.

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group having 1 to 8 carbon atoms. R ¹ , R ² and R ³ are bonded to each other. A ring may be formed.)

(In the formula, n represents an integer of 1 or 2, and R ⁴ represents a monovalent or higher linear aliphatic, branched aliphatic, cycloaliphatic and aromatic organic residue which may contain a hydroxyl group or an amino group. Is shown.) The polymerization catalyst according to claim 1, wherein the amine compound represented by the general formula (1) is triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine or triisobutylamine. . The polymerization catalyst according to claim 1 or 2, wherein the sulfonic acid represented by the general formula (2) is an alkylsulfonic acid. The polymerization catalyst according to claim 1 or 2, wherein the sulfonic acid represented by the general formula (2) is methanesulfonic acid, toluenesulfonic acid or dodecylbenzenesulfonic acid. The polymerization catalyst according to any one of claims 1 to 4, and one or more isocyanates selected from a polyisocyanate compound, a polyisothiocyanate compound, and a polyisothiocyanate compound having an isocyanato group, and a polythiol compound. A polymerizable composition for a polythiourethane optical material containing one or more thiols. Isocyanates are m-xylylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) -bicyclo- [2.2. 1] -Heptane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane and one or more compounds selected from the group consisting of hexamethylene diisocyanate and thiols 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl- 1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11 Dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercapto One or more selected from the group consisting of methylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithietane The polymerizable composition according to claim 5, wherein the polymerizable composition is two or more compounds. The addition amount of the sulfonic acid represented by the general formula (2) with respect to 100 parts by weight of the total of isocyanates and thiols is 0.05 to 0.5 parts by weight, according to claim 5 or 6, The polymerizable composition as described. The molded object which consists of polythiourethane resin obtained by hardening the polymeric composition in any one of Claim 5 to 7. An optical material comprising a polythiourethane resin obtained by curing the polymerizable composition according to claim 5. A plastic lens comprising a polythiourethane resin obtained by curing the polymerizable composition according to claim 5. A method for producing a molded article made of a polythiourethane resin, comprising cast polymerizing the polymerizable composition according to claim 5.