KR20180087228A - Polymerization catalyst for polythiourethane optical material and polymerizable composition comprising it - Google Patents

Abstract

The present invention relates to a resin composition for a polythiourethane-based optical lens characterized by using an amine carboxylic acid salt as a polymerization catalyst. The composition of the present invention can be used alone without being mixed with organotin compounds or organic tin compounds conventionally used, and has excellent solubility and mixing properties with resin compositions and also increases the reaction rate to enhance the transparency of optical lenses.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymerization catalyst for a polythiourethane-based optical material and a polymerizable composition for a polythiourethane-

The present invention relates to a novel polymerization catalyst and a polymerizable composition for a polythiourethane-based optical material containing the same, and more particularly to a novel polymerization catalyst having excellent mixing properties and transparency and a polymerizable composition containing the same.

In the case of an organic tin compound which is commonly used as a catalyst for a polythiourethane resin, the reaction rate can be controlled in the curing of the composition of the isocyanate and thiol having low reactivity, but the polymerization imbalance or whitening phenomenon is not satisfactory according to the amount thereof, Development of a catalyst capable of replacing or mixing a tin compound is required. In addition, harmonization with the global environment and reduction of the environmental load are becoming big problems in the industry. In order to solve this problem, development of environmentally friendly products and technologies is accelerating. In the technical field of the present invention, there is a movement. In particular, organotin catalysts, which are generally used as catalysts for polythiourethane resins, have become a problem due to their toxicity and environmental hormones. As a result, regulations on the use of organic tin compounds have been strengthened in developed countries. Among these, in the spectacle lens industry using a polythiourethane resin, development of a catalyst that can be substituted for an organotin catalyst is required. As a tin-free, non-metal catalyst in which a general thermosetting resin can be obtained, an amine salt compound, an amine compound, a tertiary amine ether compound and a phosphine compound are known (see Patent Documents 1, 2, 3, 4, 5 and 6).

Patent Document 1: Korean Patent Laid-Open No. 10-2009-0069297

Patent Document 2: JP-A-03-084021

Patent Document 3: JP-A-63-077918

Patent Document 4: JP-A-62-016484

Patent Document 5: Japanese Patent Application Laid-Open No. 09-077850

Patent Document 6: Japanese Patent Application Laid-Open No. 2000-256571

The present invention relates to a polymerization catalyst for a polythiourethane-based optical material which is an amine carboxylic acid salt represented by the general formula (1).

[1] In the present invention, a polymerization catalyst for a polythiourethane-based optical material represented by the general formula (1) is provided.

 [Chemical Formula 1]

(Wherein R ₁ , R ₂ and R ₃ are each H or a straight-chain or branched aliphatic, aliphatic, alicyclic or aromatic organic residue having a valence of 1 or more which may independently contain a hydroxyl group or a thiol group or an amino group or an unsaturated group, An organic residue having an electron-withdrawing group, and any of R ₁ , R ₂ and R ₃ may be bonded to form a ring.

In the formulas, HX is a carboxylic acid having at least one functional group selected from the group consisting of mercaptoacetic acid, mercaptopropionic acid, mercaptopyridine carboxylic acid, mercaptonic conic acid, mercaptopentadecanoic acid, mercaptobenzoic acid, mercaptohexanoic acid, Succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid,

The following [2] to [8] are each one of the preferred embodiments of the present invention.

[2] Preferably, R ₁ , R ₂ , and R ₃ of the amine carboxylic acid salt represented by Formula 1 are an alkyl group having 1 to 8 carbon atoms or an organic residue having an electron-withdrawing group, and HX is mercapto propionic acid.

[3] Preferably, the amine carboxylic acid salt represented by Formula 1 is at least one compound selected from the group consisting of triethylamine carbonate, tri-n-butylamine carbonate, triisobutylamine carbonate, N, N-dimethylcyclohexyl Amine carboxylic acid salt or N-methyldicyclohexylamine carboxylic acid salt.

[4] A polymerization catalyst according to any one of [1] to [3]; At least one isocyanate selected from a polyisocyanate compound, a polyisothiocyanate compound, and a polyisothiocyanate compound having an isocyanate group; And a polymerizable composition for a polythiourethane-based optical material containing one or more thiols selected from a polythiol compound and a thioepoxy compound.

[5] The isocyanates are preferably m-xylylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane, 2,6- (Isocyanatomethyl) cyclohexane and hexamethylene diisocyanate (isocyanatomethyl) -cyclo- [2.2.1] -heptane, 1,3-bis (isocyanatomethyl) cyclohexane, And the thiol is at least one compound selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1 , 11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 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 (Methylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiethane, and the thioepoxy Examples of the compound include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane, 1,2- , 1,3-bis (β-epithiopropylthio) propane, 1,3-bis (β-epithiopropylthio) (Β-epithiopropylthio) butane, 1,4-bis (β-epithiopropylthio) -2-methylbutane, 1,3-bis , 5-bis (β-epithiopropylthio) pentane, and 1,5-bis (β-epithiopropylthio) -2-methylpentane.

[6] The present invention also provides a polythiourethane-based resin obtained by curing the polymerizable composition described in [4] or [5].

[7] An optical material comprising the polythiourethane resin described in [6] is provided.

[8] A plastic lens made of the optical material described in [7] is provided.

[9] A process for producing a polythiourethane resin, which comprises a step of casting a polymerizable composition according to [4] or [5] to obtain a polythiourethane resin.

The polymerization catalyst of the present invention exhibits a stable polymerization activity while minimizing or eliminating organotin compounds which may be harmful to human bodies, being excellent in compatibility with a resin composition and less affected by the acidity of the additives. In other words, according to the present invention, a stable pot life can be obtained while maintaining stable polymerizability without being affected by the quality and kind of additives, monomers, etc., while being excellent in compatibility with a resin. The polymerization catalyst of the present invention can suppress the optical strain and clouding occurrence rate of the obtained resin. Such a polythiourethane-based polymerization catalyst is suitable for use in optical materials required for a high refractive index such as ultra-high refractive index and a clear and transparent optical lens.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

 The present invention relates to a polymerization catalyst for a polythiourethane-based optical material, which is an amine carboxylic acid salt represented by the general formula (1).

 [Chemical Formula 1]

R ₁ , R ₂ and R ₃ in formula (1) are, for example, methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, hexadecane, There may be mentioned a linear or higher aliphatic organic residue derived from a straight chain aliphatic compound such as ethylene, propylene, 1-butene, 2-butene or butadiene, or a linear or branched aliphatic compound having 2 or more carbon atoms such as 2-methylpropane, 2-methylbutane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 3-ethylheptane, 4-ethylheptane, 4-propylheptane, 2-methylheptane, Methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-pentene, Monovalent or higher valent organic residue derived from a branched aliphatic compound such as butene, 2-methyl-butadiene and 2,3-dimethylbutadiene, and an organic residue having at least one substituent derived from cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, 1,2- Hexane, 1,3-dimethylcyclohexane, 1,4-cyclohexadiene, 1,4-cyclohexadiene, norbornane, 2,3-dimethyl norbornane, 2,5-dimethyl norbornane, 2 Xylene, m-xylene, p-xylene, naphthalene, and naphthalene derived from an alicyclic compound such as benzene, toluene, There may be mentioned organic monomers having at least monovalent organic groups derived from aromatic compounds such as biphenyl, anthracene, perylene, styrene and ethylbenzene, and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, , Ananol, decanol, undecanol, dodecanol, and the like.

Examples of the carboxylic acid represented by HX include an aliphatic saturated carboxylic acid, an aliphatic unsaturated carboxylic acid, an aromatic carboxylic acid, and a carboxylic acid having a mercapto group as an organic carboxylic acid. Among these organic carboxylic acids, preferable organic carboxylic acids include formic acid, acetic acid, maleic acid, itaconic acid, azelaic acid, phthalic acid, acrylic acid, methacrylic acid, isobutyric acid, octylic acid, glyoxylic acid, crotonic acid, Maleic acid, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride and the like. Examples of the acid having a mercapto group include mercaptoacetic acid, mercaptopropionic acid, mercaptopyridine carboxylic acid, mercaptonic acid, mercaptopentadecanoic acid, mercaptobenzoic acid, mercaptohexanoic acid, mercaptohexanoic acid, Decanoic acid, mercaptoundecanoic acid, mercaptosuccinic acid, and the like, but are not limited thereto.

Examples of the amine compound include ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, ter-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, A mono- or higher-valent organic residue derived from a primary amine compound such as amine, myristylamine, 3-pentylamine, 2-ethylhexylamine and 1,2-dimethylhexylamine, and an organic amine compound such as diethylamine, dipropylamine, propylamine, di-n-propylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, dihexylamine, diisobutylamine, di- Amine and the like, and an organic amine having a valence of 1 or more derived from a secondary amine compound such as triethylamine, tributylamine, trihexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N, N Dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine, N, A tertiary amine having a monovalent or higher valent organic group derived from a tertiary amine compound such as N, N-diethylbenzylamine, tribenzylamine or N-methyldibenzylamine, and a tertiary amine having an electron- But are not limited to, acetate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoacetone, dimethylaminomethylene malononitrile, diethylaminoacetone, diethylaminoacetone Nitrile, 1-diethylamino-3-butanone, dimethylaminoacetonitrile and the like. However, it is not limited to these exemplified compounds.

In the amine carboxylic acid salt represented by the formula (1), R ₁ , R ₂ , and R ₃ may be bonded to each other to form a ring. Here, the phrase " arbitrary groups are combined to form a ring " means that any two or more groups out of R ₁ , R ₂ , and R ₃ are bonded to form a ring. It is more preferable that R ₁ , R ₂ , and R ₃ are alkyl groups having 1 to 8 carbon atoms. Specific examples of the amine carboxylic acid salt of the present invention include triethylamine carbonate, tri-n-propylamine carbonate, triisopropylamine carbonate, tri-n-butylamine carbonate, N, N-diisopropylethylamine carbonate, triethylenediamine carbonate, N, N'-diethylamine, N, N'-dipropylamine hydrochloride, triisobutylamine carbonate, tripentylamine carbonate, trihexylamine carbonate, trioctylamine carbonate, , N-dimethylethanolamine carbonate, N, N-diethylethanolamine carbonate, N, N-dibutylethanolamine carbonate, triethanolamine carbonate, N-ethyldiethanolamine carbonate, N, N-dimethylbenzylamine carboxylic acid salts, N, N-diethylbenzylamine carboxylic acid salts, tribenzylamine carboxylic acid salts, N-methyldibenzylamine carboxylic acid salts, N, N-dimethylcyclohexylaminecarboxylic acid Acid salts, N, N-diethylcyclohexylamine carbonate, N, N-dimethylbutylamine A salt of N-methyldicyclohexylamine carboxylic acid, a salt of N-ethyldicyclohexylamine carboxylic acid, a salt of N-methylmorpholine carboxylic acid, a salt of N-isopropylmorpholine carboxylic acid, a pyridinecarboxylic acid salt, quinoline N, N-dipropyl anilinecarboxylate, N, N-dibutyl anilinecarboxylate, N, N-dimethylaniline carboxylate, N, N-dicyclohexyl anilinecarboxylic acid salt, N, N-dibenzyl anilinicarboxylic acid salt, triphenylamine carboxylic acid salt, alpha, -, β-, or γ-picolinecarboxylate, 2,2'-bipyridylcarboxylate, 1,4-dimethylpiperazine carboxylate, tetramethylethylenediaminecarboxylate, hexamethylenetetramine 1,8-diazabicyclo- [5,4,0] -7-undecene carboxylate, and the like, but the present invention is not limited to these exemplified compounds.

Of these exemplified compounds, preferred are triethylamine carbonate, tri-n-propylamine carbonate, triisopropylamine carbonate, tri-n-butylamine carbonate, triisobutylamine carbonate, N, N-dimethylcyclohexylamine carbonate, N, N-dimethylcyclohexylamine carbonate, N, N-dimethylbutylamine hydrochloride, N-methyldicyclohexylamine carboxylic acid salt, N-ethyldicyclohexylamine carboxylic acid salt, and 1,8-diazabicyclo- [5,4,0] -7-undecene carboxylic acid salt desirable. Further, it is preferable to use at least one compound selected from the group consisting of triethylamine carboxylate, tri-n-butylamine carbonate, triisobutylamine carbonate, N, N-dimethylcyclohexylamine carbonate, N-methyldicyclohexylamine Lt; / RTI > These amine carboxylic acid salts may be used singly or in combination of two or more. These aminocarboxylic acid salts can be obtained as reagents and industrial products. However, with regard to the unavailable compounds, amine and carboxylic acid are reacted in a known synthetic method by adding a stoichiometric mole or an excess amount of carboxylic acid . For example, it is synthesized by dropwise addition of carboxylic acid to an amine or dropwise addition of an amine to a carboxylic acid in the presence or absence of a solvent. Is isolated by a known purification method such as solvent distillation removal, column chromatography, and sublimation from a reaction solution containing these amine carboxylic acid salts. If necessary, it may be subjected to known refining such as recrystallization, slushing, washing with water.

In case that the reactivity is fast, it may be diluted with a thiol compound and diluted to a concentration of about 1 to 10%. The amount of the amine carboxylic acid salt to be used is preferably one or more selected from the group consisting of a polyisocyanate compound, a polyisothiocyanate compound, and a polyisothiocyanate compound having an isocyanate group, Is preferably in the range of 0.001 part by weight or more and 1.0 part by weight or less, more preferably 0.01 part by weight or more and 0.5 part by weight or less, more preferably 0.05 part by weight or more and 0.3 part by weight or less based on 100 parts by weight of the total amount of two or more kinds of thiol Is more preferable. The amount of the amine carboxylic acid salt to be used is appropriately determined depending on the kind of the catalyst, the kind of the monomer and the additive to be used, the amount to be used, and the form of the molding.

Examples of the method of adding the catalyst to the monomers include a method of adding an amine carboxylic acid salt to a resin modifier such as an isocyanate, a thiol or an alcohol compound, or a method of mixing a mixture of isocyanate and thiol or an isocyanate and an alcohol compound To a mixture of a resin modifier such as an isocyanate, a thiol, or an alcohol compound, and the like. However, the preparation order differs depending on the type and amount of the monomers, catalyst, resin modifier, and other additives to be used, and is not limited to a single one. The method of adding the catalyst is appropriately selected in consideration of the solubility, operability, safety, convenience, and the like of the catalyst.

The polythiourethane resin of the present invention is a polythiourethane resin obtained by reacting one or more isocyanates selected from a polyisocyanate compound, a polyisothiocyanate compound, a polyisothiocyanate compound having an isocyanate group, Or two or more kinds of thiols as a main component. Further, a resin modifier may be added for the purpose of controlling the optical properties of the resulting resin, controlling the physical properties such as impact resistance and specific gravity, and adjusting the handleability of the monomer.

Examples of the polyisocyanate compound of the present invention include hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate , 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, Aliphatic polyisocyanate compounds such as bis (isocyanatoethyl) carbonate and bis (isocyanatoethyl) ether, and aliphatic polyisocyanate compounds such as isophorone diisocyanate, 1,2-bis (isocyanatomethyl) - 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 (Isocyanatomethyl) tricyclodecane, and 4,9-bis (isocyanatomethyl) tricyclodecane; and alicyclic polyisocyanate compounds such as o-xylylene diisocyanate, m- (Isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene,?,?,? ',?' - tetramethylxylylene diisocyanate, bis (Isocyanatoethyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, phenylenedi And examples thereof include aromatic polyisocyanates such as isocyanate, tolylene diisocyanate, tolylene diisocyanate, ethylphenylenediisocyanate, isopropylphenylenediisocyanate, dimethylphenylenediisocyanate, diethylphenylenediisocyanate, diisopropylphenylenediisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, Diisocyanate, bis (isocyanatophenyl) ethylene, isobutylene diisocyanate, isobutyl diisocyanate, isobutyl diisocyanate, isobutyl diisocyanate, Aromatic polyisocyanate compounds such as 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzene diisocyanate and hexahydrodiphenylmethane-4,4-diisocyanate, and bis (isocyanatoethyl) Sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, (Isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (Isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane and the like Aliphatic polyisocyanate compounds, and aromatic polyisocyanate compounds such as diphenyl sulfide-2,4-diisocyanate, diphenyl sulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzyl thioether, bis 4-isocyanatomethylbenzene) sulfide, 4,4-methoxybenzenethiethylene glycol-3,3-diisocyanate, diphenyl disulfide-4,4-diisocyanate, 2,2- 5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-di Isocyanate, 4,4-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethoxy diphenyl disulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyl disulfide- And aromatic diisocyanates such as 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, 4,5-bis (isocyanatomethyl) And sulfurated heterocyclic polyisocyanate compounds such as 1,3-dithiolane, 4,5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolane and the like. It is not. Halogen substituents such as chlorine substituents and bromine substituents of these compounds, alkyl substituents, alkoxy substituents, nitro substituents, prepolymer type modified products with polyhydric alcohols, carbodiimide modified products, urea modified products, Or a trimerization reaction product may be used. These polyisocyanate compounds may be used alone or in combination of two or more.

 Examples of the polyisothiocyanate compound of the present invention include hexamethylene diisothiocyanate, 2,2-dimethylpentane diisothiocyanate, 2,2,4-trimethylhexane diisothiocyanate, butene diisothiocyanate, Cyanate, 1,3-butadiene-1,4-diisothiocyanate, 2,4,4-trimethylhexamethylene diisothiocyanate, 1,6,11-undecatriisothiocyanate, 1,3 , 6-hexamethylene triisothiocyanate, 1,8-diisothiocyanato-4-isothiocyanato methyloctane, bis (isothiocyanatoethyl) carbonate, bis (isothiocyanato Ethyl) ether and aliphatic polyisothiocyanate compounds such as isophorone diisothiocyanate, 1,2-bis (isothiocyanato) cyclohexane, 1,3-bis (isothiocyanato methyl ) Cyclohexane, 1,4-bis (isothiocyanato methyl) cyclohexane, dicyclohexylmethane Cyclohexane diisothiocyanate, cyclohexane diisothiocyanate, dicyclohexyldimethylmethane isothiocyanate, 2,2-dimethyldicyclohexylmethane isothiocyanate, 2,5-dimethylhexane diisothiocyanate, Heptane, 2,6-bis (isothiocyanatomethyl) bicyclo- [2,2,1] -heptane, 3,6-bis (isothiocyanatoethyl) bicyclo [ Bis (isothiocyanato) tricyclodecane, 4,9-bis (isothiocyanato methyl) tricyclodecane, 4,8-bis (isothiocyanato methyl) , And 9-bis (isothiocyanato methyl) tricyclodecane, and alicyclic polyisothiocyanate compounds such as o-xylylene diisothiocyanate, m-xylylene diisothiocyanate, p- (Isothiocyanatoethyl) benzene, bis (isothiocyanatopropyl) benzene, α, α, α ', α'-tertiary (Isothiocyanatomethyl) naphthalene, bis (isothiocyanatomethyl) diphenyl ether, phenylenedisothiocyanate (isothiocyanatomethyl) naphthalene, bis , Tolylene diisothiocyanate, ethylphenylene diisothiocyanate, isopropylphenylene diisothiocyanate, dimethylphenylene diisothiocyanate, diethylphenylene diisothiocyanate, diisopropylphenylene diisothiocyanate Diisocyanate, trimethylbenzene triisothiocyanate, benzene triisothiocyanate, biphenyl diisothiocyanate, toluidine diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, 3,3-dimethyl Diisocyanate, diphenylmethane-4,4-diisothiocyanate, bibenzyl-4,4-diisothiocyanate, bis (isothiocyanatophenyl) ethylene, 3,3-dimethoxybiphenyl- - di isothi Aromatic polyisothiocyanate compounds such as cyanate, phenylisothiocyanatoethyl isocyanate, hexahydrobenzene diisothiocyanate, and hexahydrodiphenylmethane-4,4-diisothiocyanate, and aromatic polyisothiocyanate compounds such as bis Bis (isothiocyanatoethyl) sulfide, bis (isothiocyanatoethyl) sulfide, bis (isothiocyanatoethyl) sulfide, bis Bis (isothiocyanatoethylthio) methane, bis (isothiocyanatoethylthio) methane, bis (isothiocyanatoethylthio) methane, bis Aliphatic polyisothiocyanate compounds such as bis (thio) ethane, bis (isothiocyanato methylthio) ethane, and 1,5-diisothiocyanato-2-isothiocyanato-3-thiapentane And diphenyl sulfide-2,4-diisothi Diisocyanate, diphenylsulfide-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-dimethyl diphenyl disulfide- 5,5-diisothiocyanate, 3,3-dimethyl diphenyl disulfide-5,5-diisothiocyanate, 3,3-dimethyl diphenyl disulfide-6,6-diisothiocyanate, 4,4-dimethyldiphenyl disulfide-5,5-diisothiocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisothiocyanate, 4,4-dimethoxydiphenyl disulfide And aromatic diisocyanates such as 2,5-diisothiocyanatothiophene, 2,5-bis (isothiocyanato-methyl) thiophene , 2,5-diisothiocyanato tetra (Isothiocyanatomethyl) tetrahydrothiophene, 3,4-bis (isothiocyanato) methyl tetrahydrothiophene, 2,5-diisothiocyanato- Dithiane, 2,5-bis (isothiocyanato methyl) -1,4-dithiane, 4,5-diisothiocyanato-1,3-dithiolane, 4,5- Sulfide heterocyclic polyisothiocyanates such as bis (isothiocyanato methyl) -1,3-dithiolane, 4,5-bis (isothiocyanato methyl) -2-methyl-1,3- Nate compounds, and the like, but the present invention is not limited to these exemplified compounds. Halogen substituents such as chlorine substituents and bromine substituents of these compounds, alkyl substituents, alkoxy substituents, nitro substituents, prepolymer type modified products with polyhydric alcohols, carbodiimide modified products, urea modified products, Or a trimerization reaction product may be used. These polyisothiocyanate compounds may be used alone or in combination of two or more.

Among these exemplified compounds, m-xylylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) More preferred are cyclo- [2.2.1] -heptane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane and hexamethylene diisocyanate.

 Examples of the polythiol compound in the present invention include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, Dithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,2,3- 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane- (Mercaptomethyl) cyclohexane, 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) Aliphatic polythiol compounds such as 1,3-propanedithiol, bis (2-mercaptoethyl) ether and tetrakis (mercaptomethyl) methane, and aliphatic polythiol compounds such as 2,3-dimercaptosuccinic acid ), Thioferric acid bis (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto- 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 (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylol ethane tris (2-mercaptoacetate), trimethylol ethane tris 3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), glycerin tris (2-mercaptoacetate), glycerin tris 3-mercaptopropionate), 1,4-cyclohexanediol Aliphatic polythiol compounds containing an ester bond such as bis (2-mercaptoacetate) and 1,4-cyclohexanediol bis (3-mercaptopropionate), and aliphatic polythiol compounds containing 1,2-dimercaptobenzene, (Mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) Benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4- , 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, ) Benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 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) (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, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 2,5-toluene dithiol, 3,4- Di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane- Di (p-mercaptophenyl) pentane, 1,4-naphthalene dithiol, 1,5-naphthalene dithiol, 2,6-naphthalene dithiol, 2,7- , 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, Tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptoethyleneoxy) 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-tetrachlor- Mercaptomethyl) benzene, and aromatic polythiol compounds such as 2-methylamino-4,6-di All-symtriazine, 2-ethylamino-4,6-dithiol symtriazine, 2-amino-4,6-dithiol symtriazine, 2-morpholino-4,6-dithiol sym 2-cyclohexylamino-4,6-dithiol symtriazine, 2-methoxy-4,6-dithiol symtriazine, 2-phenoxy-4,6-dithiol sym- Heterocyclic polythiol compounds such as triazine, 2-thiobenzeneoxy-4,6-dithiol sym-triazine and 2-thiobutyloxy-4,6-dithiol sym-triazine, and halogen substituted compounds thereof But it is not limited to these exemplified compounds. Further, halogen substituents such as chlorine substituents and bromine substituents may be used. These polythiol compounds may be used singly or in combination of two or more.

Examples of the polythiol compound having at least one sulfide bond in one molecule include bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (Mercaptopropylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptoethylthio) methane, Bis (mercaptomethylthio) ethane, 1,3-bis (mercaptomethylthio) propane, 1,2-bis (3-mercaptopropylthio) 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) 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-trithiane , 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto- (Mercaptoethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3- Dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane And their 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 Pio Hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate) (3-mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethylether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diol bis (3-mercaptopropionate) (2-mercaptoethyl ester), 4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester) -Mercaptoethyl ester), bis (2-mercaptoethyl ester) dithiodipropionic acid, (2,3-dimercaptopropyl 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 heterocyclic polythiol compounds such as 3,4-thiopentothiols, bismuthiol, and the like, and alicyclic polythiol compounds such as 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1 , 1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercapto

Methylthio) -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, Bis (4,4-bis (mercaptomethylthio) -2-thiabutyl) -1,4-dithiane, 2,2-bis (mercaptomethylthio) , 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto- Dimercapto-2,5-dithiahexane, 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane (Mercaptopamethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiadiopropyl) 3,7-dithianan, tris (Mercaptomethylthio) ethyl methane, tris (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, tetrakis (Mercapto methylthio) ethyl methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11-tetrakis Mercapto methylthio) -1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis (mercaptomethylthio) -1, 9-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (Mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexatiaheptadecane, 3,4,8,9-tetrakis (mercaptomethylthio) -1 , 11-dimercapto-2,5,7,10-tetthaliaundecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-dimercapto-2 , 5,7,10,12,15-hexatiahexadecane, 8- [bis (mercaptomethylthio) methyl] -3,4,12,13-tetrakis (mercaptomethylthio) -1,15- Dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis [3,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithia Heptylthio] -1,3-dithi , 4,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio] -6-mercaptomethylthio-1,3-dithiane, 1,1-bis (Mercaptomethylthio) propane, 1- [4- (6-mercaptomethylthio) -1,3-dithianylthio] -1,3- , 3-dithianylthio] -3- [2,2-bis (mercaptomethylthio) ethyl] -7,9-bis (mercaptomethylthio) -2,4,6,10- 1,3-dithianylthio] -3- [2- (1,3-dithiethanyl)] methyl-2,4-dithiaphene , 4,6-bis 3- [2- (1,3-dithiethanyl)] methyl-5-mercapto-2,4-dithiapentylthio (-1,3-dithiane, [4- (6-mercaptomethylthio) -1,3-dithianylthio] -6- [4- (6-mercaptomethylthio) -1,3-dithianylthio] -1,3-dithiane , 3- [2- (1,3-dithiethanyl)] methyl-7,9-bis (mercaptomethylthio) -1,11-dimercapto-2,4,6,10-tetthaliaundecane , 9- [2- (1,3-dithiethanyl)] methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17- Mercapto-2,6,8,10,12,16-hexatiaheptadecane, 3- [2- (1,3-dithiethanyl)] methyl-7,9,13,15-tetrakis Methylthio) 1,17-dimercapto-2,4,6,10,12,16-hexatiaheptadecane, 3,7-bis [2- (1,3-dithietanyl)] methyl- Dimercapto-2,4,6,8-tetrathianone, 4- [3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetra Thiourea] -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-dithiahexylthio] -5- mercaptomethylthio- Dithiolane, 4- [3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiooctyl] -5- (Mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio] methyl-1,3-dithiane, 2- [3,4-bis (mercaptomethylthio) - Mercapto-2,5-dithiahexylthio] mercaptomethylthiomethyl-1,3-dithiethane, 2- [3,4,8,9-tetrakis (mercaptomethylthio) Bis (mercaptomethylthio) methyl-5,6-bis (mercapto-2,5,7,10-tetrathiadecylthio] mercaptomethylthiomethyl-1,3-dithiethane, 2- [ Mercapto methylthio) -8-mercapto-2,4,7-trithiooctyl] mercaptomethylthiomethyl-1,3-dithiethane, 4,5-bis 31- [2- (1,3- Thanyl)] - 3-mercapto-2-thiapropylthio J-1,3-dithiolane, 4-1- [2- (1,3-dithiethanyl)] - 3-mercapto- 4- (5-mercaptomethylthio) -4-mercapto-3-thiabutylthio] -1,3-dithiolane, 2-] bis [4- -1,3-dithiolanyl) thio] methyl-1,3-dithiane, 4- [4- (5-mercaptomethylthio-1,3-dithianyl) thio] -5-1- [2 - (1,3-dithiethanyl)] - 3-mercapto-2-thiapropylthio-1,3-dithiolane, and dithioacetals such as oligomers thereof, (Mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane (Mercaptomethylthio) -1,3-dithiabutyl] - (mercaptomethylthio) methane, tris [4,4-bis (mercaptomethylthio) Dithiabutyl] methane, 2,4,6-tris (mercaptomethylthio) -1,3,5-trithiacyclohexane, 2,4-bis (mercaptomethylthio) -1,3,5-tri (Mercaptomethylthio) -2-thiopropane, bis (mercaptomethyl) methylthio-1,3,5-trithiacyclohexane, tris [(4 -Mercaptomethyl-2,5-dithiacyclohexyl-1-yl) methylthio] methane, 2,4-bis (mercaptomethylthio) -1,3-dithiacyclopentane, 2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- ( Dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- (1,3-dimercapto-2-propylthio) (Mercaptomethylthio) -2-thiopropyl] methane, tris [4,4-bis (mercaptomethylthio) -3-thiabutyl] methane, 2,4,6- Tris [3,3-bis (mercaptomethylthio) -2-thiapropyl] -1,3,5-trithiacyclohexane, tetrakis [3,3-bis (mercaptomethylthio) ] Methane, and a polythiol compound having an orthotrithioformic acid ester skeleton such as an oligomer thereof. However, the present invention is not limited to these exemplified compounds. Further, halogen substituents such as a chlorine substituent and a bromine substituent may be used. These polythiol compounds having sulfide bonds may be used singly or in combination of two or more. Examples of the thiol compound having a hydroxyl group include 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 5-mercaptoppanol, 6-mercaptohexanol, Mercaptooctanol, and 5-mercapto-3-thiapentanol. However, the present invention is not limited to these exemplified compounds. These thiol compounds having a hydroxyl group may be used singly or in combination of two or more kinds. Among these exemplified compounds, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto- Trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,8-dimercaptomethyl-1,11-dimercapto- Triethyundecane, pentaerythritol tetrakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,3- (Mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1 , And 3-dithiane are more preferable. A thioepoxy compound may also be used in combination. Specific examples thereof include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane, 1,2- ) Ethane, 1,2-bis (β-epithiopropylthio) propane, 1,3-bis (β-epithiopropylthio) propane, 1,3- (Β-epithiopropylthio) butane, 1,4-bis (β-epithiopropylthio) -2-methylbutane, 1,3- , 1,5-bis (β-epithiopropylthio) pentane, 1,5-bis (β-epithiopropylthio) (Β-epithiopropylthio) hexane, 1,6-bis (β-epithiopropylthio) -2-methylhexane, 3,8- ) -3,6-dithiaoctane, 1,2,3-tris (beta -epithiopropylthio) propane, 2,2-bis (beta -epithiopropylthiomethyl) -Epithiopropylthio) propane, 2,2-bis (? -Epithiopropylthiomethyl) -1- (? -Epithiopropylthio) butane, 1,5-bis - (β-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4- (? - epithiopropylthio) -4- (? - epithiopropylthio) -2,2-bis (? - epithiopropylthiomethyl) Epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5-bis (β-epithiopropylthiomethyl) Octane, 1,8-bis (? -Epithiopropylthio) -4,4-bis (? -Epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8- Thio) -2,5-bis (? - epithiopropylthiomethyl) -3,6-dithiaoctane, and the like, but these compounds are not limited to these exemplified compounds.

  Examples of the resin modifier used in the present invention include olefin compounds including alcohol compounds, amine compounds, epoxy resins, organic acids and anhydrides thereof, and (meth) acrylate compounds. Examples of the alcohol compound which can be added as the resin modifier include diethylene glycol, triethylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, Hexanediol, 1,4-pentanediol, 1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, Diol, 1,8-octanediol, thiodiethanol, dithiodiethanol, thiodipropanol, dithiodipropanol, and oligomers thereof. However, the present invention is not limited to these exemplified compounds. These alcohol compounds may be used alone or in combination of two or more.

Examples of the amine compound which can be added as the resin modifier include ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, Decylamine, laurylamine, myristylamine, 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine, aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine, 2,3 O-, m-, or p-methylaniline, o-, m-, or p-methylbenzylamine, Or an aminophenol such as p-ethylaniline, aminomorpholine, naphthylamine, furfurylamine,? -Aminodiphenylmethane, toluidine, aminopyridine, aminophenol, aminoethanol, 1-aminopropanol, Ethanol, aminohexanol, methoxyethylamine, 2- (2-aminoethoxy) ethanol, 3-ethoxy A monofunctional primary amine compound such as triphenylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-isobutoxypropylamine or 2,2-diethoxyethylamine, Ethylenediamine, 1,2-, or 1,3-diaminopropane, 1,2-, 1,3- or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamino Hexane, 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'-diaminodiphenylsulfide, 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- Diamine, isophoronediamine, diaminomethylbicycloheptane , 1,3-, or 1,4-diaminomethylcyclohexane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4- aminoethylpiperidine Amines such as diethylamine, diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, (2-ethylhexyl) amine, methylhexylamine, diallylamine, N-methylallylamine, piperidine, p-toluenesulfonylamine, There may be mentioned, for example, aldehydes such as benzylamine, benzylamine, benzylamine, benzylamine, benzylamine, dibenzylamine, dibenzylamine, N, N'-dimethylethylenediamine, N, N'-dimethyl-1,2-diaminopropane, N, N'-dimethylaminopyridine, Dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,2-diaminobutane, N , N'-dimethyl-1,3-diaminobutane, N, N'-dimethyl-1,4-diaminobutane, N, N'- Diaminohexane, N, N'-dimethyl-1,7-diaminoheptane, N, N'-diethylethylenediamine, N, N, N'-diethyl-1,3-diaminopropane, N, N'-diethyl-1,2-diaminobutane, N, N'-diethyl-1,4-diaminobutane, N, N'-diethyl-1,5-diaminopentane, Diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, homopiperazine, 1,1- Piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, And secondary polyamine compounds such as tetramethylguanidine. However, the present invention is not limited to these exemplified compounds. These amine compounds may be used alone or in combination of two or more.

Examples of the epoxy resin that can be added as the resin modifier include phenol-based epoxy compounds obtained by condensation reaction of a polyhydric phenol compound such as bisphenol A glycidyl ether with an epihalohydrin compound, hydrogenated bisphenol A glycidyl Alcohol-based epoxy compounds obtained by condensation of polyhydric alcohol compounds such as dicyclohexylamine and dicyclohexylamine and epihalohydrin compounds, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 1,2- A glycidyl ester-based epoxy compound obtained by condensation of a polyvalent organic acid compound such as hexahydrophthalic acid diglycidyl ester with an epihalohydrin compound, a primary and secondary diamine compound and an epihalohydrin compound, , An aliphatic polyepoxy compound such as vinylcyclohexene diepoxide, and the like, and the like. Compounds only are not limited. These epoxy resins may be used singly or in combination of two or more kinds.

Examples of the organic acid and its anhydride which can be added as the resin modifier include thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnorbornenic acid Anhydride, methylnorbornanic anhydride, maleic anhydride, trimellitic anhydride, and pyromellitic anhydride, but the present invention is not limited to these exemplified compounds. These organic acids and their anhydrides may be used alone or in combination of two or more.

 Examples of the olefin compound which can be added as the resin modifier include benzyl acrylate, benzyl methacrylate, butoxy ethyl acrylate, butoxy methyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate Methacrylic acid esters such as glycidyl methacrylate, 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 glycol 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-alkoxyethoxyphenyl) propane, 2,2-bis (4-methoxyethoxyphenyl) propane, Bis (4-methacryloxyethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acroxyethoxyphenyl) methane, (Methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxy diethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, dimethyrol tricyclodecane diacrylate , Trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol diacrylate, glycerol Acrylate, methacrylate, pentaerythritol triacrylate, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, (Meta) acrylate compounds such as lanthanide diacrylate, lanthanide diacrylate, xylyl dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, and mercaptoethyl sulfide dimethacrylate, and allyl glycidyl ether, di Allyl compounds such as allyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate and diethylene glycol bisallylcarbonate, and allyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, And vinyl compounds such as 3,9-divinyl spiro (m-dioxane), and the like. Of these, It is not. These olefin compounds may be used alone or in combination of two or more.

In the present invention, the ratio of the raw materials containing the isocyanates and thiols used as the raw materials and the alcohol compound as the resin modifier is such that the molar ratio of the functional group of (NCO + NCS) / (SH + OH) , Preferably in the range of 0.6 to 2.0, and more preferably in the range of 0.8 to 1.2.

The temperature for preparing a polymerizable composition by mixing an isocyanate, a thiol, a catalyst and other additives is generally 25 ° C or lower. From the viewpoint of the pot life of the composition, it may be preferable to make the temperature lower. However, when the solubility of the catalyst or additive in the monomer is not good, it may be heated in advance to dissolve it in a monomer mixture of isocyanates, thiols, or monomers.

As a production method of the polythiourethane resin of the present invention, there may be mentioned a casting polymerization. That is, the polymerizable composition according to the present invention is injected between molds held by a gasket, a tape or the like. At this time, depending on the physical properties required of the plastic lens to be obtained, it is often desirable to carry out a defoaming treatment under reduced pressure, a filtration treatment such as pressurization and depressurization as necessary. Polymerization conditions are not particularly limited because they are largely different depending on the kind of the polymerizable composition, the type and amount of the catalyst used, the shape of the mold, etc., but the polymerization is carried out at a temperature of about -50 to 150 캜 for 1 to 50 hours. In some cases, it is preferable to maintain or slowly raise the temperature in the range of 10 to 150 占 폚 and cure in 1 to 25 hours.

The obtained polythiourethane resin may be subjected to treatment such as annealing if necessary. The treatment temperature is usually between 50 and 150 캜, but preferably between 90 and 140 캜, more preferably between 100 and 130 캜.

The polythiourethane resin of the present invention can be molded by a known method such as an internal release agent, a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a coloring inhibitor, a useful dye, Various additives may be added.

The polythiourethane resin of the present invention can be obtained as molded articles of various shapes by changing the mold at the time of casting polymerization and is used for various applications as optical resins such as spectacle lenses, camera lenses, light emitting diodes (LED) It is possible. In particular, it is suitable as an optical material such as a spectacle lens, a camera lens, a light emitting diode, and an optical element.

In the plastic lens using the polythiourethane resin of the present invention, a coating layer may be applied on one side or both sides, if necessary. 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 the coating layer is applied to both surfaces, the same coating layer may be applied to each surface or a different coating layer may be applied to each surface.

These coating layers each contain an ultraviolet absorber for the purpose of protecting lenses and eyes from ultraviolet rays, an infrared absorber for the purpose of protecting the eyes from infrared rays, a light stabilizer or an antioxidant for the purpose of improving the weatherability of the lens, A dye or a pigment, a discoloring dye, a discoloring pigment, an antistatic agent, or other known additives for enhancing the performance of the lens may be used in combination. With respect to the layer to be coated by coating, various leveling agents for the purpose of improving the coating ability may be used.

The primer layer is usually formed between the hard coat layer described later and the optical lens. The primer layer is a coating layer intended to improve the adhesion between the hard coat layer formed thereon and the lens, and it is also possible to improve the impact resistance depending on the case. As the primer layer, any material can be used as long as it has high adhesion to the obtained optical lens. In general, a urethane resin, an epoxy resin, a polyester resin, a melanin resin, a primer composition containing polyvinyl acetal as a main component, do. For the purpose of adjusting the viscosity of the composition, a suitable solvent that does not affect the lens may be used as the primer composition. Of course, it may be used as a solvent. The primer composition can be formed by any of a coating method and a dry method. When a coating method is used, a primer layer is formed by coating the lens by a known coating method such as spin coating or dip coating, and then solidifying the coating. In the case of carrying out by the dry method, it is formed by a known dry method such as a CVD method or a vacuum evaporation method. When forming the primer layer, the surface of the lens may be subjected to pretreatment such as alkali treatment, plasma treatment, ultraviolet ray treatment or the like, if necessary, for the purpose of improving adhesion.

The hard coat layer is a coating layer intended to impart functions such as abrasion resistance, abrasion resistance, moisture resistance, water temperature resistance, heat resistance and weather resistance to the lens surface. The hard coat layer is generally composed of an organic silicon compound having hardenability and an oxide fine particle of an element selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, And / or a composite oxide of two or more elements selected from the group of these elements is used as the hard coat composition. The hard coat composition preferably contains at least one of amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchlorates, perchlorates, salts, acids, metal chlorides and polyfunctional epoxy compounds in addition to the above components. As the hard coat composition, a suitable solvent that does not affect the lens may be used. Of course, it may be used as a solvent. The hard coat layer is usually formed by coating a hard coat composition by a known coating method such as spin coating or dip coating, and then curing. Examples of the curing method include thermal curing and curing by irradiation with energy rays such as ultraviolet rays or visible rays. In order to suppress the occurrence of interference, it is preferable that the refractive index of the hard coat layer is within a range of the refractive index of the lens with respect to ± 0.1.

The antireflection layer is usually formed on the hard coat layer as required. The antireflection layer has an inorganic or organic structure. In the case of an inorganic layer, an inorganic oxide such as SiO ₂ or TiO ₂ is used and formed by a dry method such as a vacuum evaporation method, a sputtering method, an ion plating method, an ion beam assist method or a CVD method. In the case of the organic system, a composition including an organic silicon compound and silica-based fine particles having an internal cavity is used and formed by a wet process. When the antireflection layer is used as a single layer, it is preferable that the refractive index is lower than the refractive index of the hard coat layer by at least 0.1 or more. In order to effectively exhibit the antireflection function, it is preferable that the antireflection film is a multilayer film. In this case, the low refractive film and the high refractive film are alternately laminated. In this case also, the refractive index difference 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 films such as 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 SiO ₂ film and the like.

The antifouling coat layer, the antifouling layer, and the water-repellent layer may be formed on the antireflection film layer as necessary. The method of forming the antifogging coat layer, the antifouling layer and the water-repellent layer is not particularly limited as long as it does not adversely affect the antireflection function, but the antifogging coat treatment method, Method, a water-repellent treatment method, and a material can be used. Examples of the anti-fog coating and anti-fouling treatment methods include a method of covering the surface with a surfactant, a method of adding a hydrophilic film to the surface to make it absorbent, a method of covering the surface with fine irregularities to improve the water absorbency, A method of making it water-absorbent, and a method of preventing adhesion of water droplets by performing a super water-repellent treatment. Examples of the water-repellent treatment method include a method of forming a water-repellent treatment layer by vapor deposition or sputtering of a fluorine-containing silane compound or the like, a method of forming a water-repellent treatment layer by dissolving a fluorine- .

From the polymerization catalyst of the present invention, a polythiourethane resin suitably used as a transparent resin for optical is obtained. Therefore, the present invention contributes to providing a suitable material in the field of spectacle lenses.

The polythiourethane resin obtained by the present invention is used for an optical material such as a plastic lens, a prism, an optical fiber, an information recording substrate, a filter, a light emitting diode and the like, and is suitably used particularly as a plastic lens material for spectacles.

Claims (4)

A polymerization catalyst for a polythiourethane-based optical material which is an amine mercaptopropionate represented by the general formula (1).
[Chemical Formula 1]

Wherein R ₁ , R ₂ and R ₃ are each an alkyl group having 1 to 8 carbon atoms or an organic residue having an electron-withdrawing group, wherein HX is mercapto propionic acid. The method according to claim 1,
Wherein the amine is any one of triethylamine, tri-n-butylamine, triisobutylamine, N, N-dimethylcyclohexylamine and N-methyldicyclohexylamine. Polymerization catalysts for materials. A polymerization catalyst of claim 1;
At least one isocyanate compound selected from a polyisocyanate compound, a polyisothiocyanate compound, and a polyisothiocyanate compound having an isocyanate group;
A polymerizable composition for a polythiourethane-based optical material comprising a polythiol compound. A process for producing a polythiourethane-based optical material, which comprises casting the polymerizable composition of claim 3.