JP4621146B2 - A polythiourethane-based polymerizable composition, an optical resin comprising the same, and a method for producing the same. - Google Patents

Description

  The present invention relates to a polythiourethane lens having good optical properties and resin strength.

  In recent years, plastic lenses are rapidly spreading to optical elements such as spectacle lenses and camera lenses because they are lighter and harder to break than inorganic lenses and can be dyed.

  In particular, eyeglass lenses have high refractive index, low dispersion (high Abbe number), excellent heat resistance, excellent impact resistance, easy dyeing, and cutting. Many functions are required such as excellent processability such as, and various resin materials for lenses have been developed and used so far.

Among these, polythiourethane resins have been developed as typical examples (see Patent Documents 1 and 2). Polythiourethane resin using an isocyanate compound with a specific chemical structure has a high refractive index, high Abbe number, high heat resistance and impact resistance, and gives a plastic lens with an excellent balance (Patent Literature) 3 and 4).
Japanese Patent Laid-Open No. 2-270859 JP 7-252207 A JP-A-3-124722 WO2005 / 087829A1 On the other hand, recently, in a spectacle lens, various processing is applied to a resin in order to pursue fashionability. In such processing, if the resin strength is not sufficient, the yield may be degraded due to damage during processing. Therefore, further improvement of resin strength is demanded.

  A first object of the present invention is to provide a composition that provides a lens resin having sufficient resin strength without impairing the optical properties of a conventional lens resin.

  A second problem is to provide a method for producing a resin from the composition.

As a result of intensive studies to solve the above-described problems, the present inventors have obtained an isocyanate compound represented by the formula (1) and an isocyanate compound represented by the formula (3) ,
(A) at least one polythiol compound that may have one or more (poly) sulfide bonds in one molecule;
(B) at least one polyhydroxy compound having two or more hydroxy groups in one molecule and / or (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups It has been found that a polythiourethane lens obtained by curing a polymerizable composition containing can sufficiently satisfy the required physical properties, and has completed the present invention.

That is, the present invention is as follows.
[1] An isocyanate compound represented by Formula (1) and an isocyanate compound represented by Formula (3) ;

（式（１）中、ｎは０〜３までの整数を表す。）

(In formula (1), n represents an integer from 0 to 3.)

(A) at least one polythiol compound that may have one or more (poly) sulfide bonds in one molecule;
(B) at least one polyhydroxy compound having two or more hydroxy groups in one molecule and / or (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups a polymerizable composition comprising,

[2 ] An isocyanate compound represented by the formula (4) and an isocyanate compound represented by the formula (3);

(A) at least one polythiol compound that may have one or more (poly) sulfide bonds in one molecule;
(B) at least one polyhydroxy compound having two or more hydroxy groups in one molecule and / or (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups A polymerizable composition comprising
[ 3 ] (b) In a polyhydroxy compound having two or more hydroxy groups in one molecule and / or (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups The number of moles of the hydroxy group and the thiol group is A and B, respectively. (A) The number of moles of the thiol group in the polythiol compound that may have one or more (poly) sulfide bonds in one molecule is C. And 100 × A / (A + B + C) is 0.1 to 50%, the polymerizable composition according to [1] or [2] ,
[ 4 ] (a) A polythiol compound which may have one or more (poly) sulfide bonds in one molecule is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5 -Bismercaptomethyl-1,4-dithiane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, Compound group of 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane or 4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane The polymerizable composition according to [ 3 ], wherein the polymerizable composition is one or more polythiol compounds selected from the group consisting of:
[ 5 ] (b) a polyhydroxy compound having two or more hydroxy groups in one molecule and / or a (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups , 2-mercaptoethanol, 3-mercapto-1,2-propanediol, pyrogallol, ethylene glycol or polycaprolactone diol, a compound containing at least one (poly) hydroxy group. The polymerizable composition according to [ 4 ],
[ 6 ] An isocyanate compound represented by the formula (4) and an isocyanate compound represented by the formula (3);

(A) The polythiol compound which may have one or more (poly) sulfide bonds in one molecule is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercapto At least selected from the group of compounds of methyl-1,11-mercapto-3,6,9-trithiaundecane or 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane One kind,
(B) a polyhydroxy compound having two or more hydroxy groups in one molecule and / or a (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups, The polymerizable composition according to [ 5 ], which is mercaptoethanol,
[ 7 ] A method for producing a resin obtained by curing the polymerizable composition according to any one of [1] to [ 6 ],
[ 8 ] A resin obtained by curing the polymerizable composition according to any one of [1] to [ 6 ],
[ 9 ] An optical element made of the resin according to [ 8 ],
[ 10 ] A lens comprising the optical element according to [ 9 ],
[ 11 ] A spectacle lens including the lens according to [ 10 ].

  According to the present invention, a polyisocyanate compound suitably used for a transparent resin material and a polymerizable composition containing the compound are found, and a polythiourethane resin substrate obtained by curing the polymerizable composition This makes it possible to have sufficient resin strength as a lens resin without impairing the optical properties of conventional lens resins.

  The present invention provides a composition that provides a lens resin having sufficient resin strength without impairing the optical properties of a conventional lens resin, and a method for producing a resin from the composition.

The polymerizable composition of the present invention includes an isocyanate compound represented by formula (1) and an isocyanate compound containing at least one selected from the group of compounds represented by formula (2) or formula (3);
(A) at least one polythiol compound that may have one or more (poly) sulfide bonds in one molecule;
(B) at least one polyhydroxy compound having two or more hydroxy groups in one molecule and / or (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups Is a polymerizable composition.

  Here, as the isocyanate compound according to the present invention, as the aliphatic isocyanate compound represented by the formula (1), 2,5-bis (isocyanato) -bicyclo [2,2,1] heptane, 2,6-bis ( Isocyanato) -bicyclo [2,2,1] heptane, 2,5-bis (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2,2 , 1] heptane, 2,5-bis (isocyanatoethyl) -bicyclo [2,2,1] heptane, 2,6-bis (isocyanatoethyl) -bicyclo [2,2,1] heptane, and the like. However, it is not limited only to these listed compounds.

  As the alicyclic isocyanate compound represented by the formula (2), 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,2-bis (isocyanatomethyl) Although cyclohexane etc. are mentioned, it is not limited only to these listed compounds.

  As the aromatic cyclic isocyanate compound represented by the formula (3), 1,4-bis (isocyanatomethyl) benzene, 1,3-bis (isocyanatomethyl) benzene, 1,2-bis (isocyanatomethyl) Although benzene etc. are mentioned, it is not limited only to these listed compounds.

Here, as the polythiol compound according to the present invention,
Methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 2,3-butane Dithiol, 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 methyl ether, 2,2-bis (mercaptome L) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, aliphatic polythiol compounds such as tetrakis (mercaptomethyl) methane, 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 Rubis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2 -Mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), glycerol tris (2-mercaptoacetate), glycerol Tris (3-mercaptopropionate), 1,4-cyclohexanediol bis (2-mercaptoacetate), 1,4-cyclohexanediol bis (3-mercaptoprote) Pionate), aliphatic polythiol compounds containing an ester bond, and halogen-substituted compounds such as chlorine-substituted and bromine-substituted compounds, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimethyl Mercaptobenzene, 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 (mercapto) Methyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3 Bis (mercaptoethyleneoxy) 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) 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, -Tris (mercaptoethyleneoxy) benzene, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5-tris (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 (mercapto) Methyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-te Lakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptoethyleneoxy) benzene, 2,2'-dimercaptobiphenyl, 4 , 4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, and other polythiol compounds containing a benzene ring,
2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, , 3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene and other halogen-substituted aromatic polythiols such as bromine-substituted compounds 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 Polythiols containing heterocycles such as 6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-4,6-dithiol-sym-triazine, and the like However, the present invention is not limited to these exemplified compounds.

In addition, as a (poly) thiol compound having one or more (poly) sulfide bonds in one molecule,
Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) Methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) 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 ( -Mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1, 11-mercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11- Mercapto-3,6,9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercapto Propyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercap Methyl-2,5-dimethyl-1,4-aliphatic polythiol compounds such as dithiane, and esters of these 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-mercaptopropinate), hydroxypropyl disulfide bis ( -Mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane -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-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodi Glycolic acid bis 2,3-dimercaptopropyl ester), thiodipropionate bis (2,3-dimercaptopropyl ester), dithiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionate bis (2, 3-dimercaptopropyl ester), aliphatic polythiols such as bis (2,3-dimercaptopropyl ester) dithiodipropionate, heterocyclic compounds such as 3,4-thiophenedithiol, bismuthiol,
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-dithianylthio] -1 , 3-bis (mercaptomethylthio) propane, 1- [4- (6-mercaptomethylthio) -1,3-dithianylthio] -3- [2,2-bis (mer Ptomethylthio) ethyl] -7,9-bis (mercaptomethylthio) -2,4,6,10-tetrathiaundecane, 1,5-bis [4- (6-mercaptomethylthio) -1,3-dithianylthio]- 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-dithianylthio] -6- [4- (6-mercaptomethylthio) -1,3- Dithianylthio] -1,3-dithiane, 3- [2- (1,3-dithietanyl)] methyl-7,9-bis (mercaptomethylthio) -1,11-dimercapto-2,4,6,10-tetrathiaun Can, 9- [2- (1,3-dithietanyl)] methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexa Thiaheptadecane, 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 ( Mel Captomethylthio) -6-mercapto-2,5-dithiahexylthio] -1,3-dithiolane, 4- [3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio] -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-dithietane, 2- [ , 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- (5-merca) Tomethylthio-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,
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 the like, and compounds having an ortho trithioformate skeleton such as oligomers thereof may be mentioned. However, it is not limited to these exemplified compounds. Furthermore, you may use halogen substituted bodies, such as these chlorine substituted bodies and bromine substituted bodies. These may be used alone or in combination of two or more.

  Furthermore, examples of the polyhydroxy compound having two or more hydroxy groups in one molecule according to the present invention include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Hexanediol, 2,3-butanediol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, pentaerythritol, Dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dolcitol, iditol, glycol Inositol, hexanetriol, triglycerol, diglycerol, triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, Hydroxypropylcyclohexanol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [3 4] Octanediol, butylcyclohexanediol, 1,1-bicyclohexylidenediol, cyclohexanetriol, polycaprolactone diol, multi , Lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di ( 2-hydroxyethoxy) benzene, bisphenol A-bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis- (2-hydroxyethyl ether), dibromoneopentyl glycol, polyol such as epoxy resin In addition, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid, β-oxocyclohexa Propionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-bromoglycolic acid, dicarboxycyclohexane, pyrrolemetic acid, butanetetracarboxylic acid, bromophthalic acid, etc. Examples include condensation products, addition products of the above polyols with alkylene oxides such as ethylene oxide and propylene oxide, addition products of alkylene polyamines with alkylene oxides such as ethylene oxide and propylene oxide, etc., but they are limited to these exemplified compounds. It is not a thing. Furthermore, you may use halogen substituted bodies, such as these chlorine substituted bodies and bromine substituted bodies.

  Examples of the (poly) hydroxy (poly) mercapto compound having at least one hydroxy group and at least one thiol group include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di (mercaptoacetate). ), Glycerin-1,3-di (3-mercaptopropionate), 1-hydroxy-4-mercaptocyclohexane, 2-mercaptohydroquinone, 4-mercaptophenol, 1,3-dimercapto-2-propanol, 2,3 Dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3- Mercaptopropio ), Pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3-mercaptopropionate), 1-hydroxyethylthio-3-mercaptoethylthiobenzene, bis (2-mercaptoacetate) malate, 2,4-dimercaptophenol, hydroxymethyltris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenylsulfone, 2- (2-mercaptoethyl) Mercapto groups such as thio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulcylate), hydroxyethylthiomethyl-tris (mercaptoethylthiomethyl) methane, Examples thereof include compounds containing a hydroxy group.

   Further, bis- [4- (hydroxyethoxy) phenyl] sulfide, bis- [4- (2-hydroxypropoxy) phenyl] sulfide, bis- [4- (2,3-dihydroxypropoxy) phenyl] sulfide, bis- [ 4- (4-hydroxycyclohexyloxy)] sulfide, bis- [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide, and these compounds with an average of no more than 3 molecules of ethylene oxide and / or propylene per hydroxyl group Compounds with oxide added, such as di- (2-hydroxyethyl) sulfide, bis (2-hydroxyethyl) disulfide, 1,4-dithian-2,5-diol, bis (2,3-dihydroxypropyl) sulfide Polyol compound having (poly) sulfide bond Including but not limited to these exemplified compounds. Furthermore, halogen substitution products such as chlorine substitution products and bromine substitution products may be used. These may be used alone or in combination of two or more.

  An isocyanate compound represented by formula (1) and an isocyanate compound containing at least one selected from the group of compounds represented by formula (2) or formula (3); and (a) one or more ( A polythiol compound which may have a poly) sulfide bond; and (b) a polyhydroxy compound having two or more hydroxy groups in one molecule and / or one or more hydroxy groups and one or more thiol groups. The use ratio of the (poly) hydroxy (poly) mercapto compound is such that the functional group molar ratio of NCO / (SH + OH) is usually in the range of 0.5 to 3.0, preferably in the range of 0.5 to 1.5. In particular, the range of 0.8 to 1.2 is particularly preferable.

Among the compounds listed above, as the isocyanate compound, 2,5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and 1,4-bis (isocyanatomethyl) benzene,
(A) As at least one polythiol compound that may have one or more (poly) sulfide bonds in one molecule, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
(B) at least one polyhydroxy compound having two or more hydroxy groups in one molecule and / or (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups As described above, a resin obtained by combining and curing 2-mercaptoethanol can obtain a lens resin having sufficient resin strength without impairing the optical properties of conventional lens resins.

  (B) a polyhydroxy compound having two or more hydroxy groups in one molecule and / or a hydroxy in a (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups When the number of moles of the thiol group is A and B, respectively, (a) the number of moles of the thiol group in the polythiol compound that may have one or more (poly) sulfide bonds in one molecule is C 100 × A / (A + B + C) is preferably in the range of 0.1 to 50%, more preferably in the range of 3.0 to 45%, and particularly preferably in the range of 5.0 to 40%.

    The polythiourethane-based lens of the present invention can be produced by heat-curing the polymerizable composition.

  Since the polythiourethane lens of the present invention generates heat when the hydroxyl group reacts with the isocyanate compound, it is preferable to start polymerization after cooling to 25 ° C. or lower. A particularly preferable cooling temperature is 10 ° C to 20 ° C. Furthermore, the polythiourethane-based lens of the present invention is mainly composed of a urethane bond by an isocyanate group and a hydroxy group and / or a thiol group and / or a thiocarbamic acid S-alkyl ester bond. Even if it contains a urea bond or biuret bond, there is no problem. For example, it is often the case that an isocyanate group is further reacted with a urethane bond or a thiocarbamic acid S-alkyl ester bond to increase the crosslinking density to give a preferable result. In this case, the reaction temperature is increased to at least 100 ° C. and a large amount of isocyanate component is used. Alternatively, it is also possible to use a urea bond or biuret bond by partially using an amine or the like. Thus, when using things other than the polyol compound, polythiol compound, and thiol compound having a hydroxy group that react with an isocyanate compound, it is necessary to pay particular attention to the point of coloring.

  Also, depending on the purpose, various substances such as chain extenders, crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, etc. may be added as in known molding methods. Good. In order to adjust to a desired reaction rate, a thiocarbamic acid S-alkyl ester or a known reaction catalyst used in the production of polyurethane can be appropriately added. The polyurethane-based lens of the present invention is usually obtained by cast polymerization.

  Specifically, the isocyanate compound represented by formula (1) and at least one isocyanate compound selected from the group of compounds represented by formula (2) or formula (3), and (a) 1 in one molecule At least one polythiol compound that may have one or more (poly) sulfide bonds, (b) a polyhydroxy compound having two or more hydroxy groups in one molecule, and / or one or more hydroxy groups. At least one (poly) hydroxy (poly) mercapto compound having at least one thiol group is mixed. If necessary, this mixed solution is defoamed by an appropriate method and then poured into a mold, and is usually gradually heated from a low temperature to a high temperature for polymerization.

  The addition order of the catalyst to be used may be added to a mixed solution composed of an isocyanate compound and a thiol compound, or may be previously dissolved in an isocyanate compound to prepare a master batch and then added to the mixed solution. The polythiourethane lens of the present invention thus obtained is suitable as a material for optical elements such as eyeglass lenses and camera lenses.

  In addition, the polythiourethane lens of the present invention has an anti-reflection, high hardness imparting, improved wear resistance, improved chemical resistance, anti-clouding property, or imparted fashionability as necessary. Physical and chemical treatments such as polishing, antistatic treatment, hard coat treatment, non-reflective coat treatment, dyeing treatment, and light control treatment can be performed.

Hereinafter, the present invention will be specifically described by way of examples. In addition, among the performance tests of the obtained resin, refractive index, heat resistance, specific gravity, resin strength, and dyeability were evaluated by the following test methods.
1) Refractive index (ne) and Abbe number (νe)
Measurements were made at 20 ° C. using a Purfrich refractometer.
2) Heat resistance 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.
3) Specific gravity It measured by the Archimedes method at 20 degreeC.
4) Resin strength test 4-i) Bending test: Using a test piece obtained by processing a polythiourethane resin into a thickness of 2.5 mm, a length of 65 mm, and a width of 25.0 mm using AUTOGRAPH AGS-J manufactured by Shimadzu Corporation. The maximum point stress (N / mm ² ) when a load was applied to the center of the test piece at a descending speed of 1.2 mm / min was measured.
4-ii) Tensile strength test: Using an AUTOGRAPH AGS-J manufactured by Shimadzu Corporation, a resin flat plate adjusted to have a lens diameter of 45 mm and a thickness of 2.5 mm, assuming two-point frame processing, with two drills Drill a 1.6mm diameter hole, pass a 1.6mm metal shaft through the hole, attach both ends of the sample to the fixture, and then pull at a speed of 5mm / min to measure the maximum point test force. Then, a value (kgf / mm) obtained by dividing the obtained maximum point test force by the resin thickness was calculated.
The composition ratio of the prepared resin is shown in [Table-1], and the evaluation results are shown in [Table-2].

Example 1
2,57-37 g of 2,5-bis (isocyanatomethyl) -bicyclo [2,2,1] heptane, 0.20 g of Zelec UN (acidic phosphate ester) as an internal release agent, and Biosorb 583 as an ultraviolet absorber 0.05 g was added and mixed and dissolved at 20 ° C. After dissolution, 14.49 g of 2-mercaptoethanol and 22.32 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were added, mixed and dissolved to obtain a uniform solution. Further, 0.10 g of dibutyltin dichloride as a curing catalyst was mixed and dissolved in 5.82 g of 1,4-bis (isocyanatomethyl) benzene, added to the previously dissolved homogeneous solution, and then mixed and dissolved. This uniform solution was defoamed at 600 Pa for 1 hour, filtered through a 1 μm Teflon (registered trademark) filter, and then poured into a mold composed of a glass mold and a tape. This mold was put into an oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over about 20 hours. After completion of the polymerization, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 120 ° C. for 4 hours. The obtained resin was colorless and excellent in transparency and high in refractive index (ne) of 1.596 and Abbe number (νe) of 40.

Example 2
45.93 g of 2,5-bis (isocyanatomethyl) -bicyclo [2,2,1] heptane, 0.20 g of Zelec UN (acidic phosphate ester) as an internal mold release agent, and Biosorb 583 as an ultraviolet absorber 0.05 g was added and mixed and dissolved at 20 ° C. After dissolution, 16.16 g of 2-mercaptoethanol and 19.95 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were added, mixed and dissolved to obtain a uniform solution. Furthermore, 0.05 g of dibutyltin dichloride as a curing catalyst was mixed and dissolved in 17.96 g of 1,4-bis (isocyanatomethyl) benzene, added to the previously dissolved homogeneous solution, and then mixed and dissolved. This uniform solution was defoamed at 600 Pa for 1 hour, filtered through a 1 μm Teflon (registered trademark) filter, and then poured into a mold composed of a glass mold and a tape. This mold was put into an oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over about 20 hours. After completion of the polymerization, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 120 ° C. for 4 hours. The obtained resin was colorless and highly transparent, and had a refractive index (ne) of 1.601 and an Abbe number (νe) of 39.

Comparative Example 1
To 62.20 g of 2,5-bis (isocyanatomethyl) -bicyclo [2,2,1] heptane, 0.10 g of dibutyltin dichloride as a curing catalyst, and ZEREC UN (acidic phosphate ester) 0. 30 g and 0.05 g of Biosorb 583 as an ultraviolet absorber were added and mixed and dissolved at 20 ° C. After dissolution, 11.90 g of 2-mercaptoethanol and 25.90 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were added, mixed and dissolved to obtain a homogeneous solution. This uniform solution was defoamed at 600 Pa for 1 hour, filtered through a 1 μm Teflon (registered trademark) filter, and then poured into a mold composed of a glass mold and a tape. This mold was put into an oven and polymerized by gradually raising the temperature from 25 ° C. to 120 ° C. over about 20 hours. After completion of the polymerization, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 120 ° C. for 4 hours. The obtained resin was colorless and excellent in transparency and high in refractive index (ne) 1.600 and Abbe number (νe) 41.

Symbols E, F, G, and H in [Table 1] represent the following contents.
E: Isocyanate compound. The numerical value represents the number of moles of the isocyanato group.
F: A polythiol compound which may have one or more (poly) sulfide bonds in one molecule. The numerical value represents the number of moles of thiol groups.
G: A polyhydroxy compound having two or more hydroxy groups in a molecule and / or a (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups. The numerical value represents the number of moles of thiol groups.
H: a polyhydroxy compound having two or more hydroxy groups in a molecule and / or a hydroxy group and a thiol in a (poly) hydroxy (poly) mercapto compound having at least one hydroxy group and at least one thiol group When the number of moles of the group is A and B, respectively, and the number of moles of the thiol group in the polythiol compound that may have one or more (poly) sulfide bonds in one molecule is C, the number of moles of the hydroxy group Of the total number of moles of thiol groups and hydroxy groups (%): 100 × A / (A + B + C)

  From the above results, it was found that the resin of the present invention is a transparent resin excellent in resin strength as compared with the comparative example and having a balanced refractive index, Abbe number, heat resistance and specific gravity.

  According to the present invention, as an optical material in the field of high refractive index, a transparent resin excellent in resin strength and balanced in optical properties, heat resistance and specific gravity can be obtained, and a material suitable particularly in the field of spectacle lenses is provided. To contribute.

Claims (11)

An isocyanate compound represented by formula (1) and an isocyanate compound represented by formula (3) ;

(In formula (1), n represents an integer from 0 to 3.)

(A) at least one polythiol compound that may have one or more (poly) sulfide bonds in one molecule;
(B) at least one polyhydroxy compound having two or more hydroxy groups in one molecule and / or (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups A polymerizable composition comprising: An isocyanate compound represented by formula (4) and an isocyanate compound represented by formula (3);

(A) at least one polythiol compound that may have one or more (poly) sulfide bonds in one molecule;
(B) at least one polyhydroxy compound having two or more hydroxy groups in one molecule and / or (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups A polymerizable composition comprising: (B) A polyhydroxy compound having two or more hydroxy groups in one molecule and / or a hydroxy group in a (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups When the number of moles of thiol groups is A and B, respectively, (a) the number of moles of thiol groups in a polythiol compound that may have one or more (poly) sulfide bonds in one molecule is C 100 * A / (A + B + C) is 0.1 to 50%, The polymerizable composition according to claim 1 or 2. (A) The polythiol compound which may have one or more (poly) sulfide bonds in one molecule is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-bismercapto Methyl-1,4-dithiane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 4,7 -In the group of compounds of dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane or 4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane The polymerizable composition according to claim 3, wherein the polymerizable composition is at least one polythiol compound selected from the group consisting of: (B) a polyhydroxy compound having two or more hydroxy groups in one molecule and / or a (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups, A compound containing at least one (poly) hydroxy group selected from the group consisting of mercaptoethanol, 3-mercapto-1,2-propanediol, pyrogallol, ethylene glycol and polycaprolactone diol. 4. The polymerizable composition according to 4. An isocyanate compound represented by the formula (4) and an isocyanate compound represented by the formula (3);

(A) The polythiol compound which may have one or more (poly) sulfide bonds in one molecule is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercapto At least selected from the group of compounds of methyl-1,11-mercapto-3,6,9-trithiaundecane or 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane One kind,
(B) a polyhydroxy compound having two or more hydroxy groups in one molecule and / or a (poly) hydroxy (poly) mercapto compound having one or more hydroxy groups and one or more thiol groups, The polymerizable composition according to claim 5, which is mercaptoethanol. The manufacturing method of resin which hardens the polymeric composition in any one of Claims 1-6. Resin which hardens the polymeric composition in any one of Claims 1-6. An optical element made of the resin according to claim 8. A lens comprising the optical element according to claim 9. An eyeglass lens comprising the lens according to claim 10.