JP2003246859A - Resin used for lens and method for producing lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin used for a lens, which has a high heat resistance and can prevent breakage or deformation of the lens at a demolding process in production of a episulfide-type lens using an episulfide compound as a starting material, capable of improving the productivity of the lens. <P>SOLUTION: In the production of the episulfide type lens by cast-polymerizing a polymerizable composition containing a compound having at least two episulfide groups in the molecule, the polymerization is carried out so that the lens obtained contains ≤0.3 mass% of the residual episulfide group therein. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin used for an optical material such as a plastic lens, a prism, an optical fiber, an information recording substrate, a filter and a light emitting diode, and is particularly suitable as a resin for an eyeglass plastic lens. The present invention relates to a lens used and a manufacturing method thereof.

[0002]

2. Description of the Related Art Plastic lenses are lighter in weight and less susceptible to cracking than inorganic lenses and can be dyed, so that they have rapidly become popular in optical materials such as spectacle lenses and camera lenses in recent years.

The optical performances required of these plastic lenses are high refractive index, high Abbe number, and physical properties such as high heat resistance, low specific gravity and workability.

Among these performances, high heat resistance and low specific gravity have been realized at a high level even in the present high refractive index plastic lenses. Currently, as a resin widely used for these purposes, there is a resin obtained by radical polymerization of diethylene glycol bis (allyl carbonate) (hereinafter referred to as DAC). This resin has various characteristics such as excellent impact resistance, light weight, excellent dyeability, and good workability such as machinability and abrasivity. . However, this resin has a low refractive index nd of 1.50, which increases the center thickness and edge thickness of the lens, and thus a resin for lenses having a higher refractive index has been desired.

D. A. A polyurethane resin (Patent Document 1 or the like), a sulfur-containing O- (meth) acrylate resin (Patent Document 2 or the like), or thio (meth), which has a higher refractive index than the C resin, has a sulfur atom introduced into the resin. Acrylate resins (Patent Document 3, etc.) are known. Polyurethane resin is a well-balanced resin having a high refractive index and good impact resistance.

However, since the refractive index and the Abbe number have contradictory physical properties such that the Abbe number decreases as the refractive index increases, it is very difficult to improve both at the same time. Therefore, studies for increasing the refractive index while suppressing the decrease of the Abbe number are being actively conducted.

The most typical proposal in these examinations is
It is a method using an episulfide compound in Patent Document 4 and Patent Document 5, Patent Document 6, Patent Document 7, and Patent Document 8. In addition, the applicants of the present invention have also disclosed Patent Document 9, Patent Document 10,
Patent Document 11, Patent Document 12, Patent Document 13 and the like have proposed resins for high refractive index lenses using episulfide compounds.

According to these methods, a high refractive index can be realized while having a relatively high Abbe number. However, these patents do not describe the episulfide group remaining in the resin, and the effect of the episulfide group existing in the resin on various physical properties was not clear. Therefore, it was important to define the amount of episulfide groups present in the resin.

[0009]

[Patent Document 1] Japanese Patent Publication No. 4-58489

[Patent Document 2] JP-A-4-161410

[Patent Document 3] Japanese Patent Publication No. 3-59060

[Patent Document 4] JP-A-9-110979

[Patent Document 5] Japanese Patent Laid-Open No. 9-71580

[Patent Document 6] Japanese Patent Laid-Open No. 9-255781

[Patent Document 7] Japanese Unexamined Patent Publication No. 10-2982878

[Patent Document 8] Japanese Unexamined Patent Publication No. 11-166037

[Patent Document 9] WO89 / 10575

[Patent Document 10] Japanese Patent Laid-Open No. 11-140070

[Patent Document 11] Japanese Unexamined Patent Publication No. 11-183702

[Patent Document 12] Japanese Patent Application Laid-Open No. 11-189592

[Patent Document 13] Japanese Patent Application No. 11-68448

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an episulfide-based lens resin made of an episulfide compound as a raw material, which has stable physical properties and quality.

[0011]

In view of the above situation, the inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, the heat resistance of the resin has been improved due to the influence of the episulfide group existing in the resin. The present invention has led to the present invention, and found that there is a case where the mold release property with respect to the glass mold at the time of mold release is deteriorated, the quality of the obtained resin for a lens is deteriorated, and the productivity is decreased. .

That is, the present invention provides the following formula (1) in one molecule (A):

[0013]

[Chemical 8]

(Wherein R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom). In the production of an episulfide-based lens obtained by casting polymerization of a polymerizable composition containing an episulfide compound having one or more of the indicated structures, the amount of the episulfide group present in the obtained resin is 0.3 mass. The present invention relates to a method for producing a lens and a resin for a lens obtained by the method, which is characterized in that polymerization is performed so as to be not more than 0.1%.

(B): A method for producing a lens of (A) in which an episulfide compound is represented by the following formula (2) and a lens resin.

[0016]

[Chemical 9]

(In the formula, R ^{5 to} R ¹⁰ are each 1 to 1 carbon atoms.
10 hydrocarbon groups or hydrogen atoms are shown. Y is a substituent or an unsubstituted linear, branched or cyclic C1-C10
Represents a hydrocarbon group, a substituted or unsubstituted 1,4-dithiane group, or an arylene group. m represents an integer of 0 to 2,
n represents an integer of 0-4. )

(C): A method for producing a lens of (A) in which an episulfide compound is represented by the following formula (3), and a lens resin.

[0019]

[Chemical 10]

(In the formula, R ^{11 to} R ¹⁶ are each a carbon number of 1 to 1)
Represents 10 hydrocarbon groups or hydrogen atoms. )

In the present invention, the expression that the episulfide group present in the resin is 0.3% by mass or less means that the number of moles of the episulfide group in the resin is quantified by the analysis method described below, and the molecular weight of the episulfide group portion (59 / 1 mol) to calculate the mass of the episulfide group portion in the resin, and the value is divided by the mass of the resin.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

With the lens resin of the present invention, the episulfide group present in the resin is 0.3% by mass or less, whereby a lens having excellent heat resistance and good releasability can be obtained.
On the contrary, the episulfide group present in the resin is 0.3% by mass.
If the content exceeds the limit, the heat resistance of the resin will be reduced,
The releasability at the time of release may be deteriorated, or the lens may be damaged or deformed during release.

Specific examples of the episulfide resin used as a raw material in the present invention include bis (β-epithiopropyl) sulfide and bis (β-epithiopropyl).
Disulfide, bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,2-bis (β-epithiopropylthio) propane, 1,3-bis (β -Epithiopropylthio) propane, 1,3-bis (β-epithiopropylthio) -2-
Methyl propane, 1,4-bis (β-epithiopropylthio) butane, 1,4-bis (β-epithiopropylthio) -2-methylbutane, 1,3-bis (β-epithiopropylthio) butane 1,5-bis (β-epithiopropylthio) pentane, 1,5-bis (β-epithiopropylthio) -2-methylpentane, 1,5-bis (β
-Epithiopropylthio) -3-thiapentane, 1,6
-Bis (β-epithiopropylthio) hexane, 1,6
-Bis (β-epithiopropylthio) -2-methylhexane, 3,8-bis (β-epithiopropylthio)-
3,6-dithiaoctane, 1,2,3-tris (β-epithiopropylthio) propane, 2,2-bis (β-epithiopropylthio) -1,3-bis (β-epithiopropylthiomethyl) ) Propane, 2,2-bis (β-epithiopropylthiomethyl) -1- (β-epithiopropylthio) butane, 1,5-bis (β-epithiopropylthio) -2- (β-epi Thiopropylthiomethyl) -3
-Thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1- (β-epithiopropylthio) -2,2 -Bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1, 8-bis (β-epithiopropylthio) -4,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8
-Bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio)
-2,5-bis (β-epithiopropylthiomethyl)-
3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,
1,1-tris [{2- (β-epithiopropylthio)
Ethyl} thiomethyl] -2- (β-epithiopropylthio) ethane, 1,1,2,2-tetrakis [{2- (β
-Epithiopropylthio) ethyl} thiomethyl] ethane, 1,11-bis (β-epithiopropylthio)-
4,8-bis (β-epithiopropylthiomethyl)-
3,6,9-Trithiaundecane, 1,11-bis (β
-Epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio)-
5,7-bis (β-epithiopropylthiomethyl)-
Chain-like aliphatic β-, such as 3,6,9-trithiaundecane
Epithiopropylthio compound and 1,3-bis (β
-Epithiopropylthio) cyclohexane, 1,4-bis (β-epithiopropylthio) cyclohexane, 1,
3-bis (β-epithiopropylthiomethyl) cyclohexane, 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane , 2,5-bis [{2- (β-epithiopropylthio) ethyl} thiomethyl] -1,4-dithiane and other cycloaliphatic β-epithiopropylthio compounds, and 1,3-bis ( β-epithiopropylthio) benzene, 1,4-bis (β-epithiopropylthio) benzene, 1,3-bis (β-epithiopropylthiomethyl) benzene, 1,4-bis (β
-Epithiopropylthiomethyl) benzene, bis {4-
(Β-epithiopropylthio) phenyl} methane, 2,
2-bis {4- (β-epithiopropylthio) phenyl} propane, bis {4- (β-epithiopropylthio) phenyl} sulfide, bis {4- (β-epithiopropylthio) phenyl} sulfone, Aromatic β such as 4,4′-bis (β-epithiopropylthio) biphenyl
-Epithiopropylthio compounds and the like, 3-mercaptopropylene sulfide, 4-mercaptobutene sulfide and the like, mercapto group-containing epithio compounds and the like can be mentioned, but not limited to these exemplified compounds. Further, these compounds may be used alone or in combination of two or more kinds.

In the polymerizable composition of the present invention, not only a mixture of these episulfide resins, but also polysulfide oligomers such as dimers, trimers, and tetramers of these resins, and episulfide resin are synthesized. There is also a problem with episulfide resins having a mercapto group formed when epihalohydrin is deficient, and inorganic acids and organic acids used during episulfide synthesis, solvents, unreacted raw materials and other by-products and impurities such as organic compounds and inorganic compounds. It may be included in a range that does not become.

When obtaining a lens in the method of the present invention,
A lens can be produced by polymerizing by heating or standing at room temperature in the presence or absence of a curing catalyst, but without a curing catalyst, the polymerization does not proceed well and causes poor polymerization or does not polymerize. There are cases. As the curing catalyst used in producing the lens of the present invention, amines, phosphines, Lewis acids, radical polymerization catalysts,
Cationic polymerization catalysts and the like are usually used.

Specific amines include ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, t-butylamine, cyclohexylamine, 2-aminoethanol, dibutylamine, triethylamine, tri-n-butylamine. , Tri-n-hexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N, N-diethylethanolamine, N, N-din-butylethanolamine, N, N-dimethylbenzylamine, diethylbenzyl Amine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, N, N-dimethyl Diphosphate, beta-picoline, piperidine, 2,2'-bipyridyl, dicyandiamide, hexamethylenetetramine, 1,8-diazabicyclo (5,
4,0) -7-undecene and the like. Examples of the phosphines are trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,2. -Bis (dimethylphosphino) ethane and the like. Examples of Lewis acids include dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, tetrachlorotin, dibutyltin oxide, zinc chloride, zinc acetylacetone,
Examples thereof include aluminum chloride, aluminum fluoride, triphenylaluminum, tetrachlorotitanium, calcium acetate and the like. As the radical polymerization catalyst, 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile),
2,2'-azobis (2,4-dimethylvaleronitrile), t-butylperoxy-2-ethylhexanoate, n-butyl-4,4'-bis (t-butylperoxy) valerate, t- Butyl peroxybenzoate and the like.Cationic polymerization catalysts include diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, and triphephenophosphoric acid. Nyl sulfonium hexafluoroarsenic acid and the like can be mentioned, but the compounds are not limited to these exemplified compounds. You may use these individually or in mixture of 2 or more types.

Of these exemplified compounds, preferred compounds include N, N-diisopropylethylamine and N.
-Methyldicyclohexylamine, N, N-dimethylcyclohexylamine, N, N-diethylethanolamine, and good results can be obtained by mixing two or more of these tertiary amines having different catalytic activities. .

A preferable example of the combination of tertiary amines having different catalytic activities cannot be unconditionally limited depending on the kind of the episulfide compound used and the kind of the resin modifier, but N, N-dimethylcyclohexylamine and N are used.
-Methyldicyclohexylamine, a combination of N, N-dimethylcyclohexylamine and N, N-diisopropylethylamine, N, N-diethylethanolamine and N-methyldicyclohexylamine, and the like.

The amount of the curing catalyst added is in the range of 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of the composition comprising the episulfide resin. . If the addition amount of the curing catalyst is less than 0.001% by mass, it may cause poor polymerization. On the other hand, although it is possible to exceed 10% by mass, the pot life may be shortened, and inconveniences such as deterioration of transparency, optical properties, or weather resistance may occur.

The lens monomer in the present invention is mainly composed of a resin for adjusting the optical properties such as the refractive index of the obtained lens, adjusting various physical properties such as specific gravity, adjusting the viscosity of the monomer, and other handling. A resin modifier can be added for the purpose of improvement.

As the resin modifier, episulfide compounds other than those contained in the polymerizable composition according to the present invention, epoxy compounds, olefins containing (meth) acrylates, amine compounds, thiol compounds, polyphenols. And amino acids and mercaptoamines, organic acids and anhydrides, and mercapto organic acids.

Specific examples of preferable epoxy compounds as the resin modifier include a phenolic epoxy compound obtained by a condensation reaction of a polyhydric phenol compound such as bisphenol A glycidyl ether and an epihalohydrin compound, and hydrogenated bisphenol A glycidyl compound. An alcohol-based epoxy compound obtained by condensation of a polyhydric alcohol compound such as ether and an epihalohydrin compound,
3,4-epoxycyclohexylmethyl-3 ', 4'-
Glycidyl ester-based epoxy compounds obtained by condensation of polyhalogenated organic compounds such as epoxycyclohexanecarboxylate and 1,2-hexahydrophthalic acid diglycidyl ester with epihalohydrin compounds, condensation of primary and secondary diamine compounds with epihalohydrin compounds In addition to the amine-based epoxy compounds obtained by the above, and other aliphatic polyepoxy compounds such as vinylcyclohexene diepoxide, etc., the compounds are not limited to these exemplified compounds. Also, these alone,
Two or more types may be mixed and used.

Specific examples of preferable olefins as the resin modifier include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy. Methyl 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 diethylene Methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis (4-acoxyethoxyphenyl) Propane, 2,2-bis (4-methacryloyl ethoxy phenyl) propane, 2,2-bis (4
-Acloxydiethoxyphenyl) propane, 2,2-
Bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) Methane, 1,1-bis (4-acryloxydiethoxyphenyl) methane, 1,1-bis (4-methacryloxydiethoxyphenyl) methane, dimethyloltricyclodecanediacrylate, trimethylolpropane triacrylate, trimethylol Propane trimethacrylate, glycerol diacrylate,
Glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate,
Methylthioacrylate, methylthiomethacrylate,
(Meth) acrylate compounds such as phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl Allyl compounds such as isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, vinyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m-dioxane), diisopropenyl Examples thereof include benzene, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

Each of the above resin modifiers may be used alone or in combination of two or more.

Specific examples of preferable amine compounds as the resin modifier include ethylamine, n-propylamine, isopropylamine, n-butylamine and s.
ec-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, myristylamine, 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine,
Aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine, 2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline, benzylamine, phenethylamine, 2,3-, or 4-methylbenzylamine, o-, m-, or p -Methylaniline, o-, m-, or p-ethylaniline, aminomorpholine, naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine, aminopyridine, aminophenol, aminoethanol, 1-aminopropanol, 2-aminopropanol, Aminobutanol, aminopentanol, aminohexanol, methoxyethylamine, 2- (2-aminoethoxy) ethanol, 3-ethoxypropylamine,
Monofunctional primary amine compounds such as 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-isobutoxypropylamine and 2,2-diethoxyethylamine, ethylenediamine,
1,2- or 1,3-diaminopropane, 1,2
-, 1,3-, or 1,4-diaminobutane, 1,
5-diaminopentane, 1,6-diaminohexane,
1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3-,
Alternatively, 1,4-diaminocyclohexane, o-, m-
Alternatively, p-diaminobenzene, 3,4- or 4,
4'-diaminobenzophenone, 3,4- or 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'- or 4,4'-diaminodiphenyl sulfone, 2,7-diaminofluorene,
1,5-, 1,8-, or 2,3-diaminonaphthalene, 2,3-, 2,6-, or 3,4-diaminopyridine, 2,4-, or 2,6-diaminotoluene, m -Or p-xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1,3
-Or 1,4-diaminomethylcyclohexane,
2-, or 4-aminopiperidine, 2-, or 4-aminomethylpiperidine, 2-, or 4-aminoethylpiperidine, N-aminoethylmorpholine, N
-Primary polyamine compounds such as aminopropylmorpholine, diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctyl Amine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzyl Monofunctional secondary amine compounds such as amine, dicyclohexylamine, N-methylaniline, N-ethylaniline, dinaphthylamine, 1-methylpiperazine and morpholine, N, N'-dimethylethylenediamine, N, N'- Methyl-1,2-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,2-diaminobutane,
N, N'-dimethyl-1,3-diaminobutane, N,
N'-dimethyl-1,4-diaminobutane, N, N'-
Dimethyl-1,5-diaminopentane, N, N'-dimethyl-1,6-diaminohexane, N, N'-dimethyl-1,7-diaminoheptane, N, N'-diethylethylenediamine, N, N'- Diethyl-1,2-diaminopropane, N, N'-diethyl-1,3-diaminopropane, N, N'-diethyl-1,2-diaminobutane,
N, N'-diethyl-1,3-diaminobutane, N,
N'-diethyl-1,4-diaminobutane, N, N'-
Diethyl-1,5-diaminopentane, N, N'-diethyl-1,6-diaminohexane, N, N'-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine , 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4
2-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4-di- (4-piperidyl) butane, tetramethylguanidine, etc. Examples thereof include, but are not limited to, the exemplified compounds. These may be used alone or in combination of two or more. Among these exemplified compounds, benzylamine and piperazines are more preferable.

Specific examples of preferable thiol compounds include methyl mercaptan, ethyl mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 1,2,
3-trimercaptopropane, tetrakis (mercaptomethyl) methane, 1,2-dimercaptocyclohexane, bis (2-mercaptoethyl) sulfide, 2,3
-Dimercapto-1-propanol, ethylene glycol bis (3-mercapto propionate), diethylene glycol bis (3-mercapto propionate), diethylene glycol bis (2-mercapto glycolate), pentaerythritol tetrakis (2-mercapto thioglycolate) ), Pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptothioglycolate),
Trimethylolpropane tris-3-mercaptopropionate), 1,1,1-trimethylmercaptoethane,
1,1,1-trimethylmercaptopropane, 2,5-
Dimercaptomethylthiophane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
2,5-dimercaptomethyl-1,4-dithiane, 2,
5-bis {(2-mercaptoethyl) thiomethyl}-
1,4-dithiane, 1,3-cyclohexanedithiol, 1,4-cyclohexanedithiol, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9
-Trithiaundecane, 4,7-dimercaptomethyl-
Aliphatic thiols such as 1,11-dimercapto-3,6,9-trithiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and benzyl mercaptan and thio. Phenol,
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 2,2′-dimercaptobiphenyl,
4,4'-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) sulfone, 2,2-bis (4-mercaptophenyl) propane, 1 , 2,3-Trimercaptobenzene, 1, 2,
Examples thereof include aromatic thiols such as 4-trimercaptobenzene and 1,2,5-trimercaptobenzene, but are not limited to these exemplified compounds. Also,
These may be used alone or in combination of two or more.

Specific examples of preferable polyphenols include a phenolic hydroxyl group on the aromatic ring.
One or more, and as the monophenol, phenol, o-cresol, m-cresol, p-cresol, 3-methoxyphenol, 4-ethoxyphenol, 4-n-propoxyphenol, 3-butoxyphenol, nonylphenol, 2 -N-propylphenol, 2,3,4,6-tetrachlorophenol, 2,
3,5,6-Tetrafluorophenol, 2,4,6-
Tribromophenol, 2,6-dichloro-4-fluorophenol, 2,6-dichloro-4-nitrophenol, 2,3,4-trichlorophenol, 4-bromo-
2-chlorophenol, 2,4-dibromophenol,
2-chloro-4-nitrophenol, 2,3-dichlorophenol, 2-fluoro-4-nitrophenol,
3,5-xylenol, 2,3-difluorophenol, 2,4-dinitrophenol, 2-bromophenol, 2-amino-4-chloro-5nitrophenol, 2
-Chlorophenol, 4-amino-2,6-dichlorophenol, 2-nitrophenol, 2-amino-4-nitrophenol, thymol, carvacrol, α-naphthol, 2-aminophenol and the like can be mentioned. , Catechol, 3-chlorocatechol,
Resorcin, hydroquinone, chlorohydroquinone,
Examples include pyrogallol and fluoroglucine, but the invention is not limited to these exemplified compounds. These polyphenol compounds may be used alone or in combination of two or more.

Specific examples of preferable mercapto organic acids include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, and thiosalicylic acid, but are limited to these exemplified compounds. is not. These may be used alone or in combination of two or more.

Specific examples of preferable organic acids and their anhydrides include thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydro. Examples thereof include phthalic anhydride, methylnorbornene anhydride, methylnalbornane anhydride, maleic anhydride, trimellitic anhydride, and pyromellitic anhydride, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

In addition to these resin modifiers, internal release agents, light stabilizers, ultraviolet absorbers, and
Various known additives such as antioxidants, dyes and fillers may be added.

The lens of the present invention is usually obtained by cast polymerization. Specifically, an additive such as an episulfide compound and a polymerization catalyst is added, and this mixed solution is degassed if necessary, and then poured into a mold and thermally polymerized.

In the lens resin of the present invention, it is important that the episulfide group present in the resin is 0.3% by mass or less, and the episulfide group present in the resin is 0.3% by mass or less.
The content of not more than mass% can be achieved, for example, by taking the following measures and controlling the polymerizability and the polymerization conditions. Depending on the type of episulfide compound used, the type of additives, resin modifiers, etc., the type and amount of curing catalyst used,
Optimize the polymerization conditions. The curing catalyst to be used may be a combination of two or more types of catalysts having different activities. During the polymerization, the curing catalyst should be set so as to prevent the polymerization reaction from running out of control and suddenly occurring, or conversely heating to prevent the polymerization from proceeding. Determine the type and amount of use. As the polymerization conditions, the curing temperature is gradually raised in the range of 30 ° C. to 100 ° C., and finally cured at a temperature of 80 ° C. or higher. 6
The temperature is raised in the range of 21 hours to 21 hours. Impurities and high molecular weight compounds that affect the polymerizability contained in the episulfide compound used are reduced and removed. In the resin obtained by these measures, the episulfide group present in the resin is 0.3% by mass or less, and good results are obtained.

Further, in the lens using the cured resin of the present invention, improvements such as antireflection, high hardness impartation, abrasion resistance improvement, chemical resistance improvement, antifogging property impartation, or fashionability impartment, etc. are carried out as required. Therefore, a physical or chemical treatment such as surface polishing, antistatic treatment, hard coating treatment, anti-reflection coating treatment, dyeing treatment and the like can be performed. or,
The obtained resin molded body may be subjected to a treatment such as annealing if necessary.

The episulfide type lens of the present invention thus obtained is colorless and transparent, has excellent optical and mechanical properties, and is suitable as a material for optical elements such as spectacle lenses and camera lenses.

[0046]

EXAMPLES The present invention will be specifically described below with reference to examples. The number of remaining functional groups of the obtained resin, evaluation of releasability, and heat resistance were evaluated by the following test methods. -Amount of episulfide group in resin: The lens is cut to a thickness of about 1 mm, and the surface is ground to a thickness of 0.2 mm or less with a paper file. An episulfide group was quantified from the absorbance of the prepared sample using an infrared spectrophotometer and calculated.

Releasing property evaluation method: After completion of the polymerization, the composition was cooled to room temperature and naturally released, and ◯ was given, and when cold water was used for release, Δ was given.

Heat resistance: Tg temperature was measured by the TMA penetration method (load 50 g, needle tip 0.5 mmφ, temperature rising rate 10 ° C./min).

Example 1 100 g of bis (2,3-epithiopropyl) disulfide as an episulfide compound and 20 mg of N, N-dimethylcyclohexylamine as a curing catalyst.
Further, 10 g of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a resin modifier was mixed and dissolved. This monomer mixture was degassed at a vacuum degree of 667 Pa for 0.5 hour, and then poured into a molding mold composed of a glass mold and a gasket.
The mold containing this monomer mixture was allowed to stand at 30 ° C. for 10 hours, then gradually heated to 30 ° C. to 80 ° C. and polymerized in 21 hours. After the polymerization was completed, the mold was gradually cooled to room temperature, and spontaneously released from the mold to obtain a lens. For the resin obtained at the same time, the episulfide group existing in the resin was examined, and as a result,
And the heat resistance was 78.0 ° C. The evaluation of the obtained resin is shown in Table 1.

Example 2 100 g of bis (2,3-epithiopropyl) disulfide as an episulfide compound and 20 mg of N, N-dimethylcyclohexylamine as a curing catalyst.
Further, 10 g of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a resin modifier was mixed and dissolved. This monomer mixture was degassed at a vacuum degree of 667 Pa for 0.5 hour, and then poured into a molding mold composed of a glass mold and a gasket.
The mold containing this monomer mixture was allowed to stand at 30 ° C. for 10 hours, then gradually heated to 30 ° C. to 80 ° C. and polymerized in 21 hours. After the polymerization was completed, the mold was gradually cooled to room temperature, and spontaneously released from the mold to obtain a lens. At the same time, the obtained resin was heat-treated at 120 ° C. for 3 hours. As a result, the episulfide group present in the resin was below the detection limit (0.2% by mass or less), and a lens having high heat resistance was obtained. The evaluation of the obtained resin is shown in Table 1.

Example 3 4,8-Dimercaptomethyl-1,1 as a resin modifier
1-dimercapto-3,6,9-trithiaundecane 1
The same operation as in Example 1 was carried out except that 5 g of benzylamine was used instead of 0 g. Table 1 shows the releasability, the amount of episulfide groups present in the resin, and the heat resistance.

Example 4 As a curing catalyst, 20 mg of N, N-dimethylcyclohexylamine and 10 mg of N-methyldicyclohexylamine were used.
The same operation as in Example 1 was performed except that 0 mg was used. Releasability and the amount of episulfide groups present in the resin,
The heat resistance is shown in Table 1.

Comparative Example 1 100 g of bis (2,3-epithiopropyl) disulfide as an episulfide compound and 20 mg of N, N-dimethylcyclohexylamine as a curing catalyst.
Further, 10 g of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a resin modifier was mixed and dissolved. This monomer mixture was degassed at a vacuum degree of 667 Pa for 0.5 hour, and then poured into a molding mold composed of a glass mold and a gasket.
A mold containing this monomer mixture was placed at 25 ° C for 48 hours.
Polymerization took place in time. After the completion of the polymerization, the mixture was gradually cooled to room temperature, but it was not released by itself, but was released by cooling with cold water. Regarding the resins obtained at the same time, the amount of episulfide groups present in the resin was examined, and the result was 4.0% by mass and the heat resistance was 47.0 ° C. The evaluation of the obtained resin is shown in Table 1.

Comparative Example 2 After maintaining the polymerization conditions at 30 ° C. for 10 hours, 30 ° C. to 60 ° C.
The same operation as in Comparative Example 1 was performed except that the temperature was gradually raised to 0 ° C. and the polymerization was performed for 12 hours. After the completion of the polymerization, the mold was gradually cooled to room temperature, but the mold was not released. Therefore, the mold was released using cold water. For the resins obtained at the same time, the amount of episulfide groups present in the resin and the heat resistance were examined, and the results are shown in Table 1.

Comparative Example 3 The same operation as in Comparative Example 1 was carried out except that the polymerization conditions were gradually raised from 30 ° C. to 100 ° C. and the polymerization was carried out for 5 hours. . After the completion of the polymerization, the mold was gradually cooled to room temperature, but the mold was not released. Therefore, the mold was released using cold water. For the resins obtained at the same time, the amount of episulfide groups present in the resin and the heat resistance were examined, and the results are shown in Table 1.

[0056]

[Table 1]

[0057]

EFFECTS OF THE INVENTION According to the present invention, a lens having excellent releasability and high heat resistance can be obtained by reducing the content of episulfide groups in the resin to 0.3% by mass or less.

As a result, it is possible to prevent the lens from being damaged or deformed at the time of releasing the lens during the manufacture of the lens, which leads to an improvement in the productivity of the lens.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Chitose Shimakawa             30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Chemicals             Within the corporation (72) Inventor Nobuo Kawato             30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Chemicals             Within the corporation (72) Inventor Seiichi Kobayashi             30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Chemicals             Within the corporation (72) Inventor Yoshinobu Kanamura             30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Chemicals             Within the corporation F-term (reference) 4J030 BA03 BA04 BA31 BB67 BC02                       BC14 BC15 BC17 BC25 BC34                       BC37 BC38 BF07 BG25

Claims (11)

[Claims] 1. A compound represented by the following formula (1) in one molecule: (In the formula, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ² , R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. In an episulfide-based lens resin obtained by casting polymerization of a polymerizable composition containing an episulfide compound having one or more structures represented by the formula (3), the episulfide group present in the obtained resin is 0.3% by mass. The following resin is a resin for lenses. 2. The following formula (1) in one molecule: (In the formula, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ² , R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. In an episulfide-based lens resin obtained by casting polymerization of a polymerizable composition containing an episulfide compound having one or more structures represented by the formula (1), at least one of the following conditions (provided that the combination with The resin for lenses is characterized in that the episulfide group present in the resin obtained by the polymerization is 0.3% by mass or less. Two or more curing catalysts having different activities are used in combination. Curing is performed by gradually raising the temperature in the range of 30 to 100 ° C. and finally curing at a temperature of 80 ° C. or higher, at which time the temperature is raised in the range of 6 to 21 hours. Impurities and high molecular weight compounds contained in the episulfide compound used that affect the polymerizability are reduced and removed. 3. The resin for a lens according to claim 2, which is polymerized under the above conditions. 4. The resin for lenses according to claim 3, wherein a tertiary amine is used as a curing catalyst, and a thiol compound or a monofunctional primary amine is used as a resin modifier. 5. The lens resin according to claim 1, wherein the episulfide compound is represented by the following formula (2). [Chemical 3] (In the formula, R ^{5 to} R ¹⁰ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Y represents a substituent or an unsubstituted linear, branched or cyclic hydrocarbon having 1 to 10 carbon atoms. Represents a group, a substituted or unsubstituted 1,4-dithiane group, and an arylene group, m represents an integer of 0 to 2, and n represents 0 to 4
Represents the integer. ) 6. The lens resin according to claim 5, wherein the episulfide compound is represented by the following formula (3). [Chemical 4] (In the formula, R ^{11 to} R ¹⁶ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.) 7. A compound represented by the following formula (1) in one molecule: (In the formula, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ² , R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. In the method for producing an episulfide-based lens obtained by casting polymerization of a polymerizable composition containing an episulfide compound having one or more structures represented by the formula (1), at least one of the following conditions (provided that The method for producing a lens is characterized in that the episulfide groups present in the obtained resin are 0.3 mass% or less by polymerization (excluding combination). Two or more curing catalysts having different activities are used in combination. Curing is performed by gradually raising the temperature in the range of 30 to 100 ° C. and finally curing at a temperature of 80 ° C. or higher, at which time the temperature is raised in the range of 6 to 21 hours. Impurities and high molecular weight compounds contained in the episulfide compound used that affect the polymerizability are reduced and removed. 8. The method for producing a lens according to claim 7, wherein the polymerization is performed under the above conditions. 9. The method for producing a lens according to claim 8, wherein a tertiary amine is used as a curing catalyst, and a thiol compound or a monofunctional primary amine is used as a resin modifier. 10. The episulfide compound has the following formula (2):
The method for manufacturing a lens according to any one of claims 7 to 9, represented by: [Chemical 6] (In the formula, R ^{5 to} R ¹⁰ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Y represents a substituent or an unsubstituted linear, branched or cyclic hydrocarbon having 1 to 10 carbon atoms. Represents a group, a substituted or unsubstituted 1,4-dithiane group, and an arylene group, m represents an integer of 0 to 2, and n represents 0 to 4
Represents the integer. ) 11. An episulfide compound is represented by the following formula (3):
11. The method for manufacturing the lens according to 10 represented by. [Chemical 7] (In the formula, R ^{11 to} R ¹⁶ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.)