JP2007051301A - Lens with improved mold-releasability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin for a lens, having high heat resistance, capable of preventing breakage or deformation at mold release of the lens, and providing improved productivity of the lens when producing the episulfide lens using an episulfide compound as a raw material. <P>SOLUTION: The polymerization is carried out so that the content of the episulfide group present in the obtained lens may be ≤0.3 mass% in the production of the episulfide lens obtained by casting and polymerizing a polymerizable composition containing a compound having two or more episulfide groups in the molecule. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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 in particular, a lens suitably used as a resin for a plastic lens for spectacles and its production. Regarding the method.

Since plastic lenses are lighter and harder to break than inorganic lenses and can be dyed,
It is rapidly spreading to optical materials such as eyeglass lenses and camera lenses.

The optical performance that is continuously required for these plastic lenses is a high refractive index, a 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 with current high refractive index plastic lenses. Currently, resins widely used for these purposes include those obtained by radical polymerization of diethylene glycol bis (allyl carbonate) (hereinafter referred to as DAC). This resin has various features such as excellent impact resistance, light weight, excellent dyeability, and good workability such as machinability and abrasiveness. . However, this resin has a refractive index nd as low as 1.50, and the center thickness and edge thickness of the lens are increased, so that a lens resin having a higher refractive index has been desired.

D. A. As those having a refractive index higher than that of C resin, polyurethane resin (Japanese Patent Publication No. 4-58489 etc.), sulfur-containing O- (meth) acrylate resin (Japanese Patent Laid-Open No. Hei 4-161410 etc.) introduced with sulfur atoms in the resin, A thio (meth) acrylate resin (Japanese Patent Publication No. 3-59060) is known. Polyurethane resin is a resin with an excellent balance such as high refractive index and good impact resistance.

However, with respect to the refractive index and the Abbe number, it is very difficult to improve both at the same time because of the contradictory physical properties that the Abbe number decreases as the refractive index increases.
In view of this, studies have been actively conducted to increase the refractive index while suppressing the decrease in the Abbe number.

Among these examinations, the most typical proposals are Patent Document 1 (Japanese Patent Laid-Open No. 9-110579), Patent Document 2 (Japanese Patent Laid-Open No. 9-71580), and Patent Document 3 (Japanese Patent Laid-Open No. 9-2557).
81), Patent Document 4 (Japanese Patent Laid-Open No. 10-298878), and Patent Document 5 (Japanese Patent Laid-Open No. 11-166037). The present applicants also disclosed Patent Document 6 (WO89 / 10575), Patent Document 7 (JP-A-11-140070), Patent Document 8 (JP-A-11-183702), Patent Document 9 (JP-A-11-1).
No. 89592) and Patent Document 10 (Japanese Patent Laid-Open No. 11-322930) have proposed a resin for a high refractive index lens using an episulfide compound.

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 groups remaining in the resin, and the effects of the episulfide groups present in the resin on various physical properties have not been clarified. Therefore, it was important to define the amount of episulfide groups present in the resin.
Japanese Patent Laid-Open No. 9-110979 JP-A-9-71580 Japanese Patent Laid-Open No. 9-255781 JP-A-10-298878 Japanese Patent Laid-Open No. 11-166037 WO89 / 10575 Japanese Patent Laid-Open No. 11-140070 Japanese Patent Laid-Open No. 11-183702 Japanese Patent Laid-Open No. 11-189592 JP 11-322930 A

An object of the present invention is to provide a lens resin having stable physical properties and quality in an episulfide lens resin using an episulfide compound as a raw material.

In view of such a situation, the present inventors have intensively studied to solve the above problems,
Due to the influence of the episulfide group present in the resin, the heat resistance of the resin is reduced, or the release property from the glass mold at the time of release is deteriorated, and the quality of the obtained lens resin is blurred,
It discovered that productivity might fall and it came to this invention.

  That is, the present invention provides the following formula (1):

(In the formula, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ and R ⁴ are each 1 to 10 carbon atoms.
10 hydrocarbon groups or hydrogen atoms are shown. In the production of an episulfide-based lens obtained by cast polymerization of a polymerizable composition containing an episulfide compound having one or more of the structures shown by (1), the episulfide group present in the resulting resin is 0. The present invention relates to a method for producing a lens, wherein the polymerization is carried out so as to be 3% by mass or less, and a lens resin obtained by the method.

(B): The manufacturing method and lens resin of the lens of (A) whose episulfide compound is represented by following formula (2).

(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 substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. Represents a substituted or unsubstituted 1,4-dithiane group or an arylene group, m represents an integer of 0 to 2, and n represents
Represents an integer of 0 to 4; )

(C): The episulfide compound relates to a method for producing the lens of (A) represented by the following formula (3) and a lens resin.

(In the formula, R ^{11 to} R ¹⁶ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.)

In the present invention, the fact 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 later, and the molecular weight of the episulfide group portion (59/1 mole). The mass of the episulfide group portion in the resin is calculated by multiplying by and divided by the mass of the resin.

According to the present invention, by making the episulfide group present in the resin 0.3 mass% or less,
A lens having excellent releasability and high heat resistance can be obtained.

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

  The present invention is described in detail below.

The lens resin according to the present invention has an episulfide group present in the resin of 0.3% by mass or less, whereby a lens having excellent heat resistance and good releasability can be obtained. Conversely, if the episulfide group present in the resin exceeds 0.3% by mass, the heat resistance of the resin is reduced,
In some cases, the releasability at the time of releasing may be deteriorated, or the lens may be damaged or deformed at the time of releasing.

Specific examples of the episulfide resin used as a raw material in the present invention include bis (β
-Epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (
β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,2-bis (β-epithiopropylthio) propane, 1,3-bis (β-epithiopropyl) Thio) propane, 1,3-bis (β-epithiopropylthio) -2-methylpropane, 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-epithiopropylthiomethyl) -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, 1,1
1-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-epithio) Chain aliphatic β-epithiopropylthio compounds such as propylthiomethyl) -3,6,9-trithiaundecane, 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,
Cycloaliphatic β-epithiopropylthio compounds such as 2,5-bis [{2- (β-epithiopropylthio) ethyl} thiomethyl] -1,4-dithiane, 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 {
Aromatic β such as 4- (β-epithiopropylthio) phenyl} sulfide, bis {4- (β-epithiopropylthio) phenyl} sulfone, 4,4′-bis (β-epithiopropylthio) biphenyl -Epithiopropylthio compounds and the like, 3-mercaptopropylene sulfide, 4-mercaptobutene sulfide and the like, and mercapto group-containing epithio compounds can be exemplified, but are not limited to these exemplified compounds. These compounds may be used alone or in combination of two or more.

The polymerizable composition of the present invention lacks not only a mixture of these episulfide resins, but also other polysulfide oligomers such as dimers, trimers and tetramers of these resins, and epihalohydrin in the synthesis of episulfide resins. Episulfide resins having a mercapto group to be generated in the case of the above, and further, inorganic acids and organic acids, solvents,
Organic compounds such as unreacted raw materials and other by-products, impurities, and inorganic compounds may be included as long as they do not cause a problem.

When a lens is obtained by the method of the present invention, polymerization can be carried out by heating or standing at room temperature in the presence or absence of a curing catalyst, and a lens can be produced, but when there is no curing catalyst, the polymerization proceeds well. May cause poor polymerization or may not polymerize. 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 examples of 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-di-n-butylethanolamine, N, N-dimethylbenzylamine, diethylbenzylamine N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine,
N, N-dimethylaniline, β-picoline, piperidine, 2,2′-bipyridyl, dicyandiamide, hexamethylenetetramine, 1,8-diazabicyclo (5,4,0) -7-
Undecene etc. are mentioned. Examples of phosphines include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,2 -Bis (dimethylphosphino) ethane etc. are mentioned. Lewis acids include dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, tetrachlorotin, dibutyltin oxide, zinc chloride, acetylacetone zinc, aluminum chloride, aluminum fluoride, triphenylaluminum, tetrachlorotitanium, calcium acetate, etc. Can be mentioned. 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-butylperoxybenzoate and the like. As the cationic polymerization catalyst, diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, triphenylsulfonium hexafluoroarsenic acid, etc. Can be mentioned It is not limited only to these exemplary compounds. These may be used alone or in admixture of two or more.

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

Preferable examples of combinations of tertiary amines having different catalytic activities are not limited in general depending on the type of episulfide compound used or the type of resin modifier, but N, N-dimethylcyclohexylamine and N-methyldicyclohexyl Examples thereof include a combination of amine, N, N-dimethylcyclohexylamine and N, N-diisopropylethylamine, N, N-diethylethanolamine and N-methyldicyclohexylamine.

The addition amount of the curing catalyst is 0.001 with respect to the total weight of the composition comprising the episulfide resin.
It is used in the range of 10 to 10% by mass, preferably in the range of 0.01 to 5% by mass. If the addition amount of the curing catalyst is less than 0.001% by mass, polymerization failure may be caused. On the other hand, even if it exceeds 10% by mass, the pot life is shortened, and there may be inconveniences such as a decrease in transparency, optical properties, or weather resistance.

In the lens monomer of the present invention, the resin is improved mainly for adjustment of optical physical properties such as refractive index of the lens obtained, adjustment of various physical properties such as specific gravity, adjustment of monomer viscosity, and other handling. A resin modifier can be added for the purpose.

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

Specific examples of preferred epoxy compounds as resin modifiers include phenolic epoxy compounds obtained by condensation reaction of polyphenol compounds such as bisphenol A glycidyl ether and epihalohydrin compounds, hydrogenated bisphenol A glycidyl ether, and the like. Alcohol-based epoxy compounds obtained by condensation of polyhydric alcohol compounds and epihalohydrin compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-hexahydrophthalic acid diglycidyl ester, etc. Glycidyl ester epoxy compounds obtained by condensation of polyvalent organic acid compounds and epihalohydrin compounds, amine epoxidation obtained by condensation of primary and secondary diamine compounds with epihalohydrin compounds Objects, etc. and, there may be mentioned vinyl cyclohexene diepoxide and an aliphatic polyhydric epoxy compound such as, but not limited to only these exemplified compounds. These may be used alone or in combination of two or more.

Specific examples of preferred olefins as the resin modifier include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl 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 Lenglycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, Bisphenol A
Dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2
-Bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxy)
Propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,
1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis ( 4-methacryloxydiethoxyphenyl) methane, dimethyloltricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol Tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, key (Meth) acrylate compounds such as lylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate , Styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, vinyl compounds such as 3,9-divinylspirobi (m-dioxane), and diisopropenylbenzene, but are limited to these exemplified compounds. Is not to be done. These may be used alone or in combination of two or more.

Any of the above resin modifiers can be used alone or in combination of two or more.

Specific examples of preferred amine compounds as resin modifiers include ethylamine,
n-propylamine, isopropylamine, n-butylamine, sec-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, amino Butanol, aminopentanol, aminohexanol, methoxyethylamine, 2- (2-aminoethoxy) ethanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-iso Monofunctional 1 such as butoxypropylamine, 2,2-diethoxyethylamine
Quaternary amine compounds, 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, 1,1
0-diaminodecane, 1,2-, 1,3-, or 1,4-diaminocyclohexane,
o-, m- or p-diaminobenzene, 3,4- or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenyl sulfide, 3,3′- or 4,4′-diaminodiphenylsulfone, 2,7-diaminofluorene, 1,5-, 1
, 8-, or 2,3-diaminonaphthalene, 2,3-, 2,6-, or 3,4-
Diaminopyridine, 2,4-, or 2,6-diaminotoluene, m-, or p-
Xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1,3-
1,4-diaminomethylcyclohexane, 2-, or 4-aminopiperidine, 2-, or 4-aminomethylpiperidine, 2-, or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine Primary polyamine compounds such as diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine,
Dihexylamine, dioctylamine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, Monofunctional secondary amine compounds such as N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N-ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine, N, N'-dimethylethylenediamine, N, N'- Dimethyl-1,
2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N,
N′-dimethyl-1,4-diaminobutane, N, N′-dimethyl-1,5-diaminopentane, N, N′-dimethyl-1,6-diaminohexane, N, N′-dimethyl-1,7 −
Diaminoheptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2
-Diaminopropane, N, N'-diethyl-1,3-diaminopropane, N, N'-diethyl-1,2-diaminobutane, N, N'-diethyl-1,3-diaminobutane, N, N
'-Diethyl-1,4-diaminobutane, N, N'-diethyl-1,5-diaminopentane, N, N'-diethyl-1,6-diaminohexane, N, N'-diethyl-1,7- Diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2
, 6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane,
1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane,
, 4-di- (4-piperidyl) butane, secondary polyamine compounds such as tetramethylguanidine, and the like, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more. Of these exemplified compounds, more preferred are benzylamine and piperazines.

Specific examples of preferred 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-mercaptopropionate) ), Diethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (2-mercaptoglycolate), pentaerythritol tetrakis (2-mercaptothioglycolate), pentaerythritol tetrakis (3-mercaptopropionate)
, Trimethylolpropane tris (2-mercaptothioglycolate), trimethylolpropane tris3-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-1,11-dimercapto-3,6
, 9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3
Aliphatic thiols such as 1,6,9-trithiaundecane, and benzyl mercaptan, thiophenol, 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, Aromatic thiols such as 4-trimercaptobenzene and 1,2,5-trimercaptobenzene Including but not limited to these exemplified compounds. These may be used alone or in combination of two or more.

Specific examples of preferred polyphenols include those having one or more phenolic hydroxyl groups in the aromatic ring, and monophenols include 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, Examples of the polyphenol include catechol, 3-chlorocatechol, resorcin, hydroquinone, chlorohydroquinone, pyrogallol, and fluoroglucin, but are not limited to these exemplified compounds. .
These polyphenol compounds may be used alone or in admixture of two or more.

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

Specific examples of preferred organic acids and anhydrides include thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride , Methylnorbornenoic anhydride, methylnalbornanoic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride and the like, 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, various known additives such as internal mold release agents, light stabilizers, UV absorbers, antioxidants, dyes, fillers, etc. are added within a range where there is no problem depending on the purpose. Also good.

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 deaerated as necessary, and then injected into a mold and polymerized by heating.

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. In order to make the episulfide group present in the resin 0.3% by mass or less, For example, this can be achieved by taking the following measures and managing the polymerizability and polymerization conditions.

(A) Depending on the type of episulfide compound used, additives, resin modifiers, etc.
Optimize the type and amount of curing catalyst, polymerization conditions, etc. 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 will avoid the polymerization reaction from going out of control and suddenly occurring, or conversely heating to prevent the polymerization from proceeding. Determine the type and amount of use.

(B) 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. The temperature is raised in the range of 6 hours to 21 hours.

(C) Reduce or remove impurities, high molecular weight substances, and the like that affect the polymerizability contained in the episulfide compound to be used. The resin obtained by these measures has an episulfide group present in the resin of 0.3% by mass or less, and good results are obtained.

Furthermore, in the lens using the cured resin of the present invention, if necessary, antireflection, imparting high hardness,
In order to improve wear resistance, chemical resistance, antifogging, or fashion, etc., physical or surface polishing, antistatic treatment, hard coat treatment, anti-reflective coating treatment, dyeing treatment, etc. Chemical treatment can be applied. Moreover, about the obtained resin molding, you may perform processes, such as annealing, as needed.

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

Hereinafter, the present invention will be specifically described by way of examples. In addition, the number of residual functional groups, release property evaluation, and heat resistance of the obtained resin were evaluated by the following test methods.

-Amount of episulfide group in the resin: The lens is cut to a thickness of about 1 mm, and the surface is polished to a thickness of 0.2 mm or less with a paper file. The episulfide group was quantified and calculated from the absorbance of the prepared sample using an infrared spectrophotometer.

-Releasability evaluation method: after polymerization was completed, the product was cooled to room temperature and naturally released, and the product released using cold water was evaluated as Δ.

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

Example 1
As an episulfide compound, bis (2,3-epithiopropyl) disulfide is 10
0 g is mixed with 20 mg of N, N-dimethylcyclohexylamine as a curing catalyst and 10 g of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a resin modifier. Dissolved. This monomer mixture was reduced to 0 at a vacuum of 667 Pa.
. After degassing for 5 hours, it was poured into a molding mold consisting of a glass mold and a gasket. The mold containing the monomer mixture was allowed to stand at 30 ° C. for 10 hours and then kept at 30 ° C. to 80 ° C.
The temperature was gradually raised to ° C. and polymerization was carried out in 21 hours. After completion of the polymerization, the mold was gradually cooled to room temperature, and then released spontaneously to obtain a lens. As a result of examining the episulfide group present in the resin for the resin obtained at the same time, it was 0.22% by mass, and the heat resistance was 78.
It was 0 ° C. The evaluation of the obtained resin is shown in Table 1.

Example 2
As an episulfide compound, bis (2,3-epithiopropyl) disulfide is 10
0 g is mixed with 20 mg of N, N-dimethylcyclohexylamine as a curing catalyst and 10 g of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a resin modifier. Dissolved. This monomer mixture was reduced to 0 at a vacuum of 667 Pa.
. After degassing for 5 hours, it was poured into a molding mold consisting of a glass mold and a gasket. The mold containing the monomer mixture was allowed to stand at 30 ° C. for 10 hours and then kept at 30 ° C. to 80 ° C.
The temperature was gradually raised to ° C. and polymerization was carried out in 21 hours. After completion of the polymerization, the mold was gradually cooled to room temperature, and then released spontaneously to obtain a lens. The resin obtained at the same
Heat treatment for hours was applied. As a result, episulfide groups present in the resin are below the detection limit (0
. 2% by mass or less), a lens having high heat resistance was obtained. The evaluation of the obtained resin is shown in Table 1.

Example 3
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9 as a resin modifier
-All the same operations as in Example 1 were carried out except that 5 g of benzylamine was used instead of 10 g of trithiaundecane. Table 1 shows the releasability, the amount of episulfide groups present in the resin, and the heat resistance.

Example 4
The same operation as in Example 1 was performed except that 20 mg of N, N-dimethylcyclohexylamine and 100 mg of N-methyldicyclohexylamine were used as curing catalysts. Table 1 shows the releasability, the amount of episulfide groups present in the resin, and the heat resistance.

Comparative Example 1
As an episulfide compound, bis (2,3-epithiopropyl) disulfide is 10
0 g is mixed with 20 mg of N, N-dimethylcyclohexylamine as a curing catalyst and 10 g of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a resin modifier. Dissolved. This monomer mixture was reduced to 0 at a vacuum of 667 Pa.
. After degassing for 5 hours, it was poured into a molding mold consisting of a glass mold and a gasket. The mold containing the monomer mixture was polymerized at 25 ° C. for 48 hours. After polymerization is complete
Although it was gradually cooled to room temperature, it was not released naturally and released by cooling with cold water. As a result of investigating the amount of episulfide groups present in the resin, the resin obtained at the same time 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, the same operation as in Comparative Example 1 was performed except that the temperature was gradually raised to 30 ° C. to 60 ° C. and polymerization was performed in 12 hours. After the polymerization was completed, the mixture was gradually cooled to room temperature, but did not release, so the release was performed using cold water. The resin obtained simultaneously was examined for the amount of episulfide groups present in the resin and the heat resistance, and the results are shown in Table 1.

Comparative Example 3
The same operation as in Comparative Example 1 was performed except that the polymerization conditions were gradually raised from 30 ° C. to 100 ° C. and polymerization was performed in 5 hours. After the polymerization was completed, it was gradually cooled to room temperature but did not release,
Release was performed using cold water. The resin obtained simultaneously was examined for the amount of episulfide groups present in the resin and the heat resistance, and the results are shown in Table 1.

Claims (5)

The following formula (1) in one molecule

(Wherein R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ² , R ³ and R ⁴ are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom). In an episulfide-based lens obtained by cast polymerization of a polymerizable composition containing an episulfide compound having at least one compound, polymerization is performed under conditions that satisfy all of the following conditions (a), (b), and (c): Thus, the lens having improved releasability, characterized in that the episulfide group present in the obtained resin is 0.3% by mass or less.
(A) Two or more curing catalysts having different activities are used in combination.
(B) In the curing, the temperature is gradually raised in the range of 30 to 100 ° C., and finally cured at a temperature of 80 ° C. or higher, and the temperature is raised in the range of 6 to 21 hours.
(C) Impurities and high molecular weight substances affecting the polymerizability contained in the episulfide compound to be used are reduced and removed.   The lens according to claim 1, wherein a thiol compound or a monofunctional primary amine is used as a resin modifier.   The lens according to claim 1 or 2, 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. The lens according to any one of claims 1 to 3, wherein the episulfide compound is represented by the following formula (2).

(In the formula, R ^{5 to} R ¹⁰ each represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. Y represents a substituted or unsubstituted linear, branched or cyclic hydrocarbon having 1 to 10 carbon atoms. 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 an integer of 0 to 4). The lens according to claim 4, wherein the episulfide compound is represented by the following formula (3).

(In the formula, R ^{11 to} R ¹⁶ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.)