JP3084028B2 - Polysulfide resin and lens made of the resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polysulfide-based resin having a high refractive index, extremely low dispersion, and having extremely low sulfur odor during handling and post-processing of a monomer. Lens.

[Conventional technology]

Plastic lenses are lighter and harder to break than inorganic lenses, and are easier to dye. Therefore, plastic lenses have been rapidly spread in optical devices such as spectacle lenses and camera lenses in recent years.

Currently widely used resins for these purposes include diethylene glycol bis (allyl carbonate)
(Hereinafter referred to as DAC) by radical polymerization. This resin has various features, such as being excellent in impact resistance, being lightweight, being excellent in dyeability, being excellent in workability such as cutting property and polishing property. I have. However, the refractive index is an inorganic lens (n _D = 1.52)
N _D = 1.50 compared to, it is necessary to increase the center thickness, edge thickness and curvature of the lens in order to obtain optical properties equivalent to a glass lens, and it is possible to avoid overall wall thickness Absent.

As a resin for a lens which gives a high refractive index, a lens composed of a polyvalent allyl compound, a polyvalent acrylic compound and a polyfunctional thiol (JP-A-59-87123, JP-A-59-193924, JP-A-63-23403)
2) has been proposed.

[Problems to be solved by the invention]

The above-mentioned lens made of resin for a lens that provides a high refractive index has a higher refractive index than a lens using a DAC, but is still insufficient in refractive index, and in order to improve the refractive index, naphthalene is included in the molecule. It has disadvantages such as large dispersion and poor weather resistance due to having an aromatic ring such as a ring. Furthermore, many of the polyfunctional polythiols used in these resins have a strong sulfur odor, and have a problem of giving a worker an unpleasant sensation when handling the monomer or during post-processing.

[Means for solving the problem]

In view of such a situation, the present inventors have further studied and found that a polyfunctional thiol represented by the formula (I) And a resin obtained by reacting the mercapto compound with a compound having two or more reactive unsaturations in one molecule, and a lens comprising the resin. It has been found that the above-mentioned problems have been solved, and that it has excellent optical properties.

That is, the present invention provides a compound of the formula (I) Which is obtained by reacting 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane represented by the following formula with a compound having two or more reactive unsaturated bonds in one molecule. Is a unit represented by the formula (II), And a unit represented by the formula (III) (Wherein, R ₁ represents a residue derived from a compound having a reactive unsaturated bond, R ₂ represents a hydrogen atom or a residue derived from a compound having a reactive unsaturated bond, R ₃ represents a hydrogen atom, methyl Group, an ethyl group, a chloromethyl group, or a bromomethyl group, and n represents an integer of 2 or more). Is obtained by mixing 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and a compound having two or more reactive unsaturated bonds in one molecule and polymerizing and curing the mixture. A method for producing a polysulfide resin for optical use, and 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane represented by the formula (I), and two or more per molecule. Is a polysulfide resin lens obtained by mixing and polymerizing and curing a compound having a reactive unsaturated bond.

Examples of the compound having two or more reactive unsaturated bonds in one molecule used in the present invention include a total of two or more acryloyl groups, methacryloyl groups, vinyl groups, allyl ether groups, allyl carbonate groups in one molecule, It is a compound having an arylidene group or the like. They are broadly classified into acetal compounds, phenol and bisphenol compounds, isocyanuric acid derivatives, triazine compounds, other polyhydric alcohols and polythiol derivatives, and other compounds. Hereinafter, these will be described specifically.

Acetal Compound The acetal compound used in the present invention is (unsaturated dioxane type) And / or (unsaturated dioxolane type) Is an unsaturated cycloacetal compound having at least two unsaturated cycloacetal groups in one molecule.

Examples of these acetal compounds include the following compounds (i) to (v).

(I) Diarylidenepentaerythritol, triarylidenesorbitol, dialylidene-2,2,6,6-tetramethylolcyclohexanone or a mixture thereof.

(Ii) (a) dialylidenepentaerythritol and / or dialylidene-2,2,6,6-tetramethylolcyclohexanone and (b) ethylene glycol, diethyl glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,6-hexanediol, polyethylene glycol, hydrogenated bisphenol A, bisphenol A-ethylene oxide adduct, bisphenol A-propylene oxide adduct, trimethylolpropane, trimethylolethane, pentaerythritol, diphenyl Ethylene oxide adducts of pentaerythritol, phthalic acid, isophthalic acid and terephthalic acid, polyols such as polyesters having a terminal hydroxyl group having a molecular weight of 1500 or less, (c) dithioglycol, dipentene dimercap Per molecule such as tan, ethylcyclohexyldimercaptan, polythiol such as 1,6-hexanedimercaptan, thioglycolic acid, β-mercaptopropionic acid, or an ester compound obtained by reacting mercaptosuccinic acid with the above polyol. A compound containing a total of two or more hydroxyl groups and / or mercapto groups, (d) phenols such as novolak, bisphenol F and bisphenol A obtained by phenol, cresol and their formalin condensation, (e) benzenesulfonamide, o- Toluenesulfonamide, p-toluenesulfonamide,
Arylsulfonamides such as chlorobenzenesulfonamide, or (f) reaction products with mixtures thereof.

(Iii) monoarylidenetrimethylolpropane and / or monoarylidenetrimethylolethane and tolylene diisocyanate, polyalkylene allyl isocyanate, metaphenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate,
Reaction products with isocyanate compounds such as isophorone diisocyanate.

(Iv) monoarylidenetrimethylolpropane and / or monoarylidenetrimethylolethane and succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid Addition half esterified with anhydride.

(V) monoarylidenetrimethylolpropane and / or addition half-esterified product of monoarylidenetrimethylolethane and carboxylic anhydride, and polyhydric glycidyl ether type epoxy compound, phthalic acid, adipic acid, dimer acid, etc. A compound obtained by reacting with an epoxy compound such as a glycidyl ester type epoxy compound.

Phenol and bisphenol compounds The phenol and bisphenol compounds used in the present invention are phenols and bisphenols having at least two acryloyl groups, methacryloyl groups, allyl ether groups and allyl carbonate groups in one molecule. Examples of those used for (1) are those represented by the formula (IV).

(R ₄ n ₁ XR ₅ ) n ₂ (IV) wherein n ₁ and n ₂ are integers of 1 to 4, X is a structure represented by the formulas (1) to (6), and R ₄ and R ₅ Are each independently (16)
It has the structure shown by the formula.

Here, Y in the formula (1) has a structure represented by the formulas (7) to (15).

(In the formula (16), R ₆ and R _{7 each} represent a hydrogen atom, a methyl group, an ethyl group, a chloromethyl group, or a bromomethyl group;
The integer of 5, p and q are 0 or 1. The isocyanuric acid derivative used in the present invention is an isocyanuric acid derivative having at least two acryloyl groups, methacryloyl groups, allyl ether groups, and allyl carbonate groups in one molecule. It is an isocyanuric acid derivative obtained by reacting isocyanuric acid with acrylic acid, methacrylic acid, allyl chloroformate, allyl alcohol, allyl halide, glycidyl acrylate, and glycidyl methacrylate. Examples of the polyhydric alcohol include the following.

1) A polyhydric alcohol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to isocyanuric acid.

2) adding epichlorohydrin to isocyanuric acid,
A polyhydric alcohol obtained by reacting a polyhydric alcohol with an epoxy compound obtained by dehydrochlorination.

3) Polyhydric alcohol obtained by methylating the reaction product of isocyanuric acid and acrylamide.

Representative examples include tris (2-acryloyloxyethyl) isocyanurate, tris (2-methacryloyloxyethyl) isocyanurate, bis (2-acryloyloxyethyl) -2-hydroxyethyl isocyanurate, and bis (2-methacryloyloxy). Ethyl) -2-hydroxyethyl isocyanurate, bis (2-acryloyloxyethyl) -2-acetoxyethyl isocyanurate, bis (2-methacryloyloxyethyl) acetoxyethyl isocyanurate, bis (2-acryloyloxyethyl) allyl isocyanurate And bis (2-methacryloyloxyethyl) allyl isocyanurate, triallyl isocyanurate and the like.

Triazine-based compound The triazine-based compound used in the present invention is a triazine-based compound having at least two acryloyl groups, methacryloyl groups, allyl ether groups, and allyl carbonate groups in one molecule, and represented by the formula (V) Or compounds obtained by oligomerizing these via formaldehyde, polyhydric alcohol, ethylene oxide, or the like.

(V) In the formula, X ¹ , Y ¹ , and Z are hydrogen, an alkyl group, or an alkoxyl group modified with (meth) acryl or Is shown.

(However, R ₈ and R ₉ are hydrogen, methyl group, ethyl group, aliphatic alkyl group such as propyl group, aromatic alkyl group such as benzyl group, or (In the formula, R ₁₀ and R ₁₁ represent a hydrogen atom, a methyl group, an ethyl group, a chloromethyl group, or a bromomethyl group, r is an integer of 0 to 5, and s, t, and u are 0 or 1.) Show. Typical examples of this triazine compound include (1) N, N'-bis (meth) acryloylmethyl-N,
N ', N ", N" -tetrakismethoxymethylmelamine, N,
N, N ', N "-tetrakis (meth) acryloylmethyl-
N ', N "-bisethoxymethylmelamine, (2) N, N, N', N ', N", N "-hexakis (2- (meth) acryloylethoxymethyl) melamine, (3) 2,4- Bis [N, N-bis [(2- (meth) acryloylethoxy) ethoxymethyl]] amino-6-ethoxy-1,3,5-triazine; (4) 2,4-bis [p- (2- ( (Meth) acryloylethoxy) phenyloxy] -6-[[N, N-bis [(2
-(Meth) acryloylethoxy) ethoxymethyl]]
Amino] -1,3,5-triazine, (5) 2,2-bis [4-[[N, N ', N "-trismethoxymethyl-N', N"-(2- (meth) acryloylethoxy ) Methyl] melamineloxy] phenyl] propane.

The polyhydric alcohol used for the oligomerization includes ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,6-hexanediol, hydrogenated bisphenol A, trimethylolpropane, pentaerythritol, phthalic acid, and isophthalic acid. And ethylene oxide adducts of acid and terephthalic acid.

Other polyhydric alcohols and polyhydric thiol derivatives The polyhydric alcohol derivatives other than those described above used in the present invention include: 1) ethylene glycol, trimethylolpropane,
Aliphatic polyhydric alcohols such as pentaerythritol, propylene glycol, glycerin, sorbitol, neopentyl glycol, dichloroneopentyl glycol, dibromoneopentyl glycol, and dipentaerythritol;

2) [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, bis (2-hydroxyethyl) sulfide, 1,2-bis (2-hydroxyethylmercapto)
Ethane, bis (2-hydroxyethyl) disulfide,
1,4-dithiane-2,5-diol, bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiobutal) methane, 4,4′-thiobis (6-t
ert-butyl-3-methylphenol), 1,3-bis (2
Sulfuric acid-containing polyhydric alcohols such as -hydroxyethylthioethyl) cyclohexane and polyhydric alcohols to which alkylene oxides such as ethylene oxide and propylene oxide are added, and acrylic acid, methacrylic acid, allyl chloroformate, allyl alcohol, halogenated Allyl, glycidyl acrylate, and glycidyl methacrylate are reacted.

The polyvalent thiol derivative used in the present invention is a polythiol, a polythiol having at least one sulfur atom other than a mercapto group, a compound having a hydroxyl group and a mercapto group, a compound having a hydroxyl group and at least one other than a mercapto group. Compounds having two sulfur atoms, such as methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 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, 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol ( 3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3
-Dimercaptopropyl methyl ether, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropanebis (2-mercaptoacetate), tri Methylolpropanebis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3
Aliphatic mercaptopropionate) and their halogen-substituted compounds such as chlorine-substituted and bromine-substituted compounds, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene , 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl)
Benzene, 1,2-bis (mercaptoethyl) benzene,
1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4- Bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3- Trimercaptobenzene,
1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene,
1,3,5-tris (mercaptoethyl) benzene, 1,2,3-
Tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2 1,4-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) benzene, 1,2,4-tris (mercaptoethyleneoxy) ) Benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetra Mercaptobenzene, 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 (mercaptomethyl) benzene, 1,2,
3,5-tetrakis (mercaptomethyl) benzene, 1,2,
4,5-tetrakis (mercaptomethyl) benzene, 1,2,
3,4-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3, 4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptoethyleneoxy) benzene, 2,5
-Toluene dithiol, 3,4--Toluene dithiol, 2,4
-Dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol , 1,3-diphenylpropane-2,
2-dithiol, phenylmethane-1,1-dithiol, 2,
Aromatic polythiols such as 4-di (p-mercaptophenyl) pentane, and 2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2
-Chlorine-substituted products such as dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, and 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene; Halogen-substituted aromatic polythiols also 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,
Methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-4, Polythiols containing a heterocycle such as 6-dithiol-sym-triazine, and halogen-substituted compounds such as chlorine-substituted and bromine-substituted products thereof, as bifunctional or more polythiols containing at least one sulfur atom in addition to a mercapto group Is, for example, 1,2
-Bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5 -Tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5-tetrakis (mercaptomethylthio) benzene, 1,2,4,5
-Tetrakis (mercaptoethylthio) benzene, 1,2,
3,4-tetrakis (mercaptoethylthio) benzene,
Aromatic polythiols such as 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, and alkylated nuclei thereof, bis (mercaptomethyl) Sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercapto) Methylthio) 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 (merca (Ptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (3-mercapto) Propylthiomethyl) methane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide,
Bis (mercaptopropyl) disulfide and the like and esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis ( 2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2- Mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2
-Mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2-mercaptoacetate), hydroxypropyldisulfidebis (3-mercaptopropionate), 2-mercaptoethyletherbis (2 -Mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diolbis (2-mercaptoacetate), 1,4-dithiane-2,5-diolbis ( 3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4
Bis (2-mercaptoethyl ester) thiodibutylate, bis (2-mercaptoethyl ester) dithiodiacrylate, bis (2-mercaptoethyl ester) dithiodipropionate, bis (2-mercaptoethyl 4,4-dithiodibutylate) Ethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester) , Bis (2,3) dithiodipropionate
-Dimercaptopropyl ester), heterocyclic compounds such as 3,4-thiophenedithiol, bismuthiol, and 2,5-dimercapto-1,3,4-thiadiazole. Further, halogen-substituted products such as a chlorine-substituted product and a bromine-substituted product thereof.

Examples of the mercapto compound having a hydroxy group include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, and 2,4-dimercapto. Phenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4
-Dimercapto-2-propanol, 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-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3-mercaptopropionate). Further, halogen-substituted products such as chlorine-substituted and bromine-substituted products thereof.

Examples of the mercapto compound having a hydroxy group and containing at least one sulfur atom in addition to the mercapto group include, for example, hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-
3-mercaptoethylthiobenzene, 4-hydroxy-
4'-mercaptodiphenylsulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethylsulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulcylate), hydroxyethylthiomethyl-tris (mercaptoethylthiomethyl) )
Methane and the like. Further, halogen-substituted products such as a chlorine-substituted product and a bromine-substituted product thereof.

Such as polyvalent thiols and ethylene oxide,
It is obtained by reacting a polyhydric alcohol to which an alkylene oxide such as propylene oxide is added, with acrylic acid, methacrylic acid, allyl chloroformate, allyl alcohol, allyl halide, glycidyl acrylate, and glycidyl methacrylate.

Other Compounds Other compounds include: 1) allyl esters, methallyl esters of polycarboxylic acids such as diallyl phthalate, diallyl succinate, thiodiacetic acid, dithiodiacetic acid, thiodipropionic acid, dithiodipropionic acid, and malic acid; ) Vinyl compounds such as divinylbenzene and divinyl adipate; 3) reaction products of polyisocyanates with allyl alcohol such as isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate and MDI; 4) polyolefin compounds such as dicyclopentadiene and dibutene. No.

The above compounds having two or more reactive unsaturated bonds in one molecule may be used alone or as a mixture of two or more.

The ratio of the mercapto compound represented by the formula (I) and the compound having two or more reactive unsaturated bonds in one molecule may be such that the molar ratio of unsaturated bond / SH (functional group) is usually in the range of 0.5 to 3.0. , Preferably in the range of 0.5 to 1.5.

The resin of the present invention can be obtained by heating the monomer mixture or irradiating ultraviolet rays. At that time, a thermal polymerization initiator or a photopolymerization initiator may be used.

When performing thermal polymerization, benzoyl peroxide, diisopropylperoxydicarbonate, azobisisobutyronitrile, azodicyclohexanecarbonitrile, tert-butylperoxy-2-ethylhexanoate, azobismethylvaleronitrile or these A general radical polymerization initiator such as a mixture of the above can be used.

In the case of ultraviolet curing, generally known benzoyl, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, 2-hydroxy-2-benzoyl-
Photosensitizers such as propane, benzyl, thioxanthone, diphenyl disulfide and the like can be used.

These polymerization initiators are generally
The upper limit is about 10% by weight.

The polysulfide resin of the present invention is usually obtained by a cast polymerization method. Specifically, a compound having two or more reactive unsaturated bonds in one molecule and a mercapto compound represented by the formula (I) are mixed. At that time, if necessary, the above-mentioned polymerization initiator, ultraviolet absorber, antioxidant, oil-soluble dye, filler and the like are added, and the mixture is injected into a mold and polymerized.

The polysulfide-based resin of the present invention obtained in this way has no discomfort due to sulfur odor during handling of the monomer or discomfort due to sulfur odor during post-processing, and has not only a high refractive index in physical properties, but also an extremely high refractive index. It has low dispersion, low moisture absorption and is colorless and transparent, and has features of light weight, excellent weather resistance, excellent impact resistance, and optical element materials such as spectacle lenses and camera lenses,
Suitable as a glazing material.

Further, the lens of the present invention can be produced by a casting polymerization method using the polysulfide resin of the present invention as a material, and if necessary, antireflection, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting antifogging property are provided. Alternatively, in order to improve the fashionability or the like, physical and chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment, and light control treatment can be performed.

[Examples and Comparative Examples]

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, the performance of the obtained lens was evaluated by the following test methods.

Refractive index, Abbe number: 20 ° C using a Pulfrich refractometer
Was measured.

Weather resistance: The lens resin was set in a weatherometer equipped with a sunshine carbon arc lamp, and after 20 hours, the lens was taken out and compared with the hue of the lens resin before the test.

The evaluation criteria were no change (○), slight yellowing (△),
Yellowing (x).

 Appearance: Observed visually.

Odor: Those with a strong sulfur odor at the time of mixing the monomer were rated as (x), those with almost no sulfur odor (○), and those with a little were (△).

Example 1 25 g of triallyl isocyanurate and 1,2-bis [(2-
Mercaptoethyl) thio] -3-mercaptopropane 26
g, add 0.5 g of azobisisobutyronitrile,
It was poured into a mold consisting of a glass mold and a gasket, and then cured by heating. The resin thus obtained was colorless and transparent, had excellent impact resistance, and had a refractive index n _D = 1.63 and an Abbe number ν _D = 40. Further, there was no sulfur odor at the time of handling the monomer and at the time of post-processing.

Examples-2 to 8, Comparative Examples-1 to 3 Resinification was performed using the composition shown in Table 1 in the same manner as in Example 1, and the results are shown in Table 1.

Claims (3)

(57) [Claims] (1) Formula (I) Which is obtained by reacting 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane represented by the following formula with a compound having two or more reactive unsaturated bonds in one molecule. Is a unit represented by the formula (II), And a unit represented by the formula (III) (Wherein, R ₁ represents a residue derived from a compound having a reactive unsaturated bond, R ₂ represents a hydrogen atom or a residue derived from a compound having a reactive unsaturated bond, R ₃ represents a hydrogen atom, methyl Group, an ethyl group, a chloromethyl group, or a bromomethyl group, and n represents an integer of 2 or more). 2. Formula (I) Is obtained by mixing 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and a compound having two or more reactive unsaturated bonds in one molecule and polymerizing and curing the mixture. A method for producing an optical polysulfide resin. 3. Formula (I) 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and a compound having two or more reactive unsaturated bonds in one molecule are mixed and polymerized and cured. Polysulfide resin lens.