JP2615182C - - Google Patents

Description

The present invention relates to a method for manufacturing a high refractive index optical element and a high refractive index plastic lens, and a method for manufacturing the same.
The resulting optical element and plastic lens, especially with polythiol
Contains sulfur-containing aliphatic polyisocyanate excluding modified adduct of sulfur and sulfur atom
No polyol, no hydroxyl group, and sulfur atom other than mercapto group
Containing no polythiol and no hydroxy group and having no more than a mercapto group
Casting polymerization by adding an internal release agent to a mixture with an active hydrogen compound selected from the group consisting of polythiols containing at least one sulfur atom outside
Method for producing high-refractive-index plastic lens, and obtained by the method
Related to plastic lenses. Plastic lenses are lighter and harder to break than inorganic lenses, and can be dyed.
In recent years, optical elements such as spectacle lenses, camera lenses, prisms, optical waveguides, etc.
It is becoming popular. [Prior art] Diethylene glycol bis (allyl carbonate) is used as a material for these lenses.
G) (hereinafter referred to as DAC) by radical polymerization. These resins are
Excellent impact resistance, light weight, excellent dyeability, machinability
And various characteristics such as good workability such as polishing. However, the lens obtained from the DAC has a refractive index of an inorganic lens (n _D = 1.
52) _D = 1.50, which is equivalent to that of a glass lens.
To achieve this, it is necessary to increase the center thickness, edge thickness, and curvature of the lens.
Inevitably become thicker. For this reason, lens resins with a higher refractive index
Is desired. Further, as one of the lens resins giving a high refractive index, an isocyanate compound is used.
Reaction with a hydroxy compound such as diethylene glycol (JP-A-57-136)
601) or containing a halogen atom such as tetrabromobisphenol A
Reaction with hydroxy compounds (JP-A-58-164615), diphenylsulfur
Reaction with a hydroxy compound containing a fido skeleton (JP-A-60-194401)
Plastic lenses made of polyurethane resin obtained by
You. Further, the present inventors have developed isocyanate resin as a resin for high refractive index plastic lenses.
Reaction of a sulfur compound with a hydroxy compound containing a sulfur atom (JP-A-60-217)
229) and a reaction with a polythiol compound (JP-A-60-199016,
Japanese Patent Application Laid-Open No. Sho 62-267316).
The tic lens was proposed earlier. However, although the lenses made of these known resins have a higher refractive index than lenses using a DAC, they are still insufficient or need to be improved in refractive index.
Because a compound with many halogen atoms or aromatic rings in the molecule is used
Disadvantages such as large dispersion, poor weather resistance, or high specific gravity
. In addition, in the production of these plastic lenses,
As an example of using an internal release agent to improve mold release, butyl phosphate is added to DAC.
There is a known method of adding such a material, but usually there is no necessity, and the appearance of the molded product is impaired.
Therefore, no internal mold release agent is actively used (Seiichi Mima, Polymer Die
Jest, 3, 39 (1984)). On the other hand, polyurethane, thiocarbamic acid S-alkyl ester-based lenses, etc.
When molding a urethane-based plastic lens, separate the lens from the mold after polymerization.
The mold is difficult. Therefore, the present inventors, as a method of improving the releasability, an external release agent
(Japanese Patent Application Laid-Open No. 62-267316) or a polyolefin resin mold
The method used (JP-A-62-236818) was previously proposed. [Problems to be Solved by the Invention] However, in the above-described method, these polyurethane plastic lenses are injected.
In mold polymerization, the method for improving mold release is still insufficient. That is, in the method using the external release agent, the surface treatment substance on the inner surface of the mold is
Because it partially migrates to the surface or inside of the polymerized lens, unevenness may occur on the lens surface,
There are problems such as clouding of the lens, and when using the mold repeatedly,
However, each time a mold release process is required, an industrial manufacturing method is cumbersome.
In addition, the productivity of the lens is reduced, which is extremely uneconomical. On the other hand, in the method using a polyolefin resin mold, the resin
The surface of the molded lens has poor surface accuracy due to deformation of the
It proved difficult to use in the required fields. [Means for Solving the Problems] The present inventors have proposed a sulfur-containing aliphatic polyol excluding a modified adduct with polythiol.
A mixture of a socyanate and an active hydrogen compound having two or more functional groups
By adding a mold release agent, high surface accuracy and excellent weather resistance can be achieved using a commonly used glass mold without performing special mold release treatment on the mold surface.
That it is possible to produce highly efficient plastic lenses industrially very efficiently.
And completed the present invention. That is, the present invention provides one or two types excluding modified adducts with polythiols.
Above sulfur-containing aliphatic polyisocyanate and polyol containing no sulfur atom
, A polymer having no hydroxyl group and containing no sulfur atom other than the mercapto group
Having no thiol or hydroxy group and at least one other than a mercapto group
An active hydrogen compound selected from the group consisting of polythiols containing one sulfur atom
High refractive index plus, characterized by adding an internal release agent to the mixture of
Tic lens manufacturing method, and plastic lens obtained by the manufacturing method
About. The most important feature of the present invention is that it is not conventionally used due to the physical properties of the lens.
Preferable internal mold release agent for polyurethane plastic lens production
The point is to use it aggressively. And surprisingly, it uses an internal release agent
With high transparency, optical homogeneity and surface accuracy required for lenses
It was for the first time found that lenses could be manufactured industrially. In this regard, the present invention
Is a pioneer in the field of manufacturing polyurethane-based plastic lenses
It must be called a wonderful invention. Sulfur except adduct modified with polythiol used as a raw material in the present invention
Examples of the aliphatic polyisocyanate containing thiodiethyl diisocyanate
Thiodipropyl diisocyanate, thiodihexyl diisocyanate,
Tylsulfone diisocyanate, dithiodimethyl diisocyanate, dithiodi
Acyclic sulfur-containing fats such as ethyl diisocyanate and dithiodipropyl diisocyanate
Aliphatic isocyanate, bis [(4-isocyanatomethyl) phenyl] sulfy
Aliphatic sulfur-containing isocyanate containing an aromatic ring such as 1,4-dithiane-2,5-di
Cyclic sulfur-containing aliphatic isocyanates such as isocyanates, and aliphatics containing heterocycles
And sulfur-containing isocyanates. In addition, halogen-substituted compounds such as chlorine-substituted products and bromine-substituted products,
These buret formation reaction products, adduct reaction products with trimethylolpropane, dimerization or trimerization reaction products, and the like can also be used. These may be used alone or in combination of two or more.
. The active hydrogen compound used as a raw material is a polyol containing no sulfur atom.
, A polymer having no hydroxyl group and containing no sulfur atom other than the mercapto group
Thiol, does not have a hydroxy group, and at least one other than a mercapto group
A polythiol containing a sulfur atom is exemplified. Examples of the polyol containing no sulfur atom include ethylene glycol and diol.
Ethylene glycol, propylene glycol, dipropylene glycol, butylene
Glycol, neopentyl glycol, glycerin, trimethylolethane,
Trimethylolpropane, butanetriol, 1,2-methylglucoside,
Antaerythritol, dipentaerythritol, tripentaerythritol,
Rubitol, erythritol, threitol, ribitol, arabinitol,
Silitol, Allitol, Manitol, Dorsitol, Iditol, Glyco
, Inositol, Hexanetriol, Triglycerose, Diglyperol,
Triethylene glycol, polyethylene glycol, tris (2-hydroxy
Tyl) isocyanurate, cyclobutanediol, cyclopentanediol,
Cyclohexanediol, cycloheptanediol, cyclooctanediol,
Clohexanedimethanol, hydroxypropylcyclohexanol, tricycl
B [5, 2, 1, 0 ^2.6 Decane-dimethanol, bicyclo [4,3,0] -no
Nandiol, dicyclohexanediol, tricyclo [5,3,1,1] dode
Candiol, bicyclo [4,3,0] nonane dimethanol, tricyclo [5,
3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3
, 1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexane
Xanediol, 1,1'-bicyclohexylidenediol, cyclohexanet
Riol, maltitol, lactitol, dihydroxynaphthalene, trihydro
Xinaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benze
Triol, biphenyltetraol, pyrogallol, (hydroxynaphthyl
) Pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2-hydroxyethoxy) benzene,
Bisphenol A-bis- (2-hydroxyethyl ether), tetrabromobi
Sphenol A, tetrabromobisphenol A-bis- (2-hydroxyethyl
Polyol), dibromoneopentyl glycol, epoxy resin, etc.
Oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexyl
Sancarboxylic acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid
Acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-bromoglycol
Luic acid, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid
A condensation reaction product of the above polyol with an organic polybasic acid such as bromophthalic acid,
The polyol and alkylene oxide such as ethylene oxide and propylene oxide
Addition reaction product with the side, alkylene polyamine and ethylene oxide,
Addition reaction products with alkylene oxides such as propylene oxide;
It is. Furthermore, even when a halogen-substituted product such as a chlorine-substituted product or a bromine-substituted product is used,
Good. Polyyl containing no hydroxy group and containing no sulfur atom other than mercapto group
Examples of the thiol include methanedithiol, 1,2-ethanedithiol,
1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol
Thiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2
, 3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cy
Clohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3
, 4-Dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2
, 3-dithiol, bicyclo [2,2,1] pepto-exo-cis-2,3-
Dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid
Bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-
Mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-
Mercaptoacetate), 2,3-dimercapto-1-propanol (3-mer
Captopropionate), diethylene glycol bis (2-mercaptoacetate)
G), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropylmethyl
Ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol
, Bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mer
Captoacetate), ethylene glycol bis (3-mercaptopropionate)
), Trimethylolpropane tris (2-mercaptoacetate), trimethylo
Propane tris (3-mercaptopropionate), pentaerythritol
Tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (
Aliphatic polythiols such as 3-mercaptopropionate) and chlorination thereof
Halogen-substituted compound such as a substituted or brominated compound, 1,2-dimercaptobenzene,
3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (me
Rucaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,
4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene
Benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercapto
Triethyl) benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1
1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercapto
Methyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene
Then, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (meth
Rucaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1
1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1
, 2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (merca
1,3,5-tris (mercaptomethyl) benzene, 1
, 2,3-Tris (mercaptoethyl) benzene, 1,2,4-tris (Merka
(Ptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1
, 2,3-Tris (mercaptomethyleneoxy) benzene, 1,2,4-tris
(Mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethy
Lenoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) ben
Zen, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5
-Tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramer
Captobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (Merka
(Ptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) ben
Zen, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3
, 4-Tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis
(Mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl
B) benzene, 1,2,3,4-tetrakis (mercaptomethyleneoxy) ben
Then, 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-te
Trakis (mercaptoethyleneoxy) benzene, 2,2'-dimercaptobif
Phenyl, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzi
2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naph
Talendithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithio
, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-diene
Thiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-ant
Helixenedimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,
2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenyl
Methane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane
Aromatic polythiols such as 2,5-dichlorobenzene-1,3-dithio-
1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4
, 5-Tribromo-1,2-dimercaptobenzene, 2,3,4,6-tetrac
Chloro-1, bromine substitution etc. of lor-1,5-bis (mercaptomethyl) benzene
Halogen-substituted aromatic polythiols, 2-methylamino-4,6-dithio-
Le-sym-triazine, 2-ethylamino-4,6-dithiol-sym-to
Liazine, 2-amino-4,6-dithiol-sym-triazine, 2-morpho
Reno-4,6-dithiol-sym-triazine, 2-cyclohexylamino-
4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol
-Sym-triazine, 2-phenoxy-4,6-dithiol-sym-tria
Gin, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-4,6-dithiol-sym-triazine
Polythiols containing heterocycles such as, and their chlorine-substituted and bromine-substituted products
And halogen-substituted compounds. Having no hydroxy group and at least one sulfur atom other than the mercapto group
As a polythiol containing, for example, 1,2-bis (mercaptomethylthio)
E) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis
(Mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene
Benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mer
Captoethylthio) benzene, 1,2,3-tris (mercaptomethylthio)
Benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-
Tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoe
Tylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene,
1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetra
Lakis (mercaptomethylthio) benzene, 1,2,3,5-tetrakis (mer
Captomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethyl
Thio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benze
1,2,3,5-tetrakis (mercaptoethylthio) benzene,
4,5-tetrakis (mercaptoethylthio) benzene and the like,
Aromatic polythiols such as killed products, bis (mercaptomethyl) sulfide, bis
(Mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide,
Bis (mercaptoethylthio) methane, bis (2-mercaptoethylthio) methane
, Bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethyl
Ruthio) ethane, 1,2-bis (mercaptoethylthio) ethane, 1,2-bis
(Mercaptopropylthio) ethane, 1,3-bis (mercaptomethylthio) p
Lopan, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (
3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethy
Ruthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane
, 1,2,3-tris (3-mercaptoethylthio) propane, tetrakis (me
Rucaptomethylthio) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl)
Methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimerca
1,4-dithiane, bis (mercaptomethyl) disulfide, bis (meth
(Lucaptoethyl) disulfide, bis (mercaptopropyl) disulfide, etc.
Esters of thioglycolic acid and mercaptopropionic acid;
Xymethyl sulfide bis (2-mercaptoacetate), hydroxymethyls
Rulfidobis (3-mercaptopropionate), hydroxyethyl sulfide
Bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-meth
Rucaptopropionate), hydroxypropyl sulfide bis (2-mercap
Triacetate), hydroxypropyl sulfide bis (3-mercaptopropio)
Nate), hydroxymethyl disulfide bis (2-mercaptoacetate),
Hydroxymethyl disulfide bis (3-mercaptopropionate), hydro
Xyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl
Disulfide bis (3-mercaptopropionate), hydroxypropyldis
Rulfidobis (2-mercaptoacetate), hydroxypropyl disulfide
Bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (
2-mercaptoacetate), 2-mercaptoethyl ether bis (3-merca
Tolpropionate), 1,4-dithiane-2,5-diolbis (2-merca
Butacetate), 1,4-dithiane-2,5-diolbis (3-mercapto
Propionate), thioglycolic acid bis (2-mercaptoethyl ester),
Bis (2-mercaptoethyl ester) thiodipropionate, 4,4-thiodib
Bis (2-mercaptoethyl ester), bis (2) dithiodiglycolate
-Mercaptoethyl ester), bis (2-mercaptoate) dithiodipropionate
Butyl ester), bis (2-mercaptoethyl ester) 4,4-dithiodibutylate
), Bis (2,3-dimercaptopropyl ester) thiodiglycolate,
Bis (2,3-dimercaptopropyl ester) odipropionate, dithiodig
Bis (2,3-dimercaptopropyl ester) recholate, dithiodipropio
Aliphatic polythiols such as bis (2,3-dimercaptopropyl ester) acid,
Heterocyclic compounds such as 3,4-thiophenedithiol, bismthiol, and 2,5-dimercapto-1,3,4-thiadiazole are exemplified. Furthermore,
A halogen-substituted product such as a chlorine-substituted product or a bromine-substituted product may be used. These active hydrogen compounds may be used alone or in combination of two or more.
They may be used in combination. The usage ratio of these polyisocyanates and active hydrogen compounds is NCO / (
SH + OH) (functional group molar ratio) is usually in the range of 0.5 to 3.0, preferably 0.1 to 3.0.
It is in the range of 5 to 1.5. The polyurethane-based plastic lens of the present invention comprises a urethane resin or a thiocarbamate.
It is made from a S-alkyl mate resin, and isocyanate group and
Urethane bond by hydroxy group or isocyanate group and mercapto group
Thiocarbamic acid S-alkyl ester bond, but depending on the purpose
In addition to the above two types of bonds, allohanate bonds, urea bonds, biuret bonds,
Even if it is contained, of course, it does not matter. For example, a urethane bond or a thiocarbamic acid S-alkyl ester bond
In addition, it is preferable to further increase the crosslink density by reacting an isocyanate group.
Often gives results. In this case, the reaction temperature is increased to at least 100 ° C or higher.
Combs and uses a lot of isocyanate components. Alternatively, some amines are used together
However, urea bonding and biuret bonding can also be used. The hydroxy compound reacting with the isocyanate compound,
When using compounds other than capto compounds, it is necessary to pay particular attention to coloring.
You. In addition, depending on the purpose, as in the known molding method, a chain extender, a crosslinking agent,
Add various substances such as stabilizer, UV absorber, antioxidant, oil-soluble dye, filler, etc.
Is also good. In order to adjust to the desired reaction rate, polyurethane, S-alkaline thiocarbamate
A known reaction catalyst used in the production of a kill ester can be appropriately added.
Wear. The plastic lens of the present invention is usually obtained by cast polymerization. In particular
A mixture of a sulfur-containing aliphatic polyisocyanate excluding an adduct modified product with polythiol, an active hydrogen compound, and an internal release agent is injected into a mold and polymerized.
. The internal release agent used in the present invention is, for example, a fluorine-based nonionic surfactant
, Silicon-based nonionic surfactant, alkyl quaternary ammonium salt, acidic phosphoric acid
Esters, liquid paraffin, wax, higher fatty acids and their metal salts, higher fatty acids
Esters, higher fatty alcohols, bisamides, polysiloxanes, fatty acids
Min ethylene oxide adducts and the like, among these, monomer combinations,
It is appropriately selected from polymerization conditions, economy, and ease of handling. These internal release agents may be used alone or as a mixture of two or more.
You may. Fluorinated nonionic surfactants and silicones used as internal release agents in the present invention.
Recon-based nonionic surfactants have a perfluoroalkyl group or dimethyl
Has a hydroxyalkyl group or a phosphate group.
And the former fluorine-based nonionic surfactant is Unidyne DS
-401 (manufactured by Daikin Industries, Ltd.), Unidyne DS-403 (daikin industry)
Co., Ltd.), F-top EF122A (Shin-Akita Chemical Co., Ltd.), F-top
EF126 (manufactured by Shin-Akita Chemical Co., Ltd.), F-Top EF301 (manufactured by Shin-Akita Chemical Co., Ltd.)
Manufactured by Dow Chemical Co., Ltd.)
There is Q2-120A, which is a prototype of the product. Also, an alkyl quaternary ammonium salt used as an internal mold release agent in the present invention
Are commonly known as cationic surfactants, and alkyl quaternary
Ammonium halides, phosphates, sulfates, etc.
Trimethyl cetyl ammonium chloride, trimethyl stearyl ammonium
Ium chloride, dimethylethylcetylammonium chloride, triethyl
Dodecyl ammonium chloride, trioctyl methyl ammonium chloride
And diethylcyclohexyldecyl ammonium chloride. The acidic phosphate used as the internal mold release agent in the present invention is
Propyl acid phosphate, diisopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, octyl acid phosphate,
Dioctyl acid phosphate, isodecyl acid phosphate, diisodecyl
Acid phosphate, tridecyl acid phosphate, bis (tridecyl acid phosphate)
C) phosphate, JP-506 (Johoku Chemical Co., Ltd.) and the like. In the present invention, the metal salt of a higher fatty acid used as an internal mold release agent is stearyl.
Acid, oleic acid, octanoic acid, lauric acid, behenic acid, ricinoleic acid, etc.
Zinc salt, calcium salt, magnesium salt, nickel salt, copper salt, etc.
Are zinc stearate, zinc oleate, zinc palmitate, zinc laurate,
Calcium thearate, calcium oleate, calcium palmitate, lau
Calcium phosphate, magnesium stearate, magnesium oleate, lau
Magnesium phosphate, magnesium palmitate, nickel stearate, ole
Nickel inmate, nickel palmitate, nickel laurate, copper stearate
, Copper oleate, copper laurate, copper palmitate and the like. The higher fatty acid ester used as the internal mold release agent in the present invention is, for example,
High-grade fats such as stearic acid, oleic acid, octanoic acid, lauric acid, ricinoleic acid
Fatty acid and ethylene glycol, dihydroxypropane, dihydroxybutane, neo
Esters with alcohols such as pentyl glycol and dihydroxyhexane
. The amount of the internal mold release agent used may be one or a mixture of two or more types.
Is usually in the range of 0.1 to 10,000 ppm based on the total weight of the product, preferably
Ranges from 1 to 5,000 ppm. The lower limit of the range of the addition amount is determined as the minimum amount for the release ability to be exhibited.
The limit is that if the amount is extremely high, the glass or metal mold
It is not preferable because mold release occurs and the lens easily becomes cloudy.
These phenomena largely depend on the type, type of monomer, combination and polymerization conditions.
To be right, 10,000 ppm is not limiting. The polymerization temperature and time vary depending on the type of monomer and additives such as a release agent.
Normally at -20 ° C to 200 ° C, preferably at room temperature to 150 ° C, suitably at 50 to 120 ° C
0.5-72 hours. The polymerized lens may be annealed as needed. The plastic lens of the present invention obtained in this way has high surface accuracy and excellent
Optical properties, light weight, excellent impact resistance, spectacle lenses, camera lenses, prisms
It is suitable for use as an optical element material such as an optical waveguide. Further, the plastic lens of the present invention may have anti-reflection, high hardness,
Improvement of abrasion, chemical resistance, anti-fog, or fashion
Surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment,
Physical or chemical treatment such as dyeing treatment and light control treatment can be performed. EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, the obtained ren
Resin, and lens performance tests, refractive index, Abbe number, weather resistance, mold release,
The appearance was measured by the following test method. Refractive index, Abbe number: Measured at 20 ° C. using a Pulfrich refractometer. Weather resistance: Weather meter equipped with sunshine carbon arc lamp
After 200 hours, the lens is taken out and the lens before the test is taken out.
And the hue were compared. The evaluation criteria were no change (○), slight yellowing (△), and yellowing (x). Releasability: After polymerization, drive a Teflon wedge between lens and mold.
The mold released without any resistance (○), and the mold that was not completely or partially released (×
). Appearance: Observed visually. Example 1 18.4 g (0.09 mol) of dithiodiethyl diisocyanate and 1,2,6-
Hexanetriol 8.0 g (0.06 mol) and isopropyl acid phosphate
And 0.03 g of the glass mold, and in a mold consisting of a glass mold and a gasket
Injected. Next, the temperature was gradually raised from room temperature to 120 ° C., and heat curing was performed in 28 hours.
. After polymerization, the lens is easily released, and the obtained lens is colorless and transparent and has good surface accuracy. Examples 2 to 29 In the same manner as in Example 1, a lens was formed with the composition shown in Table 1. Table 1 shows the results of the performance test.
Shown in Comparative Examples 1 to 24 A lens was formed with the composition shown in Table 2 in the same manner as in Example 1 except for the following mold treatment.
Was. Table 2 shows the results. No treatment: Glass mold used, no release agent used External release treatment: The inner surface of the glass mold was external release agent YSR manufactured by Toshiba Silicone Co., Ltd.
Reuse of external release treatment applied and baked in -6209: After external release treatment, and once used for polymerization,
Use PP mold as it is: Create a mold by injection molding of polypropylene,
Used in place of smold. As is clear from the above results, the production of polyurethane plastic lenses was
Or use a mold release agent when using a glass or metal lens mold
In the method, the lens did not release from the matrix after polymerization. Also uses an external release agent
The method of doing is that when the surface accuracy is impaired or when the master mold is repeatedly used,
Each time, it is necessary to remove the old release agent from the matrix and to treat the new release agent.
It was not suitable as a typical production method. Also, replace the glass or metal lens mold with a polypropylene lens mold.
In the method using, the lens is released without using a release agent,
The required surface accuracy has been impaired. The present invention provides an internal mold release that has previously been deprecated for use in manufacturing lenses.
Demand for polyurethane plastic lenses as lenses
It discloses for the first time that it can be manufactured industrially without impairing its performance.
You. [Effect of the Invention] The polyurethane-based plastic obtained by using the casting polymerization method of the present invention.
Cleanse is easy to release from the glass lens mold and obtains the lens.
Has high transparency, optical homogeneity, and good surface accuracy. The casting polymerization method of the present invention provides a polyurethane-based plastic resin having excellent performance.
This is a method of industrially obtaining a glass.

Claims (1)

[Claims] 1. Aliphatic polyisocyanate containing one or more sulfur atoms, excluding adduct modified products with polythiol, and polyol containing no sulfur atom, having no hydroxy group, and containing no sulfur atom other than mercapto group An internal mold release agent is added to a mixture with one or more active hydrogen compounds selected from the group consisting of polythiols and polythiols having no hydroxy group and containing at least one sulfur atom other than the mercapto group. A high-refractive-index optical element, which is subjected to cast polymerization. 2. An optical element obtained by the manufacturing method according to claim 1. 3. Aliphatic polyisocyanate containing one or more sulfur atoms, excluding adduct modified products with polythiol, and polyol containing no sulfur atom, having no hydroxy group, and containing no sulfur atom other than mercapto group An internal mold release agent is added to a mixture with one or more active hydrogen compounds selected from the group consisting of polythiols and polythiols having no hydroxy group and containing at least one sulfur atom other than the mercapto group. A method for producing a high-refractive-index plastic lens, characterized by performing cast polymerization. 4. A plastic lens obtained by the method according to claim 3.