CN1020308C - Resin for plastic lens having high-refractive index, lens comprising the resin, and method for preparation of the lens - Google Patents
Resin for plastic lens having high-refractive index, lens comprising the resin, and method for preparation of the lens Download PDFInfo
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- CN1020308C CN1020308C CN 89101862 CN89101862A CN1020308C CN 1020308 C CN1020308 C CN 1020308C CN 89101862 CN89101862 CN 89101862 CN 89101862 A CN89101862 A CN 89101862A CN 1020308 C CN1020308 C CN 1020308C
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Abstract
The present invention relates to resin useful in preparing plastic lenses having a high refractive index comprising reacting an aliphatic polyisocyanate compounds having at least one sulfur atom with one or more of active hydrogen compounds selected from the group consisting of a polyol, a polythiol having sulfur atoms only in a mercapto groups, and a polythiol having at lest one sulfur atom other than in the mercapto groups: lenses containing the above mentioned resin: and a method for the preparation thereof characterized by adding an internal release agent to the mixture of the above-mentioned raw materials in casting lenses from the resin and lenses obtained by this method.
Description
The present invention relates to a kind of resin that is used to prepare high refractive index plastic lens, the method that contains the lens of this resin and prepare this lens.
In recent years, plastic lens is rapidly and more habitually as the optical element of glasses, camera and similar products, this be because plastic lens than inorganic lenses fragmentation in light weight, more difficult and easy coloring more.
People have used a kind of resin of being made through radical polymerization by two (allyl carbonate) (back abbreviates DAC as) of diglycol to prepare this class lens.The impact strength height of this resin, in light weight and show fabulous colorability and the outstanding processing characteristics of cutting and polishing.
Yet by the lens of above-mentioned resins, its refractive index (n
D=1.50) be lower than the refractive index (n of inorganic lenses
D=1.52).In order to obtain the optical property identical, need the thickness of the thickness at increase center and periphery and increase the curvature of lens with glass lens.So just make lens become very thick.For above-mentioned reasons, wish to have a kind of resin of high index of refraction.The resin that was used to prepare lens in the past and had a high index of refraction comprises the resin (United States Patent (USP) 4 by isocyanate compound and diglycol prepared in reaction, 443,588), by the resin (Japanese patent application publication No. 164 of isocyanate compound with hydroxyl compound (as tetrabromo for the bisphenol-A) prepared in reaction that contains halogen atom, 615/1983), or by isocyanate compound and the resin (Japanese patent application publication No. 194,401/1985) that contains the hydroxyl compound prepared in reaction of diphenyl sulfide skeleton.
The inventor once proposed to contain the high refractive index plastic lens of urethane resin or analog in the past, this resin can by isocyanate compound with
The reaction of compound and make (United States Patent (USP) 4,680,369 and 4,780,552), or and make (United States Patent (USP) 4,689,387) and Japanese patent application publication No. 267,316/1987 by isocyanate compound and polythiol reaction).
Contain the refractive index height of the lens of these known resin than the lens that contain DAC, not enough but such refractive index is still disliked.In order to improve refractive index, these resins are used and are contained the compound of many halogen atoms or aromatic ring, thereby make these resins have shortcomings such as high dispersive effect, against weather difference and high specific gravity.
People have known that adding a kind of inner pattern releasing agent applicable in this lens-like process of preparation can improve demolding performace.In this process, butylphosphoric acid ester is added among the DAC,, will damages the outward appearance (Seiichi Mima, " polymkeric substance digest " 1984 3.39 or the like) of moulded products if do not add.
When preparing lens, lens are taken out in mould after being difficult in polymerization with polyurethane and S-alkylthio carbamate.In order to address this problem, the inventor has invented a kind of method (Japanese patent application publication No. 236,818/1987) of using the method (Japanese patent application publication No. 296,316/1987) of external release agent and using the mould of being made by polyolefin resin.
Yet it is not enough that above-mentioned these release methods are still disliked for the release property that improves casting polymerizable lens of the present invention.
In the method for using external release agent, some biography of finish materials of handling mould inner surface moves on to the surperficial and inner of polymerizable lens, thereby causes lens surface out-of-flatness and muddiness, and mould of every usefulness will carry out demoulding processing.Therefore this method is complicated, has also reduced the throughput rate of lens simultaneously, is uneconomic.
In addition, the polyolefin resin mould is out of shape in high temperature, causes the precision of lens surface very poor.Therefore this method can not be used in the occasion that needs high surface accuracy.
The invention solves the problems of the prior art and shortcoming, proposed a kind of former resin property have been made improved resin, produce the method for this resin, the lens made from resin and surpass prior art, and the method for preparing this lens with premium properties.
An object of the present invention is to provide a kind of resin with good optical property.
Another object of the present invention provides a kind of colourless transparent resin that is applicable to lens with high index of refraction.
A further object of the present invention provides a kind of with plant-scale method of effectively and economically producing lens.
A further object of the invention provides a kind of refractive index height, surface accuracy height, excellent optical performance, plastic lens that impact strength is good, and it is in light weight, be applicable to glasses and camera.
Other purpose of the present invention and advantage will be partly by listing in the following instructions, and partly will be by apparent in the instructions or in the invention process, obtain.Objects and advantages of the present invention can realize and obtain by the measure pointed out especially in the claims and combination thereof.
Realize purpose of the present invention, carry out general description here.The method of production resin proposed by the invention comprises: one or more contain the aliphatic polyisocyanate compound of a sulphur atom at least and react with (b) one or more active hydrogen compounds with (a), and this active hydrogen compounds is selected from polyol compound, only contains the multi-thioalcohol compound of sulphur atom and the multi-thioalcohol compound that contains a sulphur atom in sulfydryl except the sulphur atom that contains again at least in sulfydryl.
The invention provides the method for a kind of usefulness resins lens of the present invention, it comprises: one or more contain the aliphatic polyisocyanate compound of a sulphur atom at least with (a), (b) (it is selected from polyol compound to one or more active hydrogen compounds, only in sulfydryl, contain sulphur atom multi-thioalcohol compound and except sulfydryl with sulphur atom contain the multi-thioalcohol compound of a sulphur atom and (c) at least a inner pattern releasing agent applicable more at least, make potpourri, and, carry out the casting polymerization and form said lens this potpourri injection mould.
Resin of the present invention has good optical property and high index of refraction, and is colourless.Plastic lens of the present invention has high surface accuracy and good against weather, and presents good impact strength and optical property, and its available common glass mold does not need any special demoulding processing and carries out the production of industrially scalable very effectively.
To be described in detail optimum implementation of the present invention below.
At least contain a sulphur atom and be applicable to that the typical aliphatic polyisocyanate compound of the inventive method comprises the non-annularity aliphatic polyisocyanate compound that contains sulphur atom, as two isocyanic acid sulfo-diethylesters, two isocyanic acid sulfo-dipropyls, two isocyanic acid sulfo-dihexyls, two isocyanic acid diformazan sulfonium esters, two isocyanic acids, two sulfo-dimethyl esters, two isocyanic acids, two sulfo-diethylesters and two isocyanic acid dithio dipropyl esters; The aliphatic isocyanate that contains a sulphur atom and an aromatic ring is as two (4-isocyanato-methyl) phenyl) thioether; The cyclic aliphatic isocyanates that contains sulphur atom, as 1,4-dithiane-2,5-diisocyanate; And the aliphatic isocyanate that contains a sulphur atom and a heterocycle.
The halogen substituted compounds of these polyisocyanates, as chlorine substituent and bromine substituent, their biuret reaction product, the addition reaction product of polyisocyanates and hydroxymethyl-propane, and the dimers of polyisocyanates and trimerization reaction product also are applicable to method of the present invention.
Polyisocyanate compound can use separately, also can two or more mix use.
The typical active hydrogen compounds that is applicable to the inventive method comprises polyol compound, only contains the multi-thioalcohol compound of sulphur atom in sulfydryl, and the sulphur in sulfydryl contains the multi-thioalcohol compound of a sulphur atom former more at least.
The typical polyol compound that is suitable for comprises polyalcohols, as ethylene glycol, and diglycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerine, trimethylolethane, trimethylolpropane, butantriol, 1,2-methyl glucoside, pentaerythrite, bipentaerythrite, tripentaerythritol, sorbierite, erythrite, threitol, ribitol, arabitol, xylitol, allitol, mannitol, how western sugar alcohol, iditol, glycol, inositol, hexanetriol, triglycerin, two glycerine, triethylene glycol, polyglycol, three (2-hydroxyethyl) isocyanuric acid ester, two butylene glycols, ring pentanediol, cyclohexanediol, the ring heptandiol, ring ethohexadiol, cyclohexanedimethanol, hydroxypropyl cyclohexanol, three rings (5,2,1,0
2.6) the decane dimethanol, two ring-(4,3,0) nonanediols, two cyclohexanediols, three rings (5,3,1,1)-and the n-dodecane glycol, two ring (4,3,0) nonane dimethanols, three ring (5,3,1,1)-n-dodecane diethanol, hydroxypropyl three ring (5,3,1,1)-n-dodecane alcohol, spiral shell (3,4) ethohexadiol, butyl cyclohexanediol, 1,1-two cyclohexylene glycol, phloroglucite, maltol (maltitol), lactonaphthol (lactitol), dihydroxy naphthlene, trihydroxynaphthalene, tetrahydroxy naphthalene, dihydroxy benzenes, the benzene triol, hexichol tetrol, pyrogallol, (hydroxyl naphthyl) pyrogallol, the trihydroxy phenanthrene, bisphenol-A, Bisphenol F, xylyleneglycol, two (2-hydroxyl-oxethyl) benzene, bisphenol-A-two-(2-hydroxyethyl ether), tetrabromo is for bisphenol-A, and tetrabromo is for bisphenol-A-two (2-hydroxyethyl ethers), two bromo dimethyltrimethylene glycol and epoxy resin; The condensation reaction products of these polyvalent alcohols and organic multicomponent acid, organic multicomponent acid comprises oxalic acid, glutamic acid, hexane diacid, acetate, propionic acid, cyclohexane-carboxylic acid, β-oxo cyclohexane propionic acid, trimer acid, phthalic acid, m-phthalic acid, salicylic acid, 3-bromo acid, 2-bromo glycollic acid, the dicarboxyl cyclohexane, 1,2,4,5-benzenetetracarboxylic acid, BTCA and bromophthalic acid; The addition reaction product of above-mentioned polyvalent alcohol and alkylene oxide, this alkylene oxide comprises oxirane and epoxypropane; The addition reaction of alkylene polyamines and alkylene oxide, this alkylene oxide comprises oxirane and epoxypropane.
The halogen substituted compound of above-mentioned polyol compound all is applicable to method of the present invention as the compound that chlorine replaces and bromine replaces.
The typical multi-thioalcohol compound that only contains sulphur atom in sulfydryl that is applicable to the inventive method comprises aliphatic polythiol class, as first two mercaptan, 1, the 2-dithioglycol, 1, the 1-dimercaptopropane, 1,2-dimercaptopropane, 1, the 3-dimercaptopropane, 2, the 2-dimercaptopropane, 1,6-ethanthiol, 1,2,3-trithioglycerin, 1,1-hexamethylene two mercaptan, 1,2-hexamethylene two mercaptan, 2,2-dimethylpropane-1,3-two mercaptan, 3,4-dimethoxy-butane-1,2-two mercaptan, 2-methylcyclohexane-2,3-two mercaptan, two ring (2,2,1) seven-extensions-suitable-2,3-two mercaptan, 1,1-pair-(mercapto methyl) cyclohexane, thiomalic acid two (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propyl alcohol (2-mercaptoacetate), 2,3-dimercapto-1-propyl alcohol (3-mercaptopropionic acid ester), diglycol two (2-mercaptoacetate), diglycol two (3-mercaptopropionic acid ester), 1,2-dimercapto propyl methyl ether, 2,3-dimercapto propyl methyl ether, 2, two (mercapto methyl)-1 of 2-, 3-dimercaptopropane, two (2-mercaptoethyl) ether, 1,2-ethylidene glycol two (2-mercaptoacetate), 1,2 ethylene glycol two (3-mercaptopropionic acid ester), trimethylolpropane two (2-mercaptoacetate), trimethylolpropane (3-mercaptopropionic acid ester), pentaerythrite four (2-mercaptoacetate) and pentaerythrite four (3-mercaptopropionic acid ester) and their halogen substituted compounds are as the compound that chlorine replaces or bromine replaces; Many thiophenols of aromatic series class, as 1,2-thioresorcin, 1, the 3-thioresorcin, 1,4-thioresorcin, 1, two (mercapto methyl) benzene of 2-, 1, two (mercapto methyl) benzene of 3-, 1, two (mercapto methyl) benzene of 4-, 1, two (mercaptoethyl) benzene of 2-, 1, two (mercaptoethyl) benzene of 3-, 1, two (mercaptoethyl) benzene of 4-, 1,2-two (the inferior methoxyl of sulfydryl) benzene, 1,3-two (the inferior methoxyl of sulfydryl) benzene, 1,4-two (the inferior methoxyl of sulfydryl) benzene, 1, two (sulfydryl ethoxy) benzene of 2-, 1, two (sulfydryl inferior ethoxyl) benzene of 3-, 1, two (sulfydryl inferior ethoxyl) benzene of 4-, 1,2,3-tri-thiol benzene, 1,2,4-tri-thiol benzene, 1,3,5-tri-thiol benzene, 1,2,3-three (mercapto methyl) benzene, 1,2,4-three (mercapto methyl) benzene, 1,3,5-three (mercapto methyl) benzene, 1,2,3-three (mercaptoethyl) benzene, 1,2,4-three (mercaptoethyl) benzene, 1,3,5-three (mercaptoethyl) benzene, 1,2,3-three (the inferior methoxyl of sulfydryl) benzene, 1,2,4-three (the inferior methoxyl of sulfydryl) benzene, 1,3,5-three (the inferior methoxyl of sulfydryl) benzene, 1,2,3-three (sulfydryl inferior ethoxyl) benzene, 1,2,4-three (sulfydryl inferior ethoxyl) benzene, 1,3,5-three (sulfydryl inferior ethoxyl) benzene, 1,2,3,4-four sulfydryl benzene, 1,2,3,5-four sulfydryl benzene, 1,2,4,5-four sulfydryl benzene, 1,2,3,4-four (mercapto methyl) benzene, 1,2,3,5-four (mercapto methyl) benzene, 1,2,4,5-four (mercapto methyl) benzene, 1,2,3,4-four (mercaptoethyl) benzene, 1,2,3,5-four (mercaptoethyl) benzene, 1,2,4,5-four (mercaptoethyl) benzene, 1,2,3,4-four (the inferior methoxyl of sulfydryl) benzene, 1,2,3,5-four (the inferior methoxyl of sulfydryl) benzene, 1,2,4,5-four (the inferior methoxyl of sulfydryl) benzene, 1,2,3,4-four (sulfydryl inferior ethoxyl) benzene, 1,2,3,5-four (sulfydryl inferior ethoxyl) benzene, 1,2,4,5-four (sulfydryl inferior ethoxyl) benzene, 2,2 '-dimercapto biphenyl, 4,4 '-dimercapto biphenyl, 4,4 '-the dimercapto bibenzyl, 2, the 5-toluene-dithiolate, 3,4-toluene-dithiolate, 1,4-naphthyl disulfide phenol, 1,5-naphthyl disulfide phenol, 2,6-naphthyl disulfide phenol, 2,7-naphthyl disulfide phenol, 2,4-dimethyl benzene-1, the 3-dithiol, 4,5-dimethyl benzene-1, the 3-dithiol, 9,10-anthracene dimethylene thiophenol, 1,3-two (right-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenyl propane-2,2-dithiol, phenylmethane-1,1-dithiol and 2, two (right-the sulfydryl phenyl) pentanes of 4-; The aromatic series thiophenol (chloro and bromo compound) that halogen replaces, as 2,5-dichlorobenzene-1,3-dithiol, 1, two (right-chlorophenyl) propane-2 of 3-, 2-dithiol, 3,4,5-three bromo-1,2-thioresorcin and 2,3,4,6-tetrachloro-1, two (mercapto methyl) benzene of 5-; The polythiol that contains heterocycle, as 2-methylamino-4,6-two mercaptan-sym-triazine, 2-ethylamino--4,6-two mercaptan-sym-triazine, 2-amino-4,6-two mercaptan-sym-triazine, 2-morpholino-4,6-two mercaptan-sym-triazine, 2-cyclohexylamino-4,6-two mercaptan-sym-triazine, 2-methoxyl-4,6-two mercaptan-sym-triazine, 2-phenoxy group-4,6-two mercaptan-sym-triazine, 2-sulfo-phenoxy group-4,6-two mercaptan-sym-triazine and 2-sulfo-butoxy-4,6-two mercaptan-sym-triazine and their halogen substituted compound are as chloro and bromo compound.
In sulfydryl, contain the typical multi-thioalcohol compound that at least also contains a sulphur atom the sulphur atom and comprise the aromatic series multi-thioalcohol compound, as 1, two (mercapto methyl sulfo-) benzene of 2-, 1, two (mercapto methyl sulfo-) benzene of 3-, 1, two (mercapto methyl sulfo-) benzene of 4-, 1, two (mercaptoethyl sulfo-) benzene of 2-, 1, two (mercaptoethyl sulfo-) benzene of 3-, 1, two (mercaptoethyl sulfo-) benzene of 4-, 1,2,3-three (mercapto methyl sulfo-) benzene, 1,2,4-three (mercapto methyl sulfo-) benzene, 1,3,5-three (mercapto methyl sulfo-) benzene, 1,2,3-three (mercaptoethyl sulfo-) benzene, 1,2,4-three (mercaptoethyl sulfo-) benzene, 1,3,5-three (mercaptoethyl sulfo-) benzene, 1,2,3,4-four (mercapto methyl sulfo-) benzene, 1,2,3,5-four (mercapto methyl sulfo-) benzene, 1,2,4,5-four (mercapto methyl sulfo-) benzene, 1,2,3,4-four (mercaptoethyl sulfo-) benzene, 1,2,3,5-four (mercaptoethyl sulfo-) benzene, 1,2,4,5-four (mercaptoethyl sulfo-) benzene and their cycloalkylation compound; The aliphatic series multi-thioalcohol compound, as two (mercapto methyl) thioether, two (mercaptoethyl) thioether, two (sulfydryl propyl group) thioether, two (mercapto methyl sulfo-) methane, two (2-mercaptoethyl sulfo-) methane, two (3-sulfydryl propyl dithiocarbamate) methane, 1, two (the 2-mercapto methyl sulfo-) ethane of 2-, 1, two (mercaptoethyl sulfo-) ethane of 2-, 1, two (the 3-sulfydryl propyl dithiocarbamate) ethane of 2-, 1, two (mercapto methyl sulfo-) propane of 3-, 1, two (the 2-mercaptoethyl sulfo-) propane of 3-, 1, two (the 3-sulfydryl propyl dithiocarbamate) propane of 3-, 1,2,3-three (mercapto methyl sulfo-) propane, 1,2,3-three (2-mercaptoethyl sulfo-) propane, 1,2,3-three (sulfydryl propyl dithiocarbamate) propane, four (mercapto methyl sulphomethyl) methane, four (2-mercaptoethyl sulphomethyl) methane, four (3-sulfydryl propyl dithiocarbamate methyl) methane, two (2,3-dimercapto propyl group) thioether, 2,5-dimercapto-1, the 4-dithiane, two (mercapto methyl) disulfide, two (mercaptoethyl) disulfide, two (sulfydryl propyl group) disulfide, and the ester of these compounds and mercaptoacetic acid or mercaptopropionic acid formation, methylol thioether two (2-mercaptoacetate), methylol thioether two (3-mercaptopropionic acid ester), hydroxyethyl thioether two (2-mercaptoacetate), hydroxyethyl thioether two (3-mercaptopropionic acid ester), hydroxypropyl thioether two (2-mercaptoacetate), hydroxypropyl thioether two (3-mercaptopropionic acid ester), methylol disulfide two (2-mercaptoacetate), methylol disulfide two (3-mercaptopropionic acid ester), hydroxyethyl disulfide two (2-mercaptoacetate), hydroxyethyl disulfide two (3-mercaptopropionic acid ester), hydroxypropyl disulfide two (2-mercaptoacetate), hydroxypropyl disulfide two (3-mercaptopropionic acid ester), 2-mercaptoethyl ether two (2-mercaptoacetate), 2-mercaptoethyl ether two (3-mercaptopropionic acid ester), 1,4-dithiane-2,5-glycol two (2-mercaptoacetate), 1,4-dithiane-2,5-glycol two (3-mercaptopropionic acid ester), thiodiglycolic acid two (2-mercaptoethyl ester), sulfurous base dipropionic acid two (2-mercaptoethyl ester), 4,4-sulfurous base two butyric acid two (2-mercaptoethyl ester), two thiodiglycolic acids two (2-mercaptoethyl ester), two sulfurous base dipropionic acids two (2-mercaptoethyl ester), 4,4-two sulfurous bases two butyric acid two (2-mercaptoethyl ester), thiodiglycolic acid two (2,3-dimercapto propyl diester), sulfurous base dipropionic acid two (2,3 ,-dimercapto propyl diester), methyl-carbithionic acid two (2,3-dimercapto propyl diester) and two propane thioic acids two (2,3-disulfide group propyl diester); Heterogeneous ring compound, as 3,4-thiophene dithiol, Bi Simo mercaptan (bismuthiol) and 2,5-dimercapto-1,3,4-thio biphosphole.
Also can use the halogen substituted compound of above-mentioned multi-thioalcohol compound, as chloro or bromo compound.These active hydrogen compounds can use separately, perhaps mix with its two or more and use.
The molar ratio of the functional group of polyisocyanates and the functional group of active hydrogen compounds, i.e. NCO/(OH+SH) be about 0.5 to about 3.0, be preferably about 0.5 to about 1.5.
In plastic lens of the present invention, use urethane resin or S-alkylthio carbamate resins as raw material.Therefore in plastic lens, produce carbamate linkage between isocyanate functional group and the hydroxyl, or and isocyanate functional group and sulfydryl between produce S-alkylthio carbamate linkage.Yet, except containing above-mentioned bonding, can also contain allophanic acid ester linkage, urea bonding, biuret bonding or similar bonding according to the final use of lens at the plastic lens under the situation of the present invention.
For example, isocyanate groups can further react with carbamate linkage or S-alkylthio carbamate linkage, thereby improves cross-linking density.In the case, temperature of reaction is decided to be 100 ℃ or higher, and used isocyanates component should be excessive.Another way is to use amine or its analog to utilize these urea bondings or biuret bonding.When reacting, the compound beyond isocyanate compound and hydroxyl compound or the sulfhydryl compound must be careful color.
The final use of lens can add multiple additives to obtain property in starting material according to the present invention.Typical case's useful additives comprises cahin extension agent, crosslinking chemical, light stabilizer, ultraviolet light absorber, antioxidant, oil-soluble dyes and filler.
For reaction rate being adjusted to needed degree of being, can add a kind of known catalysts that is generally used for making polyurethane or S-alkylthio carbamate.
Plastic lens of the present invention can prepare with the casting polymerization.One or more aliphatic isocyanate compounds that will contain sulphur atom, one or more active hydrogen compounds and at least a inner pattern releasing agent applicable mix the back and form a kind of potpourri; It is poured in the mould, carries out polymerization then.
Be used for the inner pattern releasing agent applicable that typical case of the present invention is suitable for and comprise fluorine-containing non-ionic surfactant, siliceous non-ionic surfactant, alkyl quaternary ammonium salts, acid phosphoric acid ester, whiteruss, wax, higher fatty acid and metallic salt thereof, high-grade aliphatic ester, higher aliphatic, bisamide, polysiloxane and aliphatic amine ethylene oxide adduct.Can take all factors into consideration the simplification of monomer, polymerizing condition, economy and processing and suitably select above-mentioned inner pattern releasing agent applicable.
Inner pattern releasing agent applicable can use separately or use with its two or more mixing.
The fluorine-containing non-ionic surfactant or the siliceous non-ionic surfactant that are used for inner pattern releasing agent applicable of the present invention are respectively to carry a perfluoroalkyl or a dimethylpolysiloxane--based, a hydroxyalkyl and a phosphate-based compound.Can buy the suitable fluorine-containing ionic surfactant pack of typical case from the market and draw together Unidain
TM: the product of DS-401 and DS-403(Daikinkogyo company limited), F-Top
TM: EF122A, the product of EF126 and EF301(Shinakita chemistry company limited).Typical siliceous non-ionic surfactant is the test products Q2-120A of DoW chemical company.
The alkyl quaternary amine salt that is suitable for as the typical case of inner pattern releasing agent applicable comprises cationic surfactant in the present invention, and as the alkyl quaternary amine salt, it comprises haloid, phosphate and the sulfuric ester of alkyl quaternary amine.Its typical chlorides comprises pivaloyl chlorination ammonium, trimethyl stearoyl chlorination ammonium, dimethyl ethyl cetyl chloride ammonium, triethyl dodecyl chlorination ammonium, tri-n-octyl methyl ammonium chloride and diethyl cyclohexyl cetyl chloride ammonium.
The acid phosphoesterase compound that is suitable for the typical case of inner pattern releasing agent applicable of the present invention comprises the iso propylbenzoic acid phosphate, diisopropyl acid phosphoric acid ester, butyl acid phosphoric acid ester, dibutyl acid phosphoric acid ester, octyl group acid phosphoric acid ester, dioctyl acid phosphoric acid ester, isodecyl acid phosphoric acid ester, diiso decyl acid phosphoric acid ester, three decyl alcohol acid phosphoric acid esters and two (three decyl alcohol acid) phosphate.
Exemplary high-level fatty acid metal salts as inner pattern releasing agent applicable comprises zinc salt, calcium salt, magnesium salts, nickel salt, mantoquita and other stearate, oleate, caprylate, laurate, behenic acid salt and ricinate, for example zinc stearate, zinc oleate, zinc palmitate, zinc laurate, calcium stearate, calcium oleate, calcium palmitate, calcium laurate, dolomol, magnesium oleate, Magnesium dilaurate, magnesium palmitate, nickel stearate, oleic acid nickel, palmitic acid nickel, lauric acid nickel, copper stearate, copper oleate, lauric acid copper and copper palmitate in the present invention.
Comprise the lipid of higher fatty acid (as stearic acid, oleic acid, sad, lauric acid and castor oil acid) as the exemplary high-level fatty acid ester of inner pattern releasing agent applicable in the present invention and such as alcohols such as 1,2 ethylene glycol, dihydroxypropane, dihydroxy butane, neopentyl glycol and dihydroxy-hexanes.
Inner pattern releasing agent applicable can use separately also can two or more mixing form use, its consumption is from about 0.1 to about 10,000ppm, preferably from about 1 to about 5,000ppm(is as the criterion with the general assembly (TW) of monomer mixture).
The inner pattern releasing agent applicable consumption is as being less than 0.1ppm, and stripping feature is bad, and as surpassing 10,000ppm can make lens become muddy, and eyeglass can cause the lens surface precision to worsen with mold separation in polymerization process prematurely.
When carrying out polymerization according to the type of used monomer and release agent, temperature range from approximately-20 ℃ to about 200 ℃, preferably from room temperature to about 150 ℃, better from about 50 ℃ to about 120 ℃, from 0.5 to 72 hour its reaction time.
Lens after the polymerization can be carried out patent if desired.
Plastic lens of the present invention has high surface accuracy, good optical property, and it is in light weight, impact strength is high, is applicable to make glasses and camera and so on optical element.
In addition, plastic lens of the present invention can carry out physics and chemical treatment, as surface grinding processing, antistatic treatment, hard coating is handled, and does not reflect coating and handles, painted processing and the delustring processing for preventing to reflect, strengthen hardness, improve wearing quality and chemical resistance, prevent to become muddy, can satisfy needs of pattern renewal or the like.
The following examples and Comparative Examples are further described and illustrate in order to the present invention as demonstration of the present invention.The performance test of resin and lens, particularly refractive index, Abbe number, against weather, the test of release property and outward appearance will be carried out as follows.
Refractive index and Abbe number: under 20 ℃, measure with Pulfrich refractometer.
Against weather: resin sample is placed in the weatherometer that is equipped with the daylight carbon arc lamp, after 200 hours, takes out resin sample.Then with sample with being used to make lens not after tested resin carry out color and luster relatively.The grade of using " O ", " △ " and " X " expression to be evaluated respectively is " not changing ", " yellowing a little " and " flavescence ".
Release property: when the lens after the polymerization take out in mould unimpededly, represent its release property with " 0 ", when whole or part lens can not take out in mould, with " X " expression, can squeeze into a teflon voussoir and with its taking-up this moment between lens and mould.
Outward appearance: evaluate by visual inspection.
Example 1
With 18.4 gram (0.09 mole) two sulfo-diethyl diisocyanate and 8.0 gram (0.06 moles) 1,2, the 6-hexanetriol mixes.Made potpourri is injected the mould of being made up of glass molds and sealing gasket, temperature is slowly risen to 120 ℃ from room temperature, finished polymerization through 28 hours.The gained lens are colourless, and against weather is good, refractive index η
20 DBe 1.57, Abbe number η
20 DBe 44, proportion is 1.32.
Example 2-18 and Comparative Examples 1-3
According to the program of example 1, make lens with component ratio listed in the table 1.Various The performance test results are listed in the table 1.
Example 19
With 18.4 gram (0.09 mole) two thio-ethyl diisocyanate, 8.0 gram (0.06 mole) 1,2,6-hexanetriol and 0.03 gram iso propylbenzoic acid phosphate mix, the potpourri that makes is injected the mould of being made up of glass molds and sealing gasket, be warming up to 120 ℃ gradually from room temperature, finished polymerization through 28 hours.Be easy to after the polymerization in mould, take out lens, like this lens of Huo Deing be colourless and surface accuracy good, its refractive index η in addition
20 DBe 1.57, Abbe number γ
20 DBe 44.
Example 20-47
According to the program of example 19, make lens with component ratio listed in the table 2, various The performance test results are listed in the table 2.
Comparative Examples 4-27
According to the program of example 19, to carry out following mould in addition and handle, to make the component ratio of lens and list in table 3, The performance test results is also listed in the table 3.
(1) do not handle ... using glass mold not have any demoulding handles.
(2) the outer demoulding is handled ... use external release agent YSR-6209
TM(Toshiba silicon company product), and it is roasting molten and condense on the inside surface of glass mold.
(3) repeated use of outer demoulding processing ... through outside the glass mold of the demoulding after handling be used for not doing any further processing after polymerization is used once and reusing.
(4) use polypropylene molds ... make a polypropylene molds with the instead of glass mould and do not carry out any surface treatment with injection moulding method.
Instructions and embodiment are described according to the present invention, and other embodiment is conspicuous for the people who knows prior art.Instructions and embodiment only are that the definite scope of invention and elite will be pointed out in the claim of back for example.
Claims (3)
1, a kind of preparation method who is used for the resin of high refractive index plastic lens, this method comprise that with (a) one or more contain the aliphatic polyisocyanate compound of sulphur atom and react with (b) one or more active hydrogen compounds that are selected from polyol compound and multi-thiol compound and form.
2, the process for preparing resins of claim 1, wherein used multi-thiol compound are the multi-thiol compounds that also contains at least one sulphur atom except that sulfydryl.
3, the process for preparing resins of claim 1, the wherein used aliphatic polyisocyanate compound that this contains sulphur atom to the ratio of this active hydrogen compounds be about 0.5 to about 3.0 moles of isocyanate functional groups to 1 mole of (SH+OH) functional group.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32842/88 | 1988-02-17 | ||
| JP3284288 | 1988-02-17 | ||
| JP33872/88 | 1988-02-18 | ||
| JP33871/88 | 1988-02-18 | ||
| JP37523/88 | 1988-02-22 | ||
| JP3752588 | 1988-02-22 | ||
| JP37525/88 | 1988-02-22 | ||
| JP37515/88 | 1988-02-22 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92113162 Division CN1029425C (en) | 1988-02-17 | 1992-11-14 | Method of producing high refraction rate plastic lens and products thereby |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1036270A CN1036270A (en) | 1989-10-11 |
| CN1020308C true CN1020308C (en) | 1993-04-14 |
Family
ID=26371429
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89101862 Expired - Lifetime CN1020308C (en) | 1988-02-17 | 1989-02-17 | Resin for plastic lens having high-refractive index, lens comprising the resin, and method for preparation of the lens |
| CN 92113162 Expired - Lifetime CN1029425C (en) | 1988-02-17 | 1992-11-14 | Method of producing high refraction rate plastic lens and products thereby |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92113162 Expired - Lifetime CN1029425C (en) | 1988-02-17 | 1992-11-14 | Method of producing high refraction rate plastic lens and products thereby |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1020308C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL149732A0 (en) * | 1999-11-18 | 2002-11-10 | Ppg Ind Ohio Inc | Method of preparing an optical polymerizate |
| CN105348157B (en) * | 2015-12-18 | 2018-01-16 | 苏州大学 | Cystamine diisocyanate monomer, polymer based on the monomer and its preparation method and application |
-
1989
- 1989-02-17 CN CN 89101862 patent/CN1020308C/en not_active Expired - Lifetime
-
1992
- 1992-11-14 CN CN 92113162 patent/CN1029425C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1036270A (en) | 1989-10-11 |
| CN1072021A (en) | 1993-05-12 |
| CN1029425C (en) | 1995-08-02 |
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