WO2013103276A1 - Copolymer composition, for highly refractive optical lens, comprising thioepoxy compound, polyisocyanate compound, and polythiol compound, and method for manufacturing optical lens - Google Patents

Abstract

The present invention relates to a copolymer composition for a highly refractive optical lens, said composition comprising a thioepoxy compound, a polyisocyanate compound, and a polythiol compound, and more particularly, to a copolymer composition and a method for manufacturing an optical lens which does not have a surface ring defect even in a high power lens, the mold for which has a large radius of curvature. In the present invention provides the copolymer composition comprising the thioepoxy compound, the polyisocyanate compound, and a bis(2-mercaptoethyl) sulfide, the optical lens in which the composition is polymerized, and the method for manufacturing the optical lens. The copolymer composition and the optical lens in which the composition is polymerized, according to the present invention, exhibit very few surface ring defects on the surface of the lens even in a high-power lens (having an optical power of approximately at least -6.00), exhibits superior surface precision, and can be manufactured at a high yield. According to the present invention, ring defects on the surfaces of lenses are rare even in a highly refractive high-power lens, and a thioepoxy-based optical material, which has superior surface precision, can be used to manufacture lenses at a high yield. The optical lens manufactured according to the present invention can replace existing optical lenses and can be utilized in various areas, including lenses for glasses, polarized lenses, and camera lenses.

Description

A copolymer composition for a high refractive optical lens comprising a thioepoxy compound, a polyisocyanate compound, and a polythiol compound, and a method of manufacturing the optical lens

The present invention relates to a copolymer composition for a high refractive optical lens comprising a thioepoxy compound, a polyisocyanate compound, and a polythiol compound. Particularly, the present invention relates to a copolymer composition in which surface ring defects do not occur even in a high temperature lens having a large radius of curvature of the mold. A method of manufacturing an optical lens.

Korean Patent Publication Nos. 1993-0006918, 1992-0005708 and the like propose a thiourethane lens in which a polythiol compound and a polyisocyanate compound are reacted. Korean Patent Publication No. 10-0681218 proposes a thioepoxy watch plastic lens. The thiourethane-based lens has the advantages of high refractive index and excellent impact strength, but there are disadvantages such as softness of the lens surface and central depression, and also a problem in that Abbe's number decreases rapidly as the refractive index increases. The thioepoxy lens has the advantage of having a high refractive index and a high Abbe number, but there are problems such as fragile lens and poor dyeing.

In order to solve the problems of the thiourethane lens and the thioepoxy lens, a method of copolymerizing these two kinds of resins, that is, a method of copolymerizing a thioepoxy compound, a polythiol compound, and a polyisocyanate compound, has been proposed. Patent Documents No. 10-0417985, Japanese Patent Laid-Open No. Hei 11-292950, and Japanese Patent Laid-Open No. Hei 11-352302 have been proposed.

However, in a copolymer lens copolymerizing a thioepoxy compound, a polythiol compound, and a polyisocyanate compound, release of separation and the like occurs in advance before demolding during the manufacture of a high-temperature lens having a large curvature radius of the mold (about -6.00 degrees or more). There is a problem that ring defects appear on the surface, which causes deterioration of the quality of the copolymer lens having various optical advantages, deterioration of the suitability as spectacle lenses, and lowering the lens yield to increase the production cost. .

In the present invention, to solve the surface ring defect phenomenon appearing in high refractive optical lens made by copolymerizing a thioepoxy compound, a polythiol compound and a polyisocyanate compound, especially a high temperature lens (about -6.00 degrees or more) having a large curvature radius of the mold . SUMMARY OF THE INVENTION An object of the present invention is to provide a copolymer optical lens having a low surface ring defect and having excellent surface precision and a method of manufacturing the same.

The present inventors have concentrated on the surface ring defect phenomenon which is a problem in the method of forming a copolymer from a thioepoxy compound, an isocyanate compound, and a thiol compound by mold polymerization. As a result, 3 has been mainly used in the polyurethane-based optical resin composition. Unlike the case of using a polythiol compound having two or more thiol groups, it was unexpectedly found that when the bis (2-mercaptoethyl) sulfide having two thiol groups was used, almost no surface ring defects appeared. The lens thus obtained showed little surface ring defect even in the high temperature lens, and it was confirmed that the surface precision was very good.

In the present invention,

There is provided a copolymer composition for a high refractive optical lens comprising a thioepoxy compound, a polyisocyanate compound and bis (2-mercaptoethyl) sulfide. The copolymer composition of the present invention may preferably further include a phosphate ester compound added with ethylene oxide or propylene oxide as an internal mold release agent. In addition, the copolymer composition of the present invention may further include other polythiol compounds other than the bis (2-mercaptoethyl) sulfide, and may further include an olefin compound as a reactive resin modifier.

Moreover, in this invention, the high refractive optical lens obtained by casting-polymerizing the said copolymer composition is provided. The optical lens in particular comprises an spectacle lens or a polarizing lens.

In addition, in the present invention, there is provided a method for producing a high refractive optical lens in which the copolymer composition is polymerized.

In the present invention, "high refractive index" or "high refractive index" is meant to include both high refractive index and ultra high refractive index of 1.67 or more, unless otherwise specified.

The high refractive optical lens polymerized with the copolymer composition of the present invention has a very low ring defect on the lens surface, excellent surface precision, and can be produced with high yield even with a high temperature lens (about -6.00 degrees or more).

In the copolymer composition of the present invention, the thioepoxy compound is an episulfide compound having a thioepoxy group. For example, bis (2, 3- epithiopropyl) sulfide, bis (2, 3- epithiopropyl) disulfide, 2, 3- epidithiopropyl (2, 3- epithiopropyl) disulfide, 2,3-epidithiopropyl (2,3-ethiothiopropyl) sulfide, 1,3 and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3 and 1,4-bis ( β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-ethiothiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-ethiothiopropylthio) cyclohexyl] propane, Episulfide compounds having an alicyclic skeleton such as bis [4- (β-epithiopropylthio) cyclohexyl] sulfide; 1,3 and 1,4-bis (β-ethiothiopropylthiomethyl) benzene, bis [4- (β-ethiothiopropylthio) phenyl] methane, 2,2-bis [4- (β-ethiothiopropyl Thio) phenyl] propane, bis [4- (β-ethiothiopropylthio) phenyl] sulfide, bis [4- (β-ethiothiopropylthio) phenyl] sulphine, 4,4-bis (β-ethiothiopropyl Episulfide compounds having an aromatic skeleton such as thio) biphenyl; 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthioethylthiomethyl) -1,4-dithiane, 2,5- Epi having a dithiane chain skeleton such as bis (β-ethiothiopropylthioethyl) -1,4-dithiane, 2,3,5-tri (β-ethiothiopropylthioethyl) -1,4-dithiane Sulfide compounds; 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane, 1,2-bis [(2-β-ethiothiopropylthioethyl) thio]- 3- (β-epithiopropylthio) propane, tetrakis (β-ethiothiopropylthiomethyl) methane, 1,1,1-tris (β-ethiothiopropylthiomethyl) propane, bis (β-ethiothiopropyl Episulfide compounds having an aliphatic skeleton such as sulfide and bis (β-epithiopropyl) disulfide. In addition to the thioepoxy compound, halogen substituents such as chlorine substituents and bromine substituents of compounds having episulfide groups, alkyl substituents, alkoxy substituents, nitro substituents and prepolymer-modified compounds with polythiols can also be used.

As a thioepoxy compound, Preferably, bis (2, 3- epithiopropyl) sulfide, bis (2, 3- epithiopropyl) disulfide, 2, 3- epidithiopropyl (2, 3- epithio Propyl) sulfide, 2,3-epidithiopropyl (2,3-epithiopropyl) disulfide, 1,3 and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3 and 1 , 4-bis (β-epithiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthio One or more of ethylthiomethyl) -1,4-dithiane and 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane may be used. .

The polyisocyanate compound in the copolymer composition of the present invention is not particularly limited, and a compound having at least one isocyanate group and / or isothiocyanate group may be used. For example, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexanediisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, hexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis (isocy Aliphatic isocyanate compounds such as anatoethyl) carbonate and bis (isocyanatoethyl) ether; Isophorone diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, Alicyclic isocyanate compounds such as dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane isocyanate and 2,2-dimethyldicyclohexyl methane isocyanate; Xylylene diisocyanate (XDI), bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis ( Isocyanatomethyl) diphenyl ether, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzene tree Isocyanate, diphenyl diisocyanate, toluidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate , Bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, hexahydrobenzenediisocyanate, Aromatic isocyanate compounds such as hexahydrodiphenylmethane-4,4'-diisocyanate; Bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl Disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis ( Sulfur-containing aliphatic isocyanate compounds such as isocyanatomethylthio) ethane and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane; Diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylthioether, bis (4- Isocyanatomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide Feed-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate, 4, 4'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyldisulfide-3 Sulfur-containing aromatic isocyanate compounds such as 3'-diisocyanate; 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) Tetrahydrothiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiorane, 4,5-bis (isocyanatomethyl) -1,3-dithiorane, 4,5-bis ( One or two or more compounds selected from sulfur-containing heterocyclic isocyanate compounds such as isocyanatomethyl) -2-methyl-1,3-dithiolane can be used. In addition, as long as it is a compound having at least one or more isonate groups and / or isothiocyanate groups, one or two or more kinds thereof may be used, and halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents and alkoxy of these isocyanate compounds. Substituents, nitro substituents, prepolymer-modified products with polyhydric alcohols or thiols, carbodiimide-modified products, urea-modified products, biuret-modified or dimerized products, and trimerized reaction products can also be used. As polyisocyanate compound, Preferably, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (H12MDI), xylylene diisocyanate (XDI), 3,8-bis (iso Cyanatomethyl) tricyclo [5,2,1,02,6] decane, 3,9-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,8-bis (Isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, 2,6-bis (iso One or more selected from cyanatomethyl) bicyclo [2,2,1] heptane is used.

The copolymer composition of the present invention includes bis (2-mercaptoethyl) sulfide having two thiol groups as the polythiol compound. Unlike polythiol compounds having three or more thiol groups conventionally used as polythiols in copolymer resins, surface ring defects occur in resins copolymerized using bis (2-mercaptoethyl) sulfide having two thiol groups. This rarely appeared. In addition, the copolymer composition of the present invention may further contain another polythiol compound while containing bis (2-mercaptoethyl) sulfide as the main polythiol. Examples of other polythiol compounds include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 2, 2-bis (mercaptomethyl) -1,3-propanedithiol, tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol, 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercapto Propaneyl) sulfide, bis (2,3-dimercaptopropanyl) disulfide, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1,2-bis (2- ( 2-mercaptoethylthio) -3-mercaptopropylthio) ethane, bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, bis (2- (2-mercaptoethylthio) ) -3-mercaptopropyl) disulfide, 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio ] Propylthio-propane-1-thiol, 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio) propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3 , 6,9,12-tetrathiatetradecane-1,14-dithiol, (S) -3- ((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4R, 14R) -4,14-bis (mercaptomethyl) -3,6,9,12,15 -Pentathiaheptan-1,17-dithiol, (S) -3-((R-3-mercapto-2-((2-mercaptoethyl) thio) propyl) thio) propyl) thio) -2- ((2-mercaptoethyl) thio) propane-1-thiol, 3,3'-dithiobis (propane-1,2-dithiol), (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R, 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13, 16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaeryte Lithol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaeryte Lithol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) Ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane and the like can be used. In addition, if it is a compound which has one or more thiol groups, it can use 1 type or in mixture of 2 or more types. Moreover, the polymerization modified body obtained by the prepolymerization with an isocyanate, a thioepoxy compound, a ethane compound, or the compound which has an unsaturated bond as a resin modifier to a polythiol compound can also be used.

The copolymer composition of the present invention particularly preferably comprises a phosphate ester compound added with ethylene oxide or propylene oxide as an internal release agent. One of the major causes of surface ring defects is that the ring remains on the surface as it releases before release during polymerization. When the phosphate ester compound added with ethylene oxide or propylene oxide is used as an internal mold release agent, the problem of release separation in advance can be solved, thereby minimizing surface ring defects. As the internal release agent, preferably 4-PENPP [polyoxyethylenenonylphenol ether phosphate (5% by weight of 5 mole of ethylene oxide added, 80% by weight of 4 mole added, 10% by weight of 3 mole added), 1 Mole added 5% by weight)], 8-PENPP [polyoxyethylenenonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added) , 7 mole added 6% by weight, 6 mole added 6% by weight)], 12-PENPP [polyoxyethylenenonylphenol ether phosphate (13 mole added by ethylene oxide 3% by weight, 12 mole added by 80) Weight%, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 16-PENPP [polyoxyethylene nonylphenol ether phosphate (17 mol added ethylene oxide added) 3% by weight, 79% by 16 mole added, 10% by weight 15 mole added, 4% by weight 14 mole added, 4% by weight 13 mole added)], 20-PENPP [polyoxy on Lennonylphenol ether phosphate (with 21 moles of ethylene oxide added 5% by weight, 20 moles added 76% by weight, 19 moles added 7% by weight, 18 moles added 6% by weight, 17 moles added 4 wt%)], 4-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 wt% of propylene oxide added, 80 wt% of 4 mol added, 10 wt% of 3 mol added, 1 mol) 5 wt% added)], 8-PPNPP [polyoxypropylene nonylphenol ether phosphate (3 wt% of 9 mol added propylene oxide, 80 wt% added 8 mol, 5 wt% added 9 mol, 7 mole added 6% by weight, 6 mole added 6% by weight)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (13 mole added propylene oxide 3% by weight, 12 mole added 80%) %, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 16-PPNPP [polyoxypropylene nonylphenol ether phosphate (prop) 3 mol% of 17 mol added, 17 mol added 79 weight percent, 15 mol added 10 weight percent, 14 mol added 4 weight percent, 13 mol added 4 weight percent) , 20-PPNPP [polyoxypropylene nonylphenol ether phosphate (5% by weight of 21 mol of propylene oxide, 76% by weight of 20 mol added, 7% by weight of 19 mol added, 18 weight added %, 17 mole added 4% by weight)] and Zelec UN ^™ are used. Various substituents including the halogen compound substituents of such phosphate ester compounds can be used for the same purpose.

In order to improve the optical properties of the copolymer optical resin, the copolymer composition of the present invention may further include an olefin compound as a reactive resin modifier for the purpose of controlling impact resistance, specific gravity, monomer viscosity, and the like. As an olefin compound which can be added as a resin modifier, for example, benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2 Hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxy ethyl acrylate, phenoxy ethyl methacrylate, phenyl methacrylate, ethylene glycol di Acrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol Dimethacrylate, Polyethylene Glycol Diacrylate, Polyethylene Glycol Dimethac Latex, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2 , 2-bis (4-hydroxyethoxyphenyl) propane, 2,2-bis (4-methoxyethoxyphenyl) propane, 2,2-bis (4-hydroxydiethoxyphenyl) propane, 2, 2-bis (4-methoxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-hydroxyethoxyphenyl) methane, 1,1-bis ( 4-Methoxyethoxyphenyl) methane, 1,1-bis (4-acryoxydiethoxyphenyl) methane, 1,1-bis (4-methoxydiethoxyphenyl) methane, dimethyloltricyclodecane Acrylate, trimetholpropane triacrylate, trimetholpropane trimethacrylate, glycerol diacrylate, Liserol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, (Meth) acrylate compounds, such as xylene dithiol diacrylate, xylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, and mercaptoethyl sulfide dimethacrylate; Allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, and diethylene glycol bisallyl carbonate; And vinyl compounds such as styrene, chlorostyrene, methyl styrene, bromostyrene, dibromostyrene, divinylbenzene, and 3,9-divinylspirobiby (m-dioxane). However, the compounds that can be used are not limited to these exemplary compounds. You may use these olefin compounds individually or in mixture of 2 or more types.

The copolymer optical lens of the present invention is obtained through template polymerization. That is, the copolymer composition of this invention is inject | poured between the shaping | molding mold hold | maintained with the gasket or the tape. Under the present circumstances, it is preferable to perform the defoaming process under reduced pressure, the filtration process of pressurization, reduced pressure, etc. according to the physical property calculated | required at the time of the plastic lens obtained, etc. in many cases. Since the polymerization varies greatly depending on the copolymer composition, the type and the amount of the catalyst used, the shape of the mold, and the like, the polymerization is carried out over a period of 1 to 50 hours at a temperature of about -50 to 150 ° C. In some cases, it is preferable to maintain or gradually raise the temperature in a temperature range of 10 to 150 ° C. and to cure in 1 to 48 hours.

The thioepoxy compound, isocyanate compound, and thiol compound copolymer obtained by hardening may perform annealing etc. as needed. Treatment temperature is normally performed between 50-150 degreeC, and it is preferable to carry out at 90-140 degreeC.

The composition of the present invention is preferably subjected to mold polymerization by adding a phosphate ester compound as an internal mold release agent. Description of the phosphate ester compound is the same as above. In addition, depending on the purpose of the polymerization, various additives such as chain extenders, crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, anti-colorants, oil-soluble dyes, fillers, adhesion improving agents, and the like may be added. In particular, the catalyst used plays an important role. In the type of catalyst, epoxy curing agents are mainly used, but strong amines intensify the isocyanate reaction, so it is necessary to pay attention to its use. In the present invention, amine salts, phosphonium salts, phosphines and tertiary amines having no electron withdrawing groups, Lewis acids, radical initiators and the like are mainly used, and the type and amount of the catalyst may vary depending on the case.

The copolymer resin of this invention can be obtained with the molded object of various shapes by changing the mold at the time of casting polymerization, and can be used for various optical lenses, such as an eyeglass lens, a polarizing lens, and a camera lens.

You may use the plastic lens using the copolymer resin of this invention, giving a coating layer to single side | surface or both surfaces as needed. Examples of the coating layer include a primer layer, a hard coat layer, an antireflection film layer, an antifogging coat film layer, an antifouling layer, and a water repellent layer. These coating layers may be formed alone, or a plurality of coating layers may be formed in multiple layers. When providing a coating layer on both surfaces, you may give the same coating layer to each surface, or may give a different coating layer.

The optical lens obtained by casting and polymerizing a thioepoxy compound, a polyisocyanate compound, and a polythiol compound obtained in accordance with the present invention has very low surface ring defects on the lens surface, excellent surface precision, and can be easily manufactured with high yield.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, these examples are only for illustrating the present invention in more detail, the scope of the present invention is not limited by these examples.

Test and evaluation method

Surface ring defect: If there is no ring-shaped defect around the center of the lens by irradiating mercury arc lamp which is not separated in advance and the surface state is USHIO USH-102D If there is a ring-shaped defect centered on the center of the lens by irradiating a mercury arc lamp that is separated in advance or the surface condition is USHIO USH-102D, then '×' (the surface ring is defective) ).

Refractive index (nE), Abbe number: It was measured at 20 ℃ using an Abe refractometer, IT and DR-M4 model of Atago.

Example 1

89 g of bis (2,3-epithiopropyl) sulfide as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, 8- which is a phosphate ester as an internal mold release agent PENPP [polyoxyethylenenonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, 6% by weight, 7 moles added Added 6% by weight)] 0.15g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dye HTAQ (20ppm) and PRD (10ppm), UV absorber HOPBT 1.5g mixed and dissolved at 20 ℃ , Homogeneous solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered with the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical properties of the obtained resin were refractive index (nE) 1.697 and Abbe number 35. The state of dissolution before injection into the mold was visually observed, and after demolding, it was confirmed that there was no surface ring defect, no abnormality, no whitening was observed, and a resin of stable quality was obtained even at high tap water of -7.00 degrees or more.

Example 2

89 g of bis (2,3-epithiopropyl) disulfide as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, 8- which is a phosphate ester as an internal mold release agent PENPP [polyoxyethylenenonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, 6% by weight, 7 moles added Added 6% by weight)] 0.15g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dye HTAQ (20ppm) and PRD (10ppm), UV absorber HOPBT 1.5g mixed and dissolved at 20 ℃ , Homogeneous solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered with the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical properties of the obtained resin were refractive index (nE) 1.738 and Abbe number 34. The state of dissolution before injection into the mold was visually observed, and after demolding, it was confirmed that there was no surface ring defect, no abnormality, no whitening was observed, and a resin of stable quality was obtained even at high tap water of -7.00 degrees or more.

Example 3

60 g of bis (2,3-epithiopropyl) sulfide as a thioepoxy compound, 20 g of isophorone diisocyanate as an isocyanate compound, 20 g of bis (2-mercaptoethyl) sulfide as a thiol compound, Zelec UN which is a phosphate ester as an internal mold release agent 0.15 g of ^TM , 0.05 g of tetrabutylphosphonium bromide, 0.05 g of triphenylphosphine, organic dyes HTAQ (20 ppm) and PRD (10 ppm), and 1.5 g of UV absorber HOPBT were mixed and dissolved at 20 ° C. to make a homogeneous solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered with the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical property of obtained resin was refractive index (nE) 1.666 and Abbe's number 36. The state of dissolution before injection into the mold was visually observed, and after demolding, it was confirmed that there was no surface ring defect, no abnormality, no whitening was observed, and a resin of stable quality was obtained even at high tap water of -7.00 degrees or more.

Example 4

60 g of bis (2,3-epiopropyl) disulfide as a thioepoxy compound, 20 g of isophorone diisocyanate as an isocyanate compound, 20 g of bis (2-mercaptoethyl) sulfide as a thiol compound, 8- which is a phosphate ester as an internal release agent PPNPP [Polyoxypropylenenonylphenol ether phosphate (3% by weight of 9 moles of propylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, 6% by weight, 7 moles added) Added 6% by weight)] 0.15g, tetrabutylphosphonium bromide 0.05g, triphenylphosphine 0.05g, organic dyes HTAQ (20ppm) and PRD (10ppm), UV absorber HOPBT 1.5g mixed and dissolved at 20 ℃ , Homogeneous solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered with the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical properties of the obtained resin were refractive index (nE) 1.692 and Abbe number 35. The state of dissolution before injection into the mold was visually observed, and after demolding, it was confirmed that there was no surface ring defect, no abnormality, no whitening was observed, and a resin of stable quality was obtained even at high tap water of -7.00 degrees or more.

Example 5

89 g of bis (2,3-epiopropyl) disulfide as a thioepoxy compound, 5 g of dicyclohexyl methane diisocyanate (H12MDI) as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, as an internal release agent Phosphoric acid ester 12-PENPP [polyoxyethylenenonylphenol ether phosphate (13 wt% ethylene oxide added 3 wt%, 12 mol added 80 wt%, 11 mol added 8 wt%, 9 mol added 3 Weight%, 4 mol added 6% by weight)] 0.15 g, tetrabutylphosphonium bromide 0.05 g, triphenylphosphine 0.05 g, organic dyes HTAQ (20 ppm) and PRD (10 ppm), UV absorber HOPBT 1.5 g The mixture was dissolved at a temperature of 0 ° C. to obtain a uniform solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered with the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical properties of the obtained resin were refractive index (nE) 1.695 and Abbe number 35. The state of dissolution before injection into the mold was visually observed, and after demolding, it was confirmed that there was no surface ring defect, no abnormality, no whitening was observed, and a resin of stable quality was obtained even at high tap water of -7.00 degrees or more.

Example 6

89 g of bis (2,3- epithiopropyl) sulfide as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 5 g of bis (2-mercaptoethyl) sulfide as a thiol compound, and 2,3-bis (2- Mercaptoethylthio) propane-1-thiol, 8-PENPP [polyoxyethylene nonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide, 80% of 8 moles of ethylene oxide), which is a phosphate ester as an internal release agent, 9 mol added 5 wt%, 7 mol added 6 wt%, 6 mol added 6 wt%)] 0.15 g, tetrabutylphosphonium bromide 0.2 g, triphenylphosphine 0.1 g, organic dye HTAQ ( 20 ppm), PRD (10 ppm), and 1.5 g of the ultraviolet absorber HOPBT were mixed and dissolved at 20 ° C. to obtain a homogeneous solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered with the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical property of obtained resin was refractive index (nE) 1.702 and Abbe's number 35. The state of dissolution before injection into the mold was visually observed, and after demolding, it was confirmed that there was no surface ring defect, no abnormality, no whitening was observed, and a resin of stable quality was obtained even at high tap water of -7.00 degrees or more.

Comparative Example 1

89 g of bis (2,3- epithiopropyl) sulfide as a thioepoxy compound, 5 g of isophorone diisocyanates as an isocyanate compound, 6 g of 1,2-bis (2- mercaptoethylthio) -3- mercaptopropane as a thiol compound It carried out similarly to Example 1 except having been a copolymer composition which uses. After the end of the polymerization, the mold was taken out of the oven. Although the mold release property was good from the mold, it was separated in advance before demolding in high temperature water of -7.00 degree water or more, and the obtained resin was further annealed at 130 degreeC for 4 hours. The physical properties of the obtained resin were similar to those of refractive index (nE) 1.697 and Abbe number 35, but the surface ring defect phenomenon did not disappear even after annealing. In the high water lens, stable lens quality was not obtained.

[Comparative Examples 2-4]

It carried out similarly to Example 1 except using it as the composition of Table 1 below. After the end of the polymerization, the mold was taken out of the oven. Although the releasability from the mold was good, it was separated beforehand in high temperature water of -7.00 or more degrees, and the obtained resin was further annealed at 130 ° C for 4 hours. However, even after annealing, the surface ring defect phenomenon did not disappear. In the high water lens, stable lens quality was not obtained.

The resin composition and the result of the said Example and a comparative example are put together in Table 1 below.

Table 1

Abbreviation

HOPBT: 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole (2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole)

HTQA: 1-hydroxy-4- (p-tolludine) -entroquinone (1-hydroxy-4- (p-toluidine) anthraquinone

PRD: perinone dye

EPDS: Bis (2,3-Ethiothiopropyl) sulfide

EDPDS: Bis (2,3-Ethiothiopropyl) Disulfide

IPDI: isophorone diisocyanate

BMES: bis (2-mercaptoethyl) sulfide

DMTMP: 2,3-bis (2-mercaptoethylthio) propane-1-thiol

8-PENPP: polyoxyethylene nonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, 6% by weight of 7 moles added, 6 mol added 6% by weight)

12-PENPP: polyoxyethylene nonyl phenol ether phosphate (3% by weight of 13 moles of ethylene oxide, 80% by weight of 12 moles added, 8% by weight of 11 moles added, 3% by weight of 9 moles added, 4 mol added 6% by weight)

8-PPNPP: polyoxypropylene nonylphenol ether phosphate (3% by weight of 9 mole of propylene oxide, 80% by weight of 8 mole added, 5% by weight of 9 mole added, 6% by weight of 7 mole added, 6 mol added 6% by weight)

Zelec UN ^TM: trade name with an acidic phosphate ester compound prepared in four Srepan Zelec UN ^TM

DOP: Dioctylate Phosphate

According to the present invention, even in a high refractive index lens, a thioepoxy optical material having very low ring defects on the lens surface and excellent surface precision can be manufactured with high lens yield. The optical lens manufactured according to the present invention may be widely used in various fields in place of the existing optical lens, and specifically, may be used as an eyeglass lens, a polarizing lens, a camera lens, or the like.

Claims (11)

1. A copolymer composition for high refractive optical lenses comprising a thioepoxy compound, a polyisocyanate compound, and bis (2-mercaptoethyl) sulfide.
2. The method of claim 1, wherein 4-PENPP [polyoxyethylenenonylphenol ether phosphate (5% by weight of 5 mol of ethylene oxide added, 80% by weight of 4 mol added, 10% by weight of 3 mol added, 1 mol) 5 wt% added)], 8-PENPP [polyoxyethylenenonylphenol ether phosphate (3 wt% of 9 mol added ethylene oxide, 80 wt% added 8 mol, 5 wt% added 9 mol, 7 mole added 6% by weight, 6 mole added 6% by weight)], 12-PENPP [polyoxyethylene nonylphenol ether phosphate (13 mole added ethylene oxide 3% by weight, 12 mole added 80% by weight) %, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 16-PENPP [polyoxyethylene nonylphenol ether phosphate (17 mol added ethylene oxide added) 3 wt%, 16 mol added 79 wt%, 15 mol added 10 wt%, 14 mol added 4 wt%, 13 mol added 4 wt%)], 20-PENPP [polyoxyethylene Nonylphenol Ter phosphate (21% added ethylene oxide 5%, 20 mol added 76%, 19 mol added 7%, 18 mol added 6%, 17 mol added 4% by weight ), 4-PPNPP [Polyoxypropylenenonylphenol ether phosphate (5% by weight of 5 mole of propylene oxide, 80% by weight of 4 mole added, 10% by weight of 3 mole added, 1 mole added) 5% by weight)], 8-PPNPP [polyoxypropylenenonylphenol ether phosphate (3% by weight of 9 mole of propylene oxide, 80% by weight of 8 mole added, 5% by weight of 9 mole added, 7 mole added) 6 wt%, 6 mol added 6 wt%)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (13 wt% propylene oxide 3 wt%, 12 mol added 80 wt%, 11 Mole added 8% by weight, 9 mole added 3% by weight, 4 mole added 6% by weight)], 16-PPNPP [polyoxypropylene nonylphenol ether phosphate (propylene oxy) 3 mol% of 17 mol added, 79 weight percent added, 16 mol added 10 weight percent, 14 mol added 4 weight percent, 13 mol added 4 weight percent)], 20- PPNPP [polyoxypropylene nonylphenol ether phosphate (21% addition of 5% by weight of propylene oxide, 20% addition of 76% by weight, 19% addition of 7% by weight, 18% addition of 6% by weight, 17 Molar addition 4% by weight)] and Zelec UN ^™ further comprise at least one phosphate ester compound selected from the group consisting of internal release agents.
3. The compound according to claim 1 or 2, wherein the thioepoxy compound is bis (2,3-ethiothio) sulfide, bis (2,3-ethiothio) disulfide, (2,3-ethiothiopropyl) (2,3-Epithiopropyl) sulfide, 2,3-Epidithiopropyl (2,3-Ethiothiopropyl) disulfide, 1,3- and 1,4-bis (β epithiopropylthio) cyclo Hexane, 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5- Bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, and 2- (2-β-ethiothiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane Copolymer composition, characterized in that at least one selected from the group consisting of.
4. The polyisocyanate compound according to claim 1 or 2, wherein the polyisocyanate compound is isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, xylylene diisocyanate, 3,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 3,9-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,8-bis (isocyanatomethyl) Tricyclo [5,2,1,02,6] decane, 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, and 2,6-bis (isocyanatomethyl) ratio Copolymer composition, characterized in that at least one member selected from the group consisting of cyclo [2,2,1] heptane.
5. The copolymer composition according to claim 1 or 2, further comprising a polythiol compound other than the bis (2-mercaptoethyl) sulfide.
6. The other polythiol compound according to claim 5, wherein the other polythiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis (2-mercaptoethylthio) propane- 1-thiol, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol, 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercapto Propaneyl) sulfide, bis (2,3-dimercaptopropanyl) disulfide, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1,2-bis (2- ( 2-mercaptoethylthio) -3-mercaptopropylthio) ethane, bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, bis (2- (2-mercaptoethylthio) ) -3-mercaptopropyl) disulfide, 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio ] Propylthio-propane-1-thiol, 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio) propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3 , 6,9,12-tetrathiatetradecane-1,14-dithiol, (S) -3- ((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4R, 14R) -4,14-bis (mercaptomethyl) -3,6,9,12,15 -Pentathiaheptan-1,17-dithiol, (S) -3-((R-3-mercapto-2-((2-mercaptoethyl) thio) propyl) thio) propyl) thio) -2- ((2-mercaptoethyl) thio) propane-1-thiol, 3,3'-dithiobis (propane-1,2-dithiol), (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R, 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13, 16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaeryte Lithol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaery Lithol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) Ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane The copolymer composition characterized by the above.
7. The copolymer composition according to claim 1 or 2, further comprising an olefin compound as a reactive resin modifier.
8. The high refractive optical lens obtained by casting-polymerizing the copolymer composition of Claim 1 or 2.
9. The high refractive optical lens of claim 8, wherein the optical lens is a spectacle lens or a polarizing lens.
10. A method for producing a high refractive optical lens in which the copolymer composition of claim 1 or 2 is subjected to mold polymerization.
11. The method of claim 10,

    To the copolymer composition by adding a phosphate ester compound added with ethylene oxide or propylene oxide as an internal mold release agent,

    The phosphate ester compound is 4-PENPP [polyoxyethylenenonylphenol ether phosphate (5% by weight of 5 mol of ethylene oxide added, 80% by weight of 4 mol added, 10% by weight of 3 mol added, 1 mol) 5 wt% added)], 8-PENPP [polyoxyethylenenonylphenolethofate (3 wt%, 9 mol added ethylene oxide, 80 wt% added, 9 mol added 5 mol Weight%, 7 mol added 6 weight%, 6 mol added 6 weight%)], 12-PENPP [polyoxyethylene nonyl phenol ether phosphate (13 weight added ethylene oxide 3 weight%, 12 mol added) 80 wt%, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 16-PENPP polyoxyethylene nonylphenol ether phosphate (17 mol ethylene oxide) 3 weight percent added, 16 mol added 79 weight percent, 15 mol added 10 weight percent, 14 mol added 4 weight percent, 13 mol added 4 weight percent), 20-PENPP [polyoxy ethyl Nonylphenol ether phosphate (21% added ethylene oxide 5% by weight, 20 moles added 76% by weight, 19 moles added 7% by weight, 18 moles added 6% by weight, 17 moles added 4 Wt%)], 4-PPNPP [polyoxypropylenenonylphenol ether phosphate (5 wt% with 5 mol of propylene oxide, 80 wt% with 4 mol, 10 wt% with 3 mol, with 1 mol addition 5 wt%)], 8-PPNPP [polyoxypropylene nonylphenol ether phosphate (3 wt% of 9 mol added propylene oxide, 80 wt% added 8 mol, 5 wt% added 9 mol, 7 Mole added 6% by weight, 6 mole added 6% by weight)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (13% by weight of propylene oxide 3%, 12 moles added 80% by weight) , 11 mole added 8% by weight, 9 mole added 3% by weight, 4 mole added 6% by weight)], 16-PPNPP [polyoxypropylene nonylphenoletherphosphate (pro 3 parts by weight of 17 mole added, 79 parts by weight added by 16 moles, 10 parts by weight added by 4 parts by weight, 14 parts by weight added by 4 parts by weight, 4 parts by weight by 13 moles added); 20-PPNPP [polyoxypropylene nonylphenol ether phosphate (21% added propylene oxide 5%, 20% added 76%, 19 mol added 7%, 18 mol added 6% by weight) , 17 mole added 4% by weight)] and Zelec UN ^™ are at least one member selected from the group consisting of.