WO2010076942A1 - Light weight high refraction resin composition for optical lens using novel thiol compound and optical lens using the same - Google Patents

Abstract

The present invention relates to a resin composition which can be used for manufacturing a plastic optical lens. More specifically, the lightweight high-refraction resin composition for optical lenses and an optical lens using the same are obtained by reacting novel thiol compound and isocyanate compound. The optical lens manufactured using the resin compound of the present invention: is light due to a low specific gravity, is highly heat-resistant due to a high heat distortion temperature, and reduces production costs due to a low rate of raw materials and a high yield rate.

Description

Lightweight High Refraction Resin Composition for Optical Lenses Using Novel Thiol Compounds and Optical Lenses Using the Same

The present invention relates to a resin composition for plastic optical lenses, and more particularly to a lightweight high refractive resin composition for optical lenses using a novel thiol compound and an optical lens using the same.

Plastic lenses are used in the production of various optical lenses today because they are lightweight and have excellent impact resistance, and are easy to dye as compared to glass lenses. As a material of a plastic optical lens, polyethyleneglycol bisallyl carbonate, polymethyl methacrylate (PMMA), a mixture of modified diaryl phthalate and ethylene glycol bisallyl carbonate, etc. have been generally used. However, since these plastic lens materials have a low refractive index of about 1.50 to 1.55, the thickness of the lens is increased in order to increase the number of tap water. Therefore, there is a disadvantage that the aesthetics of the lens worsens, which cancels the superiority such as light weight of the plastic lens. In particular, the myopia lens made of a mixture of diaryl phthalate and ethylene glycol bisallyl carbonate has a problem that birefringence and chromatic aberration occur, as well as aesthetic problems in which the edge thickness of the plastic lens becomes thick when the tap water is high. Accordingly, there is a need for a plastic lens material that can reduce the thickness of the lens due to its high refractive index and to reduce the chromatic aberration and exhibit low dispersion while making the most of the advantages of the low specific gravity plastic lens.

Korean Patent Publication No. 1992-0005708 provides a plastic lens material that can produce a thin lens thickness with a refractive index of 1.65 or more, but has high chromatic aberration and low heat resistance problems, and a high specific gravity of 1.33 to 1.36, resulting in a high lens density. There is a problem that becomes heavy.

In Korean Patent 1987-0008928, 0.05M xylene diisocyanate and 0.025M pentaerythritol tetrakismercaptopropionate are thermally cured to produce urethane plastic optical lenses having excellent transparency and tensile strength and low dispersion. However, the optical lens has a high refractive index of 1.593, but the heat resistance is low, there is a problem that the lens center portion is deformed during the hard and multi-coating on the lens surface, there is a disadvantage that the lens is heavy due to the high specific gravity of 1.30 ~ 1.34.

In addition, Korean Patent Publication No. 1993-0006918 discloses an alicyclic isocyanate compound and a pentaerythritol tetrakismercaptopiopinate or 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane. By curing, a high refractive index urethane-based plastic optical lens having a refractive index of 1.593 is manufactured, but the optical lens manufactured as described above has a problem that the lens is heavy due to its high specific gravity of 1.30 to 1.34.

Prior to the present invention, the inventors have filed a patent application entitled “Lightweight high refractive resin for an optical lens and an optical lens using the same” which is an invention for an optical lens resin that can have a high refractive index while retaining the advantages of a light and impact resistant plastic lens. 10-2007-0077515 has been filed. The present invention further develops these properties to provide a resin composition for an optical lens including a novel polythiol compound which can lower the specific cost, but also lower the raw material cost and high yield, thereby greatly reducing the production cost.

In order to achieve the above object, in the present invention,

There is provided a resin composition for an optical lens comprising a thiol compound and an isocyanate compound represented by the following formula (1).

Formula 1

Moreover, in this invention, the plastic spectacle lens obtained by thermosetting the said resin composition for optical lenses is provided.

The optical resin composition and the optical lens obtained in the present invention have high refractive index and low specific gravity, and are light and excellent in optical properties such as impact resistance, heat resistance, moldability, dyeing property, light transmittance and Abbe's number. Therefore, the edge thickness of the lens can be made thin even at high degrees of water, and at the same time, it can be usefully used for manufacturing glasses of high degree of water because of its light weight. In particular, compared to the resin composition prepared according to the applicant's prior application of "lightweight high refractive resin for optical lenses and optical lenses using the same" (Patent Application No. 10-2007-0077515), the specific gravity is lighter and heat distortion temperature is Its higher heat resistance makes it possible to reduce production costs by 30 ~ 40% due to lower raw material costs and higher yields.

The lightweight high refractive resin composition for an optical lens of the present invention includes a novel thiol compound and an isocyanate compound represented by Chemical Formula 1.

The resin composition of the present invention comprises 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2 (2-mercaptoethylthio) -propylthio] -ethylthio} -propane-1-thiol; And 2- (2-mercaptoethylthio) propane-1,3-dithiol, and may further include one or two or more thiol compounds selected from the group consisting of.

The isocyanate compound is an alkylene diisocyanate compound; Alicyclic diisocyanate compounds; Heterocyclic diisocyanate compounds; Aliphatic thiodiisocyanate compounds and the like.

 In the alkylene diisocyanate compound, for example, Ethylene diisocyanate; Trimethylene diisocyanate; Tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; Octamethylene diisocyanate; Nonamethylene diisocyanate; 2,2-dimethylpentane diisocyanate; 2,2,4-trimethylhexanediisocyanate; Decamethylene diisocyanate; Butene diisocyanate; 1,3-butadiene-1,4-diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; 1,6,11-undecanetriisocyanate; 1,3,6-hexamethylenetriisocyanate; 1,8-diisocyanato-4-isocyanatomethyloctane; 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane; Bis (isocyanatoethyl) carbonate; Bis (isocyanatoethyl) ether; 1,4-butylene glycol dipropyl ether-1,2-diisocyanate; 1,4-butylene glycol dipropyl ether-1,3-diisocyanate; 1,4-butylene glycol dipropyl ether-1,4-diisocyanate; 1,4-butylene glycol dipropyl ether-2,3-diisocyanate; 1,4-butylene glycol dipropyl ether-2,4-diisocyanate; Methyllysine diisocyanate; Lysine triisocyanate; 2-isocyanatoethyl-2,6-diisocyanatohexanoate; 2-isocyanatopropyl-2,6-diisocyanatohexanoate; Mesityrylylenetriisocyanate; 2,6-di (isocyanatomethyl) furan and the like.

In the alicyclic diisocyanate compound, for example, 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; 4,9-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane; 2,5-Bis (isocyanatomethyl) bicyclo [2,2,1] heptane; 2,6-bis (isocyanatomethyl) bicyclo [2,2,1] heptane; Isophorone diisocyanate; Bis (isocyanatomethyl) cyclohexane; Dicyclohexyl methane diisocyanate; Cyclohexanediisocyanate; Methylcyclohexanediisocyanate; Dicyclohexyldimethylmethane diisocyanate; 2,2'-dimethyldicyclohexylmethane diisocyanate; Bis (4-isocyanato-n-butylidene) pentaerythritol; Dimer acid diisocyanate; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethylbicyclo [2,2,1] -heptane; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 1,3,5-tris (isocyanatomethyl) -cyclohexane; Dicyclohexylmethane-4,4-diisocyanate (H₁₂MDI) and the like.

Examples of the heterocyclic diisocyanate compound include thiophene-2,5-diisocyanate; Methyl thiophene-2,5-diisocyanate; 1,4-dithiane-2,5-diisocyanate; Methyl 1,4-dithiane-2,5-diisocyanate; 1,3-dithiolane-4,5-diisocyanate; Methyl 1,3-dithiolane-4,5-diisocyanate; Methyl 1,3-dithiolane-2-methyl-4,5-diisocyanate; Ethyl 1,3-dithiolane-2,2-diisocyanate; Tetrahydrothiophene-2,5-diisocyanate; Methyltetrahydrothiophene-2,5-diisocyanate; Ethyl tetrahydrothiophene-2,5-diisocyanate; Methyl tetrahydrothiophene-3,4-diisocyanate; 1,2-diisothiocyanatoethane; 1,3-diisothiocyanatopropane; 1,4-diisothiocyanatobutane; 1,6-diisothiocyanatohexane; p-phenylenediisopropylidenediisothiocyanate; Cyclohexanediisothiocyanate, and the like.

As said aliphatic thiodiisocyanate compound, For example, xylene thiodiisocyanate, 4-isocyanato-4'-isothiocyanato diphenyl sulfide; 2-isocyanato-2'-isothiocyanatodiethyl disulfide; Thiodiethyl diisocyanate; Thiodipropyl diisocyanate; Thiodihexyl diisocyanate; Dimethyl sulfon diisocyanate; Dithiodimethyl diisocyanate; Dithiodiethyl diisocyanate; Dithiodipropyl diisocyanate; Dicyclohexylsulphi-4,4'- diisocyanate; 1-isocyanatomethylthia-2,3-bis (2-isocyanatoethylthia) propane and the like.

The isocyanate compound is preferably isoprone diisocyanate; 1,6-hexamethylenedisocyananeate; And 4,4′-dicyclohexylmethane diisocyanate (H ₁₂ MDI).

In addition, the reaction mixture may further include an activated hydrogen compound as a reactant. As used herein, “activated hydrogen compound” includes pentaerythritol tetrakismercaptopropionate; Pentaerythritol tetrakismercaptoacetate; Ethylene glycol; Diethylene glycol; Propylene glycol; Dipropylene glycol; Butylene glycol; Neopentyl glycol; glycerin; Trimethylol ethane; Butanetriol; 1,2-methylchloride; Pentaerythritol; Dipentaerythritol; Tripentaerythritol; Sorbitol; Ethylene glycol; Thritol libitol (Treitol, Ribitol); Arabinitol; Xylitol; Alitol; Mannitol; Dolitol; Hydritol; Glycols; Inositol; Hexanetriol; Triglycerol; Diglycerol; Triethylene glycol; Polyethylene glycol; Tris (2-hydroxyethyl) isocyanurate; Cyclobutanediol; Cyclopentanediol; Cyclohexanediol; Cycloheptanediol; Cyclooctanediol; Cyclohexanedimethanol; Hydroxypropylcyclohexanol; Dihydroxynaphthalene; Trihydroxynaphthalene; Tetrahydroxynaphthalene; Dihydroxybenzene; Benzenetriol; Diphenyltetraol; Pyrogalol; (Hydroxynaphthyl) pyrogalol; Trihydroxyphenanthrene; Bisphenol A-tetrabrom; Bisphenol A-bis (2-hydroxyethyl ether); Polyols containing sulfur atoms such as 1,3-bis (2, hydroxyethylthioethyl) -cyclohexane; 1,2-ethanedithiol; 1,1-propanedithiol; 1,2-propanedithiol; 1,3-propanedithiol; 2,2-propanedithiol; 1,6-hexanedithiol; It means one or two or more compounds selected from the group consisting of 1,2,3-propanetriol and the compound represented by the following formula (2). As an activating hydrogen compound, Preferably, pentaerythritol tetrakismercaptopropionate; Pentaerythritol tetrakismecaptoacetate; And 2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2 (2-mercaptoethylthio) propylthio] ethylthio} propane-1-thiol compound each alone or 2 More than one species can be used together.

The use ratio of the isocyanate compound to the mixture of the thiol compound represented by the formula (1) and the active hydrogen compound is in the range of 0.5 to 3.0 functional molar ratio of (NCO) / (OH + SH), preferably 0.5 to 1.5. to be.

The resin composition of the present invention obtained by reacting the thiol compound 30 to 70 wt% with the isocyanate compound 30 to 70 wt% has a solid phase refractive index (nD, 20 ° C) of 1.572 to 1.632, a liquid phase refractive index of 1.520 to 1.570, a solid phase specific gravity of 1.15 to 1.26, Abbe number 32-50 of a solid resin, and liquid viscosity (20 degreeC) 5-800 cps.

The resin composition of the present invention may include from 0.0007 to 9% by weight of the ultraviolet absorber based on the total weight of the reaction mixture, preferably 0.5 to 3% by weight in order to improve the light stability of the prepared resin. If the UV absorber is used in a smaller amount than the above range, it is difficult to effectively block ultraviolet rays harmful to the eyes, and when it is used beyond this range, it is difficult to dissolve in the optical lens composition, and spot patterns appear on the surface of the cured optical lens or transparency of the optical lens. Problem may occur. As the ultraviolet absorbent, any known ultraviolet absorbent surface usable for the optical lens can be used. For example, ethyl-2-cyano-3,3-diphenyl acrylate; 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 4-dodecyloxy-2-hydroxybenzophenone; 4-benzoxoxy-2-hydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; 2,2'- dihydroxy-4,4'- dimethoxy benzophenone etc. can be used individually or in mixture of 2 or more types. Preferably, 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole, 2-hydroxy having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention. -4-methoxybenzophenone; Ethyl-2-cyano-3,3-diphenylacrylate; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3,5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole and 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like These may be used alone or in combination of two or more.

The lightweight resin for an optical lens of the present invention may include a known organic dye for improving the initial color of the lens and satisfying consumer's preference. In the embodiment of the present invention 1-hydroxy-4- (para- toluidine) anthraquinone [1-hydroxy-4- (p-toluidin) -anthraquinone], perinone dye (perinone dye) and the like for an optical lens composition 1 By adding 0.001 to 10,000 ppm, preferably 0.005 to 1,000 ppm per kg, it is possible to prevent the optical lens from becoming yellow by the addition of an ultraviolet absorber.

In addition, the resin composition of the present invention may further include an internal mold release agent. Examples of the internal mold release agent include fluorine-based nonionic surfactants having a perfluoroalkyl group, a hydroxyalkyl group or a phosphate ester group; Silicone nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts, ie, trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt; The component selected from the acidic phosphate ester can be used individually or in combination of 2 or more types. Preferably, acidic phosphate ester is used, and as acidic phosphate ester, isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl phosphate; Tridecanoic acid phosphate; Bis (tridecanoic acid) phosphate or the like may be used alone or in combination of two or more thereof. In the embodiment of the present invention, ZELEC UN ™ (DUPONT, Inc.), which is an acidic phosphate ester, showed the best demolding when demolding the mold from the lens after curing. The internal mold release agent may be used in an amount of 0.0001 to 10% by weight based on the total weight of the reaction mixture. Preferably, 0.005 to 2% by weight of the mold release agent in the lens has a high polymerization yield. If the amount of the release agent is less than 0.005%, a phenomenon may occur in which the lens adheres to the surface of the glass mold when the molded optical lens is separated from the glass mold, and if more than 2% by weight, the lens is separated from the glass mold during the polymerization of the mold. There is a problem that may cause stains on the surface.

As the polymerization initiator used to react the thiol compound and the isocyanate compound, an amine or tin compound may be used. As a tin type compound, Butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Stannous oxide; Dibutyl dilaurate; Tetrafluorotin; Tetrachlorotin; Tetrabromotin; Tetraidotin; Methyl tin trichloride; Butyltin trichloride; Dimethyltin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; Triphenyltin chloride; Dibutyltin sulfide; Di (2-ethylsecyl) tin oxide and the like may be used alone or in combination of two or more thereof. When such a tin compound was used, the polymerization yield was high and there was no bubble generation. The amount of use is preferably 0.0001 to 10% by weight based on the total weight of the reaction mixture.

When the resin composition for optical lenses of the present invention is thermoset, a plastic optical lens is obtained. Such plastic optical lenses include eyeglass lenses in particular. Preferred embodiments for preparing the spectacle lens by thermal curing the composition of the present invention are as follows. First, a polymerization initiator is finally added to the composition constituting the resin of the present invention, substituted with nitrogen to remove air in the mixing vessel (reactor), and then stirred under reduced pressure for 2 to 5 hours, and the stirring is stopped, followed by degassing under reduced pressure. Inject into the mold. The mold is preferably a glass mold or a metal mold fixed with polyester, polypropylene adhesive tape, or plastic gasket. The glass mold infused with the mixture was placed in a forced circulation oven, maintained at 33 to 37 ° C. for 2 hours, heated to 38 to 42 ° C. for 3 hours, heated to 80 to 90 ° C. for 10 hours, and 120 to 140 ° C. for 2 to 4 hours. After raising the temperature at 120 to 140 ° C. for 2 hours and cooling at 60 to 80 ° C. for 2 hours, the solid is released from the mold to obtain an optical lens. The optical lens thus obtained is annealed at a temperature of 120 to 140 ° C. for 1 to 4 hours to obtain a final desired plastic optical lens.

In addition, the optical lens obtained by the above method can be subjected to hard coating and multi-coating treatment in order to increase the optical characteristics. The hard coat layer may be formed of at least one silane compound having functional groups such as an epoxy group, an alkoxy group, a vinyl group, and at least one metal oxide colloid such as silicic acid oxide, titanium oxide, antimony oxide, tin oxide, tungsten oxide, and aluminum oxide. After impregnating the lens into the coating composition or by spin coating to form a coating layer with a thickness of 0.5 ~ 10㎛ on the surface of the optical lens, the coating film is completed by heating or UV curing.

The multi-coating layer, that is, the anti-reflective coating layer, may be formed by vacuum deposition or sputtering metal oxides such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide, and yttrium oxide. Can be. Most preferably, the silicon oxide film and the zirconium oxide film are alternately vacuum-deposited three times or more on both surfaces of the hard coating film of the lens, and finally, the silicon oxide film is vacuum deposited. In addition, an indium tin oxide (ITO) layer may be further provided as a water film layer between the final silicon oxide and the zirconium oxide film as necessary. The optical lens of the present invention may be used after coloring by adding a disperse dye or a photochromic dye to the hard liquid, if necessary.

The optical lens made of the light weight high refractive resin composition of the present invention has a low specific gravity, so that the lens is very light. In particular, GST (2,3-bis (2-mercaptoethylthio) prepared according to the applicant's prior application "Lightweight high refractive resin for optical lenses and optical lenses using the same" (Patent Application No. 10-2007-0077515) Propane-1-thiol), ETS4 (2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2 (2-mercaptoethylthio) -propylthio] -ethylthio} -propane -1-thiol), GMT (2- (2-mercaptoethylthio) propane-1,3-dithiol), MMPPT (2- (2-mercaptoethylthio) -3- {2- [3-mer Compared to Capto-2 (2-mercaptoethylthio) -propylthio] -ethoxy} -propane-1-thiol), the specific gravity is lower and lighter, and the heat distortion temperature is higher, so that the heat resistance is better. In addition, the raw material cost is about 30% lower and the VOLUME yield of the reactor during manufacturing is about 27%, so the overall production cost is significantly lowered to about 30-40%.

EXAMPLE

Hereinafter, the present invention will be described in 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.

Example 1

New thiol compound Y1S4A, (2-mercapto-ethylthio) -3- [4- (1- {4- [3-merca-pto-2- (2-mercaptoethylthio) -propyl] -phenyl} -1-methylethyl)- Preparation of phenoxy] -propane -propane-1-thiol Derivatives (Compound I)

To a 2 L flask, 200 g (0.535 mol, epoxy equivalent 187) of bisphenol A diglycidyl ether derivative and an aqueous NaOH solution (solution containing 5 ml of water in 0.5 g of NaOH) were added, and 83.56 g (1.07 mol) of 2-mercaptoethanol was added. Slowly added dropwise in the range of 50 ~ 60 ℃ and after the addition was finished to mature for about 1 hour at 60 ℃ to obtain an intermediate. The reaction solution was cooled to 30 ° C., 195.33 g (2.577 mol) of thiourea and 278.92 mL (3.208 mol) of 36% concentrated hydrochloric acid were added, and the mixture was refluxed at 110 ° C. for 3 hours 30 minutes. After the reaction was completed, the reaction solution was cooled and 240.18 ml of 25% aqueous ammonia was slowly added dropwise not to exceed 30 ° C. Then, 400 ml of toluene was added, hydrolyzed and cooled at 80 ° C. for 1 hour and 30 minutes, and the organic layer was separated with a separating funnel, washed with 150 ml of 36% concentrated hydrochloric acid, and washed with 150 ml of deionized water. Water was removed from the organic layer obtained by separation to obtain the desired thiol compound, Compound I (Y1S4A) (equivalent to 148.63), at a yield of 286.1 g and 90%.

Compound I

Example 2

New thiol compound Y1S4B, (2-mercapto-ethylthio) -3- [4- (1- {4- [3-mer capto-2- (2-mercaptoethylthio) -propyl] -phenyl} -1-methyl-ethyl) Preparation of -phenoxy] -pro pane-propane-1-thiol Derivatives (Compound II)

To a 2 L flask, 211 g (0.535 mol, epoxy equivalent 198) of bisphenol A diglycidyl ether derivative and an aqueous NaOH solution (solution of 5 ml of water in 0.5 g of NaOH) were added, and 83.56 g (1.07 mol) of 2-mercaptoethanol was added. Slowly added dropwise in the range of 50 ~ 60 ℃ and after the addition was finished aged for 1 hour at 55 ℃ to obtain an intermediate. The reaction solution was cooled to 30 ° C., 195.33 g (2.577 mol) of thiourea and 278.92 mL (3.208 mol) of 36% concentrated hydrochloric acid were added, and the mixture was refluxed at 110 ° C. for 3 hours 30 minutes. After the reaction was completed, the reaction solution was cooled and 240.18 ml of 25% aqueous ammonia was slowly added dropwise not to exceed 30 ° C. Then, 400 ml of toluene was added, hydrolyzed and cooled at 80 ° C. for 1 hour and 30 minutes, and the organic layer was separated with a separating funnel, washed with 150 ml of 36% concentrated hydrochloric acid, and washed with 150 ml of deionized water. Water was removed from the organic layer obtained by separation to obtain the desired thiol compound, Compound II (Y1S4B) (equivalent 154.13) in 286.9 g, 87% yield.

Compound Ⅱ

Example 3

Novel Thiol Compounds Y1S4C, (2-mercapto-ethylthio) -3- [4- (1- {4-

Preparation of [3-mercapto-2- (2-mercapto-ethylthio) -propyl] -phenyl} -1-methyl-ethyl) -phenoxy] -propane-propane-1-thiol derivative (Compound III)

To a 2 L flask, 246 g (0.535 mol, epoxy equivalent 230) of bisphenol A diglycidyl ether derivative and an aqueous NaOH solution (solution dissolved in 5 g of water in 0.5 g of NaOH) were added, and 83.56 g (1.07 mol) of 2-mercaptoethanol was added. Slowly added dropwise in the range of 50 ~ 60 ℃ and after the addition was finished aged for 1 hour at 55 ℃ to obtain an intermediate. The reaction solution was cooled to 30 ° C., 195.33 g (2.577 mol) of thiourea and 278.92 mL (3.208 mol) of 36% concentrated hydrochloric acid were added, and the mixture was refluxed at 110 ° C. for 3 hours 30 minutes. After the reaction was completed, the reaction solution was cooled and 240.18 ml of 25% aqueous ammonia was slowly added dropwise not to exceed 30 ° C. Then, 400 ml of toluene was added, hydrolyzed and cooled at 80 ° C. for 1 hour and 30 minutes, and the organic layer was separated with a separating funnel, washed with 150 ml of 36% concentrated hydrochloric acid, and washed with 150 ml of deionized water. Water was removed from the separated organic layer to obtain the desired polythiol compound, Compound III (Y1S4C) (equivalent 170.13), at a yield of 309.5 g and 85%.

Compound III

Example 4

New thiol compound Y1S4D, (2-mercapto-ethylthio) -3- [4- (1- {4-

Preparation of [3-mercapto-2- (2-mercapto-ethylthio) -propyl] -phenyl} -1-methyl-ethyl) -phenoxy] -propane-propane-1-thiol derivative (Compound IV)

To a 2 L flask, 316 g of bisphenol A diglycidyl ether derivative (0.535 mol, epoxy equivalent 295) and an aqueous NaOH solution (solution containing 5 ml of water in 0.5 g of NaOH) were added, and 83.56 g (1.07 mol) of 2-mercaptoethanol was added. Slowly added dropwise in the range of 50 ~ 60 ℃ and after the addition was finished aged for 1 hour at 55 ℃ to obtain an intermediate. The reaction solution was cooled to 30 ° C., 195.33 g (2.577 mol) of thiourea and 278.92 mL (3.208 mol) of 36% concentrated hydrochloric acid were added, and the mixture was refluxed at 110 ° C. for 3 hours 30 minutes. After the reaction was completed, the reaction solution was cooled and 240.18 ml of 25% aqueous ammonia was slowly added dropwise not to exceed 30 ° C. Then, 400 ml of toluene was added, hydrolyzed and cooled at 80 ° C. for 1 hour and 30 minutes, and the organic layer was separated with a separating funnel, washed with 150 ml of 36% concentrated hydrochloric acid, and washed with 150 ml of deionized water. Water was removed from the separated organic layer to obtain the desired polythiol compound, Compound IV (Y1S4D) (equivalent to 202.63) in a yield of 346.9 g and 80%.

Compound IV

Example 5

New thiol compound Y1S4E, (2-mercapto-ethylthio) -3- [4- (1- {4-

Preparation of [3-mercapto-2- (2-mercapto-ethylthio) -propyl] -phenyl} -1-methyl-ethyl) -phenoxy] -propane-propane-1-thiol derivative (Compound V)

To a 2 L flask, 486.85 g (0.535 mol, epoxy equivalent 455) of bisphenol A diglycidyl ether derivative and an aqueous NaOH solution (solution dissolved in 5 ml of water in 0.5 g of NaOH) were added and 83.56 g (1.07 mol) of 2-mercaptoethanol Was slowly added dropwise in the range of 50-60 ° C. and aged at 55 ° C. for about 1 hour after the dropwise addition was completed to obtain an intermediate. The reaction solution was cooled to 30 ° C., 195.33 g (2.577 mol) of thiourea and 278.92 mL (3.208 mol) of 36% concentrated hydrochloric acid were added, and the mixture was refluxed at 110 ° C. for 3 hours 30 minutes. After the reaction was completed, the reaction solution was cooled and 240.18 ml of 25% aqueous ammonia was slowly added dropwise not to exceed 30 ° C. Then, 400 ml of toluene was added, hydrolyzed and cooled at 80 ° C. for 1 hour and 30 minutes, and the organic layer was separated with a separating funnel, washed with 150 ml of 36% concentrated hydrochloric acid, and washed with 150 ml of deionized water. Water was removed from the separated organic layer to obtain the desired thiol compound, Compound V (Y1S4E) (equivalent 282.63), at a yield of 471.7 g and 78%.

Compound V

Example 6

Manufacture of Optical Lens

56.39 g of Compound I (Y1S4A) prepared in Example 1; 19.82 g of isophorone diisocyanate; 23.79 g of hexamethylene diisocyanate; 1.50 g of 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole as an ultraviolet absorber; 1.0 g of polyoxyethylene nonylphenyl phosphate as a releasing agent; 70 ppm of 1-hydroxy-4- (para-toluidine) anthraquinone (Blue) as an organic dye; Perinone dye 30 ppm; 0.1 g of dibutyltin dichloride as a polymerization initiator was placed in a mixing vessel equipped with a stirrer, and substituted with nitrogen to remove air in the mixing vessel, followed by stirring under reduced pressure for 2 hours. The mixture was injected into a glass mold (diopta-5.00, center thickness 1.2 mm) fixed by using nitrogen gas. The glass mold injected with the mixture was placed in a forced circulation oven, maintained at 33 ° C. for 2 hours, heated at 33 ° C. to 40 ° C. for 3 hours, heated at 40 ° C. to 90 ° C. for 10 hours, and heated at 90 ° C. to 130 ° C. for 4 hours, After holding for 2 hours at 130 ° C and cooling for 2 hours at 130 ° C to 70 ° C, the glass mold was detached to obtain a plastic optical lens.

The manufactured lens was evaluated for physical properties in the following manner and the results are shown in Table 1 below. As a result of the evaluation, as shown in Table 1, the manufactured lens had a high refractive index (nD) of 1.588, an Abbe number of 38, high optical properties such as impact resistance, light resistance, and transparency, and low specific gravity of 1.21.

Property evaluation

(1) Refractive index and Abbe's number: It measured using the Abe refractometer (1T model) of Atago.

(2) Specific gravity: It was calculated by measuring the volume and weight of the optical lens using an underwater substitution method.

(3) Heat deflection temperature (Tg): Measured using a Thermomechanical Analyzer (TMA).

(4) Edge bubble: After casting, 10 lenses were visually observed and marked as X when there was a bubble of 0.5 mm moving, and O when there was no bubble.

(5) Poor polymerization

A lens was placed on a USHIO mercury lamp (USH-102D) and visually observed to indicate non-uniformity.

Examples 7-50

Manufacture of Optical Lens

Except having set it as the composition of Tables 1-6, it carried out similarly to Example 6, and manufactured the optical lens. Lenses prepared using the compounds of Y1S4B, Y1S4C, Y1S4D and Y1S4E having different equivalents prepared in Examples 2 to 5 had better deformability, heat resistance, and light resistance than the lenses prepared using the compounds of Y1S4A of Example 1 . Their tendency was Y1S4A> Y1S4B> Y1S4C> Y1S4D> Y1S4E. In particular, spectacle lenses made of Y1S4C, Y1S4D, and Y1S4E did not have better deformability than Y1S4A, and had severe yellowing. In particular, the compound resin containing n = 4 or more in the general formula (1) was difficult to demould as the viscosity is high and the number of hydroxy groups was difficult, the bubble was severe. When the spectacle lens was manufactured using Y1S4C resin, demolding, striae, and poor polymerization were seen, but not severe. However, the spectacle lens manufactured using the resins of Y1S4D and Y1S4E had a high bubble viscosity and poor defoaming, resulting in severe foaming and greatly increasing striae and poor polymerization. The physical properties of the prepared lens were also evaluated in the same manner and shown in Tables 1 to 6 together.

Comparative Examples 1 to 6

Manufacture of Optical Lens

The optical lens was manufactured in the same manner as in Example 6 except for using the composition shown in Table 7 below. Physical properties of the prepared spectacle lens were also evaluated in the same manner and shown in Table 7 together.

Table 1

TABLE 2

TABLE 3

Table 4

Table 5

Table 6

TABLE 7

Abbreviation of Tables 1-7

[Monomer]

ETS4: 2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2 (2-mercaptoethylthio) propylthio] ethylthio} propane-1-thiol

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

GMT: 2- (2-mercaptoethylthio) propane-1,3-dithiol

PETMP: pentaerythritol tetrakismercaptopropionate

(pentaerythritol tetrakis (3-mercaptopropionate))

MMPPT: 2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2 (2-mercaptoethylthio) -propylthio] -ethoxy} -propane-1-thiol

IPDI: isopron diisocyanate

HDI: 1,6-hexamethylenedisocyananeate

H ₁₂ MDI: 4,4'-dicyclohexylmethane diisocyanate

[Organic Dyes]

HTAQ: 1-hydroxy-4- (p-toluidine) anthraquinone

      (1-hydroxy-4- (p-toluidin) anthraquinone)

PRD: perinone dye

[Release agent]

POEP: Polyoxyethylene nonyl phenyl phosphate

[UV absorber]

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

(2- (2'-hydroxy-5'- t -octylphenyl) benzotriazole)

[Polymerization Initiator]

BTC: dibutyltin dichloride

The resin composition of the present invention can be usefully used in various optical lenses because of its high refractive index, light weight, and low production cost. In particular, the resin composition of the present invention can thin the edge thickness of the lens even at a high degree of power and can reduce the production cost by 30% or more significantly compared to the existing lens. It is expected to be.

Claims (13)

1. Resin composition for an optical lens comprising a thiol compound and an isocyanate compound represented by the formula (1).

   [Formula 1]

   
2. The compound of claim 1, wherein 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2 (2-mercaptoethylthio) -propylthio] ethylthio} -propane-1-thiol; And one or two or more thiol compounds selected from the group consisting of 2- (2-mercaptoethylthio) propane-1,3-dithiol.
3. The method of claim 1, wherein the isocyanate compound is an alkylene diisocyanate compound; Alicyclic diisocyanate compounds; Heterocyclic diisocyanate compounds; And an aliphatic diisocyanate compound and at least one compound selected from the group consisting of optical lens resin compositions.
4. The method according to claim 3, wherein the isocyanate compound is isopron diisocyanate; 1,6-hexamethylene diisocyanate; 4,4'-cyclohexyl methane diisocyanate (H ₁₂ MDI); Xylene diisocyanate; And one or two or more compounds selected from the group consisting of tolylene diisocyanate.
5. The method of claim 1, wherein the resin composition further comprises an activated hydrogen compound, the ratio of use of the isocyanate compound to the mixture of the thiol compound and the activated hydrogen compound is (NCO) / (OH + SH) functional molar ratio of 0.5 ~ The resin composition for optical lenses which is the range of 3.0.
6. The method according to claim 5, wherein the activated hydrogen compound is pentaerythritol tetrakismercaptopropionate; Pentaerythritol tetrakismecaptoacetate; Trimethylolpropane tris (mercaptopropionate); Trimethylol ethane tris (mercaptopropionate); And 1 type selected from the group consisting of 2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2 (2-mercaptoethylthio) propylthio] ethylthio} propane-1-thiol or Resin composition for optical lenses which is a 2 or more types of compound.
7. The said resin composition is obtained by making 30-70 weight% of thiols and an activated hydrogen compound, and 30-70 weight% of isocyanate compounds, and the solid-state refractive index (nD, 20 degreeC) 1.572-1.632 , Liquid refractive index 1.520 ~ 1.570, solid phase specific gravity 1.15 ~ 1.28, solid phase The resin composition for optical lenses whose Abbe's number of resin is 32-50, and liquid viscosity (20 degreeC) 5-800 cps.
8. The method according to claim 1, 0.0007 to 9% by weight of the ultraviolet absorbent based on the total weight of the resin composition; A resin composition for an optical lens, further comprising 0.0001 to 10% by weight of an internal release agent and 0.0001 to 10% by weight of a polymerization initiator.
9. The method according to claim 8, wherein the ultraviolet absorber is 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 4-dodecyloxy-2-hydroxybenzophenone; 4-benzooxy-2-hydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; And 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, or a resin composition for an optical lens, which is selected from the group consisting of 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
10. The method according to claim 8, wherein the internal mold release agent isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl phosphate; Tridecanoic acid phosphate; And one or two or more acidic phosphate esters selected from the group consisting of bis (tridecanoic acid) phosphates.
11. The resin composition of claim 8, wherein the polymerization initiator is a tin-based or amine-based compound.
12. The method of claim 11, wherein the tin-based compound, Butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Oxalic acid stannous; Dibutyl dilaurate; Tetrafluorotin; Tetrachlorotin; Tetrabromotin; Tetraiodine tin; Methyl tin trichloride; Butyltin trichloride; Dimethyltin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; Triphenyltin chloride; Dibutyltin sulfide; And di (2-ethylsecyl) tin oxide, and a resin composition for an optical lens, which is one or two or more compounds selected from the group consisting of:
13. A plastic spectacle lens obtained by thermosetting the resin composition for an optical lens of claim 1.