KR101915818B1 - Optical Resin Composition using polytiolester composition and the Plastic Ophthalmic Lens using it - Google Patents

Abstract

The present invention relates to a resin composition for an optical lens comprising a bispentaerythritol derivative and a polythiol ester compound prepared by using a raw material having high purity obtained by purifying a thiol-based acid, and an optical lens using the resin composition. A spectacle lens manufactured by mixing an optical resin composition obtained by mixing 35 to 70% by weight of a polythiol ester compound and 30 to 65% by weight of a diisocyanate compound and further adding an ultraviolet absorber, a releasing agent and a polymerization initiator, The multi-membrane is not easily cracked by heat, is less deformed by heat, and has excellent tendency, formability, dyeability, Abbe number, transparency and ultraviolet light shielding ability as well as industrial safety glasses lens size (127cm, And an excellent impact resistance which is in conformity with the test (experiment).

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition for an optical lens using a polythiol ester compound, and an optical lens using the resin composition.

The present invention relates to a resin composition for an optical lens excellent in heat resistance and impact resistance using a polythiol ester compound prepared by using a raw material having high purity obtained by purifying a bispentaerythritol derivative and a thiol-based acid, and an optical lens using the same More specifically, it has excellent optical properties such as lightness, moldability, dyeability, Abbe number and transparency, but also has a high initial heat distortion temperature of the solid resin, so that it is resistant to impact even after multi-coating and the multi- have.

Glass lenses, which have been widely used as optical lenses for a long time, have a low coefficient of thermal expansion, which causes less distortion of the lens due to changes in external temperature and has a merit that the surface of the multi-layer treated with the surface has less damage due to the temperature change in order to increase the transmittance. However, since the glass lens is weak in impact and heavy in weight, it is now being replaced by a plastic lens which is light in weight, excellent in impact resistance, and excellent in workability such as dyeing compared to a glass lens.

The monomer of the plastic lens is required to have a low specific gravity, a high refractive index, a high Abbe number and a high heat resistance, and the development of an optical lens material has been continuously studied.

In order to produce an optical lens, uniform resin composition is required in order to obtain the optical lens manufacturing easiness and the uniform quality of the optical lens. In order to produce a uniform and clear lens with a uniform color, A composition is required.

In recent years, as the demand for the transmittance and the stability level of plastic lenses has increased, most optical lenses, in particular the spectacle lenses, are subjected to multi-coating (SiO ₂ , ZrO ₂ ) on both surfaces of the lens to increase the transmittance. There is a problem that the lens is easily broken by concentrating the impact applied from the outside in one place.

Copolymers of diaryl isophthalate, diaryl isophthalate and diethylene glycol bisaryl carbonate to which divalent alcohol is added, known in Korean Patent Publication No. 1992-0004464, xylene diisocyanate known in Korean Patent Laid-open Publication No. 1994-004010 Even in the case of plastic spectacle lenses manufactured using 1,2-bis (mercaptoethyl) -3-mercaptopropane or polymethylmethacrylate copolymer, the spectacle lens easily breaks due to multi-coating in order to increase the transmittance Respectively.

Injection molded polycarbonate optical lens has a relatively high impact strength after multi-coating, but it has a disadvantage in that it is severely deformed by heat during use due to the characteristics of the thermoplastic resin. However, the thickness of the lens is thinner than the thicker edge This causes a problem of eye dizziness when the spectacle lens is worn, and the Abbe number, which is an important optical characteristic, is lowered.

Resins for thermally intercalated plastic lenses have been proposed as an alternative to solve the problems with respect to the thermal stability of the lenses made of the thermoplastic resin. In Korean Patent Nos. 0638194 and 0688698, a modified polythiol and a diisocyanate are mixed A method of manufacturing an optical lens is known. However, the impact resistance and the heat resistance were improved to some extent, but the injection rate into the glass mold was very slow due to the high viscosity of the monomer composition liquid for casting the lens, and it was difficult to remove the bubbles generated during the injection, And the injection mark remains on the lens. Further, defects due to polymerization imbalance occur frequently, refractive index is as low as about 1.523, and the edge of the lens is thickened.

Korean Patent Publication No. 472837 improves the impact strength of a lens by adding a dihydric alcohol to a diisocyanate followed by mixing with a tetravalent polythiol and thermally curing to produce an optical lens. However, although the optical lens composition according to the above patent can increase the impact strength in the state of raw paper (plastic lens not subjected to post-processing), after the multi-coating, the impact resistance is lowered to satisfy FDA standard (127cm 16.3g) I did not. In addition, when the diisocyanate was added with dihydric alcohol in advance to prepare the monomer composition for an optical lens, many defects occurred due to the high viscosity of the composition. The optical lens composition is sufficient as a strength for forming a vitreous spectacle lens, but is often insufficient as a spectacle lens that is safe for impact.

In Korean Patent No. 771176, an impact resistant optical lens was prepared by reacting diisophorone diisocyanate and hexamethylene diisocyanate with tetravalent polythiol. The manufactured optical lens passed the FDA impact test (127cm 16.3g), but not the industrial safety spectacle lens standard (127cm, 44g), not only in the raw state but also after multi-coating. In addition, since the coefficient of thermal expansion of the solid resin is high, it is deformed by heat in a high-temperature industrial field, a steam film, or the like, and the multi-film of the lens is easily split. The cracking of the multi-layer film significantly reduces the transmittance of the lens, which results in a problem that the function as the optical lens is lost.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a thiol-based compound containing a bispentaerythritol derivative and an intermolecular condensation thioester compound containing a mononuclear species, a trinuclear species, an alkali metal and an alkaline earth metal, The acid was purified to obtain a high purity raw material, and the polythiol ester compound was prepared.

The optical lens using the resin composition for an optical lens containing the polythiol ester compound according to the present invention is excellent in optical properties such as light weight, moldability, dyeability, Abbe number, transparency and ultraviolet barrier property, It has the advantage of satisfying the industrial safety standard (127cm, 44g).

In addition, since the initial heat distortion temperature is low, it is possible to provide a clear plastic spectacle lens while being clear (85 DEG C, 60 minutes) without cracking of the multi-layer due to heat.

SUMMARY OF THE INVENTION

35 to 70% by weight of one or more polythiol ester compounds represented by the formula (1);

One or two of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4-methylene bis (cyclohexyl isocyanate) (H ₁₂ MDI), and trimethyl-1,6-diisocyanatohexane And 30 to 65% by weight of a diisocyanate compound (component II) obtained by mixing the above-mentioned diisocyanate compound (II).

(R ₁ = alkylene having 1 to 4 carbon atoms; x = 0 to 2; y = 0 to 2; z = 0 to 2)

Another object of the present invention is to provide a resin composition for an optical lens, which further comprises an ultraviolet absorber, a release agent, and a polymerization initiator in the resin composition for an optical lens. Preferably, the resin composition further comprises 0.001 to 6 parts by weight of an ultraviolet absorber, 0.0001 to 6 parts by weight of a release agent, and 0.001 to 6 parts by weight of a polymerization initiator, based on 100 parts by weight of the resin composition for an optical lens.

Further, another object of the present invention is to provide an optical lens using the resin composition for an optical lens.

The spectacle lens obtained by thermosetting the composition for an optical lens according to the present invention is clear, transparent, has a high initial heat distortion temperature, is excellent in heat resistance of the multi-layer film and does not cause cracking of the multi- 127cm, 44g), and it has the effect of being usefully used in high temperature environment and various industrial fields.

The polythiol ester compound used in the present invention is a hexanediol polythiol ester compound in which six thiol groups are present in one molecule, and bispentaerythritol-ether-hexakis (3-mercaptopropionate), bispentaerythritol- 35 to 70% by weight of one or more of hexakis (mercaptoacetate), hexakis (3-mercapto-propionyloxymethyl) -ethane and hexakis (mercaptoacetyloxymethyl) Can be used.

The polythiol ester compound according to the present invention can be produced by reacting mercaptopropionic acid or mercaptoacetic acid containing an intermolecular condensation thioester compound with mercuric acid having a purity of 95% or more obtained by purifying mercuric acid or a mixture of mononuclear species, trinuclear species, alkali metals and alkaline earth metals A bispentaerythritol derivative having a high purity which has undergone a purification process to remove impurities is a colorless transparent product obtained by condensation reaction with para-toluenesulfonic acid as an esterification catalyst and has a YI value of less than 1.

The composition containing the polythiol ester compound according to the present invention is excellent in impact resistance and heat resistance, and can obtain a clear optical lens with no cloudiness and clearness.

In the condensation reaction for obtaining the polythiol ester compound, mercaptopropionic acid and mercaptoacetic acid can be purified by fractional distillation to increase the purity. Industrial reagents of bispentaerythritol derivatives have a purity of at least 86% , Monomers prepared by passing activated carbon, silica gel and alumina column to remove trinary species, alkali metals and alkaline earth metals are used while being stored at 15 ° C.

If, during the manufacturing process, 3-mercaptopropionic acid having a purity of 88% containing 86% bispentaerythritol and intermolecular condensation thioester compound containing a mononuclear species, a trinuclear species, an alkali metal and an alkaline earth metal and a purity of 85% In the case of cross-linking a diisocyanate with a polythiol ester compound having a YI (yellow index) value of 3 or more obtained by the reaction of acetic acid, the obtained optical lens is not preferable because it can not obtain a clear and transparent lens having an impact resistance, heat resistance, .

The polythiol ester compounds in which 6 thiol reactors are present are 1,2-bis- (mercaptoethyl) -3-mercaptopropane in which three reactors are present or pentaerythritol tetrakis mercaptothrene in which four reactors are present Unlike phytonate or pentaerythritol tetrakis mercaptoacetate, irregularity is large when crosslinked with diisocyanate, so that the initial heat distortion temperature of the solid resin is high. This is because the spectacle lens is manufactured to reduce the phenomenon of multi- You can give. In addition, the impact strength was measured by using hexakis (3-mercapto-propionyloxymethyl) -ethane, hexakis (mercapto-acetyloxymethyl) -ethane, 1- (2,2,2-tris (Mercapto propionyloxymethyl) ethoxy) -3- (2,2,2-tris (3-mercaptopropionyloxymethyl) ethoxy) -2,2-bis (3-mercaptopropionyloxymethyl ) Propane is used, the impact strength is increased by further increasing the hydrogen bonding between the molecules when 1,2-bis- (mercaptoethyl) -3-mercaptopropane, which is a thiol compound having no ester group in the molecule, is used .

Preferred are bispentaerythritol-ether-hexakis (3-mercaptopropionate), bispentaerythritol-ether-hexakis (mercaptoacetate), hexakis (3-mercapto-propionyloxymethyl) Ethane, hexakis (mercapto-acetyloxymethyl) -ethane, 1- (2,2,2-tris (3-mercaptopropionyloxymethyl) ethoxy) -3- (3-mercaptopropionyloxymethyl) ethoxy) -2,2-bis (3-mercaptopropionyloxymethyl) propane, 1- (2,2,2- Bis (mercaptoacetyloxymethyl) propane, 1- (2,2-bis (3-mercaptoethoxy) (2,2,2-tris (mercaptopropionyloxymethyl) ethoxy-2,2-dimethyl-propionyloxymethyl) -2- (3- (3-mercaptopropionyloxymethyl) ethoxy) -3- Bis (mercaptopropionyloxymethyl) propane, 1- (2,2-bis (mercaptoacetyloxymethyl) -2 - (2- (mercaptoacetyloxymethyl) ethoxy) -3- (2,2,2-tris (mercaptoacetyloxymethyl) ethoxy-2,2-bis (mercaptoacetyloxymethyl) , Or a mixture thereof is preferably used.

Hexaquis (3-mercapto-propionyloxymethyl) -ethane and hexakis (mercapto-acetyloxymethyl) -ethane. However, in this case, the refractive index and heat resistance of the optical lens can be improved to some extent, but since the symmetry of these molecules is large and there is no atom having electron attracting ability such as oxygen at the center, the intramolecular and intermolecular interactions are reduced, And the composition may be injected into a glass mold and cause defects such as the generation of air bubbles at the edge of the lens upon thermal curing, which is not preferable.

Diisocyanate compound is isophorone diisocyanate (IPDI) alone or isophorone diisocyanate to hexamethylene diisocyanate (IPDI) (HDI), 4,4'- methylenebis (cyclohexyl isocyanate) for use in the invention ₍₁₂ H MDI) and trimethyl-1,6-diisocyanatohexane are used as the diisocyanate compound.

When isophorone diisocyanate (IPDI) alone is used, the thermal expansion coefficient can be reduced, but bubbles may be generated at the edges of the lens during curing, and the impact strength may be somewhat lowered. However, when isophorone diisocyanate (IPDI) is added with hexamethylene diisocyanate (HDI), 4,4'-methylenebis (cyclohexyl isocyanate) (H ₁₂ MDI) and trimethyl-1,6-diisocyanatohexane 40 wt.% Of the total weight of the glass lens, the initial heat distortion temperature is increased without generating air bubbles at the edges of the lens, and a spectacle lens having excellent impact strength can be obtained. 40% or more of hexamethylene diisocyanate (HDI), 4,4'-methylene bis (cyclohexyl isocyanate) (H ₁₂ MDI) and trimethyl-1,6-diisocyanatohexane are mixed with isophorone diisocyanate (IPDI) The thermal resistance of the solid-state resin sharply drops, and the coefficient of thermal expansion sharply increases. Preferably, hexamethylene diisocyanate (HDI), 4,4'-methylenebis (cyclohexylisocyanate) (H ₁₂ MDI) and trimethyl-1,6-diisocyanatohexane are added to isophorone diisocyanate (IPDI) Or a mixture of two or more species in an amount of about 5 to 30% is preferably used. Further, although xylylene diisocyanate can be used in combination to increase the refractive index, there is a problem that the impact resistance is low, which is not preferable.

In the present invention, 0.001 to 6 parts by weight of an ultraviolet wetting agent may be used for 100 parts by weight of the resin composition for an optical lens, in order to improve the light resistance of the plastic spectacle lens and to block ultraviolet rays. As the ultraviolet ray absorbing agent to be used, any known ultraviolet ray absorbing agent that can be used in the plastic spectacle lens can be used without limitation and is not particularly limited for the present invention. For example, ethyl-2-cyano-3,3-diphenylacrylate, 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; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and the like, or a mixture of two or more thereof. 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole, which has good ultraviolet ray absorbing ability in a wavelength range of 400 nm or less and has good solubility in the composition of the present invention, 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- Butyl-5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'- -Chloro-2H-benzotriazole, 2,2-dihydroxy-4,4'-dimethoxybenzophenone, and the like can be used.

In order to improve the initial color of the lens, the composition of the present invention may further comprise an organic dye.

In the examples of the present invention, 1-hydroxy-4- (p-toluidino) anthraquinone and perinone dyes were used. By adding such an organic dye in an amount of 0.001 to 50,000 ppm, preferably 0.005 to 1000 ppm, per 1 kg of the monomer composition, it is possible to prevent the lens from being yellowed by adding the ultraviolet absorbent.

In the present invention, the releasing agent may be a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group or a phosphate ester group, a silicone-based nonionic surfactant having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group, an alkyl quaternary ammonium salt, A component selected from cetyl ammonium salt, trimethylstearyl, dimethylethyl cetyl ammonium salt, triethyldodecyl ammonium salt, trioctyl methyl ammonium salt, diethyl cyclohexadecyl ammonium salt, phosphoric acid ester and phosphonic acid ester may be used singly or in combination of two or more have. Preferably, phosphoric acid esters or phosphonic acid esters are used. Examples of the phosphoric acid ester include isopropyl acid phostate; Diisopropyl acid phosphate; Butyl acid phosphate; Octyl acid phosphate; Dioctyl acid phosphate; Isodecylic acid phosphate; Diisodecyl acid phosphate; Tridecanolic acid phosphate; Bis (tridecanolic acid) phosphate, and the like, or a mixture of two or more thereof. As a result of the use in the examples of the present invention, ZELEC UN (DUPONT Co.), which is phosphate ester, showed the best deformation when the mold was demolded from the lens after curing. The amount of the releasing agent to be added may be 0.0001 to 6 parts by weight based on 100 parts by weight of the resin composition for an optical lens, but preferably 0.001 to 4 parts by weight. When the added amount of the releasing agent is less than 0.0001 parts by weight, the glass mold surface is attached to the lens when the formed spectacle lens is separated from the glass mold. When the amount exceeds 4 parts by weight, the lens is separated from the glass mold during the casting polymerization There has been a problem that the surface of the lens is stained.

The polymerization initiator used in the present invention may be an amine-based or tin-based compound. As the tin compound, butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Stannous octoate; Dibutyl tin dilaurate; Tetrafluoro-tin; Tetrachlorotin; Tetrabromoquite; Tetraiodide tin; Methyl tin trichloride; Butyltin trichloride; Dimethyl tin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; triphenyltin chloride; Dibutyltin sulfide; Di (2-ethyl sec-butyl) tin oxide, etc. may be used alone or in combination of two or more. When such a tin compound was used, the polymerization yield was high and bubbles were not generated. The amount to be used is preferably 0.001 to 6 parts by weight based on 100 parts by weight of the resin composition for an optical lens.
The resin composition for an optical lens of the present invention thus prepared preferably has a liquid refractive index (nD) of 1.20 to 1.59, a refractive index of a solid phase (nD) of 1.30 to 1.63, an Abbe number of 28 to 52, 2000 cps.

The optical resin composition of the present invention is thermally cured to obtain a plastic optical lens, particularly a plastic spectacle lens. A preferred embodiment for producing a spectacle lens by thermosetting the composition of the present invention is as follows. First, the polymerization initiator is added to the composition of the present invention, and then the air is removed from the blending container by substituting with nitrogen. Thereafter, the mixture is subjected to reduced pressure stirring for 2 to 5 hours, stirring is stopped, do. The mold preferably uses a glass mold or a metal mold fixed with a plastic gasket or a polyester or polypropylene adhesive tape. The glass mold in which the mixture was injected was placed in a forced circulation oven and maintained at 33 to 37 DEG C for 2 hours, heated at 38 to 42 DEG C for 3 hours, heated at 80 to 90 DEG C for 10 hours, Maintained at 120 to 140 캜 for 2 hours, cooled at 60 to 80 캜 for 2 hours, and then the solid material is released from the mold to obtain an optical lens. The optical lens thus obtained is annealed at a temperature of 120 to 140 DEG C for 1 to 4 hours to obtain a final desired plastic spectacle lens (raw paper).

The optical lens obtained by the above method was subjected to hard coating and multi-coating treatment in order to improve the optical characteristics. The formation of the hard coat layer is carried out by mixing at least one silane compound having a functional group such as an epoxy group, an alkoxy group and a vinyl group with at least one metal oxide colloid such as silicon oxide, titanium oxide, antimony oxide, tin oxide, tungsten oxide, Was coated on the surface of the optical lens with a thickness of 0.5 to 10 占 퐉 by impregnation or spin coating, and then the coating film was completed by heating or UV curing.

The multi-coating layer, that is, the antireflection coating layer can be formed by a method of vacuum-depositing or sputtering a metal oxide such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide or yttrium oxide. Most preferably, the silicon oxide and the zirconium oxide film are repeatedly vacuum-deposited on the double-sided hard coating film of the lens three times or more, and then the silicon oxide film is finally vacuum-deposited. Depending on demand, an ITO layer may be further interposed between the silicon oxide and the zirconium oxide film as a water film layer on the last layer.

The plastic spectacle lens of the present invention can be used by coating a dispersion liquid or a photochromic dye with a hard liquid, if necessary.

Hereinafter, examples and comparative examples of the present invention will be described in detail, but the present invention is not limited thereto.

Example  One

Polythiol  Preparation of ester compounds

Preparation of polythiol ester compound BPEHMP ( bispentaerythritol - ether- hexakis (3- mercaptopropionate))

A 2-liter four-necked flask was charged with 3-mercaptopropionic acid (551 g, 5.19 mol) having a purity of 93.0%, fractionated distillation, 94.0% bispentaerythritol Ether (220.00 g, 0.86 mol), para-toluenesulfonic acid (5 g) and toluene (500 g) were added and the by-product water was continuously withdrawn under reflux with heating. React for about 10 hours and cool to room temperature. The amount of by-product water is 99.4% of the theoretical production number. The reaction solution was washed with a base, followed by water washing, and toluene and a trace amount of water were removed under heating and reduced pressure. Thereafter, 657 g (0.84 mol) of BPEHMP was obtained by filtration. YI: 0.80.

Preparation of polythiol ester compound BPEHMA ( bispentaerythritol - ether - hexakis (mercaptoacetate)

Instead of using 3-mercaptopropionic acid, mercaptoacetic acid (thioglycolic acid) having a purity of 95.0% was used, and DPEHMA was obtained in a similar manner to the synthesis of BPEHMP. YI: 0.81

Preparation of polythiol ester compound HMPME ( hexakis (3 - mercaptopropionyloxy - methyl ) - ethane)

Instead of using dipentaerythritol ether, hexa (hydroxymethyl) ethane with a purity of 93.0% was used, except that HMPME was obtained in a similar manner to the synthesis of BPEHMP. YI: 0.81

Preparation of polythiol ester compound HMMAE ( hexakis ( mercaptoacetyloxy - methyl ) - ethane)

Instead of using dipentaerythritol ether, hexa (hydroxymethyl) ethane with a purity of 93.0% was used, but HMMAE was obtained in a similar manner to the synthesis of BPEHMA. YI: 0.84

Manufacture of optical lenses

In the production of the optical material and the lens of the present invention, monomer composition was prepared by mixing 438 g of hexamethylene diisocyanate (HDI) with 409 g of isophorone diisocyanate (IPDI) in 548 g of BPEHMP to obtain 2- (2'hydroxy- 18 g of 5'-t-octylphenol) -2H-benzotriazole, 0.9 g of dibutyl phthalate as a mold releasing agent, 20 ppm of 1-hydroxy-4- (p-toluidino) anthraquinone , 10 ppm of perynone red (Red) and 1.8 g of polymerization initiator zeolityl tin dilaurate were placed in a mixing container equipped with a stirrer, and air was removed from the mixing container by replacing with nitrogen, followed by stirring under reduced pressure for 2 hours, Degassed, and injected into a glass mold fixed with a polyester adhesive tape (Diopta-5.00).

(2) The glass mold in which the mixture was injected was maintained in a forced circulation oven at 35 DEG C for 2 hours, at 40 DEG C for 3 hours, at 120 DEG C for 12 hours, at 120 DEG C for 2 hours, at 70 DEG C for 2 hours After cooling and curing by heating, the mold was released from the solid material to obtain an optical lens having a center thickness of 1.2 to 2.2 mm.

(3) The optical lens obtained in (2) was processed to a diameter of 72 mm, ultrasonically washed with caustic soda liquor, and annealed at 120 ° C for 2 hours.

(4) The lens obtained in (3) was surface nicked in a 5% KOH solution, impregnated with a Fincotter ST11 water-8H hard solution, and thermally cured. Then, silicon oxide, zirconium oxide, silicon oxide, ITO , Zirconium oxide film, silicon oxide, zirconium oxide, and water film (fluorine resin) were vacuum deposited to obtain hard coated and multi coated optical lenses.

Physical properties test method

The physical properties of each optical lens were measured by the following physical property test method, and the results were recorded in Table 1.

(YI or dYI, Yellow Index, Yellow Index): The YI value was measured using a SHIMADZU Model UV-2450 and an IRS-2200 light condensing device mounted on a plastic spectacle lens manufactured using the polythiol ester compound The polythiol ester compound was prepared by adding distilled water to a quartz cell having two 1 cm lengths and holding a base line, placing the polythiol ester compound in a quartz cell containing distilled water, Measure the YI value. In addition, the color of the polythiourethane plastic lens was fixed to a lens fixing device holding air as a reference point, and a color YI value was measured. In the color evaluation, the value of YI indicates the yellow index and it is a value that can be measured by color chromatic aberration. The smaller the YI value, the better the color.

2) Refractive index and Abbe number: Measured using an Abbe refractometer which is a 1T and DR-M4 model of ATAGO.

3) Light transmittance: Measured using a SHIMADZU UV 2450 spectrophotometer.

4) Multi-membrane cracking due to heat: When the lens specimen was left in an oven at 85 ° C for 60 minutes and then observed with naked eyes, A, a crack of 1 mm or less, 10 or less cracks, B, C, respectively.

5) Impact resistance: We measured the weight of a steel ball which does not break even one lens by dropping the steel ball from 127cm height to 10g in 10 multi-coated finished lens (-5.00, center thickness 1.2mm).

6) Whether bubbles are generated at the edges of the lens during thermal curing: After the thermal curing, the lens is demolded from the mold to see whether bubbles are formed at the edge of the lens. If no bubbles occur in 10 lenses, B is less than 3 mm, B is less than 1 mm, and C is more than 3 mm.

Example  2 to 16

Compositions and lenses were prepared in the compositions shown in Tables 1 and 2, respectively, in the same manner as in Example 1, and the results of the tests are shown in Tables 1 and 2.

Comparative Example  1-8

Obtained by the reaction of 86% bispentaerythritol containing mononuclear species, trinuclear species, alkali metal and alkaline earth metal as industrial reagents with 3-mercaptopropionic acid containing 88% of thiocarboxylic acid and 88% of thioacetic acid containing intermolecular condensation thioester compound The polythiol ester compound was used as a monomer resin for an optical lens.

Compositions and lenses were prepared in the compositions shown in Table 3, respectively, in the same manner as in Example 1, and the experimental results are shown in Table 3.

Comparative Example  9

The procedure of Example 1 was repeated except that 438 g of isophorone diisocyanate (IPDI) was mixed with 15 g of hexamethylene diisocyanate and 518 g of trimethylolpropane tris (mercaptopropionate) (TMPMP) to prepare an optical resin composition , And the characteristics thereof are shown in Table 3.

Comparative Example  10-16

Compositions and lenses were prepared in the compositions shown in Table 4, respectively, in the same manner as in Comparative Example 9, and the results of the tests are shown in Table 4.

Abbreviations in Tables 1 to 4

Monomer

BPEHMP: bispentaerythritol-ether-hexakis (3-mercaptopropionate)

BPEHMA: bispentaerythritol-ether-hexakis (mercaptoacetate)

HMPME: hexakis (3-mercaptopropionyloxy-methyl) -ethane

HMMAE: hexakis (mercaptoacetyloxy-methyl) -ethane

TMPMP: trimethylolpropane tris (mercaptopropionate)

TMEMA: trimethylol ethane tris (mercaptoacetate)

PETMP: pentaerythritol tetrakis mercaptopropionate

IPDI: isophorone diisocyanate

HDI: hexamethylene diisocyanate

H ₁₂ MDI: 4,4-methylene-bis (cyclohexyl isocyanate)

TMDI: trimethyl-1,6-diisocyanato (trimethyl-1,6-diisocyanatohexane)

      -hexane)

XDI: xylylene diisoscyanate < RTI ID = 0.0 >

Ultraviolet absorber

HMBT: 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole

HBMCBT: 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole

HBPBT: 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole

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

DHBP: 2,4-dihydroxybenzophenone

HMBP: 2-hydroxy-4-methoxybenzophenone

HOOBP: 2-hydroxy-4-octyloxybenzophenone

THBP: 2,2 ', 4,4'-tetrahydroxybenzophenone

DHMBP: 2,2'-dihydroxy-4,4'-dimethoxybenzophenone

BHMCBT: 2- (3'-t-butyl-2'-hydroxy-5'-methylphenyl) -5- chlorobenzenetriazole

Release agent

IPP: isopropyl faurate

DIPP: Diisopropyl phosphate

DBP: dibutyl acid phosphate

OP: Octylic acid phosphate

DOP: dioctyl acid phosphate

IDP: isodecylic acid phosphate

Organic dye

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

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

PRD: Perinone dye

Polymerization initiator

BTL: butyl tin dilaurate

BTC: dibutyl tin dichloride

Claims (6)

Represented by the general formula (1), bispentaerythritol-ether-hexakis (3-mercaptopropionate); Bispentaerythritol-ether-hexakis (mercaptoacetate); Hexakis (3-mercapto-propionyloxymethyl) -ethane; 35 to 70% by weight of a hexa-valent polythiol ester compound in which six thiol groups are present in one molecule selected from the group consisting of hexacis (mercaptoacetyloxymethyl) -ethane,
Isophorone diisocyanate (IPDI); Hexamethylene diisocyanate (HDI); 4,4-methylene bis (cyclohexyl isocyanate) (H ₁₂ MDI); And 30 to 65% by weight of a diisocyanate compound obtained by mixing one or more of trimethyl-1,6-diisocyanatohexane,
The polythiol ester compound is obtained by refluxing mercapto propionic acid or mercaptoacetic acid containing an intermolecular condensation thioester compound, mercapto acid having a purity of 95% or higher and bispentaerythritol having a mononuclear, trinuclear, alkali metal and alkaline earth metal removed A derivative obtained by condensation reaction under an esterification catalyst, and a YI value of less than 1.
[Chemical Formula 1]

(R ₁ = alkylene having 1 to 4 carbon atoms; x = 0 to 2; y = 0 to 2; z = 0 to 2) delete delete The resin composition for an optical lens according to claim 1, further comprising 0.001 to 6 parts by weight of an ultraviolet absorber, 0.0001 to 6 parts by weight of a release agent, and 0.001 to 6 parts by weight of a polymerization initiator based on 100 parts by weight of the resin composition for an optical lens. The resin composition for an optical lens according to claim 1, wherein the refractive index (nD) of the liquid phase is 1.20 to 1.59, the refractive index (nD) of the solid phase is 1.30 to 1.63, the Abbe number is 28 to 52 and the viscosity of the liquid phase is 30 to 2000 cps The resin composition for an optical lens. An optical lens produced by curing a resin composition according to any one of claims 1, 4, and 5.