KR101890332B1 - Siloxane thiol oligomer for optical materials - Google Patents

Abstract

The embodiment relates to a siloxane thiol oligomer for optical materials. The siloxane thiol oligomer according to the embodiment contains a Si-O-bond, which is a basic chemical structure of the glass, in the thiol structure, thereby providing advantages of the glass lens while maintaining the advantages of the plastic lens, such as high transparency, Abbe number and heat resistance. In addition, since the siloxane thiol oligomer contains a metal component in a copolymerized state, the siloxane thiol oligomer has not only an excellent refractive index but also secures the light resistance by automatically blocking a UV region without using an ultraviolet absorber, thereby being usefully used for manufacturing lenses.

Description

[0001] SILOXANE THIOL OLIGOMER FOR OPTICAL MATERIALS [0002]

The examples relate to a siloxane thiol oligomer used as a raw material for a polythiourethane-based optical material and a method for producing the same. The examples also relate to a polymerizable composition comprising the siloxane thiol oligomer, a polythiourethane compound obtained therefrom and an optical material.

Plastic materials of various resins are widely used as optical materials such as eyeglass lenses and camera lenses because they are lightweight and easily breakable and excellent in dyeability compared with optical materials made of inorganic materials such as glass. In recent years, higher performance of optical materials is required, and specifically high transparency, high refractive index, low specific gravity, high heat resistance, and high impact resistance are required.

BACKGROUND ART Polythiourethane-based compounds are widely used as optical materials because of their excellent optical properties and mechanical properties. The polythiourethane compound can be prepared by reacting a polythiol compound with an isocyanate compound, and the physical properties of the polythiol compound greatly affect the physical properties of the polythiourethane compound to be produced.

Lenses made from polythiourethane compounds are widely used because of their high refractive index, light weight and relatively high impact resistance. However, since the polythiourethane-based lens has a lower Abbe number than a glass lens, the sharpness of the polythiourethane-based lens is so low that the eye fatigue is large when the lens is worn and the heat resistance is low compared with the glass lens.

In recent years, efforts have been made to improve the optical properties such as transparency and refractive index by increasing the purity of the raw material itself or controlling the reaction in an attempt to obtain transparency at the glass level.

For example, Korean Patent No. 10-1338568 discloses a method for producing a polythiol compound by hydrolyzing an isothiouronium salt obtained by reacting a (poly) halogen compound or a (poly) alcohol compound with a thiourea, It is disclosed that a colorless transparent (poly) thiol compound is obtained because the calcium content in the urea is 1.0 wt% or less. Korean Patent No. 10-1356387 discloses a transparent hybrid material for optics obtained from an organic compound containing at least two thiol oligosiloxane hybrids, vinyl oligosiloxane hybrids or vinyl groups.

Korean Patent No. 10-1338568 Korean Patent No. 10-1356387

However, the technique disclosed in Korean Patent No. 10-1338568 regulates only the purity of the thiourethane, which is a raw material of the polythiol compound, so that there is a limit to the transparency of the glass level and the Abbe number. Further, the transparent hybrid material for optics disclosed in Korean Patent No. 10-1356387 is obtained by the reaction between thiol and vinyl (thio-ene reaction) and is not a technique commonly used in the industry. Therefore, And it is difficult to realize a sufficient refractive index only by this reaction, and the impact resistance and the heat resistance are lower than those of the conventional polythiourethane system, so that it is difficult to apply it to an actual plastic lens.

Accordingly, the examples are siloxane thiol oligomers for optical materials having properties such as high transparency, Abbe number, high refractive index, and high heat resistance, which are advantages of glass lenses while maintaining the advantages of polythiourethane plastic lenses, and polythiourethane And a polythiourethane-based plastic lens.

The present invention provides a method for preparing a siloxane thiol oligomer by non-hydrolytic condensation of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3)

[Chemical Formula 1]

(2)

(3)

In this formula,

And R _1, R _2, R _4, R ₅ and R ₆ are each independently C _{1 -20} alkyl, C _{6 -20} aryl, or a C _{1 -10} C _{6 -20} aryl substituted by alkyl,

R ₃ is C _{1 -20} alkylene, phenylene, or phenylene substituted with C _{1 -10} alkyl,

l is an integer of 1 to 3,

m is an integer of 0 to 2,

n is an integer of 1 to 3,

l + m + n = 4,

M is aluminum, titanium, zirconium or germanium,

p is the valence of M;

Further, the examples provide a siloxane thiol oligomer obtained by non-hydrating condensation reaction of the compound represented by the formula (1), the compound represented by the formula (2), and the compound represented by the formula (3).

In addition, the examples provide a polymerizable composition comprising the siloxane thiol oligomer, the polythiol compound different from the siloxane thiol oligomer, and the isocyanate compound.

Furthermore, the embodiment provides a method for producing a polythiourethane-based plastic lens by thermally curing the polymerizable composition in a mold.

Further, the embodiment provides a polythiourethane-based plastic lens obtained by the above-mentioned production method.

The siloxane thiol oligomer according to the embodiment provides a high transparency, Abbe number and heat resistance, which are advantages of a glass lens while maintaining the merits of a plastic lens, by containing a Si-O- bond, which is a basic chemical structure of glass, in the thiol structure can do. In addition, since the siloxane thiol oligomer contains a metal component in a copolymerized state, it has not only an excellent refractive index but also a UV area is automatically blocked, so that light resistance can be secured without using an ultraviolet absorber. And can be usefully used in the manufacture of lenses.

The present invention provides a method for preparing a siloxane thiol oligomer by non-hydrolytic condensation of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3)

[Chemical Formula 1]

(2)

(3)

Wherein R, R _1, R _2, R _4, R ₅ and R ₆ are each independently C _{1 -20} alkyl, C _{6 -20} aryl, or C _{1 -10} substituted C _{6 -20} aryl-alkyl, R ₃ is phenylene substituted by C _{1 -20} alkylene, phenylene or C _{1 -10} alkyl, l is an integer of 1 to 3, m is an integer of 0 to 2, and n is an integer of 1 to 3 M + is aluminum, titanium, zirconium or germanium, and p is the valence of M.

More specifically, R _1, R _2, R _4, R ₅ and R ₆ are independently selected from phenyl substituted with alkyl of C _{1 -10} alkyl, phenyl, or C _{1 -10} of, R ₃ is C _{1 -10,} respectively is phenylene optionally substituted with alkylene, phenylene, or C _{1 -10} alkyl, M can be zirconium.

Here, x and y satisfy the following equations (1) and (2), respectively, when the alkoxy equivalents of the compounds represented by Formulas 1 and 3 are x and the hydroxide equivalent of the compound represented by Formula 2 is y. The alkoxy equivalents of the compounds represented by the above formulas (1) and (3) are defined as molar numbers of introduction / alkoxy number and the hydroxyl equivalent of the compound represented by the above formula (2)

[Equation 1]

x / y? 0.70

&Quot; (2) "

x / y? 1.43.

Wherein the compound represented by Formula 1 is at least one selected from the group consisting of (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, mercaptopropyltriphenoxysilane, or 11-mercaptoundecyltrimethoxysilane, and specifically may be 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane.

The compound represented by Formula 2 may be diphenylsilanediol or diisobutylsilanediol.

Wherein the compound represented by Formula 3 is selected from the group consisting of aluminum ethoxide, germanium ethoxide, titanium ethoxide, zirconium ethoxide, zirconium propoxide, titanium propoxide, aluminum isopropoxide, germanium isopropoxide, Butoxide, zirconium isopropoxide, aluminum tributoxide, aluminum t-butoxide, titanium butoxide, titanium t-butoxide, zirconium butoxide and zirconium t-butoxide, Zirconium ethoxide or titanium ethoxide.

The siloxane thiol oligomer may have a weight average molecular weight ranging from 500 to 5,000, and specifically from 1,000 to 3,000. Further, the SH value (SHV) of the siloxane thiol oligomer may be 400 to 700 g / eq., Specifically 400 to 650 g / eq. In addition, the viscosity of the siloxane thiol oligomer may be 500 to 100,000, and specifically 1,000 to 50,000. Within the above range, it is possible to maintain the workability while securing the hardening density.

The siloxane thiol oligomer may be prepared by a non-hydrating condensation reaction of the compound represented by the formula (1), the compound represented by the formula (2), and the compound represented by the formula (3). At this time, an organic material capable of forming a metal chelate with the compound represented by Formula 3 may be further added during the non-hydrating condensation reaction.

Specifically, the siloxane thiol oligomer is obtained by reacting a compound represented by the general formulas (1) and (3) with a compound represented by the general formula (2), for example, alkoxysilane having a mercapto group, and non- . ≪ / RTI > The siloxane thiol oligomer obtained therefrom can partially have a glass network structure by containing a Si-O- linkage, which is a basic chemical structure of glass, in the thiol structure. In addition, the siloxane thiol oligomer can be obtained in a liquid phase having a low viscosity, which is easy to control the molecular weight.

At this time, when the metal oxide is non-hydrated and reacted with silanol, the reactivity of the metal oxide is higher than that of the alkoxysilane. Therefore, it is necessary to prepare a uniform copolymer by controlling the reactivity of the metal oxide to a level similar to alkoxysilane. The reaction rate can be controlled by adding an organic material capable of forming a metal chelate with the metal oxide. Further, the metal oxide and the organic substance may be reacted for a sufficient time to form a metal chelate, for example, 30 minutes or more, 40 minutes or more, or 1 hour or more.

It said organic material is acetylacetone, perfluoro acetylacetone, oleic acid (C ₁₇ H ₃₃ COOH), benzoyl-2-furanyl Russo methane, 1,3-bis (4- pyridyl) -1,3-propane dione, benzoyl Benzoyl acetone, di (4-dibromo) benzoylmethane, d, d-di-camphoryl methane, 4,4-dimethoxydibenzoylmethane, 2,6- (Perfluoro-2-propoxypropionyl) methane, 1,3-di (2-thienyl) -1,3-propanedione, 3- Acetyl) -d-camphor, 6,6,6-trifluoro-2,2-dimethyl-3,5-hexanedione, 1,1,1,2,2,6,6,7,7,7 -Decafluoro-3,5-heptanedione, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, 2-furyl trifluoroacetone , Heptafluoroacetyl acetone, 3- (heptafluorobutyryl) -d-camphor, 4,4,5,5,6,6,6-heptafluoro-1- (2-thienyl) 3-hexanedione, 4-methylbenzoyl-2-furanyl methane, 6-methyl-2,4-heptanedione, 2- Phenyl-1,3,4-oxadiazol-2-yl) -2,4-pentanedione, 3-phenyl-2,4-pentanedione, pivaloyltrifluoro 1-phenyl-3- (2-thienyl) -1,3-propanedione, 3- (tert-butylhydroxymethylene) -d-camphor, trifluoroacetylacetone, 2,2,3,3,7,7,8,8,9,9,9-tetradecafluoro-4,6-nonanedione, 2,2,6,6-tetramethyl-3,5-heptane Dione, 4,4,4-trifluoro-1- (2-naphthyl) -1,3-butanedione, 2,2,6,6-tetramethyl- 6-trimethyl-3,5-heptane dione, acetone as 2,2,7- trimethyl-3,5-octane-dione, and 2-thenoyl trifluoromethyl, C _{1 -20} saturated fatty acid, unsaturated fatty acid or C _{1 -20} Lt; / RTI >

Specifically, it may be acetylacetone, perfluoroacetylacetone or oleic acid.

The organic material may be used in an appropriate amount depending on the kind of the compound represented by the formula (3). For example, the compound may be added in an amount of 0.1 to 0.6 equivalent based on 1 equivalent of the compound represented by the formula (3), specifically 0.2 to 0.5 equivalent.

The compound represented by the formula (3) may be used in an amount of 0.2 to 0.8 moles per mole of the compound represented by the formula (1). If it is larger than 0.8 mol, the refractive index is increased but the viscosity is high, so that the transmittance is lowered and the YI value is increased. If it is lower than 0.2 mol, the refractive index can not be increased sufficiently and the ultraviolet blocking ability is also lowered.

The non-hydrocondensation reaction can be carried out in the presence of a catalyst for smooth reaction, and the catalyst can be selected from the group consisting of magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, radium hydroxide and mixtures thereof, And may be barium hydroxide in terms of the efficiency of the reaction.

The amount of the catalyst is not particularly limited, but may be 0.01 to 1 part by weight, and more preferably 0.05 to 0.2 part by weight based on the total weight of the compounds represented by the formulas (1) and (2).

The non-hydrating condensation reaction may be carried out at a temperature of 10 to 120 ° C, and specifically at a temperature of 40 to 90 ° C.

The non-hydropolycondensation reaction is a byproduct of alcohol production, and the generated alcohol must be removed to induce continuous positive reaction. In order to effectively remove the alcohol, nitrogen is continuously added during the reaction in a reaction tank equipped with a water determination device such as a dean-stark, and when the reaction is completed, the residual alcohol is completely removed by distillation under reduced pressure Process is required. By this process, high purity siloxane thiol oligomer can be obtained.

Accordingly, the present invention provides a siloxane thiol oligomer obtained by non-hydrolytic condensation of the compound represented by the formula (1), the compound represented by the formula (2), and the compound represented by the formula (3).

Further, the examples provide a polymerizable composition comprising the siloxane thiol oligomer, the polythiol compound different from the siloxane thiol oligomer, and the isocyanate compound.

The polymerizable composition may contain the siloxane thiol oligomer in an amount of 5 to 40% by weight, specifically 5 to 30% by weight, based on the total weight of the siloxane thiol oligomer and the polythiol compound different from the siloxane thiol oligomer. If it is less than the above range, it is difficult to sufficiently realize the advantage of glass. If it is larger than the above range, the viscosity becomes high and processing becomes difficult.

The polythiol compound different from the siloxane thiol oligomer is not particularly limited, but may be an organic polythiol.

Specific examples of the organic polythiol include bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, 4-mercaptomethyl-1,8-dimercapto- Propane dithiol, bis (2-mercaptoethylthio) propane-1-thiol, 2,2-bis (mercaptomethyl) (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, 2- (2-mercaptoethylthio) propane- Bis (2-mercaptoethyl) thio] -3-mercaptopropane, bis (2,3-dimercaptopropane) sulfide, bis (2-mercaptoethylthio) -3-mercaptoethylthio) ethane, 2- (2-mercaptoethylthio) -3-2-mercapto-3- [ Propylthio] propylthio-propane-1-thiol, 2,2-bis- (3-mercaptoethylthio) (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- (Mercaptopropylthio) propane-1,2-dithiol, (4R, 14R) -4,14-bis (mercaptomethyl) -3,6,9,12,15-pentatihaheptane- ((2-mercaptoethyl) thio) propylthio) propylthio) -2 - ((2-mercaptoethyl) thio) propane (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-tetramethyl- Dithiol, (7R, 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13,16-hexatiaoctadecane-1,18- Dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto- 6,9-trithiandecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithia (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol ether Tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,4'-tetrakis (mercaptomethylthio) (Mercaptomethylthio) -1,3-dithiane, or 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane.

Specifically, there may be mentioned pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis [(2-mercaptoethyl) thio] Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3, 6,9-trithiandecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, or a mixture thereof.

The isocyanate compound may be a conventional one used for the synthesis of polythiourethane.

Specifically, the isocyanate compound is selected from the group consisting of isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1 (Isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,2-bis (isocyanatomethyl) cyclohexane, isocyanatomethylcyclohexane, But are not limited to, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, (Isocyanatoethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatohexyl) sulfide, Bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis Diisocyanato-2-isocyanatomethyl-3-thiapentane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) 2,5-bis (isocyanatomethyl) thiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, Thiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis 1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolane, and the like; (Isocyanatoethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatoethyl) Examples of the aromatic diisocyanate compound include aromatic diisocyanates such as phenyl ether, phenylenediisocyanate, ethylphenylenediisocyanate, isopropylphenylenediisocyanate, dimethylphenylenediisocyanate, diethylphenylenediisocyanate, diisopropylphenylenediisocyanate, trimethylbenzene triisocyanate, Toluene diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanato Phenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzene diisocyanate, hexahydrate Xylene diisocyanate, p-xylene diisocyanate, xylene diisocyanate, X-xylene diisocyanate, 1,3-bis (isocyanatomethyl) ) Cyclohexane, diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis -Isocyanatomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyldisulfide-4,4-diisocyanate, 2,2-dimethyl diphenyl disulfide Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4- Diisocyanate, 5,5-diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyl di It may be selected from the feed-3,3-diisocyanate and mixtures thereof.

Specifically, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate and the like can be used.

The polymerizable composition may further contain an additive such as an internal mold release agent, a heat stabilizer, a reaction catalyst, and a blueing agent depending on the purpose.

Examples of the internal release agent include 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; Alkyl quaternary ammonium salts such as trimethylcetylammonium salt, trimethylstearyl, dimethylethylcetylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, diethylcyclohexadecylammonium salt and the like; And acidic phosphate esters may be used singly or in combination of two or more.

Examples of the thermal stabilizer include a metal fatty acid salt, phosphorus, lead, and an organosilicate.

As the reaction catalyst, a known reaction catalyst used in the production of a polythiourethane resin may be appropriately added. Dialkyltin halide systems such as dibutyltin dichloride and dimethyltin dichloride; Dialkyltin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctanoate and dibutyltin dilaurate; Dialkyltin dialkoxides such as dibutyltin dibutoxide and dioctyltin dibutoxide; Dialkyltin dithioalkoxide systems such as dibutyltin di (thiobutoxide); Dialkyltin oxides such as di (2-ethylhexyl) tin oxide, dioctyltin oxide, and bis (butoxy dibutyltin) oxide; And a dialkyltin sulfide system such as dibutyltin sulfide feed. Specifically, it may be selected from the group consisting of dialkyltin halide systems such as dibutyltin dichloride, dimethyltin dichloride and the like.

The bluing agent has an absorption band in the wavelength range from orange to yellow in the visible light region and has a function of adjusting the color of the optical material made of the resin. Specifically, the bluing agent may include a material that exhibits blue to violet, but is not particularly limited. Examples of the bluing agent include dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments, but they can be appropriately selected in accordance with physical properties and resin color required for the produced optical component. These bluing agents may be used alone or in combination of two or more.

The bluing agent is preferably a dye in view of the solubility in the polymerizable composition and the transparency of the resulting optical material. Specifically, the dye may be a dye having a maximum absorption wavelength of 520 to 600 nm, and more particularly, a dye having a maximum absorption wavelength of 540 to 580 nm. Further, in view of the structure of the compound, the dye is preferably an anthraquinone dye. The method of adding the bluing agent is not particularly limited and may be added to the monomer system in advance. Specifically, the method of adding the bluing agent may be a method of dissolving the monomer in a monomer, or a method of preparing a master solution containing a high concentration of a bluing agent and diluting the monomer solution or other additives using the master solution and adding You can use branching methods.

The embodiment provides a method for producing a polythiourethane-based plastic lens obtained by thermally curing a polymerizable composition as described above in a mold. Furthermore, the embodiment provides the polythiourethane-based plastic lens obtained by the above-mentioned production method.

Specifically, the polymerizable composition is degassed under reduced pressure, and then injected into a lens molding mold. Such degassing and mold injection can be performed, for example, at a temperature range of 20 to 40 캜. After injection into the mold, the polymerization is usually carried out by gradually heating from a low temperature to a high temperature.

The temperature of the polymerization reaction may be, for example, 20 to 150 ° C, and specifically 25 to 120 ° C.

Then, the polythiourethane-based plastic lens is separated from the mold.

The polythiourethane-based plastic lens can be manufactured into various shapes by changing the mold of the mold used in the production. Specifically, it may be in the form of a spectacle lens, a camera lens, or the like.

The reaction mole ratio of the SH group / NCO group in the polymerization reaction may be 0.7 to 1.3, specifically 0.8 to 1.2, more specifically 0.9 to 1.1.

The plastic lens may have a solid-state refractive index (nd 20) of 1.55 to 1.70, 1.67 to 1.69, 1.67 to 1.685, or 1.672 to 1.681 at a temperature of 20 ° C, (See Experimental Example (2)).

The plastic lens may have a heat distortion temperature (Tg) of 110 to 130 ° C, 110 to 125 ° C, or 115 to 125 ° C (see Experimental Example (3)).

The plastic lens may have a transmittance of 10% or less, 8% or less, or 6% or less at a wavelength of 380 nm (see Experimental Example (4)).

Examples include the siloxytithiol oligomers; A polythiol compound different from the siloxane thiol oligomer; And a polymerizable composition comprising an isocyanate compound,

Wherein the siloxane thiol oligomer is contained in an amount of 5 to 40% by weight based on the total weight of the siloxane thiol oligomer and the polythiol compound different from the siloxane thiol oligomer, the solid-state refractive index (nd20) of the lens is 1.55 to 1.70, To 50, and a transmittance at 380 nm of 10% or less.

The above-mentioned polythiourethane-based plastic lens can be used for surface polishing, antistatic treatment, hard coat treatment, anti-reflection treatment, anti-reflection treatment, anti- It can be improved by performing physical and chemical treatments such as a coat treatment, a dyeing treatment, and a dimming treatment.

As described above, the siloxane thiol oligomer according to the embodiment contains the Si-O- linkage, which is the basic chemical structure of the glass, in the thiol structure, and thus the high transparency and the Abbe number, which are advantages of the glass lens while maintaining the advantages of the polythiourethane- And so on. In addition, since the siloxane thiol oligomer contains a metal component in a copolymerized state, it has not only an excellent refractive index but also a UV area is automatically blocked, so that light resistance can be secured without using an ultraviolet absorber. And can be usefully used in the manufacture of lenses.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.

Example  One: Siloxane Thiol Oligomeric  Produce

Mechanical stirrer To a three-neck 1 L round-bottomed flask equipped with a Dean-Stark stirrer, a thermometer connected to a thermostat and a heating mantle, 137.5 g (0.7 mol) of 3-mercaptopropyltrimethoxysilane (KBM-803, ), 81.5 g (0.3 mol) of zirconium ethoxide (Gelist) and 30.3 g (0.3 mol) of acetylacetone were charged into the reactor and stirred for 40 minutes to allow the zirconium ethoxide and acetylacetone to be chelated. Next, 216.3 g (1 mole) (x / y = 0.62) of diphenylsilanediol (SiSiB® PC8228, Power Chemical Company) was added and 2 g of barium hydroxide was added as a catalyst, followed by reaction at 75 ° C. for 5 hours . At this time, a nitrogen pipe was installed inside the reactor, and nitrogen was continuously injected to remove methanol generated in the reaction inside the reactor to induce the reaction to the reaction. After 5 hours, the temperature was lowered to 40 占 폚 and distillation under reduced pressure of 1 MPa was carried out to remove remaining methanol in the reaction product to prepare a transparent viscous siloxane polythiol oligomer containing thiol, phenyl and zirconium in the molecular structure. The SH value (SHV) of the obtained siloxane thiol oligomer was 624.8 g / eq. .

Example  2: Polymerizable  Preparation of composition

3 g of the siloxane thiol oligomer prepared in Example 1 and 47 g of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane as an organic polythiol were mixed to prepare a first solution, 53 g of xylene diisocyanate, 0.015 g of dibutyltin chloride, and 0.1 g of Zelec (R) UN (acidic phosphoric acid alkyl ester release agent, Stepan) were uniformly mixed to prepare a second liquid. The first solution and the second solution obtained above were uniformly mixed to prepare a polymerizable composition.

Example  3: Polymerizable  Preparation of composition

5 g of the siloxane thiol oligomer prepared in Example 1 and 45 g of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane as an organic polythiol were mixed to prepare a first solution, 54 g of xylene diisocyanate, 0.015 g of dibutyltin chloride and 0.1 g of Zelec® UN were uniformly mixed to prepare a second liquid. The first solution and the second solution obtained above were uniformly mixed to prepare a polymerizable composition.

Example  4: Polymerizable  Preparation of composition

15 g of the siloxane thiol oligomer prepared in Example 1 and 40 g of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane as an organic polythiol were mixed to prepare a first solution, 54 g of xylene diisocyanate, 0.015 g of dibutyltin chloride and 0.1 g of Zelec® UN were uniformly mixed to prepare a second liquid. The first solution and the second solution obtained above were uniformly mixed to prepare a polymerizable composition.

Comparative Example  One: Siloxane Thiol Oligomeric  Produce

In a three-necked 1 L round-bottomed flask equipped with a mechanical stirrer cooling tube, Dean Stark, a thermometer connected to a thermostat and a heating mantle, 196.4 g (1) of 3-mercaptopropyltrimethoxysilane (KBM-803, 216.3 g (1 mole) (x / y = 0.67) of diphenylsilanediol (SiSiB® PC8228, Power Chemical Company) were charged and 2 g of barium hydroxide was added as a catalyst, followed by reaction at 75 ° C. for 5 hours . At this time, a nitrogen pipe was installed inside the reactor, and nitrogen was continuously injected to remove methanol generated in the reaction inside the reactor to induce the reaction to the reaction. After 5 hours, the temperature was lowered to 40 占 폚 and distillation under reduced pressure at 1 MPa was carried out to remove remaining methanol from the reaction product to prepare a transparent viscous siloxane thiol oligomer containing a thiol group and a phenyl group in the molecular structure. The SHV of the obtained siloxane thiol oligomer was 417.6 g / eq. .

Comparative Example  2: Polymerizable  Preparation of composition

15 g of the siloxane thiol oligomer prepared in Comparative Example 1 and 40 g of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane as an organic polythiol were mixed to prepare a first solution, 54 g of xylene diisocyanate, 0.015 g of dibutyltin chloride and 0.1 g of Zelec® UN were uniformly mixed to prepare a second liquid. The first solution and the second solution obtained above were uniformly mixed to prepare a polymerizable composition.

Comparative Example  3: Polymerizable  Preparation of composition

As the organic polythiol, a first liquid of 48 g of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 52 g of m-xylene diisocyanate, 0.015 g of dibutyltin chloride, Were uniformly mixed to prepare a second solution. The first solution and the second solution obtained above were uniformly mixed to prepare a polymerizable composition.

Category (g) Example 2 Example 3 Example 4 Comparative Example 2 Comparative Example 3 The first sum Example 1 3 5 15 - - Comparative Example 1 - - - 15 - Organic polythiol 47 45 40 40 48 Second sum m-XDI 53 54 54 54 52 DBTC 0.015 0.015 0.015 0.015 0.015 Zelec® UN 0.1 0.1 0.1 0.1 0.1

Experimental Example  : Property check

(One) SH value( SHV )

Approximately 0.1 g of each of the siloxane thiol oligomers obtained in the above Examples 1 and 2 was added to the beaker, and then 40 mL of chloroform was further added. After stirring for 10 minutes, 20 mL of isopropyl alcohol was further added and stirred for 10 minutes. The solution was titrated with 0.1 N iodine standard solution, and the SH value was calculated by applying the following equation (1) (theoretical value = 91.3):

[Equation 1]

SH value (g / eq.) = Sample weight (g) / {0.1 X amount of iodine consumed (L)}.

(2) the solid refractive index (nd 20) and Abe number

The polymerizable compositions prepared in Examples 2 to 4 and Comparative Examples 2 and 3 were degassed at 600 Pa for 1 hour and then filtered through a Teflon filter of 3 占 퐉. The filtered polymerizable composition was injected into a glass mold template assembled by tape. The mold was heated from 25 ° C to 120 ° C at a rate of 5 ° C / minute and polymerized at 120 ° C for 18 hours. Then, the cured resin in the glass mold mold was further cured at 130 캜 for 4 hours, and then the molded body (plastic lens) was released from the glass mold mold. The obtained optical material was subjected to an Abbe refractometer DR-M4 to obtain a refractive index and an Abbe number at 20 占 폚.

(3) Heat resistance (thermal deformation)

The glass transition temperature (Tg, thermal deformation) of the plastic lens of item (2) above was measured using a TMA Q400 (TA corporation) under the peening method (load of 50 g, pin line of 0.5 mmφ, Temperature) was measured.

(4) Yellow Index (Y.I.) and transmittance

A plastic lens was produced in the same manner as in the item (2), except that a circular lens plate having a thickness of 9 mm and a diameter of 75 mm was used. At this time, no coating was performed. The chromaticity coordinates x and y of the lens were measured using a color chromaticity meter CT-210 manufactured by Minolta Co., and then the yellow index was calculated by applying the measured values to the following equation (2). Transmittance at 380 nm and 550 nm wavelengths in the UV spectrum obtained using the same instrument is shown as transmittance:

 &Quot; (2) "

YI = (234x + 106y + 106) / y.

Example 2 Example 3 Example 4 Comparative Example 2 Comparative Example 3 Refractive index (nd 20) 1.672 1.675 1.681 1.665 1.671 Abe number 40 42 43 44 38 Thermal deformation (℃) 117 118 121 115 101 Y.I. 3.6 3.7 3.8 2.9 4.5 550 nm Transmittance (%) 90.1 91.5 92.1 92.1 88.3 380 nm Transmittance (%) 6.2 1.4 0 45.2 46.7

As shown in Table 2, it can be seen that the plastic lenses obtained from Examples 2 to 4 are equivalent or superior in terms of refractive index, Abbe number, thermal deformation, yellow index and transmittance in comparison with Comparative Examples 2 and 3, In particular, it can be seen that the yellow index, the Abbe number and the transmittance are greatly improved. In addition, the transmittance at 380 nm is 10% or less, which shows that UV is effectively blocked. Thus, it is expected that the plastic lens manufactured in the embodiment can be used in a light, high-temperature-resistant, transparent and clear image.

Claims (19)

delete delete delete delete delete delete delete delete delete delete delete A siloxane thiol oligomer having an SH value of 400 to 700 g / eq. Obtained by non-hydrolytic condensation of a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula
A polythiol compound different from the siloxane thiol oligomer; And
A polymerizable composition comprising an isocyanate compound:
[Chemical Formula 1]

(2)

(3)

In this formula,
R ₁ , R ₂ , R ₄ , R ₅ and R ₆ are each independently C _1-20 alkyl, C _6-20 aryl, or C _6-20 aryl substituted with C _1-10 alkyl,
R ₃ is C _1-20 alkylene, phenylene, or phenylene substituted with C _1-10 alkyl,
l is an integer of 1 to 3,
m is an integer of 0 to 2,
n is an integer of 1 to 3,
l + m + n = 4,
M is aluminum, titanium, zirconium or germanium,
p is the valence of M;
13. The method of claim 12,
Wherein the siloxane thiol oligomer is included in an amount of 5 to 40 wt% based on the total weight of the siloxane thiol oligomer and the polythiol compound different from the siloxane thiol oligomer.
13. The method of claim 12,
Wherein the isocyanate compound is selected from the group consisting of 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate and toluene diisocyanate.
A process for producing a polythiourethane-based plastic lens by thermally curing the polymerizable composition of claim 12 in a mold.
A polythiourethane-based plastic lens obtained by the manufacturing method of claim 15.
17. The method of claim 16,
Wherein the Abbe's number of the plastic lens is 30 to 50.
17. The method of claim 16,
Wherein the plastic lens has a solid-phase refractive index (nd20) of 1.55 to 1.70.
17. The method of claim 16,
Wherein the transmittance of the plastic lens at 380 nm is 10% or less.