KR101813258B1 - Siloxane thiol oligomer for optical materials - Google Patents

Abstract

The present invention relates to a siloxane thiol oligomer for optical materials. The siloxane thiol oligomer according to an embodiment of the present invention contains Si-O- bonds, which are a basic chemical structure of glass, in a thiol structure, thereby maintaining advantages of plastic lenses and providing properties such as high transparency and Abbes number, thermal resistance, etc., which are advantages of glass lenses. Accordingly, the siloxane thiol oligomer can be usefully used for manufacturing various plastic lenses such as eyeglass lenses, camera lenses, etc.

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 due to 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.

Thus, the Examples are siloxane thiol oligomers for optical materials having advantages of high transparency, Abbe's number and high heat resistance, which are advantages of glass lenses while maintaining the advantages of polythiourethane-based plastic lenses, and polythiourethane compounds and poly To provide a thiourethane-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) and a compound represented by the following formula (2)

[Chemical Formula 1]

(2)

In this formula,

R _1, R _2, R ₄ and R ₅ are each independently a 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.

Further, the embodiment provides a siloxane thiol oligomer obtained by non-hydrolytic condensation reaction between the compound represented by the formula (1) and the compound represented by the formula (2).

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 Therefore, it can be usefully used for manufacturing various kinds of plastic lenses such as spectacle lenses and camera 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) and a compound represented by the following formula (2)

[Chemical Formula 1]

(2)

In this formula,

R _1, R _2, R ₄ and R ₅ are each independently C _{1 -20} alkyl, C _{6 -20} aryl, or C _{1 -10} substituted C _{6 -20} aryl-alkyl, R ₃ is C _{1 -20} alkylene, phenylene, or C _{1 -10,} and a phenylene group substituted with alkyl, l is an integer from 1 to 3, m is an integer from 0 to 2, n is an integer from 1 to 3, l + m + n = 4.

More specifically, R _1, R _2, R ₄ and R ₅ are each independently a C _{1 -10} alkyl, phenyl, or C _{1 -10} is phenyl substituted by alkyl, R ₃ is C _{1 -10} alkylene, phenylene , Or phenylene substituted with C _{1 -10} alkyl.

Here, x and y satisfy the following formula (1) or (2), respectively, when the alkoxy equivalent of the compound represented by the formula (1) is x and the hydroxide equivalent of the compound represented by the formula (2) is y. In this case, the alkoxyl equivalent of the compound represented by the formula (1) is defined as the molar number of introduction / alkoxy number, and the hydroxyl equivalent of the compound represented by the formula (2) is defined as the number of mols /

[Equation 1]

x / y? 0.70

&Quot; (2) "

x / y? 1.43.

The compound represented by the above-mentioned formula (1) is preferably 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 or 3-mercaptopropylmethyldimethoxysilane.

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

The siloxane thiol oligomer may be prepared by a non-condensation reaction of a compound represented by the general formula (1) and a compound represented by the general formula (2), for example, alkoxysilane having a mercapto group and silanol in the absence of water. 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.

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 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 siloxane thiol oligomers obtained by non-hydrolytic condensation of the compound represented by Formula 1 and the compound represented by Formula 2.

Specifically, the siloxane thiol oligomer may be selected from the group consisting of compounds represented by the following formulas (3) to (6):

(3)

 [Chemical Formula 4]

[Chemical Formula 5]

 [Chemical Formula 6]

Wherein R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ and R ₁₁ are each independently substituted with C _{1 -20} alkyl, C _{6 -20} aryl or C _{1 -10} alkyl a C _{6 -20} aryl, R ₃ is C _{1 -20} alkylene, phenylene, or C _{1 -10,} and a phenylene group substituted with alkyl, R _6, R ₉ and R ₁₂ are, each independently C during Annals _1-10 alkyl, C _1-10 alkoxy, C _1-10 and, during or hydroxy substituted siloxane as alkylthio or hydroxy,

n1 is an integer of 0 to 2, m1 is an integer of 0 to 2, n1 is an integer of 1 to 3, l2 is an integer of 0 to 1, n2 is an integer of 1 to 2, M3 is an integer of 0 to 1,

l1 + m1 + n1 = 3, l2 + n2 = 2, and m3 + n3 = 2.

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 siloxane thiol oligomer may contain 5 to 40 wt%, specifically 5 to 30 wt%, 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, an ultraviolet absorber, 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.

Examples of the ultraviolet absorber include benzophenone, benzotriazole, salicylate, cyanoacrylate, oxanilide, 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 compound by thermally curing a polymerizable composition as described above in a mold. Further, 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 from 1.55 to 1.75, 1.55 to 1.70, 1.65 to 1.75, 1.65 to 1.70 or 1.65 to 1.67 at a temperature of 20 캜, (See Experimental Example (2)).

The plastic lens may have a thermal deformation temperature (Tg) of 105 to 130 ° C, 105 to 120 ° C, or 105 to 115 ° C (see Experimental Example (3)).

The plastic lens may have a transmittance of 90 to 95%, 90 to 94%, or 90 to 93% at a wavelength of 550 nm (see Experimental Example (4)).

As described above, the examples include the siloxane thiol 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, (Nd20) of 1.55 to 1.70 and Abbe's number of 30 to 50. The plastic lens according to claim 1,

The plastic lens may be subjected to surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, anti-reflection treatment, anti-reflection treatment, anti- A dyeing treatment, a dimming treatment, and the like.

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 can be usefully used in the production of various plastic lenses such as spectacle lenses and camera 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  Manufacturing 1

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, 196.4 g (1 mol) of 3-mercaptopropyltrimethoxysilane (KBM-803, ) And 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 of 1 MPa was carried out to remove methanol remaining in the reaction product to prepare a transparent viscous siloxane thiol oligomer containing a thiol and a phenyl group in the molecular structure. The SH value (SHV) of the obtained siloxane thiol oligomer was 417.6 g / eq. .

Example  2: Siloxane Thiol Oligomeric  Manufacturing 2

196.4 g (1 mole) of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shinnetsu) and 216.3 g (1 mole) of diphenylsilanediol (SiSiB® PC8228, Power Chemical Company) , 180.3 g (1 mole) of 3-mercaptopropylmethyldimethoxysilane (KBM-802, manufactured by Shinnetsu) and 432.6 g (2 mol) of diphenylsilanediol (SiSiB® PC8228, Power Chemical Company) = 0.5) was used in place of the silanol thiol oligomer. The SHV of the obtained siloxane thiol oligomer was 620.1 g / eq. .

Example  3: Polymerizable  Preparation of composition

, 53 parts by weight of m-xylene diisocyanate (m-XDI), 0.015 part by weight of dibutyltin chloride (DBTC) as a polymerization catalyst, 0.1 part by weight of Zelec (R) UN (acidic alkyl phosphate release agent, Stepan) And 0.05 parts by weight of BIOSORB (R) 538 (co-agent) as an ultraviolet absorber were uniformly mixed to prepare a first liquid. 3 parts by weight of the siloxane thiol oligomer obtained in Example 1 and 47 parts by weight of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (organic polythiol) were uniformly mixed to prepare a second solution Respectively. The first solution and the second solution obtained above were uniformly mixed to prepare a polymerizable composition.

Example  4 to 8 and Comparative Example  1 to 3: Polymerizable  Preparation of composition

A polymerizable composition was prepared in the same manner as in Example 3 except that the components and the content (parts by weight) were changed as shown in Table 1 below.

division Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 The first sum m-XDI 53 54 54 53 53 54 52 52 52 DBTC 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 Zelec® UN 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 BIOSORB® 538 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Second sum Example 1 3 5 15 0 0 0 0 One 0 Example 2 0 0 0 3 5 15 0 0 One Organic polythiol 47 45 40 48 45 42 48 48 48

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 3 to 8 and Comparative Examples 1 to 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). The transmittance at a wavelength of 550 nm in the spectrum obtained using the same instrument is shown as transmittance:

 &Quot; (2) "

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

Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Refractive index (nd 20) 1.669 1.668 1.665 1.668 1.667 1.665 1.671 1.669 1.669 Abe number 41 43 44 42 44 45 38 38 39 Heat deformation temperature (캜) 105 109 115 104 107 109 101 102 102 Y.I. 3.6 3.2 2.9 3.4 3.1 2.8 4.5 4.3 4.2 Transmittance (%) 90.1 91.5 92.1 90.5 91.4 92.4 88.3 89.1 89.3

As shown in Table 2, it can be seen that the plastic lenses obtained from Examples 3 to 8 are equivalent or superior in terms of refractive index, Abbe number, thermal deformation, yellow index and transmittance in comparison with Comparative Examples 1 to 3, In particular, it can be seen that the yellow index, the Abbe number and the transmittance are greatly improved. Thus, it is expected that the plastic lens manufactured in the embodiment can be used lightly, can withstand a high temperature, can form a transparent and clear image, and can be usefully used.

Claims (14)

A polymerizable composition comprising: a siloxane thiol oligomer obtained by non-hydrolytic condensation of a compound represented by the following formula (1) and a compound represented by the following formula (2); a polythiol compound different from the siloxane thiol oligomer; and an isocyanate compound:
[Chemical Formula 1]

(2)

In this formula,
R ₁ , R ₂ , R ₄ and R ₅ 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.
The method according to claim 1,
Wherein x and y satisfy the following formula (1) or (2), wherein x represents an alkoxy equivalent of the compound represented by the formula (1) and y represents a hydroxyl equivalent of the compound represented by the formula (2)
[Equation 1]
x / y? 0.70
&Quot; (2) "
x / y? 1.43.
The method according to claim 1,
Wherein the compound represented by Formula 1 is selected from the group consisting of (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Mercaptopropyltriphenoxysilane, and 11-mercaptoundecyltrimethoxysilane. ≪ RTI ID = 0.0 > 11. < / RTI >
The method according to claim 1,
Wherein the compound represented by Formula 2 is diphenylsilanediol or diisobutylsilanediol.
The method according to claim 1,
Wherein the non-hydropolymerization reaction is carried out in the presence of a catalyst and the catalyst is selected from the group consisting of magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, radium hydroxide and mixtures thereof.
delete The method according to claim 1,
Wherein the siloxane thiol oligomer is selected from the group consisting of compounds represented by the following formulas (3) to (6):
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In this formula,
_{R 1, R 2, R 4} , R 5, R 7, R 8, R 10 and R ₁₁ are independently a C ₆ substituted with C _1-20 alkyl, C _6-20 aryl, or C _1-10 alkyl, each _{Lt; /} RTI >
R ₃ is C _1-20 alkylene, phenylene, or phenylene substituted with C _1-10 alkyl,
R ₆ , R ₉ and R ₁₂ are each independently a siloxy, a C _1-10 alkyl, a C _1-10 alkoxy, a C _1-10 alkylthio or a siloxy substituted by hydroxy, or hydroxy,
l1 is an integer of 0 to 2, m1 is an integer of 0 to 2, n1 is an integer of 1 to 3,
l2 is an integer of 0 to 1, n2 is an integer of 1 to 2,
m3 is an integer of 0 to 1, n3 is an integer of 1 to 2,
l1 + m1 + n1 = 3,
l2 + n2 = 2,
m3 + n3 = 2.
delete The method according to claim 1,
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.
The method according to claim 1,
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 obtained by heat-curing the polymerizable composition of claim 1 in a mold.
A polythiourethane-based plastic lens obtained by the manufacturing method of claim 11.
13. The method of claim 12,
Wherein the plastic lens has a solid-phase refractive index (nd20) of 1.55 to 1.70.
13. The method of claim 12,
Wherein the Abbe's number of the plastic lens is 30 to 50.