KR100573431B1 - Sulfur Containing Polyisocyanates and polythiourethane for Plastic Lens - Google Patents

Abstract

The present invention relates to a sulfur-containing isocyanate compound and a sulfur-containing urethane-based resin for an optical lens, and more particularly to a novel isocyanate compound containing two or more sulfur atoms in a molecule thereof, and to a polythiol having two or more thiol functional groups. By producing sulfur-containing urethane resin for optical materials by mixing, a novel isocyanate compound having a high refractive index and excellent optical properties such as light stability and high transparency, which can be usefully used as an optical material such as a plastic lens, and a urethane system using the same It is about resin.

Sulfur, isocyanate compound, polythiol, refractive index, Abbe's number, lens

Description

Sulfur-Containing Polyisocyanates and Polythiourethane for Plastic Lens}             

1 shows the IR spectrum of the isocyanate compound (1-a) according to Preparation Example 1 of the present invention.

The present invention relates to a sulfur-containing isocyanate compound and a sulfur-containing urethane-based resin for an optical lens, and more particularly to a novel isocyanate compound containing two or more sulfur atoms in a molecule thereof, and to a polythiol having two or more thiol functional groups. By producing sulfur-containing urethane resin for optical materials by mixing, a novel isocyanate compound having a high refractive index and excellent optical properties such as light stability and high transparency, which can be usefully used as an optical material such as a plastic lens, and a urethane system using the same It is about resin.

Plastic lenses have been used for various optical lenses until recently because they are lightweight and have excellent impact resistance and are easier to dye than glass lenses. Generally, polyethylene glycol bisallyl carbonate (CR-39), polymethyl methacrylate (PMMA), and a mixture of modified diaryl phthalate and ethylene glycol bisallyl carbonate have been used as materials for plastic lenses. However, since these plastic lens materials have a refractive index of about 1.50 to 1.55, they have disadvantages such as high dispersion and poor weather resistance or high specific gravity because they use a compound having a large number of halogen atoms or aromatic rings in the molecule to improve the refractive index. have. In addition, when the frequency is high, lenses made of these plastic materials become thicker, resulting in poor aesthetics. In addition, myopia lenses made of these materials have problems such as thick edge thickness and birefringence and chromatic aberration. Therefore, in order to make the thickness of the lens thin while maximizing the advantages of the low specific gravity plastic lens, it is desired to improve the material of the plastic lens so that the chromatic aberration is low, the refractive index is high, and the dispersion is low.

As a material having such a performance, for example, (1) metha xylene diisocyanate (XDI) to 2,5-bis (2-mercaptoethylthiomethyl) -1,4-dithiane [Korean Patent Publication No. 1991-011993 No.], pentaerythritol tetrakismercaptopropionate [Korean Patent Publication No. 1987-0008928], 1,2-bis (mercaptoethyl) -3-mercaptopropane [Korean Patent Publication No. 199-004010], etc. And (2) an aliphatic linear-containing bifunctional isocyanate compound and a polythiol compound resin [Japanese Patent Laid-Open No. 1990-153302], (3) an aliphatic bifunctional Resins of soluble isocyanate compounds and polythiol compounds [Japanese Patent Laid-Open No. 1998-45707], (4) Resins of aliphatic sulfur-containing tetrafunctional isocyanate compounds and polythiol compounds [JP-A-2000-44532 Is disclosed.

However, the polymers of the above (1) are limited in combination with the polythiol as a polymerization counterpart, and the refractive index is increased, but there is a problem that the Abbe number is lowered and the chromatic aberration is increased. On the other hand, the resin of (2) and the resin of (3) have a high refractive index and can be improved in terms of chromatic aberration. However, since the resin is an uncrosslinked polymer obtained with a bifunctional isocyanate compound, solvent resistance is poor. The polymer of (4) is excellent in solvent resistance because it is a crosslinked polymer obtained from a tetrafunctional isocyanate compound, but the plastic lenses obtained therefrom were not satisfactory in heat resistance, impact resistance, refractive index, and light transmittance.

In order to solve the above problems, the present inventors have prepared an isocyanate compound containing two or more sulfur atoms in a molecule and having excellent refractive index and optical properties, and using the same to prepare a sulfur-containing urethane resin in an optical material. The present invention was completed by increasing the sulfur content to increase the refractive index and increasing the crosslinking density to have excellent optical properties.

Accordingly, the present invention provides a resin for a sulfur-containing urethane-based optical lens using the development of a novel isocyanate compound having excellent optical properties (heat resistance, solvent resistance, light weight, high refractive index, dyeing) and improved light transmittance. There is this.

The present invention is characterized by a sulfur-containing isocyanate compound represented by the following formula (1).

In Chemical Formula 1, n represents an integer of 1 to 2.

In addition, the sulfur-containing urethane-based resin comprising an isocyanate compound represented by the formula (1) alone or a mixture of an isocyanate compound represented by the formula (1) and an isocyanate compound other than this compound and a polythiol compound having two or more thiol functional groups and The plastic lens obtained by casting-polymerizing this resin is further characterized.

Referring to the present invention in more detail as follows.

The present invention is to prepare a novel isocyanate compound containing two or more sulfur atoms in the molecule, by mixing the polythiol having two or more thiol functional groups to produce a sulfur-containing urethane resin for optical materials, having a high refractive index, It has excellent optical properties such as stability and high transparency and can be usefully used as an optical material such as a plastic lens.

The isocyanate compound according to the present invention represented by Chemical Formula 1 contains two or more sulfur atoms in a molecule, and thus has excellent refractive index and optical properties. The isocyanate compound represented by Chemical Formula 1 may be synthesized by the following method.

First, the compound represented by Chemical Formula 1 is obtained from the compound represented by the following Chemical Formula 2.

In Formula 2, n represents an integer of 1 to 2.

From the compound group represented by (CH ₂ ) n of the compound represented by the formula ( ₂ ), n is a compound having 1 to 2 is obtained as follows. In other words, a carboxylic acid ester compound having n = 1 and m = 1 is obtained from alpha, alpha'-dichloro-m-xylene and methyl thioglycolate.

In addition, alpha, alpha'-dichloro-m-xylene was prepared by reacting thiourea with alpha, alpha'-dimercapto-m-xylene, which was then reacted with methyl acrylate to indicate n = 2. A carboxylic acid ester compound is obtained.

From the compound represented by Formula 2, a carbonyl hydrazide compound represented by the following Formula 3 is obtained.                     

In Chemical Formula 3, n represents an integer of 1 to 2.

The compound represented by Chemical Formula 3 is reacted with NaNO ₂ in a hydrochloric acid solution to prepare a carbonyl azide compound, followed by potential reaction to obtain an isocyanate compound represented by Chemical Formula 1.

In addition, the present invention is a sulfur containing an isocyanate compound of formula (1) obtained by the above reaction or a mixture of isocyanate compounds of formula (1) and an isocyanate compound other than this compound and a polythiol compound having two or more thiol functional groups Urethane-based resins.

The isocyanate compound including the isocyanate compound represented by the formula (1) includes not only the isocyanate compound represented by the formula (1) but also any other isocyanate compound added for the purpose of adjusting the physical properties of the urethane resin of interest or for ease of operation. do. As an isocyanate compound other than the isocyanate compound of General formula (1), For example, bis (isocyanatomethylthio) methane, bis (isocyanatomethylthio) ethane, Ethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, xylene diisocyanate, etc. can be used. Of these, bis (isocyanatomethylthio) methane, bis (isocyanatomethylthio) ethane, isoholandiisocyanate or xylenediisocyyanate are preferred.

The amount of the isocyanate compound which is an essential component and may additionally be contained as an essential component is suitably determined by the required physical properties or workability, but is used in the range of 0 to 80% by weight based on the isocyanate compound of Formula 1 It is preferably 0 to 50% by weight.

Since the isocyanate compound represented by Formula 1 has a high refractive index itself, the refractive index of the optical material made of the isocyanate compound and the polythiol compound is also high.

Polythiol used in the present invention is 1,3-propanedithiol, 1,2,3-propanetriol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1, 2-dithiol, 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,3-bis (mercaptoethyl) benzene, 1,2,4-trimer Captobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris ( Mercaptoethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, bis ( Mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mer Tomethylthio) methane, bis (2-mercaptomethylthio) methane, bis (3-mercaptomethylthio) methane, 1,2-bis (mercaptomethylthio) methane, 1,2- (2-mercapto Ethylthio) ethane, 1,2- (3-mercaptopropylthio) ethane, 1,3-bis (2-mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1 , 3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptoethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2, 3-tris- (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropyl Thio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercapto Propyl) sulfide, 2,5-dimercapto-1,4-dithiane, bis (mercaptomethyl) di Sulfide, bis (mercaptoethyl) disulfide, bis (mercaptoporophyll) disulfide, 1,2-bis (2-mercaptoethylthio) 3-propanethiol, 2-mercaptoethylthio-1, A thiol compound containing two or more thiol functional groups, more specifically, two to four thiol functional groups may be used as 3-propanethiol, and the like, but the present invention is not limited thereto.

In addition, the mixing ratio of the isocyanate compound represented by the general formula (1) and the polythiol having two or more thiol functional groups is such that the molar ratio of the functional group (NCO / SH) is 0.5 to 2.5 (preferably 0.5 to 1.5) to impair the physical properties of the lens. It is preferable in that it does not, and if a mixing ratio is out of the said range, there exists a problem in heat resistance or weather resistance.

The sulfur-containing urethane-based resin has a high sulfur content in the resin molecule, thus has a high refractive index, and has a high optical crosslink density by increasing the number of thiol groups in the molecule. Therefore, the sulfur-containing urethane-based resin according to the present invention has a high refractive index, colorless transparency excellent in heat resistance, no optical distortion, light weight, excellent weather resistance, dyeing resistance, impact resistance, processability, eyeglass lenses, camera lenses It is preferable as optical element materials, glazing materials, paints, adhesive materials, and the like.                     

The present invention also includes a plastic lens obtained by molding the sulfur-containing urethane resin. Specifically, an isocyanate compound and a polythiol are mixed, and the mixture is defoamed by a suitable method if necessary, and then injected into a glass mold, and the temperature is gradually raised from a low temperature of 0 to 5 ° C to a high temperature of about 100 to 180 ° C. Polymerization. In this case, in order to improve weather resistance and initial color of the optical lens, additives such as UV absorbers, anti-colorants, antioxidants, dyes, and the like may be used. Moreover, you may add various substances, such as a chain extender, a crosslinking agent, an oil dissolving dye, and a filler, depending on the objective. Dibutyltinlaurylate, dibutyltindichloride and triethylamine may be used as catalysts to improve the polymerization reactivity, and silicone-based, fluorine-based surfactants and acidic phosphate esters may be used to easily separate the optical lens formed from the glass mold. (GELEX UN) etc. can also be mixed with the said compound beforehand, and can be used.

The polymerization temperature and time vary depending on the type of monomer and the type of additive, but are usually -20 to 200 ° C, preferably room temperature to 150 ° C, and more preferably 50 to 120 ° C for 0.5 to 72 hours. The plastic lens of the present invention thus obtained has high surface precision and excellent physical properties, is light and excellent in impact resistance, and is suitable for use in optical materials such as spectacle lenses and camera lenses.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Preparation Example 1

NaOH (24 g, 0.6 mol) was dissolved in methanol (250 mL), cooled (iced), and methyl thioglycolate (63.6 g, 0.6 mol) was added slowly and stirred for 10 minutes. Alpha, alpha'-dichloro-m-xylene (52.6 g, 0.3 mol) is dissolved in a mixed solvent of THF and methanol (100 mL, 1: 1 volume ratio), added dropwise for 30 minutes, removed the ice cooler, and stirred at room temperature for 2 hours. It was. The resulting solid was filtered off, the solvent was evaporated under reduced pressure, the residue was dissolved in ethyl acetate, washed with water, dried with anhydrous MgSO ₄ , and the solvent was evaporated under reduced pressure to give 93 g of a colorless oil (2-a) (yield: 98.6%). Got.

(2-a)

(2-a)

In addition, the result of confirming the colorless oil (2-a) by the ¹ H NMR spectrum is as follows;

¹ H NMR (CDCl ₃ ): δ 3.09 (s, 4H), 3.73 (s, 4H), 3.82 (s, 4H), 7.22-7.30 (m, 4H).

The colorless oil (93 g, 0.296 mol) was diluted in methanol (200 mL), and 80% hydrazine (57 g, 4 eqv.) Diluted in methanol (100 mL) was added dropwise, followed by 4 hours at 80 ° C. After the reaction, the mixture was cooled and the solvent was removed under a reduced pressure to obtain 99. 7 g as a very sticky oil. The obtained hydrazide was dissolved in 500 ml of 15% hydrochloric acid without being separated and purified, and then toluene (200 ml) was added, followed by cooling and stirring at 0 ° C.                     

NaNO ₂ (43 g, 2 eqv.) Was dissolved in water (100 mL) and added dropwise to the reaction solution for 30 minutes while being careful not to exceed 5 ° C., and stirred at the same temperature for 2 hours. The organic layer was separated and the water layer was washed once with toluene, the organic layers were collected, the moisture was removed with MgSO ₄ , filtered, the organic layers were collected, and the organic layer was slowly heated at 40-60 ° C. and stirred for 1 hour until the generation of gas stopped. After the generation of the gas, the mixture was cooled to room temperature in a nitrogen atmosphere, the produced white solid was filtered off, and the solvent was distilled off under reduced pressure, and then pale yellow 1,3-bis (3-isocyanato-2-thio-propyl) benzene ( 1-a) 62 g (yield 75%) were obtained as an oil. The refractive index of the oil was 1.6118.

(1-a)

(1-a)

The analysis results for determining the structure of the oil (1-a) are as follows;

bp 175 ° C / 0.01 torr; ¹ H NMR (CDCl ₃ ): δ 3.69-3.88 (m, 4H), 4.11-4.39 (m, 4H), 7.23-7.35 (m, 4H); ¹³ C NMR (CDCl ₃ ): δ 35.04, 43.64, 128.05, 129.06, 129.38, 137.10; FT-IR (Cm ⁻¹ ): 2244, 2271 (NC = O).

Preparation Example 2

1,3-bis (mercaptomethyl) benzene (34.0 g, 0.2 mol) and ethyl acrylate (42.05 g, 2.1 eqv.) Were diluted in TFH (100 mL) and stirred in an Ice-Water bath. TBAFH (Tetrabutylammoniumfluoridehydrate, 1.05 g, 0.02 eqv.) an end little by little added, raised to a 75 ℃ after 4 hours, and, after distilling off the THF and dissolved in dichloromethane, washed with 5% NaHCO ₃ aqueous solution and with water, MgSO ₄ After removing moisture with dichloromethane, dichloromethane was distilled off under reduced pressure to obtain 42.5 g (98.6%) of colorless oil (2-b).

(2-b)

(2-b)

In addition, the result of ¹ H NMR spectrum of the colorless oil (2-b) is as follows;

¹ H NMR (CDCl ₃ ): _δ 1.30 (m, 6H), 2.61 (m, 4H), 2.83 (m, 4H), 3.73 (s, 4H), 4.17 (m, 4H), 6.86-7.20 (m, 4H).

After diluting the colorless oil (42.5 g, 0.115 mol) in methanol (50 mL), 80% hydrazine (21.7 g, 3 eqv.) Diluted in methanol (30 mL) was added dropwise, followed by 10 hours at 65 ° C. After the reaction, the mixture was allowed to cool and the solvent was distilled off under reduced pressure to obtain 47.58 g of a hydrazide compound. The obtained hydrazide compound was dissolved in 7.2% by weight HCl (172 g) without being separated and purified, suspended in benzene (150 mL), and cooled to 0 ° C. NaNO ₂ (17.8 g, 2 eqv.) Was dissolved in water (30 mL) and added dropwise to the reaction solution for 30 minutes while being careful not to exceed 5 ° C., and stirred at the same temperature for 2 hours. The organic layer was separated and the water layer was washed once with toluene, the organic layers were collected, the moisture was removed with MgSO ₄ , filtered, the organic layers were collected, and the organic layer was slowly heated at 40 to 60 ° C. and stirred for 1 hour until the generation of gas stopped. After the generation of gas, the mixture was cooled to room temperature in a nitrogen atmosphere, and the produced white solid was filtered off. Then, 22 g of pale yellow 1,3-bis (4-isocyanato-2-thio-butyl) benzene (1-b) ( Yield 62%) was obtained as an oil. The refractive index of the oil was 6.106.

(1-b)

(1-b)

The analysis results for determining the structure of the oil (1-b) are as follows;

¹ H NMR (CDCl ₃ ): δ 2.52-2.85 (m, 4H), 3.62-3.71 (m, 4H), 4.11-4.39 (m, 4H), 7.23-7.35 (m, 4H); ¹³ C NMR (CDCl ₃ ): δ 34.4, 38.6, 45.6, 122.3, 127.3, 127.4, 128.05, 129.06, 138.1, 138.3 .; FT-IR (Cm ⁻¹ ): 2300-2220 (NC = O).

Preparation Example 3

NaOH (22 g, 0.55 mol) was dissolved in methanol (100 mL), cooled (iced), and methyl thioglycolate (53 g, 0.5 mol) was added and stirred. The ice cooler was removed and dibromomethane (43.5 g, 0.25 mol) was slowly added dropwise at room temperature for 1 hour (the reaction started with heating), followed by stirring at room temperature for 15 hours. Methanol of the reaction solution was removed under reduced pressure, the residue was dissolved in ethyl acetate, washed with water, moisture was removed with anhydrous MgSO ₄ , and the solvent was removed under reduced pressure to give 42.6 g of a colorless oil (yield 76%).

The colorless oil (42.6 g, 0.19 mol) was diluted in ethanol (150 mL), 80% hydrazine (24.5 g, 4 eqv.) Diluted in ethanol (100 mL) was added dropwise, followed by 2 hours at 80 ° C. After the reaction, the reaction mixture was confirmed to form a white solid, and then cooled. The solid was filtered, washed with ethanol, and dried to obtain 36.6 g (yield 86%) of the hydrazide compound as a white solid at room temperature.

The obtained hydrazide compound (36.6 g, 0.163 mol) was suspended in 15 wt% HCl (200 g) and benzene (100 mL) and then cooled with ice-salt. Sodium nitrite (22.5 g, 2.2 eqv.) Dissolved in water (50 g) was added dropwise (1 hour) at 0 ° C, stirred for 1 hour while cooling, the organic layer was separated, washed once with brine, and then magnesium sulfate Dried over and filtered and heated to reflux for 1 h. The solvent was evaporated under reduced pressure, and the remaining residue was distilled off under reduced pressure to obtain 28 g (yield 90%) of pale pink bis (isocyanatomethylthio) methane (3). When stored at room temperature of the obtained product, the color disappears and becomes colorless.

(3)

(3)

The analysis results for determining the structure of the product (3) are as follows;

bp = 110-120 ° C./0.001 torr; ¹ H NMR (CDCl ₃ ): δ 2.8 (s, 2H, SCH ₂ ), 3.5 (m, 4H, CH ₂ -NCO); FT-IR (Cm ⁻¹ ): 2300-2220 (NC = O).

Preparation Example 4

NaOH (22 g, 0.55 mol) was dissolved in methanol (100 mL), cooled (ice) and methyl thioglycolate (53 g, 0.5 mol) was added to produce a stiff white solid. The ice cooler was removed and dibromoethane (47 g, 0.25 mol) was slowly added dropwise at room temperature for 1 hour (the reaction started while heating), followed by stirring at room temperature for 15 hours. Methanol of the reaction solution was removed under reduced pressure, the residue was dissolved in ethyl acetate, washed with water, moisture was removed with anhydrous MgSO ₄ , and the solvent was removed under reduced pressure to obtain 52 g of a colorless oil (yield 87.6%).

The colorless oil (52 g, 0.218 mol) was diluted in ethanol (150 mL), and 80% hydrazine (28 g, 4 eqv.) Diluted in ethanol (100 mL) was added dropwise, followed by 2 hours at 80 ° C. After the reaction, the reaction mixture was confirmed to form a white solid. The mixture was left to cool. The solid was filtered, washed with ethanol, and the white solid hydrazide compound was dried at room temperature to give 52.38 g (yield 90%).

The hydrazide compound (52.38 g, 0.22 mol) obtained above was suspended in 15 wt% HCl (210 g, 4 eqv.) And chloroform (150 mL) and then cooled with ice-salt. Sodium nitrite (30.5 g, 2.0 eqv.) Dissolved in water (50 g) was added dropwise (1 hour) at 10 ° C. or lower, and after 1 hour of reaction under cooling, the organic layer was separated and the water layer was extracted with dichloromethane. Washed once, dried over magnesium sulfate, filtered and heated to reflux for 1 hour. The solvent was evaporated under reduced pressure, and the residue was distilled under reduced pressure to obtain 35.4 g (yield 78.8%) of pale pink bis (isocyanatomethylthio) ethane (4). The resultant product gradually disappears and becomes colorless when stored at room temperature.

(4)

(4)

The analysis results for determining the structure of the product (4) are as follows;

bp = 110-120 ° C./0.001 torr; ¹ H NMR (CDCl ₃ ): δ 2.8 (m, 4H, SCH ₂ ), 3.5 (m, 4H, CH ₂ -NCO); FT-IR (Cm ⁻¹ ): 2300-2220 (NC = O).

Example 1

1,3-bis (3-isocyanato-2-thio-propyl) benzene (0.3 mol) and 1,2-bis (2-mercaptoethylthio) 3-propanethiol (0.2 prepared in Preparation Example 1) Mole), dibutyltin dichloride (1.6 x 10 ^-5 moles, 0.005 g) was degassed by stirring for 1 hour under vacuum, and injected into a glass mold assembled with a plastic gasket. The glass mold injected with the mixture was placed in a forced circulation oven and maintained at 30 ° C. for 2 hours, heated at 30 ° C. to 40 ° C. for 4 hours, maintained at 40 ° C. for 4 hours, and heated at 40 ° C. to 120 ° C. for 8 hours. The mixture was kept at 120 ° C for 2 hours, cooled at 120 ° C to 60 ° C for 4 hours, and then the glass mold was detached to obtain a plastic lens.

Example 2

1,3-bis (4-isocyanato-2-thio-butyl) benzene (0.3 mol) and 1,2-bis (2-mercaptoethylthio) 3-propanethiol (0.2 prepared in Preparation Example 2) Mole), a mixture of dibutyltin dichloride (1.6 × 10 ⁻⁵ moles, 0.005 g) was degassed by stirring for 1 hour under vacuum and injected into a glass mold assembled with a plastic gasket. The glass mold injected with the mixture was placed in a forced circulation oven and maintained at 30 ° C. for 2 hours, heated at 30 ° C. to 40 ° C. for 4 hours, maintained at 40 ° C. for 4 hours, and heated at 40 ° C. to 120 ° C. for 8 hours. The mixture was kept at 120 ° C for 2 hours, cooled at 120 ° C to 60 ° C for 4 hours, and then the glass mold was detached to obtain a plastic lens.

Examples 3 to 10

In Table 1, 1,3-bis (3-isocyanato-2-thio-propyl) benzene and 1,3-bis (3-isocyanato-2-thio prepared in Preparation Example 1 and Preparation Example 2 The same experiment as in Example 1 was performed except that the monomer composition including bis (isocyanatomethylthio) methane and bis (isocyanatomethylthio) ethane obtained in Preparation Example 3 and Preparation Example 4 was obtained. A plastic lens was obtained.

Comparative Example 1

The same experiment as in Example 1 was conducted except that 0.1 mol of pentaerythritol tetrakismercaptopropionate (PETMP), 0.2 mol of m-xylene diisocyanate, and 1.6 × 10 ^-5 mol of dibutyltin dichloride were used as the polythiol compound. To obtain a plastic lens.

Comparative Examples 2 to 3

The same experiment as in Comparative Example 1 was conducted except that the monomer composition shown in Table 1 was used to obtain a plastic lens.

Test Example

Evaluation of physical properties of the plastic lens obtained in Examples 1 to 10 and Comparative Examples 1 to 3 was carried out as follows, and the results are shown in Table 1 below.

1. Refractive index and Abbe number: An Abbe refractometer (1T model of Atac Corporation) was used.

2. Light transmittance: Measured using a spectrophotometer.

3. Light resistance: The plastic lens was exposed to QUV / Spray model (5w) of Q-Pannel lad products (20w) for 20 hours and marked with O, if no color change.

4. Heat resistance: The heat deflection temperature (10 ° C./min) was measured using DSC.

5. Impact resistance: 16.8 g of steel balls were dropped at the height of 127 cm at the center of the lens so that the lens was marked as O when the lens was not broken, and × when broken.

division Isocyanate (mol) Polythiol (mol) Refractive index (nD) Abbe (νD) Light transmittance (%) Light resistance Heat resistance (℃) Impact resistance Example One ITP (0.3) GST (0.2) 1.654 34 91.0 O 99 O 2 ITB (0.3) GST (0.2) 1.653 34 91.0 O 98 O 3 ITP (0.2) ITM (0.1) GST (0.2) 1.66 32 96.1 O 97 O 4 ITB (0.2) ITM (0.1) GST (0.2) 1.66 32 95.3 O 97 O 5 ITP (0.2) ITE (0.1) GST (0.2) 1.66 32 96.0 O 102 O 6 ITB (0.2) ITE (0.1) GST (0.2) 1.66 32 95.5 O 99 O 7 ITP (0.2) XDI (0.1) GST (0.2) 1.67 32 94.7 O 92 O 8 ITB (0.2) XDI (0.1) GST (0.2) 1.67 32 95.1 O 95 O 9 ITP (0.2) IPDI (0.1) GST (0.2) 1.66 37 96.1 O 97 O 10 ITP (0.2) IPDI (0.1) GST (0.2) 1.65 37 95.0 O 96 O Comparative example One  XDI (0.2) PETMP (0.1) 1.59 36 87.7 O 87 O 2  HMDI (0.1) IPDI (0.1) PETMA (0.1) 1.55 48 86.8 O 89 O 3 XDI (1.5) 1,3,5-TMB (0.1) 1.56 32 87.0 × 94 O ITP: 1,3-bis (3-isocyanato-2-thio-propyl) benzene ITB: 1,3-bis (4-isocyanato-2-thio-butyl) benzene ITM: CH ₂ (SCH ₂ NCO ) ₂ bis (isocyanatomethylthio) methane, ITE: CH ₂ (SCH ₂ CH ₂ NCO) ₂ bis (isocyanatomethylthio) ethane XDI: m-xylene diisocyanate IPDI: isoprone diisocyanate GST: 1, 2-bis (2-mercetoethylthio) 3-propanethiol HMDI: hexamethylenediisocinate 1,3,5-TMB: 1,3,5-trimercaptobenzene PETMP: pentaerythritol tetrakis (mercapto Propionate) PETMA: pentaerythritol tetrakis (mercaptoacetate)

As shown in Table 1, the plastic lens obtained by using the novel polyisocyanate compound according to the present invention (Examples 1 to 10) has a high refractive index of 1.65 to 1.67, and has weather resistance, impact resistance, heat resistance, light stability, and light transmittance. It was confirmed that the back is excellent. On the other hand, the plastic lenses (Comparative Examples 1 to 3) manufactured using the conventional polyisocyanate compound have a low refractive index of 1.59 or less and have poor light resistance or low heat resistance and low light transmittance.

As described above, the novel isocyanate compounds according to the present invention have high refractive index, and the sulfur-containing urethane resin prepared by mixing with a polythiol compound having two or more thiol functional groups, which is a feature of the present invention, also has a high refractive index. It has excellent optical properties such as light stability, high transparency, and the like. Therefore, the sulfur-containing urethane-based resin of the present invention can be usefully used for optical media such as recording media substrates, color filters, and ultraviolet absorption filters used in glasses, camera lenses, prisms, optical fibers, optical disks, magnetic disks, and the like.

Claims (6)

Sulfur-containing isocyanate compounds represented by the following Chemical Formula 1; [Formula 1]

In Chemical Formula 1, n represents an integer of 1 to 2. Sulfur-containing urethane resins comprising an isocyanate compound represented by the following formula (1) and a polythiol compound having 2 to 4 thiol functional groups; [Formula 1]

In Chemical Formula 1, n represents an integer of 1 to 2. 3. The bis (isocyanatomethylthio) methane, bis (isocyanatomethylthio) ethane, A sulfur-containing urethane resin further comprising an isocyanate compound selected from ethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate and xylene diisocyanate. The method of claim 2, wherein the polythiol compound is 1,3-propanedithiol, 1,2,3-propanetriol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane -1,2-dithiol, 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropio Nate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,3-bis (mercaptoethyl) benzene, 1,2,4 -Trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5 -Tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene , Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, ratio S (mercaptomethylthio) methane, bis (2-mercaptomethylthio) methane, bis (3-mercaptomethylthio) methane, 1,2-bis (mercaptomethylthio) methane, 1,2- (2 Mercaptoethylthio) ethane, 1,2- (3-mercaptopropylthio) ethane, 1,3-bis (2-mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) Propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercapto ethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1 , 2,3-tris- (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthio) propane, 1,2,3-tris (3- Mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3- Dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, bis (mercap) Methyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptoporophyll) disulfide, 1,2-bis (2-mercaptoethylthio) 3-propanethiol and 2-mercaptoethylthio- Sulfur-containing urethane-based resin, characterized in that selected from 1,3-propanethiol. The sulfur-containing urethane-based resin according to claim 2, wherein the mixing ratio of the isocyanate and the polythiol is 0.5 to 2.5 in the molar ratio of the functional group (NCO / SH). A plastic lens obtained by casting polymerization of the resin of claim 2.

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