KR20030039952A - Polythiol Compounds for Plastic Glasses - Google Patents

Abstract

PURPOSE: A polythiol compound for a plastic glasses lens and a plastic glasses lens obtained by using the polythiol compound are provided, to improve the refractive index, the Abbe's number, the heat resistance, the impact resistance, the dying property and the transparency, to reduce the weight and to inhibit the generation of bubbles at the edge of a lens. CONSTITUTION: The polythiol compound is represented by the formula 1, wherein n is an integer of 1-3, m is an integer of 1-3, and n+m is 4. The plastic glasses lens is prepared by reacting the polythiol of the formula 1 with poly diisocyanate and/or poly diisothiocyanate. Preferably 1-20 wt% of pentaerythritol tetrakis mercaptoacetate is added to the reaction. Preferably the poly diisocyanate is prepared by using m-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate; and the poly diisothiocyanate is prepared by using 1,2-diisothiocyanatehexane or 1,6-diisothiocyanatehexane.

Description

Polythiol compound for plastic spectacle lenses

The present invention is useful as a material for sulfur-containing plastic spectacle lenses, and more particularly, has excellent refractive index and Abbe's number while having excellent optical properties such as impact resistance, light weight, moldability, dyeing property, transparency, and the like, in particular, a lens during polymerization. The present invention relates to a plastic spectacle lens material having excellent heat resistance, with no bubble generation at the edge, and a method for producing a high refractive plastic lens using the same.

Plastic lenses are being used nowadays because they are excellent in light weight, dyeability and impact resistance compared to glass lenses. Representative plastic lenses include polyethylene bisallyl carbonate, polymethyl methacrylate, modified diallyl phthalate and mixed cured products of polyethylene bisallyl carbonate, but the edge thickness of lenses with high refractive index is low due to low refractive index. There is a thick issue.

In order to solve the above problems, Patent KR JP 40546 proposes a method of mixing pentaerythritol tetrakis (mercaptopropionate) and pentaerythritol tetrakis (mercaptoacetate) in m-xylene diisocyanate at a predetermined ratio. It was. In this case, however, in order for the lens to have sufficient heat resistance, the ratio of pentaerythritol tetrakis (mercaptoacetate) to pentaerythritol tetrakis (mercaptopropionate) must be 20% or more. In this case, however, bubbles are generated during the curing of the resin, thereby making it impossible to manufacture the plastic lens.

In patent KR 0136698, a plastic lens is prepared by mixing a diisocyanate compound with 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and pentaerythritol tetrakis (mercaptopropionate). Used. However, this also has a problem that not only does not have sufficient heat resistance, but also a lot of expense and waste water in the production of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane.

The present invention has excellent optical properties, namely, solvent resistance, transparency, light weight, dyeing properties, etc., while having a high refractive index, especially heat resistance, heat curing process during the silicone coating process to increase the surface strength of the plastic lens It is an object of the present invention to provide a polythiol compound useful as a plastic spectacle lens raw material without deformation of the central portion of the lens and no bubble generation during curing.

The present invention proposes a polythiol compound represented by component (I) as an optical plastic lens material.

(In the above formula, n = 1-3 is an integer, m = 1-3 is an integer, and n + m is an integer of 4.)

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The novel polythiol compound for plastic ophthalmic lens of the present invention reacts pentaerythritol with mercaptopropionate and mercaptoacetate together, and has at least one mercaptoacetate group in one molecule, and also includes mercaptopropionate. It is characteristic that we are doing.

Pentaerythritol tetrakis (mercaptopropionate) and pentaerythritol tetrakis (mercaptoacetate) are mixed with m-xylene diisocyanate to produce a plastic spectacle lens as described in patent publication KR 40546. Mixing kiss (mercaptoacetate) more than 20% can significantly improve the heat resistance, but the pentaerythritol tetrakis (mercaptoacetate) is poorly mixed with pentaerythritol tetrakis (mercaptopropionate) and precipitates upon resin curing. In addition, there is a problem that bubbles are generated during the curing of the resin even when prepolymerization and defoaming. These problems can be solved by reacting pentaerythritol with mercaptopropionate and mercaptoacetate in a single molecule to produce a substance like component (I).

To prepare component (I), in one step, 1 mol of pentaerythritol and 0.4-0.6 mol of mercaptoacetate were esterified at 140 ° C. for 6 hours under reduced pressure, followed by 0.5-0.7 mol of mercaptopropionate in two steps. After the reaction for 10 hours in the same manner as in step 1, 0.1 mol of the remaining mercaptopropionate was removed under reduced pressure to obtain component (I).

Component (I) is polyisocyanate, ie ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,2- It was cured with diisocyanate compounds such as diisothiocyanate benzene, 1,2-diisothiocyanate hexane and 1,6-diisothiocyanate hexane to obtain a plastic spectacle lens with excellent optical properties.

The present invention may add ultraviolet absorbers, antioxidants, organic dyes, etc. to component (1) and polyisocyanate compounds to improve optical properties, and to increase the polymerization reactivity, dibutyltin dilaurate, dibutyltin di Chloride, triethylamine and the like can be added.

In order to easily separate the molded plastic spectacle lens from the glass mold, an acidic phosphate ester such as silicone-based or fluorine-based surfactants, DuPont's Gelek UN or NE can be added directly to the mixture of component (I) and polydiisocyanate, or methanol or ethanol. After dissolving in a solvent such as methylene chloride, it may be applied to a glass mold.

The composition prepared by mixing the polyisocyanate and the additive with the substance of component (I) of the present invention is a raw material for plastic spectacle lenses having high refractive index and Abbe number and excellent impact resistance, transparency, thermal stability, and particularly heat resistance.

Example

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

Example 1

Component (I) was prepared by subjecting pentaerythritol 34.04 (0.25 mol) to 36.84 g (0.4 mol) of mercaptoacetate at 140 ° C. under reduced pressure for 6 hours, followed by mercaptopropionate 74.3 (0.7 mol). After the reaction under reduced pressure for 10 hours, 10.6 g (0.1 mol) of the remaining mercaptopropionate was removed, and 0.4 mol of mercaptoacetate and 0.6 mol of mercaptopropionate were added to 0.25 mol of pentaerythritol. Got. The distribution of n, m of component (I) was measured by GPC method after adding 0.4 mol of mercaptoacetates to 0.25 mol of pentaerythritol.

(44% for n = 1, m = 3, 52% for n = 2, m = 2, 4% for n = 3, m = 1)

Elemental analysis

C H S

Theoretical value (%) 39.5 5.3 27.5

% Measured 39.3 5.6 27.7

¹ H-NMR (solvent: CDCl ₃ , internal standard: TMS)

(ppm) = 1.61 (t, 1H), 2.01 (t, 1H), 2.63-2.78 (br, 2H), 3.24-3.27 (m, 2H)

IR 2568 Cm ^-1 (-SH of polythiol)

To prepare a plastic glasses lens, 45 g of m-xylene diisocyanate (-NCO / -SH molar ratio was set to 0.1: 0.1) and 0.05 g of dibutyltin dichloride were added to 55 g of component (I). Air bubbles were removed by stirring under reduced pressure for 1 hour and 30 minutes, and then injected into a diopter -5.00 lens working mold made of a glass mold and gasket coated with a releasing agent (Gelec UN of DuPont), and the temperature was increased from 20 to 120 ° C. Curing with increasing gradually over time. After completion of the curing, after cooling at 80 ° C. for 4 hours, the plastic eyeglass lens was detached from the glass mold, and the edge was polished and washed, followed by annealing at 120 ° C. for 2 hours to prepare a plastic eyeglass lens. The prepared spectacle lenses were evaluated for physical properties in the following manner and the results are shown in Table 1.

Refractive Index and Dispersion: Measured using an Abe refractometer Atacosa 1T model.

Light transmittance: Measured using a spectrophotometer.

Heat resistance: 5 g was added to the test piece using the thermomechanical analyzer (manufactured by Parkin Elmar Co., Ltd.), and heated at 2.5 ° C. per minute to measure the heat deformation start temperature.

Impact resistance: If the 16.8g steel ball is dropped from the height of 127cm to the center of the plastic lens, the lens will not be broken. Marked with broken Marked as.

Specific gravity: measured by submerged method.

Light resistance: 200 hours of exposure to the QUV / Spray model (5w) of plastic lenses from Q-Panhel lad products. , if there is Marked as.

Whether bubbles are generated during curing: If 10 or more plastic lenses are produced at the edge of the lens by manufacturing 10 plastic lenses as described above, If less than one occurs Marked as.

Example 2-11

Lenses were prepared in the compositions shown in Table 1 according to the same operation as in Example 1, and the test results and the like were described in this table.

Comparative Example 1

44 g of m-xylene diisocyanate, 53.5 g of pentaerythritol tetrakis (mercapto propionate), 2.5 g of pentaerythritol tetrakis (mercaptoacetate) (-NCO / -SH molar ratio was 0.1: 0.1), dibutyltin 0.05 g of dichloride was added thereto, and the mixture was stirred under reduced pressure for 1 hour and 30 minutes under nitrogen stream while maintaining the temperature at 10 ° C., and then the same lens as in Example 1 was prepared, and the results are shown in Table 1.

Comparative Example 2-3

Except for varying the addition ratio of pentaerythritol tetrakis (mercaptopropionate) and pentaerythritol tetrakis (mercaptoacetate) to m-xylene diisocyanate, it was prepared in the same manner as in Comparative 1 and the results are shown in Table 1. Indicated.

Table 1

¹⁾ Polythiol which added 0.6 mol of mercaptoacetate and 0.6 mol of mercaptopropionate to 0.25 mol of pentaerythritol

²⁾ Polythiol obtained by adding 0.5 mol of mercaptoacetateto and 0.5 mol of mercaptopropionate to 0.25 mol of pentaerythritol

³⁾ Polythiol having 0.6 mol of mercaptoacetate and 0.4 mol of mercaptopropionate added to 0.25 mol of pentaerythritol

⁴⁾ Polythiol obtained by adding 0.25 mol of mercaptoacetate to 0.3 mol of pentaerythritol, and 0.3 mol of mercaptopropionate.

⁵⁾ Polythiol having 0.3 mol of mercaptoacetate and 0.7 mol of mercaptopropionate added to 0.25 mol of pentaerythritol

PETMP: pentaerythritol tetrakis mercaptopropionate

PETMA: pentaerythritol tetrakis mercaptoacetate

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Claims (6)

Formula (1) (In the above formula, n = 1-3 is an integer, m = 1-3 is an integer, and n + m is an integer of 4.) Polythiol compound for the manufacture of plastic spectacle lenses Plastic eyeglass lens obtained using formula (1) according to claim 1 A plastic spectacle lens obtained by the reaction of formula (1) according to claim 1 with polydiisocyanate and / or polydiisothiocyanate. The plastic glasses lens obtained by using the polydiisocyanate of Claim 3 as m-xylene diisocyanate, p-xylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. The plastic eyeglass lens obtained using the polydiisothiocyanate of Claim 3 using 1, 2- diisothiocyanate hexane, 1, 6- diisothiocyanate hexane. The plastic spectacle lens obtained by adding 1-20% of pentaerythritol tetrakismercaptoacetate to claim 3.