KR100497579B1 - Plastic optical lens material and the lens using polymer containing sulfur - Google Patents

Abstract

The present invention provides a plastic spectacle lens material obtained by reacting a polythiol compound represented by component (I) with polydiisocyanate and / or polydiisothiocyanate as an optical plastic spectacle lens material, and a plastic spectacle lens using the same. do. The plastic spectacle lens material of the present invention has excellent optical properties such as impact resistance, light weight, moldability, dyeing property, transparency, high refractive index and Abbe's number, and especially, it has very high heat resistance without bubble generation at the edge of the lens during polymerization. Has excellent properties.

Ingredient (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.)

Description

Plastic optical lens material using sulfur-containing polymer and plastic eyeglass lens using the same {Plastic optical lens material and the lens using polymer containing sulfur}

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

Plastic lenses are widely used today 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, Korean Patent No. 40546 uses a method of mixing pentaerythritol tetrakis (mercaptopropionate) and pentaerythritol tetrakis (mercaptoacetate) in m-xylene diisocyanate at a predetermined ratio. Presented. 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 Korean Patent No. 0136698, a plastic lens was prepared by mixing a diisocyanate compound with 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and pentaerythritol tetrakis (mercaptopropionate). Used to. 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, ie, 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 The purpose is to provide a plastic spectacle lens raw material without deformation of the central portion of the lens and no bubbles generated during curing.

To this end, in the present invention, a plastic spectacle lens material obtained by reacting a polythiol compound represented by component (I) with polydiisocyanate and / or polydiisothiocyanate as an optical plastic lens material and a plastic spectacle lens using the same to provide.

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

The polythiol compound used in the plastic spectacle lens material of the present invention reacts pentaerythritol to mercaptopropionate and mercaptoacetate together, so that at least one mercaptoacetate group is present in one molecule, and mercaptopropionate is used. It is characteristic to include.

Pentaerythritol tetrakis (mercaptopropionate) and pentaerythritol tetrakis (mercaptoacetate) are mixed together with m-xylene diisocyanate to produce a plastic spectacle lens as in Korean Patent Publication No. 40546. If 20% or more of erythritol tetrakis (mercaptoacetate) is mixed, the heat resistance can be greatly improved, but the pentaerythritol tetrakis (mercaptoacetate) is poorly mixed with pentaerythritol tetrakis (mercaptopropionate), thereby hardening the resin. There is a problem that precipitates out, and there is a problem that bubbles occur during curing of the resin even when prepolymerization and defoaming. These problems can be solved by reacting pentaerythritol with mercaptopropionate and mercaptoacetate together in one 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- Plastic excellent in optical properties by curing with polydiisocyanate compounds or polydiisothiocyanate compounds such as diisothiocyanate benzene, 1,2-diisothiocyanate hexane, 1,6-diisothiocyanate hexane A spectacle lens material can be obtained.

The present invention may add ultraviolet absorbers, antioxidants, organic dyes, etc. to component (1) and polyisocyanate compounds to improve optical properties, and 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 and used.

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

Example

Hereinafter, the present invention will be described in detail by Examples and Comparative Examples, but the present invention is not limited by the following Examples.

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. In addition, the results of NMR and IR analysis for component (I) are shown in FIGS. 1 and 2, respectively.

(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 forming mold consisting of a glass mold and gasket coated with a release agent (Zelec UN) from 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 edges were polished and washed, followed by annealing at 120 ° C. for 2 hours to prepare a plastic eyeglass lens. The prepared spectacle lens was subjected to physical property evaluation 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.

Examples 2-11

Lenses were prepared and tested in the compositions shown in Table 1 in the same manner as in Example 1. The results and the like are shown in Table 1.

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 removed under reduced pressure and stirred for 1 hour and 30 minutes under nitrogen stream while maintaining the temperature at 10 ° C., and the process after bubble removal was performed in the same manner as in Example 1.

Comparative Examples 2 to 3

It prepared by the same method as the comparison 1 except having changed the addition ratio of pentaerythritol tetrakis (mercapto propionate) and pentaerythritol tetrakis (mercapto acetate) to m-xylene diisocyanate.

delete

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

A composition obtained by reacting a polydiisocyanate and / or polydiisothiocyanate with a polythiol compound of component (I) according to the present invention, and a composition prepared by adding other additives used in the resin for eyeglass lenses It has a high refractive index and Abbe number, and can be used as a raw material for plastic spectacle lenses having excellent impact resistance, transparency and thermal stability.

1 is an NMR analysis result of component (I) obtained in Example 1 of the present invention, and FIG. 2 is an IR analysis result of component (I) obtained in Example 1 of the present invention.

Claims (6)

delete delete A plastic spectacle lens material obtained by reacting a polythiol compound represented by the formula (1) with a polydiisocyanate or polydiisothiocyanate or a mixture thereof. 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.) The method of claim 3, wherein the polydiisocyanate is m-xylene diisocyanate; p-xylene diisocyanate; Ethylene diisocyanate; Trimethylene diisocyanate; Hexamethylene diisocyanate; Any one or a mixture thereof selected from isoprone diisocyanate, Wherein said polydiisothiocyanate is 1, 2-diisothiocyanate hexane or 1,6-diisothiocyanate hexane or a mixture thereof. The plastic spectacle lens material according to claim 3, further obtained by adding 1 to 20% of pentaerythritol tetrakismercaptoacetate. A plastic spectacle lens made of the plastic spectacle lens material of claim 3.