JPS63207805A - Production of plastic lens material - Google Patents

Abstract

PURPOSE:To obtain a lens material having excellent impact resistance as well as dyeability and high refractive index, by polymerizing and curing a mixture consisting of a specific urethane poly(meth)acrylate, (meth)allyl group-containing compound and polythiol compound and three-dimensionally crosslinking the resultant polymer. CONSTITUTION:The titled material obtained by polymerizing and curing a monomeric mixture consisting of (A) 30-89wt.% urethane poly(meth)acrylate having >=2 (meth)acryloyloxy groups in one molecule, (B) 1-50wt.% compound having >=2 (meth)acrylic groups in one molecule (e.g. diallyl o-phthalate) and (C) 10-50wt.% polythiol compound having >=2 mercapto groups in one molecule (e.g. ethylene glycol dithioglycolate). Furthermore, the component (A) is preferably an addition reaction product of 2-hydroxypropyl methacrylate with xylylene diisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a plastic lens material, and more particularly, to a method for producing a plastic lens material, and more specifically, a three-dimensionally crosslinked impact resistant material,
The present invention relates to a method for manufacturing a high refractive index plastic lens material with excellent dyeability.

[Conventional technology]

Plastic lenses are becoming widely used in optical products due to their ease of molding and light weight. Particularly in eyeglass lenses, the weight of the entire eyeglass has a large effect on both the physiology and the optics of the eyeglass, so it is desired that the lens be light, and in recent years, resins made of polydiethylene glycol bisallyl carbonate have become the mainstream for plastic eyeglass lenses.

However, although this plastic eyeglass lens can reduce the weight to half that of inorganic glass, it has a refractive index of 1.
Since the refractive index is as low as 49 to 1.50, the center thickness, burnt thickness, and curvature increase by t when compared with inorganic glass, and a plastic lens with a high refractive index is desired. In addition, in the case of producing a wide variety of products such as eyeglass lenses, the less productive method is used, which requires polymerization time of 10 hours or more to obtain lenses using the cast polymerization method. It is also desired.

Epoxy (meta) as a solution to these problems
A method of obtaining a lens by injecting acrylate, a compound having an allyl group, and a compound having a mercapto group into a lens mold, and polymerizing and curing it with ultraviolet rays (JP-A-59-S7X2
s-1 etc.) have been proposed.

[Problem that the invention seeks to solve]

However, although the above method can produce a plastic lens with a high refractive index in a short time, the mixing ratio of the allyl compound or (meth)acrylate compound and the polyfunctional thiol compound at an equivalent ratio of 1=0.8 to 1.5 is insufficient. Because of its use, it has a strong sulfur odor characteristic of compounds with mercapto groups, which poses problems in terms of workability and environmental protection at production sites. Furthermore, the resulting plastic has five drawbacks, including poor impact resistance.

[Means for solving problems]

In view of the above-mentioned problems, the present inventors have developed
The present invention was developed as a result of extensive research into providing high-refractive-index plastic lenses with excellent dyeability and good productivity.

That is, the present invention uses 50% by weight of urethane boryl having two or more (meth)acryloyloxy groups in one molecule and 1
This is a method for producing a plastic lens material, characterized by polymerizing and curing a polythiol compound having two or more mercapto groups in the molecule (a monomer mixture consisting of C110 to 50% by weight).

The first component of the present invention, urethane poly(meth)acrylate having two or more (meth)acryloyloxy groups in one molecule, is the main component of the plastic lens material of the present invention, and is used to form lenses. Good impact resistance,
It provides a dyeing function and can be produced by an addition reaction between a compound having two or more incyanate groups in the molecule and a (meth)acrylate monomer containing a hydroxyl group. Incyanate compounds having two or more incyanate groups in the molecule include aliphatic,
Aromatic or cycloaliphatic isocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate,
Examples include dimer acid diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, naphthalene diisocyanate, etc. These incyanates and amino groups, hydroxyl groups, carboxyl groups, water Compounds having two or more incyanate groups in the molecule obtained by reaction with a compound having at least two or more active hydrogen atoms, or trimers to pentamers of the above diisocyanate compounds may also be used. can. The hydroxyl group-containing (meth)acrylates to be reacted with the incyanate compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples include acrylates, and addition reaction products of monoepoxy compounds with ethyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and (meth)acrylic acid.

The addition reaction between the incyanate and the hydroxyl group-containing (meth)acrylate can be carried out by a known method, for example, by heating a mixture of the hydroxyl group-containing (meth)acrylate and a catalyst such as diptyltin dilaurate at 50°C to 90°C in the presence of the incyanate compound. It can be produced by dropping under certain conditions. Among the urethane poly(meth)acrylates obtained in this way, to obtain a plastic lens material with a high refractive index, cyclohexane diisocyanate, inphorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenyl diisocyanate, naphthalene diisocyanate, and biphenyl are used. Diisocyanates and the like are preferred. In particular, from the viewpoint of the viscosity of the monomer mixture and the refractive index of the resulting plastic lens material, a reaction product of xylylene diisocyanate and 2-hydroxypropyl methacrylate is preferred. The compound (B) containing one or more of these urethane poly(meth)acrylates serves as a reactive diluent for the main component, urethane poly(meth)acrylate. be. Compounds having two or more allyl groups in one molecule (Bl is preferably one having a phenyl group, biphenyl group, naphthalene group, adamantane group, etc. structure in the molecule in order to obtain a plastic lens material with a high refractive index) .As such, diallyliso7
tallate, diallyliso7thaleate, diallyliso7thaleate, dimethallyl isophthalate, diallyl terephthalate, dimethallyltere7thaleate, diethylene glycol bisallyl carbonate, 2.2'-biphenylic acid diallyl ester, 2.2'-biphenylic acid dimethallyl ester, adamantane- Examples include diallylnaphthalene diacetate and diallyl 2,3 dicarboxylic acid ester.

The third component of the present invention is a polythiol compound having two or more mercapto groups in one molecule (C1 is a captive component and (
It copolymerizes with the Bl component to increase the degree of polymerization. Such polythiol compounds (specific examples of C1 include ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, pentaerythritol trithiopropionate, pentaerythritol tetrathioglycolate, etc.) can be mentioned.

The plastic lens material of the present invention has (
Compound (B) having two meth)acryloyloxy groups
A monomer mixture consisting of 1 to 50% by weight and a polythiol compound (C110 to 50% by weight) having two or more mercapto groups in one molecule is polymerized by irradiating it with ultraviolet rays in the presence of a photopolymerization initiator, for example. It can be produced by curing.If the mixing ratio of each component is less than 30% by weight of urethane poly(meth)acrylate (A), it will not cure sufficiently, and if it exceeds 89% by weight, the viscosity of the monomer mixture will increase. The workability of cast polymerization decreases.In addition, if the blending ratio of the compound (Bl) is less than 1% by weight, the dilution effect is insufficient, the viscosity of the monomer mixture increases, and the workability of cast polymerization decreases.
If it exceeds 0% by weight, the impact resistance of the resulting plastic lens material will decrease. On the other hand, polythiol compound (C)
If the blending ratio is less than 10% by weight, sufficient curing will not occur;
If it exceeds % by weight, the odor of the polythiol compound will affect workability.

Particularly preferred blending ratios are that the ratio of the prisoner component to the component (B) is 1:0.02 to 1 by weight, and the ratio of the total amount of components (4) and 031 to the component (C) is 1:0 by weight. .1 to 0.5.

Examples of photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzophenone, acetophenone, jetoxyacetophenone, 1,1-dimethoxy-1-phenylacetophenone, benzyl, methylphenylglyoxylate,
Examples include benzyl dimethyl ketal. The amount of photopolymerization initiator used is 1:0.0005 to 0.05 in weight ratio to the monomer mixture.

In order to polymerize and cure the monomer mixture by irradiating ultraviolet rays, ultraviolet rays with a wavelength of 2000 to 8000i are preferable;
Normal atmosphere is sufficient for the irradiation atmosphere. Further, as a light source, a known chemical lamp, xenon lamp, low pressure mercury lamp, high pressure mercury lamp, etc. can be used.

Furthermore, in the present invention, in addition to the above-mentioned polymerization curing method using ultraviolet irradiation, it is also possible to apply a known polymerization curing method using irradiation with X-rays, electron beams, visible light, and the like.

In carrying out the present invention, during polymerization, various ultraviolet curable monomers/oligomers, other copolymerizable monomers, anti-yellowing agents such as triphenylphosphine, Ultraviolet absorbers, bluing dyes, etc. may be added.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, "parts" in the examples indicate "parts by weight."

Moreover, physical property evaluation in this example was measured according to the method described below.

(2) Refractive index: Measured using an Atsube refractometer.

(2) Pencil hardness: Measured according to JIS-5400.

(3) Visible light transmittance: Measured according to ASTM-D1003-61.

(4) Optical distortion: distortion inspection machine (portable Po1aro
id 5cope: 8 (manufactured by Denrika Glass Co., Ltd.) to determine the presence or absence of optical distortion.

(5) Processability: Lenses were processed using an eyeglass lens beading machine and judged visually.

O...Smooth cutting without chipping of edges A surface was obtained.

×・・・Unable to obtain a smooth cutting surface Ta.

(6) Impact resistance: Tests were conducted according to FDA standards for lenses with a center wall thickness of 2B.

O...Excellent.

×...Inferior.

(7) Dyeability: Sumikaronpur-E-FBL (manufactured by Sumitomo Chemical Co., Ltd.) 1.5J' dispersed in 11 water is heated to 80°C, and the lens is immersed in this dye bath for 5 minutes. The dyeability was then visually judged by comparing it with a similarly dyed lens manufactured from a homopolymer of diethylene glycol bisallyl carbonate.

○...Stainability is the same or better There is.

×: Poor staining properties.

Example 1 (Production of urethane diacrylate) 188 parts of xylylene diisocyanate and 0.2 parts of hydroquinone monomethyl ether were placed in a three-necked flask.
A mixture of 310 parts of 2-hydroxypropyl acrylate and 0.5 part of dibutyltin dilaurate was added dropwise to the mixture over 3 hours while stirring at 60°C. After dropping, add 7 more
The reaction was continued at 0°C for 3 hours to obtain urethane diacrylate.

(Production of plastic lens material) To 60 parts of the above urethane diacrylate, 20 parts of dimethallyl orne phthalate, 20 parts of trimethylolproban trithioglycolate, 0.5 part of benzophenone, and 0.1 part of triphenylphosphine were added. , and mixed and dissolved by stirring at 60°C.

This monomer mixture is injected into a mold consisting of glass for lens molding for finished products with a diameter of 70 mm and an internal capacity of 201 mm, and for semi-finished products with an internal capacity of 801 mm, and a gasket made of polyethylene-vinyl acetate copolymer. Chemical lamp (ultra high output lamp for photopolymerization manufactured by Kishita Denki Co., Ltd. FLR120E
H-BA-371AC) for 30 minutes to cure.

After demolding from the glass bottle, the lens was held at 110° C. for 1 hour to remove internal distortion of the lens.

At the same time, flat plates with a thickness of 2 mm were obtained using a mold made of flat glass, and the physical properties of these cured products were evaluated. The results are shown in Table 1.

Examples 2 to 4, Comparative Examples 1 to 4 Lenses were manufactured in the same manner as in Example 1 using the monomers shown in Table 1. The results are also listed in Table 1.

However, the abbreviations of the monomers in Table 1 are as follows.

UDMI: Urethane dimethacrylate obtained by reacting xylylene diisocyanate and 2-hydroxyglobyl methacrylate UDM2: Urethane dimethacrylate obtained by reacting isophorone diisocyanate and 2-hydroxyglobyl methacrylate DMOP Nidimethalyl orthophthalate DATP Nidialyl terephthalate TMTG: ) Limethylolpropane trithioglycolate PETG: Pentaerythritol tetrathioglycolate DGB: Diethylene glycol bisallyl canibonate EM 1: Epoxy dimethacrylate consisting of bisphenol A type jepoxy and methacrylic acid B Z M: Penzyl methacrylate [Effects of the Invention] The present invention can produce a high refractive index plastic lens material with excellent translucency, impact resistance, and dyeability with good productivity, and has excellent industrial effects.

Claims (1)

[Claims] 1) Urethane poly(meth)acrylate (A) 30 having two or more (meth)acryloyloxy groups in one molecule
~89% by weight, 1 to 50% by weight of compound (B) having two or more metaallyl groups in one molecule, and polythiol compound (C) having two or more mercapto groups in one molecule 10
1. A method for producing a plastic lens material, comprising polymerizing and curing a monomer mixture consisting of ~50% by weight. 2) Urethane poly(meth)acrylate (A) having two or more (meth)acryloyloxy groups in one molecule is 2
- The method for producing a plastic lens material according to claim 1, wherein the material is an addition reaction product of hydroxypropyl methacrylate and xylylene diisocyanate.