JPS63199210A - Manufacturing method of plastic lens material - Google Patents

Abstract

PURPOSE:To obtain the titled material having excellent transparency, impact resistance and dyeability and high refractive index, by polymerizing a monomer mixture of specific composition comprising urethane poly(meth)acrylate as a main component and curing. CONSTITUTION:First (A) 30-80wt.% urethane poly(meth)acrylate containing plural (meth)acryloyloxy groups is blended with (B) 1-50wt.% monomer (e.g. phenyl acrylate, etc.) shown by the formula (R is H or methyl; m and n are 0 or 1) and (C) 10-50wt.% polythiol compound (e.g. ethylene glycol dithioglycolate, etc.) containing plural mercapto groups. Then the mixture, for example, is polymerized and cured by irradiation with ultraviolet rays is the presence of a photopolymerization initiator to give the aimed material. A reaction product of xylylene diisocyanate and 2-hydroxypropyl methacrylate is preferable as the component A.

Description

[Detailed description of the invention]

More specifically, three-dimensionally cross-linked impact resistance,
4 [Prior technology] Plastic lenses are widely used in optical products due to their ease of molding and light weight. It is becoming. 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 resin or plastic eyeglass lenses made of polydiethylene glycol bisallyl carbonate have become mainstream. However, although this plastic eyeglass lens can reduce the weight to half that of inorganic glass, it has a refractive index of T4
Since the refractive index is low at 9 to 1.50, the center thickness, edge thickness, and curvature tend to be large compared to 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, it is necessary to use the E-type polymerization method, which requires polymerization time of 10 hours or more to obtain lenses, which is a less productive method. High-quality manufacturing methods are also highly desired. Epoxy (meta) as a solution to these problems
A method for obtaining lenses by press-fitting acrylate, a compound having an allyl group, and a compound having a mercapto group into a lens mold and polymerizing and curing them with ultraviolet light (%
No. 6, etc.) have been proposed. [Problem to be solved by the invention] However, although the above method can produce a plastic lens with a high refractive index in a short time, it is possible to produce a plastic lens with a high refractive index in a short time. Since it is used at a mixing ratio of 18 to 1.5, it has a strong sulfur odor characteristic of compounds having mercapto groups, which poses problems in workability at production sites and in 3J environmental integrity. Furthermore, the resulting plastic has the disadvantage of poor impact resistance. [Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted intensive studies on high refractive index plastic resins with excellent translucency, impact resistance, and dyeability, and have developed the present invention. It's arrived. That is, the present invention provides urethane poly(meth)p? having two or more [meth]acrylo6kyl groups in one molecule. Acrylate (~30 ~ weight ratio, general formula [l] (wherein R is a hydrogen atom or a methyl group ks m and n
indicates 0 or 1) Monomer (B) 1 to 50% by weight and a polythiol compound having two or more mercapto groups in one molecule (monomer temperature metal material consisting of 10 to 50% by weight of carbon) (meth)acrylate (A) is a main component of the plastic lens material of the present invention, and it imparts excellent durability to the molded lens. It provides impact properties and dyeing properties, and can be produced by 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 include aliphatic, aromatic or alicyclic incyanates such as tetramethylene diincyanate, hexamethylene diincyanate, trimethylhexamethylene diincyanate, dimer acid diincyanate, Cyclohexane diincyanate, Inholo 7 diincyanate,
Examples include tolylene diincyanate, xylylene diisocyanate, diphenyl meta-7 diincyanate, m-7 22 diincyanate, naphthalene diincyanate, etc., or combinations of these incyanates with active hydrogen such as amine groups, hydroxyl groups, carboxyl groups, and water. Two or more incyanate groups in the molecule obtained by reaction with a compound having at least two atoms! or trimers to pentamers of the above-mentioned diincyanate compounds can also be used. Contains a hydroxyl group to be reacted with the incyanate compound

[Meta]acrylates include 2-hydroxyethyl (methanoacrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and monoepoxy compounds such as butylglycidyl Ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and [
Examples include addition reaction products with metacoacrylic 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 human mixyl group-containing (meth)acrylate and a catalyst such as dibutyltin dilaurate in the presence of the incyanate compound at 50°C to 90°C. It can be produced by dropping it under conditions of ℃. Among the urethane poly(meth)acrylates thus obtained, in order to obtain a plastic lens material with a high refractive index, cyclohexane diinocyanate, inphoron diinocyanate, xylylene diisocyanate, di722methane diinocyanate, m-phinocyanate, etc. Diincyanate, naphthalene diincyanate, biphenyl diincyanate 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-hydroxyglobyl methacrylate is preferred. These urethane poly(meth)acrylates (N can be used alone or as a mixture of two or more types. is the main component of urethane poly(meth)acrylate) (which serves as a reactive diluent for AJ. Specific examples of the monomer include phenyl acrylate ζ benzyl acrylate, phenoxyethyl acrylate,
Examples include phenyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate. These monomers can be used alone or in combination of two or more. The mercapto group in one molecule, which is the fifth component of the present invention, is
A polythiol compound having two or more (03 is a compound that copolymerizes with component (6) and (copolymer) and plays a role of increasing the degree of polymerization by 7. Specific examples of polythiol compounds <O) include ethylene glycol dithioglycolate. , trimethylolpropane trithioglycolate, trimethylolpropane trithiolopionate, pentaerythritol trithiosropionate, pentaerythritol tetrathioglycolate, etc. The plastic lens material of the present invention includes the above-mentioned ) Acrylate (from 30 to 50 tons) by weight, general formula [monomer represented by eyes (BJ 1 to 50 tons by weight)
%, and polythiol compound (c)t. It can be produced by irradiating ultraviolet 411 in the presence of a photopolymerization initiator in a tm type monomer mixture consisting of 50 to 50% by weight to polymerize and cure it. The mixing ratio of each component is urethane poly(meth)acrylate (if the gradient is less than 30% by weight, it will not cure sufficiently, and if it exceeds 30% by weight, the viscosity of the monomer mixture will be high.) Workability of pouring polymerization or decrease. Also general ceremony [! If the blending ratio of the monomer represented by " is less than 1% by weight, the dilution effect will not be sufficient, the viscosity of the monomer mixture will increase, and the workability of cast polymerization will decrease; if it exceeds 50% by weight, The impact resistance of the resulting plastic lens material decreases.-If the blending ratio of polythiol compound (07) is less than 10% by weight, it will not cure sufficiently, and if it exceeds 50% by weight, the workability will be affected due to the odor of the polythiol compound. A particularly preferable blending ratio is a weight ratio of component (A) and component (B) of 1:[
102-1, the total amount of component (A) and component (B) and (0
) The ratio of the components is 1:α1 to α5 by weight. Examples of photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzopheno 7, acetophenone, jetoxyacetophenone, 1,1-dimethoxy-1-phenylacetophenone, benzyl, methylphenylglyoxylate, penzyl dimethyl Coutard et al. The amount of photopolymerization initiator to be used is 1:αooos to (105) by weight relative to the monomer mixture. In order to polymerize and cure the monomer mixture by irradiation with ultraviolet rays, ultraviolet rays with a wavelength of 2000 to 6000λ are preferable. ,
Normal atmosphere is sufficient for the irradiation atmosphere. Also, f
As for t and @, well-known chemical run 1, 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 addition, when carrying out the present invention, various ultraviolet curing type upper polymers may be used during polymerization to the extent that the effects of the present invention are not impaired.
, oligomers, other copolymerizable monomers, anti-yellowing agents such as triphenylphosphine, ultraviolet absorbers, bluing dyes, and the like may be added. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, "parts" indicate "parts by weight." Moreover, physical property evaluation in this example was measured according to the method described below. (υ refraction Wh: Measured using an Atsube refractometer. (2) Pencil hardness: Measured according to J-8-5400. (3) Visible light transmittance: ASTM D1005-6
Measured according to 1. (4) Optical distortion: blur inspection machine (portable Po1a
Roid 8qope (manufactured by Nippon Rika Glass Co., Ltd.) was used to determine the presence or absence of optical distortion. (5) Processability: All lenses were processed using a beading machine for eyeglass lenses and judged visually. O: Edges were not chipped and a smooth cut surface was obtained. ×: A smooth cut surface was not obtained. (6) Impact resistance: Lens '1 FDA (manufactured by Sumitomo Chemical Co., Ltd.) with center wall thickness of 2 mm.Heat the entire liquid dispersed in 1.5 t'ilA water to 80 ℃, and add it to the dye bath. The lenses were immersed for 5 minutes, and the dyeability was visually judged by comparing them with lenses dyed in the same way from a diethylene/I7col bisallyl carbonate homopolymer. ○: Dyeing property is the same or superior. X: Poor staining properties. Example 1

[Production of urethane diacrylate]

Put 188 parts of xylylene diisocyanate and 02 parts of hydroquinone monomethyl ether into a three-necked flask,
While stirring at 0° C., a mixture of 310 parts of 2-hydroxypropylacrylate and 05 parts of dibutyltin dilaurate was added dropwise over 3 hours. After the completion of dripping, another 70
The reaction was continued for 3 hours at °C to obtain urethane diacrylate. (Production of glass lens material) To 60 parts of the above urethane diacrylate, 20 parts of benzyl methacrylate, 20 parts of trimethylolglopane trithioglycolate, 5 parts of penzophenono α, and 1 part of triphenylphosphine a were added, and the mixture was stirred at 60°C. Mix and dissolve. This monomer mixture was placed in a mold consisting of glass for finished products with a straight pole of 70 m and an internal capacity of 20 mm, and for semi-finished products with an internal capacity of 80 m, and a gasket made of polyethylene-vinyl acetate copolymer. Chemical lamp (manufactured by Shishita Denki Co., Ltd., ultra-high output lamp IFLR for photopolymerization)
1201! :H・BA-571AC) for 30 minutes to cure. After being removed from the glass mold, the lens was held at 110° C. for 1 hour to remove internal distortion of the lens. At the same time, a 2 m thick flat plate 1r was obtained using a flat glass mold, and the physical properties of these cured products were evaluated. The results are shown in Table 1. Examples 2-4. Comparative Examples 1 to 4 Lenses were manufactured in the same manner as in Example 1 using the monomers shown in Table 1. All results are listed in Table 1. However, the abbreviations of the monomers in Table 1 are as follows. UDML: Urethane dimethacrylate obtained by reacting xylylene diisocyanate with 2-hydroxypropyl methacrylate UDM2: Urethane dimethacrylate obtained by reacting inophorone diyntanate with 2-hydroxyglobyl methacrylate BZM: Penzyl Methacrylate P M = phenyl methacrylate pH! M: Phenoxyethyl methacrylate TMTG:
) IJ Methylolpropane trithioglycolate PKTG: Pentaerythritol tetrathioglycolate DGB = Diethylene glycol bisallyl carbonate 1M1: Eboxy dimethacrylate consisting of bisphenol penta-deaf jepoxy and methacrylic acid [Effects of the invention] The present invention has translucency and gf1 resistance. A high refractive index 1-rus nac lens material with excellent impact resistance and dyeability can be manufactured 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, a unit represented by the general formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R represents a hydrogen atom or a methyl group, and m and n represent 0 or 1.) A plastic lens characterized by polymerizing and curing a monomer mixture consisting of 1 to 50% by weight of a polymer (B) and 10 to 50% by weight of a polythiol compound (C) having two or more mercapto groups in one molecule. Method of manufacturing the material. 2) Urethane poly(meth)acrylate (A) having two or more (meth)acryloyloxy groups in one molecule is 2-
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.