JPS636086B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a resin for plastic lenses.

[Prior Art] Plastic lenses have the advantage of being easier to manufacture than glass lenses, and are also lightweight and have good impact resistance, making them highly safe when used in eyeglass lenses. Conventional plastic lens resins include:
Acrylic resin, polycarbonate resin, allyl diglycol carbonate resin, polystyrene resin, etc. are used. Among these, diethylene glycol bisallyl carbonate, which is a thermosetting resin, is widely used as a plastic lens for eyeglasses for vision correction. This resin has various features such as excellent impact resistance, lens power that does not change significantly with changes in temperature, and good machinability and workability.

However, diethylene glycol bisallyl carnate has a refractive index of 1.50, and when a lens is made from this resin, it has the disadvantage that the lens is thicker than a glass lens. This is particularly noticeable when the lens power increases.

In particular, in recent years, there has been a demand for plastic lenses to be smaller and thinner, and there has been a need for resins for plastic lenses that have a high refractive index that makes this possible.

As a known example close to the present invention, JP-A-56-
There are Publication No. 149012 and Japanese Unexamined Patent Publication No. 149013,
Further, as prior art, there are JP-A-58-89606 and JP-A-58-162615. These techniques are certainly effective in improving the refractive index. However, these known examples and prior examples all use epoxy resins made of monoepoxides that have one oxysilane ring in the molecule, so their toughness and processability are unsatisfactory, and their heat resistance and
There were also requests for improvement in stainability.

As another known example, a technique has been proposed in which halogenated phthalic anhydride is used as a means for imparting flame retardancy to epoxy resins. (Unexamined Japanese Patent Publication No. 49-22499
Publication No.). However, this technology also had unsatisfactory toughness and workability, making it difficult to apply it to lenses.

[Problems to be Solved by the Invention] In order to improve the problems of the prior art described above, the present inventors used an epoxy compound having a plurality of oxirane rings to form a three-dimensional crosslinked structure with the epoxy group alone. The purpose of the present invention is to provide a method for producing a resin for lenses that has a high refractive index and improves toughness, processability, flexural modulus, dyeability, etc. by copolymerizing a vinyl monomer. .

[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.

``A method for producing a resin for plastic cleaning by polymerizing at least the following components A, B, and C, wherein the acid anhydride group in component B is 0.5 to 1.5 per 1 epoxy group in component A. 1. A method for producing a resin for plastic lenses, characterized by carrying out a polymerization reaction in a range in which the amount of plastic lenses is reduced.

Component A: at least one selected from glycidyl ethers of phenols, glycidyl ethers of alcohols, glycidyl esters of carboxylic acids, and alicyclic epoxides, and
An epoxy compound having two or more oxirane rings.

Component B: at least one acid anhydride selected from tetrabromo phthalic anhydride, tetrachlorophthalic anhydride, and chlorendic anhydride.

Component C: at least one vinyl monomer selected from the group consisting of acrylic acid alkyl ester, methacrylic acid alkyl ester, styrene, styrene derivatives, diallyl phthalate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and diethylene glycol bisallyl carbonate. Quantity. The resin for plastic lenses obtained by the present invention has a high refractive index and also has various properties required for eyeglass lenses, such as mechanical properties such as impact resistance and bending elasticity, as well as excellent processability and dyeability. It is.

Component A used in the present invention is a compound selected from glycidyl ethers of phenols, glycidyl ethers of alcohols, glycidyl ethers of carboxylic acids, and alicyclic epoxides.

Specific examples of glycidyl ethers of phenols include bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A.
-bis(hydroxyethyl ether), bisphenol F, resorcinol phenol novolak, cresol novolak and the like.

Specific examples of glycidyl ethers of alcohols include butanediol, polyethylene glycol, polypropylene glycol, dibromoneopentyl glycol, and the like.

Examples of glycidyl esters of carboxylic acids include phthalic acid, isophthalic acid, and tetrahydrophthalic acid.

Examples of alicyclic epoxides include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy )
Cyclohexane-meta-dioxane, bis(3.
Examples include 4-epoxycyclohexyl) adipate.

Component B of the present invention is an acid anhydride containing a halogen, and a compound selected from tetrabromo phthalic anhydride, tetrachlorophthalic anhydride, and chlorendic anhydride can be used.

For the purpose of further promoting the curing reaction of the resin, curing accelerating catalysts such as various imidazoles, tertiary amines, and metal salts can be used in the resin of the present invention.

Regarding the usage ratio of component A and component B, the ratio of component B to one epoxy group in component A is usually 0.5 to 1.5, preferably about 0.6 to 1.2. used in

When the amount of component B used is outside the above range, it is difficult to obtain the desired resin, and there is a problem in particular that impact resistance and bending elasticity are reduced.

Furthermore, as the vinyl monomer of component C, alkyl esters of acrylic acid such as methyl, ethyl, butyl, octyl, and lauryl esters of acrylic acid, methyl, ethyl, butyl of methacrylate,
A compound selected from alkyl esters of methacrylic acid such as octyl and lauryl esters, styrene and its derivatives, diallyl phthalate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and diethylene glycol bisallyl carbonate is used.

Among these, methyl acrylate and methyl methacrylate are particularly preferred.

The amount of the vinyl monomer added may be any amount as long as it can achieve the purpose and effect depending on the degree of desired characteristics of the above-mentioned eyeglass lens, but preferably, the amount of the vinyl monomer added can be any amount that can achieve the purpose and effect. Total 100
It is not more than 70 parts by weight.

The present invention generally describes the method for manufacturing plastic lenses using the resin for plastic lenses of the invention as follows.

Manufacturing methods are broadly divided into cast polymerization and injection molding.

The feature of the cast polymerization method is that raw monomers are directly polymerized and cured, and at the same time, they are molded into a lens shape. Therefore, the lenses have the characteristics of little molding distortion and excellent optical uniformity, and it is said that most commercially available prescription lenses made of plastic are made using this method.

On the other hand, injection molding is a method in which pre-polymerized resin is injected into the shape of a lens, and methacrylic resin and polycarbonate resin for sunglasses and fashion glasses are manufactured using this method. In injection molding, it is necessary to ensure that the lens molded product has little optical molding distortion, and mold design and molding condition settings are important issues.

For example, to specifically explain the case of the cast polymerization method, the reaction is preliminarily advanced to some extent (prepolymerization) using components A to B of the present invention, and dissolved gas such as air is removed under vacuum. This is a method in which the material is degassed, then poured into a mold, heated, and polymerized.

The heating temperature is initially relatively low (e.g. 40~50℃).
℃), and as the reaction progresses, the temperature is increased.
It is preferable to raise the temperature to about 110° C. and carry out slow addition polymerization in order to reduce distortion of the lens.

Furthermore, after adding a polymerization initiator, polymerization may be carried out as described above. Various known polymerization initiators can be used, but should be selected depending on the desired reaction temperature. For example, 1,1-azobiscyclohexane carbonate, diisopropyl peroxycarbonate, 1,1'-azobiscyclohexane nitrate, di-tert-butyl peroxide and the like are suitable.

The plastic lens containing the resin of the present invention as a resin component has the following characteristics compared to commercially available plastic lenses.

1. A strong plastic cleanser can be obtained.

2 Excellent impact resistance.

3. A colorless and transparent resin is obtained.

4. Shrinkage rate during molding polymerization is relatively small.

5 High refractive index.

6 Excellent bending elasticity.

Plastic lenses containing the resin of the present invention as a resin component can be modified using known physical or chemical methods to achieve surface modifications such as antireflection, high hardness, abrasion resistance, improved chemical resistance, and antifogging properties. It is possible to apply the method.

[Examples] The present invention will be explained in more detail with reference to Examples below.

The wavelength of the refractive index used in the example is 5892.9
This is the value of Å on the D line.

In the examples, the bending elastic modulus was in accordance with JIS K7203.
However, the shape of the test piece shall be 30mm x 10mm x 3mm.
The distance between the fulcrums was 22 mm.

For dyeing properties, molded lenses are immersed in a 0.8% aqueous solution of Nikon Light staining agent "Brown" (trade name)92.
The sample was immersed at ℃ for 5 minutes, and then the total light transmittance was measured using a color computer SM-3 manufactured by Suga Test Instruments. The better the stainability, the lower the value.

Moreover, the epoxy equivalent used in the examples is the number of grams of a compound containing 1 mole of epoxy groups.

Example 1 The following (a) to (c) were injected into a glass lens mold using a silicone rubber gasket.

Part by weight (a) 3,4-epoxycyclohexylmethyl-
3,4-Epoxycyclohexanecarboxylate (epoxy equivalent: 131-143) 30 (b) Tetrabromo phthalic anhydride (molecular weight 463.5)
70 (c) Tin octylate 3 (d) Diaryl phthalate (vinyl polymer) 40 (e) Di-tert-butyl peroxide 0.5 In the above, for each epoxy group in component (a), (b) The component has 0.7 acid anhydride groups, and tetrabromo phthalic anhydride is a white powder with a bromine content of about 67%. This powder dissolves in 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate with slight heating.

The injected mixture was heated in a hot air oven set at 80°C for 2 hours, then at 100°C for 10 hours, and then at 120°C.
Heating was continued for 10 hours to carry out the curing reaction.

The resulting resin molded product was hard, transparent, and extremely tough. Flexural modulus is 410Kg/mm ² ,
The total light transmittance of the dyed material is 70%, and the refractive index is
It was high at 1.59.

Example 2 The following compositions (a) to (e) were poured into a glass lens mold using a silicone rubber gasket.

Part by weight (a) “Epicote 828” (bisphenol A type epoxy resin manufactured by Ciel Chemical Co., Ltd.) Epoxy equivalent: 184-194 30 (b) Tetrachlorophthalic anhydride 30 (c) 1,8-diazabicyclo ( 5.4.0) Undecene-7 octylic acid 40 (d)) Diallyl phthalate 30 (e) Di-tert-butyl peroxide 0.5 In the above, for each epoxy group in component (a), (b) The number of acid anhydride groups in component ) is 0.7, and tetrachlorophthalic anhydride is an odorless white powder with a chlorine content of about 50%. This powder is dissolved in a mixture of diallyl phthalate and "Epicote 828". Then, a curing accelerating catalyst and a polymerization initiator were added to this dissolved solution to prepare a uniform solution. Then, the solution injected into the lens mold was placed in a hot air oven set at 80°C and heated for 2 hours, then continued to be heated at 100°C for 10 hours and then at 120°C for 10 hours to cause a curing reaction.

The resulting resin molded product was hard, transparent, and extremely tough. Flexural modulus is 381Kg/mm ² ,
The total light transmittance of the dyed material is 73%, and the refractive index n ²⁰
was as high as 1.59.

Example 3 After heating 45 g of chlorendic anhydride and 30 g of diethylene glycol bisallyl carbonate to about 40°C and dissolving them, "Epicote 828" (bisphenol A type epoxy resin manufactured by Ciel Chemical Co., Ltd., epoxy equivalent: 184 to 194) was added. ), 1 g of tin octylate, 0.3 g of di-tert-butyl peroxide as a polymerization initiator, and 20 g of diallyl phthalate were added and mixed uniformly.

In the above, the number of acid anhydride groups in component (b) was 0.9 for each epoxy group in component (a).

Pour this mixture into a glass lens mold and heat it at 80℃2.
Heating was continued at 100°C for 10 hours and then at 120°C for 10 hours to cause a curing reaction.

The obtained resin molded product was hard and transparent, had a bending modulus of 370 Kg/mm ² and had excellent elasticity, and the dyed product had a total light transmittance of 68% and had excellent dyeability.
Furthermore, the refractive index was high at 1.57.

Example 4 The following (a) to (e) were injected into a glass lens mold using a silicone rubber gasket.

Part by weight (a) 1,4-butane diglycidyl ether (epoxy equivalent: 101) 20 (b) Tetrabromo phthalic anhydride (molecular weight 463.5)
60 (c) Methyl acrylate 20 (d) Tin octylate 1 (e) Di-tert-butyl peroxide 3 In the above, for each epoxy group in component (a), the acid anhydride in component (b) The number of physical bases is 0.7,
Dissolves in 1,4-butane diglycidyl ether and methyl acrylate with slight heating.

The injected mixture was heated in a hot air oven set at 80°C for 2 hours, then at 100°C for 10 hours, and then at 120°C.
Heating was continued for 10 hours to carry out a curing reaction.

The resulting resin molded product was hard, transparent, and extremely tough. Flexural modulus is 415Kg/mm ² ,
The total light transmittance of the dyed material is 65%, and the refractive index is
It was high at 1.56.

Example 5 The following (a) to (e) were placed in the same lens type as in Example 4.
Injected.

Part by weight (a) Phthalic acid diglycidyl ester (epoxy equivalent: 139) 20 (b) Tetrabromo phthalic anhydride (molecular weight 463.5)
60 (c) Styrene 30 (d) Tin octylate 2 (e) Di-tert-butyl peroxide 0.5 In the above, for each epoxy group in component (a), the acid anhydride group in component (b) is 0.7, and tetrabromo phthalic anhydride dissolves in phthalic acid diglycidyl ether and diallyl phthalate with slight heating.

The injected mixture was subjected to a curing reaction under the same conditions as in Example 4.

The resulting resin molded product was hard, transparent, and extremely tough. Flexural modulus is 390Kg/mm ² ,
The total light transmittance of the dyed material is 75%, and the refractive index is
It was high at 1.60.

Comparative Example 1 50 parts by weight of bisphenol A-monoglycidyl ether methacrylate 50 parts by weight of tetrapromophthalic anhydride 3 parts by weight of tin octylate were mixed, heated and dissolved at 80°C, and poured into the same glass lens mold as in Example 1. did. From 80℃ in a hot stove
The temperature was raised to 150°C over 20 hours to complete polymerization.

The resulting resin molded product was hard and transparent, with a high refractive index of 1.57, and a flexural modulus of 250 kg/mm ²
The total light transmittance of the dyed material was 85%, making it difficult to dye.

In addition, heat resistance was poor as it softened when heated to 100°C.

[Effects of the Invention] By the method of the present invention, it is possible to provide a resin for eyeglass plastic lenses that has good impact resistance, flexural modulus, and dyeability, and has a high refractive index.

Claims (1)

[Scope of Claims] 1. A method for producing a resin for plastic lenses in which at least the following components A, B, and C are polymerized, wherein one epoxy group in component A is treated with acid anhydride in component B. A method for producing a resin for plastic lenses, characterized by carrying out a polymerization reaction in a range of 0.5 to 1.5 physical groups. Component A: at least one selected from glycidyl ethers of phenols, glycidyl ethers of alcohols, glycidyl esters of carboxylic acids, and alicyclic epoxides, and
An epoxy compound having two or more oxirane rings. Component B: at least one acid anhydride selected from tetrabromo phthalic anhydride, tetrachlorophthalic anhydride, and chlorendic anhydride. Component C: at least one vinyl monomer selected from the group consisting of acrylic acid alkyl ester, methacrylic acid alkyl ester, styrene, styrene derivatives, diallyl phthalate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and diethylene glycol bisallyl carbonate. Quantity. 2. The method for producing a resin for plastic lenses according to claim 1, characterized in that the amount of component C added is 70 parts by weight or less based on 100 parts by weight in total of components A and B.