JPS6324201A - Resin lens having high refractive index - Google Patents

Abstract

PURPOSE:To obtain a resin lens having a high refractive index by mixing a specified aromatic compound contg. OH with glycidyl methacrylate, glycidyl acrylate or allylglycidyl ether and a vinyl monomer or diepoxide copolymerizable with the glycidyl compound and by bringing the mixture into reaction and polymn. CONSTITUTION:A resin lens having a high refractive index is obtd. by bringing a mixture (a) of 10-60mol% component A with 40-90mol% component B or a mixture (b) of >=60pts.wt. of the mixture (a) with <=40pts.wt. component C into reaction and polymn. The component A is an aromatic compound contg. OH represented by formula I, II or III (where X is halogen other than F, m is an integer of 0-5 n is an integer of 1-3, each of p and q is an integer of 0-4, r is an integer of 0-7 and s is an integer of 1-4). The component B is glycidyl methacrylate, glycidyl acrylate or allylglycidyl ether, and the component C is is a vinyl monomer or vinyl monomer or diepoxide copolymerizable with the component B.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a high refractive index resin lens.

[Prior art]

Traditionally, inorganic glass lenses have been widely used in optical equipment, but recently lenses made of synthetic resin have become more popular.
Due to its light weight, impact resistance, processability, stability, dyeability, mass productivity, and other advantageous features, it has begun to be widely used together with inorganic glass lenses.

On the other hand, there are various requirements regarding the physical properties of lenses, and among them, there is an extremely high demand for the material to have a high refractive index. This is because it can be manufactured with a small thickness. By using lenses with a high refractive index, lens systems that play an important role in optical instruments such as microscopes, cameras, and telescopes can be made compact and lightweight, and eyeglass lenses can also be made lightweight. Since it is possible to reduce the so-called edge thickness and reduce the so-called edge thickness, there are great practical advantages. As described above, it is of great significance to make lenses with a high refractive index, and therefore there is a strong desire to provide resin lenses made of materials with a high refractive index.

To be more specific, the materials used for resin lenses for eyeglasses, which are currently in widespread use, are diethylene glycol bisallyl carbonate resin and polymethyl methacrylate, both of which have a refractive index of about 1. It is low, below .50.

[Summary of the invention]

The present invention aims to provide a high refractive index resin lens, which is characterized by a mixture (a) consisting of 10 to 60 mol% of the following component A and 40 to 90 mol% of the following component B; It can be obtained by reacting and polymerizing a mixture (b) of 60 parts by weight or more of mixture (a) and 40 parts by weight or less of component C below.

Component A: one or more hydroxyl-containing aromatic compounds represented by any of the following general formulas (I) to (I[[)] (wherein, X is a halogen atom other than fluorine) , m is an integer of θ to 5, n is an integer of 1 to 3, p and q are integers of 0 to 4,
r is an integer of 0 to 7; S is an integer of 1 to 4;) component B 1 selected from nigericidyl methacrylate, glycidyl 7 acrylate and allyl glycidyl ether;
The high refractive index resin lens according to the present invention consists of a vinyl monomer or dieboxide copolymerizable with component C, component B, or two or more kinds of component C, ie, a high refractive index resin lens according to the present invention. B component 4 is an epoxy monomer having a polymerizable group
By reacting and polymerizing a mixture (a) consisting of 0 to 90 mol%, or by reacting and polymerizing a mixture (b) of 60 parts by weight or more of the mixture (a) and 40 parts by weight or less of the C component. can get.

〔effect〕

Since the lens of the present invention is made of a copolymer of component A having an aromatic ring, particularly preferably a halogen-substituted aromatic ring, it has a high refractive index of nf-1.58 or more. Because the component that has an epoxy group that reacts with the compound also has a radically polymerizable double bond, an extremely highly crosslinked structure is formed in the resulting copolymer, and as a result, the resulting lens has excellent solvent resistance and resistance. It has extremely excellent impact resistance, scratch resistance, etc., and is therefore particularly suitable as a lens for spectacles.

The lens of the present invention is made of a copolymer having a crosslinked structure, and since both component A and component A have low viscosity and high fluidity, they are poured into a casting container and poured into the casting container. The reaction and polymerization can be carried out in a mold container, and therefore, it can be manufactured very easily by using cast polymerization.As a result, the lens of the present invention has a high refractive index and This results in extremely low cost.

Conventionally, for example, a compound having a halogen-substituted aromatic ring is reacted with a compound having a reactive double bond, such as acrylic acid or methacrylic acid, to synthesize a compound containing one or more reactive double bonds. However, this has often been isolated and purified to form a lens material, and then used to manufacture resin lenses by cast polymerization. However, according to such a method, the lenses obtained are expensive, and it is often difficult to sufficiently purify the monomer, so there is a strong possibility that the lenses obtained will be colored.

In addition, since the hexamer used as a lens material in this method has a high melting point or high viscosity, casting polymerization itself is difficult and lens manufacturing is not easy.

In contrast, the lens of the present invention is produced by reacting and polymerizing a component having an epoxy group capable of reacting with component A having a hydroxyl group and having a radically reactive double bond together with component A. Therefore, there is no need to synthesize monomers in advance, and each component has low viscosity and high fluidity, so cast polymerization using a cast container can be used. Therefore, a colorless and transparent crosslinked polymer with a high refractive index can be produced very easily and at low cost.

The lens of the present invention is obtained by polymerizing and reacting a mixture of components A and B (a) or a mixture of component C (b).

Since component A contains an aromatic ring, a lens with a high refractive index can be obtained. The aromatic ring here is preferably a halogen-substituted aromatic ring, and component A needs to have at least one hydroxyl group for reacting with the epoxy group of the component.

Specific examples of such A component include iodophenol, bromophenol, tribromophenol, dibromohydroquinone, bisphenol A1, tetrabromobisphenol A, (α-)naphthol, (I,7-)
Mention may be made of dihydroxynaphthalene, dichloronaphthol, tetrachloronaphthol, bromonaphthol, and others.

However, it is not limited to these.

Component B is a component necessary for polymerizing and forming a crosslinked structure by reacting with the hydroxyl group of component A,
It is a component that dominantly determines mechanical strength such as impact resistance and scratch resistance, and solvent resistance of the formed lens. As this component B, at least one selected from glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether is used.

Furthermore, a vinyl monomer or diepoxide copolymerizable with the B component can be used as the C component. By using this component C, it is possible to further improve the various properties required for eyeglass lenses, such as the solvent resistance, scratch resistance, heat resistance, and dyeability of the lens, as well as to reduce the viscosity of the mixture during casting. To give specific examples of component C, which can easily perform cast polymerization by lowering the or esters of polyhydric alcohols and acrylic or methacrylic acids, such as phenyl acrylate, phenyl methacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, (B) styrene, α-methylstyrene, chlorostyrene , aromatic vinyl compounds such as divinylbenzene and diisopropenylbenzene, various allyl compounds such as (C) diallyl phthalate and diethylene glycol bisallyl carbonate, and others.

In addition, dieboxides include (A) diglycidyl ethers such as bisphenol A1, tetrabromobisphenol A, tetrabromobisphenol A bis(hydroxyethyl) ether, and bisphenol F; (B) 2 such as ethylene glycol, butanediol, and neopentyl glycol; (C) diglycidyl esters of dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, etc. The ratio of component A and component B varies depending on the type. However, the A component is in the range of 10 to 60 mol% and the B component is in the range of 40 to 90 mol%, preferably the A component is in the range of 25 to 50% and the B component is in the range of 50 to 75%. When the ratio of both is outside this range, if the A component is in excess, a part of the human component will remain unreacted after the polymerization process, and if the B component is in excess, the resulting lens will be This is not preferable because it may result in a low refractive index.

In addition, component C can be used in an amount within 40% by weight of all components. If this proportion is 40% by weight or more, it is not preferable because the crosslinking density connecting the main chain and the epoxy resin decreases.

The polymerization of the mixture (a) or (b) of the components A to C is carried out using a conventional radical polymerization initiator. This reaction and polymerization are preferably carried out in particular by cast polymerization. Cast polymerization is a well-known technique, and therefore can be carried out as appropriate under conditions according to well-known knowledge. As the radical polymerization initiator, well-known initiators such as diacyl peroxide, dialkyl peroxide, and dialkyl peroxydicarbonate can be used. However, the addition reaction between component A and component B does not always occur easily; for example, when the reaction rate is significantly slower than the radical polymerization of component A and component C,
There is a possibility that the reaction may not be completed. Therefore, in the polymerization of the mixture (a) or (b), it is preferable to use an epoxy curing catalyst in addition to the radical polymerization initiator. Examples of epoxy curing catalysts include amine carboxylates such as ethanolamine acetate, Mention may be made of quaternary ammonium carboxylates such as methylammonium and amines such as triethylamine, pyridine, and metal salts such as stannous chloride and tin octylate.

When mixing and polymerizing the above components, add antistatic agents, colorants, ultraviolet absorbers, heat stabilizers, antioxidants, and other auxiliary agents depending on the expected use of the resulting copolymer lens. Can be added.

As the casting container used for cast polymerization, plate-shaped, lens-shaped, cylindrical, prismatic, conical, spherical, or other molds or molds designed according to the purpose are used. The material may be any suitable material such as inorganic glass, plastic, or metal. It is also possible to treat the above-mentioned mold etc. in advance to improve the release of the mold during mold release.
The reaction and polymerization may be carried out by, for example, heating a mixture of monomers, a polymerization initiator, and a curing catalyst added as necessary in such a container.

However, the lens of the present invention was also developed by Mr. Li, who carried out a certain degree of polymerization in a separate reaction vessel to obtain a prepolymer or syrup, and poured this into a casting vessel to complete the polymerization within the casting vessel. can be manufactured.

After the above-mentioned operations, in order to complete the polymerization that may not have been completed, or to further improve the hardness of the copolymer, or to remove the distortion contained in it by heat treatment or cast polymerization. Needless to say, post-processing such as annealing can be performed.

The lens of the present invention is characterized in that the lens material is a crosslinked copolymer as described above, and therefore, in addition to directly obtaining the lens by casting polymerization, it is possible to obtain a plate material or other copolymer. It can also be manufactured by cutting it out.

Furthermore, by performing surface polishing, antistatic treatment, and other post-treatments as necessary, the mechanical properties of the lens of the present invention can be further improved. Furthermore, in order to increase the surface hardness, it is of course possible to coat the surface with an inorganic material or with an organic coating agent by dipping or the like.

Example 1 2.4.6- 66 parts by weight of tribromophenol and 34 parts by weight of glycidyl methacrylate (the ratio of mol % of both is 45155) were mixed and dissolved, and 110.1 parts by weight of monochloride and lauroyl were mixed and dissolved. Peroxide 0
．． 5 parts by weight was added, this mixture was poured into a glass mold, and the mixture was heated at 60°C for 2 hours and at 65°C for 16 hours for 8 hours.
Reaction and polymerization were carried out under sequential conditions such as 2 hours at 0°C and 2 hours at 100°C to obtain a colorless and transparent lens of the present invention.

The polymer in this lens has excellent solvent resistance, including acetone, methyl ethyl ketone, benzene, ethyl alcohol, and
It was completely insoluble in common solvents such as tetrahydrofuran.

Furthermore, the refractive index of this lens was as high as nW=1.607.

Example 2 20.9 parts by weight of tribromophenol, 34.3 parts by weight of tetrabromobisphenol A and 44.8 parts by weight of glycidyl methacrylate (the ratio of these mole % is 14.3/14.3/71.4). After mixing and dissolving, 0.1 part by weight of stannous chloride and 0.6 part by weight of lauroyl peroxide were added to this mixed solution, and this mixed solution was poured into a glass mold under the same conditions as in Example 1. The reaction and polymerization were carried out to obtain a colorless and transparent lens of the present invention.

The copolymer of this lens had a highly crosslinked three-dimensional structure and was completely insoluble in organic catalysts such as acetone, methyl ethyl ketone, tetrahydrofuran, and benzene.

Further, the refractive index of this lens was as high as n-1.59.

Example 3 32.1 parts by weight of α-naphthol and 37.9 parts by weight of glycidyl methacrylate (ratio of mol% of both was 4515 parts by weight)
5) and 30 parts by weight of styrene were mixed and dissolved, 0.05 parts by weight of stannous chloride and 0.5 parts by weight of lauroyl peroxide were added thereto, and this mixed solution was poured into a glass mold. Reaction and polymerization were carried out under the same conditions as in Example 1 to obtain a colorless and transparent lens of the present invention.

This lens was immersed in various solvents, but no change was observed in common solvents such as benzene, toluene, tetrahydrofuran, acetone, etc., indicating that a three-dimensional crosslinked structure was firmly formed.

Further, the refractive index of this lens was as high as n W = 1.594.

Example 4 2.4.6-) 33.4 parts by weight of ripromophenol and 26.6 parts by weight of allyl glycidyl ether (the ratio of mol% of both is 30/70) and 30 parts by weight of diallyl phthalate were prepared. Mix and dissolve, and add 0.1 part by weight of stannous chloride and 1 part by weight of isopropenyl peroxydicarbonate.
．． 5 parts by weight were added. This mixture was poured into a glass mold, heated to 45°C for 6 hours, and then heated to 50°C for 16 hours.
Reaction and polymerization were performed under sequentially changing conditions: 5°C for 3 hours, 80°C for 2 hours, and 100°C for 1 hour, to obtain a colorless and transparent lens of the present invention.

The copolymer of this lens is highly cross-linked,
It was completely insoluble in common solvents such as acetone, methyl ethyl ketone, benzene, and ethyl alcohol, and showed excellent solvent resistance.

Further, the refractive index of this lens was as high as n''7-1.592.

Claims (1)

[Claims] 1) 10 to 60 mol% of the following component A and 40 to 9 mol% of the following component B
A mixture (a) consisting of 0 mol%, or the mixture (
A high refractive index resin lens, characterized in that it is obtained by reacting and polymerizing a mixture (b) of 60 parts by weight or more and 40 parts by weight or less of component C below. Component A: One or more types of hydrated acid group aromatic compounds represented by any of the following general formulas (I) to (III) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X is a halogen atom other than fluorine, m is an integer from 0 to 5, and n is 1 An integer of ~3, p and q are integers of 0 to 4,
r represents an integer of 0 to 7, and s represents an integer of 1 to 4. ) Component B: 1 selected from glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ether
Species or two or more types C component: Vinyl monomer or diepoxide copolymerizable with B component