JPS61247715A - Resin for plastic lens - Google Patents

Abstract

PURPOSE:The titled high refraction index lens excellent in impact resistance, surface hardness, etc., obtained by polymerizing a specified phosphorus- containing compound with a radical-polymerizable vinyl monomer. CONSTITUTION:20-80wt% phosphorus-containing compound of the formula (wherein Ph is phenyl and X is H or methyl) obtained by reacting phenylphosphonic dichloride with allyl alcohol or methallyl alcohol in the presence of a base such as triethylamine is copolymerized with 80-20wt% radical- polymerizable vinyl monomer having a refractive index nD<20>of a homopolymer >=1.55 (e.g., phenyl acrylate) at 40-120 deg.C for 10-30hr in the presence of a radical polymerization initiator (e.g., benzoyl peroxide).

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to a resin for plastic lenses having a high refractive index. More specifically, it relates to a resin for plastic lenses having a high refractive index and excellent impact resistance, surface hardness, etc., which is made by copolymerizing a phosphorus-containing compound represented by the general formula (1) with a vinyl monomer as one component. It is something.

(B) Prior Art In recent years, plastic lenses have become popular in eyeglass lenses, camera lenses, optical elements, etc. because they are lighter, less likely to break, and can be dyed compared to inorganic glass lenses.

Diethylene glycol bisallyl carbonate (CR-39) has been mainly used as a conventional resin for plastic lenses, particularly as a resin for eyeglass lenses.

In addition, polycarbonate (
no 1.58-1.59) and polystyrene (no
1.58 to 1.60), etc. are known.

Furthermore, JP-A-51-79353 and JP-A-53-
Japanese Patent No. 7787 proposes a resin for plastic lenses in which diethylene glycol bisallyl carbonate and a monomer having a higher refractive index are copolymerized.

(c) Problems to be solved by the invention A resin obtained by polymerizing diethylene glycol bisallyl carbonate in the presence of a radical polymerization initiator and three-dimensionally crosslinking it is
It is a resin for plastic lenses that is lightweight, has excellent impact resistance, and has a high surface hardness and good workability.

However, the refractive index n of the above resin is 1.50, which is lower than the refractive index n of 1.52 to 1.53 of inorganic glass used for eyeglasses, such as crown glass, and has the same optical properties as inorganic glass. In order to obtain these characteristics, it is necessary to increase the center thickness, edge thickness, and curvature of the lens, and it is unavoidable that the lens as a whole becomes thicker.

In addition, high refractive index resins such as polycarbonate (no. 1.58 to 1.59) and polystyrene (no. 1.58 to 1.60) are thermoplastic and are polymers with a two-dimensional structure. Processability after lens molding, especially rounding, etc., is difficult, and dimensional stability is also poor.

JP-A-51-79353 and JP-A-53-778
The resin for plastic lenses prepared by copolymerizing diethylene glycol bisallyl carbonate and a monomer having a higher refractive index as disclosed in Publication No. 7 has a high refractive index (for example, no.
1.55 or higher), it is not only difficult to obtain a resin for plastic lenses, but also has other properties such as impact resistance,
It has many problems in practical use because it has problems such as surface hardness.

(d) Means for Solving the Problems The present inventors have made extensive efforts to develop a three-dimensionally crosslinked resin for plastic lenses that has characteristics such as high refractive index, high impact resistance, and high surface hardness. , has completed the present invention.

That is, the present invention provides O represented by the general formula (I)
X]11 Ph-P-(0-CH2-C=CH2)2 (1)(
(wherein, ph is a phenyl group, and X is a hydrogen atom or a methyl group) A plastic made by copolymerizing a phosphorus-containing compound and a radically polymerizable vinyl monomer whose homopolymer has a refractive index n20° of 1°55 or more. This invention relates to resin for lenses.

As the phosphorus-containing compound represented by the general formula CI) of the present invention,
Examples include diallylphenylphosphonate and diallylphenylphosphonate.

These compounds can be synthesized by reacting phenylphosphonic acid dichloride with allyl alcohol or methallyl alcohol in the presence of a base such as triethylamine.

Refractive index n 2 G of the homopolymer of the present invention. Examples of radically polymerizable vinyl monomers having a value of 1.55 or more include phenyl acrylate, phenyl methacrylate, nuclear chlorine-substituted phenyl acrylate, nuclear chlorine-substituted phenyl methacrylate, nuclear bromine-substituted phenyl acrylate, and nuclear bromine-substituted phenyl. methacrylate, benzyl acrylate,
Acrylates such as benzyl methacrylate, nuclear chlorine-substituted benzyl acrylate, nuclear chlorine-substituted benzyl methacrylate, nuclear bromine-substituted benzyl acrylate, nuclear bromine-substituted benzyl methacrylate, α-naphthyl acrylate, α-naphthyl methacrylate, β-naphthyl acrylate and β-naphthyl methacrylate; Examples include methacrylates.

Furthermore, styrenes such as styrene and nuclear chlorine-substituted styrene,
(2) Vinylnaphthalenes such as -vinylnaphthalene and 2-vinylnaphthalene, and cinnamate esters such as benzyl cinnamate and vinyl cinnamate ester can also be mentioned.

Moreover, the refractive index n20 of these homopolymers. It is also possible to use two or more kinds of radically polymerizable vinyl monomers having a value of 1.55 or more.

The ratio of the phosphorus-containing compound represented by the general formula (1) of the present invention and the radically polymerizable vinyl monomer whose refractive index n20Il of the homopolymer is 1.55 or more is generally 20 to 20%. 80% by weight, vinyl monomer 80-20% by weight
It is preferable to use it within the range of .

When the amount of the phosphorus-containing compound is less than 20% by weight, the surface hardness of the resin obtained by copolymerization is significantly reduced, and processability and the like are also deteriorated.

Moreover, if the phosphorus-containing compound exceeds 80% by weight, the impact resistance and the surface hardness due to changes over time may deteriorate, resulting in poor practicality.

Refractive index n20 of the phosphorus-containing compound and homopolymer represented by general formula (1). Examples of radical polymerization initiators used in the copolymerization of radically polymerizable vinyl monomers having 1.55 or more include diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, benzoyl peroxide, t -butyl peroxyisobutyrate, di-t-butyl peroxide, and the like.

The amount of these radical polymerization initiators used is 0.05% based on the total amount of the phosphorus-containing compound and the radically polymerizable vinyl monomer.
~5% by weight, especially 0. A range of 5 to 4% by weight is preferred.

Additionally, additives such as ultraviolet absorbers, antioxidants, color inhibitors, and fluorescent whitening agents can be added as necessary during copolymerization of the phosphorus-containing compound and the radically polymerizable vinyl monomer.

The copolymerization reaction is generally carried out at a temperature of 40~
It is carried out at 120°C for 10 to 30 hours.

Refractive index nzo of the phosphorus-containing compound and homopolymer represented by the general formula CI). As a method for copolymerizing a radically polymerizable vinyl monomer having a value of 1.55 or more, a cast polymerization method is usually employed.

For example, two well-polished glass molds are assembled via a gasket made of ethylene-vinyl acetate copolymer, and a phosphorus-containing compound and a vinyl monomer are copolymerized in that space.

(E) Effects of the Invention In the plastic cleanser resin of the present invention, since the phosphorus-containing compound represented by the general formula (I) has a high refractive index, it is easy to adjust the refractive index to n20o 1.55 or more. .

In addition to having properties such as high impact resistance and high surface hardness, it is also excellent in terms of flame retardancy and dyeability.

(f) Examples Next, the present invention will be described in detail by giving Examples, but the present invention is not limited to these.

The various physical properties of the obtained resin were measured as follows.

(1) Refractive index: Measured at 23°C using an Atsube refractometer. Monobromonaphthalene was used as the contact liquid.

(2) Impact resistance: 15.9 m diameter on a 31 m thick flat plate.
A steel ball weighing 16.3 g was dropped from a height of 100 cm 5 times, and those that did not break any of the 5 times were evaluated as good.

(3) Pencil hardness: Based on the method of JISK5400.

Example 1 50 parts by weight of diallylphenylphosphonate and 50 parts by weight of benzyl methacrylate, which were well mixed in advance, were placed in a casting mold consisting of two glass plates and a silicone rubber gasket.
Parts by weight and diisopropyl peroxycarbonate2.
A mixture consisting of 4 parts by weight was injected.

Next, the mold was placed in a heating furnace and heated at 60° C. for 3 hours, at 80° C. for 2 hours, at 90° C. for 2 hours, and at 100° C. for 2 hours to effect copolymerization. After cooling, the resin was taken out from the mold.

The resin produced is colorless and transparent with a refractive index of no 1°566.
It was good. Other results are shown in Table 1.

Example 2 A colorless and transparent resin was obtained by carrying out copolymerization in the same manner as in Example 1, except that vinyl cinnamate ester was used instead of benzyl methacrylate. The results are shown in Table 1.

Comparative Examples 1-2 Copolymerization was carried out in the same manner as in Example 1, except that the ratio of diallylphenyl phosphonate to benzyl methacrylate and the amount of radical initiator used were changed to obtain a colorless and transparent resin. The results are shown in Table 1.

Comparative Example 3 Homopolymerization was carried out in the same manner as in Example 1, except that 100 parts by weight of diallylphenylphosphonate and 3 parts by weight of diisopropyl peroxycarbonate were used to obtain a colorless and transparent resin. The results are shown in Table 1.

Claims (1)

[Claims] There are mathematical formulas, chemical formulas, tables, etc. represented by the general formula [I] (where Ph is a phenyl group and X is a hydrogen atom or a methyl group) Phosphorus-containing compounds and alone The refractive index n^2^0_D of the polymer is 10
A plastic lens resin made by copolymerizing a radically polymerizable vinyl monomer having a molecular weight of 55 or more.