JPH05271347A - Polymerizable composition and high refractive index plastic lens obtained therefrom - Google Patents

Abstract

PURPOSE:To provide the subject composition useful for plastic lenses, etc., excellent in the impact resistance, transparency, safety, high refractive index and high Abbe number by adding a prescribed amount of a nucleus-substituted phenol glycidyl ether to a specific mixture. CONSTITUTION:5-20 pts.wt. of a nucleus-substituted phenol glycidyl ether such as o-phenylphenyl glycidyl ether is added to 100 pts.wt. of a mixture comprising (A) 20-70wt.% of a compound of the formula (R is H, methyl) and (B) 80-30wt.% of a radical-polymerizable unsaturated monomer mixture solution of methyl (meth)acrylate, etc., containing at least one kind or more of styrenic monomers such as styrene to provide the objective composition. The composition is copolymerized in the presence of a radical polymerization initiator into a polymer used for a plastic lens having a high refractive index, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic lens having a high refractive index, particularly improved impact resistance, and a polymerizable composition as a raw material thereof.

[0002]

2. Description of the Related Art In recent years, the plasticization of lenses for optical equipment and lenses for eyeglasses is rapidly progressing, and there is a demand for cheaper and better workability.

Diethylene glycol bisallyl carbonate has been used for many years as a general-purpose product for eyeglass lenses for vision correction. However, since the refractive index of diethylene glycol bisallyl carbonate is as low as 1.50, a lens having a high power becomes thick, and not only the lightness, which is a characteristic of plastics, cannot be utilized, but also the appearance becomes poor.

Along with this, a large number of compounds capable of imparting a refractive index of 1.60 or more to resins have been announced. Among them, the compound represented by the general formula (I) shown below (hereinafter referred to as the component A) is the main component of the resin having not only a high refractive index but also excellent moldability, transparency and heat resistance. It is known that it can be (for example, JP-B-58-14449, JP-A-58-72101, JP-A-60-2).
58501, JP-A-63-191812,
JP-A-63-215706 and JP-A-1-2998.
No. 07 publication).

[0005]

[Chemical 2]

(R represents a hydrogen atom or a methyl group.)
However, these plastic lenses are insufficient in impact resistance by a falling ball test (FDA falling ball impact strength) required in the United States, for example, and have not occupied a large market.

[0007]

The inventors of the present invention have made extensive studies in view of such a situation, and as a result, as a result, the impact resistance was improved without impairing the refractive index and the Abbe number and without deteriorating the moldability. The present invention has been completed by finding out a polymerizable composition to be improved.

That is, the present invention comprises 5 to 20 parts by weight of a glycidyl ether of a nucleus-substituted phenol, to 100 parts by weight of a mixture consisting of the components A and B represented by the following general formula (I). A high-refractive-index plastic lens excellent in impact resistance, comprising a polymerizable composition and a copolymerization of the polymerizable composition in the presence of a radical polymerization initiator. [A component]

[0009]

[Chemical 3]

(R represents a hydrogen atom or a methyl group) 20 to 70% by weight [Component B] Radical-polymerizable unsaturated monomer mixture liquid containing at least one styrene compound 80 to 30% by weight

The addition of an epoxy compound to a lens monomer mixture mainly composed of the component A has already been disclosed in Japanese Patent Laid-Open No. 336002/1993, which discloses the adhesion between a plastic lens and a hard coat film. The purpose is to improve sex. Specifically, ordinary plastic lenses are hard coated to improve the surface hardness and at the same time reduce surface reflection, but high refractive index plastic lenses generally have good adhesion to the hard coat film. Since it is bad and it is difficult to use as a commercial product as it is, an attempt is made to solve this point by adding about 5% by weight of an epoxy compound having an aromatic ring such as bisphenol A diglycidyl ether. However, this publication only mentions the improvement of the adhesion to the hard coat film, and does not refer to other physical properties, particularly important impact resistance. Furthermore, as an example of a suitable glycidyl compound, bisphenol A,
Phenol Novolac, Orthocresol Novolac,
Only the glycidyl ethers of DPP novolac and tris-hydroxyphenylmethane are mentioned, and no mention is made of other glycidyl compounds, in particular of the nucleoside-substituted phenols. When the present inventors made a lens with the composition disclosed in this publication and examined the impact resistance, a slight improvement was observed, but it was still insufficient for the US falling ball test (FDA falling ball impact strength). It was
Therefore, the effect of improving the impact resistance of the lens of the present invention is specific to the glycidyl ether of the nucleus-substituted phenol.

The polymerizable composition of the present invention will be described in more detail below. The component A in the composition not only has sufficient transparency, refractive index, and Abbe number, which are the physical properties required for a high refractive index lens, but is also excellent in flame retardance because it contains bromine. ing. However, since it is solid at room temperature, it must be dissolved in the B component.

The component B in the composition is a radical-polymerizable unsaturated monomer mixture containing at least one styrenic compound. The styrenic compound contained therein can dissolve the component A well. The refractive index of the homopolymer is as high as 1.58 or more, and it is the most suitable as the polymerizable solvent for the component A.

Examples of suitable styrene compounds include styrene, α-methylstyrene, vinyltoluene,
Examples include divinylbenzene, halostyrenes (eg, chlorostyrene, dibromostyrene, tribromostyrene), and the like, and mixtures thereof.

Other radical-polymerizable unsaturated monomers that can be used simultaneously with the styrene compound include (meth) acrylic acid esters [(meth) acrylic acid esters are acrylic acid esters throughout the present invention. It is a generic term for the compounds and methacrylic acid esters. ], Maleic acid diesters, fumaric acid diesters, allyl compounds, and mixtures thereof. These unsaturated monomers have good copolymerizability with the component A and the styrene compound, and can be mixed with the component B.

Examples of suitable (meth) acrylic acid esters are alkyl (meth) acrylates [eg methyl (meth) acrylate, ethyl (meth) acrylate], phenyl (meth) acrylate, halophenyl (meth) acrylates. [For example, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, dichlorophenyl (meth) acrylate], benzyl (meth) acrylate, phenoxyethyl methacrylate, halophenoxyalkyl (meth) acrylates [for example, bromophenoxyethyl (meth) acrylate , Dibromophenoxyethyl (meth) acrylate,
Dichlorophenoxyethyl (meth) acrylate], polyfunctional (meth) acrylates [eg ethylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra] (Meth) acrylate, 2,2-bis {4,4 '-(meth) acryloyloxyethoxyphenyl} propane,
2,2-bis {4,4 '-(3- (meth) acryloyloxy-2-hydroxypropyloxy) phenyl} propane] and the like, and mixtures thereof.

Examples of suitable maleic acid diesters include dialkyl maleates (eg, diethyl maleate, dipropyl maleate, dibutyl maleate, ditricyclo maleate [5.2.1.0 ^2,6 ]).
Decyl etc.) diaralkyl maleates (eg dibenzyl maleate), diaryl maleates [eg diphenyl maleate, bis (dibromophenyl maleate) etc.] and mixtures thereof.

Examples of suitable fumaric acid diesters include dialkyl fumarate (eg, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, ditricyclo fumerate [5.2.1.0 ^2,6 ] decyl, etc. ),
Examples thereof include diaralkyl fumarate (eg, dibenzyl fumarate), diaryl fumarate (eg, diphenyl fumarate, bis (tribromophenyl) fumarate), and a mixture thereof.

Examples of suitable allyl compounds include allyl esters (eg diallyl phthalate, allyl benzoate, diallyl maleate, allyl methacrylate), allyl carbonates (eg diethylene glycol bisallyl carbonate, tetrabromobisphenol A). Diallyl carbonate, etc.), and mixtures thereof.

The glycidyl ether of the nucleus-substituted phenol added to the mixture of the component A and the component B itself does not participate in the polymerization so much, but the resin obtained by polymerizing the polymerizable composition of the present invention impairs other physical properties. It is particularly excellent in that it gives flexibility without increasing the impact resistance, and thus becomes a factor to increase impact resistance.

As the glycidyl ether, those having a refractive index of 1.58 or more are preferably used. This is because if the refractive index is 1.58 or less, the refractive index of the resin obtained will decrease, and the target high refractive index plastic lens cannot be obtained. Further, it is preferable to use a liquid one as the glycidyl ether because it is easy to handle and compatible with other components.

Examples of suitable compounds used as the glycidyl ether of such a nucleus-substituted phenol include phenyl-substituted phenylglycidyl ethers (eg o-phenylphenylglycidyl ether, p-phenylphenylglycidyl ether) and halophenylglycidyl ether. Classes (eg bromophenyl glycidyl ether, dibromophenyl glycidyl ether), and mixtures thereof. Of these, particularly preferred is o-
Phenyl phenyl glycidyl ether, and mixtures thereof.

The amount of each component of the polymerizable composition used is
A component is 20 to 70% by weight, B component is 80 to 30% by weight
And the glycidyl ether of the nucleus-substituted phenol is A
5 to 2 with respect to 100 parts by weight of the mixture of the component and the component B
0 parts by weight. If the amount is out of these ranges, it may be difficult to dissolve the component A, optical distortion may occur, or polymerization may be insufficient or impact resistance may be deteriorated.

The high refractive index plastic lens of the present invention is obtained by polymerizing the above polymerizable composition in the presence of a radical polymerization initiator. That is, the lens is
Adding a radical polymerization initiator to the polymerizable composition of the present invention,
It is obtained by injecting it between molds held by an elastomer gasket or a spacer, and polymerizing by gradually raising the temperature from room temperature to 80 ° C. to 100 ° C. in a hot air circulation furnace.

The type of radical polymerization initiator used in the present invention is not limited to one, but as a representative one, peroxydicarbonates [eg diisopropyl peroxydicarbonate (IPP), di-sec. −
Butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate], diacyl peroxides [eg benzoyl peroxide (BPO),
Decanoyl peroxide, lauroyl peroxide, acetyl peroxide], alkyloxyperesters [tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexanate, tert-butylperoxypivalate], Alternatively, an azo compound [eg, azobisisobutyronitrile (AIBN), azobis (2,4-dimethylvaleronitrile)] can be mentioned.

The proportion of these radical polymerization initiators used is
0.01 to 100 parts by weight of the polymerizable composition of the present invention
10 parts by weight, preferably 0.05 to 5 parts by weight.
If the amount is less than 0.01 parts by weight, the curing will not be sufficient, and if the amount is more than 10 parts by weight, the curing will be unnecessarily increased, which may cause cracks and decrease in impact resistance.

When producing the high refractive index plastic lens of the present invention, 0.1 to 20 parts by weight of a polymerization retarder and an ultraviolet absorber may be added to 100 parts by weight of the polymerizable composition of the present invention, if necessary. .. Suitable polymerization retarders include phenols [eg hydroquinone, P-tert-butylcatechol, paramethoxyphenol, 3- (4 '
-Hydroxy-3 ', 5'-di-tert-butylphenyl) propionic acid-n-octadecane], sulfides (eg, allyl sulfide, phenyl sulfide),
Examples thereof include sulfoxides (eg phenyl sulfoxide), thiols (eg thiophenol) and the like. Suitable as the ultraviolet absorber are 2-hydroxyphenylbenzotriazoles [for example, 2- (hydroxy-5-t
ert-Butylphenyl) benzotriazole], 2-
Examples thereof include hydroxybenzophenones (eg, 2,4-dihydroxybenzophenone), α-cyano-β-phenylcinnamic acid esters (eg, α-cyano-β-phenylethylcinnamate), and the like.

[0028]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The methods for measuring various physical properties of the obtained polymer are as follows. (1) Refractive index (n _D ) and Abbe number (ν _D ) Refractive index (n _D ) using an Abbe refractometer 3T manufactured by Atago Co.
And the Abbe number (ν _D ) were measured at room temperature. As the contact liquid, α-bromonaphthalene was used. (2) Impact resistance Ten polymers with a diameter of 78 mm, a radius of curvature of 0.1 m, and a center thickness of 2 mm were used. 1
Even if it was a piece, it was broken. (3) Specific gravity Using a polymer having a specific gravity of 30 mm × 30 mm × 3 mm, it was measured by DENSIMETER D-1 manufactured by Toyo Seiki Seisakusho.

Examples 1 to 9 Polymerizable compositions were prepared in the proportions (weight basis) shown in Table 1, and 100 parts by weight of azobis-2,4-dimethylvaleronitrile as a radical polymerization initiator was added to 0.2 parts by weight. By weight, this was poured into a casting mold composed of two glass plates and a gasket to carry out polymerization. In addition, polymerization of the sample for measuring refractive index, Abbe number and specific gravity is 30 mm ×
Use a casting mold to obtain a polymer of 30 mm x 3 mm, and use 78 m in diameter for polymerization of the impact resistance test sample.
m, a radius of curvature of 0.1 m, and a casting mold with which a center thickness of 2 mm was obtained. Polymerization was carried out by gradually raising the temperature from 35 ° C to 90 ° C over 17 hours using a hot air circulation furnace,
It was held at 0 ° C for 1 hour and then gradually cooled to 60 ° C. Table 1 shows the physical properties of the obtained polymer.

Comparative Examples 1 to 3 As a system in which o-phenylphenylglycidyl ether was not added, polymerizable compositions were prepared in the proportions (weight basis) shown in Table 2 and polymerized under the same conditions as in Examples. Table 2 shows the results of an impact resistance test conducted on the obtained lenses under the same conditions as in the examples.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

According to the present invention, it is possible to provide a new polymerization composition for a plastic lens having a high refractive index (1.58 or more). Further, according to the present invention, by using this composition for polymerization, not only the refractive index, the Abbe number, the transmittance, etc., but also the impact resistance is excellent, the physical properties are well balanced, and the plastic lens is not easily cracked and is safe. be able to.

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[Procedure amendment]

[Submission date] May 6, 1992

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[Name of item to be corrected] Claim 1

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[Chemical 1] (R represents a hydrogen atom or a methyl group.) 20 to 70 wt% [Component B] Radical-polymerizable unsaturated monomer mixture liquid containing at least one styrene compound 80 to 30 wt%

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[Procedure amendment]

[Submission date] June 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

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When producing the high refractive index plastic lens of the present invention, 0.1 to 20 parts by weight of a polymerization retarder and an ultraviolet absorber may be added to 100 parts by weight of the polymerizable composition of the present invention, if necessary. .. Preferable examples of the polymerization retarder are phenols [eg, hydroquinone, p-tert-butylcatechol, p-methoxyphenol, 3- (4 ').
-Hydroxy-3 ', 5'-di-tert-butylphenyl) propionic acid-n-octadecane], sulfides (eg allyl sulfide, phenyl sulfide),
Examples thereof include sulfoxides (eg phenyl sulfoxide), thiols (eg thiophenol) and the like. Suitable as the ultraviolet absorber are 2-hydroxyphenylbenzotriazoles [for example, 2- (hydroxy-5-t
ert-Butylphenyl) benzotriazole], 2-
Examples thereof include hydroxybenzophenones (eg, 2,4-dihydroxybenzophenone), α-cyano-β-phenylcinnamic acid esters (eg, α-cyano-β-phenylcinnamic acid ethyl ester), and the like.

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[Table 1]

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[0032]

[Table 2]

Claims (4)

[Claims] 1. A polymerizable composition obtained by adding 5 to 20 parts by weight of a glycidyl ether of a nucleus-substituted phenol to 100 parts by weight of a mixture of an A component represented by the following general formula (I) and a B component. [Component A] (R represents a hydrogen atom or a methyl group.) 20 to 70 wt% [Component B] Radical-polymerizable unsaturated monomer mixture liquid containing at least one styrene compound 80 to 30 wt% 2. The polymerizable composition according to claim 1, wherein the glycidyl ether of the nucleus-substituted phenol is a glycidyl ether of a phenyl-substituted phenol. 3. The polymerizable composition according to claim 1, wherein the glycidyl ether of the nucleus-substituted phenol is o-phenylphenylglycidyl ether. 4. A high refractive index plastic lens excellent in impact resistance, which is obtained by copolymerizing the polymerizable composition according to claim 1 in the presence of a radical polymerization initiator.