JPH05271348A - Composition for optical material and material for optical application - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a specific organic sulfur compound and a specified monomer as main components, and useful for plastic lenses, etc., little in the optical strain, having a high refractive index and a high Abbe number and excellent in the optical transparency, heat resistance, solvent resistance and impact resistance. CONSTITUTION:The objective composition contains (A) an organic sulfur compound of the formula (R is H, methyl; n is 0-2) preferably in an amount of 1-95wt.% and (B) a copolymerizable monomer having a radical-polymerizable double bond, such as styrene preferably in an amount of 99-5wt.% as main components. The composition is polymerized and cured to give a material for optical applications.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material composition which provides an optical material having excellent optical properties such as refractive index and transparency and various mechanical properties and useful for plastic lenses for eyeglasses, and the optical material. The present invention relates to an optical material obtained by polymerizing and curing an optical composition.

[0002]

2. Description of the Related Art In recent years, synthetic resin materials excellent in light weight, moldability, impact resistance and dyeability have been used as lens materials instead of inorganic glass. Known examples of the synthetic resin material include polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polystyrene, and polycarbonate. The polymethyl methacrylate and polydiethylene glycol bisallyl carbonate are excellent in lightness and impact resistance, but when used as a lens because of their low refractive index of about 1.49, a lens thicker than inorganic glass is required, It has a drawback that it is not suitable for high magnification and light weight. Also,
The polystyrene and polycarbonate have a high refractive index of about 1.58 to 1.59, but since they are thermoplastic resins, they have a problem that optical distortion due to birefringence is likely to occur during injection molding. There are drawbacks such as lack of resistance and scratch resistance.

Therefore, recently, some technical proposals have been made to improve these conventional drawbacks with a high refractive index. For example, JP-A-53-7787 discloses a copolymer of diethylene glycol biscarbonate and diallyl isophthalate, and JP-A-59-81318.
JP-A-59-1 discloses a copolymer of diallyl phthalate and unsaturated fatty acid alcohol benzoate.
Japanese Patent No. 91708 discloses a copolymer of di (meth) acrylate having bisphenol A and diallyl isophthalate with diethylene glycol bisallyl carbonate and the like.

However, the above-mentioned copolymer has a problem that the refractive index is relatively low at 1.52 to 1.55, and unreacted allyl monomer is likely to remain.

Further, Japanese Patent Application Laid-Open No. 57-28115 discloses that
As a copolymer of a styrene-based vinyl monomer and an unsaturated carboxylic acid heavy metal salt, JP-A-60-55007 proposes a copolymer of a nuclear halogen-substituted diallyl phthalate and a nuclear halogen-substituted allyl benzoate. Has been done. The copolymer has a high refractive index of about 1.58 to 1.60, but since it uses an allylic monomer having a metal salt or a halogen-substituted aromatic ring, the specific gravity of the polymer is large and the lens is heavy. Therefore, there is a drawback that the weight reduction is impaired.

Further, JP-A-55-13747 discloses a copolymer of a nuclear halogen-substituted styrene, a di (meth) acrylate having bisphenol A, a benzyl methacrylate monomer and a phenol methacrylate monomer. Japanese Patent No. 133211 proposes a polymer of a hydroxydi (meth) acrylate having an aromatic ring and a diisocyanate compound and a styrene monomer. In the case of the polymer, although the refractive index is as high as about 1.60, it is difficult to control the polymerization reaction, the specific gravity is large, and the weather resistance is problematic.

Further, JP-A-2-58001 and JP-A-2-289622 disclose a compound having two or more unsaturated groups in one molecule or divinylbenzene and two thiol groups in one molecule. An optical material obtained by reacting with a compound having is disclosed. However, the compound having the thiol group has a strong malodor, and further, in the optical material obtained by the reaction, it is difficult to perform a surface treatment such as a hard coat, which is particularly important when it is put into practical use as a plastic lens for eyeglasses. There is a problem.

[0008]

DISCLOSURE OF THE INVENTION The object of the present invention is to have no bad odor peculiar to sulfur compounds, to be excellent in handleability at the time of curing, to facilitate reaction control and molding at the time of polymerization and curing, for plastic lenses or other It is possible to obtain an optical material having a desirable refractive index, transparency, etc. as an optical material, excellent in various mechanical properties, heat resistance, solvent resistance and impact resistance, and having a small specific gravity and a light weight. It is to provide a composition for an optical material that can be used.

Another object of the present invention is to provide an optical material composition capable of obtaining an optical material in which a cured resin has excellent dyeability and which can be easily surface-treated such as a hard coat and an antireflection film. To provide things.

[0010]

According to the present invention, an organic sulfur compound represented by the following general formula (1) (hereinafter referred to as organic sulfur compound A) and a radically polymerizable compound capable of copolymerizing with the organic sulfur compound Provided is a composition for an optical material, which comprises a monomer having a double bond as a main component.

[0011]

[Chemical 2]

Further, according to the present invention, there is provided an optical material obtained by polymerizing and curing the composition for optical material.

The present invention will be described in more detail below.

The organic sulfur compound used as an essential component in the composition for optical materials of the present invention is represented by the general formula 2
Is an organic sulfur compound A represented by In the organic sulfur compound A, when n is an integer of 3 or more, the production is difficult.

When the organic sulfur compound A is specifically listed, the compounds represented by the following chemical formulas 3 to 8 can be preferably mentioned, and they can be used alone or as a mixture when used.

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

In order to prepare the organic sulfur compound A, for example, p-xylene diol and p-chloromethylstyrene are mixed with an alkali metal salt such as sodium hydroxide or potassium hydroxide or a basic catalyst such as triethylamine. It can be easily obtained by reacting at -10 to 120 ° C for 30 minutes to 48 hours in the air or in an atmosphere of an inert gas such as nitrogen.

In the composition for optical materials of the present invention,
The content of the organic sulfur compound A is not particularly limited, but is 1% by weight with respect to the entire composition for optical materials.
It is preferably not less than 95% by weight. When the content is less than 1% by weight, a desired refractive index cannot be obtained, and when it exceeds 95% by weight, mechanical properties become insufficient, which is not preferable.

In the composition for optical materials of the present invention,
The radical polymerizable double bond-containing monomer used as the other essential component is not particularly limited as long as it has a radical polymerizable double bond, and specific examples thereof include styrene and p. -Methylstyrene, α-
Methyl styrene, p-chlorostyrene, o-chlorostyrene, p-bromostyrene, o-bromostyrene, vinyl acetate, vinyl propionate, (meth) acrylic acid, 2
-Hydroxyethyl (meth) acrylate, ethyl (meth) acrylate, N, N-dimethylacrylamide,
N-methylacrylamide, methyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, bromphenyl (meth) acrylate, (meth) acrylonitrile, 2,2-bis (4- ( (Meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloylpolyethoxyphenyl) propane,
2,2-bis (4'-2 ''-hydroxy-3 ''-(meth) acryloxypropoxyphenyl) propane, diethylene glycol bisallyl carbonate, diallyl tetraphthalate, diallyl phthalate, p-divinylbenzene, m-divinylbenzene , Divinylbiphenyl, ethylene glycol bis (meth) acrylate, diethylene glycol bis (meth) acrylate, polyethylene glycol bis (meth) acrylate, triethylene glycol bis (meth) acrylate, tetraethylene glycol bis (meth) acrylate, dipropylene glycol bis ( Preferable examples include (meth) acrylate, bisphenol A bis (meth) acrylate, diallyl tetrachlorophthalate, diallyl isophthalate, and allyl methacrylate. It can, in use, can be used alone or as a mixture.

Further, the composition for optical materials of the present invention contains UV
Additives such as an absorbent and a coloring preventing agent may be added as necessary.

The optical material of the present invention is a material obtained by polymerizing and curing the composition for optical material. On this occasion,
In the composition for optical material, since the organic sulfur compound A used as an essential component has two radically polymerizable double bonds in one molecule, the composition for optical material is polymerized and cured. The resulting optical material forms a crosslinked polymer that is insoluble in the solvent.

The optical material of the present invention can be prepared by, for example, curing the composition for optical material by photopolymerization or heat polymerization in the presence of a radical polymerization initiator. As the radical polymerization initiator, 10
An organic peroxide or an azo compound having a time half-life temperature of 160 ° C. or lower can be used, and specifically, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate. , T-butylperoxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, t-butylperoxyacetate, t-peroxyoctoate, t-butylperoxybenzoate, azobisisobutyronitrile and the like are used. In this case, they can be used alone or as a mixture. The amount of the radical polymerization initiator used is 10 per 100 parts by weight of the composition for optical materials.
It is not more than 5 parts by weight, particularly preferably not more than 5 parts by weight.

To carry out the heat polymerization, for example, the composition for optical material and the radical polymerization initiator are directly charged into a desired mold and preferably at a polymerization temperature of 0 to 200 ° C. for 1 to 48 hours. It can be polymerized by heating. At this time, it is desirable that the polymerization system is carried out under an atmosphere of an inert gas such as nitrogen, carbon dioxide or helium. In addition, the composition for optical materials may be prepolymerized, for example, at 0 to 200 ° C. for 0.5 to 48 hours before the above-mentioned heat polymerization, charged into a desired mold, and post-polymerized to be cured.

Further, for the purpose of improving the surface properties of the obtained optical material, a hard coat, an antireflection film, etc., after curing,
Various surface treatments can also be applied.

[0030]

The composition for optical materials of the present invention is 1.55.
It has the above refractive index, high Abbe number, small optical distortion, excellent optical transparency, heat resistance, solvent resistance, and impact resistance. Material for use can be obtained. Further, in the composition for optical materials of the present invention, the organic sulfur compound A used as an essential component does not have a bad odor peculiar to sulfur compounds, and the reaction control during polymerization and curing is easy.

Further, in the present invention, various surface treatments such as hard coating and dyeing of the optical material obtained after curing can be easily carried out, so that it can be used for plastic lenses such as eyeglass lenses, camera lenses and optical materials. It is useful as other optical materials.

[0032]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0033]

Example 1 8 g of the organic sulfur compound shown in Table 1 and 2 g of p-chlorostyrene were mixed to obtain a composition for optical materials.
Then, 0.05 g of t-butylperoxybenzoate was added to and mixed with the composition for optical materials, charged into two glass molds, placed in a thermostat bath at 80 ° C., and cured at a curing temperature of 80 ° C. The mixture was heated for an hour, further heated to 100 ° C. in 3 hours, and finally heated at 100 ° C. for 3 hours. Finally 1
Annealing treatment was performed at 00 ° C. for 2 hours to obtain a cured resin. The obtained cured resin was taken out of the mold, and the refractive index, Abbe number, b * value and heat resistance were measured according to the following methods. The results are shown in Table 1.

Refractive index and Abbe number: An Abbe refractometer (manufactured by Atago Co., Ltd.) was used, and measurement was carried out using a methyl iodide saturated solution as an intermediate solution.

B * value (yellowness): measured using a photometer model 1001 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller this value, the smaller the yellowness and the better.

Heat resistance: No deformation or discoloration in an oil bath at 130 ° C. was evaluated as ◯, and deformation or discoloration was evaluated as x.

[0037]

Examples 2 to 9 Cured resins were prepared in the same manner as in Example 1 except that the compositions for optical materials shown in Table 1 were used.
Each measurement was performed. The results are shown in Table 1.

[0038]

[Table 1]

[0039]

Comparative Examples 1 to 3 A cured resin was prepared in the same manner as in Example 1 except that the compounds shown in Table 2 were used, and each measurement was performed. The results are shown in Table 2.

[0040]

[Table 2]

Claims (2)

[Claims] 1. A composition for an optical material comprising an organic sulfur compound represented by the following general formula 1 and a monomer having a radical-polymerizable double bond copolymerizable with the organic sulfur compound as main components. [Chemical 1] 2. An optical material obtained by polymerizing and curing the composition for optical material according to claim 1.