JP3149535B2 - Composition for optical material and optical material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for an optical material and an optical material, and more particularly to a composition for an optical material and an optical material useful for a plastic lens for eyeglasses having excellent refractive index, transparency and heat resistance. About the material.

[0002]

2. Description of the Related Art In recent years, plastic materials excellent in transparency, light weight, safety, workability and the like have been used as lens materials instead of inorganic glass. As the plastic material, for example, polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polystyrene, and polycarbonate are known. Polymethyl methacrylate and polydiethylene glycol bisallyl carbonate are excellent in light weight and impact resistance, but have a refractive index as low as about 1.49 to 1.50, so when used as a lens, a lens thicker than inorganic glass. Is not suitable for miniaturization and weight reduction.
Although the polystyrene and the polycarbonate have a high refractive index of about 1.58 to 1.60, they are thermoplastic resins, and therefore have a problem that optical distortion due to birefringence is likely to occur during injection molding. There are drawbacks such as lack of solvent properties and scratch resistance, and there is a demand for an optical material having not only a high refractive index but also other excellent properties.

Accordingly, various resins having a high refractive index and excellent other properties have been developed and reported. For example, Japanese Patent Application Laid-Open No. 55-13747 proposes a copolymer of a halogen-substituted styrene, di (meth) acrylate having bisphenol A, a benzyl methacrylate monomer and a phenol methacrylate monomer. However, such a polymer has a problem that the specific gravity is high although the refractive index is high. Also, JP-A-63-462
No. 13 proposes a copolymer of polythiol and diisoyanate. However, in the case of the copolymer, although it has excellent mechanical strength such as impact resistance, it has a problem that it is inferior in heat resistance, still has a high refractive index, and further has heat resistance, solvent resistance, and At present, there is no report of an optical material having excellent other properties such as impact properties.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a plastic lens or other optical material having a desirable refractive index and transparency, various mechanical properties, heat resistance, solvent resistance and impact resistance. An object of the present invention is to provide an optical material and a composition for an optical material which are excellent in properties, have a small polymerization shrinkage, and are easy to control and mold during the polymerization and curing.

[0005]

According to the present invention, (A)
5 to 95 parts by weight of a diol compound containing a diol represented by the following general formula (hereinafter referred to as diol compound 1), and (B) at least one unsaturated dicarboxylic acid and / or
Or an unsaturated polyester obtained by polycondensation with 95 to 5 parts by weight of a dicarboxylic acid mixture containing an unsaturated dicarboxylic anhydride and a vinyl monomer component containing a vinyl monomer having a refractive index of a homopolymer of 1.53 or more as an essential component Is provided.

[0006]

Embedded image

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

Hereinafter, the present invention will be described in more detail.

In the composition for optical materials of the present invention, the unsaturated polyester used as an essential component is a diol compound (hereinafter referred to as component (A)) as a raw material component and a dicarboxylic acid mixture (hereinafter referred to as component (B)). ) And
It is a polymer obtained by polycondensing the raw material components. The kinematic viscosity of the unsaturated polyester is preferably in the range of 10 to 10 ⁶ centipoise. The kinematic viscosity is 10
If it is less than 10, the polycondensation reaction is insufficient, and if it exceeds 10 ⁶ , the workability of the composition is undesirably deteriorated.

In the unsaturated polyester, the component (A) used as a raw material component is a diol compound including the diol compound 1 represented by the general formula (2). At this time, in the general formula 2, n and m represent an integer of 1 or more, and preferably in the range of 1 to 15. When n or m is more than 15, the refractive index and heat resistance of the obtained material are unpreferably reduced.

Specific examples of the diol compound 1 include the following chemical formulas 3 to 12, and the like. When used, they can be used alone or as a mixture.

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

The diol compound 1 can be easily prepared by, for example, adding ethylene oxide to bisphenol A in the presence of an acid or a basic catalyst.

In the component (A), diols that can be used other than the diol compound 1 include ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1,4-
Butanediol, di (2-hydroxyethyl) phthalate and the like can be preferably used, and when used, they can be used alone or as a mixture.

In the component (A), the mixing ratio of the diol compound and the other diol is preferably such that the mixing ratio of the diol compound is 50% by weight or more. When the blending ratio of the diol compound 1 is 50
When the amount is less than% by weight, the refractive indexes of the composition and the optical material are undesirably reduced.

The component (B) used as a raw material component of the unsaturated polyester is a dicarboxylic acid mixture containing at least one kind of unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride. As the unsaturated dicarboxylic acid that can be used at this time, maleic acid, fumaric acid, itaconic acid and the like can be preferably used, and when used, they can be used alone or as a mixture. Further, as the unsaturated dicarboxylic anhydride, maleic anhydride,
Preference is given to itaconic anhydride and the like, and when used it can be used alone or as a mixture. As the component (B), other dicarboxylic acids can be used in addition to the unsaturated dicarboxylic acids and unsaturated dicarboxylic anhydrides. Examples of the other dicarboxylic acids include phthalic anhydride, phthalic acid, and isophthalic acid. , Terephthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride and the like, and when used, they can be used alone or as a mixture.

The mixing ratio of the unsaturated dicarboxylic acid and / or the unsaturated dicarboxylic acid in the component (B) is preferably at least 5% by weight. 5% by weight
If it is less than this, heat resistance is undesirably reduced.

In preparing the unsaturated polyester used as an essential component in the present invention, the mixing ratio of the component (A) to the component (B) is preferably 5 to 9%.
The range of 95 to 5% by weight of the dicarboxylic acid mixture is 5% by weight. If the ratio is outside the above range, the physical properties deteriorate and the material cannot be used as an optical material.

In order to prepare the above-mentioned unsaturated polyester, for example, after mixing the above-mentioned diol compound and a dicarboxylic acid mixture, it is preferable to mix the mixture under an inert gas stream.
Heating and dehydration can be performed in a temperature range of 0 to 250 ° C. At this time, the reaction can be performed without a catalyst, but preferably, paratoluenesulfonic acid, methanesulfonic acid, or the like can be used as a catalyst.

In the present invention, the specific vinyl monomer component used as an essential component together with the unsaturated polyester is a vinyl monomer having a homopolymer having a refractive index of 1.53 or more (hereinafter referred to as vinyl monomer 2). In this case, the vinyl monomer 2 that can be used preferably has an average molecular weight of 1 to 1
When it is 000 or more, it is not particularly limited as long as it is a vinyl monomer having a refractive index of 1.53 or more, and specifically, for example, styrene, methyl nucleus-substituted styrene, α-methyl styrene, chloro nucleus Substituted styrene, bromo-nucleus substituted styrene, phenyl (meth) acrylate, benzyl (meth) acrylate, bromophenyl (meth)
Acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, divinylbenzene, triallyl (iso) cyanurate, vinyl benzoate, bisphenol A dimethacrylate, tetra Preferable examples include diallyl chlorophthalate. When used, they can be used alone or as a mixture.

In the present invention, other vinyl monomer components other than the vinyl monomer 2 can be used as the vinyl monomer component. Examples of the other vinyl monomers include ethyl vinyl ether, butyl vinyl ether, vinyl acetate, vinyl propionate, (meth) acrylic acid, N-vinylpyrrolidone, (meth) acrylamide, methyl (meth) acrylate, butyl (meth) acrylate, and allyl. (Meth) acrylate, (meth) acrylonitrile, diethylene glycol bisallyl carbonate, ethylene glycol bis (meth) acrylate, diethylene glycol bis (meth) acrylate,
Preferred are polyethylene glycol bis (meth) acrylate and the like, and when used, they can be used alone or as a mixture.

The mixing ratio of the other vinyl monomer is desirably not more than 50% by weight based on the weight of the vinyl monomer 2. When the content ratio exceeds 50% by weight,
It is not preferable because the refractive index decreases.

The mixing ratio of the unsaturated polyester and the vinyl monomer component is such that the vinyl monomer component is 1 to 90 to 5% by weight of the unsaturated polyester.
The content is preferably in the range of 0 to 95% by weight. When the mixing ratio of the vinyl monomer is less than 10% by weight, the refractive index and heat resistance of the obtained resin decrease, and when it exceeds 95% by weight, the impact resistance and heat resistance of the obtained material decrease, which is preferable. Absent.

In the present invention, additives such as an oxidation stabilizer, an ultraviolet absorber, a dye, a pigment, and a filler can be added to the composition for an optical material as required.

The optical material of the present invention is a material obtained by polymerizing and curing the composition for optical material, and is a material made of a three-dimensional crosslinked resin because the unsaturated polyester has a plurality of double bonds. .

In order to prepare the optical material of the present invention, for example, the composition for an optical material is polymerized in the presence of a radical polymerization initiator by a radical polymerization method such as bulk polymerization, suspension polymerization, and solution polymerization. In particular, a cast molding method of directly heating and curing in a desired mold can be preferably used. As the radical polymerization initiator,
Specifically, for example, benzoyl peroxide, diisopropylperoxydicarbonate, di-n-propylperoxycarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-
2-ethylhexyl peroxydicarbonate, t-butylperoxydiisobutyrate, lauroyl peroxide,
T-butyl peroxy neodecanoate, azobisisobutyronitrile, azobisdimethylvaleronitrile, and the like can be preferably mentioned, and when used, they can be used alone or as a mixture. The amount of the radical polymerization initiator to be used is from 0.01 to the entire composition for the optical material.
It is 10% by weight, particularly preferably 0.1 to 5% by weight.

In order to carry out the heat polymerization, for example, the composition for an optical material and a radical polymerization initiator are charged directly into a desired mold and heated at preferably 30 to 150 ° C. for 5 to 72 hours. Can be done. On this occasion,
The polymerization system is desirably performed in an atmosphere or atmosphere, for example, with the replacement of an inert gas such as nitrogen, carbon dioxide, or helium.

[0037]

The optical material obtained by polymerizing and curing the optical material composition of the present invention has a refractive index of 1.55 or more, a high Abbe number, a small polymerization shrinkage, and an optical transparency. It is a resin with excellent properties such as heat resistance, solvent resistance and impact resistance. Therefore, for glasses lenses, camera lenses, plastic lenses such as optical materials, or
It is useful as an optical material such as a high refractive index film.

[0038]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

[0039]

Synthesis Examples 1 to 3 A raw material composition shown in Table 1 was added to a 500 cc four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube, and was heated at 80 ° C. for 3 hours under a nitrogen gas stream. The mixture was heated and stirred at 140 ° C. for 2 hours and further at 200 ° C. for 3 hours to carry out a dehydration condensation reaction to obtain an unsaturated polyester having a molecular weight shown in Table 1.

[0040]

[Table 1]

[0041]

Example 1 Unsaturated polyester 5 obtained in Synthesis Example 1
g and 5 g of p-chlorostyrene were mixed, and 0.3 g of diisopropyl peroxydicarbonate was mixed with the mixture to obtain a raw material monomer. Then, the composition was charged into two glass molds, and cured at a temperature of 40 ° C. for 10 hours.
The polymerization was carried out by heating at 0 ° C. for 5 hours and further at 60 ° C. for 5 hours. Finally, an annealing treatment is performed at 100 ° C. for 1 hour.
A cured resin was obtained. The obtained cured resin was taken out of the mold, and the refractive index, Abbe number, polymerization condensation rate, heat resistance and impact resistance were measured according to the following methods. Table 2 shows the results.

Refractive index and Abbe number: Measurement was performed using an Abbe refractometer (manufactured by Atago Co., Ltd.) and using a methyl iodide saturated solution as an intermediate solution. Polymerization condensation rate: The specific gravity p of the raw material monomer and the specific gravity q of the resin were measured and calculated according to the formula (1-p) / q. Heat resistance: After leaving in an oil bath at 120 ° C. for 2 hours, those without deformation and discoloration were rated as Δ, and those with deformation or discoloration were rated as X. -Impact resistance: measured according to ASTM-0256.

[0043]

Examples 2 to 6 Cured resins were prepared in the same manner as in Example 1 except that the raw material monomers shown in Table 2 were used, and each measurement was performed. Table 1 shows the results.

[0044]

[Table 2]

[0045]

Comparative Examples 1 to 3 Cured resins were prepared in the same manner as in Example 1 except that the starting monomers shown in Table 3 were used, and each measurement was performed. Table 3 shows the results.

[0046]

[Table 3]

Claims (2)

(57) [Claims] 1. A composition comprising (A) 5 to 95 parts by weight of a diol compound containing a diol represented by the following general formula 1, and (B) at least one unsaturated dicarboxylic acid and / or unsaturated dicarboxylic anhydride. An optical material composition comprising, as essential components, an unsaturated polyester obtained by polycondensing 95 to 5 parts by weight of a dicarboxylic acid mixture and a vinyl monomer component containing a vinyl monomer having a refractive index of 1.53 or more of a homopolymer. Embedded image 2. An optical material obtained by polymerizing and curing the composition for an optical material according to claim 1.