JPS61275312A - Resin for optical material - Google Patents

Abstract

PURPOSE:To obtain a resin for optical materials, having high heat resistance, high hardness, low double refractive index, low dispersion and low water absorptivity, by radical-polymerizing a specified cyclohexylpropane compound with a specified (meth)acrylate compound. CONSTITUTION:A resin for optical materials is obtained by radical-polymerizing 95-40wt% compound of formula I with 5-60wt% compound of formula II. In the formulas, R1 is H or CH3, R2 in formula I is -OCH2CH2- or formula II, m and n are each 0-3, and R2 in formula III is -CH3, -CH2-CH3 or -CH2OH. As the compound of formula I, 2,2'-bis[4'-(beta-methacryloyloxy)cyclohexyl]propane is particularly preferable because of curability and performances of a cured product. Examples of the compounds of formula III include trimethylolpropane trimethacrylate.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a resin for optical materials that provides a cured product having high heat resistance, high hardness, low birefringence, low dispersion, and low water absorption. In particular, it can be used for various lenses, prisms, optical discs, etc.

(Prior Art) Plastic optical materials are lightweight, have transparency comparable to glass, and are easily moldable.

Since mass production is possible, demand for various lenses, prisms, optical disks, etc. has been increasing in recent years.

As plastic optical materials, thermoplastic resins such as polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, and diethylene glycol bisallyl carbonate resin are generally used.

However, with the above resin systems, only products with low heat resistance and surface hardness can be obtained.For example, in the case of optical disk substrates, the substrate may warp or twist due to the influence of heat and moisture. When used for this purpose, there is a problem in that the plastic surface is scratched by dust and the like, resulting in a lack of optical stability.

In order to improve those shortcomings, Japanese Patent Application Laid-Open No. 55-1374
In Publication No. 7, bisphenol A dimethacrylate or 2,2-bis(4-methacroyloxyethoxydiphenyl)furopane in combination with tostyrene, 1jn-chlorostyrene, phenyl (meth)acrylate, benzyl (meth)acrylate, etc. Although polymerization has been proposed, it does not satisfy the required performance and has practical problems.

On the other hand, when used in optical disk substrates, various lenses, and prisms, in addition to the above performance, it is essential to satisfy necessary optical qualities such as high light transmittance, low birefringence, and low dispersion.
There is a strong desire to provide materials with these properties.

(Object of the Invention) In view of the above-mentioned circumstances, an object of the present invention is to provide a resin for optical materials, particularly a resin for optical materials having high heat resistance, high hardness, low birefringence, low dispersion, and low water absorption. .

(Structure of the invention) The object of the present invention is achieved by the following configuration.

The resin for optical materials of the present invention is obtained by radical polymerizing a composition consisting of 95 to 40 weight percent of a compound represented by the following general formula (I) and 5 to 60 weight percent of a compound represented by general formula (I0). It is characterized by consisting of the obtained copolymer.

A compound represented by the general formula (I) [wherein R1 is H'! fc ld C1(a; R
2 is 10C&Ca! - or -C-CH2-CH-;
m and n are O~3. ] CH2QC-C-CH2 [Wherein, R1 or CHa; R2 is -CHa, -CH2-CH3 or -CH20FI. ]
Specific examples of the compound represented by the general formula (I) used in the present invention include 2,2'-bis[4-(β-methacroyloxy)cyclohexyl]propane, 2,2'-bis(4- (β-methacroyloxy)cyclohexyl]
Furopane, 212'-bis(4-(β-methacroyloxyjethoxy)cyclohexyl]propane, 2.2'
-bis[4-(β-methacroyloxytriethoxy)
cyclohexyl]propane, 2,2'-bis(4-(acroyloxyethoxy)cyclohexyl)furopane,
212'-bis(4-(β-methacroyloxyα-methylethoxy)cyclohexyl]furopane, 282'-
Examples include bis(4-(acroyloxyα-methylethoxy)cyclohexyl)propane.Among these, 2.2' is particularly preferable in terms of curability and performance of the cured product.
-bis(4/ (β-methacroyloxy)cyclohexyl]propane, 2.2'-bis[4-(β-methacroyloxyethoxy)cyclohexyl]propane, 2
．． 2'-bis[4-(β-methacroyloxy-α-methylethoxy)cyclohexyl]furopane, 2.2'
-(4-(acroyloxyethoxy)cyclohexyl) Probanca.

In addition, as the compound 11 represented by the general formula (m), trimethylolpropane trimethacrylate, trimethylolpropane acrylate, trimethylolethane trimethacrylate, trimethylolethane triacrylate, pentaerythritol trimethacrylate, pentaerythritol triacrylate, etc. can give.

The usage range of the compound represented by general formula (I) is 95 to 4
0 weight 1% is 89, preferably 90 to 600 to 60 weight %.Also, the usage range of the compound represented by the general formula (ID is 5 to 6
At 0% by weight, there is dust, when it is less than 5% by weight, the properties of the cured product such as heat resistance are insufficient, and on the other hand, when it is 60% by weight or more,
The usage range is 5 to 60% by weight, preferably 10 to 50% by weight, since sinks and cracks occur in the cured product, making it unsuitable.
Heavy Ik%.

Furthermore, in addition to the general formula as above (i), a radically polymerizable monomer generally used as a viscosity modifier is added to
It can be used at 0% by weight or less as long as it does not reduce the excellent properties of the optical resin of the present invention. For example, vinyl compounds such as styrene, chlorostyrene, dichlorostyrene, vinyltoluene, divinylbenzene, vinyl acetate, vinyl chloride, methyl acrylate, phenyl (meth)
Acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate
Examples include (meth)acrylic compounds such as acrylate, and allyl compounds such as diethylene glycol bisallyl carbonate and diallyl phthalate.

The radical initiator used in the polymerization is not particularly limited, and examples include peroxides such as benzoyl peroxide, diisopropyl peroxycarbonate, lauroyl peroxide, and tert-butyl peroxy pivalate;
Known radical initiators include azo compounds such as azoisobutyronitrile, photosensitizers such as benzophenone, benzoin ethyl ether, benzyl, acetophenone, and anthraquinone, and sulfur compounds such as diphenyl sulfate and thiocarbamate.

Examples are shown below. In addition, parts in the examples are parts by weight, %
indicates weight %.

In addition, various physical properties obtained in the examples were measured by the following test methods.

(I) Refractive index: Measured with an Atsube refractometer according to JIS-7105.

(2) Dispersion value: Measured using an Atsube refractometer and expressed using the Atsube number below.

(3) Light transmittance: Measure the light transmittance at 500 m using a spectrophotometer.

(4) Birefringence: Measured under polarized light microscope rjlL boundary.

(5) Heat resistance: Measured using a heat deformation tester according to ASTM-D-648.

(6) Hardness: Measured using a pencil hardness tester according to JIS-6911.

(7) Water absorption rate: Measured according to JIS-6911.

Example 1 0.5 part of benzoyl peroxide was added to a mixture of 60 parts of 2.2'-his[:4-(β-methacroyloxyethoxy)cyclohexyl]furopane and 40 parts of trimethylolpropane trimethacrylate, and the mixture was heated to 60°C. After heating and stirring and mixing uniformly, defoaming is performed, and this liquid is divided into 50 nm diameter particles.
The mixture was poured into a mold consisting of a glass plate and a silicone rubber spacer, and polymerization was carried out by holding the mixture at 60°C for 24 hours, at 80°C for 2 hours, and at 100°C for 2 hours.

When the cured product was taken out from the mold, a colorless and transparent cured product was obtained. Table 1 shows the evaluation results of various physical properties of the cured product.

Example 2 2.3 parts of benzoin ethyl ether was added to a mixture of 50 parts of 2'-bis(4-(acroyloxyethoxy)cyclohexyl]propane and 50 parts of trimethylolpropane triacrylate, and the mixture was heated to 60°C and mixed uniformly. After stirring and mixing, the liquid was defoamed, poured into a mold made of a glass plate with a diameter of 120 m and silicone rubber, irradiated with ultraviolet rays for 1 minute using a high-pressure mercury lamp with an output of 80 W/cIM, and then poured from the mold. When the cured product was taken out, a colorless and transparent cured product was obtained.Table 1 shows the evaluation results of various physical properties of the cured product.
It was shown to.

Example 3 2.2'-bis(4-(β-methacroyloxyethoxy)cyclohexyl]propane 508L)! A mixture of 40 parts of J-methylolpropane trimethacrylate and 10 parts of cyclohexyl methacrylate was added and 0.5 part of benzoyl peroxide was added and cured under the same conditions as in Example 1 to obtain a colorless and transparent cured product.

Table 1 shows the evaluation results of various physical properties of the cured product.

Comparative Example 1 0.5 part of benzoyl peroxide was added to 31177100 parts of 2.2'-his(4-(β-methacroyloxyethoxy)cyclohexyl), and a colorless and transparent cured product was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of various physical properties of the cured product.

Comparative Example 2 0.5 part of benzoyl peroxide was added to 100 parts of 4.4'-bis(β-methacroyloxyjetoxyphenyl)propane, and a colorless and transparent cured product was obtained in the same manner as in Example 1. . Table 1 shows the evaluation results of various physical properties of the cured product.
It was shown to.

The abbreviations in Table 1 represent the following meanings.

HBPAMA di2,2'-bis[4-(β-methacroyloxyethoxy)cyclohexyl]propane HBPAA di2,2'-bis[4-(acroyloxyethoxy)cyclohexyl] Propane TMPTMA: Trimethylolpropane trimethacrylate TMPTA : ) Limethylolpropane triacrylate CHHA Rainbow chlorohexyl methacrylate BPAD
MA: 4.4'-bis(β-methacroyloxyjetoxyphenyl)furopane (blank below)

Claims (1)

[Claims] 1) A resin for optical materials obtained by radical polymerization of 95 to 40% by weight of a compound represented by general formula (I) and 5 to 60% by weight of a compound represented by general formula (II) . ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 is H or CH_3; R_2 is -OCH
_2CH_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
;m and n are 0-3. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R_1 is H or CH_3; R_2 is -CH_
3 or -CH_2-CH_3 or -CH_OH. ]