JPS6010202A - Plastic lens - Google Patents

Abstract

PURPOSE:To improve refractive index and optical characteristic by copolymerizing diallyl phthalate and allyl benzoate. CONSTITUTION:The diallyl phthalate, diallyl isophthalate, diallyl terephthalate monomer expressed by the general formula ( I ) [in which X is halogen except fluorine, (a) is 0, 1, 2, 3 or 4 integer] and the benzoate monomer expressed by the general formula (II) [in which X is halogen except fluorine, (b) is 0, 1, 2, 3, 4 or 5 integer] are copolymerized in the presence of a radical polymn. initiator. The general formula ( I ) is incorporated in a 50-90wt% range and (II) in a 10-50wt% range and the refractive index is regulated to >=1.57. Then the plastic lens has excellent dyeability and impact resistance and is suitable for spectacles.

Description

[Detailed description of the invention]

The present invention relates to a synthetic resin lens that has a relatively high refractive index for a synthetic resin, has excellent optical properties, is dyeable, and has high impact resistance. Conventionally, optical materials made of glass have excellent scratch resistance, but have drawbacks such as being heavy and easily broken. On the other hand, synthetic resin optical materials have the advantages of being light, hard to break, easily dyed, and highly fashionable, and polymethyl methacrylate, diethylene glycol bis(allyl carbonate), and the like are already in use. However, the optical material made of synthetic resin has a low refractive index of about 1.49, and when molded into a lens, the material must be significantly thicker than inorganic glass. Particularly in negative lenses, the edge thickness of the lens becomes significantly thicker, and there is a strong demand for thinner lenses. Furthermore, synthetic resins with a high refractive index, such as polycarbonate-1 and polystyrene, have problems in scratch resistance, chamferability, heat resistance, and the like. In order to improve the above-mentioned drawbacks,
No. 47 proposes copolymerization of bisphenol A-based dimethacrylate and styrene derivatives or phenylmethacrylate-1 derivatives. However, these polymers have poor weather resistance. It yellows easily and has problems with heat resistance. In addition, JP-A-57
-Bis-(oxyalkylene phenyl) diallyl carbonate 1-. It has been proposed to copolymerize bis-(oxyalkylene phenyl) diallyl ether, a styrene derivative, and a naphthalene dicarboxylic acid allyl ester derivative. However, these copolymers are difficult to dye and do not fully satisfy the quality required for lenses. The present invention was developed as a result of extensive research to overcome the above-mentioned drawbacks, and the present invention was developed based on diallylphtasy 1-. By copolymerizing the simple substance and derivatives of diallyl isophthalate, diallyl terephthalate 1 to allylbenzony 1 in the presence of a radical polymerization initiator, it has a high refractive index of 1.57 or more. This was done in order to create a synthetic resin lens that is dyeable and has excellent physical and chemical properties. The copolymer of the lens according to the present invention contains 50 to 90% by weight of one or more monomers whose general formula is represented by (1) and one or more 11-mers whose general formula is represented by (II). It can be obtained by copolymerizing a mixture of monomers containing 10 to 50% by weight of in the presence of a radical polymerization initiator. [In the formula, X is a halogen excluding fluorine, and a is 0. ■. Integer of 2.3 or 4] [In the formula, X is halogen excluding fluorine, b is 0.1°2.3
．． Integer of 4 or 5] The present invention will be described in detail below. Diallylphtasys having a nuclear halogen-substituted aromatic ring 1 to 1 to be used in the present invention. Diallylisophthalate-1. The halogen of diallyl terephthalene-1 to allylbenzony-1- is not particularly limited and may be chlorine, bromine, or iodine, excluding fluorine, but chlorine is preferred. It is bromine. The number of halogens contained in the aromatic ring is not particularly limited, and in formula (1), 1 to 4 halogens;
In I), 1 to 5 can be used. Typical examples suitably used in the general formula (1) include tetrachlordiallyl phthalate, trichlordiallyl phthalate 1-, dichlorodiallyl phthalate, te]-labrom diallyl phthalate-1-, 1 -ribrom diallyl phthalate 1-, dibrom diallyl phthalate, tetrachloro diallyl isophthale 1-, trichlor diallyl isophthale 1-, dichloro diallyl isophthale 1-
-, TeI-rabrom diallyl isophthalate-1-, tribrom diallyl isophthalate-1-, dibrom diallyl isophthalate, tetrachloro diallyl terephthalate, trichloro diallyl terephthalate, dichloro diallyl terephthalate, tetrabrom diallyl terephthalate,
Tribrom diallyl terephthalate, dichlordiallyl terephthalate, diallyl phthalate-1~, diallyl isophthalate, diallyl terephthalate chlorodiallyl phthalate-1-, chlorodiallyl isophthalate, prom diallyl phthalate-1~, prom diallyl isophthalate 1~
, gross diallyl terephthalate, prom diallyl terephthalate, etc. are used. On the other hand, typical examples suitably used in general formula (II) include pentachlorallyl benzony-1-, tetrachlorallylbenzony-1-11-lichlorallylbenzoe-1-, dichlorallyl Benzoate, chlorallyl benzony I~, allyl benzoate, pentabromoallyl benzony-1, te 1-labroun allyl benzony 1~. 1 heribromoallyl benzoate, dibromoallyl benzoate, bromoallyl benzoate, etc. are used. The radical polymerization initiator is not particularly limited and any known one can be used, but representative examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide,
,1. bis(t-butylperoxy)cyclohexane,
2,2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzine hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide oxide, isobutyl peroxide, acetyl peroxide, lauroyl peroxide, benzoyl peroxide, octatool peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl oxydicarbonate l-1t-butyl peroxyacetate-1 -1t-butylperoxybenzoate and the like are used. The preferable amount of diallyl phthalate, diallyl terephthalate, and diallyl isophthalate-1 used in the present invention is 50 to 90% by weight. When the amount of monomers and derivatives of diallyl terephthalate and diallyl isophthalate-1 to diallyl phthalate-1 exceeds 90% by weight, the solvent resistance is particularly poor. Although it improves heat resistance, there are problems with impact resistance and moldability. Furthermore, when the amount of the secondary monomer used is 50% or more,
The heat resistance and solvent resistance are particularly poor, making it undesirable as a lens for spectacles, for example. On the other hand, the preferable amount of the second monomer allylbenzony 1 to simple substance and derivatives used is 10 to 50% by weight. When the amount of allyl benzoate alone or derivative used exceeds 50% by weight, although the impact resistance is improved, the polymerization reaction rate is significantly reduced, making casting impossible. In addition, when the amount of allyl benzoate used alone or in the M jζr form is less than 10 nebulae, the impact resistance decreases. The high refractive index synthetic resin lens of the present invention having a refractive index of 1.57 or more has diallylphtasy 1 to 1.57. diallyl isophthalate,
Simple substance and 1ilN of diallyl terephthalene-1: 12
By pouring a mixture of allyl benzoate, allyl benzoate alone, a derivative, and a polymerization initiator into a mold assembled with a glass mold and a resin gasket, and curing using means such as heating or ultraviolet irradiation. Get nine. The high refractive index synthetic resin lens of the present invention has a refractive index of ], 57
As described above, the lens is transparent, dyeable, and has high impact resistance, and is preferable as a synthetic resin lens for eyeglasses. Next, embodiments of the present invention will be described in more detail. In addition, all the parts in Examples and Comparative Examples are based on the double star standard. First, the test method for the measured values obtained in Examples and Comparative Examples will be described below. Heat resistance;] Heated at 20°C for 24 hours, coloring changed by 7 degrees. Those with no deformation were considered good. Solvent resistance: Immersed in isopropyl alcohol and acetone for 24 hours at room temperature, resulting in roughening on two surfaces. Those with no clouding or deformation were considered good. Impact resistance: A steel ball drop test I- was performed on a flat plate with a center thickness of 2 mm according to FDA standards, and those that did not break were evaluated as good. Refractive index: Measured by the minimum deviation angle method. Workability: Those that could be processed with diamond foil were rated as good. Dyeability: A molded lens was immersed in a dyeing bath, and those whose total light transmittance decreased to 50% in 30 minutes or less were evaluated as good. Moldability: Lenses with a smooth surface after molding were rated as good. [Examples 1 to 3] Tetrachlorodiallyl phthale-1 was mixed with monochloroallyl benzene 1-1 in the composition shown in Table 1, and 3% by weight of benzoyl peroxide was added as a radical polymerization initiator.
and stirred thoroughly. This mixed monomer was heated to 40°C and poured into a casting mold consisting of two glass molds and a polyethylene gasket 1.
Polymerization was carried out using an electric furnace by linearly increasing the temperature from 50° C. to ]00” C over 24 hours. After the polymerization was completed, the polymer was removed from the cast mold and its 1.5” property was investigated. The results are shown in Table-1.

[Comparative Examples 1-2] Polymerization was carried out in the same manner as in Examples 1-3. Display the results -
Shown in 2.

[Comparative Example 3] 3% by weight of isopropyl peroxydicarbonate was added as a polymerization initiator to diethylene glycol bis(allyl carbonate) monomer, and the mixture was heated at 40°C to 80°C in an electric furnace.
The reaction was carried out under polymerization conditions of 24 hours at °C, and the obtained polymer was removed from the cast mold and various properties were investigated. The results are shown in Table-2.

Comparative Example 41 3% by weight of benzoyl peroxide as a polymerization initiator was added to styrene monomer and thoroughly stirred. This mixed monomer was poured into a casting mold consisting of a polyethylene gasket and two glass molds, and polymerized under the same temperature settings as in Examples 1 to 3. This polymer was removed from the cast mold and various properties were investigated. The results are shown in Table-2. [Examples 4 to 6] Instead of tetrachlorodiallyl and phthalate as the first monomers in Examples 1 to 3, tribromo diallyl isophthalate was used as the first monomer, and monochloroallyl benzoate was used as the second monomer. Table 1 shows the characteristics of the copolymerized lens. However, the polymerization conditions were the same as in Examples 1 to 3.

[Examples 7 to 9] Instead of monochloroallyl benzoate as the second monomer in Examples 1 to 3, dichlorallyl benzoate was used as the second monomer, and the first monomer was te-1-rachlordiallyl. The characteristics of the terephthalate compound lens are listed below.
Shown in 1. Polymerization was carried out in the same manner as in Examples 1-3. The abbreviations in the following table are: C1aDAP; tetrachlordiallyl phthalate-1 to Br
5DAIP; tribromodiallylisophthalate-1-
'C1a DATP; Tetrachlordiallyl terephthalate CIABz; Monochloroallyl benzoate C1
28BZ; Dichloroallyl benzoate CR-39; Diethylene glycol bis(allyl carbonate) PSI: Polystyrene; O indicates excellent, Δ indicates slightly inferior, and × does not meet the specifications at all.

Claims (1)

[Scope of Claims] ■ A synthetic resin characterized in that the main component is a two-component copolymer of general formula (1) and general formula (II), which is copolymerized in the presence of a radical polymerization initiator. lens. [In the formula, X is halogen excluding fluorine, a is 0.1°2.3
or an integer of 4] [In the formula, X is a halogen excluding fluorine, and b is 0.1°2.3
．． An integer of 4 or 5] 2 A patent claim containing general formula (1) in a range of 50 to 90% by weight and containing general formula (II) in a range of 10 to 50% by weight and having a refractive index of 1.57 or more Synthetic resin lens according to item 1 in the range -