JPS6010201A - Plastic lens - Google Patents

Abstract

PURPOSE:To improve refractive index and optical characteristic by copolymerizing diallyl phthalate and benzyl methacrylate. CONSTITUTION:The diallyl phthalate 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 benzyl methacrylate monomer expressed by the general formula (II) [in which R1 is hydrogen or alkyl group, 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 is useful as a lens 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 and excellent optical properties. Conventionally, optical materials made of glass have excellent scratch resistance, but have drawbacks such as being heavy and easily broken. On the other hand, optical materials made of synthetic resins have advantages such as being light, hard to break, easily dyed, and have good fascination properties, and polymethyl methacrylate, diethylene glycol bis(allyl carbonate), etc. have already been used. 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. For 14' to 1'1+lenses, the edge thickness of the lens becomes significantly thicker, and 7I9
: There is a very strong demand for lenses that are beautiful. In addition, synthetic resins with high refractive index, such as polycarbonate and polystyrene,
It has problems with scratch resistance, beading workability, heat resistance, etc. In order to improve the above-mentioned drawbacks,
No. 47 proposes copolymerization of bisphenol A-based dimethacrylate and a styrene derivative or a phenyl methacrylate derivative. However, these polymers have poor weather resistance, are prone to yellowing, and have problems in heat resistance. Furthermore, in JP-A-57-104101, it was proposed to copolymerize bis-(oxyalkylene phenyl) diallyl carbonate, bis-(oxyalkylene phenyl) diallyl ether, a styrene derivative, and a naphthalene dicarboxylic acid allyl ester derivative. There is. However, these copolymers are difficult to dye and do not fully satisfy the quality required for lenses. As a result of intensive research to overcome the above-mentioned drawbacks, the present invention has been developed by copolymerizing diallyl phthalate alone and its derivatives with benzyl methacrylate alone and its derivatives in the presence of a radical polymerization initiator, thereby achieving a refractive index of n=1. It has a high refractive index of .57 or higher, as well as processability, heat resistance, dyeability, impact resistance, and easy moldability. This was done to realize a synthetic resin lens with excellent solvent resistance. 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 (I) and one or more monomers whose general formula is represented by °(IF). It can be obtained by copolymerizing a mixture of monomers containing 10 to 50% by weight of monomers in the presence of a radical polymerization initiator. 0 Early [In the formula, X is halogen excluding fluorine, a is 0. l. [An integer of 2.3 or 4] [In the formula, R1 is hydrogen or an alkyl group, X is a halogen excluding fluorine, and b is an integer of 0, 1, 2, 3, 4, or 5] Copolymerization of the lens of the present invention Of course, a synthetic resin that replaces inorganic glass must have a high refractive index, but it also has other characteristics such as processability. Because it has excellent impact resistance, dyeability, heat resistance, easy moldability, and solvent resistance, it can be used for almost the same purposes as inorganic glass. That is, it can be suitably used not only for lenses of cameras, glasses, etc., but also for prisms, etc. The present invention will be explained in detail below. The halogen of diallyl phthalate or benzyl methacrylate having a nuclear halogen-substituted aromatic ring used in the present invention is
Chlorine, bromine, and iodine other than fluorine can be used without particular limitation, but chlorine is preferred. It is bromine. The number of halogens contained in the aromatic ring is not particularly limited, and 1 to 4 halogens can be used.
0 Typical examples suitably used in the general formula (1) include 1,2,3.4te-1-lachlorodiallyl phthalate, 1,2.3trichlorodilyl phthalate, 1,
2.4 trichlordiallyl phthalate, 1.2 dichlorodiallyl phthalate 1-. 1゜3 dichlorodiallyl phthalate, 1,4 dichlordiallyl phthalate, 2,3 dichlordiallyl phthalate, chlordiallyl phthalate,
2-chlorodiallyl phthalate, 1,2,3.4-tetrabromodiallyl butarate, 1, 2.3)-ribrom diallyl phthalate, 1,2,41-ribrom diallyl phthalate, 1,2 dibrom diallyl phthalate, 1 .3 Dibrom diallyl phthalate, ■, 4 Dibrom diallyl phthalate 1-. 2,3-dibrom diallyl phthalate, prom-diallyl phthalate-1, 2-brom diallyl phthalate, etc. are used. On the other hand, examples of typical compounds suitably used in general formula (II) include penzylmethaglyre-1. 1.2,3.4 tetrachlorobenzyl methacrylate,
1,2.3 trichlorobenzyl methacrylate, 1,2
Dichlorobenzyl methacrylate, orthochlorobenzyl methacrylate, parachlorobenzyl methacrylate, methachlorobenzyl methacrylate +) I/-t, 1,2
, 3.4 Tetrabromobenzyl methacrylate,! ,2
．． 3 tribromobenzyl methacrylate-+-11,2 dibromobenzyl methacrylate-1-, orthobromobenzyl methacrylate, metabromobenzyl methacrylate,
Parabromobenzyl methacrylate and the like are used. Further, the radical polymerization initiator is not particularly limited and any known one can be used, but typical examples include methyl ethyl monoperoxide, cyclohexadamper peroxide, methyl cyclohexanone peroxide,
■、1. Bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, t
-Butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzine hydroperoxide, di-1-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, isobutyl peroxide, acetyl peroxide, lauroyl peroxide, benzoyl peroxide, octatool peroxide, diisopropyl peroxydecarbonate-1, di-2-ethylhexyl peroxydicarbonate, t-butylperoxyacetate].
tt-butylperoxybenzony is used. The preferred amount of diallylphthale-1 used in the present invention is 90% by weight, while the preferred amount of pendyl methacrylate and derivatives is 10% by weight.
It weighs 50 lbs. Use of diallyl phthalate alone and derivatives When n: exceeds 90 double nebulae, processability, dyeability, and refractive index. Although it improves solvent resistance, heat resistance, etc., it has poor impact resistance. Moldability becomes a problem. Furthermore, if the amount of diallylphtasy 1 or its simple substance and derivatives used is less than 50% by weight, the refractive index will be less than 1.57 and the heat resistance and solvent resistance will be particularly poor, making it unsuitable for eyeglass lenses, for example. do not have. The amount of benzyl methacrylate alone and derivatives used is 50
When the weight exceeds the weight, although impact resistance and moldability improve, the refractive index becomes 1.57 or less, and solvent resistance, heat resistance, workability, and dyeability decrease. In addition, when the amount of benzyl methacrylate alone and derivatives used is less than 10% by weight, processability and dyeability deteriorate. Although the refractive index, solvent resistance, heat resistance, etc. are improved, impact resistance and moldability become problems. The high refractive index synthetic resin lens of the present invention with a refractive index of 1.57 or more is produced by mixing a mixed solution of diallyl phthalate alone and its derivatives, benzyl methacrylate alone and its derivatives, and a polymerization initiator using a glass mold and a resin gasket. It is obtained by pouring it into an assembled mold and curing it using means such as heating or ultraviolet irradiation. The high refractive index synthetic resin lens of the present invention has a refractive index of 1.57.
As described above, it is transparent, can be dyed, and has excellent physicochemical properties such as processability, solvent resistance, moldability, TiWr properties, and heat resistance, and is particularly preferred as a synthetic resin lens for mm. be. Next, embodiments of the present invention will be described in more detail. Note that all parts in Examples and Comparative Examples are based on weight. Here, the test method for the measured values obtained in the Examples and Comparative Examples will be described below. Heat resistance: Heated at 120°C for 24 hours, coloring changed by 9 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 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 a lens whose total light transmittance was reduced to 50% in 30 minutes or less was evaluated as good. Moldability: Lenses with a smooth surface after molding were rated as good.

[Examples 1 to 3] Tetrachloro diallyl phthalate taglylate was mixed in the composition shown in Table 1, and 3% by weight of benzoyl peroxide as a radical polymerization initiator was added and thoroughly stirred. This mixed monomer is heated to 40°C and poured into a casting mold consisting of two glass molds and a polyethylene gasket, and polymerization is carried out at 50°C to 80°C using an electric furnace.
The temperature was increased linearly over 24 hours. After the polymerization was completed, the polymer was removed from the cast mold and its properties were 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 1.

[Comparative Example 3] 3 weight percent 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 casting mold and various properties were investigated. Table this result.
Shown in 1.

[Comparative Example 4] 3% by weight of benzoyl peroxide as a polymerization initiator was added to styrene monomer and thoroughly stirred for 41 minutes. This mixed slurry was poured into a casting mold made of a polyethylene force sket and two glass molds, and polymerized under the same temperature settings as in Examples 1 to 3. This polymer is removed from the casting mold,
Ift characteristics were investigated. The results are shown in Table 1.

[Examples 4 to 6] Copolymerization using tetrabrom diallyl phthalate as the first monomer and benzyl methacrylate as the second monomer instead of tetrachloro diallyl phthalate as the first monomer in Examples 1 to 3 Table 2 shows the properties of the molded lens. However, the polymerization conditions were the same as in Examples 1 to 3.

[Examples 7 to 9] Instead of benzyl methacrylate as the second monomer in Examples 1 to 3, tetrachlorbenzyl methacrylate was used as the second monomer, and tetrachlordiallyl was used as the first monomer. Table 3 shows the properties of the copolymerized lens with a lid-1 closure. Polymerization was carried out in the same manner as in Examples 1-3. The abbreviations in the following table are: CL 1) AP: Te 1 to Lachlorsialyl phthalate 1
~13zMA: Benzyl methacrylate 1 to CR-3 diethylene glycol bisubonate) PSL: Polystyrene Br4DAP: Te1 ~ brom diallyl phthalate) -C
14 I3zMA: Te1herachlorobenzyl methacrylate-1~ Indicates that ○ is excellent, Δ is slightly inferior, and ×11 does not meet the specifications at all.

Claims (1)

[Claims] A synthetic resin lens characterized in that the main component is a two-component copolymer of general formula (1) (IL) and general formula (■), which is copolymerized in the presence of a radical polymerization initiator. [In the formula, X is a halogen excluding fluorine, a is o, 1°2.3
or an integer of 4] [In the formula, R□ is hydrogen or an alkyl group, or a halogen excluding fluorine, and b is an integer of 0, 1, 2, 3.4, or 5] 2. 50 to 90 weight of general formula (1) %, and the synthetic resin lens according to claim 1, which contains general formula (II) in an amount of 10 to 50% and has a refractive index of 1.57 or more.