JPS6012502A - Plastic lens - Google Patents

Abstract

PURPOSE:To obtain a plastic lens having a high refractive index, superior workability, heat resistance, dyeability, shock resistance and solvent resistance by copolymerizing a liq. mixture contg. one or more kinds of monomers selected among diallyl phthalate and derivs. thereof and one or more kinds of monomers selected among allyl cinnamate and derivs. thereof in a specified ratio in the presence of a radical polymn. initiator. CONSTITUTION:The preferred amount of one or more kinds of monomers selected among diallyl phthalate and derivs. thereof represented by formula I (where X is halogen except fluorine, and a is an integer of 0-4) is 50-80wt% of the amount of one or more kinds of monomers selected among allyl cinnamate and derivs. thereof represented by formula II (where X is halogen except fluorine, and b is an integer of 0-5). In case of >80wt%, the shock resistance and moldability of the resulting copolymer are not satisfactorily improved. In case of <50wt%, the refractive index is reduced, and satisfactory solvent resistance and heat resistance are not always provided.

Description

[Detailed description of the invention]

The present invention relates to a synthetic resin lens that has a relatively high refractive index as a synthetic resin and has excellent optical properties. Conventionally, optical materials made of inorganic 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 the advantages of being light, hard to break, dyeable, and highly fashionable, and polymethylmethacrylate-1~, diethylene glycol bis(allyl carbonate), etc. are already in use. has been done. However, the optical material made of synthetic resin has a refractive index of about 1.4.
9, and when molded into a lens, it has to be thicker than inorganic glass. Especially with negative lenses, the edge thickness of the lens becomes significantly thicker,
There is a strong demand for thin lenses. In addition, high refractive index synthetic resin optical materials such as polycarbonate and polystyrene are
It has problems with scratch resistance, machinability, heat resistance, etc. In recent years, synthetic resin lenses with a high refractive index and improved solvent resistance, beading properties, scratch resistance, etc. have been proposed in order to improve the drawbacks of the synthetic resin optical materials mentioned above. There are problems with weather resistance, dyeability, etc., and no lens has yet appeared that fully satisfies the quality required for a lens. As a result of extensive research in order to overcome the above-mentioned deficiencies, the present invention has been made by copolymerizing diallylphtasy 1 to its simple substance and derivatives with allyl cinnamate 71 and its derivatives in the presence of a radical polymerization initiator. This was done to realize a refractive resin lens. The copolymer of the lens according to the present invention contains 50 to 80% by weight of one or more diallylphtasy monomers and derivatives having the general formula (I) and having the general formula (IT). One or more allyl cinnamate monomers and derivatives
It can be obtained by copolymerizing a monomer mixture containing 0 to 50% by weight in the presence of a radical polymerization initiator. [In the formula, X is a halogen excluding fluorine, a is o, and ■. An integer of 2.3 or 4] [In the formula, X is a halogen excluding fluorine, b is o, and ■. 2.3.4 or an integer of 5] The obtained copolymer has a high refractive index and is excellent in processability, impact resistance, solvent resistance, and dyeing properties, so it has almost the same properties as inorganic glass. Can be used for any purpose. 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. As the diary 3-luphthalate monomers and derivatives represented by the general formula N) used in the present invention, known ones can be used, including those with nuclear halogen substitution. As the halogen, chlorine, bromine, and iodine other than fluorine can be used without particular limitation, but chlorine and bromine are preferable. Further, the number of halogens is not particularly limited, and 1 to 4 halogens can be used. Typical examples that are preferably used include chlordiallyl orthophthalate, chlordi≠dalyl isotalate, bromdiallyl orthophthalate, bromdiallyl isophthalate, dichlordiallyl orthophthalate,
dichlordiallylisophthalate, dibromdiallylpurusophthalate, dibromdiallyl isophthalate, trichlordiallyl orthophthalate, trichlordiallyl orthophthalate, tribromdiallyl 1rusophthalate,
Tribrom diallyl isophthalate, tetrachloro diallyl isophthalate, tetrachloro diallyl isophthalate, tetrabrom diallyl orthophthalate, tetrabrom diallyl isophthalate, etc. are used. 14= Also, as the allyl cinnamate monomer and derivatives represented by the general formula (TI) used in the present invention, known monomers and derivatives including nuclear halogen substituted products can be used. Halogens include chlorine and bromine, excluding fluorine. Iodine can be used, but chlorine and bromine are preferably used. The number of halogens is also not limited, and includes 1 to allyl cinnamate, allyl bromine cinnamate, dichloro allyl 1-f cinnamate, allyl dibromo cinnamate, 1-lychlor allyl cinnamate, 1 to allyl ribo cinnamate, tetra Allyl chlorocinnamate, allyl tetrabromocinnamate, allyl pentachlorcinnamate, allyl pentabromocinnamate, etc. are used. The amount of diallylphthale-1-monomer and derivative represented by general formula (1) used in the present invention to be used is 50 to 80% by weight is preferred. Diallylphtasy 1 - The amount of monomer and derivative used is 80
If the amount exceeds 1% by weight, the improvement in 1# impact resistance and moldability will not be sufficient, which will cause problems. Furthermore, if the amount of the diallyl phthalate monomer and derivative used is less than 50% by weight, the refractive index will be lowered and solvent resistance and heat resistance will become problematic, making it undesirable as a lens for spectacles, for example. Further, the radical polymerization initiator is not particularly limited and any known one can be used, but a radical polymerization initiator suitable for diallylphthale-1 is preferably used. Typical examples include ■, 1-bis(t-butylperoxy)/
3,3.5-trimethylcyclohexane, 2,2-bis(t-butylperoxy)octane, dicumyl peroxide, hexane, benzoyl peroxide, t
-butylperoxy(2-ethylhexanony-1-),
T-butyl peroxybenzoate is used. The amount of radical polymerization initiator used depends on the polymerization type 9 polymerization conditions,
Types of copolymer components 9 It cannot be specifically limited depending on the composition ratio, etc., but generally it is 1.0 to 10% by weight based on the total monomers.
It is suitable to use within the range of . The copolymerization method η of monosubstrates and derivatives of diallylphthalene 1~ represented by the general formula (I) and monomers and derivatives of allyl 1-inamate represented by the general formula (TI) is known. Chromolymerization method can be adopted. In the high refractive index synthetic resin lens of the present invention having a refractive index of 1.57 or more, the mixed liquid of both Qi polymers is placed between a glass mold held by a resin gasket 1 or a base 13. It can be obtained by injecting and curing using means such as heating or ultraviolet irradiation. In this case, it is also possible to prepolymerize each liquid alone or in a mixture by heating or the like before pouring into the mold to increase the viscosity of the mixture, and then perform casting polymerization. The high refractive index synthetic resin lens of the present invention has a refractive index of 1.57.
It is durable, dyeable, and impact resistant. It has excellent physical properties such as solvent resistance, processability, and moldability, and is particularly preferred as a lens for EI SR. In order to explain the present invention more specifically, Examples and Comparative Examples are shown below. In addition, the test method of the 1-Ware characteristic value in Examples and Comparative Examples is shown below. 7- 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, swelling, 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. Workability: Those that could be processed with diamond foil were rated as good. Refractive index: Measured by the minimum deviation angle method. Dyeability: A molded lens was immersed in a dyeing bath, and those whose total light transmittance was reduced to 50% in 30 minutes or less were rated as good. Moldability: Lens surfaces that were smooth and free from distortion after molding were rated as good. [Examples 1 to 3] Tetrachloro diallyl phthalate and allyl cinnamate were mixed in the proportions shown in Table 1, and the amount of radical polymerization was 8.3% of benzoyl peroxide was added as an initiator and thoroughly stirred at 60°. The temperature was raised to C. Add this mixture to 2
The mixture was poured into a mold consisting of a glass mold and a gasket I- made of polyethylene, and cast polymerization was carried out. Polymerization was carried out using an air heating furnace, and the temperature was gradually increased from 60°C to 90°C in 15 hours, and then further heated at 90°C for 10
Polymerized for hours. After the polymerization was completed, the mold was taken out from the air oven, slowly cooled to room temperature, and then molded into a female mold from a glass mold.The physical properties of the copolymer were measured and are shown in Table 1.

[Ratio 11℃M Examples 1-2] "X 1M" Tetrachloro diallyl phthalate and allyl cinnamate were mixed in the proportions shown in Table 1 in the same column as Examples 1-3, and polymerization was carried out in the same manner as in Examples 1-3. The results are shown in Table 1.

[Comparative Examples 3 to 4] Polymerization of only each monomer of Examples 1 to 3 was carried out in Examples 1 to 3.
Polymerization was carried out in the same manner. The results are shown in Table-1.

Examples 4 to 6 Polymerization was carried out in the same manner as in Examples 1 to 3, using allyl chlorocinnamate in place of allyl cinnamate in Examples 1 to 3. The results are shown in Table-2.

[Examples 7 to 9] Terabrom diallyl phthalate-1 was used instead of tetrachloro diallyl phthalate in Examples 1 to 3, and Examples 1 to 9 were
Polymerization was carried out in the same manner as in 3. The results are shown in Table-2.

[Comparative Example 5] Diethylene glycol bisallyl carbonate-1~(Wl
iProduct name CR39) Isoprobil baroxydicarbo was added to the monomer as a radical polymerization initiator. Table 2 of the results
It was shown to.

[Comparative Example 6] Styrene monomer as a radical polymerization initiator at 80°C
Polymerization was carried out by linear warming for 24 hours until
'Il! +'i Ri na Jl, 2. -2.

[Comparative Example 7] Injection molding machine using polycarbonate resin material. 1. Injection molding was performed using a mold for lenses at a resin temperature of 300°C, a mold temperature of 120°C, and a holding pressure of DOOKB/cm2, and after removal from the mold, annealing was performed at 120°C for 1 hour. The results are shown in Table-2. The symbols in the table below are as follows. C14DAP: Tetrachlorodiallyl phthalate-1
1r41) AP: Te1-rabrom diallylphthale 1
-〇: Allyl cinnamate C], AC: Allyl para-chlorocinnamate r, rt-3
9: Diethyl 1 non-glycol bisallyl carbonate St: Styrene PC: Polycarbonate 1~ In addition, the symbols for characteristic evaluation in the table have the following meanings.

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 (TI), which is copolymerized in the presence of a radical polymerization initiator. lens. [In the formula, X is a halogen excluding fluorine, a is o, and ■. Integer of 2.3 or 4] [Halogen in the formula or excluding fluorine, b is o, 1°2.3
．． an integer of 4 or 5] 2. Claims: a refractive index of 1.57 or more containing general formula CI) in a range of 50 to 80% by weight and containing general formula (II) in a range of 20 to 50% by weight Synthetic resin lens according to item 1.