JPH0572401A - High refractive index plastic lens - Google Patents

Abstract

(57) [Abstract] [Purpose] Good moldability, transparency, dyeability, impact resistance, light weight, little yellowing during polymerization, and diethylene glycol bis ( (EN) Provided is a high refractive index plastic lens which can be manufactured by an allyl carbonate) polymer lens manufacturing facility and does not generate a harmful gas in a combustion process even when it becomes a waste. [Structure] Diallyl isophthalate, diethylene glycol bis (allyl carbonate), and diallyl terephthalate are copolymerized.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has good moldability, transparency, dyeability, and impact resistance, is lightweight, has little yellowing during polymerization, and does not require a new local exhaust facility. The present invention relates to a high-refractive-index plastic lens which can be manufactured in a bis (allyl carbonate) polymer lens manufacturing facility and does not generate harmful gas in combustion treatment even when it becomes waste.

[0002]

2. Description of the Related Art In recent years, plastic lenses have rapidly spread in place of glass lenses. This is because plastic lenses are lighter in weight than conventional glass lenses and are superior in impact resistance and workability, and because they are easy to dye, they are fashionable for spectacle lenses. There is also a point that the nature is enhanced.

Generally, the material used in the plastic lens is a transparent plastic composed of a homopolymer or a copolymer of diethylene glycol bis (allyl carbonate), methyl methacrylate, styrene, polycarbonate, etc. Particularly, a polymer of diethylene glycol bis (allyl carbonate), which is a thermosetting resin, is most suitable because it has excellent moldability, ball-scraping processability, polishing processability, heat resistance, dyeing property, chemical resistance, scratch resistance, and light resistance. It is supposed to be.

However, the polymer of diethylene glycol bis (allyl carbonate) has a refractive index of about 1.50, which is lower than the refractive index of about 1.523 of the conventional glass lens (crown glass). The concave lens has a drawback that the peripheral thickness of the lens is larger than that of the glass lens, and this has a problem that it becomes remarkable particularly when the power of the lens is large.

Therefore, in order to solve these problems, a high refractive index has been investigated for various plastic lens materials as well as diethylene glycol bis (allyl carbonate) polymers.

Particularly, like diethylene glycol bis (allyl carbonate), a lens obtained by polymerizing a monomer having an allyl group in the molecule is excellent in moldability. Many proposals have been made using a monomer having an allyl group in this molecule.

A high refractive index plastic lens made of a copolymer of diethylene glycol bis (allyl carbonate) and diallyl isophthalate is disclosed in JP-A-53-7787.
It is disclosed in the publication. A high refractive index plastic lens made of a copolymer of diethylene glycol bis (allyl carbonate), diallyl phthalate and a benzyl methacrylate or phenyl methacrylate derivative is disclosed in JP-B-57-42841. A high refractive index plastic lens made of a copolymer of diethylene glycol bis (allyl carbonate), benzyl methacrylate and diallyl isophthalate is disclosed in Japanese Patent Publication No. 2-39.
It is disclosed in Japanese Patent Publication No. 761. A high-refractive-index plastic lens made of a copolymer of diethylene glycol bis (allyl carbonate) and nuclear halogen-substituted diallyl phthalate is disclosed in JP-A-60-12503.

We also have a high refractive index plastic lens characterized by comprising a copolymer containing diallyl phthalate, diethylene glycol bis (allyl carbonate) and glycidyl methacrylate (JP-A-64-15).
No. 702), a diallyl ester having an aromatic ring, diethylene glycol bis (allyl carbonate), an allyl cinnamate or a copolymer with glycidyl cinnamate and a high refractive index plastic lens (JP-A-1-24444).
No. 01), a high-refractive-index plastic lens composed of a copolymer of a diallyl ester having an aromatic ring, diethylene glycol bis (allyl carbonate) and a maleic acid diester (JP-A-1-246501).

In general, in order to obtain a high refractive index plastic, it is known that the monomer contains an aromatic compound, contains halogen (excluding fluorine) and sulfur, contains a metal salt, and the like. , A method for obtaining a high refractive index plastic lens using an aromatic monomer substituted with halogen (excluding fluorine) (Japanese Patent Publication No. 3-19521, Japanese Patent Laid-Open No. 60-249101, etc.), It is disclosed in a sulfur-containing urethane high-refractive-index plastic lens obtained by polymerizing an aromatic-containing polyisocyanate and a polythiol having a sulfur atom introduced into the molecule (JP-A-63-46213, etc.).

[0010]

SUMMARY OF THE INVENTION In the above proposal for increasing the refractive index of a plastic lens material, Japanese Patent Laid-Open No. 53-53750 is proposed.
The copolymer of diethylene glycol bis (allyl carbonate) and diallyl isophthalate disclosed in JP-A-7787 is a monomer having an allyl group in its molecule, like a homopolymer of diethylene glycol bis (allyl carbonate). Since the polymerization reaction proceeds by itself, the moldability is good. Further, the refractive index can be changed to about 1.50 to 1.57. However, as the ratio of diallyl isophthalate in the copolymer increases and the refractive index increases, the yellowing at the time of polymerization becomes more severe as compared with the homopolymer of diethylene glycol bis (allyl carbonate), and it is practically used as an eyeglass lens. There is a problem that it becomes unbearable.

The copolymer of diethylene glycol bis (allyl carbonate), diallyl phthalate and benzyl methacrylate or phenyl methacrylate derivative disclosed in JP-B-57-42841 uses diallyl phthalate which is easily colored during polymerization. Therefore, diethylene glycol bis (allyl carbonate)
In comparison with the homopolymer of No. 1, there is a problem in that yellowing becomes more severe during polymerization, and it becomes difficult to put into practical use as an eyeglass lens. Further, the benzyl methacrylate or phenyl methacrylate derivative has a methacryl group, which has a higher radical polymerization reactivity than an allyl group, in the molecule. Therefore, as the ratio of benzyl methacrylate or phenyl methacrylate derivative in the copolymer increases, it becomes difficult to control the polymerization reaction rate. For this reason, a phenomenon in which the polymerized molded product peels from the mold appears, and the precision of the plastic lens decreases due to such a phenomenon, and the surface becomes uneven, so that a uniform refractive index cannot be obtained. Further, benzyl methacrylate and phenyl methacrylate are highly volatile liquids, and the health of workers may be impaired unless a local exhaust facility is provided.

Diethylene glycol bis (allyl carbonate) disclosed in Japanese Patent Publication No. 2-39761.
In the copolymer of benzyl methacrylate and diallyl isophthalate, it becomes difficult to control the polymerization reaction rate as the mixing ratio of benzyl methacrylate increases. Therefore, the phenomenon that the polymerized molded product peels from the mold appears, and the precision of the plastic lens decreases due to this phenomenon.
The surface becomes uneven and does not show a uniform refractive index. Further, as described above, benzyl methacrylate is a highly volatile liquid, and unless a local exhaust facility is provided, the health of workers may be impaired.

A copolymer of diethylene glycol bis (allyl carbonate) and a nuclear halogen-substituted diallyl phthalate disclosed in JP-A-60-12503, and JP-B-3-19521, JP-A-60-
In a method for obtaining a high refractive index plastic lens using an aromatic monomer substituted with halogen (excluding fluorine) disclosed in Japanese Patent Publication No. 249101, etc., by introducing a halogen element excluding fluorine into the molecule, Although the refractive index is increased, there is a problem that the specific gravity becomes large and the molded lens becomes heavy.

Further, a high refractive index plastic lens using an aromatic monomer substituted with halogen (excluding fluorine) disclosed in Japanese Patent Publication No. 3-19521 and Japanese Patent Laid-Open No. 60-249101. In the method of obtaining, the phenomenon that the volumetric shrinkage due to the polymerization is large, and therefore the polymerized molded product is peeled from the molding die, the precision of the plastic lens is lowered by such a phenomenon, and the surface becomes uneven,
It does not show a uniform refractive index. Further, strain and striae are likely to occur, the dyeability is inferior to that of diethylene glycol bis (allyl carbonate) homopolymer, and physical properties such as impact resistance are insufficient.

When the monomer contains a metal salt, the refractive index is increased as the content of the metal salt is increased, but the specific gravity is increased and the molded lens becomes heavy.

Recently, the treatment of plastic waste has become a problem. In the case of a thermoplastic resin, it can be reused by thermoforming. In the case of a plastic spectacle lens, since it is a thermosetting resin, it is difficult to recycle it.
Therefore, if the plastic spectacle lens becomes a waste, some treatment is required. A material formed only of carbon, hydrogen, and oxygen does not easily generate a toxic gas even when burned, and waste treatment is easy. However, chlorine-containing materials are difficult to process because they generate harmful hydrogen chloride gas and organic chlorine compound gas when burned. A material containing bromine is a flame-retardant material and has a drawback that it is difficult to process. Further, a material containing sulfur or nitrogen, such as a sulfur-containing urethane material disclosed in JP-A-63-46213, is difficult to process because it produces harmful sulfur oxide gas or nitrogen oxide gas when burned. ..

The present invention has been made in view of the above problems, and its object is to have good moldability, transparency, dyeability and impact resistance, and to be lightweight and to be used during polymerization. Less yellowing, can be manufactured with diethylene glycol bis (allyl carbonate) polymer lens manufacturing equipment without newly installing local exhaust equipment, etc. Even if it becomes waste, it does not generate harmful gas in combustion processing High In providing a plastic lens having a refractive index, it was found that a copolymer of diallyl isophthalate, diethylene glycol bis (allyl carbonate) and diallyl terephthalate as a third component is suitable, and the present invention is completed. It has come.

[0018]

The high refractive index plastic lens aimed at by the present invention can be obtained by copolymerizing diallyl isophthalate, diethylene glycol bis (allyl carbonate) and diallyl terephthalate.

The preferred amount of diallyl isophthalate used is 1
0 to 70% by weight, the preferred amount of diethylene glycol bis (allyl carbonate) used is 20 to 60% by weight, and the preferred amount of diallyl terephthalate used is 10 to 5%.
It is 0% by weight.

When the total amount of diallyl isophthalate and diallyl terephthalate used is less than 40% by weight, almost no increase in the refractive index is observed, and when it exceeds 80% by weight, the physical and chemical properties are poor, and it is used for spectacles. Not suitable as a lens. The amount of diallyl isophthalate used is 70% by weight
If it exceeds, the yellowing of the lens becomes noticeable. The usage of diethylene glycol bis (allyl carbonate) is 2
If the amount is less than 0% by weight, the obtained lens has poor physical and chemical properties such as surface hardness, impact resistance, and weather resistance. On the other hand, if it exceeds 60% by weight, the physical and chemical properties are improved, but the refractive index is low. Further, if the amount of diallyl terephthalate used is less than 10% by weight, yellowing of the lens becomes noticeable, while if it exceeds 50% by weight, the impact resistance of the obtained lens decreases, which is not preferable.

The high refractive index plastic lens of the present invention comprises
A mixture of diallyl isophthalate, diethylene glycol bis (allyl carbonate), diallyl terephthalate, and a polymerization initiator is poured into a mold assembled with a glass mold and a resin gasket, and heated or irradiated with ultraviolet light. It is obtained by curing.

The method for producing the plastic lens of the present invention is not particularly limited. For example, as a conventional casting molding method, the above monomers are mixed, and a preparation liquid prepared by adding a polymerization initiator used for polymerization and curing by heating is poured into a molding die, followed by heat treatment. Then, a method of polymerizing and curing is adopted. In such a casting molding method, a glass mold is used as the molding die, and the molding die is assembled with a resin gasket. After injecting the preparation liquid prepared as described above into this mold,
Seal the inlet and heat treat.

The polymerization initiator used for polymerization and curing by heating is not particularly limited, but typical examples thereof include diisopropyl peroxydicarbonate, di-secondary butyl peroxydicarbonate and di-2-.
Peroxydicarbonates such as ethylhexyl peroxydicarbonate, decanoyl peroxide, lauroyl peroxide, diacyl peroxides such as acetyl peroxide, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-
Examples thereof include alkyl oxyperesters such as ethyl hexanate and tertiary butyl peroxypivalate, and azo compounds such as azobisisobutyronitrile.
Although the amount of these polymerization initiators cannot be unconditionally limited,
Generally, it is 0.05 to 8% by weight, preferably 0.1 to 5% by weight, based on the total amount of each monomer.

A photopolymerization method can also be adopted as the method for producing the plastic lens of the present invention. In this case, a photosensitizer, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone, acetophenone, etc., is added to the mixed liquid of the respective monomers in an amount of 0. 01-8% by weight
Is added and polymerized and cured by irradiation with an ultraviolet lamp, a mercury lamp or the like. Here, it goes without saying that the above-mentioned polymerization initiator may be used in combination.

Further, in the case of preparing the preparation liquid by mixing the respective monomers, for the purpose of improving the moldability of the plastic lens and other characteristics, for example, an antistatic agent, an anti-coloring agent, an ultraviolet absorber, It is possible to add a release agent or the like without any problem.

The high refractive index plastic lens of the present invention thus obtained has antireflection, high hardness, and
Formation of a film by a known surface treatment or formation of a dyed layer by a dyeing treatment for imparting scratch resistance, antifogging property and the like can be suitably performed.

[0027]

EXAMPLES Next, the present invention will be described more specifically by way of examples. In the examples, the characteristics of the obtained high refractive index plastic lens were evaluated by the following test methods. (1) Refractive index Measured by an Abbe refractometer manufactured by Atago. (2) Transmittance The luminous transmittance measured by "ASC-Model 304" manufactured by Asahi Bunko Co., Ltd. was adopted. (3) Impact resistance For a lens with a center thickness of 1.3 mm and a frequency of -5 Dp, F
Tested according to DA standard. (4) Dyeability Dyeing agent (“Asahi Plassel Dyeing Agent AG-BG”, manufactured by Asahi Glass Co., Ltd.) 5.0 g, auxiliary agent (“AG coat dyeing auxiliary agent”,
Asahi Glass Co., Ltd.) A liquid prepared by dispersing 7.0 g in 1 l of water is 90
Heat to ℃ and immerse the lens in this dye bath for 3 minutes for CR
Those showing a dyeing property equivalent to that of the -39 homopolymer were accepted.

(5) Surface hardness JIS-691 using a Barcol hardness meter 934-1 type
It carried out according to 1. (6) Initial Coloring Visually, the case where the degree of coloring was mild was regarded as acceptable. (7) Separation Number of Molded Body and Mold After polymerizing 20 sheets using a lens mold having a frequency of −5.00, the state of separation between the mold and the molded body is observed with the naked eye to separate the mold from the molded body. The number of peeled sheets was defined as the number of peeled pieces. (8) Striae 100W ultra-high pressure mercury lamp irradiation device (Ushio Electric Co., Ltd., "U
The lens was held over the parallel rays emitted from the "I-100" type and the "HB-101A" type), and those in which no shadow appeared in the image of the lens projected on the white screen were regarded as acceptable. (9) Specific gravity It was measured using a specific gravity bottle.

Example 1 A mixed solution containing 30 parts by weight of diallyl isophthalate, 30 parts by weight of diethylene glycol bisallyl carbonate, 40 parts by weight of diallyl terephthalate, and 2.8 parts by weight of diisopropyl peroxydicarbonate was prepared. This mixed solution is poured into a mold assembled using two glass molds and a polyethylene gasket,
After sealing the inlet, the temperature rising heat treatment was performed from 30 ° C. to 95 ° C. for 18 hours. Then, the polymerization-cured lens was taken out from the mold and further heat-treated at 120 ° C. for 1 hour to obtain a lens having a frequency of −5.00 Dp. The properties of this lens were evaluated according to the test method described above. The characteristics are shown in Table 1.

Examples 2 to 5 Cast molding was carried out in the same manner as in Example 1 except that the raw material composition was changed to the amounts shown in Table 1 to obtain lenses. The characteristics of this lens were evaluated. The characteristics are shown in Table 1.

Comparative Examples 1 to 4 Cast lenses were molded in the same manner as in Example 1 except that the raw material composition was changed to the amounts shown in Table 1 to obtain lenses. The characteristics of this lens were evaluated. The characteristics are shown in Table 1.

[0032]

[Table 1]

The abbreviations and symbols in Table 1 have the following meanings. (1) The abbreviations in the raw material composition column have the following meanings. I: diallyl isophthalate, CR: diethylene glycol bis (allyl carbonate), T: diallyl terephthalate, IPP: diisopropyl peroxydicarbonate, ME
BPP: 2,2-bis (4-methacryloxyethoxy-3,5-dibromophenyl) propane, CSt: parachlorostyrene, St:
Styrene (2) The symbols in impact resistance, dyeability, coloring, and striae have the following meanings. ○: Pass, ×: Fail

As shown in Table 1, in Examples 1 to 5, the copolymers of diallyl isophthalate, diethylene glycol bis (allyl carbonate) and diallyl terephthalate had good moldability as a lens and had a high refractive index. It also satisfies the required characteristics. On the other hand, Comparative Example 1 is an example in which diallyl terephthalate is not contained, but the initial coloring is remarkable, which is not preferable as a lens. Further, Comparative Example 2 is an example in which diallyl isophthalate is not contained, but the impact resistance is insufficient, which is not preferable as a lens. Comparative Example 3 using a bromine-substituted aromatic monomer
In Nos. 4 to 4, the refractive index of the copolymer is increased, but the volume shrinkage due to the polymerization is large, which causes peeling from the mold, and striae are also observed. Impact resistance, dyeing It is clear that they are both unsuitable as a lens because of their poor performance.

[0035]

INDUSTRIAL APPLICABILITY The present invention solves various problems of the conventional high-refractive-index plastic lens, and particularly has an excellent effect that yellowing during polymerization is small and moldability and dyeability are good. .. Therefore, the effect that the center thickness and the edge thickness of the lens can be reduced as a plastic lens and the appearance is extremely excellent is also recognized.

Claims (2)

[Claims] 1. A high-refractive-index plastic lens containing a three-component copolymer of diallyl isophthalate, diethylene glycol bis (allyl carbonate) and diallyl terephthalate as a main component. 2. 10-70% by weight of diallyl isophthalate
And diethylene glycol bis (allyl carbonate) 2
High refractive index, characterized in that the main component is a three-component copolymer of 0 to 60% by weight and diallyl terephthalate 10 to 50% by weight, and that the molded product has a refractive index of 1.530 or more and less than 1.560. Rate plastic lens.