JPS6180201A - Synthetic resin lens - Google Patents

Abstract

PURPOSE:To improve the adhesiveness of an antireflection film and to improve the yield thereof by copolymerizing at least one kind of polymerizable monomer which yields a transparent polymer and org. phosphorus compd. having double bonds copolymerizable therewith. CONSTITUTION:The lens is formed by copolymerizing the polymerizable monomer which yields a transparent polymer, for example, diethylene glycol bis-allyl carbonate and the org. phosphorus compd. having double bonds copolymerizable therewith, for example, a phosphorus compd. having (meth)acryloyl group and (meth)acryloyl oxy group. The org. phosphorus compd. having double bonds is incorporated into the polymerizable monomer preferably at 0.5-10wt%, more preferably 1-5wt% by the weight thereof. The improvement in the adhesiveness of the antireflection film is not admitted if the proportion is less than said range and the moldability of the lens by the copolymerization is adversely affected if the proportion exceeds said range. The adhesiveness is thus improved and since the need for a stage for forming a precoat layer is eliminated, the cause for the decrease in the yield is eliminated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a synthetic resin lens, and particularly to a synthetic resin lens with excellent adhesion of an antireflection film formed on the lens surface, and relates to a spectacle lens, It is used in optical lenses such as camera lenses.

[Conventional technology]

゛ In general, transparent synthetic resins such as poly(diethylene glycol bisallyl carbonate), polymethyl methacrylate, polycarbonate, polystyrene, polyvinyl chloride, etc., in addition to transparency, have their own properties such as quantity, ease of processing, and resistance to pinching. It is applied to the minute hand of various optical components by taking advantage of its advantages such as flexibility. Among optical components, the use of synthetic resin lenses in particular is expanding to include, for example, eyeglass lenses, camera lenses, projector lenses, Fresnel lenses, automobile headlight lenses, and prisms.

For synthetic resin lenses, polymethyl methacrylate is used as a material for sunglasses because it is easily mass-produced, and polycarbonate is used for safety glasses such as caps because of its excellent impact resistance. Poly(diethylene glycol bisallyl) is used as a material for synthetic resin lenses. Carbonate) is mainly used in eyeglass lenses for vision correction due to its good transparency. However, not only lenses made of transparent synthetic resin materials but also glass lenses have light reflection on the lens surface, which reduces the light transmittance, causing the brightness to be flat when viewed through the lens, and ghosts. A reflex called ``me'' appears. For this reason, an antireflection film is usually provided on the lens surface in order to reduce reflection on the lens surface and increase light transmittance. The anti-reflection coating is
For example, Mg'F cave, LiF.

Tbl! '4 + Inorganic fluorides such as cryolite, or gold i*m oxides such as 810, Rlot, ZrO2, 0eO1, WOI, etc., are deposited on the lens surface in a single layer or in multiple layers using methods such as Makabe vapor deposition and Yasbuttering. A coating is formed.

Synthetic resin lenses have inferior heat resistance compared to glass lenses when forming an anti-reflection film on their surfaces.
There are restrictions on the anti-reflective film materials and formation methods, and the properties of the anti-reflective film are not necessarily satisfied in terms of adhesion to the lens surface or durability of the anti-reflective film. There is a problem in that the anti-reflection film peels off when used for long periods. For these reasons, various proposals have been made regarding means for forming an antireflection film on the surface of a synthetic resin lens. For example, the adhesion of the anti-reflection film can be improved by chemically treating the surface of a synthetic resin lens with an alkaline aqueous solution, acid, amine, etc., or by physical treatment using plasma, sputter etching, corona discharge, etc. The method is well known.

In addition, as a method of forming a single layer of primer on the surface of a synthetic resin lens and forming an antireflection film thereon, a silane coupling agent, a melamine resin, etc. have been proposed as the material for the single layer of primer, and the applicant of the present invention Also published in 1983-1989
No. 2.54 proposes a single-layer primer material made of modified melamine resin.

[Problem to be solved by the invention]

Chemical or physical treatment of the lens surface in forming an anti-reflection film on the surface of a synthetic resin lens requires additional steps before and after the treatment, and physical treatment requires expensive equipment. It is inevitable that there will be disadvantages in terms of cost, such as the need for In addition, the formation of a single layer of primer leads to a decrease in yield in the formation process, and depending on the type of primer material, the formed single layer of primer deteriorates over time, and the adhesion of the anti-reflection film also decreases. However, there is a problem in that the film peels off.

[Means to solve the problem]

In view of the above-mentioned problems, the present inventor has developed a method for forming an anti-reflection film on a synthetic resin lens, in which the lens surface is specially treated to improve the adhesion between the lens surface and the anti-reflection film.
In order to solve the above problems by modifying the synthetic resin lens base material without forming a single layer of primer, various research and studies have been carried out.
We have considered this. As a result, the surface of the lens is made of a copolymer made by copolymerizing a monomer that provides a transparent polymer suitable for a synthetic resin lens and an organic phosphorus compound having a specific double bond that can be copolymerized with the monomer. The present invention was completed based on the knowledge that the formed antireflection film has excellent adhesion and does not impair transparency, mechanical properties, etc.

That is, the present invention provides a synthetic resin lens that is made of a copolymer of at least one polymerizable monomer that provides a transparent polymer and an organic phosphorus compound having a double bond that can be copolymerized with the monomer. The present invention provides a synthetic resin lens having an anti-reflection film with excellent adhesion.

In the present invention, the polymerizable monomer that provides the transparent polymer is not particularly limited as long as it is a well-known type for lenses and is compatible with and copolymerizes with organic phosphorus compounds having double bonds. . In addition, if the prepolymer is in the form of a silt and an organic phosphorus compound having a double bond is dissolved, the polymerization proceeds through a copolymerization process to obtain a copolymer and a lens can be molded. Can be used.

A polymerizable monomer that provides a transparent polymer is diethylene glycol bisallyl carbonate.

Diallyl phthalate, methyl methacrylate.

Methyl acrylate, cyclohexyl methacrylate,
2-Hydroxyethyl methacrylate.

2-Hydroxyethyl acrylate), 2,2-His(4
-methacryloyloxyethoxyphenyl)propane,
Styrene, α-methylstyrene.

Examples include chlorstyrene. Such monomers may be a mixture of two or more types.

Among the monomers exemplified above, diethylene glycol bisallyl carbonate is the most preferred one in terms of compatibility with organic phosphorus compounds having double bonds, transparency as a copolymer lens, visibility, mechanical strength, etc. can be mentioned. Moreover, a synthetic resin lens made by copolymerizing diethylene glycol bisallyl carbonate and an organic phosphorus compound having a double bond has particularly excellent adhesion of the antireflection film formed on its surface. (below,
The polymerizable monomer that provides the transparent polymer is diethylene glycol pisallyl carbonate) K. ) In the present invention, the organic phosphorus compound having a double bond is preferably a phosphorus compound having a (meth)acryloyl group and a (meth)acryloyloxy group, and the reaction of a (meth)acryloyl group, a (meth)acryloyloxy group, etc. The presence of a sexual group is required. Examples of such phosphorus compounds include 2-
Acryloylethyl acid phosphate, 2-methacryloylethyl acid phosphate.

2-acryloyloxyethyl acid phosphate),
2-methacryloyloxyethyl acid phosphate, tris(2-acryloyloxyethyl) phosphate, tris(2-methacryloyloxyethyl) phosphate, diphenyl-2-acryloyl ethyl phosphate, diphenyl-2-methacryloyl ethyl phosphate, diphenyl-2-acryloyl oxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, diptyl-2-acryloyl ethyl phosphate, diptyl-2-methacryloyl ethyl phosphate, diptyl-2-acryloyloxyethyl phosphate, diptyl-2-methacryloyloxyethyl phosphate), Examples include dioctyl-2-acryloyloxyethyl phosphate and dioctyl-2-methacryloyloxyphosphate. The surface of a lens formed by copolymerizing diethylene glycol bisallyl carbonate and the phosphorized/metallic material mentioned above is suitable for forming an antireflection film, and the formed antireflection film, especially metal oxide-based antireflection IE, is suitable for forming an antireflection film. The film has excellent adhesion. The reason for this improvement in adhesion is not clear, but organic phosphorus molecules exist extremely uniformly on the lens surface and in the thickness direction, and this increases the affinity of anti-reflective coating materials, especially metal oxide-based anti-reflective coating materials. It is assumed that this will improve the performance.

In the synthetic resin lens according to the present invention, it is preferable that the organic phosphorus compound having a copolymerizable double bond is copolymerized in a ratio of 0.5 to 10 times the polymerizable monomer. The weight ratio is more preferably 1 to 5. If the amount is less than this range, the adhesion of the antireflection film will not be improved, while if it exceeds this range, the moldability of lenses due to copolymerization will be adversely affected.

The copolymerization method in the present invention is carried out by radical polymerization. In such polymerization, the suitable heavy metal initiator is diisopropyl peroxycarbonate, which is commonly used in the polymerization of diethylene glycol bisallyl carbonate; carbonate, di-n-propyloxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate,
peroxycarbonates such as bis(4-tart-phthylcyclohexyl)peroxycycarbonate), tert-butylperoxyisopropyl carbonate,
Alternatively, peroxides such as benzoyl peroxide and lauryl peroxide can be used. Such a polymerization initiator is usually used in an amount of 1 to 51 t relative to the monomer.
Although S is added, an amount within this range is sufficient in the present invention.

In the synthetic resin lens of the present invention, additives,
For example, benzophenone tetraconductors such as 2,4-dihydroxybenzophenone, 2-hydroquine-4-methoxybenzophenone, and 2-hydroxy-4-octoxybenzophenone as UV absorbers, pensitoazole substituted products, and hinderers as oxidation-resistant agents. Dophenol, hindered amine, etc., quaternary ammonium salt as an antistatic agent, nonionic surfactant, etc. may be blended.

In the present invention, the method for molding lenses by copolymerization is not particularly limited, although a common casting method is employed. A mixed solution prepared by adding and dissolving a monomer polymerization initiator, which is usually in liquid form, is injected into a mold, ie, a cell, into which a glass mold has been previously installed using a gasket, and is heated and polymerized. Molding method of the present invention
This is carried out by injecting into a cell a mixture of diethylene glycol bisallyl carbonate, a required amount of an organic phosphorus compound having a double bond, and a polymerization initiator, and heating the mixture. The heating temperature as a polymerization condition varies depending on the type of monomer used, but in the case of diethylene glycol bisallyl carbonate, the temperature is gradually raised from room temperature of about 25°C to about 95°C, and the time required is 16°C. It is appropriate to allow the polymerization to complete over a period of ˜40 hours. After cooling, the lens molded from the cell is dammed, and an antireflection film is immediately formed. If necessary, an antireflection film is formed after a cleaning process.

Typical methods for forming antireflection films on synthetic resin lenses include vacuum evaporation, ion blating, OVD, and sputtering, but the synthetic resin lenses of the present invention can be formed using any of these methods. Can be adopted.

Anti-reflective coating materials are typically eg silica.

Alumina, zirconia, magnesium oxide, cerium oxide, beryllium oxide, indium #.

Metal oxides such as hafnium oxide; or fluorides such as magnesium fluoride, cerium fluoride, sodium fluoride, lithium fluoride, and sodium fluoride are used; Such antireflective coating materials can be used. Further, a small amount of gold, silver, copper, chromium, aluminum, etc. may be added to the above-mentioned antireflection film material to color it. Anti-reflective coatings made of the above anti-reflective coating materials are usually formed by laminating several types of anti-reflective coating materials to form a multilayer structure with a specific film thickness, or by forming one specific type into a single-layer structure. However, the synthetic resin lens of the present invention may be of any type. Among antireflection coating materials, 5102 has the most remarkable effect of improving adhesion through chemical bonding with phosphorus molecules that are homogeneously present in the lens. For example, BiO! , Zr(h) alternately formed to have a thickness of 100%, the anti-reflection film has excellent adhesion and durability as well as anti-reflection performance.
Even in forced environmental tests, no peeling or occurrence of electrical components was observed.

〔Example〕

EXAMPLES The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Diethylene glycol bisalicarbonate (product of Asahi Pen Chemical Co., Ltd.) 1000F was used as a polymerizable monomer to give a transparent polymer, and diphenyl-2-acryloyloxyethyl phosphate (manufactured by Daiwa Co., Ltd.) was added as an organic phosphorus compound having a double bond. Irukagaku Kogyo product: AR-6320f
Add diisopropyl peroxydicarbonate (pyrrole PP) as a polymerization initiator and mix well.
: Nippon Oil & Fats Co., Ltd. product) 34.5f was added and dissolved to prepare a transparent liquid mixture. This mixture was injected into a lens molding cell formed by a glass mold and gasket, maintained at 33°C for 1.5 hours, and then heated from 33°C to 6°C.
℃ for 14 hours, and 63℃ for 45 minutes.
C. to 93.degree. C. for 45 minutes and then to 93.degree. C. for 1 hour, maintaining and increasing the temperature at each temperature was repeated, and it took a total of about 18 hours to complete one heat cycle. Next, the lens was allowed to cool to room temperature, and the lens was released from the mold using a conventional method. No difference in mold releasability was observed between the lens and the homopolymerized lens of diethylene glycol bisallyl carbonate. The lens thus formed has a diopter of 0.00, a thickness of approximately 2.5 tm at the center, and is completely transparent.
The nighttime transmittance measured by onmLnsp-o:t was 93 inches.

The obtained lens was washed with a neutral detergent solution, tap water, distilled water,
After sequentially performing ultrasonic cleaning in a bath filled with inpropyl alcohol, it was dried (17), inserted into a vacuum oven, and I
X 10 = Torr, substrate temperature 60-100°C,
The film thickness of the residual oxide is 10g per day from the lens surface side O,0
45, Zr0z O,032, SingO,010,Z
rO* 0.0B6.81nz O,089 (each μm
) A vacuum evaporation process was performed to form an anti-reflection film to a designed value.

A lens with anti-reflection coating was placed in a needle groove tank maintained at a temperature of 50℃ and a relative immersion degree of 95℃ for a moisture resistance test.
After holding for 0 days, the adhesion of the anti-reflection 1F film was tested by Goban 1 test, i.e., cut into squares at 1% intervals.
4 (Evaluation was made by a peel test method using a 4-square adhesive tape.

Table 1 shows the test results for both surfaces of the lens with concave and convex surfaces according to the goblin test. As shown in Table 1, the convex surface is 100/1
No peeling was observed in oo.

Examples 2 to 3 The diphenyl 2-acryloyloxyethyl phosphate of the organic phosphorus compound having a double bond in Example 1 was replaced with diphenyl 2-methacryloyloxyethyl phosphate [(&) Oiri Kagaku Kogyo product] and 2-acryloyloxyethyl A lens with an antireflection film was obtained by molding in the same manner as in Example 1, except that acid phosphate (P-mu, a product of Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) was used.

The obtained lens was tested for moisture resistance in the same manner as in Example 1, and then subjected to a cross-over test.

Table 1 shows the test results of the concave and convex surfaces of the lens using the goblin test, and no peeling was observed on the convex surface.

Example 4 Diethylene glycol bisallyl carbonate) 90 (l
100f of diallyl freter) was mixed with 20% of diphenyl 2-acryloyloxyethyl phosphate.
t, diisopropyl peroxydicarbonate 30f1
Add 10f of tart-butyl peroxide and 0.22 g of 2-hydroxy-4-methoxybenzophenone as an ultraviolet absorber and dissolve the transparent mixture.
Manufactured. This mixed solution was injected into a lens molding cell formed by a glass mold and a gasket, and heated to 33°C.
The temperature was maintained at
The temperature was maintained and raised repeatedly for 45 minutes at 93° C. and 1 hour at 93° C., and it took about 47 hours in total to complete the thermal polymerization. Next, the lens was allowed to cool to room temperature and released from the mold using a conventional method. No difference was observed in mold releasability from Examples 1 to 3,
A lens with a night transmittance of 92 cm was obtained using a similar shape.

The obtained lens was treated with an antireflection film in the same manner as in Example 1 to form an antireflection film, and then a cross-over test after moisture resistance was performed.

Table 1 shows the test results of the concave and convex surfaces of the lens using the goblin test, and no peeling was expected on the convex surface.

Comparative Example 1 A lens having an anti-reflection film chisel was obtained by molding in the same manner as in Example 1 except that diphenyl 2-acrylyloxyethyl phosphate was treated with energizer. The obtained lens was subjected to a thy resistance test in the same manner as in Example 1, and then to a goblin eye test.

Table 1 shows the test results for both sides of the uneven surface using the goblin test, and it was almost completely peeled off.

Comparative Example 2 A condensate obtained by precondensing a precombined product of fine particulate silica and diol with alkyl ether methylol melamine was applied as a primer layer to the surface of a lens molded in the same manner as in Example 1. After forming a single layer of primer made of a back melamine resin diluted with butanediol to a solid content of 20 parts, an antireflection film was formed on the primer layer in the same manner as in Example 1. The obtained lens was subjected to a moisture resistance test in the same manner as in Example 1, and then a cross-over test was carried out.The test results for both the concave and convex surfaces of the lens are shown in Table 1. Most of the lenses were peeled off on both the concave and convex surfaces.

〔Effect of the invention〕

The synthetic resin lens of the present invention is a synthetic resin lens obtained by copolymerizing at least one kind of polymerizable monomer that provides a transparent polymer and an organic phosphorus compound having a double bond. The formed anti-reflection film has excellent adhesion and therefore has the effect of being excellent in durability. In particular, in the past, it was necessary to perform a special treatment on the lens surface or to form a precoat layer, and the occurrence of defects caused by such a process caused a decrease in yield, but the synthetic resin lens of the present invention Since such a step is not required, the cause of a decrease in yield is eliminated, and it is recognized that it is advantageous in terms of control.

Claims (4)

[Claims] (1) A synthetic resin lens, characterized in that the lens is made of a copolymer of at least one polymerizable monomer that provides a transparent polymer and an organic phosphorus compound having a double bond that can be copolymerized with the monomer. Synthetic resin lenses with excellent anti-reflection film adhesion. (2) The synthetic resin lens according to claim 1, wherein the organic phosphorus compound having a double bond is a phosphorus compound having a (meth)acryloyl group and a (meth)acryloyloxy group. (3) The synthetic resin according to claim 1, which is a copolymer containing 0.5 to 10% by weight of an organic phosphorus compound having a double bond based on the polymerizable monomer. made lens. (4) The synthetic resin lens according to claim 1, wherein the polymerizable monomer is diethylene glycol bisallyl carbonate.