JPS61162002A - Composition body of high refractive index plastic lens - Google Patents

Abstract

PURPOSE:To provide a lens which is highly resistant to weather and light and is effective particularly for decreasing the yellowing when irradiated with UV rays by coating a transparent film having a specific value or below of coeff. of oxygen permeability on the surface of the high refractive index resin lens having an arom. ring at the main chain and/or side chain. CONSTITUTION:The composite body is obtd. by coating the transparent film consisting mainly of the org. polymer having <=100X10<-12>cm<3>.cm/cm<2>.sec.cmHg coefft. of oxygen permeability on the surface of the high refractive index resin lens having the arom. ring at the main chain and/or side chain. PVA, polyvinyl acetate and cellulose are preferably used for the ease of the film formation as the more specific examples of the transparent material to be used. There is substantially no effect of the coating and the improvement in the light resistance is not expected if the coefft. of the oxygen permeability of the org. polymer used for coating exceeds 100X10<-12>cm<3>.cm/cm<2>.sec.cmHg. The transparent film having <=50X10<-12>cm<3>.cm/cm<2>.sec.cmHg is further preferable in order to provide the effect with the thinnest possible film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a high refractive index plastic lens for optical use such as an eyeglass lens or a camera lens, which has excellent light control properties.

[Conventional technology]

Plastic lenses have excellent impact resistance and transparency, are lightweight, and are easy to dye.
Demand has increased in recent years.

However, on the other hand, plastic lenses generally have lower mechanical strength than inorganic glass lenses, and measures such as increasing the center thickness of the lens have been taken to compensate for this drawback. Furthermore, since plastic has a lower refractive index than inorganic glass, it has a serious drawback in that, especially in negative altitude number lenses, the edges become extremely thick, resulting in poor appearance and a tendency for people to avoid wearing them. In recent years, increasing the refractive index of plastic base materials has been studied for the purpose of these improvements, and many proposals have been made (Japanese Patent Publication No. 58-17527).
No. 14449, Japanese Patent Publication No. 58-14449, Japanese Unexamined Patent Publication No. 1987-14449
28117, JP 57-54901, JP 57-102601, JP 57-1049
No. 01, JP-A-58-18602, JP-A-Sho. 5
Publication No. 8-72101 9% Publication No. 87124/1983.

JP-A-59-95708, JP-A-59-9610
Publication No. 9).

As is clear from such prior art, aromatic rings are introduced into the main chain and/or side chains of resins for plastic lenses in order to increase the refractive index of the resin, and fluorine is removed from the aromatic rings in order to further improve the refractive index. Introduction of halogen groups has been made. Although these resins have a high refractive index, they have the disadvantage that they become colored during one polymerization, or that they become yellow when exposed to ultraviolet light after nine polymerizations. As a means for preventing this coloring, a known method is used in which additives such as ultraviolet absorbers, antioxidants, coloring inhibitors, and fluorescent dyes are added to the sinter. Improvements to the resin itself have also been proposed. For example, copolymers of esters of nuclear halogen-substituted benzene dicarboxylic acids and resins with a refractive index of 1.55 or more (Japanese Patent Application Laid-open No. 1987-8709), bisallyl carbonate or β-methylallyl carbonate, and copolymers with a refractive index of copolymer with a resin having a value of 1.55 or more (JP-A-59-1999)
Publication No. 8710).

[Problem that the invention seeks to solve]

The improvement of light distribution using various additives such as ultraviolet absorbers and antioxidants in the conventional technology has limitations in the amount of addition, the influence of the additives on the coloring double polymerization, the decrease in dyeability, or the possibility of dye There are problems such as accelerated fading. Furthermore, there are limits to the improvement of the base material itself, and a fully satisfactory product has not been obtained.

[Means to solve the problem]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have arrived at the present invention described below.

That is, 1 the present invention provides a surface of a high refractive index resin lens having an aromatic ring in the main chain and/or side chain with an oxygen permeability coefficient of i.
oo x 10 cs-am/cs-gec-cw
+) The present invention relates to a high refractive index plastic lens composite body coated with a transparent film mainly composed of an organic polymer weighing 1 g or less.

The high refractive index resin having an aromatic ring in its main chain and/or side chain in the present invention is, for example, a polymer of a styrene derivative represented by the following general formula (1).

(Here, R' excludes hydrogen and fluorine)\logen group.

Represents a methyl group, ethyl group, methoxy group, amino group, nitro group, phenyl group, phenoxy group, n is an integer from a to 5, and when n220 R1 may be the same or different) , polymers of phenol or various substituted phenols, or (meth)acrylic esters of their ethylene oxide or propylene oxide adducts, bisphenols or substituted bisphenols, or (meth)acrylic esters of their ethylene oxide or propylene oxide adducts, Polymers of di(meth)acrylic esters, polymers of addition reaction products of mono(meth)acrylic esters having hydroxyl groups and various incyanate compounds, and (meth)acrylic esters having a biphenyl skeleton. or polymers of di(meth)acrylic esters, polymers of (meth)acrylic esters of benzyl alcohol or various substituted benzyl alcohols, polymers of divinylbenzene or various substituted divinylbenzenes, and even bisphenol A.
Specific examples thereof include a type epoxy resin, a bisphenol F type epoxy resin, and the resin is not particularly limited as long as it is a high refractive index resin having an aromatic ring. Further, there is no problem in using a copolymer resin of a monomer having these aromatic rings and a monomer having no copolymerizable aromatic ring.

In the present invention, the surface of the resin having the aromatic ring in the main chain and/or side chain has an oxygen permeability coefficient of 100 x 10""w', cm/cw2, which is mainly made of an organic polymer.
．． It is obtained by coating with a transparent film of less than gea, 2Hg, and the oxygen permeability coefficient here is a measure representing the permeability of oxygen gas, and is a value defined as the 9th order.

In other words, the amount of oxygen permeating per unit time (sea) per unit area (I) on the surface of a flat plate with a thickness of 1 cII when an oxygen partial pressure difference of 1 anHg is applied.
It is.

Oxygen permeability coefficient is 100 x 10 cy, CII
/an, sea, cmHg or less, specific examples of transparent materials include polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylonitrile, cellulose, polyvinylidene chloride, polyvinylidene chloride/vinyl chloride copolymer, polycaprolactam, Examples include polyethylene terephthalate, polyvinyl chloride, and polyoxymethylene. Among them, polyvinyl alcohol.

Polyvinyl acetate and cellulose are preferably used because they are easy to form a film. Furthermore, it is also possible to add various organic and/or inorganic compounds to the above-mentioned transparent material within a range that satisfies the oxygen permeability coefficient conditions and does not impair transparency. Main specific examples of additives used include: 1. Various surfactants can be added for the purpose of improving surface smoothness.

For example, silicone compounds, fluorine surfactants.

Organic surfactant: A surfactant can be used. Furthermore, it is easily possible to add an ultraviolet absorber for the purpose of improving weatherability, and an antioxidant for the purpose of improving heat deterioration resistance. It is also possible to add a crosslinking agent for the purpose of improving the durability of the coating, and various silane coupling agents are preferably used as crosslinking agents.

1. Examples include melamine resin, colloidal silica, and metal salts of titanium, aluminum, and zirconium. It is of course possible to add not only one type of these crosslinking agents but also two or more types, and it is also possible to add a catalyst for promoting crosslinking.

The amount of these additives should be determined experimentally, but the oxygen permeability coefficient of the organic polymer to be coated is 100.
x 10 m, > / am, sea, r
When it is larger than s Hg, there is almost no coating effect and no improvement in light resistance is expected. In order to exhibit the effect with a thin film as possible, the oxygen permeability coefficient should be 50x10 C1
1, elI/a+, sec, cmHg or less transparent film is more preferable.

The transparent material is used by coating the surface of a high refractive index plastic lens substrate, but the thickness of the coating is not particularly limited. However, from the viewpoint of maintaining adhesive strength and light resistance, the thickness is preferably applied between 0.1 micron and 20 micron.

Coating methods include coating (dip coating,
Thin film forming methods such as spin coating, spray coating, brush coating, flow coating, etc.) and plasma CVD are possible.

Furthermore, for the purpose of increasing practicality, it is also possible to form coatings of various diameters of the transparent material on the surface. For example, a method of coating with various polysiloxane compounds is useful for the purpose of improving surface hardness. Furthermore, vacuum deposition of an inorganic oxide is also possible for the purpose of antireflection.

Also for the purpose of improving the adhesion between the base material and the coating.

It is also an effective means to treat the surface of the base material in advance, and various chemical and physical methods can be applied. Particularly preferred methods include chemical treatment using alkali, acid, etc., and physicochemical treatment using corona discharge, low-temperature plasma, etc. Among these, surface treatment using low-temperature plasma is particularly preferred in terms of simplicity and effectiveness.

In order to clarify the gist of the present invention, Examples are given below.
The present invention is not limited to these examples.

In addition, in the examples, evaluation was performed by the following method.

The YI value (YELLOW-INDEX) was measured using a color computer SM-3 manufactured by Suga Test Instruments.

The YI value is correlated with the degree of yellowing, and the larger the YI value, the more intense the yellowing.

Using a steel knife, insert T'lOo goblets (1 mm square) on the surface of the adhesive composite that reach the base material, and apply cellophane adhesive tape (trade name: "Nakaguchi Tape", manufactured by Nichiban Co., Ltd.).
was strongly applied and rapidly peeled off in a 90 degree direction, and the presence or absence of peeling of the film was examined.

〔Example〕

Example 1 (1) Preparation of substrate to be coated Ethylene oxide 2 of tetrabromobisphenol A
70 parts of a monomer containing a polyfunctional acrylate monomer with 0.9 mol of hexamethylene diisocyanate added to 1 mol of a hydroxyl group-containing compound in which 1 mol of acrylic acid is bonded to a molar adduct by esterification, and 60 parts of styrene.
A base material obtained by cast polymerization using inpropyl peroxide as a polymerization initiator was subjected to low-temperature plasma treatment to obtain a surface-treated base material.

(2) Preparation of coating composition 50 parts of polyvinyl alcohol (manufactured by Nippon Gosei Kagaku Co., Ltd., trade name 1 GOHSENOL"AL-0<5) was dissolved in 450 parts of water to obtain a coating material.

(3) Preparation of coating substrate The polyvinyl alcohol aqueous solution prepared in (2) above was dip-coated on both sides of the substrate at a pulling rate of 10 mm/min to the substrate obtained in (1) above, and - The mixture was air-dried day and night at room temperature to obtain a composite.

The thickness of the coating was 6 microns. Also, the oxygen permeability coefficient is 10 x 10 cII, ex/cwl,
sea, c+nHg.

(4) Performance evaluation The composite obtained in (3) was set in a fade meter (manufactured by Suga Test Instruments) equipped with a carbon arc lamp.

After 100 hours, the composite was taken out and the degree of yellowing was evaluated. The results are shown in Table-1.

Example 2 (1) Preparation of the coating composition (a) Preparation of hydrolyzate of γ-glycidoxypropyltrimethoxysilane 256 g of γ-glycidoxypropyltrimethoxysilane in a reactor equipped with a rotor. was charged, the liquid temperature was maintained at 10°C, and 54 g of a 0.01N hydrochloric acid aqueous solution was gradually added dropwise while stirring with a magnetic stirrer. After completion of the dropwise addition, cooling was stopped to obtain a hydrolyzate of γ-glycidoxyglobyltrimethoxysilane.

(b) Paint preparation Polyvinyl alcohol (manufactured by Nippon Gosei Kagaku Co., Ltd., trade name)
-f-Senur' A L-06) (7) 15 weight 1%
To 100 g of an aqueous solution, 5% by weight of the above γ-glycidoxypropyltrimethoxysilane hydrolyzate and 40% by weight of 1,4-dioxane as a dispersion solvent were added, and 1% by weight of aluminum acetylacetonate was added, and the mixture was sufficiently dissolved. The mixture was stirred to form a paint.

(2) Preparation of coating base material The coating composition prepared in (1) above was applied to both sides of the base material by dip coating at a pulling speed of 1 o (1) for 7 minutes on a base material obtained in the same manner as in Example 1. First, preliminary drying was performed at 82°C for 12 minutes, and further drying was performed at 150°C for 2 hours to obtain a composite. What is the oxygen permeability coefficient of the film?

40 x 1. Oc+++, clI/c+n, s
ec, cmHg.

(3) Performance evaluation The composite obtained in (2) was evaluated in the same manner as in Example 1. The results are shown in Table-1.

Comparative Example 1 A substrate obtained in the same manner as in Example 1 (1) was evaluated without being coated. The results are shown in Table-1.

Comparative Example 2 (1) Preparation of coating composition 10 parts of polyvinyl butyral was dissolved in 90 parts of butanol to obtain a coating material.

(2) Preparation of coating base material The polyvinyl butyral solution prepared in (1) above was applied to both sides of the base material by dip coating on the same base material as in (1) of Example 1 at a pulling speed of 10 cm. o/12
The mixture was pre-dried for 1 minute and further dried at 90° for 0/2 hour to obtain a composite. The oxygen permeability coefficient of the film is 117
x 10-12cm3. c++++ / em 0gea
, cmHg.

(3) Performance evaluation The composite obtained in (2) was evaluated in the same manner as in Example 1. The results are shown in Table-1.

Example 3 (1) Preparation of coating composition (a) Preparation of hydrolyzate of r-glycidoxypropyltrimethoxysilane Hydrolysis of γ-glycidoxypropyltrimethoxysilane in the same manner as in Example 2 A decomposition product was obtained.

(b) Preparation of paint: 5% by weight of the above γ-glycidoxypropyltrimethoxysilane hydrolyzate and methanol-dispersed colloidal silica (manufactured by Catalysts Kasei Kogyo Co., Ltd.) for 100 g of a 15% by weight aqueous solution of polyvinyl alcohol.

Product name 03CAL-1132) 40% by weight and 40% by weight of 1,4-dioxane as a dispersion solvent were added, and further 1% by weight of aluminum acetylacetonate was added.
The mixture was sufficiently stirred to form a paint.

(2) Preparation of coating base material The coating composition prepared in (1) above was applied to a base material obtained in the same manner as in Example 1, and dried in the same manner as in (2) of Example 2. Obtained a complex. Oxygen permeability of the film (3) After the composite obtained in performance evaluation (2) was left outdoors for 4 weeks.

The degree of yellowing and adhesion of the film were evaluated. The results are shown in Table-2.

Comparative Example f3 Example 3 was prepared using a base material obtained in the same manner as in Example 1 without coating.
The performance was evaluated in the same way. The results are shown in Table-2.

Table-1 PVA: Polyvinyl alcohol aps: γ-glycidoxypropyltrimethoxysilane PVB: Polyvinyl butyral sto, : Particulate silica [Effects of the invention] The composite molded article obtained by the present invention has a coating layer with gas barrier properties. Since it is excellent, it has the following effects.

(1) Excellent weatherability and light resistance. It is particularly effective in reducing yellowing caused by ultraviolet irradiation.

(2) Preventing oxidative deterioration of resin.

(3) The service life can be extended, and there is very little change in physical properties even after long-term use.

Patent Applicant Azuma Stock Exchange Company Procedures Amendment

Claims (1)

[Claims] The surface of a high refractive index resin lens having an aromatic ring in the main chain and/or side chain has an oxygen permeability coefficient of 100×10^-^1
A high refractive index plastic lens composite body, characterized in that it is coated with a transparent film mainly made of an organic polymer with a refractive index of ^2cm^3.cm/cm^2.sec.cmHg or less.