JPS6068319A - Production of antireflection lens - Google Patents

Abstract

PURPOSE:To provide an antireflection lens having a uniform color of reflected light with a process for manufacturing an antireflection film consisting of two layers for which a liquid compsn. is used by coating the layer on a base material side by a dip coating and the layer thereon by a spin coating method. CONSTITUTION:The 1st layer on the base material side of an antireflection film is coated on a lens by dipping the lens in a liquid compsn. and rising the lens at a specified speed or at the speed varied continuously. Another liquid compsn. is coated thereon, then a uniform coated film (2nd layer) is formed on the lens by a high speed rotation. The 1st layer on the base material side has the refractive index higher by >=0.03 than either of the base material layer and the 2nd layer and the film thickness of the 2nd layer is made 20-1,000nm. A prescribed org. material, inorg. material and substd. organosilicon compd. are used for the 1st and 2nd layers.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing an antireflection lens that has a uniform reflected light color and is highly productive by applying a liquid composition to a lens base material.

BACKGROUND ART There has been a strong desire to improve the optical function of lenses, especially the antireflection function, from the viewpoint of effective use of light rays.

When lenses for spectacles are not subjected to anti-reflection processing, there is a problem in that when the lenses are worn, reflection of light rays causes reflected images called ghosts, flares, etc., which cause discomfort to the eyes. Furthermore, by providing an antireflection film that reflects light of a specific wavelength, attempts have been made to not only improve its optical function but also to increase its fashionability. Improvements in these optical functions are also strongly desired in camera lenses.

Improvement of the optical function of a lens has conventionally been achieved by forming an antireflection film on the lens base layer using a vacuum evaporation method or the like.

In this case, it is known that selection of the thickness and refractive index of the material coated on the substrate is important in order to have a high antireflection effect. For example, in the case of a single-layer coating, it is known that selecting a material with a lower refractive index than the base material and having an optical film thickness of - or an odd multiple of a given wavelength provides the minimum reflectance, or maximum transmittance. It is being

The optical film thickness here is given by the product of the refractive index of the coating forming material and the film thickness of the coating. Furthermore, it is possible to select a multilayer antireflection layer, and in this case, by appropriately selecting the film thickness and refractive index of each layer, the desired reflected light color and antireflection effect can be obtained. Some proposals regarding these have already been made (optical technology) Contact V01, 9. Volume 8, 17-23 (19
71).

The antireflection film formed by such a vapor deposition method is as follows.

Depending on the application, the following problems may arise.

(11) Since a high degree of vacuum is required, there are restrictions on the size and material of the substrate to be treated.Furthermore, the manufacturing time is long, and productivity and economic efficiency are reduced.

(2) Normally requires heating, and depending on the base material, deformation 1
This causes problems such as decomposition.

(3) The coating forming material used is mainly an inorganic oxide, which forms a dense film, but in the case of a plastic base material, it has heat resistance due to the difference in linear expansion coefficient.

Adhesion tends to decrease.

(4) The dye permeability necessary for dyeing, which is an effective means of preserving the color of the lens base material, is completely lost.

(5) A similar loss of dyeability and a decrease in heat resistance and adhesion occur in glass lenses coated with dyeable materials.

On the other hand, in JP-A-58-46301, using a liquid composition, f? :, the production of an antireflection film consisting of two layers is mentioned. This method has solved the above problems to some extent. This document discloses a dip coating method for both the first layer and the second layer, and a Svinko-1 method for both the first layer and the second layer. When the former method is applied to a lens, color unevenness occurs in the reflected light on the upper and lower sides and on the front and back sides of the lens, resulting in a product that has no commercial value. 1. The latter is a product with low productivity and very high cost, and is of little practical use.

The present inventors have made extensive studies to solve these problems, and as a result, have arrived at the present invention described below.

That is, the present invention involves coating a liquid composition on one or both sides of a lens, and in manufacturing an antireflection lens having a reflected light color, a layer (first layer) on the base material side of the antireflection film is produced.
Dip coating method, layer provided on the first layer (second layer)
are coated using a spin code method, and the first layer has a refractive index higher than 0.06 in both the base material layer and the second layer in contact with the first layer, and the film thickness of the second layer is 20 to IDD. []nm
The present invention relates to a method for manufacturing an antireflection lens characterized by the following.

In the present invention, a lens has a positive or negative curvature on at least one of its front and rear surfaces.
Preferably plus 0.2m or more or minus 0.2
A molded article having a curvature of less than or equal to m. This also includes those having an aspherical portion on at least one of the front and rear surfaces. The liquid composition for forming a coating that imparts antireflection properties to such lenses may consist of only a coating-forming substance, or may contain various volatile solvents to impart the necessary coating workability. can. Here, the liquid composition is a composition having a viscosity within a range to which ordinary coating operations can be applied, and is 10 poise or less, preferably 1 poise or less at the application temperature. That is, it is difficult to obtain a uniform coating film with a liquid composition having a higher viscosity than this.

The dip coating method used as the coating method for the first layer of the present invention is a method in which a lens is immersed in a liquid composition, and then the lens or the liquid composition layer is raised or raised at a constant or continuous speed, respectively. In this method, a liquid composition is applied to both sides or one side of the lens.

The rate of rise or fall, as well as the atmospheric conditions, etc., must be determined experimentally, but from the viewpoint of controlling the thickness of the thin film, the rate of rise or fall is preferably 0.5 to 40 per minute. 1-20cIII
It will be done in Z minutes.

Furthermore, the number of lenses to be coated at one time should be determined from the viewpoint of productivity and is not particularly limited.

Furthermore, if the above-mentioned rising or falling speed is too slow, productivity will drop significantly and not only will the benefits of the dip coating method 6- be lost, but the surface layer of the liquid composition will likely become uneven in concentration. Become.

Unevenness in film thickness may occur. This causes problems in terms of appearance. Furthermore, if the speed is faster than this, large film thickness unevenness will occur on the upper and lower parts of the lens and on the front and back surfaces.

There are problems such as the inability to obtain a uniform antireflection film.

Next, the Subincoet method used as a coating method for the second layer is a method in which a liquid composition is coated on one and/or both sides of a lens, and then a uniform coating film is formed on the lens by high speed rotation. Rotation speed is 20Or, p
, m or more, preferably 500 r, p, m or more, p. The time to reach the maximum rotational speed and speed change should be determined experimentally depending on the composition of the liquid composition, atmospheric conditions, etc.

Further, the rotation time should be determined by experimentally determining the time required for the coating film thickness to become constant in view of product variations and productivity.

Methods for applying the liquid composition onto the lens surface include immersing the lens in the liquid composition and then spin-coding it, applying the liquid composition while rotating the lens, and applying the liquid composition simultaneously with the rotation of the lens. A method of applying the composition or a method of applying the composition before rotating the lens can be applied.

Furthermore, the coating thickness can be made even more even when rotating the lens.
It is also useful and possible to shift the center of the lens and the axis of rotation for the purpose of achieving this.

Although the dip coating method has high productivity, it has a problem that the productivity is low compared to the spin coating method, although it has excellent uniformity of film thickness.

The inventors have overcome each of the above-mentioned drawbacks.

In order to take advantage of the advantages, various studies were conducted and the present invention was completed.

In other words, methods other than coating the first layer by dip coating and the second layer by spin-coating9 For example, methods using a combination of dip coating for the first layer and dip coating for the second layer have low productivity. Although this is very high, the accuracy of controlling the thickness of the second layer is low, resulting in uneven reflected light color and total light transmittance.

Furthermore, even if the method uses a combination of spin-coating for the first layer and dip-coating for the second layer, unevenness occurs in the reflected light color and total light transmittance.

Furthermore, a combination method in which the first layer is formed by spin coding and the second layer is also formed by spin coding provides a lens with good appearance and performance, but the productivity is extremely low. Among the antireflection films coated as described above, the first coat coated as the first layer has a refractive index higher than 0.06 on both the base material in contact with the first layer and the second layer. things are used.

That is, if the refractive index of the first layer film is lower than this, a lens having a sufficient antireflection function cannot be obtained. The thickness of the film applied as the second layer is 20 to 11,000.
n, preferably 40-200 nm.

That is, if the film is thinner or thicker than this, an antireflection lens with a satisfactory reflected light color cannot be obtained.

When coating the first and second layers, adhesion can be improved by applying various chemical treatments and physical treatments to the layers in contact with each other.

The film-forming substances for the first and second layers must be such that the film formed therefrom satisfies the requirements regarding the refractive index, and that they themselves or they can be dispersed or dissolved in a solvent to form a liquid composition. It is not particularly limited as long as it is.

On the other hand, from the point of view of applying liquid compositions.

Preferably used is an organic material or an inorganic material having the ability to form a transparent film dispersed or dissolved in a solvent.

On the other hand, those that are liquid themselves can be used alone, but they can also be used after being diluted with a suitable solvent. These materials can be used within the range of 2.
It is also possible to use a mixture of more than one species.

Among these materials, one example of an organic material used as a film-forming substance having a relatively high refractive index and preferably used for the first layer is polystyrene.

Polystyrene copolymers, polycarbonates, various polymer compositions having aromatic rings other than polystyrene, heterocycles, alicyclic cyclic groups or 1 n- or halogen groups other than fluorine, melamine resins, phenolic resins, epoxy resins, etc. Various thermosetting resin-forming compositions using as a curing agent, urethane-forming compositions comprising alicyclic or aromatic incyanate and/or these and polyols, and methods for introducing double bonds into the above compounds. Compositions containing various modified resins or prepolymers that enable radical curing are preferably used.

On the other hand, as an inorganic material, it has film-forming properties.

Those that can be dispersed in a solvent or are liquid themselves are used, and typical examples include alkoxides of various elements, salts of organic acids, and coordination compounds combined with coordination compounds. Suitable examples of these include titanium tetraethoxide, titanium tetra-1-propoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide,
Titanium tetra-8θC-butoxide, titanium tetra-t
ert-butoxide, aluminum triethoxide, aluminum tri-1-propoxide, aluminum tributoxide, antimony triethoxide, antimony tributoxide, zirconium tetraethoxide, zirconium tetra-1-propoxide, zirconium tetra-n-10 poxide, zirconium thiol I-ra-n-phthoxide, zirconium tetra-5ea-butoxide,
Metal alcoholate compounds such as zirconium tetra-tart-butoxide, as well as di-isopropoxytitanium bisacetylacetonate, di-ethoxytitanium bisacetylacetonate, di-ethoxytitanium bisacetylacetonate, bisacetylacetone zirconium, aluminum acetylacetonate. Chelate compounds such as aluminum di-n-butoxide monoethyl acetoacetate, aluminum di-i-propoxide monomethyl acetoacetate, tri-n-butoxide zirconium monoethyl acetoacetate, as well as zirconyl ammonium carbonate and di-hasilconium Examples include active inorganic polymers as components.

On the other hand, an example of an inorganic compound that cannot be used alone but can be used with the above-mentioned organic materials or inorganic materials as long as transparency is not impaired is aluminum.

Oxides of metal elements such as titanium, zirconium, antimony, and silicon are preferably used.

These are provided in the form of fine particles or as a colloidal dispersion in water and/or other solvents. These are mixed and dispersed in the above organic material or inorganic material.

Further, in the first layer, a material having a low refractive index can be used as long as the requirements regarding the refractive index are satisfied. Materials that can be used include, in addition to the organic materials mentioned above, vinyl copolymers including acrylic copolymers, polyester (including alkyd) polymers, cellulose polymers, urethane polymers, and There are various curing agents, compositions having curable functional groups, and the like.

Additionally, organically substituted silicon compounds can be included. These organosilicon compounds are compounds represented by the general formula %() or their hydrolysis products. Here, R' and R'' are each an alkyl group, an alkenyl group, an aryl group, or a hydrocarbon group having a halogen group, an epoxy group, an amine group, a mercapto group, a methacryloxy group or a cyan group, and Hydrolyzable substituent selected from sil, halogen or acyloxy group, a and b are each 0.1 or 2
and a+b is 0.1 or 2.

On the other hand, examples of film-forming organic materials with a relatively low refractive index that are preferably used for the second layer include vinyl copolymers containing acrylics that do not contain aromatic rings, various fluorine-substituted polymers, and aromatic rings. A polyester (including alkyd)-based polymer that does not contain

There are compositions comprising cellulose derivatives, silicone polymers, hydrocarbon polymers, prepolymers thereof, or those having a curable functional group among these, and a curing agent.

Examples of inorganic materials include inorganic silicon compounds such as various alkyl silicates, various aryl silicates, and various dicarboxysilanes. Specific representative examples of these inorganic silicon compounds include methyl silicate and ethyl silicate.

n-propyl silicate, bell o-propyl silicate,
n-butyl silicate, sθC-butyl silicate, t
ert-butyl silicate, n-hexyl silicate,
Examples include phenyl silicate, tetraacetoxysilane, tetra(2-methacryloxy)ethoxysilane, and tetramethoxyethoxysilane.

Furthermore, organically substituted silicon compounds are also preferably used. These organosilicon compounds are organosilicon compounds represented by the general formula % and/or hydrolysates thereof.

Here u 3. u 4 is an alkyl group or an alkenyl group, respectively.

It is a hydrocarbon having an aryl group, a halogen group, a methacryloxy group or a cyano group. Also RU carbon a1
~8 alkyl group, alkoxyalkyl group''!, or acyl group, ha c and d are 0 or 1, and c+
d is 1 straddle 2.

A specific representative example of these organosilicon compounds is glycidoxymethyltrimethoxysilane.

Glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-f IJ cytoxyethyltriethoxysilane, β=glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, a -glycidoxyprobyltrimethoxysilane, a-glycidoxyprobyltriethoxysilane, β
-Glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl!・Liethoxysilane, γ-glycidoxypropyltriproboxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane glycidoxypropyltrimethoxyethoxysilane, γ-glyside Xyprobyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-crisitoxybutyltriethoxysilane.

β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ -glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane.

(6,4-epoxycyclohexyl)methyltriethoxysilane, β-C3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3.4-epoxycyclohexyl)ethyltriethoxysilane,
-Epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane.

β-(3,4-epoxycyclohexyl)ethyltritoxyethoxysilane, β-(6,4-epoxycyclohexyl)ethyltriphenoxysilane.

17- γ-C3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-C6,4-epoxycyclohexyl)propyltriethoxysilane, β-(3,4-epoxycyclohexyl)butyltrimethoxysilane, β-
(6,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyljethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyljethoxysilane , β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyljethoxysilane.

β-crisitoxypropylmethyljethoxysilane, β
-glycidoxypropylmethyljethoxysilane, γ-crisitoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxy Propyl 18-ylmethyldiptoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane.

γ-glycidoxypropylethyldimethoxysilane, γ
-Glycidoxypropylethyljethoxysilane, γ-
Epoxy group-containing organosilicon compounds such as chrysitoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, and γ-glycidoxypropylphenyldiethoxysilane and its hydrolysates. Furthermore, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane.

Methyltriacetoxysilane, methyltriptoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane.

Vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane.

Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3.3-t')fluoropropyl Trimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β(amino trialkoxy, triazyloxy or triphenoxysilanes such as ethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltrinoenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, or Its hydrolyzate, dimethyldimethoxysilane, phenylmethyldimethoxysilane.

Dimethyljethoxysilane, phenylmethyljethoxysilane, γ-chloropropylmethyldimethoxysilane,
γ-chloropropylmethyljethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane.

γ-Mecryloxypropylmethyldiethoxysilane,
γ-Mercaptopropylmethyldimethoxysilane, γ-
Dialkoxysilanes or diacyloxysilanes such as mercaptopropylmethyljethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyljethoxysilane, methylvinyldimethoxysilane, and methylvinyljethoxysilane! Hydrolyzate of bamboo shoots can be mentioned.

These organosilicon compounds are preferably used after being hydrolyzed in order to lower the curing temperature and promote curing.

Furthermore, various curing agents can be used as curing accelerators, and specific typical examples include aluminum acetylacetonate, aluminum ethyl acetoacetate bisacetylacetonate, aluminum bisacetoacetate acetylacetonate, and aluminum laminate. Aluminum chelate compounds such as 'n-butoxide monoethyl acetoacetate and aluminum di-1-pro21-poxide monomethyl acetoacetate, titanate compounds such as tetranebutoxytitanium and diimpropoxybis(acetylacetonato)titanium, various organic carboxylic acids Examples include alkali metals and alkaline earth metals, and the amount added should be determined within a range that satisfies requirements regarding the performance of the cured product and the refractive index of the coating.

Two or more of these organic materials, inorganic materials, and organosilicon compounds may be used in combination as long as transparency is not impaired.

On the other hand, although it cannot be used alone, it can be used with the above-mentioned organic materials, inorganic materials, or organosilicon compounds, or mixtures thereof, with the aim of improving adhesion with the first layer, surface hardness, and dyeing properties, and their mixtures with impairing transparency. As an inorganic compound that can be used within a range that does not cause oxidation, fine particulate silica is preferably used.

As the particulate silica, colloidally dispersed silica sol is particularly preferably used from the viewpoint of transparency.

These compositions are usually diluted in volatile solvents and applied. The solvent used is not particularly limited, but the stability of the composition is important when using it.

It should be determined in consideration of wettability to the lens base material, volatility, etc. Moreover, it is also possible to use not only one type of solvent but also a mixture of two or more types.

Various surfactants may be used in the coating composition of the present invention for the purpose of improving flow during application, and in particular, block or graft copolymers of dimethylsiloxane and alkylene oxide, and Fluorine-based surfactants are effective.

Further, it is easily possible to add an ultraviolet absorber to each layer for the purpose of improving weather resistance, and an antioxidant to improve heat resistance to deterioration.

The coating composition for each layer applied in this manner can be heat-cured and/or dried in stages, or the second layer can be coated after the first layer is pre-cured and/or dried. Heat curing and/or drying is also possible. As a heating method, hot air, infrared rays, etc. can be used. The heating temperature should be determined depending on the transparent substrate to be applied and the coating composition used, but it is usually 50 to 150°C.
1 to υ, preferably 60 to 200°0.

If the temperature is lower than this, curing or drying will be insufficient, and if the temperature is higher than this, thermal decomposition will occur, causing problems such as yellowing.

Furthermore, it is also possible to cure using radiation such as ultraviolet rays, electron beams, and gamma rays by utilizing the curable functional group 1, such as a double bond in a polymer or oligomer.

Further, the film thicknesses of the first layer and the second layer of the present invention are controlled by the solid content of the coating composition and coating conditions.

Typical lens base materials of the present invention include:

Examples include glass and plastic materials. Such plastic materials include polymethyl methacrylate and copolymers thereof, polycarbonate, di-x-j-lene glycol pisallyl carbonate polymer (cR-39), polyesters, especially polyethylene terephthalate and unsaturated polyesters.

Acrylonitrile-styrene copolymers, vinyl chloride, polyurethane, epoxy resins, and the like are preferably used.

Furthermore, lens base materials such as the above-mentioned plastics and glass coated with coating materials are also preferably used. In particular, various physical properties such as adhesion, hardness, chemical resistance, durability, and dyeability can be improved by the coating material underlying the antireflection thin film of the present invention. In addition, in order to improve the hardness, it is possible to use various materials known as hardening coatings on the surface of plastics. -39449.% Publication No. 51-24368. Japanese Patent Publication No. 5
2-11269B, Special Publication No. 57-27:55).

In particular, with respect to the dyeable highly hardened coating described in Japanese Patent Publication No. 57-2735, the antireflection film having the reflected light color of the present invention is applied to the antireflection lens that is dye permeable and has high surface hardness. 25 of the invention - It can be preferably used as it can maximize the effect.

There are many possible combinations of the lens base material or coating base material and the antireflection film having the color of reflected light that achieve the object of the present invention, and the optimum range should be determined experimentally depending on the purpose.

The present invention will be described in detail below by way of examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of undercoating composition (a) Preparation of silane hydrolyzate γ-glycidoxypropyl methyljethoxysilane 10
6.8g was cooled to 610°C, and 155g of a 0.05N hydrochloric acid aqueous solution was gradually added dropwise while stirring.

After the dropwise addition was completed, stirring was continued for an additional hour at room temperature to obtain a silane hydrolyzate.

(b) Preparation of coating composition To the silane hydrolyzate, 25 g of epoxy resin ("Epicote 827", manufactured by Shell Chemical Co., Ltd.), 25 g of epoxy resin [1 Epolite 5002', manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.], Acetone alcohol 58.9
g, benzyl alcohol 29.5 g.

310g methanol, 1.5g silicone surfactant
416.7 g of methanol-dispersed colloidal silica (average particle size 12 ± 1 mμ, solid content 60%) and 12.5 g of aluminum acetylacetonate were added,
After thorough stirring, a coating composition was prepared.

(2) Preparation of the first layer coating composition 479 g of n-butyl alcohol, acetic acid in a beaker equipped with a rotor.
g #Add 0.17 g of silicone surfactant. Into this mixed solution, while stirring at room temperature, was added 51.6 g of the same methanol-dispersed colloidal silica as used in (1).
g, and further added 26 g of tetra-n-butyl titanate to prepare a coating composition.

(3) Preparation of second layer coating composition (a) Preparation of silane hydrolyzate γ-glycidoxyprobyltrimethoxysilane 56,5
g, 24.0 g of vinyltriethoxysilane,
D 5N Hydrochloric acid aqueous solution 198B was added dropwise and mixed under stirring while controlling the temperature at 10°C. After the dropwise addition was completed, the mixture was further stirred at room temperature for 1 hour to obtain a silane hydrolyzate.

(b) Preparation of coating composition: Into 696 g of the silane hydrolyzate, 143 g of n-propanol, 68 g of water, and 23 g of ethyl selon
g, (32.8 g of the same methanol-dispersed colloidal silica used in 11, 0 silicone surfactant)
．． 22 g and aluminum acetylacetonate D,
98 g was added and thoroughly stirred to obtain a coating composition.

(4) Coating, curing, and pretreatment First, using the coating composition prepared in the previous section (1), a diethylene glycol bisallyl carbonate polymer lens (diameter 7
5I11II1. It was coated onto CR-59 Praluns (2.1 mm thick) using a dip coating method and heated at 96°0 for 4 hours. The obtained undercoat layer was coated using a surface treatment plasma device (PR501A, manufactured by Yamato Scientific Co., Ltd.) at an oxygen flow rate of 100. // minutes.

Processing was performed for 1 minute at an output of 50 W.

Thereafter, the coating composition prepared in the previous section (2) was applied onto the surface-treated undercoat layer by a dip coating method. The coating conditions were a pulling rate of 10 cIII/min, and the coated lens was dried in a hot air dryer at 90°C for 10 min.
After heating and curing for a minute, it was immediately treated under constant temperature and humidity conditions of 80° 0° and 90% RH for 1 hour, and was further heated and dried for 1 hour in a hot air dryer at 110°C. The refractive index of the obtained first layer is 1.6
0, and the film thickness was 82 nm. Further, the refractive index of the undercoat layer in contact with the first layer was 1.50.

Thereafter, the coating composition prepared in the previous section (31, (b)) was spin-coded under the following conditions.The coated lens was dried by heating at 96°0 for 4 hours.

Spin code conditions Rotation speed: 3500 rpm Rotation time = 60 seconds The obtained second layer has a refractive index of 1.43 and a film thickness of 1106
It was n. Table 1 shows the total light ray transmittance of each part of the obtained lens. The lens used is a circular lens as shown in Fig. 1, and each part of the lens is located at the upper part 2.
Central part 3. Lower part 4. Left part 5. This will be referred to as the right section 6, and measurements were taken at each section.

The total light transmittance at the center was 95.7%, and it had a sufficient antireflection effect. The total light transmittance of the uncoated lens was 92.4. In addition, the total light transmittance in any part of the lens has an error of less than 0.10,
A lens with a uniform reflected light color of reddish-purple and no unevenness over the entire surface was obtained.

Example 2 (1) Preparation of first layer coating composition Example 1 (
In the same manner as in 2), 4790 g of n-butyl alcohol,
A consolidating composition was obtained from 82 g of acetic acid, 1.7 g of silicone surfactant, 316 g of methanol-dispersed colloidal silica, and 230 g of tetra-n-butyl titanate.

(2) Coating, curing, and pretreatment 10 lenses that were undercoated and plasma-treated in the same manner as in Example 1 were simultaneously coated with the coating composition of (1) in the same manner as in Example 1. It was applied to. The subsequent processing, application and curing of the second layer is as in Example 1.
I did exactly the same thing. All of the lenses thus obtained had performance equivalent to that of the lens obtained in Example 1, and the total light transmittance among the 10 lenses had a variation of less than a factor of ±02.

Comparative Example 1 (1) Preparation of first layer coating composition Example 1 (2)
), a coating composition was obtained from 235 g of n-butyl alcohol, 82 g of acetic acid, 017 g of a silicone surfactant, 31.6 g of methanol-dispersed colloidal silica, and 26 g of tetra-n-butyl titanate.

(2) Preparation of second layer coating composition (in Example 1)
39.5 g of the silane hydrolyzate prepared in 31.(a)
Stir under X pressure and then add 197 g of n-proper tool and 96 g of water.
, still cellosolve 61g, methanol-dispersed colloidal silica 32.5g, silicone surfactant 0.22g
g and aluminum acetyl acetyl acetate, -1-0,98g
was added and thoroughly stirred to obtain a coating composition.

(3) Coating Cure and Pretreatment The coating composition of (1) above was applied to a lens that had been undercoated and subjected to 7-fi brazing in the same manner as in Example 1 by a spin cord method under the following conditions.

Post-treatment was carried out in the same manner as in Example 1.

Spin code conditions Rotation speed: 6500 rpm Rotation time: 3D seconds Thereafter, the coating composition prepared in the previous section (2) was applied by dip coating. Coating conditions are pulling speed iQcm
/min, and the coated lens was heated and dried at 93° C. for 4 hours. Table 1 shows the total light transmittance of each part of the obtained lens. Total light transmittance is 95.1% in the center
However, there was a maximum difference of 2.0% in the total light transmittance of each part from the center part, and the color of the reflected light was also uneven.

Comparative Example 2 Similar to the first layer coating of Example 1, L7
Then, the first layer was applied onto the undercoated lens by dip coating, and then cured. Next, in exactly the same manner as in Comparative Example 1, a second layer was also applied by dip coating, and then cured.

The total light transmittance at the center of the obtained lens was 956, but the maximum difference between the total light transmittance at each part and the center was 2. 1) There was also unevenness in the reflected light color.

63- Table 1 Total light transmittance and reflected light color

[Brief explanation of the drawing]

FIG. 1 is a front view of the lens. 1: Lens 2: Upper lens '5: Central part of lens 4 = Lower lens 34- 5: Left part of lens 6: Right part of lens A: Pulling direction during dip coating Patent applicant Toshi Co., Ltd. Figure 1 100 - 1. Indication of the case Patent application No. 153452 filed in 1982 2. Name of the invention Method for manufacturing anti-reflection lenses 3. Person making the amendment Relationship to the case Patent applicant address 2-2-4 Nihonbashi Muromachi, Chuo-ku, Tokyo , Date of amendment order Voluntary 5, Number of inventions increased by amendment None 6, Contents of amendment in Column Z "Explanation of the specification subject to amendment r≦="'-- 1 (, 59, 10, 29' (1) Page 6 of the specification, line 15, ``Performed at a rate of 1 to 20 cR/min'' to ``1 to 20 cR/min.'' In addition, as for the atmospheric conditions, low humidity is preferable in order to prevent dew condensation on the coating film, and dew condensation is particularly likely to occur. For coating compositions, 65% RH, more preferably 501 RH is applicable.'' (2) Insert the following sentence after ``Applicable'' on page 8, line 5. ``Additionally, the film thickness It is preferable to use a method of increasing the temperature of the paint for the purpose of uniformity.'' (3) Correct ``half side'' on page 8, line 9, to ``on the other side.'' (4) ``On the other side,'' page 8, lines 10-11. ``Although it has excellent uniformity,'' should be corrected to ``It has poor uniformity.On the other hand, although the spin code method has excellent uniformity of film thickness,'' 2-(6) Correct "moro-butoxide" to "di-n-butoxide" on page 12, line 13 of the same. "Butoxide zirconium" is corrected to "butoxyzirconium." is corrected to "1-propyl." rogen group,
"Epoxy group, amine group, mercapto group, methacryloxy". 02 Same page 16, line 4, "organosilicon compound" is corrected to "organosilicon compound". a: 1 interval Page 19, line 11, "organosilicon compound" is corrected to "organosilicon compound". 04 Same page 21, line 2 "Mecryloxy" is corrected to "methacryloxy". a51 Same page 21 line 17 “acetylacetonate” is “acetylacetonate”
and correct it. 0 phrases, p. 21, lines 18-19 and p. 22, lines 6-4
Line "acetylacetonate" to "acetylacetonate"
and correct it. (a) Same page 21, line 19 "Moro-butoxide" is corrected to [di-n-butoxide J. OQ Same page 22, lines 9-10, "organosilicon compound" is corrected to "organosilicon compound". Ql Same page 23, line 6, insert the following sentence after ``Aru.''. [Among them, from the viewpoint of paint stability and uniform film thickness, lower alcohols having 1 to 5 carbon atoms, chelating solvents having 1 to 10 carbon atoms such as acetylacetone, and ethyl acetoacetate,
Furthermore, organic carboxylic acids having 1 to 10 carbon atoms such as acetic acid and butyric acid, and their methyls. Ester derivatives such as ethyl, 1-propyl, n-7' lobil, 5ec-butyl, tart-butyl, and n-butyl are preferably used. ” (a) Correct “transparent substrate” in lines 2 and 3 on page 24 to “lens substrate”. 121) Page 25, line 4, “Epoxy resins, etc.” has been changed to “epoxy resins, (halogenated) bisphenol A di(meth)acrylate polymers and their copolymers, (halogenated) bisphenol A
urethane-modified di(meth)acrylate polymers and their copolymers, etc.” (a) "Tetra-n-butyl titanate" is replaced by "titanium tetra-
n-butoxide”. (To) Same page 60, line 8, ``0..10J'' is corrected to ``[1-10%''. Q4 Same page 61, line 18, "Stil Cellosolve" is corrected to "Ethyl Cellosolve". (c) Table 1 on page 34 of the same is amended as follows. [Table 1 Total light transmittance and reflected light color] 71

Claims (1)

[Claims] Two layers of a liquid composition are applied to one or both sides of a lens, and each layer is dried and/or cured. In a method for manufacturing an antireflection lens having a reflected light color by forming an antireflection film consisting of two layers, the layer on the substrate side of the antireflection film (first layer) is coated by a dip coating method, and the first layer is coated using a dip coating method. A layer (second layer) provided thereon is applied by a spin code method, and the first layer has a refractive index higher by 0.03 or more than both the base layer and the second layer in contact with the first layer. . A method for manufacturing an antireflection lens, characterized in that the second layer has a thickness of 20 to 11000 nm.