JPS60203679A - Preparation of transparent material preventing reflection - Google Patents

Abstract

PURPOSE:To obtain the titled material having improved weather resistance, sweating resistance, and resistance to scratching, by applying a composition consisting of a specific organosilicon compound hydrolyzate, finely powdered silica and a solvent to a transparent material having high refractive index, thermosetting it. CONSTITUTION:(A) 100pts.wt. organosilicon compound shown by the formula I (R<1> is 1-10C alkyl, alkenyl, aryl, etc.; R<2> is 1-8C alkyl, alkoxy, or acyl; a is 1 or 2) having >=50pts.wt. CH3Si(OR<2>) is blended with (B) 28-350pts.wt. finely powdered silica having 1-100mmu average particle diameter, and (C) a solvent and/or a dispersant, to give a coating composition having 2-10wt% solid substance concentration. The composition is applied to the surface of a transparent material having a refractive index >=0.03 higher than that of the coated film, thermosetted to give the desired material.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to a method for producing a transparent material having an antireflection effect.

Conventional technology Conventional 9 For anti-reflection, a material with a refractive index different from that of the base material is used.
A method of forming a film on a substrate using a vacuum deposition method or the like has been used. In this case, it is known that in order to maximize the antireflection effect, it is important to select the thickness of the material that coats the base material.

For example, in a single-layer coating, selecting a material with a lower refractive index than the base material with an optical film thickness of 1/4 of the target light wavelength or an odd number multiple thereof gives the lowest reflectance, that is, the highest transmittance. It has been known.

Here, the optical film thickness is given by the product of the refractive index l of the coating forming material and the film thickness of the coating.

Furthermore, it is also possible to form a multilayer antireflection layer.

Several proposals have been made regarding the selection of film thickness in this case (Optical Technology) Contact Vol. 9 = 8.17~
23 (1971)).

The antireflection film formed by this vapor deposition method has the following problems depending on the application.

(1) Since a high degree of vacuum is required, there are restrictions on the size and material of the substrate to be processed. Also, the manufacturing time is longer;
Productivity and economic efficiency decline.

(2) Usually requires considerable heating, which may cause problems such as deformation and decomposition depending on the base material.

(3) The film-forming material used is mainly an inorganic compound, and although it forms a dense film, in the case of a plastic base material, heat resistance and adhesion tend to deteriorate due to differences in linear expansion coefficients.

(4) The dye permeability necessary for dyeing, which is an effective means for coloring transparent substrates, is completely lost.

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

Regarding the manufacturing method of anti-reflection film using liquid composition,
In JP-A-5'8-46301, 2
Although it has been shown that antireflective coatings can be obtained by applying each of the layers in liquid form, the resulting antireflective coatings suffer from durability problems.

Furthermore, Special Publication No. 52-19691, Special Publication No. 56-1
No. 8625 discloses that the substantial solid content of methyltrialkoxysilane hydrolyzate and colloidal silica is 1.
Although coating compositions having a weight exceeding 0 have been disclosed, the problem is that the resulting coating film does not have sufficient antireflection effect.

Purpose of the Invention The present inventors have conducted extensive studies in order to solve and improve these problems and provide a transparent material that has an anti-reflection effect that is excellent in weather resistance, sweat resistance, light resistance, and scratch resistance. As a result, the present invention described below was achieved.

Structure of the Invention, Namely 2 The present invention consists of 100 parts by weight of a hydrolyzate of a silicon compound, provided that (A
) 50 parts by weight or more of the components are CH,5i(OR'').

Hydrolyzate of organosilicon compound represented by (where
R1 is an alkyl group having 1 to 10 carbon atoms.

A hydrocarbon group having an alkenyl group, an allyl group, a halogen group, an epoxy group, an amino group, a mercapto group, a methacryloxy group, or a cyan group.

R2 is an alkyl group, an alkoxyalkyl group, or an acyl group having 1 to 8 carbon atoms, and a digit is 0 or 1. ) (B) Fine particulate silica with an average particle diameter of 1 to 100 mμ
28 to 650 parts by weight (C) Consisting of one type and two or more types of solvent and/or dispersant, and the substantial solid content concentration is more than 2 times or more.

An antireflective transparent material characterized in that a coating composition having a weight of more than 10% is applied to at least a part of the surface of a transparent substrate having a refractive index higher than the refractive index of the coating film by 003 or more, and then heated and cured. This relates to a manufacturing method.

Here, a transparent material is a transparent substrate having a haze value of 80 or less as calculated by the following formula, and is colored with a dye or the like or colored in a pattern if necessary. It can be included in the list. Also, on the transparent substrate,
For example, those coated with a coating material to impart scratch resistance can also be included in the transparent substrates of the present invention if they have a haze value of 80 or less according to the formula below.

In order to more effectively exhibit the effects of reducing light reflectance and improving light transmittance as intended by the present invention, it is preferable that the material be as transparent as possible. Furthermore, if the reduction in light reflectance in the present invention is sufficient on only one surface of the substrate, even if the opposite surface is covered with an opaque material, the transparent substrate as defined in the present invention Can be used as

In this case, the haze value must be defined without the opaque material on the opposite side.

Furthermore, the transparent substrate used in the present invention needs to have a refractive index higher than the coating film by 006 or more. iAlso, in the case of a transparent base material with a refractive index lower than that of the coating film, or a transparent base material with a relatively low refractive index, a coating material with a high refractive index is applied on the base material in advance and used as a transparent profiteer. You can also do it.

The transparent base material is 006 or more than the coating film of the present invention,
Preferably, a material having a refractive index as high as 005 or higher is used. Furthermore, in the case of a transparent substrate to which a coating material with a relatively high refractive index is applied, it is preferable to satisfy the following conditions in order to further improve antireflection properties.

That is, in the case of a transparent base material provided with only one layer of coating material having a high refractive index.

Coating material on the substrate - λx O,7 < n, d, < - λ x 134 Coating film 7 λ x O, 7 (n2 d2 < - λ x 13 (where n, , n, are each " $ Chichi material, refractive index of coating film # dI + d2 are respectively profiteering coating material, coach ink film (in nm) 1m is a positive integer, n
is an odd positive integer, and λ is an arbitrary reference wavelength (in nm) chosen within the visible peripheral region. ) Also, when the coating material with a high refractive index is a transparent surface material consisting of two layers.

Layer provided directly on the base material (A layer) 7λx O7< n + d + < aλ×1.3A
Layer provided on the layer (B layer) 7λ×07〈・2d2〈−λ×1.3 Coating film 7λX O,7(n, mountain〈7λ×1.3 (here n, t
n, , n are the refractive indexes of the A layer, B layer, and coating layer, respectively, and dl r ' d t g d are the A, respectively.
Layer, B layer, coating film thickness (in nm).

1 is a positive integer, 9m is a positive integer, n is an odd positive integer, and λ is an arbitrary reference wavelength (in nm units) selected within the visible peripheral region. ) A method for manufacturing the transparent profiteer having a coating material with a relatively high refractive index is a vacuum evaporation method of an inorganic oxide.

Sputtering methods, ion blasting methods, and methods using liquid composition coating are known. Inorganic oxides preferably used in vapor deposition methods include TlO2, ZrO, Ta, O. .

Sb, 0. +Y, J r AG”s +MgO+ Na
,O,,Gd,O,,Sc,O,.

La, 0. , Pr60. ,,HfO,,ZnO,C
Examples include eO,, pbo, and the like. Various organic compounds and inorganic compounds can be mentioned as those suitable for use in the liquid composition coating method, and examples of organic compounds include polystyrene and polystyrene copolymers.

Aromatic rings other than polycarbonate and polystyrene.

Various polymer compositions and melamine resins having a heterocyclic group, an alicyclic group, or a halogen group other than fluorine.

Various thermosetting resin-forming compositions using a curing agent such as phenol resin or epoxy resin, urethane-forming compositions comprising alicyclic or aromatic incyanate and/or these and polyols, and the above compounds. Compositions containing various modified resins or prepolymers that are capable of radical curing by introducing double bonds, and as inorganic compounds, oxides of metal elements such as aluminum, titanium, zirconium, and antimony are preferably used. These are provided in the form of fine particles or as a colloidal dispersion in water and/or other solvents. As the organic material in which these inorganic fine particles are dispersed, since inorganic fine particles generally have a high refractive index, those having a lower refractive index than when an organic material alone is used are also used.

In addition to the organic materials mentioned above, transparent materials such as vinyl copolymers including acrylic copolymers, polyester (including alkyd) polymers, various curing agents for curing these, and compositions with curable functional groups are also available. Yes, various organic materials that can stably disperse inorganic fine particles can be used. Further, the organically substituted silicon compound is a compound represented by the general formula % (%) or a hydrolysis product thereof. Here, R' and R' are each an alkyl group, an alkenyl group, an allyl group, or a hydrocarbon group having a halogen group, an epoxy group, an amine group, a mercapto group, a methacryloxy group or a cyano group, X-alkoxyl, alkoxyalkoxyl, Hydrolyzable substituent selected from halogen to acyloxy group, b and c are each 0.1 or 2
and b+c is 1 or 2.

Other preferred examples of liquid compositions include alkoxides of various elements, salts of organic acids, and inorganic materials that are film-forming and can be dispersed in solvents, or that are liquid themselves. Coordination compounds bonded to monovalent compounds include titanium tetraethoxide, titanium tetra-1-propoxide, titanium tetra''
-n-propoxide, titanium tetra-n-butoxide,
Titanium tetra-8ec-butoxide, titanium tetra-t
ert-butoxide, aluminum triethoxide, aluminum tri-1-propoxide, aluminum triptoxide, antimony triethoxide, antimony tributoxide, zirconium tetraethoxide, zirconium tetra-1-propoxide, zirconium tetra-n-propoxide , metal alcoholate compounds such as zirconium tetra-n-butoxide, zirconium tetra-5ec-butoxide, zirconium tetra-tert-butoxide, as well as diisopropoquine titanium bisacetylacetonenite, di-butoxytitanium bisacetylacetonate, di-butoxy Titanium bisacetylacetonate, di-ethoxytitanium bisacetylacetonate.

bisacetylacetone zirconium, aluminum acetylacetonate, aluminum di-n-butoxide monoether acetoacetate, aluminum di-1-propoxide monomethylacetoacetate) 'e) phosphorus n-
Chelate compounds such as butoxide zirconium hemoethyl acetoacetate.

Further examples include zirconyl ammonium carbonate and active inorganic polymers containing zirconium as a main component. In addition to those mentioned above.

In particular, various alkyl silicates or their hydrolysates, fine particulate silica, and especially colloidally dispersed silica sol are used as substances having a relatively low refractive index but which can be used in combination with the above-mentioned compounds.

These compositions are usually applied diluted in volatile solvents. The solvent to be used is not particularly limited, but should be determined in consideration of the stability of the composition, wettability to the transparent substrate, volatility, etc.

Moreover, not only one type of solvent but also a mixture of two or more types can be used.

Further, the above-mentioned high refractive index coating can be used not only as a single layer but also as a multilayer film of two or more layers to improve the antireflection effect.

Specific representative examples of organosilicon compounds represented by the general formula CH,5i(OR') used as component (A) of the coating composition in the present invention include:

Methyltrimethoxysilane, methyltriethoxysilane, metrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, Methyltriphenethyloxysilane is mentioned as an example.

Specific representative examples of the organosilicon compounds used in the present invention include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane, and α-glycidoxyethyltrimethoxysilane. -glycidoxyethyltriethoxysilane, β-
Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, a-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β- Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxy Silane, a-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane,
γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane Methoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(g, 4
-Epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(1,4-epoxycyclohexyl)ethyl Tributoxysilane, β-(
3,4-epoxycyclohexyl)ethyltritoxyethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3°4-epoxycyclohexyl)propyltrimethoxysilane, γ
-(3,4-epoxycyclohexyl)propyltriethoxysilane, β-(3,4-epoxycyclohexyl)butyltrimethoxysilane, β-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxy Silane, glycidoxymethylmethyljethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyljethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldimethoxysilane, Toxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyljethoxysilane, α-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyljethoxysilane.

γ-glycidoxypropylmethyljethoxysilane, γ
-glycidoxypropylmethyldiproboxysilane, γ
-Glycidoxypropylmethyldibutoxysilane, γ-
Glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane,
γ-glycidoxypropylethyljethoxysilane, γ
-Glycidoxypropylvinyldimethoxysilane, γ-
Chrysitoxypropylvinyljethoxysilane.

γ-glycidoxypropylphenyldimethoxysilane,
Epoxy group-containing organosilicon compounds such as γ-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 6. S, :S-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane.

Chloromethyltriethoxysilane, N-(β-aminoethyl)γ-aminopropyltrimethoxysilane, N-(
β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ
-aminopropylmethyldimethoxysilane + N (β
-aminoethyl) γ-aminopropyltriethoxysilane, N-'(β-aminoethyl)γ-aminopropylmethyltriethoxysilane, dimethyldimethoxysilane.

Phenylmethyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxysilane.

γ-Chloropropylmethyldimethoxysilane, γ-chloropropylmethyljethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ -Mercaptopropylmethyljethoxysilane.

Examples include methylvinyldimethoxysilane and methylvinyljethoxysilane.

Especially from the viewpoint of dye permeability and surface hardness, γ-glycidoxypropyltrialkoxysilane is preferred.

Vinyltrialkoxysilane, γ-chloropropyltrialkoxysilane, and γ-glycidoxypropylmethyldialkoxysilane are preferably used.

Furthermore, effective examples of particulate silica used as component (B) of the coating composition in the present invention include silica sol and powdered silica fine particles. Silica sols are colloidal dispersions of high molecular weight silicic anhydride in organic solvents such as water and/or alcohols. Powdered silica particles are colloidal silica particles whose surface has been subjected to hydrophobic treatment, and both are commercially available. For the purpose of this invention, particles with an average particle diameter of 1 to 100 m.mu. are used, but particles with a diameter of 5 to 30 m.mu. are preferably used. If the particle size is smaller than this, fine particulate silica will not stably exist, making it impossible to obtain consistent quality.

In addition, if the particle size is larger than this, problems such as clouding of the coating film may occur. It is necessary to contain at least part by weight. If it is less than this, durability such as surface hardness, sweat resistance, weather resistance, etc. will decrease.

In addition, component (B) is 3 parts by weight per 100 parts by weight of component (A).
It is necessary to use less than 50 parts by weight and more than 28 parts by weight. If the amount of component (B) is less than this, the surface hardness will decrease, and if it is more than this, the adhesiveness with the transparent substrate will be poor.
Problems such as cracks occur.

The coating composition of the present invention has a substantial solid content of 2% by weight or more and less than 10% by weight. That is, even if the solid content is higher or lower than this, a sufficient antireflection effect cannot be obtained and the object of the present invention cannot be achieved. In addition, component (A)
The solid weight of is defined below.

The calculated solid weight of the hydrolyzate is W, and the amount used is Mo.
) has a weight of W. If , it is a quantity defined by a linear equation.

M.

W=WoX- 0 be.

Note that R1 and R2 mean corresponding organic groups in the organosilicon compound used in component (A) described above,
a is O or 1. Further, the substantial solid content is defined as the value obtained by applying the coating composition and dividing the weight of the film after heat curing by the weight of the applied coating composition. The actual solids content is usually higher than the calculated solids content.

In the above coating composition, various solvents and/or dispersants are used as component (C) for the purpose of controlling the substantial solid content to a predetermined concentration. The solvent and/or dispersant are appropriately selected depending on the substrate used, coating method, heating method, etc. Commonly used solvents and/or dispersants include various alcohol esters, ketones, water, aromatic and aliphatic (halogenated) hydrocarbons, ethers, organic carboxylic acids, etc. It is also possible to use it as a mixed solvent. Especially from the viewpoint of workability, caramel alcohol, ethyl alcohol, flobyl alcohol, phthyl alcohol, methyl cellosolve, ethyl cellosolve, diacetone alcohol, diethylene glycol dimethyl ether, and water.

Benzyl alcohol, methyl isobutyl ketone.

Dioxane, ethyl acetate, butyl acetate and the like are preferably used. Alcohols, organic acids, etc. produced by hydrolysis of the organosilicon compound of the moat component (A) should also be considered as component (C) of the present invention.

The amount of the solvent and/or dispersant to be added should be selected depending on the object to be coated, the coating conditions, and the desired coating film thickness, and should be determined experimentally.

Hydrolysis of the organosilicon compounds used as component (A) can be carried out singly or in combination of two or more thereof, or each may be carried out individually and then mixed. It can also be carried out without a solvent or preferably in the presence of a suitable solvent with the addition of water. In this case, hydrolysis often proceeds effectively when a small amount of an acid such as hydrochloric acid or acetic acid is used in combination.

Accelerates curing of the coating composition of the present invention.

Alternatively, various curing agents can be used to enable curing at low temperatures, and examples of preferred compounds from the viewpoint of solubility and stability in the catalyst active 9 composition include aluminum acetylacetonate, Aluminum chelate compounds such as aluminum ether acetoacetate bisacetylacetoacetate acetylacetonate, aluminum di-n-butoxide monoethyl acetoacetate, aluminum di-propoxide monomethyl acetoacetate, tetraisobutoxytitanium, diimpropoxy bis(acetylacetonate) Titanate compounds such as titanium, as well as organic carboxylic acids, chromic acid, 9 hypochlorous acid, 9 boric acid.

Bromic acid, selenite, thiosulfuric acid, orthosilicic acid.

Metal salts, especially alkali metal salts or ammonium salts of thiocyanic acid, nitrous acid, aluminic acid, and carbonic acid can be used.

Among the above, particularly preferred curing catalysts are:

Alkali metal salts of organic carboxylic acids, aluminic acids, carbonates,
Alternatively, an alkoxide or acetylacetonate salt of aluminum can be used. Although these curing catalysts can be used alone, it is also possible to use a mixture of two or more types.

Also, although it is not an essential component of the present invention, it improves hardness.

It is also possible to add a hydrolyzate of tetraorthosilicate such as methyl silicate, ethyl silicate, propyl silicate, and butyl silicate for the purpose of improving the antistatic effect.

It is also possible to use various surfactants in the coating composition of the present invention for the purpose of improving flow during application, in particular block or graft copolymers of dimethylsiloxane and alkylene oxide,
Furthermore, fluorine-based surfactants are also effective.

Furthermore, it is also 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.

As a method for applying the coating composition of the present invention, methods used in ordinary coating operations can be used, but from the viewpoint of controlling the thickness of the thin film, curtain flow coating, dip coating, spin coating, etc. are preferable.

When applying the coating composition, the transparent substrate is subjected to chemical treatments such as acid treatment, alkali treatment, moist heat treatment, and hot water treatment, and physical treatments such as corona discharge treatment, plasma treatment, and flame treatment, either singly or in combination. In combination, adhesion, durability, etc. can also be improved.

The coating composition applied in this manner is cured by heating and/or drying.

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 is usually 50 to 250°C, preferably 60 to 250°C.
200°C is used.

Curing or drying may not be sufficient at low temperatures.

Furthermore, if the temperature is higher than this, thermal decomposition may occur, causing problems such as yellowing.

Further, the thickness of the coating layer of the present invention is controlled by the solid content of the coating composition, the coating method, and the coating conditions.

As the transparent substrate of the present invention, any transparent material may be used as long as the object of the present invention is required, but from the viewpoint of liquid coating, glass and plastic materials give particularly effective results. The above plastic materials include polymethyl methacrylate and its copolymers, and polycarbonate.

Diethylene glycol bisallyl carbonate (cR,
-39), polyesters, especially polyethylene terephthalate, and unsaturated polyesters.

acrylonitrile-(halogenated)styrene copolymer,
Vinyl chloride, polyurethane, epoxy resin.

Preferred are di(meth)acrylate polymers of (halogenated) bisphenol A and copolymers thereof, urethane-modified di(meth)acrylate polymers of (halogenated) bisphenol A, and copolymers thereof.

Moreover, it can also be preferably used for glass.

The above plastic further coated with a coating material.

It can also be preferably applied to transparent substrates such as glass.

For the purpose of improving the hardness of transparent substrates such as plastics with low surface hardness, it is possible to use known surface hardening coatings (Japanese Patent Publication No. 5 [1983]).
]-2sso 92. Special Publication No. 50-28446, Special Publication No. 50-39449. Special Publication No. 51-24368. Japanese Patent Application Publication No. 5
2-112698', Special Publication No. 57-2735).

In particular, when the antireflective coating of the present invention is applied to the dyeable highly hardened coating described in Japanese Patent Publication No. 57-27J5, the effect of the present invention, which is an antireflective coating that is dye permeable, can be maximized. Can be used as a good merge.

Moreover, when the above-mentioned surface hardening coating does not have a sufficiently high refractive index, it is preferable to provide a coating layer having the above-mentioned high refractive index to form a transparent base material.

There are many possible combinations of transparent substrates or coated transparent coatings and anti-reflective coatings that achieve the objectives of the present invention, and the optimum range must be determined experimentally.

The transparent material having an antireflection effect obtained by the present invention has the following characteristics in addition to the antireflection function.

01 High surface hardness and scratch resistance.

(2) Excellent weather resistance.

(3) Excellent sweat resistance.

(4) Excellent chemical resistance.

(5) To prevent contamination caused by fingerprints or sweat.

In addition, it can be easily removed. The shape of the transparent material of the present invention is not limited in any way, but it is usually in the form of a film, for example.

Often used in sheet shapes, lenses, etc.

The present invention will be explained in detail below with reference to Examples.

It is not limited to this. In addition, the solid content in each example was measured as the residual content after heating and drying at 96° for 4 hours.

Example 1 (1) Preparation of transparent substrate (a) Preparation of coating composition for high refractive index In a peaker equipped with a rotor, 5508 g of n-butanol and 12.0 g of acetic acid were added.
2 g, 5.1 g of a 5% silicone surfactant n-butanol solution is added. 47.4 g of methanol-dispersed colloidal silica (average particle size 12±1 mμ solid content 30%) and 34.5 g of tetra-n-butyl titanate were added to this mixed solution while stirring at room temperature. A coating composition was prepared.

(b) Transparent substrate A diethylene glycol bisallyl carbonate polymer lens (diameter 75.m
2.1 mm, thickness 2.1 mm, CR-59 Praruns) was spin-coded under the following conditions. The coated lens is 93℃
Heat drying was performed for 45 minutes.

Spin code conditions Rotation speed: 3500rpm Rotation time: 60 seconds After drying by heating, it was immersed in hot water at 50°C for 50 minutes.

Further, it was heated and dried at 110°C for 1 hour to produce a transparent base material. The refractive index of the surface portion of this transparent base material was 155.

421 Anti-reflection treatment (a) Preparation of silane hydrolyzate Add 13.4 g of methyltrimethoxysilane, 4.3 g of γ-dichlorolopyltrimethoxysilane, and 4 g of n-propyl alcohol, and heat to 10°C. After cooling, 6.5 g of 0.01N hydrochloric acid aqueous solution was added dropwise while stirring.

After the dropwise addition was completed, stirring was continued for another 1 hour at room temperature to obtain a silane hydrolyzate.

(b) Preparation of coating composition 32.4 g of the above silane hydrolyzate, 142.7 g of n-propyl alcohol, 22.5 g of ethyl cellosolve, 7 g of water
'0.8 go' 5% silicone surfactant n-
After adding 3.8g of probyl alcohol and mixing well,
270 g of the same methanol-dispersed colloidal silica used in (1) and 0.80 g of aluminum acetylacetonate were added and thoroughly stirred to obtain a coating composition. Solid content was 5.95 qb.

(C) Coating and curing The above t2+,
(b) The coating composition prepared in (b) is
) was spin-coded under the same conditions as JD 93 after coating.
Heat curing was performed for 4 hours in a '0 hot air dryer.

(The total light transmittance of the lens obtained as a result of the 32 test was 967, and it was an anti-reflection lens with a reddish-purple reflected light color.The total light transmittance of the lens before anti-reflection processing was 92.6. %Met.

Note that the refractive index of the coating film was 1.66.

Example 2 (1) Production of transparent substrate (a) Preparation of silane hydrolyzate γ-glycidoxypropylmethyljethoxysilane 10
6.8 g was cooled to 10° C., and 15.5 g 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 for high hardness The silane hydrolyzate is mixed with an epoxy resin (“Epicoat 827”,
Shell Chemical Co., Ltd. product) 25g, epoxy resin ('''
Epolite 3002 (product of Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) 25g, diacetone alcohol 58.9g, benzyl alcohol 29.5g, methanol 310g, and silicone surfactant 1.5g were added and mixed, and the mixture was further used in Example 1. Methanol-dispersed colloidal silica 416.
After adding 7 g of aluminum acetylacetonate and 12.5 g of aluminum acetylacetonate and stirring thoroughly, a cotting composition was prepared.

(C) Application of undercoat, curing, and pretreatment The coating composition for high hardness was applied to the diethylene glycol bisallyl carbonate polymer lens used in Example 1 by a dipping method.

Heated at 93°C for 4 hours. The cured lens was pretreated using a surface treatment plasma device (PR501A manufactured by Yamato Scientific Co., Ltd.) at an oxygen flow rate of 100 m1/min and an output of 50 W for 1 minute.

(ci) Transparent base material The high refractive index coating composition was coated on the undercoated lens of (0) above in exactly the same manner as in fi+ and (b) of Example 1 to produce a transparent base material. . The refractive index of the surface portion of this transparent base material was 1.55.

(2) Manufacture and test results of antireflection film Except for using the transparent substrate manufactured in the above (1).

Everything was carried out in the same manner as in Example 1.

The total light transmittance of the obtained lens was 9 ZO%, and the color of the reflected light was reddish-purple. The refractive index of the coating film was exactly the same as in Example 1.

The performance of the antireflection lens obtained was determined to be 1st order or υ by following the method shown in (3) below.

Steel wool hardness A Steel wool hardness after 100 hours in the sunshine weather meter A-Sweat light cycle test 41 (3) Test method 13) -1 Rub the painted surface with steel wool with steel wool hardness -1+ = 0000 to check the degree of scratches. judge. What are the criteria?

A...It won't get scratched even if it is rubbed strongly.

B... If you rub it quite strongly, it will get a little scratched.

C-... Even weak friction will heal the scratches.

D: Easily scratched with nails.

(3)-2 Sweat light cycle test J I 5-Ll 047 (Sweat waxing test method for dyed products and dyes) An anti-reflection lens was immersed in an alkaline artificial juice solution specified in J I 5-Ll 047, and after being irradiated with ultraviolet rays for a period of time, ≠ The surface was rubbed with OO steel wool (manufactured by Nippon Steel Wool ■) and the appearance was observed. This was called one cycle and was repeated until scratches appeared on the surface. The results were expressed as the number of cycles immediately before the occurrence of scratches.

A higher number of cycles means better durability against sweat, light, water, abrasion, etc.

Examples 3-5. Comparative Examples 1 to 6 (1) Transparent Substrate A lens coated with an undercoat and a back refractive index coating prepared in exactly the same manner as in Example 2 was used as a transparent substrate.

(2) Preparation of coating composition Using the silane hydrolyzate prepared in exactly the same manner as in Example 1 (21, (a)), the mixing ratio with silica sol was adjusted to the first
A coating composition was prepared in exactly the same manner as in Example 1 (2) and (b) as shown in the table.

(3) Anti-reflection treatment and test results The coating composition of (2) was used on the transparent substrate of (1) above and was coated and thermally cured in exactly the same manner as in Example 1. The obtained lenses were tested in the same manner as in Example 2, and the results are shown in Table 1.

Example 6 (1) Transparent base material A lens coated with an undercoat and a high refractive index coating produced in exactly the same manner as in Example 2 was used as a transparent base material.

(2) Preparation of coating composition (a) Preparation of silane hydrolyzate 21.2 g of methyltrimethoxysilane and 122 g of n-propyl alcohol were added, and after cooling to 10°C, 8.4 g of 001N hydrochloric acid aqueous solution was added while stirring. was dripped. After the dropwise addition was completed, stirring was continued for another 1 hour at room temperature to obtain a silane hydrolyzate.

(b) Preparation of coating composition 35.3 g of the above silane hydrolyzate 1' of propyl alcohol 39.1 F! ,, Ethyl Cellosolve 225
g, 69.0 g of water, and 6.9 g of 5% silicone surfactant n-propyl alcohol were added and mixed thoroughly.
) Same methanol-dispersed colloidal as used in '/+
), aluminum acetylacetonate 09 was further added and stirred sufficiently to obtain a coating composition. Solid content was 5.96%.

(C) Coating and curing The above +21,
The coating composition prepared in (b) was spin-coded under the same conditions as in Example 1, and after coating was heat-cured for 4 hours in a hot air dryer at 96°C.

(3) Test Results The obtained lens was tested in the same manner as in Example 2, and as a result, the total light transmittance was 97.2%, the steel wool hardness was A, and the sweat light cycle test was 69 cycles. Further, the steel wool hardness after the weather resistance test (Sunshine Weather-Ometer 100 hr) was also good at B.

Comparative Example 4 (1) Transparent Substrate A lens coated with an undercoat and a high refractive index coating produced in exactly the same manner as in Example 2 was used as a transparent substrate.

(2) Preparation of coating composition (a) Preparation of silane hydrolyzate γ-glycidoxypyltrimethoxysilane 12.0
g, n-propyl alcohol 19.2 g was added, I
After cooling to O'a, add 001N hydrochloric acid aqueous solution 2 under stirring.
8 was added dropwise. 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: 53.1 g of the above silane hydrolyzate, 124 g of n-propyl alcohol, 20.3 g of ethylceromelf, 61.8 g of water.
g15% silicone surfactant After adding 6.7 g of n-propyl alcohol and mixing well.

27.5 g of the same methanol-dispersed colloidal silica used in (1) and 0.9 g of aluminum acetylacetonate were added and thoroughly stirred to obtain a coating composition. The solid content was 671 units.

(c) Coating and curing The above +21,
The coating composition prepared in (b) was added to the coating composition prepared in (1) above.
, Spin code under the same conditions as (b), and after coating, 9
Heat curing was performed for 4 hours in a hot air dryer at 3°C.

(3) As a result of testing the obtained lens in the same manner as in Example 2, the total light transmittance was 9.6.6% and the steel wool hardness was A.
However, after 6 cycles of sweat light cycle test and weather resistance test (Sunshine Weather Ometer 100hrs)
,) had a steel wool hardness of C and poor durability.

Example 7 (1) Transparent base material A lens coated with an undercoat and a high refractive index coating produced in exactly the same manner as in Example 2 was used as a transparent base material.

(2) Preparation of coating composition (a) Preparation of silane hydrolyzate 43.0 g of methyltrimethoxysilane, 30.0 g of r-glycidoxyprobyltrimethoxysilane.

After adding 72.7 g of n-propyl alcohol and cooling to io'c, 269 g of 001N hydrochloric acid aqueous solution was added dropwise with stirring. After the dropwise addition was completed, stirring was continued for another 1 hour at room temperature to obtain a silane hydrolyzate.

(b) Preparation of coating composition Above silane hydrolyzate 33.1. n-propyl alcohol 124.0g, ethyl cellosolve 206g water 61.8g
g, 5% silicone surfactant After adding 37 g of n-propyl alcohol and mixing well.

27.5 g of the same methanol-dispersed colloidal silica used in (1) and 0.9 g of aluminum acetylacetonate were added and thoroughly stirred to obtain a coating composition. The solid content was 686%.

(C) Coating and curing The above +2+,
Coating composition prepared in (b) in the previous section (1), ←
), and after coating, heat curing was performed in a hot air dryer at 93° C. for 4 hours.

(3) As a result of testing the obtained lens in the same manner as in Example 2, the total light transmittance was 967%, the steel wool hardness was A, the sweat light cycle test was 35 cycles, and after the weather resistance test (Sunshine Weather The steel wool hardness on an Ometer (100 h'r) was also good, being A.

Examples 8 to 71 Comparative Examples 5 to 6 (1) Transparent base material A lens coated with an undercoat and a high refractive index coating produced in exactly the same manner as in Example 2 was used as a transparent base material.

(2) Preparation of coating composition In +21, (a) and (b) of Example 1,
A coating composition was prepared in exactly the same manner except that the amounts of n-propyl alcohol (a diluting solvent) and water were changed as shown in Table 2. Note that the mixing ratio of n-propyl alcohol and water was 67:33 (weight ratio).

(3) Anti-reflection treatment and test results Performed using the coating composition of (2) on a transparent substrate of (1) in exactly the same manner as in 1.

Coated and heat cured. Table 2 shows the test results for the total light transmittance of the obtained lenses.

Example 12 (11) Transparent Substrate A lens made of a copolymer of brominated bisphenol A dimethacrylate and styrene (refractive index 1.593) was used as a transparent substrate.

(2) Anti-reflection treatment and test results All Example 1 except for using the transparent base material in (11) above
Antireflection treatment was performed in the same manner as above. The resulting lens has a pale reddish-purple reflected light color and a total light transmittance of 89.
It was 6%.

Table 2 Procedural amendment C86621 Manabu Shiga, Commissioner of the Japan Patent Office (Monday/Monday, Showa) 1, Indication of the case 1982 Patent Application No. 61664 @ 2, Name of the invention Process for manufacturing an anti-reflection transparent material 3, Person making the amendment Case Relationship with Patent applicant address 2-2 Nihonbashi Muromachi, Chuo-ku, Tokyo Name (3
15) Toshi Co., Ltd. -15, Number of inventions increased by amendment None 6, Section 7 of “Detailed Description of the Invention” of Book III Subject to Amendment (1) Section 8 Correct "Refractive index J of coating film" on the 4th to 5th lines of the page to "Refractive index of coating film".

(2) On page 9, line 20, "hetero dew" was corrected to "heterocycle."

(3) Delete [Jyptoxytitanium bisacetylacetonate] on page 12, lines 15-16.

(4) Correct “Roboxizuran” in line 6 of page 16 to “Roboxysilane”.

(5) Delete "γ-glycytoxypropyl medyldiethoxysilane," from lines 7 to 8 on page 17.

(6) “Hardness is C’#5 resistant” on page 40, line 5.
Correct the hardness to be C and chu.

(7) On page 43, line 7, "The linear transmittance was 89.6%." Transmittance is 89.6
%Met. ” I corrected myself.

Claims (1)

[Claims] (CH,)5L (A) 100 parts by weight of a hydrolyzate of an organic-4 silicon compound represented by the general formula R'5i(OR"), provided that (A
) 50 parts by weight or more of the components are CH, Si ('OR')
. A hydrolyzate of an organosilicon compound represented by (where,
R' is an alkyl group having 1 to 10 carbon atoms. A hydrocarbon group having an alkenyl group, an allyl group, a halogen group, an epoxy group, an amine group, a mercapto group, a methacryloxy group or a cyano group. R2 is an alkyl group, alkoxyalkyl group, or acyl group having 1 to 8 carbon atoms, and a is 0 or 1. ) (B) Fine particulate silica with an average particle diameter of 1 to 100 mμ
28 to 650 parts by weight (C) A coating composition containing one or more solvents and/or dispersants and having a substantial solids concentration of more than 2 times but less than 10 times the refractive index of the coating film. , 0. , [] A method for producing an antireflection transparent material, which comprises applying the coating to at least a portion of the surface of a transparent substrate having a refractive index of 33 or higher and then curing the material by heating.