JPS6191601A - Production of reflection preventive transparent material - Google Patents

Abstract

PURPOSE:To obtain a coat film enhanced in reflection preventive effect, surface hardness, durability, etc., by coating the lens of an optical appliance with a soln. of an org. polysiloxane type reflection preventive transparent material as the outermost layer, and hardening it through processing in an atm. of air in a specified absolute humidity and heating. CONSTITUTION:Single or double layers of the reflection preventive films with at least the outer layer made of an org. polysiloxane transparent film are formed on the surfaces of the lenses of spectacles, and various kinds of optical appliances. At that time, the lens surface is coated with at least one of liquid org. silicon compd., such as alkyl silicate, 4-acetoxysilane, or methylvinyldieth oxysilane, and treated in an atm. of air having an absolute humidity of 6-180g/kg air in at least 1sec, and then, heat cured, thus permitting the obtained transparent material to be enhanced in reflection preventive effect, surface hardness, and resistances to heat and impact, and durability, and dyeable rapidly to optional colors.

Description

[Detailed Description of the Invention] [Industrial Application Field] Since the present invention has 1 anti-reflection function and coloring performance,
It is used in the form of lenses, sheets, or films for eyeglass lenses, various optical instruments, front panels of display devices such as word processors, or as mounting materials for show windows.

[Conventional technology]

Conventionally 9 To prevent reflection, a material with a refractive index different from that of the base material was used.
A method of forming a film on a substrate using a vacuum evaporation 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 the case of a single-layer film, the optical film thickness of a material with a lower refractive index than the base material is 1/4 to 1/4 of the wavelength of light.

It is known that selecting an odd number multiple of , gives the minimum reflectance, that is, the maximum transmittance.

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 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 Mol 9 m8.17~2
5 (1971)).

Regarding the manufacturing method of anti-reflection film using liquid composition,
JP-A-58-46101 discloses that an antireflection film can be obtained by applying two layers each in liquid form to the surface of a transparent substrate.

In addition, as a manufacturing method for colored lenses, Japanese Patent Application Laid-Open No. 59-495
In 02, dyeable on the dyeable lens substrate,
Alternatively, a method for forming an antireflection film that is dye-transmissive is disclosed.

[Problem that the invention seeks to solve]

Antireflection films formed by vapor deposition methods have the following problems depending on their use.

(1) 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) Usually requires considerable heating, and depending on the base material, it may deform or
This causes problems such as decomposition.

(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 are likely 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) Similar loss of dyeability, reduction in heat resistance and adhesion occur in glass coated with dyeable materials.

(G) Since a high degree of vacuum is required, the color depth and hue of the colored lenses to be processed change before and after anti-reflection processing, resulting in poor reproducibility.

Also, JP-A-58-46301, and JP-A-59-
49502, the antireflective film obtained by coating each of two or six layers with a liquid composition has excellent performance in heat resistance 9 surface hardness, dyeability, impact resistance, etc. However, it is strongly desired to further increase the dyeing speed in order to increase the commercial value.

[Failure to solve the problem]

The present inventors have solved and improved these problems, as well as improved dyeability, weather resistance, sweat resistance, and light resistance.

As a result of extensive studies aimed at providing a transparent material with excellent scratch resistance and antireflection effects, the present invention described below was achieved.

That is, in the present invention, at least the outermost layer is an organic polysiloxane transparent film. In a method for producing an anti-reflective transparent material in which a single-layer or multi-layer anti-reflective film is applied in liquid form to the surface of a transparent substrate and then cured by heating, after applying the outermost layer,
1 in an atmosphere with absolute humidity of 6 to 180 g/D-air
After processing for more than seconds.

This is a method for producing an antireflection transparent material, which is characterized by heating and curing.

Here, the transparent base material is a transparent base material with a haze value of 80 inches or less as determined by the following formula, and if necessary, is colored with a dye or the like, or is colored in a pattern. can also be included in this. Further, a transparent substrate coated with a coating material to impart scratch resistance, etc., can also be included in the transparent substrate of the present invention if the haze value is 80 or less according to the following formula.

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 may be Can be used as material.

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

Specific examples of such transparent substrates include polymethyl methacrylate, polycarbonate, acrylonitrile-styrene copolymer, and polyvinyl chloride.

Cellulose acetate r　po') ethylene terephthalate.

Thermoplastics such as nylon resin and polystyrene, as well as diethylene glycol bisallyl carbonate polymer (CR59), polyfunctional (meth)acrylate copolymers, (meth)acrylic acid ester copolymers of (halogenated) bisphenol A, and epoxy. Examples include thermosetting plastics such as cured resins and polyurethane. Inorganic glass may also be used as an example of a transparent substrate.

Next, in order to obtain the antireflection transparent material according to the present invention, it is necessary to provide at least one coating film on the surface of the transparent substrate. When a single layer of coating film is provided on a transparent substrate to exhibit an antireflection effect, this coating film becomes the outermost layer, and the outermost coating film has an anti-reflection effect of 0.03 or more, preferably 0. It is necessary to have a refractive index as low as .05 or more.

If the outermost coating film has a higher refractive index than the transparent base material, that is, if the transparent base material has a relatively low refractive index, an intermediate layer with a higher refractive index than the outermost coating film may be added to the surface of the transparent base material. It is necessary to adopt a multilayer structure in which one or more layers of coating material are provided and an outermost coating film is applied thereon.

When applying such an intermediate coating material having a relatively high refractive index to the surface of a transparent substrate, it is preferable to satisfy the following conditions in order to further improve antireflection properties.

(a) When a layer of intermediate coating material with a high refractive index is provided on the surface of a transparent substrate, and the outermost coating film is applied on top of it.

Intermediate coating material on the base material Outermost layer coating (Here, 101.n2 is the intermediate coating material on each base material.

The refractive index 1d11d2 of the outermost coating film is the thickness (n) of the intermediate coating material and the outermost coating film on the base material, respectively.
m unit) 2m is a positive integer, n is an odd positive integer.

λ is an arbitrary reference wavelength (in nm) chosen within the visible peripheral region. (b) When two layers of intermediate coating material with a high refractive index are provided on the surface of a transparent substrate, and the outermost coating film is applied on top of that.

First intermediate coating material (layer A) provided directly on the base material; Second intermediate coating material (3 layers) provided on layer A; Outermost coating film (here, r ``l ``2+ ''5 is each A layer, B layer,
Refractive index of the outermost coating film layer, dl, d2. d3
are the film thicknesses (n
m unit)+1 is a positive integer 9m is a positive integer, n is an odd positive integer, λ is an arbitrary reference wavelength (n
m unit). ) In the production of a transparent substrate having an intermediate coating material with a relatively high refractive index, various organic compounds and inorganic compounds are preferably used as the composition of the intermediate coating material. 1 For example, polystyrene, polystyrene copolymer, polycarbonate, various polymer compositions having an aromatic ring other than polystyrene, a heterocyclic group, an alicyclic cyclic group, or a halogen group other than fluorine, melamine resin, phenol resin, or epoxy resin, etc. By introducing double bonds into various thermosetting resin-forming compositions using curing agents, urethane-forming compositions consisting of alicyclic or aromatic incyanates and/or these and polyols, and the above compounds. , compositions containing various modified resins or prepolymers that enable radical curing.

Further, as the inorganic compound, 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, R4 and R5 are hydrocarbon groups each having an alkyl group, an alkenyl group, an allyl group, a halogen group, an epoxy group, an amino group, a mercapto group, a methacryloxy group or a cyano group, and X is an alkoxyl group, an alkoxyalkoxyl group, or a halogen group. to acyloxy groups, c and d are each 0, 1 or 2, and C◆d is 1t or 2.

Other suitable examples include alkoxides of various elements, salts of organic acids, and coordination compounds bonded to inorganic materials that have film-forming properties and can be dispersed in solvents, or are liquid themselves. Specific examples of these compounds include titanium tetraethoxide, titanium tetra-1-propoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, titanium tetra-5ea-butoxide, titanium tetra- tart-butoxide, aluminum triethoxide, aluminum tri-glopoxide, aluminum tributoxide, antimony triethoxide, antimony tributoxide, zirconium tetraethoxide, zirconium tetra-1-propoxide, zirconium tetra-n-propoxide, zirconium Tetra-n-butoxide, zirconium tetra-5
ec-buto, oxide, zirconium tetra-tert-
Metal alcoholate compounds such as butoxide, as well as di-isopropoxytitanium bisacetylacetonate, di-butoxytitanium bisacetylacetonate,
Di-butoxytitanium bisacetylacetonate, di-ethoxytitanium bisacetylacetonate, bisacetylacetone zirconium, aluminum acetylacetonate, aluminum dilobtoxide monoethylacetoacetate, aluminum dimepropoxide monomethylacetoacetate, tri-n-butoxide zirconium Examples include chelate compounds such as monoethyl acetoacetate, zirconyl ammonium carbonate, and active inorganic polymers containing zirconium as a main component. In addition to those mentioned above, various alkyl silicates or their hydrolysates, fine particulate silica, especially colloidally dispersed silica sol are used as compounds having a relatively low refractive index but which can be used in combination with the above 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, volatile electrode, etc.

Moreover, it is also possible to use not only one type of solvent but also a mixture of two or more types.

In addition to having a high refractive index, these high refractive index intermediate coating materials are preferably dyeable themselves or have dye permeability.

In the present invention, an organic polysiloxane-based transparent film is coated as the outermost layer on a transparent substrate having the above-mentioned intermediate high refractive index layer or having a high refractive index itself. The system transparent film is a transparent film obtained by coating and curing a hydrolyzate of an organosilicon compound represented by the general formula %. (Here, R1 is an alkyl group, alkenyl group, allyl group having 1 to 10 carbon atoms, or a hydrocarbon group having a rogene group, epoxy group, amine group, mercapto group, methacryloxy group or cyano group, R2 is a carbon group) The number is a methyl group, a vinyl group, a phenyl group, R5 is an alkyl group, an aryl group, an acyl group, or an alkoxyalkyl group having 1 to 8 carbon atoms, ``lb is 0, 1, or 2, and a◆b is 2 or less) Specific representative examples of these organosilicon compounds include methyl silicate, ethyl silicate) + n-propyl silicate, and i-propyl silicate.

n-butyl silicate, 5ec-butyl silicate.

t-Butylsilicate, tetraacetoxysilane/, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane Sicilan.

Methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltriethoxysilane, α-glycidoxyethyltriethoxysilane, β- Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane.

α-Glycidoxypropyltrimethoxysilane.

α-Glycidoxyprobyltriethoxysilane.

β-Glycidoxyprobyltrimethoxysilane.

β-Glycidoxyprobyltriethoxysilane.

γ-Glycidoxyzorobyltrimethoxysilane.

γ-glycidoxyglobiltriethoxysilane.

γ-Glycidoxyprobyltripropoxysilane.

γ-Glycid'xypropyltributoxysilane.

γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α
-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane.

γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane Methoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4
-Epoxycyclohexyl)ethyltrimethoxysilane, β-(3゜4-epoxycyclohexyl)ethyltriethoxysilane, β-(!,,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl) Ethyltributoxysilane.

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

γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(6,4-epoxycyclohexyl)butyltrimethoxysilane, δ-
(5,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyljethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyljethoxysilane , β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyljethoxysilane.

β-glycidoxypropyl methyljethoxysilane, γ
-Glycidoxypropylmethyljethoxysilane, γ-
Glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ
-Glycidoxypropylmethyldiphenoxysilane, γ
- Glycidoxyzolobyl ethyldimethoxysilane.

γ-glycidoxyzolobyl ethyljethoxysilane, γ
-glycidoxyzolopyrvinyldimethoxysilane, γ-
Glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane/, vinyltrimethoxysilane Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-
Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane.

γ-chloropropyltriacetoxysilane, 3,3°6
-trichloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane.

γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane t N (β-aminoethyl) γ-aminopropyltrimethoxysilane ,
N-(β-aminoethyl)γ-aminopropylmethyldimethquine silane.

γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)γ-aminopropyltriethoxysilane, N-(β-aminoethyl)
-aminoethyl) γ-aminopropylmethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyljethoxysilane, Dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-mercaptoglobilmethyldimethoxysilane, γ-mercaptopropylmethyljethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane An example is toxisilane.

It is fully possible to use not only one type of these organosilicon compounds but also a combination of two or more types.

In particular, for the purpose of significantly increasing the dyeability, it is preferable to use organosilicon compounds containing epoxy groups.However, for the purpose of improving durability, it is preferable to use organosilicon compounds containing methyl groups, vinyl groups, and γ-chloropropyl groups. be.

These organosilicon compounds are used after being hydrolyzed, and the hydrolysis is produced by adding and stirring pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid.

Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added. During hydrolysis, the general formula 10R
It is particularly preferable to add pure water or an acidic aqueous solution in an amount equal to or more than 6 times the amount of the 3 groups, but not more than 6 times the amount, from the viewpoint of accelerating curing.

During hydrolysis, alcohol and other substances are produced, so it is possible to hydrolyze without a solvent, but in order to make the hydrolysis more uniform, it is preferable to mix the organosilicon compound and a solvent before hydrolysis. is also possible. Further, depending on the purpose, it is also possible to remove an appropriate amount of the hydrolyzed alcohol etc. by heating and/or under reduced pressure before use, and it is also possible to add an appropriate solvent after that.

Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, and aromatic hydrocarbons such as toluene and xylene. Moreover, these solvents can also be used as a mixed solvent of two or more types as required. Depending on the purpose, it is also possible to accelerate the hydrolysis reaction and heat it above room temperature to advance reactions such as precondensation, or to lower the hydrolysis temperature to below room temperature to suppress precondensation. Needless to say, it is also possible to do so.

Although curing of the outermost coating film of the present invention can be achieved by heating and/or drying only one composition, various curing agents can be used in combination for the purpose of accelerating curing, enabling low-temperature curing, etc. .

As the curing agent, various epoxy resin curing agents or various organosilicon resin curing agents are used.

Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds, and metal alkoxides.

Further examples include various salts such as organic carboxylates of alkali metals and carbonates. It is also possible to use a mixture of two or more of these curing agents. Among these curing agents, the aluminum chelate compounds shown below are particularly useful for the purpose of the present invention from the viewpoints of stability of the coating material, coloring of the coating film after coating, etc.

What is the aluminum chelate compound mentioned here?

It is an aluminum chelate compound represented by the general formula AIXnY, -.

The general formula AIXnYg- is particularly useful as a curing agent in the present invention.
As the aluminum chelate compound represented by n, various compounds can be mentioned, but aluminum acetylacetonate and aluminum bisethyl are particularly preferred from the viewpoint of solubility in the composition, stability, effect as a curing catalyst, etc. These include acetoacetate monoacetylacetonate, aluminum di-n-butoxide monoethyl acetoacetate, aluminum di-1so-7'ropoxide monomethyl acetoacetate, and the like.

It is also possible to use a mixture of two or more of these.

It is also possible to use various surfactants in the outermost coating film of the present invention for the purpose of improving the flow during coating, improving the smoothness of the coating film, and lowering the coefficient of friction of the coating film surface. In particular, block or graft copolymers of dimethylsiloxane and alkylene oxide, and fluorine-based surfactants are effective. In addition, it is easy to disperse dyes and pigments and fillers, dissolve organic polymers, color the coating, and improve the practicality of the coating agent by improving its applicability, adhesion to substrates, and physical properties. possible.

Furthermore, in order to improve weather resistance, it is also possible to easily add an antioxidant to the ultraviolet absorber as a method of improving thermal deterioration.

Furthermore, silica sol, which is a colloidal dispersion of high molecular weight silicic anhydride in an organic solvent such as water and/or alcohol, is preferably used for the purpose of further improving surface hardness and antistatic properties. Moreover, various epoxy resins, melamine resins, nylon resins, etc. are preferably used for the purpose of improving dyeability.

In the present invention, the means for applying the liquid composition forming each layer include brush coating, dip coating, and roll coating.

Conventional painting methods such as spray painting, spin painting, and flow painting can be easily used.

From the viewpoint of productivity and uniformity of coating film thickness, dip coating is particularly preferred for sheet-like objects, and spin coating is particularly preferred for articles with curvature such as lenses.

According to the present invention, the coating coated in this way has an absolute humidity of 6.
g/gun-air ~ 180 g/chaos-air After being treated for 1 second or more in an atmosphere, it is heated and cured, where g/kg-air is the weight of water contained in 1 kg of air, At less than 6 g/lcg-air, no effect of improving dyeability was observed, and still at 180 g
/chaos-air, problems such as whitening of the coating film and non-uniform dyeing occur. Especially 8 g/kg-air ~14
0 g/kg-air is the preferred absolute humidity condition.

Also, as long as the humidity is within the above range, there is no particular limitation, but 2
Humidity is 20℃~1 due to ease of work and simplicity of equipment.
10°C is preferred.

Also, absolute humidity and temperature for processing time.

Further, the optimum conditions should be determined experimentally depending on the desired dyeing properties and the components of the organic polysiloxane coating film of the outermost layer, but at least 1 second is required to produce an effect.

Regarding the treatment method, it is possible to increase the humidity one after another, or it is also possible to perform the treatment suddenly under predetermined humidity conditions. Further, many combinations of methods are possible, such as keeping the absolute humidity constant and increasing only the processing temperature, or increasing the absolute humidity and temperature simultaneously and sequentially.

The treatment in the present invention should be performed before heat curing, and the effect of improving dyeability does not appear after heat curing. Here, heat curing means being exposed to a temperature of 60'C or more for 10 minutes or more.

The method for producing an antireflection transparent material according to the present invention is preferably applied to optical parts such as eyeglass lenses and sunglass lenses, pottery such as vases and pots, and various storage covers such as window displays.

Example 1 - (1) Preparation of coated transparent substrate (a) Preparation of coating composition for high refractive index intermediate coating 650.8 g of n-butanol in a peaker equipped with a rotor.
, 12.2 g of acetic acid, 5% silicone surfactant n-
Add 5.1 g of butanol solution. ° 474 g of colloidal silica (average particle size 12 ± 1 mμ solid content 60%) dispersed in methanol while stirring at room temperature.
, 34.5 g of tetra-n-butyl titanate was further added to form a coating composition.

(b) Coating on a transparent substrate A diethylene glycol bisallyl carbonate polymer lens (diameter 75 w) was immersed in a caustic soda aqueous solution using the coating composition prepared in the previous section (a) and then washed.
2.1 m thick, CR-39 Praruns) was spin-coded under the following conditions. The coated lens is 100'
It was heated and dried in O for 2 hours. The refractive index of the CR39 lens used was 1.504.

Spin code conditions: rotation speed + 550 rpm; rotation time: 30 seconds; the refractive index of the coated transparent substrate surface portion was 1.55.

(2) Outermost layer coating (a) Preparation of silane hydrolyzate 13.4 g of methyltrimethoxysilane, 4.3 g of γ-chloropropyltrimethoxysilane, and 13.4 g of n-propyl alcohol were added and cooled to 10°C. Thereafter, 6.58 g of a 0.01N aqueous hydrochloric acid 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 outermost layer coating composition 32.4 g of the above silane hydrolyzate, 142 g of n-propyl alcohol
．． 7g, ethyl cellosolve 22.5g, water 70.8g,
5 Silicone surfactant m-propyl alcohol 6
．． After adding 8 g and mixing well, 27.0 g of the same methanol-dispersed colloidal silica used in (1),
Furthermore, 0.80 g of aluminum acetylacetonate was added and thoroughly stirred to obtain a coating composition. Solid content was 5.95%.

(C) Application and cure (2) above on the coated transparent base material manufactured in the previous section (1).

The outermost layer coating composition prepared in (b) was added to the outermost layer coating composition prepared in (1) above.
), ・Spin coded under the same conditions as (b), and after coating, the temperature was 80°C2 and the absolute humidity was 44.0 g/kg-air.
After being treated in a constant temperature and humidity chamber for 60 minutes, it was heated and cured in a dryer for 4 hours.

(3) Test results The total light transmittance of the obtained lens was 96.6%.

It was an antireflection lens with a reddish-purple reflected light color. The total light transmittance of the lens before anti-reflection treatment is 92.6%.
Met. In addition, this anti-reflection lens is available in five colors: red, blue, and yellow.
The lens was dyed for 96"C945 minutes using a dyeing bath in which disperse dyes of mixed colors were dispersed and dissolved in water. This lens was dyed to a total light transmittance of 28.0%. Even after dyeing, the antireflection effect was still maintained. There was no decrease at all.In addition, when the absolute humidity was not treated at 44.0 kg-air, only so and os were dyed.

Example 2 (1) Production of transparent substrate (a) Preparation of silane hydrolyzate γ-glycidoxypropyl methyljethoxysilane 10
6.8 g was cooled to 10°C, and while stirring, 15.5 g of a 0.05 N hydrochloric acid aqueous solution was gradually added dropwise. After one drop was finished,
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 (”
Epolai) 5002”, Kyoeisha Yushi Kagaku Kogyo Co., Ltd. product) 25g, Diacetonal/'1-al 58.9g
+ 29.5g of benzyl alcohol.

310g methanol, 1.5g silicone surfactant
4-16.7 g of methanol-dispersed colloidal silica used in Example 1 and 12.5 g of aluminum acetylacetonate were added and stirred sufficiently to obtain a coating composition.

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

A transparent substrate was prepared by heating at 93°C for 4 hours.

The obtained transparent base lens was pretreated using a surface treatment plasma device (PR501A manufactured by Yamato Scientific Co., Ltd.) at an oxygen flow rate of 250 m for 47 minutes and an output SOW for 1.5 minutes.

(2) Manufacture of coated transparent substrate A high refractive index intermediate coating is formed on the undercoated transparent substrate lens of (C) in exactly the same manner as in (1) and (b) of Example 1. cover things,
A coated transparent substrate was produced. The refractive index of the surface portion of this transparent base material was 1.55.

(3) Outermost layer coating and test results Other than using the coated transparent base material manufactured in (2) above,
Everything was carried out in the same manner as in Example 1.

The total light transmittance of the obtained lens was 96.7%.

The reflected light color was reddish-purple.

The performance of the obtained antireflection lens was determined according to the method shown in (3) below and was as follows.

(4) Test method (41-1 Dyeability Disperse dye (a mixture of 6 colors of red, blue, and yellow) was immersed at 96°C for 945 minutes, and the degree of staining was measured by total light transmittance.

(4)-2 Steel wool hardness Rub the application with ≠0000 steel wool.

Assess the degree of injury. What are the criteria?

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

B...If you rub it too hard, it will get a little scratched.

C: Even weak friction causes damage.

D: Easily scratched with nails.

(4)-5 Sweat light cycle test After irradiating the anti-reflection lens with ultraviolet rays while soaking it in an alkaline artificial sweat solution specified by JIS L1047 (Sweat cycle test method for dyed products and dyes), 200% steel wool (Japanese) Rub the surface with Steel Cool Co., Ltd. to observe the appearance. 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.

Example 6. Comparative Examples 1 to 2 The same procedures as in Example 2 were carried out except that the humidity of the feed material after coating was changed. Table 1 shows the test results of the obtained lenses. If the absolute humidity is too low, the dyeability will be insufficient, and if it is too high, appearance defects such as whitening will occur.

Table 1 [Effects of the Invention] The antireflection transparent material obtained by the present invention has the following effects.

(1) It has a high antireflection effect.

(2) The dyeing speed is fast, and by selecting the dye, any colored antireflective article can be easily obtained.

(3) High surface hardness, heat resistance, and negative impact resistance.

Excellent durability.

Patent Applicant Toshi Co., Ltd. Corporate Procedures Amendment 1. Display of the case y q −) t = '/'; V Patent H(2) filed on October 12, 1982 2 Name of the invention Method for manufacturing an anti-reflective transparent material 3 Person making the amendment Relationship to the case Patent applicant address 2-2-4 Nihonbashi Muromachi, Chuo-ku, Tokyo Date of amendment order Spontaneous 5 Number of inventions increased by amendment None 6 Amendment F) vs. IA "Detailed description of the invention" column of the specification ( 1) "Scratch resistance" on page 5, line 11 of the specification is corrected to "U scratch resistance."

(3) "Alkoxyl, alkoxyalkoxyl" on page 11, lines 8-9 of the same is corrected to "alkoxy, alkoxyalkoxy".

(4) Same page 12, line 9 "tert-butoxide" is "tert-butoxide".

″ ゛ -Pestrel F large, medium 4㎜°, tantalum pentamethoxide, tantalum pentaethoxide, tantalum penta-1
- Glopoxide □, tantalum penta-n-propoxide, tantalum penta-1-butoxide.

tantalum penta-n-butoxide, tantalum penta-t
ert-butoxide”.

(5) Same page 12 line 12 Correct "di-butoxy" to "di-n-butoxy."

(6) "Di-butoxy" on page 12, line 13 is corrected to "Z-SθC-butoxy".

(7) "Di-n-butoxy" is corrected to "di-n-butoxy" on page 12, line 17.

(81, page 16, line 8 Insert the following sentence after "used":

"In particular, it is preferable to add silica sol from the viewpoint of adhesion with the organic polysiloxane composition used for the outermost layer, improvement of hardness, and dye permeability. Also, due to the refractive index, the amount added is 90% by weight or less. (10) ``Jetoxy'' on page 17, line 16 of the same is corrected to ``dimethoxy.''

U Same line 18i18 Correct "trichloro" to "trifluoro".

a’a Same page 19 line 11 Correct “methyltri” to “methyldi”.

a3 Same page 21 line 5 Correct "on reduced pressure" to "under reduced pressure J."

a41 Same page 25 line 5 Correct “coordination” to “ligand”.

a9 Same page 25 line 8 Correct "ha 1 bag" to "ha 1 kg."

αθ Same page 25 line 14 Correct "easiness" to "easiness".

αno Same page 25 line 15 Correct "humidity" to "temperature".

Same as 0, page 25, line 20 Correct "to put out" as "to put out".

Alpha wound Same page 28 line 20 Correct "cura" to "cure".

■ Same page 29 line 15 Correct "stained with" to "uniformly dyed".

Ca11 Same, 3 lines from the bottom of page 9 Correct "heterocycle" to "heterocycle."

Procedural amendment Showa year Month 60° 1 neck 7

Claims (1)

[Claims] A method for producing an antireflective transparent material in which at least the outermost layer is an organic polysiloxane transparent film, and a single layer or multilayer antireflective film is applied in liquid form to the surface of a transparent substrate, and then cured by heating. After application, absolute humidity is 6-18
1. A method for producing an antireflection transparent material, which comprises treating in an atmosphere of 0 g/kg-air for 1 second or more and then curing by heating.