JPS6059250B2 - Antireflective transparent material and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention particularly relates to a surface treatment method for imparting lower light reflectance and higher light transmittance to transparent materials.

Reducing the light reflectance of various transparent materials, and thus improving the light transmittance, is an extremely important issue, such as effective use of light and eliminating blurring of images due to reflected images, and many methods have been proposed so far. .

The idea is to reduce the light reflectance and improve the light transmittance by forming an optical thin layer, mainly made of an inorganic substance, on the surface of the base material, which has a refractive index different from that of the base material. In order to maximize the effect, it is possible to perform multi-layer coating of thin layers with different refractive indexes, to control the thickness of each thin layer to match the wavelength level of the corresponding light beam, or to continuously coat layers with different refractive indexes. Formation of a so-called heterogeneous film has been carried out. Taking the case of forming a single-layer anti-reflection thin film on the surface of a substrate as an example, the anti-reflection thin film provided on the surface of the substrate should be made of an inorganic component with a low refractive index (for example, magnesium fluoride, etc.).
It is said that it is desirable to adjust the optical thickness of the antireflection thin film to the wavelength 114 of the target light beam.

Such optical thin films are subject to limitations regarding the substrates to which they can be applied, depending on the formation process.

Among transparent materials, antireflection thin layer formation has been most widely applied to glass substrates. -Yes. In this case, the technique of coating a thin inorganic layer on the surface of the substrate, which is often used, has extremely limited application to other techniques. Examples of the above techniques include vacuum evaporation, sputtering to improve adhesion, and more! Electron beam method etc. are used.

However, in recent years, these technologies have been applied to plastic materials, which have been particularly popular in the field of eyeglass lenses among transparent materials.
Alternatively, it is difficult to apply it to plastic films and sheets where it is advantageous to form an anti-reflection layer.Especially when applying it to plastic materials that have a high hardness coating material to improve scratch resistance. There are many problems, namely, plastic materials generally do not have sufficient heat resistance to withstand the above coating process, and in some cases may cause decomposition, melting, thermal deformation, optical distortion, etc. be.

Adhesion is also generally poor. This is mainly due to the difference in expansion coefficient between the plastic material and the inorganic material coated on its surface.If the adhesion decreases significantly during heating or humidification, the inorganic material layer may crack.
Cracks may occur. A further serious problem is the significant reduction in impact resistance and flexibility of the plastic material that occurs due to the coating with such mineral layers. In other words, this indicates that the superiority of plastic materials over glass materials is lost, and is an important problem.

A known example similar to the present invention is JP-A-53-1372.
There is a target publication.

This technology involves coating the surface of a plastic substrate with polyorganosilane, which is then treated in oxygen plasma to improve its abrasion resistance and antireflection properties. However, with this technology, the antireflection properties are merely developed by the polyorganosilane coating film itself, so it is not truly excellent, and improvements have been required.

The present inventors solved these problems and developed a method for producing a transparent material with excellent antireflection effect. As a result of intensive studies, the present invention was achieved.

In order to achieve the above object, the present invention consists of the following configuration.

(1) In an antireflection transparent material having an antireflection layer on the surface of a transparent substrate, the antireflection layer has at least micropores and a fine particulate inorganic material of 1 to 300n1,μ, and An antireflective transparent material, characterized in that the layer has a lower refractive index than the substrate. (2) A vehicle component that is made of an organic compound and can be at least partially volatilized or eliminated by activated gas treatment, and a particulate inorganic substance having an average particle diameter of about 1 to 3007 nμ dispersed in the vehicle component are added to at least the surface layer. 1. A method for producing an antireflection transparent material, which comprises treating a transparent material having an antireflection property with an activated gas.

In the present invention, microvoids refer to microvoids that are optically homogeneous and do not cause optical scattering or distortion in the case of lenses and the like.

The fine particulate inorganic substance used in the present invention has an average particle diameter of about 1 to 300 TrLμ, preferably about 5 to 200 TrLμ.
, μ, and the morphological changes of the particles caused by the activated gas treatment described below are substantially absent or small.

Furthermore, although it is not a problem that some or all of the fine particles undergo chemical changes due to the gas treatment, it refers to fine particles whose morphology is maintained to the extent that the effects of the present invention can be expressed. If the particle size is too small, it is difficult to prepare, and if the particle size is too large, the transparency will generally deteriorate and the object of the present invention regarding the antireflection effect cannot be achieved, so particles within the above range are mainly used. It will be done.

Furthermore, the fact that there is virtually no or only a small change in the morphology of the fine particles due to the activated gas treatment means that the fine particle inorganic substance changes its morphology to such an extent that the pores generated by the gas treatment do not eliminate the antireflection effect. This means that it is being maintained.

The term ``hole'' as used herein also includes something similar to a simple dent.

The mechanism by which the antireflection effect is produced by the presence of these pores is not clear, but it is presumed as follows. Vacancy (substantially 1.00
When a particulate inorganic material (having a refractive index close to This is thought to be due to the fact that it has the same effect as

This is also consistent with the fact that similar effects can be obtained by coating a fine particle dispersion on a substrate and forming a corresponding thin layer, although problems such as adhesion may remain. Any type of inorganic material may be used as long as it satisfies the above-mentioned requirements, and it may also include those containing some organic substituents, but the content may be subject to other requirements other than the antireflection effect. It should be determined by performance.

Preferably Groups 1, 2, 3 and V of the periodic table
These include oxides and halides of group elements. Preferable examples of these include fine particulate materials such as zinc oxide, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, and antimony oxide.
Among them, silicon oxide and aluminum oxide are particularly preferred.

Moreover, these particulate inorganic substances can be used not only alone but also in combination of two or more types.

It is necessary that the particulate inorganic substance be contained in at least the surface layer of the transparent material.

As means for containing an inorganic substance at least in the surface layer portion, there are a method in which the inorganic substance is uniformly dispersed in the transparent material serving as the base material during the molding process, or a method in which the inorganic substance is dispersed only in the surface layer portion. Yet another method is to disperse the inorganic material in a transparent coating material and apply it to the surface of the transparent material. Various known methods can be used to disperse the above-mentioned particulate inorganic material, such as (a) mixing the particulate inorganic material and another base material (transparent material) by heating or at room temperature in the presence or absence of a solvent or other components; Method.

(b) A method in which a dispersion (fine particulate inorganic substance) and a substance serving as a substrate (hereinafter referred to as a vehicle component) are mixed in a volatile dispersion medium, and then the volatile dispersion medium is evaporated.

(c) A method is used in which a fine particulate inorganic substance is dispersed in a monomer component and then polymerized.

When applying the present invention to coating materials among the above,
Method (b) is preferred.

In this case, the coating film formed by evaporation of the volatile dispersion medium may be cured. Examples of the volatile dispersion medium include water, hydrocarbons, chlorinated hydrocarbons, esters, ketones, alcohols, and organic carboxylic acids.

Moreover, these can be used not only alone but also as a mixture of two or more. The particulate inorganic substance of the present invention is contained in a transparent material. The amount is before activated gas treatment.
5 to 8% heel weight, preferably 10% to the surface layer of 1μ or less
~7% saliva.

If the amount is less than this, the effect of addition will be small, and if it is more than this, defects such as cracking and decreased transparency will occur. Since the present invention aims to obtain a thin surface layer having an antireflection effect by treating the surface of a transparent material containing particulate inorganic substances, the shape, size, use, etc. of the underlying layer should be considered. There are no limitations regarding this.

Therefore, a method of dispersing an inorganic substance in a transparent material, a method of directly dispersing it in a base material (transparent material) as described above,
It is not particularly important whether the method is to disperse it in a coating material or to apply it to a transparent material (hereinafter referred to as a coating method), but the coating method has the following advantages. In other words, if the fine particulate inorganic substance cannot be easily dispersed in the base material, or even if it can be dispersed, there will be a significant change in the properties of the base material,
The coating method is an effective means for imparting an antireflection effect to the substrate without significantly changing the properties of the substrate.

When dispersing the above-mentioned fine particulate inorganic material, it is possible to use a fine powder form before dispersion, but in order to achieve the purpose of the present invention, it is necessary to disperse the fine particulate inorganic material in a colloidal form in a liquid dispersion medium. The ones listed above are particularly effective.

The substrate, that is, the vehicle component in which the particulate inorganic material of the present invention is dispersed, is one that partially or completely diffuses and disappears by activated gas treatment to form a microporous surface of the inorganic material. If so, although there are no particular limitations, compounds containing various elements having organic groups such as organic compounds and/or organosilicon compounds can be used, and these high molecular compounds are particularly useful. Examples of these are epoxy resins, copolymers of acrylic esters and/or methacrylic esters (including copolymers with other vinyl monomers)
, polyamide, polyester (so-called alkyd resin,
(including unsaturated polyester resin), various amino resins (including melamine resin, urea resin, etc.), urethane resin, polycarbonate, polyvinyl acetate, polyvinyl alcohol, styrene resin, transparent vinyl chloride resin, silicon resin, cellulose resin and diethylene glycol bisallyl carbonate polymer (CR-39). Furthermore, these resins can be used in combination, and cured products obtained by using them in combination with an appropriate curing agent can also be used.

In addition to plasticizers, various curing agents, curing catalysts, etc., the vehicle component may further contain various additives such as surface conditioners, ultraviolet absorbers, and antioxidants.

In the present invention, a transparent material is one that has a haze value (percentage) determined by the following formula of 80% or less, and can be colorless or dyed or pigmented! It may also be something that has been removed from the country.

In order to more effectively exhibit the effects of reducing light reflectance and improving light transmittance as intended by the present invention, transparent materials are preferred.

In particular, silicon-based polymer compounds or polymer compounds containing them, which are used as coating materials to improve the surface hardness of plastic articles, can be effectively used to improve surface hardness and provide antireflection effects. can. Compositions in which the above compounds are combined with silicon oxide-based fine particles, especially their dispersions in alcoholic solvents and/or aqueous solvents, can be used to improve surface hardness in the field of transparent materials where light transmittance is particularly required. It is particularly useful as a device that simultaneously improves light transmittance. Various methods have been proposed for providing silicon-based polymer coatings, but
Particularly effective is a method using a compound obtained by curing a compound selected from the group consisting of compounds having the following general formula and/or their hydrolysates. That is, it is a compound consisting of the general formula, where Rl and R2 are C1 to C
lO alkyl, aryl, alkyl halide, aryl halide, alkenyl, or an organic group having an epoxy group, (meth)acryloxy group, mercapto group, amino group or cyano group, bonded to silicon by a Si-C bond. R3 is a C1 to C6 alkyl group, alkoxyalkyl group or acyl group,
a and b are 0, 1, or 2, and a+b is 1 or 2.

Examples of these compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyl triethoxysilane, vinyltriacetoxysilane,
Vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-
Chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-(β-glycidoxyethoxy)propyl Trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β
-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ
-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, etc. Acyloxysilanes and methyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxy Propylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ -methacryloxypropylmethyldiethoxysilane, γ-
Dialkoxysilane or diacyloxysilane such as mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, etc. An example is

These organosilicon compounds may be used alone or in combination of two or more.

Furthermore, although not used alone, there are various tetraalkoxysilanes or their hydrolysates that can be used in combination with the above-mentioned silane compounds.

Examples of tetraalkoxysilanes include methyl silicate, ethyl silicate, n-propyl silicate, i-
Propyl silicate, n-butyl silicate, Sec-
Examples include butyl silicate and t-butyl silicate. Although these organosilicon compounds can be cured even in the absence of a catalyst, various curing catalysts that have been proposed so far can be used to further promote curing.

various acids or bases, including Lewis acids, Lewis bases, and neutral or basic salts formed therefrom;
For example, organic carboxylic acids, chromic acid, hypochlorous acid, boric acid, bromic acid, selenite, thiosulfuric acid, ortho-silicic acid,
Metal salts of thiocyanic acid, nitrous acid, aluminic acid, and carbonic acid, particularly alkali metal salts or ammonium salts, as well as alkoxides of aluminum, zirconium, and titanium, or complex compounds thereof can be used. Naturally, these can be used in combination with other organic substances, and among these, epoxy resins, acrylic copolymers, especially those having hydroxyl groups, and polyvinyl alcohol are useful. Furthermore, when used as a coating material, it is possible to use solvents and various additives to facilitate coating work or maintain good storage conditions.

When used as a covering material, a coating is applied to the base material.

Any base material may be used as long as the purpose of the present invention is required, but from the viewpoint of transparency, glass and transparent plastic materials give particularly effective results. Preferred plastic materials include polymethyl methacrylate and copolymers thereof, polycarbonate, diethylene glycol bisallyl carbonate polymer (CR-39), polyester, especially polyethylene terephthalate, unsaturated polyester, and epoxy resin. The coating method, drying and/or curing method is appropriately selected from those commonly used in the coating field. The object of the present invention is to treat the surface of a base material or coating material containing the fine particulate inorganic material obtained as described above and a vehicle component in which it is dispersed with an activated gas. A thin antireflection layer is obtained.

The activated gas here refers to ions, electrons, or excited gases generated under normal pressure or reduced pressure.

Examples of methods for generating these activated gases include:
Corona discharge, direct current under reduced pressure, high voltage discharge using low frequency, high frequency, or microwave are used. Further, as the gas for generating the activated gas, for example, oxygen, air, nitrogen, argon, freon, etc. are preferably used.

For the purpose of the present invention, an activated gas obtained by high voltage discharge using direct current, low frequency, high frequency or microwave under a pressure of 10 -2 T0rr to 10T'0rr is particularly preferred from the viewpoint of processing efficiency.

The activated gas obtained here is what is called low-temperature plasma, and is referred to in Low-Temperature Plasma Chemistry (edited by Keiichi Hozumi).
197: Nankodo) describes its characteristics and generation method in detail. The conditions for carrying out the activated gas treatment vary depending on the shape of the treatment equipment, the type of gas used, the material, composition, shape, size of the target surface, etc., and are determined to maximize the objectives of the present invention. Must be determined experimentally.

It has been confirmed from observation using an electron microscope that the thin layer after the above treatment that exhibits the effects of the present invention has fine pores.

Although the thickness of the layer in which the pores are present cannot be clearly defined at present, as the mechanism of the present invention and the shape and distribution of the pores are not clear, it is thought that a thickness of 10,007 TLμ or less, preferably 500 mμ or less, is sufficient. Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1, Comparative Example 1 (1) Preparation of silane hydrolyzate γ-glycidoxypropyltrimethoxysilane 2124y was charged into a reactor equipped with a rotor, and the liquid temperature was lowered to 10 °C.
While stirring with a magnetic stirrer, reduce the temperature to 0.
486y of 01N hydrochloric acid aqueous solution was gradually added dropwise.

After the dropwise addition was completed, cooling was stopped to obtain a silane hydrolyzate. (2) Preparation of paint Colloidal silica dispersed in methanol in the silane hydrolyzate 312.3y (product of Nissan Chemical Co., Ltd., "Methanol Silica Sol", solid content 30%, average particle size 13±1T)
Add 600y of rLμ) with stirring.

To this mixed dispersion were added 207.9 g of methanol, 60 y of diethylene glycol dimethyl ether, 1.8 y of a silicone surfactant, and 18 y of aluminum acetylacetonate, and the mixture was thoroughly stirred and mixed to obtain a paint. (2) Coating, activated gas treatment, and evaluation A diethylene glycol bisallyl carbonate polymer lens (diameter 757 WL 1 thickness 2.17 m, .CR-
39 Plano Lens) by dipping method.

The coating conditions were a pulling speed of 10 cm/min, and a coating speed of 9 (
It was heated and cured for 4 hours in a hot air dryer at 3C. The painted lenses were treated with activated gas using the method described below, and the total light transmittance before and after the treatment was measured.

As an activated gas treatment device, IPC Co., Ltd. (■NTematiOnalPlasmaCOrpOr
An IPClOO3B type low-temperature ashing device manufactured by AtiOn was used.

The output was 50 W, and the gas flow rate was 50 cc/min. Other processing conditions and evaluation results are shown in Table 1. As a comparative example, Table 1 also shows the results when no methanol-dispersed colloidal silica was added. Example 21) Preparation of paint Epoxy resin Denacol EX-614 (product of Nagase Sangyo Co., Ltd., sorbitol polyglycidyl ether)
After adding 27.8y1 methanol 48.5y1 methyl ethyl ketone 48.5y1 dichlorodimethylurea 1.38y1 dicyandiamide 0.84y and stirring and mixing thoroughly, methanol silica sol 92.7y as in Example 1 was added.
y was added with stirring to prepare a paint.

g) Coating, activated gas treatment and evaluation Painting was carried out according to Example 1 using the paint mentioned above.

The heating curing conditions were 130'C for 2 hours.

Activated gas treatment and evaluation of the painted lens were carried out in the same manner as in Example 1. The processing conditions and evaluation results are as follows.
Shown in the table. Example 3, Comparative Example 2 (1) Production of acrylic resin 100 y of n-propyl alcohol is placed in a flask equipped with a stirring device, and the temperature is raised to 90 to 95°C.

After raising the temperature, a separately prepared mixed solution having the following composition was added dropwise over 2 hours.

After the addition of the mixed solution was completed, stirring was continued, and 0.2 y of azobisisobutyronitrile was added every three times, and this was repeated four times.

After adding the last azobisisobutyronitrile, add 1 more
Heating was continued for a period of time to obtain an acrylic resin solution. (2) Preparation of paint Melamine resin ゜゜CYMEL 370゛ (product of Mitsui Toatsu Chemical Co., Ltd.) 9
y1 ethylene rehydrin 80y,. Add 47y of n-propyl alcohol and mix well.

Add to this mixture a colloidal silica sol dispersed in n-propanol (solid content 30%, average particle size 13±17TLμ) 13
3.4y was added with stirring to prepare a paint. (3) Coating, activated gas treatment, and evaluation Painting was performed according to Example 1 using the paint described above.

The heating curing conditions were 130° C. for 2 hours. Activated gas suppression and evaluation of the painted lens were carried out in the same manner as in Example 1.

The processing conditions and evaluation results are shown in Table 1. In addition, as a comparative example, the results when silica sol was not added were also shown in the first example.
Shown in the table. Example 4, Comparative Example 3 (1) Production of acrylic resin The procedure of Example 3 was repeated except that the following monomer mixed solution was used.

Mixed solution (2) Preparation of paint A paint was prepared according to Example 3 using the acrylic resin described above.

(3) Application, activated gas treatment and evaluation It was carried out according to Example 3.

The processing conditions and evaluation results are shown in Table 1. As a comparative example, Table 1 also shows the results when no silica sol was added. Example 5, Comparative Example 4 (1) Preparation of silane hydrolyzate γ-glycidoxypropylmethyldiethoxysilane at 386.3 V was charged into a reactor equipped with a rotor, and the liquid temperature was lowered to 1
While keeping it at 0℃ and stirring with a magnetic stirrer,
0. Gradually drop 55.8 y of μs normal hydrochloric acid aqueous solution.

After the dropwise addition was completed, cooling was stopped to obtain a silane hydrolyzate. (
2) Preparation of paint 125.0 q of methanol silica sol (same as in Example 1) is added to 61.2 y of the silane hydrolyzate while stirring.

To this mixed dispersion were added 50.4 y of methanol, 9.3 y of diethylene glycol dimethyl ether, and 0.4 y of silicone surfactant, and further added 7.02 y of aluminum acetylacetonate, and thoroughly stirred and mixed to obtain a paint. (3) Coating, activated gas treatment, and evaluation The coatings described above were used in accordance with Example 1.

The processing conditions and evaluation results are shown in Table 1. As a comparative example, Table 1 also shows the results when no methanol silica sol was added. Example 6 (1) Preparation of paint After dissolving 30y of cellulose acetate butyrate (manufactured by Nagase Sangyo Co., Ltd., EAB-555-0.2) in 270y of ethylene chlorohydrin, the same methanol silica sol as in Example 1 was added at 100V. were added and stirred to form a paint.

(2) Coating, activated gas treatment and evaluation Painting was carried out according to Example 1 using the paint mentioned above.

The heating conditions were 130°C for 2 hours. Activated gas treatment and evaluation of the painted lens were carried out in the same manner as in Example 1. The processing conditions and evaluation results are shown in Table 1. Example 7, Comparative Example 5 (1) Preparation of paint 441.8 y of γ-glycidoxypropylmethyldiethoxysilane hydrolyzate of Example 5 was mixed with 207.7 y of γ-chloropropyltrimethoxysilane, and the liquid temperature was 10'
0.01N hydrochloric acid aqueous solution 56.5 while stirring at
Gradually add g.

Stop cooling after dripping is complete. To the hydrolyzate 606y were added and mixed the same methanol silica sol 1354.3q1 as in Example 1, diethylene glycol dimethyl ether 103y1, methanol 791.6q1, silicone surfactant 4.5y with stirring. 40.6 y of aluminum acetylacetonate was added to this liquid mixture, and the mixture was stirred to form a paint. (2) Coating, activated gas treatment, and evaluation The coatings described above were used in accordance with Example 1.

The processing conditions and evaluation results are shown in Table 1. In addition, the surface layer of the lens treated with activated gas was examined using an electron microscope (9000
Upon close observation, irregularities and fine pores were observed on the surface and inside over a depth of 1000 angstroms from the surface layer.

As a comparative example, Table 1 also shows the results when no methanol silica sol was added.

Example 8 (1) Preparation of paint γ-glycidoxypropylmethyl of Example 5. 30.6q of diethoxysilane hydrolyzate is mixed with 38.0y of methyltrimethoxysilane, and the liquid temperature is maintained at 10°C.

While stirring, 15.1y of a 0.01N aqueous hydrochloric acid solution was gradually added dropwise. Stop cooling after dripping is complete. The hydrolyzate 8
Methanol silica sol 12 similar to Example 1 was added to 3.7y.
5f1 methanol 26.7y, diethylene glycol dimethyl ether 10.4y, silicone surfactant 0
．． After adding 3.75y of aluminum acetylacetonate and stirring and mixing, add 3.75y of aluminum acetylacetonate and mix thoroughly.
The mixture was made into a paint. (2) Coating, activated gas treatment, and evaluation The coatings described above were used in accordance with Example 1.

The processing conditions and evaluation results are shown in Table 1. Example 9 (1) Preparation of paint γ-glycidoxypropylmethyldiethoxysilane 83
．． 1' and 44.7 y of phenyltrimethoxysilane were charged, and the liquid temperature was maintained at 10°C.

While stirring, 24.3 y of a 0.0% hydrochloric acid aqueous solution was gradually added dropwise. After the completion of the droplet f, cooling was stopped, and the same methanol silica sol as in Example 1, 291.8y1, methanol 46.6y1, silicone surfactant 0.75% was added to the hydrolyzate.
9 was added and mixed while stirring. 8.75 q of aluminum acetylacetonate was added to this liquid mixture, and the mixture was stirred and mixed to obtain a paint. (2) Coating, activated gas treatment, and evaluation The coatings described above were used in accordance with Example 1.

The processing conditions and evaluation results are shown in Table 1. Example 1
0 (1) Preparation of paint Add γ-glycidoxypropylmethyldiethoxysilane hydrolyzate 442.1y described in Example 5 to ゜゜Epicote 827゛ (product of Shell Chemical Co., Ltd.) 155.4y1 diacetone alcohol 223.8V1 111.6y of benzyl alcohol was mixed to obtain a homogeneous solution.

Add methanol silica sol 14 similar to Example 1 to this solution.
Add 23 Da, 597.5y1 methanol and 3.8411 silicone surfactant and mix well.

Add 42% of aluminum acetylacetonate to this mixture.
7y was added and stirred to prepare a paint. (2) Coating, activated gas treatment, and evaluation The coatings described above were used in accordance with Example 1.

The processing conditions and evaluation results are shown in Table 1. Example 1
1 to 13 (1) Preparation of paint Add 310.0y of the silane hydrolyzate described in Example 7 to '6
Epicron 750'1 (Dainippon Ink Co., Ltd. product) 20
y1 diacetone alcohol 39.6y1 methanol 13
0.4y1 benzyl alcohol 20y1 methanol silica sol (same as in Example 1) 660.0V1 silicone surfactant 1.8y were added and mixed while stirring.

Add 20' of aluminum acetylacetonate to this mixture.
were added and stirred to form a paint. (2) Coating, activated gas treatment, and evaluation The coatings described above were used in accordance with Example 1.

The processing conditions and evaluation results are shown in Table 1. Further, the lens obtained in Example 11 was subjected to a falling ball impact test according to FDA standards, and no lens breakage was observed.

Further, even after heat treatment at 120° C. for 2 hours, no changes such as generation of cracks were observed. Examples 14-1
6 (1) Preparation of paint 66 to silane hydrolyzate 442.1y described in Example 5
Epicote 82r197.3y,. '6 Epicote 83
4゛(Shell Chemical Co., Ltd. product)) 58.9y1゛Denacol EX32O゛(Nagase Sangyo Co., Ltd. product: Trimethylolpropane polyglycidyl ether) 77.7q1
Add 235.4y of diacetone alcohol, 118.6y of benzyl alcohol, and 4.2y of silicone surfactant, mix well, dissolve, and then add 1678.6y of methanol silica sol similar to Example 1 with stirring.

Add aluminum acetylacetonate 5 to this mixed dispersion.
0.6y was added and mixed with stirring to prepare a paint. (2) Coating, activated gas treatment, and evaluation Using the paint described in the previous section, a polycarbonate lens (diameter 60T)
wt1 thickness 3.0WI1αNeralElectric
The coating was applied to ゜゜Lexan-14゛) by a dipping method at a pulling rate of 10 cm/min.

The coated lenses were heat cured for 2 hours in a hot air dryer at 130°C. Activated gas treatment and evaluation of the painted lens were carried out in the same manner as in Example 1. The processing conditions and evaluation results are shown in Table 1. Examples 17 to 19 (1) Preparation of β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane hydrolyzate β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane 168I1 was placed in a reaction vessel equipped with a rotor. Prepare and lower the liquid temperature to 20'
C and stir with a magnetic stirrer while stirring at 0.
37.2 y of 01N hydrochloric acid aqueous solution was gradually added dropwise.

After the addition was completed, stirring was stopped to obtain a hydrolyzate of β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane. (2) Preparation of paint γ-glycidoxypropylmethyldiethoxysilane hydrolyzate 394.4V described in Example 5 and β described in the previous section
205.2 y of mono(3,4 epoxycyclohexyl)ethyltrimethoxysilane hydrolyzate was mixed.

Furthermore, the following solution, which was separately prepared in advance, was added to and mixed with this mixed solution. Addition solution Papikote 827 24.
8yC "Syodyne 508" (Showa Denko K.K. product: Glycidyl phthalate ester epoxy resin) 64.6
y1 benzyl alcohol 385y1 acetylacetone 9
6.2y and silicone surfactant 4.8y were mixed. Further, methanol silica sol 1962y similar to that in Example 1 was added to the above mixed solution, and then aluminum acetylacetonate 73.4y was added and mixed with stirring to obtain a paint.

(3) Coating, activated gas treatment, and evaluation Using the paint described in the previous section, injection molded lenses of polymethyl methacrylate (produced by Mitsubishi Rayon Co., Ltd., ゜゜Acrybed ■H) with a diameter of 75 and a thickness of 1.8 were made. The coating was applied using a dipping method at a pulling rate of 10 α/min, and heated and cured in a hot air dryer at 97° C. for 2 hours.

Activated gas treatment and evaluation of the painted lens were carried out in the same manner as in Example 1.

The processing conditions and evaluation results are shown in Table 1. Example 2
0 (1) Preparation of paint Add 46.87y of the silane hydrolyzate described in Example 1 to alumina sol (Nissan Chemical Co., Ltd. product: Alumina Sol 20).
01 solid content 13.5%, average particle size: 100n1, μ×
107 nμ) 85.51 da, ethylene chlorohydrin 6
．． 0.2y of 62y1 silicone surfactant and 1.93y of aluminum acetylacetonate were added and thoroughly mixed to form a paint.

(2) Coating, activated gas treatment and evaluation It was carried out according to Example 1 using the paint mentioned above.

The processing conditions and evaluation results are shown in Table 1. Example 2
1 (1) Preparation of paint γ-glycidoxypropylmethyldiethoxysilane hydrolyzate 331. prepared according to the method described in Example 5.
A separately prepared solution below was added to 9y.

Add 227.8 diacetone alcohol to this added solution.
7yNn-butanol 223.3319, acetylacetone 84.32y1 silicone surfactant 3,94y
1,770.5 y of methanol silica sol and 45.53 y of aluminum acetylacetonate were added and thoroughly stirred and mixed to prepare a paint.

(2) Coating, activated gas treatment, and evaluation Using the paint described in the previous section, a glass lens (diameter 657n1 thickness 1
．． 8Tfn1 plano lens) was coated in the same manner as in Example 1.

The heating curing conditions were 130° C. for 2 hours. Activated gas treatment and evaluation of the painted lens were carried out in the same manner as in Example 1.

The processing conditions and evaluation results are shown in Table 1. Example 2
2 (1) Preparation of silane hydrolyzate In a reactor equipped with a rotor, methyltrimethoxysilane 3
8.0y1 28.8y of phenyltrimethoxysilane and 12.5y of acetic acid were charged, and while keeping the liquid temperature at 10°C and stirring with a magnetic stirrer, 22.9y of a 0.01N aqueous hydrochloric acid solution was gradually added dropwise.

After the dropwise addition was completed, cooling was stopped to obtain a silane hydrolyzate.
(2) Preparation of paint Colloidal silica (solid content 24.3%, average particle size 13±17 nμ) 77.0y1 Diethylene glycol dimethyl ether 6.4y1 Silicone surface active 0.2y of agent and 0.34d of sodium acetate were added and thoroughly mixed and stirred to prepare a paint.

(3) Coating, activated gas treatment, and evaluation Painting was performed according to Example 1 using the paint described in the previous section.

The heating curing conditions were 130° C. for 2 hours. Activated gas treatment and evaluation of the painted lens were carried out in the same manner as in Example 1.

The processing conditions and evaluation results are shown in Table 1. Example 2
3 Using the paint described in Example 10, a diethylene glycol bisallyl carbonate polymer sheet (thickness 2.
CR-39 sheet) was coated and treated with activated gas in the same manner as in Example 1.

The processing conditions and evaluation results for the coated sheet are shown in Table 1.
Example 24 (1) Preparation of silane hydrolyzate 112.6y of γ-glycidoxypropylmethyldiethoxysilane and 60.8y of γ-chloropropyltrimethoxysilane were charged into a reactor equipped with a rotor, and the liquid temperature was While maintaining the temperature at 10° C. and stirring with a magnetic stirrer, 33y of 0.05N hydrochloric acid aqueous solution was gradually added dropwise.

After the dropwise addition was completed, cooling was stopped to obtain a silane hydrolyzate. (
2) Preparation of paint Methanol silica sol 3309 similar to that in Example 1 was added to 154.8y of the silane hydrolyzate with stirring.

Add to this mixed solution 10.1y1 diacetone alcohol19.
8y, benzyl alcohol 10.1y1 methanol 64
．． Add 5V1 silicone surfactant 1y and mix well. 10y of aluminum acetylacetonate was added to this mixed solution and stirred to prepare a paint. (3) Coating, hydration gas treatment, and evaluation Using the paint described above, polyethylene terephthalate film (Toray Industries, Inc. product, trade name: Lumirror T-125) was used.
sand mat).

Claims (1)

[Scope of Claims] 1. In an antireflection transparent material having an antireflection layer on the surface of a transparent base material, the antireflection layer is a layer having at least micropores and fine particulate inorganic material of 1 to 300 mμ. , and the layer has a lower refractive index than the substrate. 2. Claim 1, wherein the particulate inorganic substance is one or more compounds selected from zinc oxide, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, and antimony oxide. Anti-reflective transparent material as described. 3 The vehicle is an epoxy resin, (meth)acrylic acid ester resin, polyamide resin, polyester resin, amino resin, urethane resin, polycarbonate resin, polyvinyl acetate resin, polyvinyl alcohol resin, styrene resin, transparent vinyl chloride resin, silicon resin, The antireflection transparent material according to claim 1, characterized in that it is one or more resins selected from cellulose resins. 4. The antireflective transparent material according to claim 1, wherein the vehicle is a resin obtained from an organic silane compound and/or a hydrolyzate thereof, and the particulate inorganic substance is silicon oxide. 5 A vehicle component that is composed of an organic compound and that can be at least partially volatilized or eliminated by activated gas treatment, and a vehicle component that has an average particle diameter of about 1 to 300 m dispersed in the vehicle component.
1. A method for producing an anti-reflection transparent material, which comprises treating a transparent material having microparticulate inorganic matter at least in its surface layer with an activated gas. 6. Claim 5, characterized in that the particulate inorganic substance is one or more compounds selected from zinc oxide, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, and antimony oxide. A method for producing the antireflective transparent material described above. 7 Vehicle is epoxy resin, (meth)acrylate resin, polyamide resin, polyester resin, amino resin, urethane resin, polycarbonate resin, polyvinyl acetate resin, polyvinyl alcohol resin, styrene resin, transparent vinyl chloride resin, silicon resin, 6. The method for producing an antireflection transparent material according to claim 5, wherein the resin is one or more resins selected from cellulose resins. 8. The antireflective transparent material according to claim 5, wherein the vehicle is a resin obtained from an organic silane compound and/or a hydrolyzate thereof, and the particulate inorganic substance is silicon oxide. Production method. 9. The method for producing an antireflection transparent material according to claim 5, wherein the activated gas is obtained by low-temperature plasma.