JPH08292309A - Substrate with thin film and its production - Google Patents

Abstract

PURPOSE: To provide a substrate with a superfine particle-contg. thin film which has the absorption of the superfine particles and is free from the influence of interference colors by making the refractive index of the thin film described above and the refractive index of a transparent substrate substantially the same. CONSTITUTION: This substrate is formed by providing the surface of the transparent substrate with the superfine particle-contg. thin film dispersed with the superfine particles in a matrix. The refractive index of the superfine particle-contg. thin film and the refractive index of the transparent substrate are made substantially the same. The superfine particles include the superfine particles of metals or metal oxide, such as metal colloid and zinc oxide superfine particles. The specific surface area of the zinc oxide superfine particles preferably exceeds 60m<2> /g if the zinc oxide superfine particles are used as the superfine particles. The reason lies in that the thin films is made translucent and the transmittance is degraded by scattering if the specific surface area of the zinc oxide superfine particles is <=60m<2> /g. The average grain size of the superfine particles is preferably <=100nm. The reason lies in that the thin film is made translucent and the transmittance begins to degrade if the average grain size of the superfine particles exceeds 100nm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a substrate with a thin film and a method for manufacturing the same. According to the present invention, it is possible to provide a colored filter and an ultraviolet ray cut filter having desired transmittance characteristics suitable for optical and electro-optical applications, and it is also possible to provide a colored spectacle lens. Is.

[0002]

2. Description of the Related Art In a camera used for taking photographs, a colored filter called a skylight filter is mounted on the front surface of a lens. This coloring filter is a filter having a pale pink color, has a slight absorption in the vicinity of 500 nm, and has the purpose of suppressing the development of blue-green color due to the influence of the blue sky in color photography outside the sunny weather.

Examples of this type of colored filter include (i) selenium colored glass, (ii) colloidal gold colored glass, and (iii) laminated filter.

Among the above-mentioned colored filters, the selenium-colored glass (i) and the colloidal gold-colored glass (ii) are glass obtained by heating the glass raw material which becomes the matrix and the selenium and gold raw materials which are the coloring components. After being made into a melt, it is manufactured by quenching and reheating the glass melt.
Then, the glass gob thus obtained is subjected to a series of steps of slicing, grinding, polishing, outer shape processing, and assembly,
It becomes a skylight filter product.

The above (iii) laminating filter has two
It is manufactured by sandwiching an organic colored film between a plurality of glass plates and adhering them to each other. As the glass plate, a commercially available plate glass is mainly used. The laminated glass thus obtained becomes a product after undergoing outer shape processing and assembly.

However, the above-mentioned three types of colored filters have some problems.

The melting method, which is a method for producing selenium-colored glass and colloidal gold glass, mainly requires the use of a glass having a special composition as the glass serving as the matrix (i), and therefore the production cost is high. (ii) Coloring is strongly affected by the conditions during melting and reheating. (iii) In order to use it as a filter, it has to undergo the steps of slicing, grinding and polishing. (iv) May contain toxic substances such as selenium. However, it is difficult to say that it is a method of manufacturing a filter easily and inexpensively.

Further, the laminated filter has the merit that it does not need to melt the glass and that the steps of slicing, grinding and polishing can be omitted, but (i) since an organic film and an adhesive are used. Inferior in properties such as heat resistance, weather resistance and light resistance. (ii) A step of laminating glass is necessary, and it is difficult to laminate glass accurately. There are problems such as this, this method also easy filter,
It is hard to say that it is a cheap manufacturing method, and since it uses an organic material, it is also difficult in terms of reliability.

On the other hand, an ultraviolet ray cut filter that blocks ultraviolet rays is used in a wide range of fields including the optical industry, the electro-optical industry, and other industries.

Examples of this type of ultraviolet cut filter include (i) Ce ion-containing glass and (ii) a laminated filter.

The above (i) glass containing Ce ions is a glass raw material which becomes a matrix and Ce which is an ultraviolet absorbing component.
It is manufactured by heating the above raw material and a raw material of (1) to form a glass melt, and then cooling and solidifying. The glass gob thus obtained becomes a UV cut filter product through a series of steps including slicing, grinding, polishing, outer diameter processing, and assembly.

The laminated filter of the above (ii) is manufactured by sandwiching an organic ultraviolet absorbing film between two glass plates and adhering them to each other, and a commercially available plate glass is mainly used as the glass plate. The laminated glass thus obtained is processed into an outer diameter and then assembled into a product.

However, the above-mentioned two types of ultraviolet cut filters have some problems.

In the melting method, which is a method for producing Ce ion-containing glass, it is mainly necessary to use a glass having a special composition as the glass serving as the (i) matrix, so that the production cost becomes high. (ii) A large amount of energy is required to turn the raw material into a melt. (iii) UV absorption characteristics are strongly affected by conditions such as melting and cooling and are not stable. (iv) To use as a filter, slice,
It must go through the steps of grinding and polishing. (v) May contain toxic substances such as lead. However, it is difficult to say that it is a method of manufacturing a filter easily and inexpensively.

Further, the laminated filter has the advantages that it does not need to melt the glass and that the steps of slicing, grinding, and polishing can be omitted. (I) Since an organic film and an adhesive are used, Inferior in properties such as heat resistance, weather resistance and light resistance. (ii) A step of laminating glass is necessary, and it is difficult to laminate glass accurately. There are problems such as this, this method also easy filter,
It is hard to say that it is a cheap manufacturing method, and since it uses an organic material, it is also difficult in terms of reliability.

Therefore, an object of the present invention is to easily and inexpensively provide an article suitable for use as a colored filter, an ultraviolet ray cut filter or the like having characteristics and reliability equal to or higher than those of conventional products.

[0017]

The present invention has been made to achieve the above object, and the present invention provides an ultrafine particle-containing thin film having ultrafine particles dispersed in a matrix on a transparent substrate. The gist of the invention is a substrate with a thin film, wherein the refractive index of the ultrafine particle-containing thin film is substantially the same as the refractive index of the transparent substrate.

Further, the gist of the present invention is a method for producing a substrate with a thin film, characterized in that a liquid composition containing an ultrafine particle raw material and a matrix raw material is applied onto a transparent substrate, followed by drying and heat treatment.

First, the substrate with a thin film of the present invention will be described. The substrate with a thin film of the present invention is one in which a thin film containing ultrafine particles is provided on a transparent substrate.

As a material for the transparent substrate, an organic material such as plastic and an inorganic material such as glass can be used as long as they are transparent. However, in consideration of various characteristics required for a color filter, an ultraviolet ray cut filter and the like, glass is used. It is preferable to use a transparent substrate made of. A glass or plastic substrate provided with a coating film, for example, an ultraviolet shielding film (a thin film in which ZnO ultrafine particles or TiO ₂ ultrafine particles are dispersed in a binder or a Ce ion-containing thin film), an interference color preventing intermediate film, or the like. Can also be used as a transparent substrate.

The ultrafine particle-containing thin film provided on the transparent substrate is composed of ultrafine particles and a matrix that acts as a binder for the ultrafine particles.

Examples of ultrafine particles include ultrafine particles of metal or metal oxide such as gold colloid, ultrafine zinc oxide particle, silver colloid, ultrafine copper oxide particle, nickel colloid, and platinum colloid. When zinc oxide ultrafine particles are used as the ultrafine particles, its specific surface area (measured by the BET method using nitrogen gas) is preferably more than 60 m ² / g.
The reason is that the specific surface area of the zinc oxide ultrafine particles is 60 m ² /
This is because if it is less than or equal to g, the thin film becomes semitransparent due to scattering and the transmittance is lowered.

As ultrafine particles, a soluble azo pigment (for example, c
System, 2B system, 6B system, etc.), insoluble azo pigment (eg β
-Naphthol-based, monoazo yellow-based, pyrazolone-based), phthalocyanine-based pigments (for example, copper phthalocyanine blue, fast sky blue, metal-free phthalocyanine, etc.), slene-based (for example, thioindigo-based, anthraquinone-based, perylene-based, perinone-based, etc.), dioxazine It is also possible to use organic pigment-based ultrafine particles such as a pigment, a quinacridone-based, an isoindolinone-based or the like.

The average particle size of the ultrafine particles is preferably 100 nm or less. The reason is that the average particle size of ultrafine particles is 10
This is because when the thickness exceeds 0 nm, the thin film becomes semitransparent due to scattering and the transmittance starts to decrease. The average particle size of ultrafine particles is 1 nm
It is preferably 75 nm or more and more preferably 1 nm or more and 50 nm or less.

The matrix is at least SiO ₂ .
It preferably contains an oxide and / or a fluoride as a refractive index adjusting component. Sc, Ti, Y, Z as a refractive index adjusting component
r, Nb, Mo, In, Sn, Sb, Ba, La, C
Examples thereof include oxides or fluorides such as e, Hf, Ta, W, Bi, Cd, Tl and Pb. Besides this,
As required, Li, B, Na, Mg, Al, P, K,
Oxides or fluorides such as Ca, Zn, Ga, Ge, As, Rb, Sr and Cs can be added.

When a thin film is provided on the surface of the substrate, an interference color is generated if the refractive index of the substrate and the refractive index of the thin film do not match. When not used for optical applications, this interference color does not cause any particular problem,
When it is used for optical applications such as coloring filters, ultraviolet cut filters, and spectacle lenses, reflection and absorption of a specific wavelength due to interference fringes occur, which causes adverse effects such as coloring and ghost.

As a method for preventing the interference color between the substrate and the thin film, JP-A-6-191895 and JP-A-6-19259 are available.
The method shown in Japanese Patent No. 8 has already been proposed. These methods form an interference color preventing intermediate film having a refractive index intermediate between the substrate and the thin film, between the substrate and the thin film. According to this method, the influence of the interference color can be eliminated, but (i) it is difficult to control the thickness of the intermediate film with high accuracy. (ii) The coating film must be formed more than once. Have problems such as.

Therefore, in the substrate with a thin film of the present invention,
The interference color is prevented by making the refractive index of the ultrafine particle-containing thin film substantially the same as the refractive index of the transparent substrate without forming an interference color preventing intermediate film between the substrate and the thin film. is there.

Here, "to make the refractive index of the ultrafine particle-containing thin film and the refractive index of the transparent substrate substantially the same" is, in a broad sense, matched or approximated to each other so that interference colors do not occur. More specifically, when providing the ultrafine particle-containing thin film on one main surface of the transparent substrate,
It means that the difference in refractive index between the transparent substrate and the thin film is within 10%, and when the ultrafine particle-containing thin film is provided on both main surfaces of the transparent substrate, the difference between the refractive indices of the transparent substrate and the thin film is within 5%. To do.

The reason why the difference in the refractive index between the substrate and the thin film when the thin film is provided on one surface and both surfaces of the substrate is limited to the above numerical value is as follows.

If there is a large difference in the refractive index between the substrate and the thin film,
When the difference between the peak and the dip (hereinafter referred to as ΔT) exceeds 5% due to the interference effect, the transmittance curve becomes uneven, and it becomes clear that it is visually colored. To avoid unnecessary coloring, ΔT needs to be within 5% in the visible range. In order to make ΔT within 5% in the visible range, according to the calculation by the present inventors, when a thin film is provided on one surface of a substrate,
It became clear that the difference in refractive index between the substrate and the thin film needs to be within 10%. Further, it has been clarified that when the thin films are provided on both surfaces of the substrate, the difference in the refractive index between the substrate and the thin film needs to be within 5%, which is 1/2 that in the case where the thin films are provided on one surface.

More preferably, ΔT is within 2%,
In this case, the difference in refractive index between the substrate and the thin film is within 5% when the thin film is provided on one side, and 2.5 when the thin film is provided on both sides.
Must be within%.

When white glass having a refractive index of 1.52 is used as the transparent substrate, the refractive index of the thin film satisfying the numerical condition of the refractive index difference from the substrate is 1.37 to 1 when the thin film is provided on one side.
1.67, 1.44 to 1.60 when provided on both sides.

In general, the refractive index of optical glass is in the range of 1.5 to 1.9 for visible light. The refractive index range of the thin film can be achieved by appropriately changing the compounding ratio of SiO ₂ and the refractive index adjusting component. Specifically, SiO ₂ is 2
A thin film having a refractive index substantially the same as the refractive index of the substrate can be obtained by appropriately changing the refractive index adjusting component in the range of 0 to 99% by weight and the refractive index adjusting component in the range of 80 to 1% by weight. Considering the coating property and the stability of the coating solution, SiO ₂ is 30 to 99 wt%,
The refractive index adjusting component is preferably 70 to 1 wt%.

In the substrate with a thin film of the present invention, the film thickness of the ultrafine particle-containing thin film is adjusted in accordance with the required desired transmittance characteristics and in consideration of the ultrafine particle concentration in the ultrafine particle containing thin film and the like. . The film thickness of the ultrafine particle-containing thin film is generally in the range of 0.01 to 5 μm.

In the ultrafine particle-containing thin film, the content of ultrafine particles varies depending on the type of ultrafine particles. For example, in the case of gold colloid, its content is preferably 0.1 to 40 wt%.
The reason is that if the gold content is less than 0.1 wt%, the amount of gold colloid precipitated will be small and it will be difficult to obtain the desired absorption. On the other hand, if it exceeds 40 wt%, the colloid will not be stably incorporated into the glass matrix that acts as a binder, and gold colloid will be deposited outside the film. Particularly preferably, the amount of gold is 1 to 30 wt%.

In the case of ultrafine zinc oxide particles, the content in the thin film is preferably 15 to 75 wt%. The reason is that if the content of the zinc oxide ultrafine particles is less than 15 wt%, the amount of the zinc oxide ultrafine particles is small and it becomes difficult to obtain the desired absorption. On the other hand, if it exceeds 75% by weight, the ultrafine zinc oxide particles are not stably incorporated into the matrix serving as a binder, and the ultrafine zinc oxide particles are deposited outside the film. In addition, the transparency of the film and the hardness of the film deteriorate. The amount of ultrafine zinc oxide particles is particularly preferably 20 to 70 wt%.

In the case of silver colloid, copper oxide ultrafine particles, nickel colloid, and platinum colloid, the content thereof is preferably 0.1 to 40 wt% as in the case of gold colloid, and 1 to 40% by weight.
30% by weight is particularly preferred.

In the substrate with a thin film of the present invention, a coating film such as an ultraviolet shielding film (Zn) is formed on the thin film containing ultrafine particles.
A thin film in which O ultrafine particles and TiO ₂ ultrafine particles are dispersed in a binder, a Ce ion-containing thin film, etc.), a water-repellent thin film, a colored film, or the like can be provided.

The substrate with a thin film according to the present invention, which has been described in detail above, has characteristics and reliability equal to or higher than those of conventional filters when used as a coloring filter or an ultraviolet cut filter, and does not generate interference color. Has a remarkable effect. The substrate with a thin film of the present invention can also be used as a spectacle lens that does not generate interference color.

The substrate with a thin film of the present invention preferably has a transmittance haze value of less than 2. Here, the transmittance haze value is calculated by the following formula: transmission haze value [%] = (Td / Tt) × 100 Td: scattered light transmittance [%] Tt: total light transmittance [%]. The smaller the transmission haze value, the higher the transparency, and the larger the transmission haze value, the lower the transparency.
The transmission haze value of the glass substrate coated with the ultrafine particle-containing thin film is preferably less than 2. When it is 2 or more, it becomes obvious that the transparency is deteriorated. The transmission haze value must be less than 2, preferably less than 1, to obtain the required transparency. It is particularly preferably less than 0.5.

Next, a method for manufacturing a substrate with a thin film of the present invention will be described. The method for producing a substrate with a thin film of the present invention is characterized in that a liquid composition containing an ultrafine particle raw material and a matrix raw material is applied onto a transparent substrate, followed by drying and heat treatment.

As a method for forming a thin film on a substrate, there are methods that require a vacuum system such as vacuum deposition, ion implantation, sputtering, CVD, PVD, etc., but these methods include (i) expensive equipment. Need. (ii) Since a vacuum system is used, handling is complicated and productivity is poor. (iii) A large area cannot be coated. (iV) There are restrictions on the shapes that can be coated. However, it is difficult to coat easily and cheaply.

Therefore, in the present invention, compared with the above method using a vacuum system, a wet coating method is employed, which does not require a special device and can inexpensively and easily form a thin film on the substrate surface.

This wet coating is performed by coating a liquid composition containing ultrafine particle raw material and matrix raw material on a transparent substrate. As a coating method, a dipping method, a spin method, a spray method, a roll coating method, a screen printing method, an air doctor coating method, a blade coating method, a lot coating method, a bead coating method, a gravure coating method, or the like is used.

As a raw material of gold colloid which is a kind of ultrafine particles, tetrachloroauric acid tetrahydrate, tetrachloroauric acid trihydrate, sodium tetrachloroaurate dihydrate, gold cyanide, potassium cyanide gold , Gold diethyl acetylacetonate, gold colloid itself and the like.

As a raw material for the zinc oxide ultrafine particles, zinc oxide itself, zinc acetate, nitrate, carbonate, sulfate,
Chlorides, alkoxides, acetylacetonates, etc. can be used. When zinc oxide powder is used as a raw material for zinc oxide ultrafine particles, it is preferable to use zinc oxide powder having a specific surface area of more than 60 m ² / g. When zinc oxide having a specific surface area of 60 m ² / g or less is used, the light transmittance may be deteriorated and the transparency may be lost. If the specific surface area of the zinc oxide ultrafine particles exceeds 60 m ² / g, the cohesive force may become strong. As a result, the dispersion becomes difficult and the transparency of the thin film containing zinc oxide ultrafine particles decreases. In this case, the addition of a dispersant is effective for improving the dispersed state. Examples of the dispersant include silane coupling agent, titanium coupling agent, aluminum coupling agent, unsaturated polycarboxylic acid, polyvinyl alcohol resin, polyethylene glycol, polyvinyl butyral resin, acrylic resin, ethyl cellulose, hydroxypropyl cellulose and the like. it can. The amount of the dispersant added is preferably 0.1 to 40 wt% with respect to the zinc oxide ultrafine particles.

As a raw material of silver colloid, silver itself is
Silver nitrate, acetate, etc. can be used.

Examples of the raw material of the copper oxide ultrafine particles include copper oxide itself, copper chloride, nitrate, carbonate, lead sulfate, alkoxide, acetylacetonate and the like.

Examples of the raw material of the nickel colloid include nickel itself, nickel nitrate, chloride, carbonate, sulfate, alkoxide, acetylacetonate and the like.

Examples of the raw material for the platinum colloid include platinum itself, hexachloroplatinic acid, ammonium hexachloroplatinate, potassium hexachloroplatinate, potassium tetrachloroplatinate, sodium hexachloroplatinate, and the like.

As the silicon source of the matrix raw material, (i) silicon alkoxide (eg, silicon methoxide, silicon ethoxide, silicon propoxide, oligomers thereof, etc.) or silicon alkoxide derivative (eg, methyltriethoxysilane, γ- Glycidoxypropyltrimethoxysilane, methylvinyldimethoxysilane, 3-aminopropyltriethoxysilane,
N- (2-aminoethyl) -3-aminopropyltriethoxysilane etc.) (ii) Silicone resin (for example, methyl silicone resin,
Phenyl silicone resin, methylphenyl silicone resin, etc.) or other silicone compounds (eg, isocyanate silane, silicone acetate, etc.) and the like. Further, it is also possible to use SiO ₂ fine particles together with the silicon source (i) and / or (ii).

Further, as the raw material of the refractive index adjusting component element, (i) alkoxide (for example, titanium-n-butoxide, zirconium-n-propoxide, lanthanum-i-) of the corresponding metal is used.
Propoxide, yttrium-i-propoxide, niobium ethoxide, etc.) (ii) Alkoxide derivative (eg, tri-n-butoxyacetylacetonato zirconium, diisopropoxybisethylacetate titanium, etc.) (iii) Chelate compound (eg, , Titanium tetraacetylacetonate, lanthanum triacetyltonate, lead diacetylacetonate, etc.) (iv) Other organometallic compounds (eg, yttrium methacrylate, zirconium methacrylate, etc.) (v) nitrates (eg, bismuth nitrate pentahydrate) Substances, lanthanum nitrate hexahydrate, etc. (vi) Acetates (eg, yttrium acetate tetrahydrate, lead acetate trihydrate, zirconyl acetate, etc.) (vii) Chlorides (eg, zirconyl chloride, titanium chloride) (Viii) Sulfate (eg zirconium sulfate, titanium sulfate, etc.) (ix) Oxides (eg, TiO ₂ , ZrO ₂ , CeO _2, etc.) (x) Fluorides (eg, MgF ₂ , CaF _2, etc.) (xi) Metals themselves can be mentioned.

An organic matrix raw material can be used as the matrix raw material. For example, acrylic resin, phenol resin, alkyd resin, vinyl chloride resin,
Examples thereof include butyral resin, styrene-butadiene resin, epoxy resin, unsaturated polyester resin, polyurethane resin, fluororesin and the like.

As the raw materials for phosphorus and boron among the refractive index adjusting component elements, phosphoric acid, trimethyl phosphate and the like, boric acid, tri-n-butyl borate and the like can be used.

If necessary, organic polymers such as polyethylene glycol, polyvinyl alcohol, polyvinyl acetate, hydroxypropyl cellulose, polyvinylpyrrolidone, formamide, N, N-dimethylformamide, 2-ethoxyethanol, diethanolamine,
Organic compounds such as monoethanolamine can be added.

Soluble azo pigments (for example, c type, 2B type, 6B type)
System), insoluble azo pigment (for example, β-naphthol system,
Monoazo yellow type, pyrazolone type, etc., phthalocyanine type pigment (eg copper phthalocyanine blue, fast sky blue, metal-free phthalocyanine etc.), slene type (eg thioindigo type, anthraquinone type, perylene type, perinone type), dioxazine type, quinacridone type It is also possible to use organic pigment-based ultrafine particles such as isoindolinone.

The raw material may be of any type as long as it is dissolved or homogeneously dispersed at the stage of the prepared liquid composition (coating liquid).

As a disperser required for producing the liquid composition, a ball mill, a sand mill, two rolls, 3
Main rolls, attritors, Banbury mixers, paint shakers, kneaders, homogenizers, ultrasonic dispersers and the like can be mentioned.

Next, as an example, a method for producing a coating solution using the above tetrachloroauric acid tetrahydrate, silicon alkoxide, and zirconium alkoxide will be described.

In the above two kinds of alkoxides, the zirconium alkoxide has a significantly higher hydrolysis rate than the silicon alkoxide, and therefore, when simply mixed and hydrolyzed, the zirconium alkoxide is selectively hydrolyzed to give a homogeneous mixture. No coating solution can be obtained.

There are three methods for preventing the selective hydrolysis of zirconium alkoxide to obtain a uniform coating solution.
The first method is that the hydrolysis rate of the alkoxide is affected by the number of carbon atoms of the alkyl group, and generally, the higher the number of carbon atoms, the slower the hydrolysis rate (conversely, the faster the number of carbon atoms, the faster). Is the method of using. For example, a homogeneous coating solution can be prepared by carefully hydrolyzing butoxide or amyloxide as an alkoxide of zirconium and methoxide or ethoxide as an alkoxide of silicon. The second method is a method in which a silicon alkoxide having a slow hydrolysis rate is partially hydrolyzed in advance and then reacted with a zirconium alkoxide. According to this method, since the silicon alkoxide and the zirconium alkoxide react with each other before the subsequent hydrolysis, it is possible to obtain a uniform coating liquid without causing selective hydrolysis. The third method is a method of reacting a zirconium alkoxide having a high hydrolysis rate with a chelate compound. According to this method, the alkoxide of zirconium is chelated (the alkoxyl group of the alkoxide is replaced with the chelate compound) and the hydrolysis rate becomes slower, so that a uniform coating liquid can be obtained without causing selective hydrolysis. .

Since it is particularly preferable to use the above method in combination, an example of using the first method and the second method together will be described below.

First, a silicon alkoxide such as tetraethoxysilane is added to a mixed solution of an aqueous solution of an acid catalyst such as hydrochloric acid, nitric acid, acetic acid, sulfuric acid or perchloric acid and an organic solvent such as ethanol or butyl acetate, and the mixture is stirred. A partially hydrolyzed solution of silicon alkoxide is obtained.

Next, a zirconium alkoxide such as zirconium tetrabutoxide is added to this partially hydrolyzed solution and stirred to react the zirconium alkoxide with the partially hydrolyzed silicon alkoxide.

Next, a solution of tetrachloroauric acid, which is a raw material for the gold colloid, dissolved in an organic solvent such as ethanol is added and stirred.

Next, if necessary, an acid catalyst such as hydrochloric acid, nitric acid, acetic acid, sulfuric acid, perchloric acid or ammonia, choline,
A base catalyst such as amino alcohol, water and an organic solvent such as ethanol or butyl acetate are further added and stirred. In the present invention, the liquid obtained above can be used as a coating liquid for a gold colloid-containing thin film.

The coating solution thus obtained is applied to a transparent substrate by the above-mentioned various coating methods, dried and heat-treated to obtain a substrate with a thin film having a gold colloid-containing thin film on the transparent substrate.

This heat treatment is performed at 200 to glass transition point +5.
Preference is given to working at a temperature of 0 ° C. The reason is as follows.

When the heat treatment is carried out at less than 200 ° C., (i) the water and solvent are not sufficiently removed and they remain, so that the characteristics such as the hardness of the thin film are deteriorated. (ii) Polymerization of the glass matrix does not proceed and the thin film has poor properties such as hardness. (iii) The reaction from the gold compound used as the raw material of the gold colloid to the gold colloid does not proceed and the required absorption cannot be obtained. Therefore, it becomes difficult to produce the thin film intended by the present invention.

On the other hand, when the heat treatment is performed at a temperature higher than the glass transition temperature + 50 ° C., the substrate is softened and the surface is likely to be deformed.

The transparent substrate with a gold colloid-containing thin film obtained by the above method using a silicon compound as a matrix raw material can prevent adverse effects due to interference color due to the film composition in which a refractive index adjusting portion is added to SiO _2. . In addition, when the substrate with a thin film is used for a glass filter by forming a glass matrix containing gold as a colorant and SiO ₂ as a binder component as a main component,
It is superior in durability and reliability to the filters manufactured by conventional methods. In addition, there is an advantage that a coating method can be used as a coating method, so that it can be manufactured at a lower cost than conventional methods.

Next, as another example, a method for producing a coating liquid using the above zinc oxide ultrafine particles, a silicone resin, and a zirconium chelate compound will be described.

First, ultrafine zinc oxide particles are added to an organic solvent such as ethanol or butyl acetate containing a dispersant to suspend or disperse the ultrafine zinc oxide particles in a liquid.

Next, a silicone resin is added and zinc oxide is further dispersed. Further, a zirconium chelate compound is added and dispersed. In the present invention, the liquid obtained above can be used as a coating liquid for a thin film containing zinc oxide ultrafine particles.

The coating liquid thus obtained is applied to a transparent substrate by the above-mentioned various coating methods, dried and heat-treated to obtain a substrate with a thin film having a thin film containing zinc oxide ultrafine particles on the transparent substrate. .

This heat treatment is preferably carried out at a temperature of 150 to the glass transition point of the transparent substrate + 50 ° C. The reason is as follows.

When the heat treatment is carried out at a temperature lower than 150 ° C., (i) the organic solvent and water are not sufficiently removed, and a large amount of them remains, resulting in inferior characteristics such as hardness of the thin film. (ii) Polymerization of the glass matrix does not proceed and the thin film has poor properties such as hardness. Therefore, it becomes difficult to produce the thin film intended by the present invention.

On the other hand, the glass transition temperature of the transparent substrate +50
When the heat treatment is performed at a temperature higher than ° C, the substrate is softened and the surface is likely to be deformed.

The substrate with a thin film containing zinc oxide ultrafine particles obtained by the above-described method using a silicon compound as a matrix raw material can prevent adverse effects due to interference fringes by the film composition in which a refractive index adjusting component is added to SiO _2. it can.
In addition, this substrate with a thin film formed a glass matrix containing zinc oxide as an ultraviolet absorber and SiO ₂ as a binder component as main components, so that when used in a glass filter, it is more durable than a filter manufactured by a conventional method. It is excellent in terms of reliability and reliability. Further, there is an advantage that the coating method can be used as a coating method at a lower cost than the conventional method.

The method for producing a substrate with a gold colloid-containing thin film and a substrate with a zinc oxide ultrafine particle-containing thin film has been specifically described above. However, silver colloid, copper oxide ultrafine particle, nickel colloid, platinum colloid or other ultrafine particles. A substrate with a thin film containing is also manufactured by the same method.

[0082]

EXAMPLES The present invention will be further described below with reference to examples.

[Example 1: Production example of substrate with gold colloid-containing thin film] A 0.15 M hydrochloric acid aqueous solution 265 was added to a mixed solution of 3060 g of tetraethoxysilane and 2030 g of ethanol.
g was gradually added and stirred for 3 hours, then 362 g of zirconium tetrapropoxide was added and stirred overnight. This solution was mixed with 15 wt% chloroauric acid tetrahydrate (HAuCl ₄ .4H ₂
O) -isopropanol solution 439 g, 0.15 M hydrochloric acid aqueous solution 569 g, water 557 g and isopropanol 2
By adding to the mixed solution of 2,720 g and stirring for 2 hours, 30 kg of an Au colloid thin film coating liquid was manufactured.
The composition of the thin film obtained from this coating solution was Au.
3.0 wt%, ZrO ₂ 13.0 wt%, SiO ₂ 84.0
wt%, solid content in coating liquid (assuming heat treatment)
Is 3.5 wt%. The coating solution was yellow, transparent and homogeneous. This coating solution was applied to a commercially available plate glass having a thickness of 1 mm (usually called a white plate. The composition system is soda lime silicate and has a refractive index of 1.52) by a dipping method at a speed of 30 cm / min ( Below “V”
Abbreviated). The obtained thin film was colorless, transparent and homogeneous. This substrate with a thin film was dried at 100 ° C. for 30 minutes, then placed in a heat treatment furnace, heated up to 500 ° C. at 200 ° C./hour, and held at 500 ° C. for 30 minutes. By this heat treatment, the glass with a thin film changed from colorless and transparent to red-purple transparent, and the obtained thin film was homogeneous and had a refractive index of 1.53 and a refractive index difference of 0.7% with the substrate. there were. The transmittance curve is shown in FIG. It is clear that the absorption of Au colloid appears at 530 nm.

When this glass with a thin film was incorporated into a camera and a photographing test was carried out, the same effect as when using a skylight filter (commercially available product) manufactured by the melting method was obtained, and it could be used as a skylight filter. confirmed.

Example 2 Production Example of Substrate with Gold Colloid-Containing Thin Film In this example, titanium (Ti) was selected as the refractive index adjusting component. Tetraethoxysilane 106
0.15 to a mixed solution of 3 g and 920 g of isopropanol.
92 g of M hydrochloric acid aqueous solution was gradually added and stirred for 5 hours. After adding 504 g of titanium tetrabutoxide to this solution and stirring for 1 hour, methyltriethoxysilane 1761 was added.
g was added and the mixture was stirred overnight. This solution was added to 15 wt% chloroauric acid tetrahydrate-isopropanol solution 439 g, 0.15
30 kg of an Au colloid thin film coating solution was produced by adding to a mixed solution of 593 g of M hydrochloric acid aqueous solution, 582 g of water and 24,040 g of isopropanol and stirring for 2 hours. The composition of the thin film obtained from this coating solution is A
u 3.0 wt%, TiO ₂ 11.3 wt%, SiO ₂ 8
At 5.7 wt%, the solid content in the coating liquid is 3.5 wt%. The coating solution was yellow, transparent and homogeneous. This coating liquid was applied to a commercially available plate glass (refractive index 1.52) with a thickness of 2 mm, and V
It was applied at a speed of = 15.5 cm / sec. The obtained thin film was colorless, transparent and homogeneous. This thin film substrate
After drying at 0 ° C. for 30 minutes, it was placed in a heat treatment furnace, heated to 450 ° C. at 200 ° C./hour, and kept at 450 ° C. for 30 minutes.
The glass with a thin film obtained by this heat treatment changed from colorless transparent to reddish purple transparent. The thin film was homogeneous, its refractive index was 1.53, and the refractive index difference from the substrate was 0.7%.

As a result of performing a photographing test in the same manner as in Example 1, it was confirmed that the characteristics as a skylight filter were satisfied.

[Examples 3 to 10: Production example of substrate with gold colloid-containing thin film] The same as Example 2 except that the Au content, the solid content concentration, and the pulling rate were changed as shown in Table 1. A glass with a thin film as shown in Table 1 was produced. As a result of a photography test of the obtained glass, it was confirmed that all the properties as a skylight filter were satisfied.

[0088]

[Table 1]

[Example 11: Production example of substrate with gold colloid-containing thin film] In this example, titanium (Ti) was selected as the refractive index adjusting component. A γ-glycidoxypropyltrimethoxysilane was used in place of the methyltriethoxysilane of Example 2, and a substrate with a thin film was prepared in the same manner as in Example 2. The preparation composition of the thin film is Au 3.0 wt.
%, TiO ₂ 11.3 wt% and SiO ₂ 85.7 wt%. A thin film having a refractive index of 1.53 (refractive index difference of 0.7%) was formed on a substrate having a refractive index of 1.52.

The transmittance of the obtained substrate with a thin film was the same as in FIG. In addition, as a result of a shooting test, it was confirmed that the characteristics as a skylight filter were satisfied.

Example 12 Production Example of Substrate with Gold Colloid-Containing Thin Film In this example, titanium (Ti) was selected as the refractive index adjusting component. Instead of zirconium tetrapropoxide of Example 1, diisopropoxy bis (acetylacetonato) titanium (Ti [OCH (CH) 2
₃ ] ₂ [OC (CH ₃ ) CHCOCH ₃ ] ₂ ) was used to prepare a substrate with a thin film in the same manner as in Example 1. The composition of the thin film was Au 3.0 wt%, TiO ₂ 11.3 wt%, S
It is 85.7 wt% of iO ₂ . A thin film having a refractive index of 1.52 (refractive index difference of 0%) was formed on a substrate having a refractive index of 1.52.

The transmittance of the obtained substrate with a thin film was the same as in FIG. In addition, as a result of a shooting test, it was confirmed that the characteristics as a skylight filter were satisfied.

[Example 13: Production example of substrate with gold colloid-containing thin film] In this example, titanium (Ti) was selected as the refractive index adjusting component. Instead of the chloroauric acid tetrahydrate of Example 2, sodium chloroauric acid dihydrate (NaAuC
l ₄ · 2H ₂ O) was used to prepare a thin film-provided substrate in the same manner as in Example 2. The preparation composition of the thin film is Au 3.0 wt.
%, Na ₂ O 0.5 wt%, TiO ₂ 11.2 wt%, S
It is 85.3 wt% of iO ₂ . A thin film having a refractive index of 1.52 (refractive index difference of 0%) was formed on a substrate having a refractive index of 1.52.

The transmittance of the obtained substrate with a thin film was the same as in FIG. In addition, as a result of a shooting test, it was confirmed that the characteristics as a skylight filter were satisfied.

Example 14: Production Example of Substrate with Gold Colloid-Containing Thin Film In this example, yttrium (Y) was selected as the refractive index adjusting component. A yttrium nitrate hexahydrate (Y (NO ₃ ) ₃ .6H ₂ O) was used in place of zirconium tetrapropoxide of Example 1, and a substrate with a thin film was prepared in the same manner as in Example 1. The preparation composition of the thin film is Au
3.0 wt%, Y ₂ O ₃ 18.8 wt%, SiO ₂ 78.
It is 2 wt%. A substrate with a refractive index of 1.52 has a refractive index of 1.5
A thin film having a refractive index difference of 3 (0.7% difference in refractive index) was formed.

The transmittance of the obtained substrate with a thin film was the same as in FIG. In addition, as a result of a shooting test, it was confirmed that the characteristics as a skylight filter were satisfied.

Example 15: Production Example of Substrate with Gold Colloid-Containing Thin Film In this example, niobium (Nb) was selected as the refractive index adjusting component. Instead of the zirconium tetrapropoxide of Example 1, niobium pentabutoxide (Nb
(OC ₄ H ₉ ) ₅ ) was used to prepare a substrate with a thin film in the same manner as in Example 1. The preparation composition of the thin film is Au 3.0 wt.
%, Nb ₂ O ₅ 13.4 wt% and SiO ₂ 83.6 wt%. A thin film having a refractive index of 1.53 (refractive index difference of 0.7%) was formed on a substrate having a refractive index of 1.52.

The transmittance curve of the obtained substrate with a thin film was the same as that shown in FIG. 1, and the result of the photographing test showed no problem.

[Comparative Example 1] Without using a refractive index adjusting component,
A coating solution was prepared in the same manner as in Example 1, and this was used to prepare a substrate with a thin film. The preparation composition of the thin film is Au
It is 3.0 wt% and SiO ₂ 97.0 wt%. A substrate having a refractive index of 1.52 has a refractive index of 1.44 (refractive index difference −5.3.
%) Thin film was formed. The transmittance curve of this substrate with a thin film is shown in FIG. The transmittance curve has irregularities due to the influence of interference. When a photographing test was carried out using this substrate with a thin film, peculiar coloring was observed and it was impossible to use it as a skylight filter.

[Example 16: Example of production of substrate with gold colloid-containing thin film] In this example, the substrate having a refractive index of 1.
70 glasses for eyeglass lenses (LH manufactured by HOYA Co., Ltd.)
Using I), a substrate with a thin film was prepared in the same manner as in Example 2. The composition of the thin film was Au 6.0 wt%, SiO ₂
It is 46.6 wt% and TiO _{2 is} 47.4 wt%. The refractive index of the obtained thin film was 1.60, and the refractive index difference was -0.6%.
Met. The transmittance curve of the substrate with a thin film is shown in FIG. The absorption peak position was 560 nm. The color of the obtained substrate with a thin film was reddish purple, and it was confirmed that the substrate with a thin film can be used for coloring eyeglass lenses.

Example 17 Production Example of Substrate with Gold Colloid-Containing Thin Film: 65% by weight of 28,540 g of a 3.5 wt% methyl silicone resin-isopropanol-n-butyl acetate solution.
1010 g of a wt% tetraacetylacetonato titanium-isopropanol solution was added and stirred for 1 hour. 15 wt% chloroauric acid tetrahydrate-isopropanol solution 45 was added to the solution.
0 g was added and further stirred for 30 minutes to prepare 30 kg of Au colloid thin film coating solution. The preparation composition of the thin film is Au
11.3 wt%, TiO ₂ 11.3 wt%, SiO ₂ 8
It is 5.7 wt%. A refractive index of 1.5 was obtained in the same manner as in Example 1.
A substrate with a thin film was obtained by forming a thin film having a refractive index of 1.53 (refractive index difference −0.7%) on the second substrate.

The transmittance of the obtained substrate with a thin film was the same as in FIG. In addition, as a result of a shooting test, it was confirmed that the characteristics as a skylight filter were satisfied.

Example 18 Production Example of Substrate with Thin Film Containing Ultrafine Zinc Oxide Particles 800.0 g of a mixed solvent of iso-butyl acetate / iso-propanol (1: 1 weight ratio) was added with 7 cp of Ethocel (dispersant, Dow Chemical Co., Ltd.). Company's product name) 0.
47 g (0.5 wt% based on zinc oxide ultrafine particles) was dissolved. To this solution, zinc oxide ultrafine particles 9 having a specific surface area of 65 m ² / g measured by BET method using nitrogen gas 9
After 4.0 g was added and dispersed by a paint shaker (disperser) for 1 hour using glass beads, 220.0 g of methyl silicone resin was added and further dispersed for 20 hours. To this dispersion liquid, 800.0 g of an iso-butyl acetate / iso-propanol mixed solvent (1: 1 weight ratio), 65 wt% was added.
Titanium tetraacetylacetonate (Ti (C ₅ H
119.1 g of ₇ O ₂ ) ₄ ) .iso-propanol solution
In addition, the mixture was dispersed for 30 minutes and the glass beads were removed to prepare a thin film coating solution containing zinc oxide ultrafine particles.
The composition of the thin film obtained from this coating solution was ZnO.
30.8 wt%, TiO ₂ 4.6 wt%, SiO ₂ 6
At 4.5 wt%, the solid content in the coating solution is 15.0 wt%. The coating liquid had a milky white color, and neither precipitate nor precipitate was observed. This coating solution was applied to a commercially available plate glass having a thickness of 1 mm (usually called a white plate. The composition system is soda lime silicate and has a refractive index of 1.52) by a dipping method at a pulling rate of 30 cm / min ( Hereinafter, it is abbreviated as "V"). The thin film obtained is
It was colorless and transparent and homogeneous. This thin film substrate is 150 ℃
After drying for 30 minutes, put in a heat treatment furnace and heat up to 500 ° C.
The temperature was raised at 00 ° C./hour and kept at 500 ° C. for 30 minutes. The thin film obtained by this heat treatment is colorless, transparent and homogeneous,
The refractive index was 1.53, and the refractive index difference with the substrate was 0.7%. The transmission haze value was 0.2. The transmittance curve of the obtained substrate with a thin film is shown in FIG. 4 together with the transmittance of the substrate alone. It is clear that light in the wavelength range shorter than 380 nm is sharply cut.

When this glass with a thin film was incorporated into a camera and a photographing test was carried out, it was found that the color change was improved as in the case of using an ultraviolet sharp cut filter (commercially available product) manufactured by the melting method, and the ultraviolet sharp cut was improved. It was confirmed that it can be used as a cut filter.

[Example 19: Example of production of substrate with thin film containing zinc oxide ultrafine particles] In this example, zirconium (Zr) was selected as the refractive index adjusting component. N-butyl acetate /
iso-propanol mixed solvent (1: 1 weight ratio) 78
Disperbyk-181 to 1.2g
(Dispersing agent, trade name of BYK-Chemie) 18.8 g (20 wt% with respect to zinc oxide ultrafine particles) was dissolved. 94.0 g of zinc oxide ultrafine particles having a specific surface area of 75 m ² / g measured by BET method using nitrogen gas was added to this solution, and the mixture was dispersed for 1 hour by a sand mill (dispersing machine) using zirconia beads, and then methyl was added. Silicone resin 220.0g
Was added and dispersed for another 3 hours. Acetic acid n was added to this dispersion.
- butyl / an iso-propanol mixed solvent (1: 1 weight ratio) 800.0 g, 73 wt% zirconium acetylacetonate bis ethylacetate (Zr (OC ₄ H ₉₎
(C ₅ H ₇ O ₂ ) (C ₆ H ₉ O ₃ ) ₂ ). 126.9 g of n-butanol solution was added and dispersed for 30 minutes, and the glass beads were removed to obtain a thin film coating solution containing zinc oxide ultrafine particles. It was made. The composition of the thin film obtained from this coating solution was ZnO 30.0 wt% and ZrO ₂ 7.0 wt%.
%, SiO ₂ 63.0 wt%, the solid content in the coating solution is 1
It is 5.3 wt%. The coating liquid had a milky white color, and neither precipitate nor precipitate was observed. The coating liquid was applied to a commercially available flat glass (refractive index 1.52) with a thickness of 2 mm, V = 30.0 cm /
applied at min. The obtained thin film was colorless, transparent and homogeneous. This substrate with a thin film was dried at 150 ° C. for 30 minutes, then placed in a heat treatment furnace, heated to 450 ° C. at 200 ° C./hour, and held at 450 ° C. for 1 hour. The thin film obtained by this heat treatment is colorless and transparent and homogeneous, and its refractive index is 1.
The refractive index difference with the substrate was -0.7%.
The transmission haze value was 0.2.

As a result of performing a photographing test in the same manner as in Example 18, it was confirmed that the characteristics as an ultraviolet sharp cut filter were satisfied.

[Example 20: Example of production of substrate with thin film containing zinc oxide ultrafine particles] In this example, antimony (Sb) was selected as the refractive index adjusting component. 220.0 g of methyl silicone resin was added and dissolved in 800.0 g of n-butyl acetate / methanol mixed solvent (3: 2 weight ratio). 94.0 g of zinc oxide ultrafine particles having a specific surface area of 73 m ² / g measured by BET method using nitrogen gas was added to this solution, and the mixture was mixed with a glass mill using a sand mill (disperser) to prepare 1
Dispersed for 2 hours. 723.5 g of n-butyl acetate / methanol mixed solvent (3: 2 weight ratio) was added to this dispersion liquid.
wt% 6 antimony pentoxide (Sb ₂ O ₅ ) methanol sol
9.6 g was added and dispersed for 1 hour, and glass beads were removed to prepare a thin film coating solution containing zinc oxide ultrafine particles. The composition of the thin film obtained from this coating solution was ZnO 30.1 wt%, Sb ₂ O ₅ 6.7 wt%, S
iO _{2 was} 63.2 wt%, and the solid content in the coating solution was 16.
It is 1 wt%. The coating liquid has a milky white color, and precipitates,
No precipitate was observed. This coating liquid was applied to a commercially available plate glass (refractive index 1.52) having a thickness of 2 mm, V = 30.0 cm /
applied at min. The obtained thin film was colorless, transparent and homogeneous. This substrate with a thin film was dried at 150 ° C. for 30 minutes, then placed in a heat treatment furnace, heated to 450 ° C. at 200 ° C./hour, and held at 450 ° C. for 1 hour. The thin film obtained by this heat treatment is colorless and transparent and homogeneous, and its refractive index is 1.
The refractive index difference with the substrate was 1.3%. The transmission haze value was 0.4.

As a result of performing a photographing test in the same manner as in Example 18, it was confirmed that the characteristics as an ultraviolet sharp cut filter were satisfied.

[Examples 21 to 26: Production Example of Substrates with Zinc Oxide Ultrafine Particle-Containing Thin Film] Refractive index adjusting components are shown in Tables 2 and 3.
Glasses with thin films as shown in Tables 2 and 3 were produced in the same manner as in Example 19 except that the glass was changed as shown in FIG. As a result of performing a photography test on the obtained glass, it was confirmed that all of them satisfied the characteristics as an ultraviolet sharp cut filter.

Example 27: Production Example of Substrate with Zinc Oxide Ultrafine Particle-Containing Thin Film] In this example, a glass for eyeglass lenses having a refractive index of 1.70 (HOYA LH Co., Ltd.) was used as a substrate.
Using I), a substrate with a thin film was prepared in the same manner as in Example 19. The preparation composition of the thin film was ZnO 28.1 wt%, Z
rO _{2 is} 45.9 wt% and SiO _{2 is} 26.0 wt%.
The refractive index of the obtained thin film was 1.69, and the difference in refractive index from the substrate was -0.6%. The transmittance curve of the substrate with a thin film is shown in FIG. The transmission haze value was 0.3. The obtained substrate with a thin film is colorless, transparent and homogeneous,
It was confirmed that it can be used for the purpose of blocking the ultraviolet rays of eyeglass lenses.

[Comparative Example 2] Without using the refractive index adjusting component,
A coating solution was prepared in the same manner as in Example 19, and a substrate with a thin film was prepared using this. The preparation composition of the thin film is Z
nO is 32.3 wt% and SiO _{2 is} 67.7 wt%.
A thin film having a refractive index of 1.44 (refractive index difference of -5.3%) was formed on both surfaces of the substrate on the substrate having a refractive index of 1.52. Also,
The transmission haze value was 0.2. The transmittance curve of this substrate with a thin film is shown in FIG. Since no refractive index adjusting component was used, interference occurred, and this effect caused unevenness in the transmittance curve. When a photographing test was carried out using this substrate with a thin film, peculiar coloring was observed and it was impossible to use it as an ultraviolet sharp cut filter.

Tables 2 and 3 collectively show the physical property values of the substrates with thin films obtained in Examples 18 to 27 and Comparative Example 2.

[0113]

[Table 2]

[0114]

[Table 3]

[Example 28: Production example of substrate with silver colloid-containing thin film] 1487 g of tetraethoxysilane and iso
-To a mixed solution of 858 g of propanol, 129 g of 0.15M nitric acid aqueous solution was gradually added, and the mixture was stirred for 3 hours. After 706 g of titanium butoxide was added to this solution and stirred for 1 hour, 2464 g of methyltriethoxysilane was added and further stirred for 1 hour. 118 g of silver nitrate, 0.0
1660 g of a 75 M nitric acid solution, iso-propanol 2
30 kg of a silver colloid thin film coating solution was prepared by adding 2.578 g of the mixed solution and stirring overnight. The composition of the thin film obtained from this coating solution was Ag 4.8 wt.
%, TiO ₂ 11.0 wt%, SiO ₂ 84.2 wt%,
The solid content in the coating liquid is 5.0 wt%. The coating liquid is
It was colorless and transparent. This coating solution was applied to a commercially available plate glass having a thickness of 1 mm (refractive index 1.52) at a speed of V = 30.0 cm / sec. The obtained thin film was colorless, transparent and homogeneous. This After drying a thin film with 1 hour of the substrate at room temperature, held for 1 hour at raised temperature in the heat treatment furnace placed 200 ° C. / hr to the bottom 450 ° C. air atmosphere, 2% atmosphere H _2/9
The gas was replaced with an 8% N ₂ mixed gas and kept for another hour. The glass with a thin film obtained by this heat treatment changed from colorless and transparent to yellow and transparent. The thin film was homogeneous, its refractive index was 1.51, and the refractive index difference from the substrate was -0.7%. The transmittance curve is shown in FIG. Absorption of silver colloid is 40
It is clear that it is at 0 nm.

[0116] Example 29-31: copper oxide, Preparation of nickel or platinum-containing film-coated substrate] dopant Cu ₂
A glass with a thin film was produced in the same manner as in Example 28 except that O, Ni, and Pt were used. The composition of the thin film was as follows: dopant 4.8 wt%, TiO ₂ 11.0 wt%, SiO ₂ 8
It is 4.2 wt%. The film refractive index and the difference from the substrate of the substrates with thin films obtained in Examples 29 to 31 are shown in Table 4, and the transmittance curves are shown in FIG. 8 (Cu ₂ O), FIG. 9 (Ni) and FIG. 10 (P
t).

[0117]

[Table 4]

[0118]

As described above, according to the present invention, it is possible to provide a substrate with a thin film that absorbs ultrafine particles of metal or metal oxide and is not affected by interference color. By using this substrate with a thin film, it is possible to provide a filter having characteristics and reliability equal to or higher than those of the existing colored filters and ultraviolet cut filters, more easily and cheaply than the existing colored filters and ultraviolet cut filters. it can. Further, it is possible to provide a colored spectacle lens.

[Brief description of drawings]

FIG. 1 is a transmittance curve diagram of a substrate with a thin film of Example 1.

FIG. 2 is a transmittance curve diagram of a substrate with a thin film of Comparative Example 1.

FIG. 3 is a transmittance curve diagram of the substrate with a thin film of Example 16

FIG. 4 is a transmittance curve diagram of the substrate with a thin film of Example 18.

FIG. 5 is a transmittance curve diagram of the substrate with a thin film of Example 27.

FIG. 6 is a transmittance curve diagram of a substrate with a thin film of Comparative Example 2.

FIG. 7 is a transmittance curve diagram of the substrate with a thin film of Example 28.

FIG. 8 is a transmittance curve diagram of the substrate with a thin film of Example 29.

FIG. 9 is a transmittance curve diagram of the substrate with a thin film of Example 30.

FIG. 10 is a transmittance curve diagram of the substrate with a thin film of Example 31.

Claims (14)

[Claims] 1. An ultrafine particle-containing thin film having ultrafine particles dispersed in a matrix is provided on a transparent substrate, and the refractive index of the ultrafine particle containing thin film and the refractive index of the transparent substrate are substantially the same. Substrate with a thin film. 2. The substrate with a thin film according to claim 1, wherein the ultrafine particles are ultrafine particles of a metal or a metal oxide. 3. The metal or metal oxide ultrafine particles are at least one selected from the group consisting of gold colloids, zinc oxide ultrafine particles, silver colloids, copper oxide ultrafine particles, nickel colloids, and platinum colloids. The substrate with a thin film according to 2. 4. The substrate with a thin film according to claim 3, wherein the zinc oxide ultrafine particles used as a raw material to be contained in the thin film are zinc oxide ultrafine particles having a specific surface area of more than 60 m ² / g. 5. The substrate with a thin film according to claim 1, wherein the ultrafine particles are organic pigment-based ultrafine particles. 6. The substrate with a thin film according to claim 1, wherein the ultrafine particles have an average particle size of 100 nm or less. 7. The matrix is at least SiO 2.
_The substrate with a thin film according to claim 1, comprising ₂ and an oxide and / or a fluoride which is a refractive index adjusting component. 8. The substrate with a thin film according to claim 1, wherein a thin film containing ultrafine particles is provided on one main surface of the transparent substrate, and a difference in refractive index between the transparent substrate and the thin film containing ultrafine particles is within 10%. 9. The substrate with a thin film according to claim 1, wherein ultrafine particle-containing thin films are provided on both main surfaces of the transparent substrate, and a difference in refractive index between the transparent substrate and the ultrafine particle-containing thin film is within 5%. 10. The transparent haze value of a transparent substrate with a thin film is:
The substrate with a thin film according to claim 1, which is less than 2. 11. The substrate with a thin film according to claim 1, wherein the transparent substrate is a glass substrate or a plastic substrate. 12. The substrate with a thin film according to claim 1, wherein a liquid composition containing an ultrafine particle raw material and a matrix raw material is applied onto a transparent substrate, dried and heat treated. Production method. 13. The liquid composition is added with 0.1 to 40 wt% of a dispersant with respect to the ultrafine particle raw material.
The method described in. 14. A colored filter, an ultraviolet cut filter or a colored spectacle lens, which uses the substrate with a thin film according to any one of claims 1 to 11.