JP3328493B2 - Substrate with thin film and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 cut filter having desired transmittance characteristics suitable for applications such as optical and electro-optical applications, and it is also possible to provide a colored spectacle lens. It is.

[0002]

2. Description of the Related Art A color filter called a skylight filter is mounted on the front of a lens in a camera used for photographing or the like. This coloring filter is a filter having a pale pink coloration, has a slight absorption at around 500 nm, and has the purpose of suppressing blue-green color development due to the effect of the blue sky in color photography outside the clear sky.

[0003] As this kind of colored filter, there are (i) selenium colored glass (ii) gold colloid colored glass (iii) laminated filter.

Among the above-mentioned colored filters, selenium-colored glass (i) and colloidal gold-colored glass (ii) are obtained by heating a glass material serving as a matrix and selenium / gold materials serving as coloring components. The glass melt is manufactured by quenching and reheating the glass melt.
And the glass lump obtained in this way goes through a series of processes of slicing, grinding, polishing, outer shape processing, assembly,
Skylight filter products.

[0005] The laminating filter of the above (iii) has 2
It is manufactured by sandwiching an organic colored film between two glass plates and bonding them together, and a commercially available glass plate is mainly used as the glass plate. The laminated glass obtained in this manner becomes a product through external processing and assembly.

[0006] However, the above-mentioned three types of coloring filters have some problems.

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

[0008] In addition, although the laminating filter has advantages such as no need to melt the glass and elimination of slicing, grinding and polishing steps, (i) since an organic film and an adhesive are used, Inferior properties such as heat resistance, weather resistance and light resistance. (ii) A step of bonding glass is required, and it is difficult to bond glass with high accuracy. This method also makes the filter easier,
It is difficult to say that it is a low-cost manufacturing method, and there is also a problem in terms of reliability because an organic material is used.

On the other hand, ultraviolet cut filters that block ultraviolet light are used in a wide range of fields including the optical industry, the electro-optical industry, and other industries.

As this type of ultraviolet cut filter, there are (i) glass containing Ce ions and (ii) a laminated filter.

The Ce ion-containing glass (i) is composed of a glass material serving as a matrix and Ce-absorbing component Ce.
It is manufactured by heating a raw material to form a glass melt, followed by cooling and solidification. Then, the glass lump thus obtained is subjected to a series of steps of slicing, grinding, polishing, outer diameter processing, and assembling, and becomes an ultraviolet cut filter product.

The laminated filter (ii) is manufactured by sandwiching an organic ultraviolet absorbing film between two glass plates and bonding them together, and a commercially available glass plate is mainly used as the glass plate. The laminated glass obtained in this manner is processed into an outer diameter and assembled to become a product.

[0013] However, the above two types of ultraviolet cut filters have several problems.

The melting method, which is a method for producing Ce ion-containing glass, mainly involves (i) the use of a glass having a special composition as a glass serving as a matrix, which increases the production cost. (ii) A large amount of energy is required to turn the raw material into a melt. (iii) The ultraviolet absorption characteristics are not stable due to the influence of melting and cooling conditions. (iv) For 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 an easy and inexpensive method of manufacturing a filter.

[0015] The laminating filter has the advantages of eliminating the need to melt the glass and omitting the slicing, grinding and polishing steps, but (i) uses an organic film and adhesive. Inferior properties such as heat resistance, weather resistance and light resistance. (ii) A step of bonding glass is required, and it is difficult to bond glass with high accuracy. This method also makes the filter easier,
It is difficult to say that it is a low-cost manufacturing method, and there is also a problem in terms of reliability because an organic material is used.

Accordingly, an object of the present invention is to provide easily and inexpensively articles suitable for use as colored filters, ultraviolet cut filters, and the like having properties and reliability equal to or better than conventional products.

[0017]

SUMMARY OF THE INVENTION The present invention has been made to achieve the above object, and the present invention provides an ultrafine particle-containing thin film in which ultrafine particles are dispersed in a matrix, provided on a transparent substrate. The present invention provides a substrate with a thin film, wherein the refractive index of the ultrafine particle-containing thin film and the refractive index of the transparent substrate are made substantially the same.

The present invention also provides a method for producing a substrate with a thin film as described above, which comprises applying a liquid composition containing an ultrafine particle material and a matrix material on 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 obtained by providing an ultrafine particle-containing thin film on a transparent substrate.

As the material for the transparent substrate, organic materials such as plastics and inorganic materials such as glass can be used as long as they are transparent. It is preferable to use a transparent substrate made of aluminum. The coating film on a glass or plastic substrate, for example ultraviolet shielding film (the ZnO ultrafine particles and TiO ₂ ultrafine particles such as a thin film or Ce ion-containing thin film dispersed in a binder) and that provided such interference color preventing intermediate layer Can 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 serving as a binder for the ultrafine particles.

Examples of the ultrafine particles include metal or metal oxide ultrafine particles such as gold colloid, zinc oxide ultrafine particles, silver colloid, copper oxide ultrafine particles, nickel colloid, and platinum colloid. When ultrafine zinc oxide particles are used as the ultrafine particles, the specific surface area (measured by a BET method using nitrogen gas) desirably exceeds 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, when it is less than g, the thin film becomes translucent due to scattering, and the transmittance is reduced.

As ultrafine particles, soluble azo pigments (for example, c
System, 2B system, 6B system, etc.), insoluble azo pigments (for example, β
Naphthol type, monoazo yellow type, pyrazolone type, etc.), phthalocyanine type pigments (eg, copper phthalocyanine blue, fast sky blue, metal-free phthalocyanine, etc.), sulene type (eg, thioindigo type, anthraquinone type, perylene type, perinone type, etc.), dioxazine Ultrafine particles based on organic pigments such as quinacridone, isoindolinone and the like can also be used.

The average particle size of the ultrafine particles is preferably 100 nm or less. The reason is that the average particle size of the ultrafine particles is 10
If the thickness exceeds 0 nm, the thin film becomes translucent due to scattering and the transmittance starts to decrease. Average particle size of ultrafine particles is 1nm
It is preferably from 75 nm to 75 nm, particularly preferably from 1 nm to 50 nm.

The matrix comprises at least SiO ₂ ,
It preferably contains an oxide and / or a fluoride as a refractive index adjusting component. Sc, Ti, Y, Z as refractive index adjusting components
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. In addition,
If necessary, Li, B, Na, Mg, Al, P, K,
An oxide or a fluoride such as Ca, Zn, Ga, Ge, As, Rb, Sr, and Cs can be added.

When a thin film is provided on the surface of a substrate, an interference color occurs if the refractive index of the substrate does not match the refractive index of the thin film. When not used for optical applications, this interference color is not particularly problematic,
When used for optical applications such as coloring filters, ultraviolet cut filters, and spectacle lenses, reflection and absorption of specific wavelengths occur due to interference fringes, which adversely affect coloring and ghosting.

As a method for preventing interference colors between a substrate and a thin film, JP-A-6-191895 and JP-A-6-19259.
No. 8 has already been proposed. In these methods, an interference color preventing intermediate film having a refractive index between the substrate and the thin film is formed 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 accurately control the thickness of the intermediate film. (ii) The coating must be formed more than once. Have such problems.

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

Here, "making the refractive index of the ultrafine particle-containing thin film substantially equal to the refractive index of the transparent substrate" broadly means that the refractive indices of the two are matched or approximated so that no interference color is generated. More specifically, more specifically, when providing an ultrafine particle-containing thin film on one main surface of a transparent substrate,
When the difference between the refractive index of 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 index of the transparent substrate and the thin film is within 5%. I 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 side and both sides of the substrate is limited to within the above numerical values is as follows.

If there is a large difference in the refractive index between the substrate and the thin film,
The interference curve causes irregularities in the transmittance curve, and when the difference between the peak and the dip (hereinafter, ΔT) exceeds 5%, it becomes clear that the coloring is visually observed. To avoid unnecessary coloring, ΔT needs to be within 5% in the visible region. In order to make ΔT within 5% in the visible region, according to calculations by the present inventors, when a thin film is provided on one side of a substrate,
It became clear that the difference in the refractive index between the substrate and the thin film had to be within 10%. In addition, when thin films were provided on both surfaces of the substrate, it was clarified that the difference in refractive index between the substrate and the thin film had to be within 5%, which was equivalent to 1/2 of that provided on one surface.

ΔT is more preferably within 2%,
In this case, the difference in the 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.
It must be within%.

When a white plate 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 1.5 when the thin film is provided on one side.
1.67, and 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 varying the mixing ratio of SiO ₂ and the refractive index adjusting component. More specifically, the SiO _{2 2}
A thin film having a refractive index substantially the same as the refractive index of the substrate can be obtained by appropriately varying the refractive index adjusting component from 0 to 99 wt% and the refractive index adjusting component from 80 to 1 wt%. Coatability, considering the stability of the coating solution the SiO ₂ 30~99wt%,
It is preferable that the refractive index adjusting component is 70 to 1 wt%.

In the substrate with a thin film of the present invention, the thickness of the ultrafine particle-containing thin film is adjusted in accordance with the required desired transmittance characteristic and in consideration of the concentration of the ultrafine particles in the ultrafine particle-containing thin film. . The 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 the ultrafine particles differs depending on the type of the ultrafine particles. For example, in the case of gold colloid, the content is preferably 0.1 to 40% by weight.
The reason is that when the content of gold is less than 0.1 wt%, the amount of colloidal gold deposited is small, making it difficult to obtain desired absorption. On the other hand, if the content exceeds 40% by weight, the colloid is not stably taken into the glass matrix acting as a binder, and the gold colloid precipitates out of the film. It is particularly preferred that the amount of gold is from 1 to 30% by weight.

In the case of ultrafine zinc oxide particles, the content in the thin film is preferably from 15 to 75% by weight. The reason is that when 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 desired absorption. On the other hand, if the content exceeds 75% by weight, the zinc oxide ultrafine particles cannot be stably taken into the matrix acting as a binder, and the zinc oxide ultrafine particles are deposited outside the film. Further, the transparency of the film and the hardness of the film deteriorate. The amount of the 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% by weight, as in the case of gold colloid.
Particularly preferred is 30% by weight.

In the substrate with a thin film of the present invention, a coating film, for example, an ultraviolet shielding film (Zn)
The O ultrafine particles and TiO ₂ ultrafine particles such as a thin film or Ce ion-containing thin film dispersed in a binder) can be provided water-repellent thin film, a coloring film.

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 a conventional filter when used as a color filter or an ultraviolet cut filter, and does not generate interference colors. Has a remarkable effect. Further, the substrate with a thin film of the present invention can be used as a spectacle lens that does not generate interference colors.

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 determined by the 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. If it is 2 or more, it becomes clear that the transparency is deteriorated visually. In order to obtain the required transparency, the transmission haze value must be less than 2, preferably less than 1. Particularly preferably, it is less than 0.5.

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

As a method of 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. These methods include the following: (i) expensive equipment Need. (ii) Since a vacuum system is used, handling is complicated and productivity is poor. (iii) Large areas cannot be coated. (iV) There are restrictions on the shapes that can be coated. It is difficult to coat easily and inexpensively.

Therefore, in the present invention, as compared with the above-mentioned method using a vacuum system, a special method is not required, and a wet coating method which can provide a thin film on the substrate surface easily and inexpensively is adopted.

This wet coating is performed by applying a liquid composition containing a raw material of ultrafine particles and a raw material of a matrix onto 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.

The raw materials of gold colloid, which is one kind of ultrafine particles, include tetrachloroauric acid tetrahydrate, tetrachloroauric acid trihydrate, sodium tetrachloroaurate dihydrate, gold cyanide, and potassium gold cyanide. , Gold diethylacetylacetonate, gold colloid itself, and the like.

The raw materials of the zinc oxide ultrafine particles include zinc oxide itself, zinc acetate, nitrate, carbonate, sulfate, and the like.
Chloride, alkoxide, acetylacetonate and the like can be used. When a zinc oxide powder is used as a raw material of the zinc oxide ultrafine particles, it is preferable to use a zinc oxide powder having a specific surface area exceeding 60 m ² / g. When zinc oxide having a specific surface area of 60 m ² / g or less is used, light transmittance is deteriorated and transparency may be lost. If the specific surface area of the zinc oxide ultrafine particles exceeds 60 m ² / g, the cohesive strength may be increased. As a result, dispersion becomes difficult, and the transparency of the zinc oxide ultrafine particle-containing thin film decreases. In this case, it is effective to add a dispersant to improve the dispersion state. Examples of the dispersant include a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, an unsaturated polycarboxylic acid, a polyvinyl alcohol resin, a polyethylene glycol, a polyvinyl butyral resin, an acrylic resin, ethyl cellulose, and hydroxypropyl cellulose. it can. The amount of the dispersant added is preferably 0.1 to 40% by weight based on the zinc oxide ultrafine particles.

As a raw material of silver colloid, silver itself,
Silver nitrate, acetate and the like can be used.

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

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

The raw materials of the platinum colloid include platinum itself, hexachloroplatinic acid, ammonium hexachloroplatinate, potassium hexachloroplatinate, potassium tetrachloroplatinate, sodium hexachloroplatinate and the like.

Among the matrix raw materials, the silicon source includes: (i) silicon alkoxide (eg, silicon methoxide, silicon ethoxide, silicon propoxide, oligomers thereof) or silicon alkoxide derivative (eg, methyltriethoxysilane, γ- Glycidoxypropyltrimethoxysilane, methylvinyldimethoxysilane, 3-aminopropyltriethoxysilane,
N- (2-aminoethyl) -3-aminopropyltriethoxysilane and the like) (ii) Silicon resin (for example, methyl silicone resin,
Phenyl silicone resin, methyl phenyl silicone resin, etc.) or other silicone compounds (eg, isocyanate silane, silicone acetate, etc.). Further, SiO ₂ fine particles can be used together with the silicon source (i) and / or (ii).

[0053] Further, as the refractive index adjusting Ingredients of the raw materials, the corresponding metal (i) alkoxide (e.g., titanium -n- butoxide, zirconium -n- propoxide, lanthanum -i-
(Ii) alkoxide derivatives (e.g., tri-n-butoxyacetylacetonatozirconium, diisopropoxybisethylacetate titanium, etc.) (iii) chelating compounds (e.g., propoxide, yttrium-i-propoxide, niobium ethoxide, etc.) , Titanium tetraacetylacetonate, lanthanum triacetyltonate, lead diacetylacetonate, etc.) (iv) Other organometallic compounds (eg, yttrium methacrylate, zirconium methacrylate, etc.) (v) Nitrate (eg, bismuth nitrate pentahydrate) (Vi) acetate (eg, yttrium acetate tetrahydrate, lead acetate trihydrate, zirconyl acetate, etc.) (vii) chloride (eg, zirconyl chloride, titanium chloride) (Viii) Sulfates (eg, zirconium sulfate, titanium sulfate, etc.) (ix) Oxides (for example, TiO ₂ , ZrO ₂ , CeO _2, etc.) (x) Fluorides (for example, MgF ₂ , CaF _2, etc.) (xi) Metal itself.

As the matrix material, an organic matrix material can be used. 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, and fluororesin.

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, hydroxypropylcellulose and polyvinylpyrrolidone, formamide, N, N-dimethylformamide, 2-ethoxyethanol, diethanolamine,
Organic compounds such as monoethanolamine can be added.

Soluble azo pigments (for example, c-based, 2B-based, 6B-based)
System), insoluble azo pigments (for example, β-naphthol system,
Monoazo yellow type, pyrazolone type, etc.), phthalocyanine type pigments (eg, copper phthalocyanine blue, fast sky blue, metal-free phthalocyanine, etc.), sulene type (eg, thioindigo type, anthraquinone type, perylene type, perinone type, etc.), dioxazine type, quinacridone type Ultrafine particles of organic pigments such as isoindolinones can also be used.

The raw materials are not particularly limited as long as they are dissolved or homogeneously dispersed at the stage of the prepared liquid composition (coating solution).

As a dispersing machine required for producing the liquid composition, a ball mill, a sand mill, a two-roll,
Examples of the roll include an attritor, a Banbury mixer, a paint shaker, a kneader, a homogenizer, and an ultrasonic disperser.

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.

Of the above two alkoxides, the alkoxide of zirconium has a significantly higher hydrolysis rate than the alkoxide of silicon. Therefore, simply mixing and hydrolyzing the alkoxide of zirconium selectively hydrolyzes the alkoxide of zirconium to obtain a homogeneous alkoxide. No coating liquid can be obtained.

There are three methods for preventing the selective hydrolysis of the alkoxide of zirconium and obtaining 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. Generally, the hydrolysis rate decreases as the number of carbon atoms increases (conversely, the hydrolysis rate increases as the number of carbon atoms decreases). It is a method of utilizing. For example, a careful coating solution can be prepared by carefully hydrolyzing butoxide or amiloxide as alkoxide of zirconium and methoxide or ethoxide as alkoxide of silicon. The second method is a method in which a silicon alkoxide having a low hydrolysis rate is partially hydrolyzed in advance, and then a zirconium alkoxide is reacted. According to this method, since the alkoxide of silicon and the alkoxide of zirconium have reacted before the subsequent hydrolysis, a uniform coating solution can be obtained without causing selective hydrolysis. The third method is a method in which an alkoxide of zirconium having a high hydrolysis rate is reacted with a chelate compound. According to this method, the alkoxide of zirconium is chelated (the alkoxyl group of the alkoxide is replaced with a chelate compound), and the hydrolysis rate is reduced, so that a uniform coating solution can be obtained without causing selective hydrolysis. .

It is particularly preferable to use the above-mentioned methods together. Therefore, an example of the combination of the first method and the second method 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 stirred. A partial hydrolysis solution of the silicon alkoxide is obtained.

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

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

Then, if necessary, an acid catalyst such as hydrochloric acid, nitric acid, acetic acid, sulfuric acid, perchloric acid or the like, ammonia, choline,
A base catalyst such as amino alcohol and water and an organic solvent such as ethanol and 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 thus obtained coating solution is applied to a transparent substrate by the above-mentioned various coating methods, followed by drying and heat treatment, whereby a substrate with a thin film having a gold colloid-containing thin film on the transparent substrate is obtained.

This heat treatment is performed at 200 to the glass transition point +5
It is preferably carried out at a temperature of 0 ° C. The reason is as follows.

When the heat treatment is carried out at a temperature lower than 200 ° C., (i) the water and the solvent are not sufficiently removed, and they remain, resulting in inferior properties such as hardness of the thin film. (ii) Polymerization of the glass matrix does not proceed, and properties such as hardness of the thin film are inferior. (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 necessary absorption cannot be obtained. This makes it difficult to produce a thin film intended for the present invention.

On the other hand, when the heat treatment is performed at a temperature exceeding the glass transition temperature + 50 ° C., the substrate is softened, and the surface tends to be out of order.

The transparent substrate with a thin film containing gold colloid obtained by the above-described method using a silicon compound as a matrix material can prevent adverse effects due to interference colors by a film composition obtained by adding a refractive index adjusting portion to SiO _2. . In addition, when the substrate with the thin film was used for a glass filter by forming a glass matrix containing gold as a coloring agent and SiO ₂ as a binder component as a main component,
Superior in durability and reliability compared to filters manufactured by conventional methods. In addition, there is also an advantage that the use of a coating film forming method as a coating method enables production at a lower cost than conventional methods.

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

First, ultrafine zinc oxide particles are added to an organic solvent containing a dispersant, such as ethanol or butyl acetate, and the ultrafine zinc oxide particles are suspended or dispersed 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 ultrafine zinc oxide particles.

The thus obtained coating solution is applied to a transparent substrate by the above-mentioned various coating methods, and then dried and heat-treated, whereby a substrate with a thin film having a zinc oxide ultrafine particle-containing thin film on the transparent substrate can be obtained. .

This heat treatment is preferably performed 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 performed at a temperature lower than 150 ° C., (i) the organic solvent and the water are not sufficiently removed, and a large amount of them remains, resulting in inferior properties such as hardness of the thin film. (ii) Polymerization of the glass matrix does not proceed, and properties such as hardness of the thin film are inferior. This makes it difficult to produce a thin film intended for the present invention.

On the other hand, the glass transition point temperature of the transparent substrate +50
When the heat treatment is performed at a temperature exceeding ℃, the substrate is softened, and the surface is likely to be out of order.

The substrate with a thin film containing ultrafine zinc oxide particles obtained by the above-mentioned method using a silicon compound as a matrix raw material can prevent the adverse effect of interference fringes by the film composition of SiO ₂ plus a refractive index adjusting component. it can.
In addition, the substrate with the thin film has a glass matrix composed mainly of zinc oxide as an ultraviolet absorber and SiO ₂ as a binder component, so that when used for a glass filter, the substrate is more durable than a filter manufactured by a conventional method. Excellent in terms of reliability and reliability. In addition, there is also an advantage that by using a coating film forming method as a coating method, it can be manufactured at lower cost than a conventional method.

The method for producing a substrate with a thin film containing a colloidal gold and a substrate with a thin film containing ultrafine zinc oxide particles has been specifically described above. However, silver colloid, copper oxide ultrafine particles, nickel colloid, platinum colloid or other ultrafine particles are used. Can be produced by the same method.

[0082]

The present invention will be further described with reference to the following examples.

Example 1 Production Example of Substrate with Gold Colloid-Containing Thin Film A 0.15 M aqueous hydrochloric acid solution 265 was added to a mixed solution of 3060 g of tetraethoxysilane and 2030 g of ethanol.
g, and the mixture was stirred for 3 hours. Then, 362 g of zirconium tetrapropoxide was added, and the mixture was stirred overnight. The solution, 15 wt% chloroauric acid tetrahydrate (HAuCl ₄ · 4H ₂
O) -Isopropanol solution 439 g, 0.15 M aqueous hydrochloric acid solution 569 g, water 557 g and isopropanol 2
30 kg of an Au colloid thin film coating solution was produced by adding the mixed solution of 2,720 g and stirring for 2 hours.
The preparation composition of the thin film obtained from this coating solution is Au
3.0 wt%, ZrO ₂ 13.0 wt%, SiO ₂ 84.0
Solid content in coating solution in wt% (assuming heat treatment)
Is 3.5% by weight. The coating liquid was yellow transparent and homogeneous. This coating solution was applied to a 1 mm-thick commercially available plate glass (usually called a white plate. The composition system was soda lime silicate and the refractive index was 1.52) by a dipping method at a pulling rate of 30 cm / min ( Hereafter "V"
(Abbreviated as). The obtained thin film was colorless, transparent and homogeneous. After drying the substrate with the thin film at 100 ° C. for 30 minutes, it was placed in a heat treatment furnace, heated to 500 ° C. at 200 ° C./hour, and kept at 500 ° C. for 30 minutes. The glass with a thin film changes from colorless and transparent to reddish violet transparent by this heat treatment, and the obtained thin film is homogeneous, has a refractive index of 1.53, and a refractive index difference with the substrate of 0.7%. there were. The transmittance curve is shown in FIG. It is clear that the absorption of the 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 in the case of using a skylight filter (commercially available) manufactured by a melting method was obtained. confirmed.

Example 2 Production Example of Substrate with Gold Colloid-Containing Thin Film In this example, titanium (Ti) was selected as a refractive index adjusting component. Tetraethoxysilane 106
0.15 to a mixed solution of 3 g and 920 g of isopropanol
92 g of a M aqueous hydrochloric acid solution was gradually added, followed by stirring for 5 hours. 504 g of titanium tetrabutoxide was added to this solution, and the mixture was stirred for 1 hour. Then, methyltriethoxysilane 1761 was added.
g was added and stirred overnight. This solution was mixed with 439 g of a 15 wt% chloroauric acid tetrahydrate-isopropanol solution, 0.15%
An aqueous solution of 593 g of M hydrochloric acid, 582 g of water and 24,040 g of isopropanol were added to the mixture, followed by stirring for 2 hours to produce 30 kg of an Au colloid thin film coating solution. The preparation 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 solids content in the coating solution is 3.5 wt%. The coating liquid was yellow transparent and homogeneous. This coating solution is applied to a commercially available plate glass (refractive index: 1.52) having a thickness of 2 mm.
= 15.5 cm / sec. The obtained thin film was colorless, transparent and homogeneous. This substrate with a thin film
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 and transparent to reddish purple and transparent. The thin film was homogeneous and had a refractive index of 1.53 and a difference in refractive index from the substrate of 0.7%.

A photographing test was performed in the same manner as in Example 1, and it was confirmed that the characteristics as a skylight filter were satisfied.

Examples 3 to 10: Production Examples of Substrates with Gold Colloid-Containing Thin Film In the same manner as in Example 2 except that the Au content, the solid concentration and the pulling speed were changed as shown in Table 1. A glass with a thin film as shown in Table 1 was produced. As a result of performing a photographing 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 a refractive index adjusting component. A substrate with a thin film was produced in the same manner as in Example 2 except that γ-glycidoxypropyltrimethoxysilane was used instead of methyltriethoxysilane of Example 2. The composition of the thin film was 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 (a 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 that of FIG. Further, as a result of a photographing 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 a refractive index adjusting component. Instead of zirconium tetrapropoxide of Example 1, diisopropoxy bis (acetylacetonato) titanium (Ti [OCH (CH)
₃ ] ₂ [OC (CH ₃ ) CHCOCH ₃ ] ₂ ) was used to produce 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
iO _{2 is} 85.7 wt%. A thin film having a refractive index of 1.52 (a 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 that of FIG. Further, as a result of a photographing 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 a refractive index adjusting component. Instead of chloroauric acid tetrahydrate of Example 2, sodium chloroaurate 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 composition of the thin film was Au 3.0 wt.
%, Na ₂ O 0.5 wt%, TiO ₂ 11.2 wt%, S
iO _{2 is} 85.3 wt%. A thin film having a refractive index of 1.52 (a 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 that of FIG. Further, as a result of a photographing 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 a refractive index adjusting component. A substrate with a thin film was produced in the same manner as in Example 1 except that yttrium nitrate hexahydrate (Y (NO ₃ ) ₃ .6H ₂ O) was used instead of zirconium tetrapropoxide of Example 1. The preparation composition of the thin film is Au
_{3.0wt%, Y 2 O 3 18.8wt} %, SiO 2 78.
2 wt%. A refractive index of 1.5 on a substrate with a refractive index of 1.52
A thin film having a refractive index difference of 0.7% was formed.

The transmittance of the obtained substrate with a thin film was the same as that of FIG. Further, as a result of a photographing 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 a refractive index adjusting component. Instead of zirconium tetrapropoxide in Example 1, niobium pentaboxide (Nb
Using (OC ₄ H ₉ ) ₅ ), a substrate with a thin film was produced in the same manner as in Example 1. The composition of the thin film was 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 (a 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 of FIG. 1, and there was no problem in the photographing test.

[Comparative Example 1] Without using a refractive index adjusting component,
A coating liquid was prepared in the same manner as in Example 1, and a substrate with a thin film was prepared using the coating liquid. The preparation composition of the thin film is Au
3.0 wt% and 97.0 wt% of SiO ₂ . A substrate having a refractive index of 1.52 has a refractive index of 1.44 (refractive index difference -5.3).
%). FIG. 2 shows a transmittance curve of the substrate with the thin film. Irregularities occur in the transmittance curve due to the influence of interference. When a photographing test was performed using this substrate with a thin film, a specific coloring was observed, and use as a skylight filter was impossible.

Example 16 Production Example of Substrate with Gold Colloid-Containing Thin Film In this example, the substrate had a refractive index of 1.
Glasses for spectacle lenses 70 (L manufactured by HOYA Corporation)
Using I), a substrate with a thin film was prepared in the same manner as in Example 2. The preparation composition of the thin film was Au 6.0 wt%, SiO ₂
46.6wt%, a TiO ₂ 47.4wt%. The refractive index of the obtained thin film was 1.60, and the refractive index difference was -0.6%.
Met. FIG. 3 shows the transmittance curve of the substrate with the thin film. The absorption peak position was at 560 nm. The color of the obtained substrate with a thin film was reddish purple, and it was confirmed that the substrate could be used for coloring eyeglass lenses.

Example 17: Production Example of Substrate with Gold Colloid-Containing Thin Film A 3.5 wt% methyl silicone resin-isopropanol-n-butyl acetate solution was added to 28,540 g of 65,540 g.
1010 g of a wt% tetraacetylacetonatotitanium-isopropanol solution was added and stirred for 1 hour. A 15 wt% chloroauric acid tetrahydrate-isopropanol solution 45 was added to the solution.
0 g was added and the mixture was further stirred for 30 minutes to produce 30 kg of an 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
5.7 wt%. The refractive index was 1.5 in the same manner as in Example 1.
By forming a thin film having a refractive index of 1.53 (refractive index difference -0.7%) on the substrate No. 2, a substrate with a thin film was obtained.

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

Example 18: Production Example of Substrate with Thin Film Containing Ultra Fine Zinc Oxide Ethanol 7cp (dispersant, Dow Chemical) in 800.0 g of a mixed solvent of iso-butyl acetate / iso-propanol (1: 1 weight ratio) Company product name) 0.
47 g (0.5 wt% based on the zinc oxide ultrafine particles) were dissolved. Ultrafine zinc oxide particles 9 having a specific surface area of 65 m ² / g measured by a BET method using nitrogen gas were added to this solution.
After adding 4.0 g and dispersing for 1 hour using a glass shaker with a paint shaker (dispersing machine), 220.0 g of methyl silicone resin was added and the mixture was further dispersed for 20 hours. 800.0 g of an iso-butyl acetate / iso-propanol mixed solvent (1: 1 weight ratio) was added to this dispersion, and 65 wt%
Titanium tetraacetylacetonate (Ti (C ₅ H
₇ O _{2) 4)} · iso- propanol solution 119.1g of
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 is ZnO
30.8 wt%, TiO ₂ 4.6 wt%, SiO ₂ 6
At 4.5 wt%, the solids content in the coating solution is 15.0 wt%. The coating solution was milky white, and no precipitate or precipitate was observed. This coating solution was applied to a 1 mm-thick commercially available plate glass (usually called a white plate. The composition system was soda lime silicate and the refractive index was 1.52) by a dipping method at a pulling speed of 30 cm / min ( Hereinafter, abbreviated as “V”). The resulting thin film is
It was colorless, transparent and homogeneous. 150 ° C
After drying for 30 minutes in a heat treatment furnace,
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,
Its refractive index was 1.53, and the difference in refractive index from the substrate was 0.7%. The transmission haze value was 0.2. FIG. 4 shows the transmittance curve of the obtained substrate with the thin film together with the transmittance of the substrate alone. It is clear that light in a wavelength range shorter than 380 nm is sharply cut.

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

Example 19 Production Example of Substrate with Thin Film Containing Zinc Oxide Ultrafine Particles In this example, zirconium (Zr) was selected as a refractive index adjusting component. N-butyl acetate /
iso-propanol mixed solvent (1: 1 weight ratio) 78
Disperbyk (1.2g) -181
18.8 g (20 wt% based on ultrafine zinc oxide particles) was dissolved. 94.0 g of zinc oxide ultrafine particles having a specific surface area of 75 m ² / g measured by a BET method using nitrogen gas was added to this solution, and the mixture was dispersed with a zirconia bead using a sand mill (dispersing machine) for 1 hour. 220.0 g of silicone resin
And further dispersed for 3 hours. In this dispersion, acetic acid n
800.0 g of a mixed solvent of 1-butyl / iso-propanol (1: 1 weight ratio) and 73 wt% of zirconium acetylacetonate bisethyl acetate (Zr (OC ₄ H ₉ ))
_{(C 5 H 7 O 2)} (C 6 H 9 O 3) 2) · n- butanol solution was dispersed for 30 minutes by adding 126.9g of, by removing the glass beads, zinc oxide ultrafine particles-containing thin film coating liquid Produced. The preparation composition of the thin film obtained from this coating solution was 30.0 wt% of ZnO and 7.0 wt% of ZrO _2.
%, SiO ₂ 63.0 wt%, and the solid content in the coating solution is 1%.
5.3 wt%. The coating solution was milky white, and no precipitate or precipitate was observed. The coating solution was applied to a commercially available 2 mm-thick glass plate (refractive index: 1.52) by V = 30.0 cm /
Min applied. The obtained thin film was colorless, transparent and homogeneous. After the substrate with the thin film was dried at 150 ° 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 1 hour. The thin film obtained by this heat treatment is colorless, transparent and homogeneous, and has a refractive index of 1.
51, and the refractive index difference from the substrate was -0.7%.
The transmission haze value was 0.2.

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

Example 20: Manufacturing Example of Substrate with Thin Film Containing Ultra Fine Zinc Oxide In this example, antimony (Sb) was selected as a refractive index adjusting component. To 800.0 g of a mixed solvent of n-butyl acetate / methanol (3: 2 weight ratio), 220.0 g of a methyl silicone resin was added and dissolved. To this solution, 94.0 g of ultrafine zinc oxide particles having a specific surface area of 73 m ² / g measured by a BET method using nitrogen gas was added, and 1 microgram was added with a sand mill (dispersion machine) using glass beads.
Dispersed for 2 hours. To this dispersion, 723.5 g of an n-butyl acetate / methanol mixed solvent (3: 2 weight ratio) was added.
wt% antimony pentoxide (Sb ₂ O ₅ ) methanol sol
9.6 g was added, the mixture was dispersed for 1 hour, and the glass beads were removed to prepare a zinc oxide ultrafine particle-containing thin film coating solution. The prepared composition of the thin film obtained from this coating solution was ZnO 30.1 wt%, Sb ₂ O ₅ 6.7 wt%, Sb ₂ O ₅
63.2 wt% of iO ₂ , and the solid content in the coating solution was 16.
1 wt%. The coating solution has a milky white color and precipitates,
No precipitate was observed. This coating solution was applied to a commercially available plate glass (refractive index: 1.52) having a thickness of 2 mm and V = 30.0 cm /
Min applied. The obtained thin film was colorless, transparent and homogeneous. After the substrate with the thin film was dried at 150 ° 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 1 hour. The thin film obtained by this heat treatment is colorless, transparent and homogeneous, and has a refractive index of 1.
The refractive index difference from the substrate was 1.3%. The transmission haze value was 0.4.

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

Examples 21 to 26: Production Examples of Substrates with Thin Film Containing Zinc Oxide Ultrafine Particles
In the same manner as in Example 19 except that the glass was changed as shown in Table 2, glass with a thin film as shown in Tables 2 and 3 was produced. As a result of performing a photographing test of the obtained glass, it was confirmed that all the characteristics as an ultraviolet sharp cut filter were satisfied.

Example 27: Production Example of Substrate with Thin Film Containing Zinc Oxide Ultrafine Particles In this example, a glass for spectacle lenses having a refractive index of 1.70 (HOYA Corporation LH) was used as the substrate.
Using I), a substrate with a thin film was produced in the same manner as in Example 19. The prepared composition of the thin film was 28.1 wt% of ZnO, Z
rO ₂ 45.9 wt%, SiO ₂ 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%. FIG. 5 shows the transmittance curve of the substrate with the thin film. The transmission haze value was 0.3. The resulting substrate with a thin film is colorless, transparent and homogeneous,
It was confirmed that it can be used for UV cut of eyeglass lenses.

[Comparative Example 2] No refractive index adjusting component was used.
A coating solution was prepared in the same manner as in Example 19, and a substrate with a thin film was prepared using the same. The preparation composition of the thin film is Z
32.3 wt% of nO and 67.7 wt% of SiO ₂ .
A thin film having a refractive index of 1.44 (refractive index difference -5.3%) was formed on both surfaces of a substrate having a refractive index of 1.52. Also,
The transmission haze value was 0.2. FIG. 6 shows the transmittance curve of the substrate with the thin film. Since no refractive index adjusting component was used, interference occurred, and the influence caused irregularities in the transmittance curve. When a photographing test was performed using this substrate with a thin film, a specific coloring was observed, and use as an ultraviolet sharp cut filter was impossible.

Tables 2 and 3 collectively show the physical properties 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
129 g of a 0.15 M aqueous nitric acid solution was gradually added to a mixed solution of 858 g of propanol, followed by stirring 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 the mixture was further stirred for 1 hour. 118 g of silver nitrate, 0.0
1660 g of 75 M nitric acid solution, iso-propanol 2
By adding 2.578 g of the mixed solution and stirring overnight, 30 kg of a silver colloid thin film coating solution was produced. The composition of the thin film obtained from the coating solution was 4.8 wt% Ag.
%, TiO ₂ 11.0 wt%, SiO ₂ 84.2 wt%,
The solid content in the coating solution is 5.0% by weight. The coating solution is
It was colorless and transparent. This coating solution was applied to a commercially available 1 mm thick plate glass (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 maintained 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, the refractive index was 1.51, and the refractive index difference from the substrate was -0.7%. The transmittance curve is shown in FIG. 40 absorption of silver colloid
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 preparation composition of the thin film was 4.8 wt% of dopant, 11.0 wt% of TiO ₂ , SiO ₂ 8
4.2 wt%. Table 4 shows the refractive index of the substrate with a thin film and the difference from the substrate obtained in Examples 29 to 31, and the transmittance curves are shown in FIG. 8 (Cu ₂ O), FIG. 9 (Ni), and FIG.
t).

[0117]

[Table 4]

[0118]

As described above, according to the present invention, it is possible to provide a substrate with a thin film which has absorption of ultrafine particles of metal or metal oxide and is free from the influence of interference colors. By using this substrate with a thin film, it is possible to provide a filter with characteristics and reliability equal to or higher than those of existing colored filters and UV cut filters more easily and at lower cost than existing colored filters and UV cut filters. it can. Further, a colored spectacle lens can be provided.

[Brief description of the 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 a substrate with a thin film of Example 16.

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

FIG. 5 is a transmittance curve diagram of a 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 a substrate with a thin film of Example 28.

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

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

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

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-4-46302 (JP, A) JP-A-7-92305 (JP, A) JP-A-6-118203 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G02B 5/20 G02B 1/10 G02C 7/10 G03B 11/00

Claims (8)

(57) [Claims] 1. A raw material of gold colloid which is an ultrafine particle.
Gold compound and silicon compound which is the raw material of the matrix
And the raw materials for the refractive index adjusting component, and these three raw materials are dissolved.
Use the main composition on one of the transparent glass substrates
Ultra fine particles by applying on the surface, drying and heat treatment
Is a SiO ₂ matrix containing a refractive index adjusting component .
The refractive index difference with the substrate dispersed in the matrix is 10% or less.
The thin film inside is provided on one main surface of the glass substrate.
A method for manufacturing a substrate with a thin film, comprising: 2. It is a raw material of a gold colloid which is an ultrafine particle.
Gold compound and silicon compound which is the raw material of the matrix
And the raw materials for the refractive index adjusting component, and these three raw materials are dissolved.
Unpack the liquid composition into the main table on both transparent glass substrates.
Ultra fine particles by applying on the surface, drying and heat treatment
Is a SiO ₂ matrix containing a refractive index adjusting component .
Refractive index difference with substrate dispersed within the matrix is within 5%
Are provided on both main surfaces of the glass substrate.
A method for producing a substrate with a thin film, characterized in that: 3. The method according to claim 1, wherein the heat treatment is performed at a temperature of 200.degree.
(Transition point + 50 ° C.) or lower.
3. The method for manufacturing a substrate with a thin film according to item 2. 4. A gold compound as a raw material for ultrafine particles,
Lachloroauric acid tetrahydrate, tetrachloroauric acid trihydrate,
Sodium trachloroaurate dihydrate, gold cyanide, shea
Potassium gold and gold diethyl acetylacetonate?
4. The method according to claim 1, wherein at least one member selected from the group consisting of:
A method for manufacturing a substrate with a thin film according to any of the above. 5. A raw material silicon compound in a matrix,
Silicon alkoxide, silicon alkoxide
At least one selected from a conductor and a silicone resin
The substrate with a thin film according to any one of claims 1 to 4,
Production method. 6. A metal alloy as a raw material of the refractive index adjusting component.
Coxide, metal alkoxide derivative and metal sharp
Claims wherein at least one member selected from the group consisting of
6. The method for producing a substrate with a thin film according to any one of 1 to 5. 7. A chloroauric acid tetrahydrate as a gold compound,
Te tiger silane and Mechiruto as Lee-containing compound
Liethoxysilane as a raw material for the refractive index adjusting component
Gold compound, silicon compound
Composition in which the substance and the raw material of the refractive index adjusting component are dissolved
4. The method according to claim 1, wherein the material is applied on a transparent glass substrate.
A method for producing a substrate with a thin film according to any of the above. 8. The method according to claim 1, wherein
Using a colored filter.
Manufacturing method of color filter.