JP2000094569A - Soil resistant/electromagnetic wave shielding laminate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soil resistant electromagnetic wave shielding laminate in which adhesion properties durability for a long period and practical performance are excellent and both a soil resistant function and an electromagnetic wave shielding function are equipped and to provide a method for producing the same. SOLUTION: In the soil resistant/electromagnetic wave shielding laminate the outermost layer is an inorganic thin film layer having photocatalytic activity. A conductive inorganic thin film layer of at least one layer is provided between a base material and the inorganic thin film layer having photocatalytic activity in the outermost layer. Further, this laminate is produced by releasing one kind or a plurality of metallic compounds which desirably have volatility or sublimation properties and form conductive metallic oxides by chemical reaction, on the base material and forming a conductive metallic oxide thin film layer of at least one layer and furthermore forming a metallic oxide thin film layer having photocatalytic activity on the outermost layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated antifouling / electromagnetic wave shield product having a base material made of glass or plastics, having an antifouling function and having an electromagnetic wave shielding function, and a method for producing the same. is there.

[0002]

2. Description of the Related Art In recent years, electromagnetic interference has become a problem.
For example, electronic devices are entering offices and ordinary homes due to the development of a highly information-oriented society and the advent of a multimedia society. However, the number of cases where malfunctions of these electronic devices are caused by electromagnetic waves entering from outside is increasing. is there.
In addition, it is also possible to eavesdrop on information and confidential matters of information of companies and individuals of electronic devices by receiving radio waves of the electronic devices. Furthermore, there is a concern that electromagnetic waves generated from high-voltage power transmission lines may cause health problems for the residents there.At medical sites, electromagnetic waves generated by mobile phones and laser scalpels may cause cardiac pacemakers. There is also a concern that it may cause a malfunction such as stopping. To prevent these electromagnetic interference,
The demand for shielding electromagnetic waves in offices and homes is increasing. When a building or a general house is shielded from electromagnetic waves, the entire building or house must be shielded. The reason is that a small leak does not function because there is an ingress and egress of electromagnetic waves from there. When the entire surface is shielded from electromagnetic waves, it is necessary to shield not only the roof material, the floor material, and the wall material, but also the window material as a lighting part. As a method for shielding a roof material, a floor material, a wall material, and the like from electromagnetic waves, a method of attaching or embedding a conductive material such as a wire mesh to a material used for a building or a general house is used. However, these methods are complicated in construction and at the same time, in any case, it is necessary to externally cover them with wallpaper or the like. More preferably, it becomes a material. Wallpapers, many of which are formed from polymer materials, are one of the methods to shield this polymer material from electromagnetic waves, for example,
Although a method of forming an inorganic conductive substance such as ITO (tin-doped indium oxide) on the surface of the polymer material is considered, an ITO thin film is generally formed by a sputtering method or the like. On the other hand, as a method for shielding an electromagnetic wave from a window material, a silver thin film which is an inorganic conductive thin film is formed by a sputtering method or the like. However, these general methods such as the sputtering method require ancillary equipment such as a vacuum device for forming a thin film, which not only requires a large investment, but also has a low thin film forming speed and poor productivity. Therefore, there are problems such as an increase in cost.
In order to avoid these problems, there is a demand for an electromagnetic shielding material that can be provided at low cost by forming a conductive thin film at low cost.

[0003] Further, for example, wallpaper or window glass of a building or a general house, etc., becomes dirty due to the adhesion of oil in the atmosphere and impairs the appearance. For this reason, the aesthetic appearance is maintained by performing periodic cleaning. For this reason, it is desired to maintain an aesthetic appearance without cleaning. Especially in high-rise buildings, this maintenance requires a great deal of labor and money. If maintenance-free window glass is used, it will lead to significant labor savings and cost reductions, and expectations are high. Under these circumstances, there is no material such as wallpaper or window glass that exhibits electromagnetic wave shielding properties and can always maintain an aesthetic appearance, and there is no technology that can provide these materials at low cost.

[0004]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide an electromagnetic shielding layered product which can be manufactured at low cost, can prevent dirt, is maintenance-free, and is excellent in practical performance. It is to provide a manufacturing method.

[0005]

Means for Solving the Problems As a result of diligent studies on antifouling and electromagnetic wave shielding products satisfying the above objects, the present inventors have found that the outermost layer has a photocatalytic activity such as titanium oxide having an antifouling function. A thin film layer, preferably a metal oxide thin film layer, and a laminate comprising at least one conductive inorganic thin film layer, preferably a conductive metal oxide thin film layer, between the substrate and the outermost layer. The present invention was found to be an antifouling / electromagnetic wave shielding laminate having an antifouling function and an electromagnetic wave shielding function excellent in practical performance such as adhesion and long-term durability, and completed the present invention. The reason why the laminate of the present invention is excellent in practical performance is as follows. That is, when the base material is an inorganic material in particular, the thin film layer for imparting the antifouling function and the thin film layer for imparting the electromagnetic wave shielding function are both formed of an inorganic thin film, and the base material is also an inorganic substance. Excellent interfacial adhesion. Further, when the base material is glass, the inorganic thin film layer having photocatalytic activity is a metal oxide thin film, and when the conductive inorganic thin film layer is a metal oxide thin film, an antifouling function is imparted. Both the thin film layer and the thin film layer that provides the electromagnetic wave shielding function are metal oxides, and the main component of the glass is an oxide. Since it is a material, it does not deteriorate and has excellent long-term durability. When the base material is a polymer material, the inorganic thin film material is embedded in the surface of the polymer material by a method such as adding an organic functional group to the inorganic thin film material or spraying the inorganic thin film material at a high temperature. By forming a bonding layer between the inorganic thin film material and the polymer material, it is possible to impart adhesiveness and to impart practical performance.

As a method of manufacturing this laminate, when both the inorganic thin film layer having photocatalytic activity and the conductive inorganic thin film layer are metal oxides, first, they have volatilization or sublimation properties,
In addition, a metal compound that forms a conductive oxide by a chemical reaction is released onto a substrate to form a conductive metal oxide thin film layer, and then has a volatilization or sublimation property, and a photocatalyst is formed by a chemical reaction. It can be produced by releasing a metal compound which forms an active oxide and forming a metal oxide thin film layer requiring photocatalytic activity on the outermost layer. This chemical reaction is a chemical reaction with compounds in the atmosphere, for example, water and oxygen, and compared with the sputtering method in which the same inorganic thin film is formed when the atmosphere for releasing the metal compound is an atmospheric pressure atmosphere, that is, normal pressure. No need to vacuum. Therefore, no large equipment is required. In addition, the rate of forming the inorganic thin film is extremely high because the concentration of the inorganic substance sprayed on the base material is higher than in the case where the vacuum is applied. Accordingly, the present inventors have found that an inorganic thin film can be formed at a high speed, and an antifouling / electromagnetic wave shield laminate can be manufactured at low cost, and the present invention has been completed.

That is, according to the present invention, the outermost layer is an inorganic thin film layer having a photocatalytic activity, preferably an inorganic thin film layer made of a metal oxide, and is provided between the substrate and the outermost inorganic thin film layer having a photocatalytic activity. The present invention relates to an antifouling / electromagnetic wave shield laminate product provided with at least one conductive inorganic thin film layer, preferably an inorganic thin film layer made of a metal oxide. In addition, one or more metal compounds which have a volatilization or sublimation property and form a conductive oxide by a chemical reaction, preferably a reaction with a compound in the atmosphere, are preferably used as a gaseous medium such as nitrogen gas. Together with
Preferably, it is released on a substrate under an atmospheric pressure atmosphere to form at least one conductive metal oxide thin film layer, and further has volatilization or sublimation properties, and a chemical reaction, preferably with an atmospheric compound. The metal compound which forms an oxide having photocatalytic activity by the reaction of, preferably, is accompanied by a gaseous medium such as nitrogen gas, and is preferably released under an atmospheric pressure atmosphere. The present invention relates to a method for producing an antifouling / electromagnetic wave shield laminated product characterized by forming a thin film layer.

Hereinafter, the present invention will be described in detail. First, the components of the laminate of the present invention will be described. The base material of the antifouling / electromagnetic wave shield laminate of the present invention is not particularly limited, and examples thereof include inorganic materials such as glass, ceramics and concrete, and generally referred to as polymer materials. Among them, glass and polymer materials are particularly preferred because they have high needs for antifouling and electromagnetic wave shielding in buildings or general houses. The glass is not particularly limited as long as it is generally called glass, and examples thereof include soda-lime glass, potash glass, lead glass, borosilicate glass, and silicate glass. As the shape of the glass substrate, any shape such as a plate shape, a fiber shape, a bead shape and the like can be used. Among them, a plate shape in which the need for an electromagnetic wave shield is particularly high, that is, a plate glass is preferable. In the case of sheet glass, the thickness is not particularly limited, but a commercially available thickness, that is, a thickness of 1 mm or more can be used. The polymer material is not particularly limited as long as it is an organic polymer material generally referred to. Further, it may be a synthetic polymer or a natural polymer. Examples of the synthetic polymer include polyolefin-based materials such as polyethylene and polypropylene; polystyrene-based materials such as polystyrene, ABS, AES, styrene / conjugated double bond monomer copolymers and hydrogenated copolymers thereof; Methyl methacrylate material, polycarbonate material, polyester material such as polyethylene terephthalate, polyethylene butyrate or polyethylene naphthalate, polyphenylene ether material, polyacetal material, polyvinyl chloride material, polyvinylidene chloride material, polyamide material, Examples include a polyimide material, a polyacrylonitrile material, a polyvinyl acetate material, and a polymethylpentene material. Further examples include conjugated diene-based elastomers such as polybutadiene, and biodegradable polymers such as aliphatic polyesters such as polylactic acid, which have recently been developed. These synthetic polymers may be homopolymers of individual main monomers, or may be copolymers. In addition, examples of the natural polymer include a cellulosic material and the like. Any shape such as a sheet, a film, a molded product, a fiber, and a bead can be used.

The outermost inorganic thin film layer having a photocatalytic activity having an antifouling function is excited by photocatalytic activity, ie, photoenergy, and reacts with oxygen and water on the surface to generate active oxygen and hydroxyl radicals. It is not particularly limited as long as it is an inorganic thin film having an action of decomposing an organic substance attached to its surface. Examples of the inorganic substance exhibiting such an action include titanium oxide, strontium titanate,
Tungsten oxide, zinc oxide, tin oxide, niobium oxide, cadmium sulfide, and the like can be given. Among these, metal oxides have volatility or sublimability as described above, and can form an inorganic thin film by a simple method of releasing a metal compound that forms an oxide by a chemical reaction onto a base material. It is preferable because it is possible. Further, among metal oxides, titanium oxide, particularly titanium oxide having an anatase crystal structure, is most preferable because of its high photocatalytic activity. In order to promote the photocatalytic activity of these metal oxide thin films, for example, a promoter such as platinum, nickel oxide, ruthenium oxide or the like can be mixed. The thickness of the inorganic thin film layer having photocatalytic activity is
Usually, it is 20 μm or less, preferably 10 μm or less, more preferably 2 μm or less. In general, when the thickness is too large, there is a tendency that defects such as cracks are easily generated in the inorganic thin film layer, which is not preferable. Generally, it is preferably 20 μm or less.
The lower limit is not particularly limited as long as the photocatalytic activity function is exhibited. Usually, it is preferable that it is 0.01 μm or more. The microscopic shape of the inorganic thin film preferably has a large surface area, that is, a porous surface, so that the photocatalytic activity is large. On the other hand, if the inorganic film is porous, the surface hardness is reduced and the surface is easily damaged. A shape that satisfies both is preferred.

The at least one conductive inorganic thin film layer provided between the substrate and the outermost inorganic thin film layer having photocatalytic activity is not particularly limited as long as it is an inorganic thin film exhibiting conductivity. Examples of the substance include metals such as gold, silver, and copper, or IIB, IIIA, IIIB,
Oxides of metal alone or in combination of two or more selected from IVA and IVB can be mentioned.
Among these, Zn, Cd, In, Sn and Ti
A single or a combination of two or more selected from the above is preferred because of good transparency and conductivity. In order to improve the conductivity of the metal oxide thin film, IIB, III in the periodic table are used.
A, IIIB, IVA, IVB, VA, VB, and VIA may be used alone or in combination of two or more metals. Among these, Y, B, Al, Ga, In, Ti, Zr, Sn, S
Metals such as b, Mo, W, etc. are preferable because they have a large effect of increasing conductivity by doping the metal oxide. As described above, examples of the inorganic substance exhibiting conductivity include metals and metal oxides. Among these, metal oxides are metals that have volatilization or sublimation properties and form oxides by a chemical reaction. It is preferable because an inorganic thin film can be formed by a simple method of releasing a compound onto a substrate.

In order to exhibit electromagnetic wave shielding properties, the surface resistance of these inorganic thin films is preferably 10 ³ Ω / □ or less. More preferably, it is 10 ² Ω / □ or less. The greatest application of the present invention is for window glass.
When used as a window glass, it is necessary to see the outside scenery. It is not always necessary to be transparent, but those having excellent transparency are more preferable. Among the above-described conductive materials, Sn-doped indium oxide or aluminum-doped zinc oxide, which is generally referred to as ITO, is preferable because of its excellent conductivity and transparency.

The thickness of the conductive inorganic thin film layer is usually 20 μm.
m, preferably 10 μm or less, more preferably 2 μm
m or less. In general, when the thickness is large, there is a tendency that defects such as cracks tend to occur in the conductive inorganic thin film layer, which is not preferable. Generally, it is preferably 20 μm or less. The lower limit is not particularly limited as long as the conductive function is exhibited. Normal,
It is preferably at least 0.01 μm. The transparency of the antifouling / electromagnetic wave shield laminate of the present invention is particularly necessary when used as a window glass, and the transparency depends on the type and thickness of the inorganic substance having photocatalytic activity and the conductive inorganic substance. It is determined. The total light transmittance, which is one measure of transparency, is preferably 50% or more. Further, it is more preferably at least 60%.

In the antifouling / electromagnetic wave shielding laminate of the present invention, the outermost layer is an inorganic thin film layer having photocatalytic activity,
At least one conductive inorganic thin film layer is provided between the base material and the outermost inorganic thin film layer having photocatalytic activity.For example, the base material is soda-lime glass, and the anatase-type When an inorganic thin film layer having photocatalytic activity such as titanium oxide is formed, sodium migrates to titanium oxide to form sodium titanate, which becomes an impurity and reduces the photocatalytic activity of titanium oxide. In the case of the laminate of the invention, a conductive inorganic thin film layer is provided between the glass and the titanium oxide layer exhibiting photocatalytic activity. Therefore, as a result, there is also a great effect that a decrease in photocatalytic activity can be suppressed. When the base material is a polymer material and an inorganic thin film layer having photocatalytic activity such as anatase-type titanium oxide is formed directly on the polymer material, the photocatalytic activity has a property of decomposing organic substances by light. Because it is a characteristic,
Although the polymer material itself is also decomposed, problems such as inferior durability such as peeling off due to interface deterioration occur, but in the case of the laminate of the present invention, the polymer material and the titanium oxide layer showing photocatalytic activity A conductive inorganic thin film layer is provided between them. Therefore, as a result, there is also a great effect that a decrease in durability can be suppressed.

Next, a method for producing the antifouling / electromagnetic wave shield laminate of the present invention will be described. The antifouling / electromagnetic wave shield laminate of the present invention preferably has volatilization or sublimation properties, for example, by using the equipment as shown in FIG. 1, and reacts with a chemical reaction, preferably a reaction with a compound in the atmosphere. One or more metal compounds forming a conductive metal oxide and, if necessary, a metal compound of a metal to be doped into the metal oxide, heated as necessary, and released from the slit onto the substrate, Forming at least one conductive metal oxide thin film layer, further having volatilization or sublimation, and,
A metal compound that forms a metal oxide having photocatalytic activity by a chemical reaction, preferably by reaction with a compound in the atmosphere,
Heat if necessary, release onto the substrate from the slit,
It is manufactured by forming an inorganic metal oxide thin film layer having photocatalytic activity on the outermost layer. However, the present invention is not limited to this method. For example, the conductive inorganic thin film layer can be manufactured by a method such as heating a metal such as gold, silver or copper and sputtering the same on the substrate surface. or,
When the substrate is glass or the like, the inorganic thin film layer exhibiting photocatalytic activity is applied by a sol-gel method, that is, for example, a material obtained by hydrolyzing tetraalkoxytitanium in the presence of a catalyst is coated on the substrate, and baked to, for example, a 500 ° C level It can also be manufactured by a method such as forming an anatase type titanium oxide thin film layer.

In a preferred production method of the present invention, a metal compound which is volatile or sublimable and forms a metal oxide by a chemical reaction and, if necessary, a metal compound of a metal doped into the metal oxide are used. Release on the substrate,
When manufacturing antifouling / electromagnetic shielding laminates by forming a metal oxide having photocatalytic activity and a conductive metal oxide, the metal compound as a raw material emits oxygen present in the atmosphere when released from a slit or the like. Although it may be partially formed by reacting with water or a chemical substance intentionally used, one that mainly forms a metal oxide is used. Usually, no catalyst is preferable, but a metal oxide may be formed in the presence of a catalyst (for example, a volatile acid or alkali).

An example will be given to explain the principle of the chemical reaction of a metal compound with an oxide in an easy-to-understand manner. For example, tetraalkoxy tin is used as a metal compound,
When the glass substrate is heated to 500 ° C. and released to the atmosphere without a catalyst using nitrogen gas as a gaseous medium, it is reacted with moisture in the atmosphere on the surface of the base material and reacts as follows. A metal oxide mainly composed of tin oxide is formed by a reaction presumed to be based on tin oxide. Alternatively, in the case of a polymer material, since the heat resistance is generally low, the substrate cannot be heated to a high temperature. In this case, the temperature of the tetraalkoxytin released from the slit is set to 500 ° C. using nitrogen gas as a gaseous medium. Immediately after the release, the released tetraalkoxytin reacts with moisture in the atmosphere to form a metal oxide mainly composed of tin oxide by a reaction presumably based on the following. The particles are sprayed on a polymer material set at a low temperature to form an inorganic thin film mainly composed of a metal oxide.

Sn (OR) ₄ + 2H ₂ O → SnO ₂ + 4ROH When such a metal compound is volatilized or sublimated and released from a slit, it reacts with oxygen, moisture or the like to form an oxide. If it is, there is no particular limitation. As an example, when imparting a photocatalytic activity function, for example, an alkyl compound, an alkenyl compound, a phenyl or an alkylphenyl compound, a alkoxide compound of the metal described above such as Ti, Sr, W, Zn or Sn;
Examples thereof include a halogen compound, an acetylacetonate compound, and an EDTA compound. When imparting a conductive function, for example, an alkyl compound, an alkenyl compound, a phenyl or an alkylphenyl compound, an alkoxide compound, a halogen compound, an acetylacetonate compound or an EDTA compound of a metal such as Zn, Cd, In, Sn or Ti described above. Is mentioned. When doping a metal oxide with a metal for the purpose of improving conductivity, for example, Y, B, Al, Ga, In, Ti, Zr,
Examples include the above-mentioned metal alkyl compounds, alkenyl compounds, phenyl or alkylphenyl compounds, alkoxide compounds, halogen compounds, acetylacetonate compounds, EDTA compounds, and the like such as Sn, Sb, Mo, and W. These metal compounds can be used alone, or a plurality of compounds can be used in combination even for the same metal.

As a method of releasing a metal compound from a slit or the like by volatilizing or sublimating, it is preferable to release the metal compound together with a gaseous medium. The reason for this is that the method of releasing together with a gaseous medium is capable of controlling the release amount of the metal compound to a constant amount. The gaseous medium is not particularly limited as long as it does not react with the metal compound used. Examples thereof include an inert gas such as a nitrogen gas and an argon gas, a carbon dioxide gas, an organic fluorine-based gas, and hexane and heptane. And the like. However, an inert gas is preferable from the viewpoint of safety and economy. Among them, nitrogen gas is most preferable from the viewpoint of economy.

The most preferable method of the present invention for producing an antifouling / electromagnetic wave shield laminate is to release a metal compound from a slit or the like and form an oxide by a chemical reaction with a compound such as atmospheric moisture or oxygen. Although it is a method, when carried out by this method, for example, heating the metal compound in a heating tank to a temperature at which volatilization or sublimation in a state where oxygen and moisture are absent or in a very small amount or higher, or more,
In addition, a gaseous medium free or very low of oxygen and moisture is introduced and released. The reason why oxygen and water in the metal compound or the gaseous medium are not present or are extremely small is to prevent a reaction due to a metal oxide in the apparatus before the release and a trouble such as clogging. However, depending on the type of metal compound to be used, the reaction rate of the metal compound to the oxide may be extremely slow only by discharging from the outlet such as a slit. In this case, oxygen, moisture, or a catalyst (eg, volatile acid, alkali, etc.) for increasing the reaction rate, etc., should be coexistent in the gaseous medium or the volatile layer to such an extent that no clogging occurs in the apparatus. There is also. The metal compound to be released may be one kind or a mixture. It is possible to mix and volatilize, but after mixing the volatilized material, it is also possible to spray the mixture onto the base material.

The temperature of the metal compound to be released is not particularly limited as long as it is generally equal to or higher than the temperature at which the metal compound volatilizes, but the temperature is generally generally 100 to 500 ° C. The temperature of the base material is not particularly limited. In the case of an inorganic material such as glass, the temperature is generally from room temperature to 800 ° C. In the case of a polymer material, it is often performed at room temperature to 300 ° C. This temperature setting is an important factor that determines the adhesion to the glass substrate. There are two main methods for setting temperature conditions. One is to make the release temperature higher than the substrate temperature. Another method is to make the release temperature lower than the substrate temperature. In the former, when a metal compound is released from a slit, fine particles of a metal oxide are formed by a chemical reaction immediately after the release, and an inorganic thin film is formed in such a manner that the fine particles of the high-temperature metal oxide are stacked on a base material. . In the latter, a metal oxide is formed by a chemical reaction on the substrate surface,
Further, an inorganic thin film is formed by growing the metal oxide thereon. In general, the former method is used when the temperature of a base material such as a polymer material cannot be raised to a high temperature and the base material softens at a temperature which is usually performed. In this case, when the high-temperature metal oxide particles are sprayed on the base material, the heat energy of the particles softens the base material surface and embeds the particles, and the particles are buried between the base material and the inorganic particles. An intermediate layer is formed, and the adhesion is high. The latter method is
Although the temperature of the substrate such as glass can be high, even if the metal oxide particles are sprayed on the substrate without softening at the temperature usually performed,
Used when the particles are not embedded. The formation of an inorganic thin film by growth of a metal oxide with the substrate surface as a nucleus results in high adhesion between the substrate and the inorganic thin film.

The distance between the outlet of the metal compound and the surface of the substrate is usually 50 cm or less. Although it differs depending on the shape of the outlet of the metal compound, when the diameter is 50 cm or more, the metal compound is not effectively converted to a metal oxide or the efficiency tends to be poor due to diffusion to a peripheral portion. The atmosphere for releasing the metal compound may be under reduced pressure, under normal pressure or under pressure. However, when the process is performed under a high degree of reduced pressure, for example, under an ultra-vacuum, the production rate of the metal oxide is low, and the productivity is lacking. Although there is no problem with the rate of metal oxide generation performed under pressure, it is not a preferable direction because equipment for pressurization is required. Although not limited to this, it is usually preferable to carry out at 0.1 to 10 atm. However, in general,
Most preferably, it is carried out under an atmosphere of atmospheric pressure, that is, at normal pressure. Large equipment is not necessary for industrial production,
In addition, the generation rate of the metal oxide is in a range that can be put to practical use.

In the present invention, the inorganic thin film having photocatalytic activity and the conductive inorganic thin film layer to be formed may each be a single layer or a multilayer. The outermost layer is an inorganic thin film having photocatalytic activity. At least one conductive inorganic thin film is required between the outermost layer and the base material. It is also possible that other inorganic or organic layers exist between the conductive inorganic thin film or the conductive inorganic thin film and the substrate.

The most preferred method of producing a laminated antifouling / electromagnetic wave shield of the present invention is a metal oxide which releases a metal compound through a slit or the like and has a photocatalytic activity by a chemical reaction with a compound such as moisture or oxygen in the atmosphere. The method of forming a thin film and a conductive metal oxide thin film can form a metal oxide thin film having a different function by a joint method. For example, using a plurality of facilities similar to FIG. The metal oxide thin film layer can be formed continuously and sequentially by moving a certain glass plate or the like, which is an industrially easy method. Thus, the laminate of the present invention
The glass is used as a base material, and as an antifouling / electromagnetic wave shielding glass, for example, it can be used for window glass of buildings, condominiums, general houses, etc., a cathode ray tube or front panel of a television or a plasma display, and the like. In addition, fibrous glass can be used as a heat insulating material and a shielding material, for example, by converting it into a nonwoven fabric. It can be used for antifouling / electromagnetic wave shielding wallpaper, front panel of TV and plasma display, etc., using a polymer material as a base material.

[0024]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In addition, the evaluation method of the electromagnetic wave shielding property was determined by Anritsu Corporation.
The measurement was performed using a spectrum analyzer MS623A measuring device, a tracking generator MH628A, and an anechoic chamber. A 100 × 100 mm square sample was measured in a frequency range of 100 to 1000 MHz.

(Example 1) The dry nitrogen introduction line of FIG.
Using a facility comprising a metal compound heating tank and a slit-shaped outlet, a mixture of indium trimethylacetyl acetate and tetraethoxytin (molar ratio: 91.
5 / 8.5). The heating tank is heated to 150 ° C, and the heating pipe and slit are also heated to 150 ° C by the heater.
And the blowing temperature was set to 150 ° C. A glass plate (soda-lime glass) having a thickness of 5 mm was set at a position 5 cm below the blowing slit, and heated to 500 ° C. Dry nitrogen gas was introduced into the heating tank, and a mixture of indium trimethylacetyl acetate and tetraethoxytin was released into the atmosphere under atmospheric pressure and sprayed on the surface of the glass plate. Reacted with water in the air on the surface of the glass plate, and a conductive film of indium oxide doped with tin was formed on the surface of the glass plate. The thickness of this conductive film is controlled by the amount of dry nitrogen gas introduced and the moving speed of the glass plate, and is approximately 0.5 μm.
m. As a result of measuring the conductivity of this tin-doped indium oxide (ITO) transparent conductive film, the surface resistance was 0.0
It was 1 Ω / □. Then, using the same equipment of FIG.
The heating tank was charged with tetraisopropoxy titanate.
The heating tank was heated to 120 ° C., and the heating pipe and the slit were also heated to 120 ° C. by the heater, and the blowing temperature was set to 120 ° C. The glass plate on which the conductive film made of ITO was formed was set at a position 5 cm below the blowing slit, and heated to 500 ° C. Dry nitrogen gas was introduced into the heating tank, and tetraisopropoxy titanate was released into the atmosphere at atmospheric pressure and sprayed on the surface of the conductive film made of ITO. Reacted with water in the air on the surface of the conductive film, and a transparent titanium oxide thin film mainly composed of an anatase crystal structure was formed on the surface. The thickness of this titanium oxide thin film was controlled by the amount of dry nitrogen gas introduced and the moving speed of the glass plate, and was about 0.5 μm. The adhesion between the ITO conductive thin film / titanium oxide thin film / glass laminate was extremely good. That is, even if this laminated product was scratched with a cutter knife, the interface did not peel off. The evaluation result of the electromagnetic wave shield of this laminated product was about 50 dB at an attenuation value of 800 MHz. When about 1 μm of salad oil was applied to this sample, and the sample was irradiated with black light for 48 hours, the salad oil on the irradiated surface was decomposed and disappeared by 100%, showing a good photocatalytic action. On the other hand, the glass alone did not exhibit any electromagnetic wave shielding properties, and did not decompose at all even when the same salad oil decomposition evaluation was performed.

(Example 2) The dry nitrogen introduction line of FIG.
Using a facility comprising a metal compound heating tank and a slit-shaped outlet, a mixture of indium trimethylacetyl acetate and tetraethoxytin (molar ratio: 91.
5 / 8.5). The heating tank was heated to 150 ° C., and the heating pipe and slit were heated to 500 ° C. by a heater, and the blowing temperature was set to 500 ° C. An acrylic plate having a thickness of 3 mm was set at a position 5 cm below the blowing slit, and heated to 80 ° C. Dry nitrogen gas was introduced into the heating tank, and a mixture of indium trimethylacetyl acetate and tetraethoxytin was released into the atmosphere under atmospheric pressure and sprayed on the surface of the glass plate. Immediately after the release of the slit, it reacts with water in the air to generate metal oxide particles composed of tin-doped indium oxide, and the particles are sprayed on the surface of the acrylic plate, so that tin-doped oxide oxide is formed on the surface of the acrylic plate. A conductive inorganic thin film mainly composed of a metal oxide of Joule was formed. The thickness of this conductive film was controlled by the dry nitrogen gas introduction amount and the moving speed of the acrylic plate, and was about 0.5 μm. As a result of measuring the conductivity of this tin-doped indium oxide (ITO) transparent conductive film, the surface resistance was 0.01 Ω / □. Next, using the same equipment as in FIG. 1, tetraisopropoxytitanate was charged into the heating tank. The heating tank was heated to 120 ° C., and the heating pipe and the slit were heated to 500 ° C. by a heater, and the blowing temperature was set to 500 ° C. An acrylic plate on which the conductive film made of ITO was formed was set at a position 5 cm below the blowing slit, and heated to 80 ° C.
Dry nitrogen gas was introduced into the heating tank, and tetraisopropoxy titanate was released into the atmosphere at atmospheric pressure and sprayed on the surface of the conductive film made of ITO. Reacted with water in the air on the surface of the conductive film, and a transparent titanium oxide thin film mainly composed of an anatase crystal structure was formed on the surface. The thickness of this titanium oxide thin film was controlled by the amount of dry nitrogen gas introduced and the moving speed of the glass plate, and was about 0.5 μm. The mutual adhesion of this ITO conductive thin film / titanium oxide thin film / acrylic laminate was extremely good. That is, even if this laminated product was scratched with a cutter knife, the interface did not peel off. The evaluation result of the electromagnetic wave shield of this laminated product was about 50 dB at an attenuation value of 800 MHz. When about 1 μm of salad oil was applied to this sample, and the sample was irradiated with black light for 48 hours, the salad oil on the irradiated surface was decomposed and disappeared by 100%, showing a good photocatalytic action.

[0027]

According to the present invention, the outermost layer is an inorganic thin film layer having photocatalytic activity such as titanium oxide, preferably a metal oxide thin film layer, and at least one conductive inorganic thin film is provided between the substrate and the outermost layer. The present invention provides an antifouling / electromagnetic wave shielding laminate having an antifouling function and an electromagnetic wave shielding function excellent in practical performance such as adhesion and long-term durability by laminating layers, preferably a conductive metal oxide thin film layer. be able to. In addition, when the laminate is a metal oxide in which both the inorganic thin film layer having photocatalytic activity and the conductive inorganic thin film layer are metal oxides, first, they have volatilization or sublimation properties, and the conductive oxide is formed by a chemical reaction. The metal compound to be formed is released onto the substrate, a conductive metal oxide thin film layer is formed, and then, a metal compound which has a volatilization or sublimation property and forms an oxide having photocatalytic activity by a chemical reaction. It can be manufactured by emitting a metal oxide thin film layer that requires photocatalytic activity on the outermost layer. According to this manufacturing method, since the inorganic thin film can be formed at a high speed, the above-mentioned laminate can be manufactured at low cost.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a process of forming an inorganic thin film on a substrate.

Continued on the front page F term (reference) 4F100 AA01A AA01C AA17A AA21A AA21C AA25C AA28C AA33 AA33C AB09C AB12C AB19C AB20C AB21C AB22C AB33A AB33C AG00 AG00B AK01B AR00C AT00B BA03 BA07 BA10AJJB08 BA07 BA10AJJB10 BA02 BA08 BA11 BA12 BA15 BA16 BA18 BA20 BA22 BA26 BA42 BA45 BA46 BA47 BA53 BA54 BA55 BA56 BA57 BB13 CA06 CA07 EA01 FA10 LA01 LA11 5E321 AA43 AA44 BB23 GG05 GH10

Claims (16)

[Claims] 1. An outermost layer is an inorganic thin film layer having photocatalytic activity, wherein at least one conductive inorganic thin film layer is provided between a substrate and an outermost inorganic thin film layer having photocatalytic activity. Antifouling / electromagnetic wave shield laminated product. 2. The laminated antifouling / electromagnetic wave shield according to claim 1, wherein the substrate is glass. 3. The antifouling / electromagnetic wave shield laminate according to claim 1, wherein the base material is a polymer material. 4. The conductive inorganic thin film has a surface resistance of 10 ³ Ω.
/ □ The antifouling according to any one of claims 1 to 3 below.
Electromagnetic wave shield laminated product. 5. The laminated antifouling / electromagnetic wave shield according to claim 1, wherein the inorganic thin film layer having photocatalytic activity comprises a metal oxide. 6. The antifouling / electromagnetic wave shielding glass laminate according to claim 1, wherein the inorganic thin film layer having photocatalytic activity is mainly composed of anatase-type crystal structure titanium oxide. 7. The antifouling / electromagnetic wave shield laminate according to claim 1, wherein the conductive inorganic thin film layer comprises a metal oxide or a metal oxide doped with a metal as required. 8. The conductive inorganic thin film layer according to claim 1, wherein the conductive inorganic thin film layer comprises IIB,
The antifouling / electromagnetic wave shield laminate according to any one of claims 1 to 7, comprising an oxide of one or more metals selected from IIIA, IIIB, IVA, and IVB. 9. The conductive inorganic thin film layer is made of Zn, Cd, I
9. The antifouling / electromagnetic wave shield laminate according to claim 8, comprising an oxide of one or more metals selected from n, Sn and Ti. 10. The metal which is optionally doped is
IIB, IIIA, IIIB, IVA, IV in the periodic table
The antifouling / electromagnetic wave shield laminate according to any one of claims 7 to 9, wherein at least one is selected from B, VA, VB, and VIA. 11. The metal to be doped as required
Y, B, Al, Ga, In, Ti, Zr, Sn, Sb,
The antifouling / electromagnetic wave shield laminate according to claim 10, wherein one or more kinds are selected from Mo and W. 12. A base material comprising one or a plurality of metal compounds which have volatilization or sublimation and form a conductive oxide by a chemical reaction, and a metal oxide of a metal to be doped as necessary. Releasing, forming at least one conductive metal oxide thin film layer, and further releasing one or more metal compounds which form an oxide having volatilization or sublimation properties and having photocatalytic activity by a chemical reaction. The method for producing an antifouling / electromagnetic wave shield laminate according to any one of claims 1 to 11, wherein a metal oxide thin film layer having photoactivity is formed as an outermost layer. 13. The method for producing an antifouling / electromagnetic shield laminate according to claim 12, wherein the metal compound is released together with the gaseous medium. 14. The method for producing an antifouling / electromagnetic wave shield laminate according to claim 12, wherein the chemical reaction is caused by a chemical reaction with a compound in the atmosphere. 15. The method according to claim 12, wherein the atmosphere in which the metal compound is released is an atmospheric pressure atmosphere. 16. The metal compound forming an oxide and the metal compound of a metal to be doped as necessary are an alkyl compound, an alkenyl compound, a phenyl or alkylphenyl compound, an alkoxide compound, a halogen compound, an acetylacetonate compound and an EDTA compound. The method according to any one of claims 12 to 15, which is selected from the group consisting of: