JPH09227157A - Non-fogging film-forming base material, non-fogging film using the same and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a non-fogging film-forming base material excellent in initial non-fogging properties and their durability and having electric wave penetrability and excellent heat insulation and a non-fogging film using the same and provide a method for producing the same. SOLUTION: This non-fogging film-forming base material contains a titania- containing metal oxide and electroconductive metal oxide superfine particles. This non-fogging film is obtained by coating a transparent base board with a non-fogging film comprising the non-fogging film-forming base material. This production of the non-fogging film comprises coating the transparent base board with a compound sol containing a titania sol-containing metal oxide sol and the electroconductive metal oxide super fine particles, and baking it at 300-850 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate for forming an antifogging film on the surface of a transparent substrate such as glass, and more specifically, to the antifogging property of the obtained antifogging film. The present invention relates to an antifogging film-forming substrate that can be maintained for a long period of time and can be provided with heat insulating performance, etc., an antifogging film using the same, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, inorganic glass and the like have been utilized for their properties as a transparent base material, and are widely used for articles such as window glass, mirror surface and spectacle lenses. However, in articles using these transparent substrates, dew condensation occurs on the surface of the article when used in a high-temperature and high-humidity place or a boundary surface with a large difference in temperature and humidity, which causes the surface of the article to dew. There is the problem of clouding. Up to now, there have been demands for improvement of these transparent base materials from various fields, and in order to meet these demands, various attempts have been proposed to impart antifogging property and durability.

As a method for preventing fogging on the surface of the substrate,
2. Description of the Related Art A hydrophilic film is formed on a surface of glass or the like. As the simplest method, it has been known for a long time that coating a surface of a substrate with a surfactant can prevent fogging, and the surfactant should be a water-soluble polymer such as polyacrylic acid or polyvinyl alcohol. Attempts have been made to improve the durability of the effect by compounding (for example, JP-A-52-101680). However, in such a method, only the anti-fogging property is temporarily provided, and a continuous effect cannot be expected.

Further, in Japanese Patent Laid-Open No. 55-154351, a thin film containing at least one of molybdenum oxide and tungsten oxide and phosphorus oxide is formed on a glass substrate surface by physical vapor deposition or chemical vapor deposition. Method for obtaining a hydrophilic thin film excellent in antifogging property by forming by vapor deposition or the like, JP-A-54-10
The 5120 discloses, in a gas containing P ₂ O, a method for imparting anti-fogging properties by contacting the liquid or vapor of P ₂ O _5, and Sho 53-58492 and JP-sulfonic acid A method of forming an antifogging film having excellent adhesiveness by applying a composition containing an amphoteric surfactant and an inorganic salt or an acetate salt to a substrate using a lower alcohol solution has been proposed, whichever method is used. Even in the method, it was difficult to realize long-term durability of the antifogging performance.

On the other hand, there has been a long-standing desire to mitigate the heat of direct light from the window glass of automobiles and buildings, and heat ray reflecting glass and heat ray absorbing glass have been developed as transparent heat insulating glass and adopted for window glass of automobiles. Has been done. Typical examples include a laminated structure in which a metal film such as Ag is sandwiched by a transparent dielectric material having a high refractive index such as TiO ₂ (heat-reflecting glass), and dielectric multilayers having different refractive indexes. There are those in which a film is formed on a glass substrate (heat ray reflecting glass) and those in which transition metal ions such as Fe, Ce, Co, and Se are added to soda lime glass (heat ray absorbing glass).

However, in the heat ray reflective glass using the metal film as described above, the solar radiation transmittance can be suppressed and the heat insulating effect is great, but there is a problem that radio waves are shielded. Further, in the heat ray reflective glass using the dielectric multilayer film, there is a problem that a sufficient heat insulating effect cannot be obtained although the radio wave transmission can be secured. On the other hand, in the heat ray absorbing glass, the heat insulating effect can be enhanced by increasing the addition amount of the transition metal, but there is a limit in terms of securing the visible light transmittance particularly for automobiles.

Further, as a heat insulating glass using ultrafine particles, one prepared by coating a polyester film with a pressure-sensitive adhesive with a near-infrared reflective coating in which ITO (tin-doped indium oxide) ultrafine particles are dispersed in an acrylic resin is NOF. It is marketed by the industry. However, since this film uses an acrylic resin as a binder, it cannot exhibit antifogging properties.

[0008]

As described above, according to the prior art, an antifogging film satisfying persistent antifogging property and weather resistance, which is transparent and capable of ensuring radio wave transmission and heat insulation. There was a problem that there was nothing that had sex. The present invention is intended to solve the problems of the related art, and is excellent in initial antifogging property and its durability, and also has an antifogging film forming substrate having radio wave transmission and excellent heat insulation, It is an object to provide an antifogging film used and a method for producing the same.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using titania in combination with conductive metal oxide ultrafine particles. Heading out, the present invention has been completed. That is, the antifogging film-forming substrate of the present invention is characterized by containing a metal oxide containing titania and conductive metal oxide ultrafine particles. Further, the antifogging film of the present invention is characterized in that a transparent substrate is coated with a base material layer comprising the above-mentioned antifogging film-forming base material. Furthermore, in the method for producing an antifogging film of the present invention, a composite sol solution containing a metal oxide sol containing a titania sol and conductive metal oxide ultrafine particles is applied to a transparent substrate and baked at 300 to 850 ° C. Is characterized by.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The antifogging film-forming substrate of the present invention contains the metal oxide containing titania and the conductive metal oxide ultrafine particles as described above. Here, the use of titania as the film-forming material means that even if dirt is attached to the surface of the obtained anti-fog film and the anti-fog property is deteriorated, the titania absorbs ultraviolet rays of 400 nm or less, and This is because pores are generated and an oxidation-reduction reaction occurs, whereby the attached dirt is decomposed and the antifogging property can be maintained.

As described above, the light source for exerting the photocatalytic property of titania effective for decomposing dirt is preferably one containing ultraviolet rays of 400 nm or less, for example, sunlight, mercury lamp, fluorescent lamp, halogen lamp. , Short arc xenon light and laser light. Further, in the present invention, a light source may be provided so that the portion on which the anti-fog coating is formed is directly irradiated with light, but usually a special light source is not required, and for example, indoor fluorescent lamps, the sun, etc. It is possible to obtain sufficient performance by natural light. In addition,
Silica, alumina, a metal oxide such as zirconia is added to titania to form a film-forming material as a composite metal oxide,
It is also possible to adjust the refractive index of the resulting anti-fogging film and improve the film forming property.

Next, the conductive metal oxide ultrafine particles are used to selectively shield near-infrared rays having a large thermal action in sunlight, and the near-infrared rays reflected on the surface of such fine particles are fine particles. Since it is absorbed while the reflection is repeated between, the solar radiation transmittance can be suppressed. Also,
Such ultrafine particles can also contribute to increasing the quantum efficiency of the photocatalytic function due to their conductivity.

It is possible to improve the quantum efficiency of the photocatalytic function by adding a metal such as Ag, Cu, Pt, and Zn, but in order to make the antifogging coating exhibit adiabatic performance, the quantum efficiency is improved. It is necessary to add a large amount as compared with the above case, and use of these metals may hinder the maintenance of high transparency. Therefore, as the conductive ultrafine particles to be added, it is preferable to use metal oxide ultrafine particles that have little effect on the transparency. For the above reasons, specific examples of the conductive metal oxide ultrafine particles include In ₂ O ₃ and In.
₂ O ₃ : Sn, In ₂ O ₃ : F, CdSnO ₃ , CdSn
O ₄ , SnO ₂ , SnO ₂ : F, SnO ₂ : P, SnO ₂ :
Sb and the like can be mentioned, but from the viewpoint of conductivity, I
_{n 2 O 3: Sn (ITO} ), CdSnO 4, SnO 2: Sb
Can be used particularly preferably.

Here, the ultrafine particles are used for the purpose of preventing white turbidity due to light scattering by particles and ensuring radio wave transmission. In order to prevent scattering in the visible light region, the particle size of the ultrafine particles is preferably 100 nm or less. Further, if the particle size is too small, it becomes difficult to produce the fine particles and the particles easily aggregate. Therefore, the particle size is preferably 1 nm or more. Further, as the addition amount of the conductive metal oxide ultrafine particles, if the amount is less than 1% by weight, effective heat insulating performance cannot be obtained, and if it exceeds 30% by weight, the photocatalytic effect due to titania cannot be sufficiently obtained. It is preferably 30% by weight.

Next, the antifogging film of the present invention will be described.
The antifogging film of the present invention is formed by coating a base layer (antifogging film) made of the above-mentioned antifogging film-forming substrate on a transparent substrate such as glass. In this anti-fog coating,
Titania can have an anatase structure, a rutile structure, and an amorphous crystal polymorphism. However, since the anatase structure has a large photocatalytic function, the anatase structure is preferable.

In the antifogging film of the present invention, a metal oxide layer may be provided as an intermediate layer at the interface between the antifogging film and the substrate. By providing such an intermediate layer, it is possible to prevent the elements in the substrate from diffusing into the antifogging film and prevent the quantum efficiency of the photocatalytic function from decreasing. It is also effective in improving the adhesion. Examples of the method for forming the intermediate layer include a sol-gel method, a vacuum vapor deposition method, a sputtering method, a CVD method, and a plating method, but any method may be used.

Next, the method for producing the antifogging film of the present invention will be described. The antifogging film of the present invention is obtained by applying a composite sol solution containing a metal oxide sol containing titania sol and conductive metal oxide ultrafine particles to a transparent substrate and firing at 300 to 850 ° C. In this case, as the conductive metal oxide ultrafine particles, as described above, In ₂ O ₃ , In
₂ O ₃ : Sn, In ₂ O ₃ : F, CdSnO ₃ , CdSn
O ₄ , SnO ₂ , SnO ₂ : F, SnO ₂ : P, SnO ₂ :
At least one kind of Sb can be used.

The metal oxide sol containing the titania sol is sufficient if it contains the titania sol, and may be the titania sol alone or a mixture of the titania sol and another metal oxide sol. The firing temperature is 300-
In the range of 850 ° C., titania sol produces titania with anatase structure having a large photocatalytic function,
If the temperature is lower than ℃, amorphous, and if it exceeds 850 ℃, a rutile structure is likely to be generated, and the photocatalytic function is easily deteriorated. Therefore, the firing temperature is preferably 300 to 850 ℃.

A metal alkoxide is typically used as a starting material for various metal oxide sols used in the present invention, and other materials include metal sulfates, nitrates, carbonates, ammonium salts, chlorides, and the like. Examples thereof include, but are not limited to, various salts such as halides such as bromide and organic salts such as stearates and acetates. Also, a mixture of sols prepared by using these as starting materials may be used.

Further, a commercially available sol can also be used. Specifically, as the titania sol, trade name TA-
There are 10, TA-15 (manufactured by Nissan Chemical Industries, Ltd.), Atron (manufactured by Nippon Soda Co., Ltd., etc.), and alumina sol under the trade name Aluminasol-100, Aluminasol-200, Aluminasol-300 (manufactured by Nissan Chemical Industries, Ltd.). ), AS-
3 (manufactured by Catalysts & Chemicals Co., Ltd.), etc., and as silica sol under the trade names Super Cera (manufactured by Daihachi Chemical Co., Ltd.), Ceramica (manufactured by Nitlab Research Institute), HAS (manufactured by Colcoat)
Atron SiN-500 (manufactured by Nippon Soda Co., Ltd.), CGS
-DI-600 (manufactured by Chisso Co., Ltd.) and the like, and trade names NZS-30A and NZS-30B as zirconia sol.
(Manufactured by Nissan Chemical Industries, Ltd.), AZS-A, AZS-N
B, AZS-B (manufactured by Nippon Shokubai Chemical Co., Ltd.) and the like.

In the production method of the present invention, an organic polymer is added to a composite sol solution (coating solution) containing titania sol and metal oxide ultrafine particles to prepare a sol solution, which is used as a coating solution. Applied to the substrate as
Firing may be carried out within the above temperature range, whereby a porous antifogging film can also be produced. By making it porous, the wettability with water is improved and the quantum efficiency of photocatalytic activity is improved. Examples of the organic polymer used here include water-soluble polymers such as polyethylene glycol and water-insoluble polymers such as polytetrafluoroethylene (PTFE). As a method of coating on the substrate, various methods such as a dip coating method, a spin coating method, a coating method, and a spray pyrolysis method can be applied.

[0022]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
The following performance evaluations were performed on the coating films obtained in each example, and the obtained results are shown in Table 1 together with the component composition in each example. [Evaluation Method of Antifogging Property] The antifogging property was evaluated by the wettability with water, that is, the contact angle. The contact angle which is good as the antifogging performance is 15 ° or less, and when it is more than 15 °, the antifogging performance tends to deteriorate. [Evaluation Method of Weather Resistance] The weather resistance was evaluated by setting the sample for evaluation on an exposure table inclined at 45 ° to the south, performing outdoor exposure, and then measuring the contact angle. [Evaluation of heat insulation performance] The heat insulation performance was evaluated by calculating the solar radiation transmittance in accordance with JIS R3106-1985 from the transmittance measurement data with a spectrophotometer.

Example 1 Size 100 mm × 100 m
A green heat ray absorbing glass substrate having a thickness of 3.5 mm and a thickness of 3.5 mm was sequentially washed with a neutral detergent, water and ethanol and dried to obtain a film-forming substrate. Titania sol to _{In 2 O 3: Sn (ITO} )
Ultrafine particles (particle size 5 to 15 nm) were mixed in a predetermined amount to prepare a coating solution. This coating solution was applied onto a film-forming substrate by a spin coating method, dried and baked at 400 ° C. This was repeated 10 times and then baked at 550 ° C. to obtain an ITO ultrafine particle-dispersed titania film having a thickness of about 2.5 μm. The coating composition is Titania 9
It was 9% by weight and 1% by weight of ITO. An anatase structure had formed in the titania. When the anti-fogging property of the obtained coating film was evaluated, the initial contact angle was 6 ° and good anti-fogging performance was exhibited. The solar radiation transmittance was 57%, which was improved from 60% in the case of only the green heat ray absorbing glass substrate.
Further, when the contact angle after outdoor exposure for 6 months was measured, it was 11 ° and the antifogging property was maintained. Furthermore, there was no conductivity on the surface, and radio wave transmission was secured.

Example 2 The same operation as in Example 1 was performed except that the ratio of titania and ITO ultrafine particles was changed. The composition of the obtained coating was 70% by weight of titania and ITO.
It was 30% by weight. An anatase structure had formed in the titania. When the anti-fogging property of the obtained coating film was evaluated, the initial contact angle was 8 ° and good anti-fogging performance was exhibited. The solar radiation transmittance was 41%, which was significantly improved from 60% in the case of only the green heat ray absorbing glass substrate. Also, 6
When the contact angle was measured after outdoor exposure for 15 months, it was 15
The antifogging property was maintained at °. Furthermore, there is no surface conductivity,
Radio wave transparency was secured.

Example 3 The same operation as in Example 1 was performed except that a composite sol of titania sol and silica sol was used in place of the titania sol and the amount of the ITO ultrafine particles added was increased. The composition of the obtained coating film was 70% by weight of titania, 20% by weight of silica, and 10% by weight of ITO, and an anatase structure was formed in the titania. When the antifogging property of the obtained coating film was evaluated, the initial contact angle was 7 ° and good antifogging performance was exhibited. The solar radiation transmittance was 54%, which was improved from 60% in the case of only the green heat ray absorbing glass substrate. Further, when the contact angle after outdoor exposure for 6 months was measured, it was 13 ° and the antifogging property was maintained. Furthermore, there was no conductivity on the surface, and radio wave transmission was secured.

Example 4 The same operation as in Example 1 was carried out except that a composite sol of titania sol and alumina sol was used in place of the titania sol and the amount of ITO ultrafine particles added was increased. The composition of the obtained film was 75% by weight of titania, 15% by weight of alumina, and 10% by weight of ITO, and an anatase structure was formed in the titania. When the antifogging property of the obtained coating film was evaluated, the initial contact angle was 7 ° and good antifogging performance was exhibited. The solar radiation transmittance was 52%, which was improved from 60% in the case of only the green heat ray absorbing glass substrate. Further, when the contact angle after outdoor exposure for 6 months was measured, it was 13 ° and the antifogging property was maintained.
Furthermore, there was no conductivity on the surface, and radio wave transmission was secured.

Example 5 Size 100 mm × 100 m
A green heat ray absorbing glass substrate having a thickness of 3.5 mm and a thickness of 3.5 mm was sequentially washed with a neutral detergent, water and ethanol and dried to obtain a film-forming substrate. Silica sol is applied onto the film-forming substrate by spin coating, dried and baked at 400 ° C.,
A silica film having a thickness of about 0.2 μm was obtained. In ₂ O ₃ : Sn (ITO) ultrafine particles (particle size 5 to 15 nm) were mixed with a composite sol of titania sol and silica sol in a predetermined amount to prepare a coating solution. This coating solution was applied onto a silica film on a film-forming substrate by a spin coating method, dried and then baked at 400 ° C. After repeating this 10 times, it is fired at 550 ° C. and IT of about 2.5 μm thick is formed.
An ultrafine particle dispersed titania film was obtained. The composition of the coating was 70% by weight titania, 20% by weight silica, and 10% by weight ITO. An anatase structure had formed in the titania. When the antifogging property of the obtained coating film was evaluated, the initial contact angle was 7 ° and good antifogging performance was exhibited. Solar transmittance is 5
It was 5%, which was improved from 60% in the case of only the green heat ray absorbing glass substrate. Further, when the contact angle after outdoor exposure for 6 months was measured, it was 9 ° and the antifogging property was maintained. Furthermore, there was no conductivity on the surface, and radio wave transmission was secured.

(Example 6) The same operation as in Example 5 was performed except that the firing temperature was changed to 850 ° C. The composition of the obtained coating is 70% by weight of titania, 20% by weight of silica, IT
O was 10% by weight, and an anatase structure was formed in the titania. When the antifogging property of the obtained coating film was evaluated, the initial contact angle was 7 ° and good antifogging performance was exhibited. The solar radiation transmittance was 50%, which was improved from 60% in the case of using only the green heat ray absorbing glass substrate. Further, when the contact angle was measured after the outdoor exposure for 6 months, it was 15 ° and the antifogging property was maintained. Furthermore, there was no conductivity on the surface, and radio wave transmission was secured.

(Example 7) The same operation as in Example 5 was performed except that the firing temperature was changed to 300 ° C. The composition of the obtained coating is 70% by weight of titania, 20% by weight of silica, IT
It was 10% by weight of O. An anatase structure had formed in the titania. When the anti-fogging property of the obtained coating film was evaluated, the initial contact angle was 8 ° and good anti-fogging performance was exhibited.
The solar radiation transmittance was 56%, which was improved from 60% in the case of only the green heat ray absorbing glass substrate. Further, when the contact angle was measured after the outdoor exposure for 6 months, it was 14 ° and the antifogging property was maintained. Furthermore, there was no conductivity on the surface, and radio wave transmission was secured.

(Example 8) S instead of ITO ultrafine particles
The same operation as in Example 5 was carried out except that nO ₂ : Sb ultrafine particles (particle size 10 to 20 nm) were used. The composition of the obtained coating was as follows: titania 70% by weight, silica 20% by weight, Sn
It was 10% by weight of O ₂ : Sb. An anatase structure had formed in the titania. When the antifogging property of the obtained coating film was evaluated, the initial contact angle was 7 ° and good antifogging performance was exhibited. The solar radiation transmittance was 47%, which was improved from 60% in the case of only the green heat ray absorbing glass substrate. Further, when the contact angle after outdoor exposure for 6 months was measured, it was 11 ° and the antifogging property was maintained. Furthermore, there was no conductivity on the surface, and radio wave transmission was secured.

Example 9 C instead of ITO ultrafine particles
The same operation as in Example 5 was performed except that dSnO ₄ ultrafine particles (particle diameter 10 to 20 nm) were used and the amount of silica sol was reduced. The composition of the obtained coating was 70% by weight of titania,
It was 10% by weight of silica and 20% by weight of CdSnO ₄ .
An anatase structure had formed in the titania. When the anti-fogging property of the obtained coating film was evaluated, the initial contact angle was 7 °.
And exhibited good anti-fogging performance. The solar radiation transmittance was 48%, which was improved from 60% in the case of only the green heat ray absorbing glass substrate. Further, when the contact angle was measured after the outdoor exposure for 6 months, it was 12 ° and the antifogging property was maintained.
Furthermore, there was no conductivity on the surface, and radio wave transmission was secured.

Comparative Example 1 The same operation as in Example 1 was carried out except that the ITO ultrafine particles were not added to the titania sol. The solar radiation transmittance was 60%, which was unchanged from the case of using only the green heat ray absorbing glass substrate. (Example 10) The same operation as in Example 1 was performed except that the amount of the ITO ultrafine particles added was reduced. The composition of the obtained coating was 99.9% by weight of titania and 0.1% by weight of ITO. The solar radiation transmittance was 60%, which was unchanged from the case of using only the green heat ray absorbing glass substrate.

Example 11 The same operation as in Example 1 was performed except that the amount of the ITO ultrafine particles added was increased.
The composition of the obtained coating was 60% by weight of titania and ITO4.
It was 0% by weight. When the anti-fogging property of the obtained coating film was evaluated, the initial contact angle was 10 ° and good anti-fogging performance was exhibited.
The solar radiation transmittance was 39%, which was improved from 60% in the case of only the green heat ray absorbing glass substrate. However, when the contact angle after outdoor exposure for 6 months was measured, it was 19 °
Therefore, the antifogging property was not maintained.

(Example 12) The same operation as in Example 5 was performed except that the firing temperature was 875 ° C. When the anti-fogging property of the obtained coating film was evaluated, the initial contact angle was 7 °, good anti-fogging performance was exhibited, and the solar radiation transmittance was 39%, which was 60% of the case of only the green heat ray absorbing glass substrate. It was improving. However, no anatase structure was detected, and all had a rutile structure. When the contact angle after outdoor exposure for 6 months was measured, it was 21 ° and the antifog property was not maintained.

(Example 13) The same operation as in Example 5 was performed except that the firing temperature was 280 ° C. When the anti-fogging property of the obtained coating film was evaluated, the initial contact angle was 8 °, good anti-fogging performance was exhibited, and the solar radiation transmittance was 52%, which was 60% of the case of only the green heat absorbing glass substrate. It was improving. However, no crystal structure was detected, and all had an amorphous structure. When the contact angle after outdoor exposure for 6 months was measured, it was 40 ° and the antifog property was not maintained.

[0036]

[Table 1]

[0037]

As described above, according to the present invention, since titania and the conductive metal oxide ultrafine particles are used in combination, the initial antifogging property and its durability are excellent, and the radio wave permeability is excellent. It is possible to provide an antifogging film-forming substrate having excellent heat insulating properties, an antifogging film using the same, and a method for producing the same. That is, the metal oxide coating containing hydrophilic titania (anti-fog coating) develops anti-fog properties, and the photocatalytic effect of the titania film with an anatase structure decomposes the organic hydrophobic component attached to the surface to prevent The cloudiness can be maintained for a long time. In addition, since the near-infrared rays of sunlight are shielded by the conductive metal oxide ultrafine particles contained in the antifogging coating, the heat insulating property is improved. Furthermore, since the conductive metal oxide is dispersed in the film as ultrafine particles, there is almost no deterioration in transparency due to cloudiness or absorption, and radio wave transparency can be secured. Therefore, when the antifogging film of the present invention is used for a window glass, the transparency of the window glass can be maintained even in a high humidity environment without operating the air conditioner. In particular, when it is used for a window glass of an automobile, it is particularly useful in terms of securing a visual field. Furthermore, since it also has a heat insulating property, it is effective in mitigating the heat caused by direct light.

Claims (11)

[Claims] 1. An antifogging film-forming substrate comprising a metal oxide containing titania and conductive metal oxide ultrafine particles. 2. The conductive metal oxide ultrafine particles are In
₂ O ₃ , In ₂ O ₃ : Sn, In ₂ O ₃ : F, CdSnO ₃ ,
The antifogging coating film according to claim 1, which is at least one kind of ultrafine particles selected from the group consisting of CdSnO ₄ , SnO ₂ , SnO ₂ : F, SnO ₂ : P and SnO ₂ : Sb. Base material. 3. The antifogging film-forming substrate according to claim 1, wherein the conductive metal oxide ultrafine particles have a particle size of 1 to 100 nm. 4. The content of the conductive metal oxide ultrafine particles is 1 to 30% by weight.
The antifogging film-forming substrate according to any one of item 3. 5. An antifogging film comprising a transparent substrate and a substrate layer comprising the antifogging film-forming substrate according to any one of claims 1 to 4. 6. The antifogging film according to claim 5, further comprising a metal oxide layer between the base material layer and the transparent substrate. 7. The antifogging film according to claim 5, wherein the titania in the base material layer has an anatase structure. 8. An anti-fogging film characterized in that a composite sol solution containing a metal oxide sol containing titania sol and conductive metal oxide ultrafine particles is applied to a transparent substrate and baked at 300 to 850 ° C. Production method. 9. The conductive metal oxide ultrafine particles are In
₂ O ₃ , In ₂ O ₃ : Sn, In ₂ O ₃ : F, CdSnO ₃ ,
9. The antifogging film according to claim 8, which is at least one kind of ultrafine particles selected from the group consisting of CdSnO ₄ , SnO ₂ , SnO ₂ : F, SnO ₂ : P and SnO ₂ : Sb. Method. 10. The method for producing an anti-fogging film according to claim 8, wherein the conductive metal oxide ultrafine particles have a particle size of 1 to 100 nm. 11. The conductive metal oxide ultrafine particles are added in an amount of 1 to 30% by weight.
10. The method for producing an antifogging film according to any one of items 10 to 10.