JPH09241530A - Coating method and noncombustible, highly weather-resistant film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a noncombustible, highly weather-resistant film to which can not be cope with in many uses wherein no conventional film can be used satisfactorily. SOLUTION: A substrate is primed with a compsn. mainly comprising 3-16 pts.wt. (in terms of SiO2 ) quaternary ammonium silicate, 15-85 pts.wt. inorg. filler, and 12-82 pts.wt. water (the sum of the three ingredients being 100 pts.wt.) and then coated with a compsn. mainly comprising 2-15 pts.wt. (in terms of SiO2 ) quaternary ammonium silicate and 98-85 pts.wt. water (the sum of the two ingredients being 100 pts.wt.). The formed coating layer is cured by drying at normal temp. or by drying through low-temp. heating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating method, and more specifically, to concrete or cement-based materials, calcium silicate-based materials, other ceramic-based materials, iron, aluminum, stainless steel, other metal materials, or Non-combustible / high weather resistance, high hardness, high density by applying a specific undercoating composition and overcoating composition on the surface of glass, paper, wood, etc., and drying and curing at room temperature or under low temperature heating. It also has excellent anti-pollution properties, water resistance and
The present invention relates to a coating method for obtaining a nonflammable and highly weather resistant film which is excellent in hot water resistance, heat resistance, abrasion resistance, chemical resistance, particularly alkali resistance, organic solvent resistance, semi-gloss and good in cosmetic properties.

[0002]

2. Description of the Related Art Conventionally, heat resistance, weather resistance,
For the purpose of improving chemical resistance, water repellency, hot water resistance, abrasion resistance, etc., various coating methods or coating compositions for forming coating films, or nonflammable coating films have been proposed. For example, a silicone resin composition, an organoalkoxysilane composition, a silane zirconium composition, a fluororesin composition, a sodium / potassium / lithium silicate coating film, and the like are disclosed.

However, the silicone resin composition has a low hardness even if it is sufficiently heat-treated, and there is a problem in weather resistance and abrasion resistance. Further, the organoalkoxysilane composition has a problem in alkali resistance and boiling water resistance when it is fired at a low temperature. Furthermore, the silane-zirconium-based composition requires heat treatment, has low hardness, and has a problem in workability. Further, the fluorine-based resin composition has problems that it has low hardness, is easily scratched, and tends to generate static electricity. Furthermore, the non-combustible sodium / potassium / lithium silicate coating film has poor water resistance and hot water resistance.

As described above, conventional coating compositions and coatings are hardened by heating at room temperature or low temperature, nonflammable, and have weather resistance for 30 years or more, high hardness, water resistance, hot water resistance, and water resistance. At present, a coating film excellent in alkalinity and acid resistance has not been obtained.

[0005]

The present invention has been made against the background of the above-mentioned problems of the prior art. The object of the present invention is to dry and cure at room temperature or low temperature heating (40 to 150 ° C.). It is non-combustible, has high weather resistance for 30 years or more, withstands high temperature of 1,000 ° C or more, and has high heat resistance. It has high hardness, excellent stain resistance, wear resistance, water resistance and hot water resistance. , Excellent in alkali resistance, acid resistance, organic chemical resistance, 3-5 minutes can make a beautiful cosmetic film, rust / corrosion resistant film, heat insulating film, heat radiation film, conductive film, deodorizing film,
Used in various applications where it is not possible to adequately cope with conventional products because it has features such as functional film such as moldproof film and cured film, composition is aqueous, does not contain harmful substances, and has good workability. It is to provide a non-combustible / highly weather-resistant film that can be manufactured.

[0006]

The present invention comprises a substrate surface,
(A) 3 to 16 parts by weight of (a) quaternary ammonium silicate in terms of SiO ₂ , (b) 15 to 85 parts by weight of inorganic filler, and (c) 12 to 82 parts by weight of water [however, (a ) +
(B) + (c) = 100 parts by weight] as a main component, after undercoating a coating composition (hereinafter also referred to as “(a) undercoating composition”), (b) (a) ′ quaternary ₂ to 15 parts by weight of ammonium silicate in terms of SiO ₂ and 98 to 85 parts by weight of (c) ′ water [provided that (a) ′ +
(C) '= 100% by weight] as a main component, and a coating composition (hereinafter also referred to as "(b) overcoating composition") is overcoated and cured by room temperature drying or low temperature heat drying. The present invention provides a coating method.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (a) Undercoating composition (a) quaternary ammonium silicate; In the present invention, (a) quaternary ammonium silicate is dehydrated and dried by heating at room temperature or low temperature. And forms a thin film of SiO ₂ and acts as a binder. However, since the (a) quaternary ammonium silicate is usually used in the form of an aqueous silica sol, the (a) component alone is 0.1 to 0.2 μm.
Membrane of about m is the limit and is almost useless.
When the component (a) is combined with the inorganic filler of the component (b), the quaternary ammonium silicate forming the aqueous silica sol is particulate or fibrous and has a large surface area, such as hydroxyl groups on the surface of the inorganic filler. Reacts strongly with the functional groups of, and is hardened at room temperature and low temperature, nonflammable,
High weather resistance, high heat resistance, high hardness, wear resistance, hot water resistance,
Creates a film that is resistant to alkalis, acids, and organic chemicals. The component (a) is, for example, a compound represented by the general formula (R ₄ N) ₂ O.nSiO.
₂ (wherein R is a monovalent organic group and n is a natural number) and the like, but is not limited thereto. Since the component (a) contains almost no alkali metal, removing the organic matter by heating produces a high-purity SiO ₂ film.

The component (a) is not particularly limited as long as it is a quaternary ammonium silicate, but it can be prepared, for example, by the following method. That is, (a) a quaternary ammonium silicate is a silica sol having a molar ratio of SiO ₂ : Me ₂ O (M; alkali metal) or NH ₃ of 300 or more and containing almost no anion and having a pH of 4 or less. , A quaternary ammonium salt (for example, a cationic surfactant composed of a quaternary ammonium salt), SiO ₂
0.1 to 2% by weight ratio to, and thoroughly mixed, then add an alkaline substance to adjust the pH of the silica sol to 8
The stable silica sol combined with the quaternary ammonium salt is obtained by adjusting the temperature as described above and further heating at a temperature of 60 ° C. or higher for 1 hour or longer, if necessary.

Here, the molar ratio of SiO ₂ / M ₂ O is 30.
If it is not 0 or more, a large amount of the alkali metal or NH ₃ is present on the surface of the silica particles so that the quaternary ammonium salt may be prevented from directly binding to the silica particles. Further, in order to firmly bind the quaternary ammonium salt to the silica particles, it is necessary to add the quaternary ammonium salt to a silica sol that has almost no alkali metal ions having a pH of 4 or less and other cations.

In addition to the above quaternary ammonium salt,
For example, a cationic surfactant such as an alkylamine salt, an alkylpicolinium halide, polyoxyethylene, an alkylamine, an alkylamidomethylpyridinium chloride, an alkylpyridinium chloride, an alkyldimethylbenzylammonium chloride is replaced with a quaternary ammonium salt, Alternatively, it can be added in combination with this. These quaternary ammonium salts and the above cationic surfactants are completely dissolved in water or hot water,
It is necessary to add it to the silica sol in a transparent state, and further mix with sufficient stirring.

The amount of the quaternary ammonium or the cationic surfactant added is 0.1 to ₂ % by weight with respect to SiO _{2. If the} amount is less than 0.1% by weight, the silica sol will not be stable, while 2% by weight will be obtained. On the other hand, if it exceeds%, it may become unstable and gelate. In the silica sol thus treated,
The pH of the system is adjusted to 8 or higher by adding an alkaline substance such as ammonium hydroxide, morpholine or triethanolamine. The silica sol thus obtained has a temperature of 30 at room temperature.
The liquid property is maintained for about 60 days, but when permanent stability is required, it is preferable to age at 60 ° C. or higher for 1 hour or longer.

The proportion of component (a) in the undercoat composition (a) of the present invention is 3 to 16 parts by weight, preferably 5 to 10 parts by weight, calculated as SiO ₂ . If the amount is less than 3 parts by weight, the binding force may be insufficient or the powder may be formed. on the other hand,
If it exceeds 16 parts by weight, a coating film cannot be formed or cracks may occur.

(B) Inorganic filler; (b) The inorganic filler used in (a) the undercoating composition of the present invention preferably has an average particle size or average length of 0.1 to 1.
The thickness is 00 μm, more preferably 0.3 to 30 μm. If the average particle size is less than 0.1 μm, the functionality of the inorganic filler cannot be exhibited, or the manufacturing cost is too high, while if it exceeds 100 μm, the coating film becomes rough and the adhesive strength is reduced. To do. As such an inorganic filler, a water-insoluble, particulate or fibrous one is preferable, and examples thereof include an inorganic extender pigment, a functional pigment, an inorganic pigment, and a metal powder, which are selected from these groups. 1
Species or two or more species.

Specific examples of the inorganic extender pigment and the functional pigment include commercially available silica, alumina, kaolin, zircon, tin oxide, mullite, zeolite, talc, perlite, carbon, potassium titanate whiskers, silicon carbide, and nitriding. Examples of the inorganic pigments include commercially available oxides of titanium, iron, manganese, cobalt, chromium, nickel and the like, carbon or cobattle and aluminum, two kinds of synthetic oxides such as iron and manganese, and iron. , And three kinds of synthetic oxides such as copper and chromium. In addition, metal powder such as zinc, nickel, stainless steel, aluminum, tin,
Examples thereof include antibacterial-treated zeolite and silica gel, but are not limited thereto.

The amount of such an inorganic filler (b) is
(B) 15 to 85 parts by weight, preferably 30 to 70 parts by weight in the undercoat composition. If it is less than 15 parts by weight, the functionality of the inorganic filler cannot be expressed, while if it exceeds 85 parts by weight, the adhesion and hardness are lowered, the viscosity is increased,
It is not preferable because the component (a) or the component (c) is insufficient. Such inorganic fillers are needed to make thick films,
Further coloring the coating, imparting various functionalities to the coating, such as thermal radiation, ultraviolet absorption, heat insulation, conductivity,
It provides rustproofing, antibacterial and deodorizing properties.

(C) Water: (c) Water used in (a) the undercoating composition of the present invention is an essential component for adjusting the viscosity of the composition, controlling the pot life, and dispersing the inorganic filler. Is. As this water, tap water, distilled water, and ion-exchanged water can be used. Further, it also includes water contained in the aqueous silica sol composed of the quaternary ammonium silicate which is the component (a).

The mixing ratio of (c) water in the undercoat composition (a) is 12 to 82 parts by weight, preferably 20 to 5 parts by weight.
0 parts by weight. If it is less than 12 parts by weight, the viscosity of the obtained composition may be increased or the dispersion of the inorganic filler may be deteriorated. On the other hand, if it exceeds 82 parts by weight, the resulting coating film is too thin, which is not preferable.

In addition to the above-mentioned components (a) to (c), the composition (a) for undercoating (a) of the present invention may optionally contain various surfactants, dispersants, curing modifiers, dyes, colloidal or super-compounds. It may contain fine particles of silica, alumina, and other additives.

The undercoating composition (a) of the present invention comprises (a)
When the component (b) is added to the component and the amount of water in the component (a) is insufficient, (c) water is further added as necessary to adjust the total solid content concentration to preferably 15 To 85% by weight, more preferably 30 to 75% by weight. At this time, (a) the undercoating composition can be dispersed by a high-speed stirrer, a roll mill, a ball mill, or another disperser and filtered to form a uniform and stable dispersion liquid.

(B) Topcoating composition (b) The (a) ′ quaternary ammonium silicate and (c) ′ water used in the topcoating composition are the same as those in (a) above.
It is the same as the component (a) and the component (c) used in the undercoat composition. Here, the amount of the component (a) 'used in the (b) topcoat composition is 2 to 15 parts by weight, preferably 3.5 to 7.5 parts by weight. If the amount is less than 2 parts by weight, the coating film is too thin, or the amount of impregnation into the undercoating film is too small, so that the undercoating film is not covered or the hardness does not appear, and the effect of the present invention cannot be obtained. . On the other hand, if the amount exceeds 15 parts by weight, the coating film may be cracked or powdery, which is not preferable. The amount of the component (c) '(water) used is 98 to 85 parts by weight, preferably 96.5 to 92.5 parts by weight. If it exceeds 98 parts by weight, the amount of the component (a) 'is relatively small and the effect of the present invention cannot be obtained. On the other hand, if it is less than 85 parts by weight, the amount of the component (a)' becomes too large, which is not preferable.

In addition to the above-mentioned components (a) 'and (c)', the (b) topcoat composition of the present invention may optionally contain various surface active agents in the same manner as the (a) undercoat composition. Agent,
It may contain a dispersant, a curing modifier, a dye, colloidal or ultrafine particles, silica, alumina and other additives.

The (b) topcoat composition of the present invention comprises
If the component (a) 'is used alone, or if the amount of water in the component (a)' is insufficient, (c) 'may be further added if necessary.
It is prepared by blending water. At this time, the (b) topcoat composition can be dispersed by a high-speed stirrer or other disperser to form a uniform and stable dispersion liquid.

Substrates to which the coating method of the present invention is applied include metal materials such as iron, stainless steel and aluminum, inorganic substrates such as cement, concrete, glass and ceramics, and organic substrates such as paper and wood. The surface.

For coating the coating composition [(a) undercoating composition, (b) topcoating composition] on a substrate, a coating means such as brush coating, spraying, dipping, roll coating or printing is used. be able to. Here, in order to coat (a) the undercoating composition, 1
20 to 120 g, preferably 40 to 100 g, of the solid content is applied per 1 m ² of the composition. This undercoating can be performed several times, but the total coating amount is usually ²⁰ to 180 in terms of solid content per 1 m ^2.
g, preferably 50 to 120 g. The undercoat coating film has a dry film thickness of usually 10 to 100 μm, preferably 20 to 70 μm.

Next, in order to coat (b) the overcoating composition, ² m ² per 1 m ^{2 is} calculated in terms of solid content.
~ 15g, preferably 3-10g of composition is applied.
This overcoating can be carried out several times, but the total coating amount is usually ^{2 to 2 in} terms of solid content per 1 m ^2.
It is 0 g, preferably 3 to 10 g. In addition, since the top coat film is coated with the composition for top coat on the under coat film and impregnated to form a thin film, it is difficult to calculate the dry film thickness of the top coat film.

(B) After coating the composition for topcoating, this is cured at room temperature at 5 to 30 ° C. for 1 to 8 hours, or is more than 30 ° C. and 250 ° C. or less, preferably 5
It can be easily cured by heating at a low temperature of 0 to 150 ° C. for 5 to 40 minutes to obtain a coating film. In the above-mentioned curing method, the surface of the base material is coated with (a) the undercoating composition, and subsequently (b) the overcoating composition is coated, and dried at room temperature or heated at a low temperature to cure. In addition to the above, in the present invention, after (a) the undercoating composition is coated on the surface of the substrate, it is separately dried at room temperature or heated at a low temperature under the above-mentioned conditions, and then (b) the overcoating composition. It is also possible to coat and to cure at room temperature or under low temperature heating under the above conditions.

In the present invention, since (b) the undercoating composition containing (b) an inorganic filler is used, it is possible to form a thick film by overcoating, and a corrosion-resistant film, a heat insulating film, A dew condensation preventing film, a deodorizing film, a smoothing film, etc. can be produced.

The coating film obtained by using the composition (a) for undercoating of the present invention is a coating film having good adhesion, nonflammability, high hardness and high density. At the same time, heat resistance, weather resistance, water resistance, chemical resistance, damage resistance, impact resistance,
It has excellent wear resistance and can be used for various purposes. For example, weather resistance of metal, corrosion resistant decorative film, non-combustible, heat radiation decorative film, heat deterioration prevention film, weather resistance of cement-based building materials,
It can be used for a wide range of other applications such as a chemical resistant decorative film, a weather resistance of wood or paper, a flame retardant film, a heat absorbing film on the outer surface of a cooking device.

Furthermore, the (b) topcoat composition of the present invention is transparent or translucent, smoothes the surface of the undercoat film, improves hardness, and has excellent stain resistance.
~ 5 minutes A beautiful makeup film with a gloss is formed, and this appearance can be maintained for a long time.

The coating film obtained by the present invention, when used for a metal- or cement-based construction material (inner / outer wall material, outdoor structure, etc.), is dried at room temperature or around 100 ° C. for a short time. , Weather resistance, stain resistance, hot water resistance,
It is possible to obtain a non-flammable film having high hardness and excellent chemical resistance. In addition, when used on the inside and outside of the heating furnace, the outside of the cooking device, etc., it can withstand continuous use at temperatures of 1,000 ° C or higher and is excellent in damage resistance, heat deterioration prevention, heat release, and stain resistance. A coating film is obtained. As described above, the coating film obtained by the coating method of the present invention can be used as a coating film that can be used in various applications which have hitherto been insufficient.

[0031]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the scope of the claims. In the examples, parts and% are based on weight unless otherwise specified.

Examples 1 to 16 Seven kinds of (a) undercoating compositions A to G shown in Table 1 were prepared. The composition for undercoating (b) above is placed in a stirring tank,
After adding components (a) and (b) and, if necessary, component (c) and / or other additives and stirring lightly,
Then stir at high speed (13,000 rpm) for 30 minutes,
It was made by filtering with 50 to 100 mesh.

Next, (B) overcoating compositions H to K shown in Table 2 were prepared. The above-mentioned (b) overcoating composition was prepared by adding the component (a) ', and optionally the component (c)' and / or other additives to a stirring tank, stirring lightly, and then at high speed (13,000 rpm). ) And stirring for 5 minutes. The components (a) ′ and (c) ′ that compose the component (b) are the same as the component (a), and are hereinafter referred to as the component (a) or the component (c).

The symbols in Tables 1 and 2 represent the following. (A) Component (a) -1; manufactured by Nissan Chemical Industries, Ltd., amine silicate cast 40 (SiO ₂ concentration = about 40%) (a) -2; manufactured by Nissan Chemical Co., Ltd., amine silicate cast 25 ( SiO ₂ concentration = about 25%)

(B) Inorganic filler (b) -1; Silicon dioxide (average particle size = 2 to 3 μm) (b) -2; Silicon dioxide (average particle size = 30 to 40 μm)
m) (b) -3; zirconia silicate (zircon, average particle size =
10 to 15 μm) (b) -4; Aluminum oxide (average particle size = 1 μm) (b) -5; Titanium oxide white (average particle size = 0.5 μm) (b) -6; Iron / manganese / copper synthetic oxidation Black (average particle size = 0.5 μm) (b) -7; iron oxide yellow (average particle size = 0.5 μm) (b) -8; zinc flakes (average length = 5 μm)

(C) Water (c) -1; Ion-exchanged water (d) Other additives (d) -1; Dispersant (nonionic surfactant)

[0037]

[Table 1]

[0038]

[Table 2]

Preparation of Test Piece for Evaluation Test The coating composition thus prepared was applied to various base materials shown in Table 3 and cured, and the test piece No. for evaluation test No. 1-16 (Examples 1-16) were prepared. Among the base materials, a steel plate, an aluminum plate, and a stainless steel plate were subjected to alkaline degreasing treatment, and others were subjected to cleaning treatment, respectively, as a base treatment before coating with the coating composition. An air spray gun was used for applying the coating composition, and an electric oven was used for heating. Tables 4 to 6 show the number of times the coating composition was applied and the curing conditions.

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

Evaluation test The test pieces of each of the examples prepared in Tables 4 to 6 were kept indoors for 7 days, and then the following evaluation tests were carried out. Adhesion: Based on JIS K-5400-6.15 cross cut test. Hardness: Based on JIS K-5400-6.14 pencil scratch test. Impact resistance: JIS K-5400-6.13.2 (1/2 inch,
500 g × 20 cm).

Heat resistance: 600 test pieces in an electric furnace
After holding at 5 ° C. for 5 hours, the film was allowed to cool naturally and the appearance of the coating film was observed. Non-flammability: After exposure to a city gas flame for 30 minutes, the appearance of the coating film was observed. Weather resistance: After the test piece was exposed for 8,000 hours by a sunshine carbon arc lamp weather resistance tester according to JIS K-5701, the appearance of the coating film was observed. Weather resistance: QUV test (UV irradiation 70 ° C./8 hours, condensation 50 ° C./4 hours repeated test) After 8,000 hours, the appearance of the coating film was observed.

Warm water resistance: The test piece was kept in warm water of 60 ° C. for 30 days, and then the appearance of the coating film was observed. Boiling resistance: The test piece was held in boiling water for 8 hours, allowed to cool, and this was repeated 10 times, and then the appearance of the coating film was observed. Thermal cycleability: The test piece was held at 500 ° C. for 30 minutes in an electric furnace and then naturally cooled, and this operation was repeated 10 times, and then the appearance of the coating film was observed.

Salt water spray resistance: 4% saline water was continuously sprayed on the test piece for 960 hours, and then the appearance of the coating film was observed. Alkali resistance: The test piece was dipped in a 5% aqueous solution of caustic soda and kept for 72 hours, and then the appearance of the coating film was observed. Acid resistance; drop 20% hydrochloric acid aqueous solution
After holding for a time, the appearance of the coating film was observed. Solvent resistance: After immersing the test piece in a mixed solvent of acetone / cellosolve / ethyl acetate / hydrous alcohol for industrial use / toluene = 3/2/2/1/2 (weight ratio) for 10 days, observe the appearance of the coating film did.

Abrasion resistance: After strongly rubbing the test piece with # 0000 steel wool, the appearance of the coating film was observed to determine the presence or absence of scratches. The evaluation of the appearance observation result of the coating film was as follows. ：: No peeling of the coating film was observed, and there was no change in appearance. X: Peeling, cracking or melting damage is observed in part or all of the coating film. -: Not evaluated

Contamination resistance: After drawing with a red and black oil-based ink on a test piece, the test piece was wiped with a solvent (methanol) and observed for traces. Contamination resistance: 0.1% carbon black dispersed water was applied to a test piece, heated at 60 ° C. for 1 hour, wiped with a waste cloth, and observed for traces. In the stain resistance-, those with no traces were evaluated as ◯, and those with some or all traces were evaluated as x. Water permeability: The water permeability after 72 hours was measured using ion-exchanged water by the funnel method (mg / cm ² ). The results of the above evaluation tests are shown in Tables 7-8.

[0050]

[Table 7]

[0051]

[Table 8]

[0052]

EFFECT OF THE INVENTION According to the coating method of the present invention, it can be dried and cured at room temperature or at low temperature, has non-combustibility and high weather resistance for 30 years or more, and can withstand high temperature of 1,000 ° C. or more, Heat resistance, high hardness, excellent stain resistance, abrasion resistance, water resistance, hot water resistance, alkali resistance, acid resistance, organic chemical resistance, 3-5 minutes Anticorrosion / corrosion prevention film, heat insulation film, heat radiation film, conductive film, deodorization film,
Used in various applications where it is not possible to adequately cope with conventional products because it has features such as functional film such as moldproof film and cured film, composition is aqueous, does not contain harmful substances, and has good workability. It is possible to obtain a nonflammable and highly weather resistant film.

The non-combustible / highly weather-resistant film obtained is, for example, metal weather resistance, high hardness, stain resistance, corrosion resistant decorative film, non-combustible, heat radiation decorative film, heat resistant corrosion resistant film, weather resistance of cement-based building materials, alkali resistance. It can be used in a wide range of other applications such as a stain-resistant protective decorative film, a flame-retardant film of wood or paper, prevention of heat deterioration of the outer surface of a cooking vessel, a stain-resistant heat-absorbing film, and the like.

Claims (3)

[Claims] 1. A surface of a base material, 3 to 16 parts by weight of (a) (a) quaternary ammonium silicate in terms of SiO ₂ .
(B) 15 to 85 parts by weight of inorganic filler and (c) water 12
-82 parts by weight [(a) + (b) + (c) = 10
0 part by weight] as a main component, and then (b) (a) ′ quaternary ammonium silicate in an amount of ₂ to 15 parts by weight in terms of SiO ₂ and (c) ′ water 9
8 to 85 parts by weight (however, (a) '+ (c)' = 100
% By weight] as a main component, and the coating composition is overcoated and dried by normal temperature drying or low temperature heating drying to cure. 2. The inorganic filler is selected from the group of inorganic extender pigments, functional pigments, inorganic pigments and metal powders, which have an average particle size or average length of 0.1 to 100 μm and are insoluble in water. The coating method according to claim 1, which is at least one kind. 3. A non-combustible / highly weather-resistant film obtained by the coating method according to claim 1.