JP2006152221A - Product with inorganic film and inorganic coatings therefor, and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a product with an inorganic film which has glossy surface property, exhibits excellent stain resistance against oily stains because of its high hydrophilicity, and can achieve reduction in a manufacturing cost. <P>SOLUTION: Inorganic coatings comprise an undercoating material 2 and a topcoating material 3. The undercoating material 2 contains water glass 6, a hardening agent 4 for the water glass, and aggregate. The topcoating material 3 contains the water glass 6 and silica particulates 7, but does not contain the hardening agent 4 for the water glass. The manufacturing method comprises a first step of applying the undercoating material 2 on a substrate 1 to form an undercoating layer 2a, a second step of applying the topcoating material 3 on the undercoating layer 2a to form a topcoating layer 3a, and a third step of heating the undercoating layer 2a and the topcoating layer 3a to a temperature level of not lower than normal temperature and not higher than 400°C to obtain a product 10 with an inorganic film without dealkalization processing. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a product with an inorganic coating, an inorganic coating for the product, and a method for producing the same.

  Conventionally, as a product with an inorganic film in which a glassy inorganic film is formed on a substrate, a product with an inorganic paint or a bag product is known. These products with an inorganic coating have the property of being superior in weather resistance, chemical resistance, and the like compared to products in which the coating is made of an organic substance because the inorganic coating is glassy.

  Of these, inorganic products such as calcium silicate plates, cement plates, slate plates and the like, and inorganic paints containing water glass have been used as the base material for products to which inorganic paint has been applied. When manufacturing a product using this inorganic coating material, first, as a first step, the inorganic coating material is applied on the base material to form a coating layer on the base material. And as a 2nd process, while a base material and a coating layer are heated to 140 degreeC, for example, the dealkalizing process of a coating layer is performed. In this way, a product with an inorganic paint is obtained.

  In particular, Patent Document 1 discloses an inorganic paint composed of an undercoat containing water glass, a hardener for water glass, and an aggregate, and a topcoat paint containing water glass, silica fine particles, and a hardener for water glass. It is disclosed. In Patent Document 1, zinc white is used as a curing agent for water glass of undercoat paint and topcoat paint. When a product is manufactured using this inorganic paint, first, as a first step, an undercoat paint is applied on the base material to form an undercoat layer on the base material. Thereafter, as a second step, a top coating is applied on the undercoat layer, and an overcoat layer is formed on the undercoat layer. Then, as a third step, the base material, the undercoat layer and the topcoat layer are heated to, for example, 140 ° C., and a dealkalizing treatment is performed on the undercoat layer and the topcoat layer. In this way, a product with an inorganic paint is obtained.

  On the other hand, in the glaze product, a metallic base material such as a steel plate is used as a base material, and glaze is used. Glaze is usually a borosilicate frit made into a slip with water and clay. When manufacturing a glaze product using this glaze, first, as a 1st process, a glaze is apply | coated on a base material and a glaze layer is formed on a base material. And as a 2nd process, a base material and a glaze layer are normally heated to the temperature of about 600 degreeC or more. In this way, a cocoon product is obtained.

JP 2000-327949 A

  However, a product with an inorganic coating using a conventional inorganic coating containing water glass, such as the inorganic coating disclosed in Patent Document 1, has an uneven surface and exhibits a glossy surface property. do not do. In particular, when the product is used, for example, in a range filter or the like that requires contamination resistance against oil stains, the oil stains are difficult to be removed from the surface.

  Further, when dealkalized, the water resistance of the inorganic coating is improved, but the hydrophilicity is lowered, and cracks accompanying the shrinkage of the water glass grow on the surface, so that the stain resistance is lowered. In this case, the process and the manufacturing time increase, and the cost increases.

  On the other hand, a product with an inorganic film, which is a glazed product, exhibits a glossy surface property and exhibits a certain degree of stain resistance against oil stains due to the hydrophilicity based on glass, but is heated to a temperature of about 600 ° C or higher. Therefore, it is difficult to reduce the manufacturing cost.

  The present invention has been made in view of the above-described conventional circumstances, and exhibits a glossy surface property and exhibits excellent stain resistance against oil stains due to excellent hydrophilicity for products with inorganic coatings. Realizing a reduction in manufacturing cost is an issue to be solved.

  The inventors have intensively studied to solve the above problems. In order to solve the problems of the present invention, it was discovered that it is effective to eliminate the curing agent for water glass from the top coating in the inorganic coating disclosed in Patent Document 1 and to add silica fine particles. The invention has been completed.

The inorganic paint of the present invention is an undercoating paint containing water glass, a curing agent for water glass, and an aggregate,
It is characterized by comprising a coating material for top coating which contains water glass and silica fine particles and does not contain a curing agent for water glass.

The inorganic paint of this invention is used for the manufacturing method of the product with an inorganic membrane | film | coat of this invention below. That is, in the production method of the present invention, a first step of applying an undercoat paint containing water glass, a water glass curing agent and an aggregate on a base material, and forming an undercoat layer on the base material,
A second step of forming a topcoat layer on the undercoat layer by applying a topcoat layer containing water glass and silica fine particles on the undercoat layer and not containing a water glass curing agent;
The undercoating layer and the overcoating layer are heated to a temperature not lower than room temperature and not higher than 400 ° C., and comprise a third step of obtaining a product with an inorganic film without performing a dealkalizing treatment.

  The undercoat paint for the inorganic paint of the present invention contains a curing agent for water glass, but the overcoat paint does not contain a curing agent for water glass. In the third step, the top coat layer made of the top coat without containing the water glass curing agent removes the water in the water glass by heating. Inorganic coatings formed from overcoating paints containing water glass hardeners other than silica paints and silica fine particles have low water resistance and weather resistance because the water glass hardeners elute or chemically change. . That is, it is important for ensuring the weather resistance of the inorganic film that the curing agent for water glass is not exposed on the surface.

  According to the tests of the inventors, the overcoat layer was not affected by the effect of the water glass curing agent in the undercoat layer consisting of the lower undercoat paint, even though it did not have the water glass curing agent. Cured. This is because it is considered that the water glass curing agent in the undercoat layer protrudes into the topcoat layer during the third step. Further, since the overcoat layer contains silica fine particles, it is cured by the dehydration reaction between the hydroxyl groups of the water glass and the hydroxyl groups of the silica fine particles. This silica fine particle is considered to supplement the role of the curing agent for water glass in the undercoat layer. At this time, since the dealkalization treatment is not performed, the surface of the overcoat layer is not roughened.

  For this reason, the product with an inorganic membrane | film | coat obtained can exhibit the outstanding stain | pollution resistance with respect to oil dirt by the inorganic membrane | film | coat which exhibits the glossy surface property and was excellent in smoothness and hydrophilicity.

  JP-A-2000-109722 discloses an inorganic coating containing water glass and silica fine particles and not containing a water glass curing agent. This inorganic paint is the same as the inorganic paint of the present invention in that the hydroxyl group of water glass is cured by causing a dehydration reaction with the hydroxyl group of silica fine particles. However, according to the test results of the inventors, the inorganic film obtained with this inorganic paint may be dissolved in water. The silica glass alone is insufficient in curing the water glass, and the water resistance and weather resistance are remarkably inferior. In order to sufficiently cure the water glass and improve water resistance and weather resistance, it is necessary to apply an overcoat layer containing water glass and silica fine particles on the undercoat layer containing the water glass curing agent.

  Moreover, in the manufacturing method of this invention, it only heats to the temperature of 400 degrees C or less in a 3rd process, and there is less energy consumption than manufacturing a soot product. Moreover, in the manufacturing method of this invention, since a dealkalization process is not performed, it is not necessary to perform washing | cleaning, drying, etc. which accompany it. Further, in the production method of the present invention, cost reduction is realized in that the overcoating paint does not contain an expensive water glass curing agent.

  Therefore, according to the inorganic paint and the production method of the present invention, the product with an inorganic film exhibits a glossy surface property and exhibits excellent stain resistance against oil stains due to excellent hydrophilicity, and also has a low production cost. Cost reduction can be realized.

  In the first step and the second step, the substrate is preheated to 40 to 150 ° C. and applied, so that the undercoat paint and the topcoat paint are better fixed.

Thus, the following product with an inorganic coating of the present invention is obtained. This product with an inorganic coating is a product with an inorganic coating consisting of a substrate and an inorganic coating formed on the substrate.
The inorganic film is formed on the base material, and the lower layer containing aggregate and cured water glass in a state where the curing agent for water glass remains,
The upper layer is formed on the lower layer and contains a hardened water glass in a state without a water glass curing agent.

  In this product with an inorganic coating, the inorganic coating is difficult to dissolve in water. And this product with an inorganic membrane | film | coat exhibits the glossy surface property, and can exhibit the outstanding stain | pollution resistance with respect to oil stains by the outstanding hydrophilicity. Moreover, this product with an inorganic film can be manufactured at low cost.

  Water glass hardeners included in the undercoat paint include aluminum tripolyphosphate, aluminum phosphate, aluminum hydrogen phosphate, aluminum metaphosphate, aluminum orthophosphate, primary aluminum phosphate, secondary aluminum phosphate, zirconium phosphate , Magnesium phosphate, zinc phosphate, zinc calcium phosphate, ammonium phosphate, iron phosphate, titanium phosphate, boron phosphate, zinc white (zinc oxide), activated zinc white, magnesium oxide, calcium oxide, metal aluminum powder , Kaolinite, spodumene powder, potassium silicofluoride, sodium silicofluoride, calcium silicofluoride, lead silicofluoride, copper silicofluoride, zinc silicofluoride, aluminum silicate, calcium silicate, dilime silicate, magnesium silicate, Aluminum hydroxide, aluminum chloride, ferrosi Con, manganese silicon, silicon nitrite, silicon carbide, silicon borate, silicon phosphate, primary potassium phosphate, dibasic potassium phosphate, zeolite, Na artificial zeolite, Fe artificial zeolite, bentonite (mica), sepiolite, Kanuma Soil, diatomaceous earth, allophane, metakaolin, zirconium borate, sodium borate, potassium borate, silicon borate, calcium borate, acetic acid, ammonium acetate, barium acetate, magnesium acetate, aluminum acetate, manganese acetate, zinc acetate, aluminum oxalate, ammonium oxalate, oxalic acid Calcium, magnesium oxalate, iron (II) oxalate, manganese (II) oxalate, potassium titanium oxalate, titanium titanium oxalate, zinc oxalate, methanol, ethanol, propanol, calcined gypsum, frit, etc. Acid compound, a hydroxide, can be employed oxide.

  According to the test results of the inventors, among the hardeners for water glass contained in the undercoat paint, aluminum tripolyphosphate, aluminum phosphate, aluminum metaphosphate, aluminum orthophosphate, zirconium phosphate, zinc phosphate, magnesium oxide Very particular preference is given to potassium silicofluoride and calcium silicofluoride. In particular, there is a great difference in the water resistance, adhesion and durability of the inorganic film between the case where aluminum triphosphate is included and the case where this is not included. It was confirmed that there was an effect. For this reason, it is preferable that at least a part of the curing agent for water glass is aluminum tripolyphosphate.

  When the undercoat paint contains aggregate, an inorganic film having water resistance and weather resistance can be obtained. Aggregates contained in the undercoat paint include silica (silicon dioxide), zirconia (zirconium oxide), zircon (zirconium silicate), magnesia (magnesium oxide), spinel, silicon carbide, titanium oxide, which are larger in diameter than silica fine particles. Further, oxides such as alumina (aluminum oxide), calcium carbonate, calcium hydroxide, calcium oxide, carbonates, carbides, nitrides, metal powders, silicate minerals, and the like can be employed.

  Aerosil, silica fume, colloidal silica, microsilica and the like can be used as the silica fine particles contained in the top coating.

  The silica fine particles preferably have an average particle size of 1 μm or less. According to the test results of the inventors, the product with an inorganic coating obtained with an average particle size of silica fine particles of 1 μm or less has a glossy surface property and excellent hydrophilicity against oil stains due to excellent hydrophilicity. This is because it has been particularly confirmed that it exhibits water resistance.

  When the top coating material contains a pigment, the pigment is preferably an inorganic pigment. This is because the inorganicity of the film can be maintained. If the undercoat paint forms a colored glassy material, even if the topcoat paint forms a transparent glassy material, it becomes a product with a vivid colored inorganic film. Moreover, a dispersing agent can also be added at the time of paint preparation. By adding a dispersant, it is possible to improve dispersibility and adjust the viscosity, and it becomes easy to handle undercoat paints and topcoat paints. As the dispersant, inorganic dispersants such as sodium pyrophosphate and sodium tripolyphosphate can be employed.

  When the undercoat paint contains a pigment, the pigment is also preferably an inorganic pigment. This is because the inorganicity of the film can be maintained. Moreover, a dispersing agent can also be added at the time of paint preparation. By adding a dispersant, it is possible to improve dispersibility and adjust the viscosity, and it becomes easy to handle undercoat paints and topcoat paints. As the dispersant, inorganic dispersants such as sodium pyrophosphate and sodium tripolyphosphate can be employed.

According to the test results of the inventors, the coating material for top coating is 0.5 to 10: 1: 10 to 40 parts by mass of SiO ₂ in water glass: parts by mass of silica fine particles: parts by mass of water. Is preferred. This is because it has been particularly confirmed that the product with the inorganic coating exhibits a glossy surface property within this range and exhibits excellent stain resistance against oil stains due to excellent hydrophilicity.

The top coating material is preferably a thin top coating layer because it needs to be cured under the influence of the water glass curing agent in the lower undercoat layer. Specifically, when the mass part of SiO ₂ in water glass: the mass part of silica fine particles: the mass part of water is 0.5 to 10: 1: 10 to 40, the thickness of the overcoat layer is 2 to 5000 nm. Preferably there is. When the overcoat layer is thinner than 2 nm, the gloss of the surface property is impaired. On the other hand, if the overcoat layer is thicker than 5000 nm, the curing becomes insufficient and it becomes easy to dissolve in water.

  Substrates include not only inorganic materials such as calcium silicate plates, cement plates, and slate plates, but also metallic materials such as steel plates, aluminum plates, stainless steel plates, galvanized steel plates, and materials with low heat resistance such as wood. Can also be adopted. Resin materials such as polyethylene, polypropylene, acrylic, and FRP can also be used as the base material. Moreover, the base material which apply | coated the primer layer, the glaze layer, etc. is also employable.

  It is preferable that the manufacturing method of this invention heats to the temperature of 100 degreeC or more in a 3rd process. According to the test results of the inventors, water can be evaporated more reliably from the inorganic paint.

  Embodiments 1 to 4 in which the present invention is embodied in a range filter or the like will be described below with reference to the drawings.

  First, as shown in FIG. 1A, an aluminum range filter main body was prepared as the substrate 1. Moreover, the undercoat paint 2 and the top coat 3 (see FIGS. 1B and 1C) were prepared as inorganic paints.

  As raw materials for the undercoat paint 2, No. 3 soda water glass as water glass 6 (see FIG. 3), aluminum tripolyphosphate, zirconium silicate and zinc white as water glass hardener 4 (see FIG. 2), bone Silica powder (Snow seal silica powder; SP-20, average particle size of 5 μm) and water as materials were prepared.

  Further, as a raw material for the top coating material 3, No. 3 soda water glass as the water glass 6 and Aerosil as silica fine particles 7 (see FIG. 3) having an average particle diameter of 12 nm (manufactured by Nippon Aerosil Co., Ltd .; AEROSIL 200) And water.

  These raw materials were mixed in the parts by mass shown in Table 1 to prepare an undercoat paint 2 and an overcoat paint 3.

  Then, as the first step, as shown in FIG. 1 (b), the base material 1 is preheated to 100 ° C., the base coating material 2 is applied on the base material 1, and the base coating layer 2 a is applied to the base material 1. Formed. The thickness of the undercoat layer 2a is 10,000 nm when converted from the coating amount.

  Next, as a second step, as shown in FIG. 1 (c), the base material 1 is preheated to 100 ° C., and the overcoat paint 3 is applied onto the undercoat layer 2a, and the overcoat layer 3a is applied onto the undercoat layer 2a. Formed. The thickness of the topcoat layer 3a is 100 nm when converted from the coating amount.

  Thereafter, as a third step, the base layer 1 and the undercoat layer 2a and the topcoat layer 3a were heated at 150 ° C. for 60 minutes. In the meantime, as shown in FIG. 2, the topcoat layer 3 a not containing the waterglass curing agent 4 removes moisture in the waterglass 6 by heating, and at the same time lowers the waterglass curing agent 4 in the undercoat layer 2 a. It is cured by the influence of This is probably because the water glass curing agent 4 in the undercoat layer 2a protrudes into the topcoat layer 3a. In addition, since the overcoat layer 3 a contains the silica fine particles 7, as shown in FIG. 3, the overcoat layer 3 a is also cured by causing a dehydration reaction with the hydroxyl groups of the silica fine particles 7. Thus, since the overcoat layer 3a is formed of only water glass and silica fine particles, the surface becomes smooth. At this time, since the dealkalization treatment is not performed, the surface of the overcoat layer 3a is not roughened.

  In this way, as shown in FIG. 2, the range filter as the product 10 with an inorganic film is obtained. This range filter includes a base material 1 and a glassy inorganic film 5b formed on the base material 1. The inorganic coating 5b includes a lower layer 2b in which the undercoat layer 2a is made vitreous and an upper layer 3b in which the upper coat layer 3a is made vitreous. The water glass curing agent 4 remains in the lower layer 2b, and the upper layer 3b does not have the water glass curing agent 4.

  The obtained range filter could easily remove the adhered oil stains with only water or a small amount of neutral detergent.

  In this manufacturing method, only the heating to 150 ° C. is performed in the third step, and the amount of energy consumption is less than that in manufacturing the cocoon product. Moreover, in this manufacturing method, since dealkalization treatment is not performed, it is not necessary to perform cleaning, drying, and the like associated therewith. Further, the cost reduction is realized in that the top coating material 3 does not include the expensive water glass curing agent 4.

  Therefore, according to the inorganic coating material and the manufacturing method of Example 1, it can be seen that a range filter that exhibits glossy surface properties and exhibits excellent stain resistance against oil stains due to excellent hydrophilicity can be manufactured at low cost.

  First, as the substrate 1, a fan body of a resin ventilation fan was prepared. Further, as the inorganic paint, No. 3 soda water glass was used in the same manner as in Example 1, and an undercoating paint 2 and an overcoating paint 3 mixed in parts by mass shown in Table 1 were prepared.

  And the 1st-3rd process similar to Example 1 was performed. However, a primer (Dainippon Paint; Planit # 543) is applied to the substrate 1, a sealer (Ohashi Chemical; sealer HXM-133) is applied thereon, and then an undercoat paint 2 and an overcoat paint 3 are applied. Applied. In the third step, heating was performed by radiant heat, and the surface was maintained at 100 ° C. for 5 minutes.

  In this way, the fan as the product 10 with an inorganic film is obtained. This fan was also able to easily remove the attached oil stains with only water or a small amount of neutral detergent. Other functions and effects are the same as those of the first embodiment.

  First, an aluminum plate 1 of 1800 mm × 900 mm × 3 mm was prepared as the substrate 1. In addition, as in Examples 1 and 2, as the inorganic paint, 2K potassium water glass was used, and an undercoat paint 2 and an overcoat paint 3 mixed at a mass part shown in Table 1 were prepared.

  And the 1st-3rd process similar to Example 1 was performed. However, the heating condition in the third step was set at 180 ° C. for 15 minutes.

  In this way, the kitchen bag material as the product 10 with the inorganic film is obtained. The oil that adhered to the kitchen bag could also be easily removed with water. In particular, this kitchen bag material was able to easily remove oily ink stains with water. This kitchen bag material can be used as a white board or the like with the same configuration. Other functions and effects are the same as those of the first and second embodiments.

  First, a 1200 mm × 300 mm × 10 mm cement plate 1 was prepared as the base material 1. In addition, as in Examples 1 to 3, an undercoat paint 2 and an overcoat paint 3 mixed with parts by mass shown in Table 1 were prepared. However, No. 3 soda water glass was used for the undercoating paint 2, and 2K potassium water glass was used for the overcoating paint 3.

  And the 1st-3rd process similar to Example 1 was performed. However, the heating condition in the third step was 120 ° C. for 120 minutes.

  In this way, the building material as the product 10 with an inorganic film is obtained. This building material was able to easily remove the adhered oil, earth and sand and dust with water. Other functions and effects are the same as those of the first to third embodiments.

  Next, evaluations 1 to 3 will be described. In the following evaluations 1 to 3, a cement board was used as the same base material 1 as in Example 4.

(Evaluation 1)
In Evaluation 1, Examples 1 to 3 and Comparative Products 1 to 5 were manufactured. First, as shown in FIG. 1A, a 100 mm × 100 mm × 10 mm cement board was prepared as the base material 1. Moreover, as an inorganic coating (refer FIG.1 (b), (c)), with the raw material similar to the said Examples 1-4, undercoat paint 2 and topcoat paint 3 of Examples 1-3 and the comparative product 1 and The inorganic paints of comparative products 2 to 5 were prepared. Table 2 shows the parts by mass of these raw materials used for each of the products and comparative products. Table 3 shows parts by mass of these raw materials used for each comparative product. No. 3 soda water glass was used as the water glass.

  And the Examples 1-3 and the comparative product 1 were manufactured similarly to Examples 1-4. However, the heating condition in the third step was set at 135 ° C. for 2 hours. In this way, as shown in FIG. 2, the products 10 with the inorganic film of Examples 1 to 3 and Comparative Product 1 were obtained.

  Moreover, the comparative products 2-5 were manufactured as follows. First, as a first step, an inorganic paint is applied on the substrate 1 to form a coating layer on the substrate 1. And as a 2nd process, the base material 1 and the coating layer were heated at 135 degreeC for 2 hours. Thus, comparative products 2 to 5 having a single inorganic coating film 5b were obtained.

  Tests for examining water resistance, adhesion, weather resistance, and stain resistance were performed on these Examples 1 to 3 and Comparative Products 1 to 5.

(Water resistance test)
Each product was immersed in warm water of 40 ° C. for 100 hours, and the weight loss before and after the immersion was measured to calculate the mass loss rate (wt%) of the inorganic coating 5b. Moreover, each product was immersed in 90 degreeC warm water for 8 hours, and the weight loss (wt%) of the inorganic membrane | film | coat 5b was also calculated by measuring the weight before and behind water immersion.

(Adhesion test)
A 10 cm square cut was made in 1 cm square on each of the inorganic coatings 5b, the gum tape was brought into close contact therewith, and the percentage (%) of the inorganic coating 5b remaining after vigorous peeling was measured.

(Weather resistance test)
Each product was exposed outdoors in March, and the color and peeling of the inorganic coating 5b were confirmed visually.

(Contamination resistance test)
A water contact angle was measured by spraying water droplets on the surface of the inorganic coating 5b of each product. Moreover, each article was immersed in a water tank containing room temperature water and fixed in the upper part of the water tank, and oil droplets were lifted from the bottom of each article by a tube connected to a tank outside the water tank containing oil. And the oil-in-water contact angle of the oil droplet adhering to the surface of the inorganic membrane | film | coat 5b of each goods was measured.

  Table 4 shows the results of water resistance, adhesion, weather resistance and stain resistance. In Table 4, ○ indicates that there was no change, Δ indicates that the inorganic coating 5b having an area of 0 to 3% was peeled off with respect to the area of the gum tape, and x indicates 3 with respect to the area of the gum tape. It shows that the inorganic film 5b having an area of ˜100% was peeled off.

  From Table 4, it can be seen that the product 1 is most excellent in water resistance, adhesion and weather resistance. Moreover, it turns out that each implementation product has high hydrophilicity and it is easy to remove oil in water. Thus, it can be seen that each of the products is extremely excellent in stain resistance against oil stains.

  In addition, regarding Examples 1 and 3, it can be seen that when the undercoat paint 2 contains aluminum tripolyphosphate, the water resistance, adhesion, and weather resistance are much superior to those when aluminum tripolyphosphate is not included. In addition, regarding Examples 1 and 2, when the primer coating 2 contains zinc white, it can be seen that the water resistance and weather resistance are superior to those when no zinc white is contained.

  Further, when comparing the product 1 and the comparative product 1, it can be seen that the inorganic coating 5b containing aggregate such as silica powder has better water resistance and weather resistance than the inorganic coating 5b not containing it.

(Evaluation 2)
In Evaluation 2, test products 1 to 6 were manufactured. First, as in Evaluation 1, as shown in FIG. 1A, a cement board was prepared as the base material 1. In addition, as the inorganic coating (see FIGS. 1B and 1C), the undercoat paint 2 and the overcoat paint 3 were prepared using the same raw materials as in Examples 1 to 4 and No. 3 soda water glass. Table 5 shows the parts by mass of these raw materials used for each test product.

  And each test product was manufactured similarly to the implementation products 1-3 of evaluation 1.

  Each of these test products was subjected to a test for examining the stain resistance and water resistance.

(Contamination resistance test)
A line was drawn with oil-based ink on the surface of each test article. And water was sprayed on the surface of each test article with a sprayer, and all of this surface was wiped off at once with a cloth.

(Water resistance test)
Each test product was immersed in warm water of 90 ° C. for 8 hours, and then the state of the inorganic coating 5b of each test product was confirmed.

  The results of stain resistance and water resistance are shown in Table 6. In Table 6, o indicates that there was no difference before and after each test. X shows what was not tested because powder appeared on the surface of the inorganic coating 5b.

  From Table 6, it can be seen that the test products 2 to 4 are excellent in stain resistance and water resistance. Conversely, it can be seen that an inorganic coating 5b having excellent stain resistance and water resistance can be obtained with an inorganic paint such as test products 2-4.

  In particular, it can be seen that the test product 1 cannot sufficiently supplement the role of the curing agent 4 for water glass in the undercoat layer 2a because the content of aerosil in the overcoat layer 3a is too small.

  Moreover, since the test products 5 and 6 have too much content of the aerosil in the top coat layer 3a, many aerosil which does not react with water glass exists in the top layer 2b, and adhesiveness has been impaired.

Therefore, it can be seen that it is preferable that the coating material 3 for the top coat is 0.5 to 10: 1: 10 to 40 parts by mass of SiO ₂ in water glass: parts by mass of aerosil: parts by mass of water.

(Evaluation 3)
In Evaluation 3, test products 7 to 61 were manufactured. First, as in Evaluation 1, a cement plate 1 was prepared as a base material 1 as shown in FIG. Further, as the inorganic paint (see FIGS. 1B and 1C), the undercoat paint 2 and the overcoat paint 3 were prepared from the same raw materials as in Examples 1 to 4 described above. However, as the hardener 4 for water glass, aluminum tripolyphosphate, aluminum phosphate, aluminum metaphosphate, aluminum orthophosphate, primary aluminum phosphate, secondary aluminum phosphate, zirconium phosphate, magnesium phosphate, zinc phosphate, Iron phosphate, titanium phosphate, boron phosphate, zinc white (zinc oxide), activated zinc white, magnesium oxide, calcium oxide, metallic aluminum powder, kaolinite, spodumene powder, potassium silicofluoride, sodium silicofluoride, silica Calcium fluoride, lead silicofluoride, copper silicofluoride, zinc silicofluoride, aluminum silicate, calcium silicate, dicalcium silicate, magnesium silicate, aluminum hydroxide, aluminum chloride, ferrosilicon, manganese silicon, silicon nitrite , Silicon carbide, silicon bore , Silicon phosphate, monobasic potassium phosphate, dibasic potassium phosphate, zeolite, Na artificial zeolite, Fe artificial zeolite, bentonite (mica), sepiolite, Kanuma soil, diatomaceous earth, allophane, metakaolin, zirconium borate, sodium borate, potassium borate Silicon borate, calcium borate, calcined gypsum and frit were used.

  Table 7 shows parts by mass of these raw materials used for each test product. Tables 8 and 9 show each water glass curing agent 4 in each test product.

  And each test product was manufactured similarly to the implementation products 1-3 of evaluation 1. Then, the test for examining stain resistance, water resistance, and adhesiveness was performed on each of these test products, and the hardness was measured together.

(Contamination resistance test)
As in Evaluation 1, water contact angles were measured by spraying water droplets onto the surface of the inorganic coating 5b of each test product. Further, as in Evaluation 2, a line was drawn with oil-based ink on the surface of the inorganic film 5b of each test product, and water was sprayed to wipe it off.

(Water resistance test)
Each test article was immersed in warm water of 40 ° C. for 100 hours, and then the state of the inorganic coating 5b of each test article was confirmed. Moreover, each test article was immersed in 90 degreeC warm water for 8 hours, and the state of the inorganic membrane | film | coat 5b of each subsequent test article was confirmed.

(Adhesion test)
Similar to Evaluation 1, a cut was made in the inorganic coating 5b of each test product, and a gum tape was closely adhered to the test sample, and the ratio (%) of the inorganic coating 5b remaining after peeling off vigorously was measured.

(Hardness test)
A line was drawn on the inorganic coating 5b of each test article with a pencil lead having a hardness of B, HB, or H to 9H, and the minimum hardness of the scratched core of the inorganic coating 5b was confirmed.

  Tables 8 and 9 also show the results of stain resistance, water resistance, adhesion and hardness. In Tables 8 and 9, in the stain resistance test, ◯ indicates that the oil-based ink line has been completely removed, and x indicates that the oil-based ink line remains. In the water resistance test, ◯ indicates that there was no change, Δ indicates that the inorganic coating 5b has changed color, and x indicates that the inorganic coating 5b has peeled off.

  From Table 8 and Table 9, it can be seen that the test products 7 to 61 are excellent in stain resistance and hardness. In particular, it can be seen that the aluminum phosphate-based hardener 4 for water glass can impart excellent water resistance and adhesion to the facing film 5b. Particularly, the water glass curing agent 4 is made of aluminum tripolyphosphate, aluminum phosphate, aluminum metaphosphate, aluminum orthophosphate, zirconium phosphate, zinc phosphate, magnesium oxide, potassium silicofluoride and calcium fluorosilicate. preferable.

  In the above, although this invention was demonstrated according to Examples 1-4 and evaluation 1-3, this invention is not restrict | limited to Examples 1-4 etc., In the range which does not deviate from the meaning, it changes suitably. Needless to say, this is applicable.

  The present invention can be used for a range filter, a range hood, a fan for a ventilation fan, a kitchen bag, a white board, a building material, and the like.

In relation to Examples 1 to 4 and Evaluations 1 to 3, FIG. (A) is a cross-sectional view of a substrate, FIG. (B) is a cross-sectional view of the substrate and undercoat paint in the first step, and FIG. It is sectional drawing of a board | substrate, undercoat, and the coating material for overcoating or an overcoat layer. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view of a product with an inorganic film according to Examples 1 to 4 and Evaluations 1 to 3. It is a schematic diagram of water glass and silica fine particles according to Examples 1 to 4 and Evaluations 1 to 3.

Explanation of symbols

5b ... Inorganic coating 10 ... Products with inorganic coating 1 ... Base material 6 ... Water glass 4 ... Hardener for water glass 2 ... Undercoat paint 2a ... Undercoat layer 7 ... Silica fine particles 3 ... Overcoat paint 3a ... Overcoat layer 2b ... Lower layer 3b ... upper layer

Claims (10)

An undercoat paint comprising water glass, a hardener for water glass, and an aggregate;
An inorganic coating material comprising a top coating material containing water glass and silica fine particles and not containing a water glass curing agent.   The inorganic paint according to claim 1, wherein the silica fine particles have an average particle size of 1 µm or less.   The inorganic paint according to claim 1 or 2, wherein at least a part of the curing agent for water glass is aluminum tripolyphosphate.   The inorganic paint according to any one of claims 1 to 3, wherein the undercoat paint contains an inorganic pigment. The top coat paints, SiO ₂ minutes of the mass of the water glass: parts by mass of the silica fine particles: weight of water 0.5 to 10: 1: 1 to claim, characterized in that 10 to 40 4. The inorganic paint according to any one of 4 above. A first step of applying an undercoat paint comprising water glass, a water glass curing agent and an aggregate on a substrate, and forming an undercoat layer on the substrate;
A second step of forming a topcoat layer on the undercoat layer by applying a topcoat layer containing water glass and silica fine particles on the undercoat layer and not containing a water glass curing agent;
A third step of heating the undercoat layer and the overcoat layer at a temperature of from room temperature to 400 ° C. to obtain a product with an inorganic coating without performing a dealkalizing treatment. Production method. The coating material for top coating is 0.5 to 10: 1: 10 to 40 parts by mass of SiO _{2 in the} water glass: parts by mass of silica fine particles: parts by mass of water,
The method for producing a product with an inorganic coating according to claim 6, wherein the overcoat layer has a thickness of 2 to 5000 nm.   The method for producing a product with an inorganic coating according to claim 6 or 7, wherein the third step is heated to a temperature of 100 ° C or higher.   The method for producing a product with an inorganic coating according to any one of claims 6 to 8, wherein in the first step and the second step, the base material is preheated to 40 to 150 ° C and applied. . In a product with an inorganic coating consisting of a substrate and an inorganic coating formed on the substrate,
The inorganic film is formed on the base material, with the water glass curing agent remaining, and a lower layer containing aggregate and cured water glass,
A product with an inorganic film formed on the lower layer and comprising an upper layer containing cured water glass in a state without a water glass curing agent.

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