JPS6181465A - Inorganic paint - Google Patents

Abstract

PURPOSE:To provide the titled paint for the coating of metal, etc., having excellent heat-resistance, water-resistance, flexibility, workability and rust-proofing property, and containing a water-soluble silicate, a silicon polyphosphate and a calcined product of a mixture of a zinc oxide source, a metal oxide and a colemanite compound, etc., as essential components. CONSTITUTION:The objective paint contains, as essential components, (A) a calcined product prepared by mixing (i) a zinc oxide source with (ii) a metal oxide of formula MxOy (M is III-VIII-group metal of the periodic table, O is oxygen, x and y are integer) at a molar ratio of e.g. 3:1-1:3, adding (iii) 2-50pts.wt. (based on 100pts.wt. of (i)+(ii)) of a colemanite compound or ulexite compound, and heating the mixture at >=00 deg.C, (B) a water-soluble silicate and (C) a silicon polyphosphate. A >=2-valent metal salt of preferably a weak inorganic acid may be added to the component A, B or C as an essential component.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The FJA of the present invention relates to an inorganic paint with excellent heat resistance, water resistance, flexibility and workability.

(Prior Art) In recent years, with advances in synthetic resins and superior coating methods, organic paints have made remarkable progress. However, on the other hand, the need for inorganic paints has been emphasized, and development research is being actively conducted. The reason for this is that organic paints are expected to have excellent properties such as heat resistance, flame resistance, flame resistance, and durability that cannot be obtained from organic paints. It is highly possible.

Inorganic paints that have been developed in the past can be broadly divided into silicate-based inorganic paints and phosphate-based inorganic paints, but these conventional inorganic paints generally have characteristics such as water resistance, flexibility, adhesion, and workability. The disadvantage was that it was inferior.

For example, for phosphate-based inorganic paints, phosphate is used as a binder, a mixture of zinc oxide, titanium oxide, and barium oxide is fired, a composite oxide powder is used as a hardening agent, and water or slightly alkaline water is used as a diluent. An inorganic paint containing the following has been proposed.

However, this paint is not satisfactory in terms of water resistance, bruising properties, and adhesion, as well as blistering of the paint film.

(Structure of the Invention) Therefore, in order to solve the above-mentioned drawbacks of conventional inorganic paints, the present inventors have diligently continued research and development of inorganic paints, and as a result, (a), (1) zinc oxide Source and (
ii) Metal oxide MxOy (where M is ■ in the periodic table)
At least one of the metal atoms of groups 1 to 2, oFi oxygen atoms, X and y represent arbitrary integers), and (Ill)
At least one type of fired product obtained by heating a mixture consisting of at least one type of colmanite-based compound or ulexite to 500°C or higher, (b) at least one type of water-soluble silicate, and (e) polyphosphorus. An inorganic paint obtained by diluting these with water using (a) (b) (() as an essential component of the main film-forming element of an inorganic paint, or (a ) (b)
(A composition containing R as an essential component and at least one divalent or higher valent metal salt of an inorganic weak acid is used as the essential component of the main film-forming element of an inorganic paint, and these are diluted with water. Inorganic paints have heat resistance, water resistance, flexibility, adhesion,
They discovered that it has excellent workability and also has an excellent antirust effect when applied to various metals, leading to the completion of the present invention.

The present invention will be explained in detail below.

(1) zinc oxide source used in the present invention;
) A fired product obtained by heating a mixture consisting of at least one metal oxide MxOy (where Mρ1X17 is the same as above) source and (iii) at least one colmanite compound or ulexite to 500°C or higher [ Hereinafter, these fired products will be collectively referred to as fired products (5)] are manufactured as follows. That is, a zinc oxide source containing zinc oxide to produce zinc oxide upon heating, preferably 100 mesh or less, and a metal oxide MxOy containing preferably 1 mesh to produce metal oxide MXOF upon heating.
A mixture obtained by uniformly mixing at least one metal oxide MxOy source having a mesh size of 00 mesh or less and at least one type of colmanite-based compound-layered ulexite preferably having a mesh size of 100 mesh or less by a dry or wet method,
In a heating furnace such as an electric furnace, the temperature is 500°C or higher, preferably Fi 700 to 1500°C, more preferably Fi 900°C.
By heating and firing at a temperature of ~1400°C for about 150 hours to 30 minutes, the desired fired product) can be obtained.

If the above-mentioned firing temperature is less than 500°C, it is not preferable because it takes too much time to obtain the fired product. However, even if the temperature is lower than 500°C, a desired fired product can be obtained by firing for a fairly long time.

In the present specification, "at least one of (1) a zinc oxide source, (II) a metal oxide Mx Oy source, and (Ill)
The fired product obtained by heating a mixture with at least one of a colmanite compound or ulexite to a temperature of 500° C. or higher means the following. That is, when a zinc oxide source is melted and heated, it becomes zinc oxide, and the metal oxide MxOy is formed.
At least some of the (1) zinc oxide, (1) metal oxide, and (Ill) colmanite-based compound and/or ulexite are converted into a metal oxide MxOy by heating, and some chemical It means something obtained by a reaction (for example, a solid solution of each of the above components), and is not simply a mixture of the above components.

In addition to zinc oxide, zinc oxide sources for producing the baked product (c) include, for example, zinc hydroxide, zinc carbonate, basic zinc carbonate, zinc nitrate, zinc acetate, and the like. Further, specific examples of the metal M of the metal oxide MxOy include aluminum, silicon, tin, lead, titanium,
Examples include zirconium, anti-sulfur, bismuth, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, etc. Specific examples of metal oxides MxOy include Al2O3, 5IO2, 5n, etc.
02, pbo, TiO2, ZrO2, 5b203, Bi
203, v206, Cr2O3, MoO2, WO2,
Mn2O3, Mn3O4, Fe2O3, Co01NiO
etc. are rare. Examples of the metal oxide MxOy source include hydroxides, carbonate groups, nitrates, organic acid salts, etc. of the metal M mentioned above. In addition, the colmanite-based compound used to produce the fired product (5) is colmanite (c
olemanite), molecular formula 〇85B12
Pr1ce with 0Zl ・9H20
ite), Hydrobra-ci with the molecular formula MgCaBs0゜φ6H20
It is a general term for natural minerals whose main components are a boric acid source and an alkaline earth oxide source, such as te).

Also, Ulexite has the molecular formula N
It is a natural mineral with aCaB50g・8H20.

When producing the fired product (5) used in the present invention, the mixing ratio of each raw material component is determined based on the required performance and workability of the resulting coating film (in the present invention, workability refers to the above-mentioned main factors for coating film formation). The essential composition of the base metal can be varied over a very wide range depending on the time at room temperature from dilution with water until gelation (i.e. used in conjunction with pot life). The mixing ratio with the oxide NxOy is usually preferably in the range of 95 to 5 mol of zinc oxide and 5 to 95 mol of the metal oxide MxOy in total.
In particular, it is recommended that the molar ratio of zinc oxide to metal oxide Mx Oy be in the range of 3=1 to 1:3. Zinc oxide is 95
If the amount of zinc oxide is more than 10%, the pot life may be short and workability may be poor, and if the amount of zinc oxide is less than 50%, the bond life may be too long, which is unfavorable in terms of workability.

Next, the colmanite-based compound and/or ulexite used as a raw material component in the production of the fired product (8) used in the present invention is generally used to reduce the firing time or the firing temperature when producing the fired product (8). It has been found that it is effective not only in reducing pot life, but also in controlling pot life and improving water resistance. The mixing ratio of at least one of these colmanite-based compounds and ulexites is 2 to 50 per 100 parts by weight of the total weight of zinc oxide and metal oxide MxOy! A range of parts by weight is recommended, especially a range of 2 to 20 parts by weight. In this case, if it is less than 2 parts by weight, it will not be very effective in controlling pot life or improving water resistance, and if it is more than 50 parts by weight, the pot life will be short and workability may be poor. .

Next, as the water-soluble silicate used in the present invention, for example, crystal water represented by the general formula: % formula % (where Ml represents an alkali metal and X represents an integer from 0.5 to 5) Water-soluble silicates with or without the above-mentioned alkali metals are substituted with divalent or higher valent metals such as magnesium, calcium, zinc, zirconium, etc. The acid salts are also generally referred to as ``water-soluble silicates''.The water-soluble silicate used in the present invention is preferably used in powder form, and specific examples include, for example, the well-known water glass No. 1. , Mizugarasu No. 2, and Mizugarasu No. 3 powdered commercially available products.
) and the above-mentioned water-soluble silicate (hereinafter, these mixtures are collectively referred to as mixture ■) can be varied over a wide range depending on the required performance and workability of the resulting coating film.〃ζ Usually, the above-mentioned water-soluble silicate powder is 20 to 300 parts by weight per 100 parts by weight of the above-mentioned fired product (6).
Parts by weight ranges are preferred. If the mixing ratio of water-soluble silicate powder is less than 20 parts by weight, a good coating film may not be obtained, and if it is more than 300 parts by weight, the pot life may be unfavorable. .

Next, the silicon polyphosphate used in the present invention, (1)
A silicon polyphosphate obtained by heating a mixture of a silicon dioxide source and (1) a phosphorus pentoxide source at a temperature preferably Fi300°C or higher, and which gradually phosphorus when the powder is suspended in water. It means that it is a silicon polyphosphate that releases acid and gradually dissolves in water (hereinafter, this type of silicon polyphosphate is collectively referred to as water-soluble silicon polyphosphate), and has the general formula -+5tp2o. , sun (however, n
has a highly cross-linked structure represented by (represents an integer),
It does not contain crystalline, water-insoluble silicon polyphosphate.

The water-soluble silicon polyphosphate used in the present invention is expressed by the above general formula →5iP207+n in order to reduce the high degree of crosslinking density, exude crystallinity, and adopt a structure that gradually releases phosphoric acid in an aqueous medium. It is desirable that the ratio of silicon atoms to phosphorus atoms in the silicon polyphosphate to be used is not 1:2. With the essential condition of gradual release of phosphoric acid in the aqueous medium, the water-soluble silicon polyphosphate used in the present invention can be prepared by substituting a portion of the silicon dioxide source and/or phosphorus pentoxide source with other metal oxide sources, e.g. Also included are water-soluble modified silicon polyphosphates substituted with at least one of an alkali metal oxide source, an alkaline earth metal oxide source, or a metal oxide source from Groups I to II of the Periodic Table.

Here, it means a compound that dissolves as a metal oxide source and generates the metal oxide by heating, including the metal oxide, and specific examples include, for example, Li 20
, Na2O, K2O, etc., hydroxides, carbonates, nitrates, etc. of lithium, sodium, potassium, etc., and K, MgO, CaO1BaO, etc.
Including hydroxides, carbonates, nitrates, etc. of magnesium, calcium, barium, etc., and sources of metal oxides of groups 1 to 2 of the periodic table, for example, AJzOs, TiO2 , ZrO2, etc., and hydroxides of aluminum, titanium, zirconium, and the like. Specific examples of silicon dioxide sources include natural minerals containing silicon dioxide as a main component, such as silica gel, kaolin, and acid clay. In addition, examples of the phosphorus pentoxide source include phosphoric acid, including phosphorus pentoxide. As the water-soluble silicon polyphosphate used in the present invention, Mizusawa Chemical Co., Ltd. fA! Company city HL tail MIZUKANEX-300, MI ZUKANEX-
50072 is particularly recommended.

The water-soluble silicon polyphosphate used in the present invention contributes to improving the water resistance of the resulting coating film. The composition (generally referred to as q) of the mixture of mixture ① and water-soluble silicon polyphosphate can be varied over a wide range depending on the required performance and workability of the resulting coating film, but usually the above mixture 0 The water-soluble silicon phosphate powder is preferably in the range of 5 to 150 parts by weight per 100 parts by weight.Water-soluble polysilicon powder 17 When the mixing ratio of the silicon phosphate powder is 5 parts by weight or less, the water resistance of the resulting coating film is improved. It is not very effective in improving properties, and if it is more than 150 parts by weight, there is a tendency for cracks to occur in the coating film and other unfavorable effects in terms of pot life.

The inorganic paint of the present invention uses the above composition (Q as an essential component of the main element for forming a paint film), thereby providing a paint film with excellent heat resistance, water resistance, flexibility, rust prevention, workability, etc. However, it was found that the above composition (composition in which at least one divalent or higher valent metal salt of an inorganic weak acid was added to Q) [hereinafter referred to as composition (composition (composition in which q was added with at least one divalent or higher valent metal salt of an inorganic weak acid) A composition containing at least one metal salt is collectively referred to as Composition 0] as an essential component of the main element for forming a coating film, thereby improving heat resistance, water resistance, flexibility, rust prevention, workability, etc. It was found that the health was further improved.

Dissolution of the divalent or higher valent metal salt of the inorganic weak acid used in the present invention,
This means that it is a divalent or higher metal salt of boric acid, silicic acid, titanic acid, chromic acid, zirconic acid, manganic acid, molybdic acid, tungstic acid, stannic acid, vanadic acid, lead acid, ferric acid, or aluminic acid. However, it is a general term that includes hydrated salts. Specific examples of metals with a valence of 2 or more include magbedium, calcium, barium, zinc, aluminum, molybdenum, copper, iron, cobalt, and nickel. , manganese, zirconium, lead, etc.

Specific examples of divalent or higher valent metal salts of inorganic weak acids used in the present invention include zinc borate, calcium borate,
Aluminum borate, zinc silicate, iron silicate, calcium silicate, magnesium silicate, aluminum silicate,
Molybdenum silicate, steel silicate, cobalt silicate, manganese silicate, zirconium silicate, magnesium titanate, calcium titanate, barium titanate, nickel titanate, lead titanate, zinc chromate, calcium chromate, zirconate Zinc, magnesium zirconate, calcium zirconate, manganic acid/<lJ'7m, zinc molybdate, calcium molybdate, calcium tungstate, zinc stannate, manesium stannate, calcium stannate, lead stannate, calcium nocnadate , magnesium leadate, calcium leadate, barium leadate, zinc leadate, manganese leadate, nickel leadate, cobalt leadate, calcium ferrate, zinc ferrate, manganese ferrate, calcium aluminate, manganese aluminate, etc. can give.

The mixing ratio of the divalent or higher valent metal salt of the inorganic weak acid used in the present invention is preferably in the range of 2 to 100 parts by weight based on 100 parts by weight of the composition (c). If the mixing ratio of the divalent or higher valent metal salt of the inorganic weak acid is less than 2 parts by weight, the desired effect will be small, and even if it is used in excess of 100 parts by weight, no difference in effect will be observed. The effect of a divalent or higher valent metal salt of an inorganic weak acid on the physical properties of the coating film differs depending on the type of inorganic weak acid and the type of metal. For example, hydrated zinc silicate and calcium aluminate are effective in shortening pot life, and zirconium silicate, calcium zirconate, calcium stannate, and calcium titanate are effective in improving water resistance.

In addition, calcium tungstate and the like are effective in improving hardness. Furthermore, calcium ferrate, zinc ferrate, manganese ferrate, etc. are effective in improving rust prevention. Further, for example, calcium salts generally contribute to improving water resistance, while zinc salts are generally effective in improving not only water resistance but also flexibility. This may be due to the difference in the ability of calcium atoms and zinc atoms to coordinate with oxygen atoms, in addition to the difference in the chemical bond between Ca-0 and Zn-0.

Therefore, depending on the application of the paint and the requirements for the performance of the coating film, it may be recommended to use a mixture of at least two types of the divalent or higher valent metal salts of the above-mentioned inorganic weak acids.

Next, a method for producing an inorganic paint according to the present invention will be explained.

That is, the fired product (8) obtained by the above production method, water-soluble silicic acid powder, and water-soluble silicon polyphosphate powder are mixed in desired amounts, respectively, and then this mixture is milled by a ball mill or the like to preferably 200 mesh. The composition (q) for inorganic paints of the present invention is obtained by pulverizing the composition (q) and preferably 200 mesh or less of an inorganic weak acid.
Composition 0 for an inorganic paint of the present invention is obtained by uniformly mixing a desired amount of at least one kind of metal salt having a higher valence or higher. Desired amounts of clay, extender pigments such as diatomaceous pigments, coloring pigments, antirust pigments, various metal powders, organic paints, thickeners, etc. can be added to these compositions (Q or K) as necessary. When using the inorganic paint composition of the present invention (Q'! or 0), after adjusting the viscosity by adding an appropriate amount of water or a water-containing solvent such as water-containing alcohol, the composition is conventionally coated with synthetic resin paint, etc. The coating is applied by spray coating, brush coating, roller coating, etc., which are used in traditional coatings, and then air-dried or baked to form a coating film.

(Effects of the present invention) The inorganic paint of the present invention has excellent workability, and the coating film obtained by applying it has high hardness and heat resistance. The inorganic paint of the present invention has good adhesion to inorganic and metallic objects, and also has a rust-preventive effect on metallic objects. Applications include coating inorganic building materials such as concrete, mortar, asbestos slate, asbestos-cement perlite board, pulp cement board, and rock wool board, and painting natural stone, glass, ceramics, and roof gowers 2, which require heat resistance. Painting of various metals for applications such as bridges, automobiles, vehicles, ships, various manufacturing plants, various electrical products, etc. that require anti-rust properties, replacement of enamel, machinery, electricity, architecture, civil engineering, etc. It has a wide range of applications in the field of

EXAMPLES The present invention will be explained below with reference to examples, but the present invention is not limited to the following examples.

Example 1 100 parts by weight of a homogeneous mixture of 2 moles of zinc oxide and 1 mole of titanium oxide (anatase type), each having 200 mesh or less, and 10 parts by weight of carborane, each having 200 mesh or less, were mixed uniformly, and the mixture was heated in an electric furnace at 1,200 parts by weight. After heating and firing at a temperature of 30° C. for 3 hours or more, the product was cooled and ground to 200 mesh or less to obtain the desired fired product (8). The fired product (8)
10 parts by weight, 100 mesh or less water glass No. 1 powder 1
0 parts by weight, 200 mesh or less manufactured by Mizusawa Chemical Industry Co., Ltd. (7) 5 parts by weight of MIZUKANEX-300, 5 parts by weight of kaolin clay of 200 mesh or less as a filler, and based on the above 100 parts by weight of the total solid content. 50
] After adding i parts of water, the mixture was stirred and mixed using a glass bead for 15 minutes, and then plated on an aluminum plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160°C for 1 hour.

c used in the following examples & each F [paraboloid, MIZUKAN
EX-300 and kaolin clay are each powders of 200 mesh or less, and water glass is powder of 100 mesh or less. Also, parts by weight are abbreviated as parts).

Example 2 100 homogeneous fx mixture of 1 mol of zinc oxide and 1 mol of titanium oxide (anatase type) each having 200 mesh or less
and 10 parts of carborane having a mesh size of 200 or less were mixed uniformly, heated and fired in an electric furnace at a temperature of 12oO°C for 3 hours or more, cooled, and crushed to a size of 200 mesh or less to obtain the desired fired product. . 10 parts of the fired product, 10 parts of water glass No. 1 powder, 5 parts of MIZUKANEX-3000, and 5 parts of kaolin clay were weighed, and 50 parts of water was added to 100 parts of the total solid content. After stirring and mixing for 15 minutes, the mixture was applied to an aluminum plate and an iron plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 3: 100 parts of a homogeneous mixture of 1 mol of zinc oxide and 2 mol of titanium oxide (anatase type), each having 200 mesh or less, and 10 parts of carborane, each having 200 mesh or less, were uniformly mixed and heated at 1200°C in an electric furnace. After heating and firing at a temperature of 3 hours or more, the mixture was cooled and ground to a size of 200 mesh or less to obtain the desired fired product. 10 parts of the fired product, 10 parts of water glass No. 1 powder, 5 parts of MIZUKANEX-3000, and 5 parts of kaolin clay were weighed, and after adding 50 parts of water to 100 parts of the total solid content, they were mixed in a glass bead. After stirring and mixing for 15 minutes, it was applied to an aluminum plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160°C for 1 hour.

Example 4 100 parts of a homogeneous mixture of 2 moles of zinc oxide and 1 mole of ferric oxide, each having 200 mesh or less, and 10 parts of carborane, each having 200 mesh or less, were mixed uniformly and heated in an electric furnace.
After heating and firing at a temperature of 200° C. for 3 hours or more, the mixture was cooled and pulverized to a size of 200 mesh or less to obtain the desired fired product. 10 parts of the fired product, 10 parts of water glass No. 1 powder, MI
Weighed 5 parts of ZUKANEX-300 and 5 parts of kaolin clay, added 50 parts of water to 100 parts of the total solid content, stirred and mixed with a glass bead for 15 minutes, and then applied it to an aluminum plate and a steel plate. . After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 5 A homogeneous mixture of 2 moles of zinc oxide and 1 mole of precipitated silicic acid anhydride, each containing up to 200 meshes, 1001 M to 200
After uniformly mixing with 10 parts of carborane of mesh size or less and heating and baking in an electric furnace at a temperature of 1200°C for 3 hours or more,
After cooling, the mixture was pulverized to less than 200 mesh to obtain the desired fired product. Weighed 10 parts of the fired product, 10 parts of water glass No. 1 powder, 5 parts of MIm-300, and 5 parts of kaolin clay,
After adding 50 parts of water to 100 parts of the total solid content, the mixture was stirred and mixed using a glass bead for 15 minutes, and then applied to an aluminum plate and an iron plate. After drying to the touch, place in an electric oven for 16 days.
Bake hardening was performed at a temperature of 0° C. for 1 hour.

Example 6 100 parts of a homogeneous mixture of 2 moles of zinc oxide and 1 mole of aluminum oxide, each having 200 meshes or less, and 10 parts of carborane, each having 200 meshes or less, were mixed uniformly and heated in an electric furnace at a temperature of 1200°C for 3 hours. After heating and firing as described above, the product was cooled and pulverized to a size of 200 mesh or less to obtain the desired fired product. 10 parts of the acid, water i Las No. 1 powder 10
Weighed 5 parts of MIZUKANEX-300 and 5 parts of kaolin clay, and added 5 parts to 100 parts of the total solid content.
After adding 0 parts of water, the mixture was stirred and mixed using a glass bead for 15 minutes, and then applied to an aluminum plate and an iron plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 7 100 parts of a homogeneous mixture of 2 moles of zinc oxide and 1 mole of manganese carbonate, each having 200 mesh or less, and 10 parts of carborane, each having 200 mesh or less, were mixed uniformly and heated in an electric furnace at a temperature of 1200°C for 3 hours. After heating and firing as described above, the product was cooled and pulverized to a size of 200 mesh or less to obtain the desired fired product. Weighed 3005 parts of the above-mentioned calcination and 5 parts of kaolin clay, and added 50 parts of water to 100 parts of the total solid content.

After that, the mixture was stirred and mixed using a glass bead for 15 minutes, and then coated on an aluminum plate. After drying to the touch, heat in electric oven at 160℃
Bake hardening was performed at a temperature of 1 hour.

Example 8゜10 parts of a homogeneous mixture of the fired product obtained in Example 2 and the fired product obtained in Example 5 in a weight ratio of 1=1, 1 part of water glass
Weighed 10 parts of No. 1 powder, 5 parts of MIZUKANEX-3000, and 5 parts of kaolin clay, added 50 parts of water to 100 parts of the total solid content, stirred and mixed with a glass bead for 15 minutes, and then placed on an aluminum plate. and applied it to the iron plate.

After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 9 100 parts of a homogeneous mixture of 2 moles of zinc oxide and 1 mole of titanium oxide (anatase type), each having a mesh size of 200 or less, and 4810 parts of Tlexa having a mesh size of less than 200 meshes were uniformly mixed and heated at 1200°C in an electric furnace. After heating and firing at a temperature of 3 hours or more, the mixture was cooled and ground to a size of 200 mesh or less to obtain the desired fired product. 10 parts of the fired product, 10 parts of water glass No. 1 powder, 5 parts of MIZUKANEX-3000, and 5 parts of kaolin clay were weighed, and after adding 50 parts of water to 100 parts of the total solid content, they were mixed in a glass bead. After stirring and mixing for 15 minutes, the mixture was applied to an aluminum plate and a steel plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 10 100 parts and 200 parts of a homogeneous mixture of 2 moles of zinc oxide and 1 mole of precipitated silicic acid anhydride, each containing up to 200 meshes.
Mix uniformly with 10 parts of talexite below mesh,
After heating and firing in an electric furnace at a temperature of 1200° C. for 3 hours or more, the product was cooled and ground into pieces of 200 mesh or less to obtain the desired fired product. 10 parts of the fired product, 10 parts of water glass No. 1 powder
1 part, MIZUKANEX-3005 parts, and 5 parts of kaolin clay were weighed, and 50 parts of water was added to 100 parts of the above total solid content. After stirring and mixing with a glass bead for 15 minutes, the mixture was mixed on an aluminum plate and a steel plate. Coated. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 11 100 parts of a homogeneous mixture of 2 moles of zinc oxide and 1 mole of aluminum oxide, each having 200 meshes or less, and 10 parts of talexite having 200 meshes or less were mixed uniformly, and the mixture was heated in an electric furnace at a temperature of 1200°C for 3 hours. After heating and baking for more than an hour,
After cooling, the mixture was pulverized to less than 200 mesh to obtain the desired fired product. 10 parts of the fired product, 10 parts of Water Glass No. 1 powder, 5 parts of MIZUKANEX-3000, and 5 parts of Kaolin Flay were weighed, and after adding 50 parts of water to 100 parts of the total solid content, 15 parts of water was added using glass beads. The mixture was stirred and mixed for 1 minute and then applied to an aluminum plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 12゜10 parts of the fired product obtained in Example 1, 1 part of water glass No. 1 powder
0 parts, MIZUKANEX-3005 parts, 2 parts of inorganic weak acid
Weigh out 5 parts of calcium titanate and 5 parts of kaolin clay as metal salts with a valence of 200 mesh or higher, add 50 parts of water to 100 parts of the total solid content, and stir for 15 minutes with a glass bead. It was mixed and then applied to an aluminum plate.

After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 13゜10 parts of the fired product obtained in Example 2, 1 part of water glass No. 1 powder
Weighed 0 fL, 5 parts of MIZUKANEX-300, 5 parts of calcium titanate of 200 mesh or less as a divalent or higher metal salt of an inorganic weak acid, and 5 parts of kaolin clay, and added 50 parts of water to 100 parts of the total solid content. After the addition, the mixture was stirred and mixed using a glass bead for 15 minutes, and then applied to an aluminum plate and an iron plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 14゜10 parts of the fired product obtained in Example 3, 1 part of water glass No. 1 powder
Weighed 0 parts, MIZUKANEX-3QQ 5 parts, 5 parts of calcium titanate of 200 mesh or less as a divalent or higher metal salt of an inorganic weak acid, and 5 parts of kaolin clay, and added 50 parts to 100 parts of the total solid content. After adding water,
The mixture was stirred and mixed using a glass bead for 15 minutes, and then coated on an aluminum plate.

After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 15゜10 parts of the fired product obtained in Example 4, 1 part of water glass No. 1 powder
0 parts, MIZUKANEX-3005 parts, 2 parts of inorganic weak acid
Weigh out 5 parts of calcium titanate and 5 parts of kaolin clay as metal salts with a valence of 200 mesh or higher, add 50 parts of water to 100 parts of the total solid content, and stir for 15 minutes with a glass bead. After mixing, it was applied to an aluminum plate and a steel plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 16゜10 parts of the fired product obtained in Example 5, 1 part of water glass No. 1 powder
o part, MIZUKANEX-3005 parts, 2 parts of inorganic weak acid
Weigh out 5 parts of calcium titanate and 5 parts of kaolin clay as metal salts with a valence of 200 mesh or higher, add 50 parts of water to 100 parts of the total solid content, and stir for 15 minutes with a glass bead. It was mixed and then applied to an aluminum plate.

After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 17゜10 parts of the fired product obtained in Example 6, 1 part of water glass No. 1 powder
0 parts, MIZUKANEX-3005 parts, 2 parts of inorganic weak acid
Weigh out 5 parts of calcium titanate and 5 parts of kaolin clay as metal salts with a valence of 200 mesh or higher, add 50 parts of water to 100 parts of the total solid content, and stir for 15 minutes with a glass bead. After mixing, it was applied to an aluminum plate and a steel plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 18゜10 parts of the fired product obtained in Example 7, 1 part of water glass No. 1 powder
Weighed 0 parts, MI ZUKANEX-3005 parts, 5 parts of calcium titanate of 200 mesh or less as a divalent or higher metal salt of an inorganic weak acid, and 5 parts of kaolin clay, and added 50 parts to 100 parts of the total solid content. After adding water, the mixture was stirred and mixed using a glass bead for 15 minutes, and then applied to an aluminum plate and an iron plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 19゜10 parts of a mixture of the two types of fired products used in Example 8, water, //10 parts of Lar X1 powder, MIZUKANEX-3
After weighing 0.005 parts, 5 parts of calcium titanate of 200 mesh or less as a divalent or higher metal salt of an inorganic weak acid, and 5 parts of kaolin clay, and adding 50 parts of water to 100 parts of the total solid content, The mixture was stirred and mixed using a glass bead for 15 minutes, and then coated on an aluminum plate. After being dry to the touch, it was baked in an electric furnace at a temperature of 160° C. for 1 hour.

Example 20゜10 parts of the fired product obtained in Example 9, water glass No. 1 powder i
os, MIZUKANEX-3005 parts, inorganic weak acid 2
Weigh out 5 parts of calcium titanate and 5 parts of kaolin clay as metal salts with a valence of 200 mesh or higher, add 50 parts of water to 100 parts of the total solid content, and stir for 15 minutes with a glass bead. After mixing, it was applied to an aluminum plate and a steel plate. After being dry to the touch, it was baked in an electric furnace at a temperature of 160° C. for 1 hour.

Example 21゜10 parts of the fired product obtained in Example 10, 10 parts of water glass No. 1 powder, 5 parts of MIZUKANEX-300, 5 parts of calcium titanate having 200 mesh or less as a divalent or higher metal salt of an inorganic weak acid, and kaolin clay. -5 parts were weighed out, 50 parts of water was added to 100 parts of the total solid content, and the mixture was stirred and mixed using a glass bead for 15 minutes, and then coated on an aluminum plate.

After being dry to the touch, it was baked in an electric furnace at a temperature of 160° C. for 1 hour.

Example 22゜10 parts of the fired product obtained in Example 11, 10 parts of water glass No. 1 powder, 5 parts of MIZUKANEX-300, 5 parts of calcium titanate with a valence of 200 or more as a divalent or higher metal salt of an inorganic weak acid, kaolin 5 parts of clay were weighed out, 50 parts of water was added to 100 parts of the total solid content, and the mixture was stirred and mixed using a glass bead for 15 minutes, and then coated on an aluminum plate.

After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 23゜10 parts of the fired product obtained in Example 3, 1 water glass No. 1 powder
O part, MIZUKANEX-3005 parts, 2 parts of inorganic weak acid
2. Calcium zirconate of up to 200 meshes each as a metal salt with a higher valence. s parts, 2.5 parts of zirconium silicate, and 5 parts of kaolin clay, and after adding 50 parts of water to 100 parts of the total solid content, the mixture was stirred and mixed with a glass bead for 15 minutes, and then the aluminum Applied to plates and iron plates. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 24゜10 parts of the fired product obtained in Example 3, 1 part of water glass No. 1 powder
0 parts, MIZUKANEX-3005 parts, 2 parts of inorganic weak acid
Weigh out 2 parts of calcium zirconate, 2 parts of zirconium silicate, 2 parts of calcium stannate, and 5 parts of kaolin clay, each having 200 mesh or less as metal salts with higher valences, and add 50 parts to 100 parts of the total solid content. After adding water, the mixture was stirred and mixed using a glass bead for 15 minutes, and then applied to an aluminum plate and an iron plate. After drying to the touch, place in electric oven 1
Bake hardening was performed at a temperature of 60° C. for 1 hour.

Example 25゜10 parts of the fired product obtained in Example 3, 1 part of water glass No. 1 powder
0 parts, MIZUKANDX-3005 parts, 2 parts of inorganic weak acid
Weigh out 2.5 parts of calcium titanate, 2.5 parts of calcium zirconate, and 5 parts of kaolin clay, each having 200 mesh or less as a metal salt with a higher valence, and add 50 parts of water to 100 parts of the total solid content. After the addition, the mixture was stirred and mixed using a glass bead for 15 minutes, and then applied to an aluminum plate and an iron plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 26 A paint obtained by blending in exactly the same manner as in Example 25 except that the fired product obtained in Example 1 was used instead of the fired product in Example 25 was applied to an aluminum plate and an iron plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160°C for 1 hour.

Example 27゜A paint obtained by mixing exactly the same as in Example 25 except that the fired product obtained in Example 2 was used instead of the fired product in Example 25 was applied to an aluminum plate and an iron plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

Example 28 The inorganic paint obtained in Example 16 was applied to a glass plate. After being dry to the touch, it was baked and hardened in an electric furnace at a temperature of 160° C. for 1 hour.

The coating film performance evaluation results for the samples obtained in the above examples are shown in Table M1. The evaluation method for each coating film performance is as follows.

1. Flexible iron plate: A test piece obtained by coating on an iron plate with a thickness of 0.3 ysrx was bent 1800 degrees with the coating film outside, and the appearance of the coating film was judged by visual observation.

Excellent: No cracks Good: Some cracks can be seen Fair: Many cracks Not good: Peeling of the paint film Aluminum plate: A test piece obtained by applying the coating to an aluminum plate with a thickness of 0.2 mm was coated with the paint film removed. After bending the film by 180 degrees, returning it to its original position and repeating the same operation, the appearance of the coating film was visually judged. .

Excellent: 2 or more times (no cracks even after repeating) Good: 2 times (some cracks can be seen after repeating it): Many cracks after repeating it 2 times Not good: cracks seen after 1 time 2 Water resistance test piece is placed in boiling water Judgment was made by visual observation after treatment for 2 hours.

Excellent: No change at all Good: No change on the edges Acceptable: Changes on the edges Acceptable: Major changes on the edges 3 Adhesion Judgment was made according to the cross-cut test method of JISK-5400.

4. Pencil hardness Determined according to the pencil scratch test method of JISK-5400.

5. Heat resistance test piece After processing the test piece at 500°C for 2 hours in an electric furnace, the appearance of the coating film was judged by visual observation.

Claims (1)

[Claims] 1. (a) (i) zinc oxide source; (ii) metal oxide M
xOy (where, M is a metal atom from Group III to Group VIII of the periodic table, O is an oxygen atom, and x and y are arbitrary integers)
(iii) at least one type of fired product obtained by heating a mixture consisting of at least one type of colmanite-based compound or ulexite to 500°C or higher; and (b) at least one type of water-soluble silicate. At least one species and
(c) (a) with at least one silicon polyphosphate;
b) An inorganic paint containing (c) as an essential component of the main film-forming element. 2. A composition containing (a), (b), and (c) of claim 1 as essential components and at least one divalent or higher valent metal salt of an inorganic weak acid as essential components of the main elements for forming a coating film. Inorganic paint.