JPS6058473A - Inorganic coating - Google Patents

Abstract

PURPOSE:To provide titled coating of high heat and water resistance, potential flexibility and good workability, for use on mortar, glass, etc., comprising a calcined product from zinc oxide, titanium dioxide and other metal oxide(s), acid phosphoric metal salt and inorganic weak acid metal salt. CONSTITUTION:The objective coating comprising, for example, (A) 100pts.wt. of a calcined product prepared by heating to >=600 deg.C a mixture consisting of (i) 90-10mol% of zinc oxide, (ii) 10-90mol% of titanium dioxide, and (iii) 2-50 pts.wt. per 100pts.wt. of the components (i) plus (ii), of at least one sort of compound selected from magnesium oxide, calcium oxide, and barium oxide, (B) 20- 500pts.wt. of at least one sort of acid phosphoric metal salt, and (C) 2-30pts.wt., per 100pts.wt. of the component (A) plus (B), of an inorganic weak acid metal salt (said metal being >=2 valent) (e.g. zinc borate).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an inorganic paint having excellent heat resistance, water resistance, flexibility, and workability.

In recent years, with advances in synthetic resins and the development of 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 it is expected to have excellent properties such as corrosion resistance, flame resistance, flame resistance, and durability that cannot be obtained with organic paints, and it is also advantageous from a resource perspective, as well as being a non-polluting and low-pollution paint. 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 excellent water resistance, flexibility, adhesion, and workability. Being inferior in gender was considered a drawback.

For example, for phosphate-based inorganic paints, a phosphate binder is used, a hardening agent is a double oxide powder made by baking a mixture of zinc oxide, titanium oxide, and barium oxide, and a diluent is water or slightly alkaline water. Inorganic paints containing these have been proposed. However, this paint causes blisters in the coating film and is not satisfactory in terms of water resistance, flexibility, and adhesion. Therefore, in order to solve the above-mentioned drawbacks of conventional inorganic paints, the present invention was developed. As a result of their intensive research and development of inorganic paints, they found (a) (i) zinc oxide source and @
) A mixture consisting of a titanium oxide source and at least one compound selected from the group consisting of [phase] a magnesium oxide source, a calcium oxide source, and a barium oxide source is calcined by heating to a temperature of 600°C or higher. [Hereinafter, this fired product will be collectively referred to as fired product (5) for convenience], at least one of acidic metal phosphate salts, and at least one divalent or higher valent gold scrap salt of 2 and 0 inorganic weak acids. It is an essential ingredient. m product [hereinafter referred to as (a).

A composition consisting of (bj, (Q)) is used as the main element for forming an inorganic paint film for convenience and is used as a main element for forming a film of an inorganic paint. sex,
i1 has excellent water-based properties, flexibility, and workability.
Schiff J) also discovered that it has excellent anti-corrosion effects when applied to various metals, leading to the development of the present invention.

VC and non-invention will be explained in detail below.

The fired product (5) used in the present invention is manufactured as follows. That is, a source of zinc oxide, preferably less than 100 mesh, which is extracted by heating, including zinc oxide, and a source of titanium oxide, which is prepared by heating, including titanium oxide. a titanium oxide source that preferably produces 100 meshes or less;
Obtained by uniformly mixing by a dry or wet method with at least one component of a magnesium oxide source, a calcium oxide source, and a barium oxide source that produce these oxides by heating, including magnesium oxide, calcium oxide, and barium oxide. Mixture, electric FJy, c etc. in a heating furnace at a temperature of 600°C or higher, the preferred length is 700-1400
15°C, more preferably at a temperature of 900 to 1800°C.
By heating and burning for about 0 hours to 80 minutes, the desired baked product (5) can be obtained. In addition, when producing the fired product (8), a mineralizing agent such as borax can be added if necessary. If the above firing temperature is less than 600°C, it takes time to obtain the fired product. This is not desirable because it takes too much time. However, even if the temperature is lower than 600°C, a desired fired product can be obtained by firing for a fairly long time.

[(1) zinc oxide source, (fil
"A fired product obtained by adding a mixture consisting of a titanium p-oxide source and at least one selected from the group consisting of a magnesium oxide source, a calcium oxide source, and a barium oxide source to a temperature of 600°C or higher" It means the following: In other words, a zinc oxide source turns into zinc oxide when heated, a titanium oxide source turns into titanium oxide when heated, and a magnesium oxide source, calcium oxide source, and barium oxide source turn into magnesium oxide, calcium oxide, and barium oxide when heated. Moreover, at least some zinc oxide, (...) titanium oxide, (magnesium oxide,
It means something obtained by a certain reaction caused by heating with at least one of calcium oxide and barium oxide (for example, a solid solution of each of the above components), and does not include a mere mixture of each of the above components.

In addition to zinc oxide, zinc oxide sources for producing fired products (Aw) include, for example, zinc hydroxide, zinc carbonate, basic zinc carbonate, zinc nitrate, zinc acetate, etc.In addition, titanium oxide sources include Examples of sources of titanium oxide include titanium hydroxide.Furthermore, sources of magnesium oxide, calcium oxide, and barium oxide include magnesium oxide, calcium oxide, and barium oxide, as well as the respective metals. Examples include hydroxides, carbonates, nitrates, and organic acid salts.

When producing the fired product (2) used in the present invention, the mixing ratio of each raw material component is determined by the required performance and workability of the resulting coating film. Raw composition @? The mixing ratio of zinc oxide and titanium oxide can be varied over a wide range depending on the time at room temperature from the time of dilution with water until gelation (i.e. used in relation to pot life). contains 90 to 10 mol% zinc oxide and 10 to 9 mol% titanium oxide.
A range of 0 mol % is preferable, and a molar ratio of zinc oxide to titanium oxide of 2:1 to 1:2 is particularly recommended. If the zinc oxide content is 90 mol % or more, the pot life is too short and workability is poor, and if the zinc oxide content is 10 mol % or less, the pot life is too long, which is not preferable in terms of workability.

A small amount of magnesium oxide, calcium oxide, and barium oxide (the mixing ratio of 1 m is preferably in the range of 2 to 50 parts by weight, particularly preferably in the range of 5 to 80 parts by weight, based on 100 parts by weight of the total weight of zinc oxide and titanium oxide) In this case, if it is less than 2 parts by weight, there is little effect on improving water resistance;
If the amount is more than the weight part, the pot life will be too short and productivity will be poor.

In the present invention, among alkaline earth metal oxides, magnesium oxide, calcium oxide, and barium oxide are recommended, but alkaline earth metal oxides other than these can also be used.

Next, the acidic metal phosphate used as the main component for forming a film in the inorganic paint of the present invention has at least one remaining hydroxyl group that is directly bonded to the phosphorus atom of phosphoric acid or condensed phosphoric acid. This means that they are metal salts, and specific examples thereof include monobasic aluminum phosphate, monobasic magnesium phosphate, monobasic calcium phosphate,
Monobasic zinc phosphate, monobasic copper phosphate, monobasic iron phosphate, monobasic
1J manganese phosphate, monobasic zirconium phosphate, etc.
Examples include phosphates, dibasic phosphates such as dibasic aluminum phosphate, dibasic magnesium phosphate, and dibasic calcium phosphate, sesquiphosphates such as aluminum sesquiphosphate, and pyrophosphates such as aluminum pyrophosphate. Further, for example, monophosphorus salts alone or in combination with other acidic phosphate metal salts, preferably at 150 to 800°C.
Examples include acidic condensed phosphates obtained by heating and dehydration at a temperature of . Better results were often obtained when the above acidic metal phosphates were used as a mixture of two or more than when used alone. %, monobasic aluminum phosphate or monobasic aluminum phosphate? A mixture of a water-soluble acidic metal phosphate, such as acidic condensed aluminum phosphate obtained by heating and dehydration, and a water-insoluble acidic metal phosphate, such as dibasic calcium phosphate, is often used to produce good results. The results were obtained.

The proportion of the above-mentioned acidic metal phosphate used as a main component for forming a film in the inorganic paint of the present invention is preferably in the range of 20 to 500 parts by weight, based on 100 parts by weight of the above-mentioned fired product. If it is less than 500 parts by weight, the pot life will be too short and the cropping performance will be poor, and if it is more than 500 parts by weight, the pot life will be too long and the cropping performance will be poor.

The present invention is a composition (a) in which a divalent or higher valent metal salt of an inorganic weak acid is added to a mixture of the above-mentioned fired product (2) and an acidic metal phosphate. Surprisingly, when used as the main element for forming a paint film, it improves the water resistance of the paint film compared to conventional phosphate-based inorganic paints.
It has been found that flexibility and adhesion are improved, and VC and pot life (and therefore productivity) can be significantly changed.

The divalent or higher valent metal salt of an inorganic weak acid used in the present invention is:
It means divalent or higher gold halide salts of boric acid, silicic acid, titanic acid, chromic acid, zirconic acid, manganic acid, molybdic acid, tungstic acid, stannic acid, vanadic acid, and lead acid. It is a general term that broadly includes hydrated salts. Specific examples of divalent or higher-valent metals include magnesium and calcium.

Barium, zinc, aluminum, molybdenum, copper iron, cobalt, nickel, manganese, zirconium, lead, etc. can be mentioned.Specific examples of divalent or higher valent metal salts of inorganic weak acids used in the present invention include, for example, zinc borate, Calcium borate, aluminum borate, zinc silicate, iron silicate, calcium silicate, magnesium silicate, aluminum silicate, molybdenum silicate, lead silicate, cobalt silicate, manganese silicate, zirconium silicate, titanic acid Calcium, magnesium titanate, barium titanate, nickel titanate, lead titanate, zinc chromate, calcium chromate, zinc zirconate, calcium zirconate, magnesium zirconate, barium manganate, zinc molybdate, calcium molybdate, Calcium tungstate, zinc stannate, calcium stannate, magnesium stannate, lead stannate, calcium vanadate, magnesium lead acid, calcium lead acid, barium lead acid, zinc lead acid, manganese lead acid, nickel lead acid, lead acid Cobaltona etc. can be given.

The proportion of the divalent or higher valent metal salt of the above-mentioned inorganic weak acid used in the present invention is 2 to 80 parts by weight based on 100 parts by weight of the above-mentioned fired product (2) and the acidic metal phosphate. % [The range of 5 to 20 parts by weight is preferred. If it is less than 2 parts by weight, it will have little effect on improving water resistance, and 80
If the amount is more than the weight part, the pot life is generally too short and the chart-making properties tend to be poor. As the divalent or higher valent metal salt of the inorganic weak acid used in the present invention, zinc salts, calcium salts, magnesium salts, and zirconium salts rx of silicic acid, titanic acid, zirconic acid, and stannic acid are particularly recommended.

Furthermore, the effect of rattan on the physical properties of the coating film differs depending on the type of metal. For example, calcium salts generally provide coating M with very good water resistance, whereas zinc salts may be inferior to calcium salts in improving water resistance, but they do not improve the flexibility of coating Eγ. Generally, zinc salts are superior to calcium salts. 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 2i of the divalent or higher valent metal salts of the above-mentioned inorganic weak acids.

As mentioned above, by using a divalent or higher valent metal salt of an inorganic weak acid as a component of a coating material, the physical properties of the coating film are greatly improved. The reason is presumed to be as follows. In other words, among the divalent or higher valence metal salts of the inorganic weak acid, the divalent or higher metals react with the hydroxyl group directly bonded to the phosphorus atom contained in the acidic metal phosphate, resulting in the high concentration of the acidic metal phosphate. It contributes to molecular weight formation and coating film formation, and this effect cannot be expected from monovalent metals. Therefore, monovalent metal salts of inorganic weak acids are not preferred. The inorganic weak acid residues left behind by the reaction of divalent or higher-valent metals with hydroxyl groups directly bonded to phosphorus atoms are initially microdispersed in the gaps between polymer chains that are being formed, and then sequentially form a network. It forms, reacts with the hydroxyl group directly bonded to the phosphorus atom, which is highly hydrophilic and therefore seems to have a great influence on water resistance, and consumes the hydroxyl group, or fills the gaps in the polymer chains. By performing the function 2 as a filler, it forms a dense structure in the coating film, and thus contributes to improving water resistance. Therefore, there will be an essential difference in the microstructure of the coating film when a divalent or higher valent metal salt of an inorganic weak acid is not used and when it is used. In addition, in the divalent or higher valent gold hexasalt of the above-mentioned inorganic weak acid, in addition to the essential difference in Cal bond as mentioned above, the oxygen atoms of calcium and zinc (particularly the oxygen atoms contained in the polymer chains forming the coating) This may be due to the difference in the coordination ability for 4C (oxygen atom), and therefore the difference in the crosslinking density of the polymers forming the coating film. Calcium probably has a stronger coordination ability;
Therefore, it has a high crosslinking density, which is probably why it has better water resistance than zinc, but is inferior in susceptibility.

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

That is, after mixing desired amounts of the baked product (6) obtained by the above production method, at least 1 g of acidic phosphate metal salt powder, and at least one divalent or higher valent metal salt of an inorganic weak acid, This mixture is pulverized using a ball mill or the like, preferably to a size smaller than a zoo mesh, to obtain the inorganic paint of the present invention. This inorganic paint contains the desired amount of extender pigments such as clay and quinceumen, coloring pigments, anti-rust pigments, organic paints, thickeners, etc., as necessary. Can be added. When using the inorganic paint of the present invention, the viscosity is adjusted by adding an appropriate amount of water or a water-containing solvent such as hydroalcohol, and then the inorganic paint of the present invention is applied by slathering, brushing, or roller coating, which are conventionally used for coating composite resin paints. Is it a coating film that is applied using a coating method, etc., and then air-dried or baked? Form.

The inorganic paint of the present invention has VC-F properties, and the coating film obtained by applying it has high hardness and heat resistance, is nonflammable, has excellent water resistance and flexibility, and has inorganic and It has good adhesion to metallic objects, and also has a rust-preventive effect on metallic objects. Therefore, the inorganic paint of the present invention can be used for concrete,
mortar, asbestos slate, asbestos cement perlite board,
Inorganic materials such as pulp cement board and rock wool board 5! j Coatings for building materials, coatings for natural stone, glass, ceramics, roof glass, etc., coatings for all types of applications that require arc resistance, bridges, automobiles, vehicles, and ships that require rust prevention. It has a wide range of applications in the fields of machinery, electricity, architecture, civil engineering, etc., coating various manufacturing plants, various electrical products, and replacing enamel.

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

Note that Example 2 and subsequent examples are carried out based on Example 1, and matters different from Example 1 will be described.

Example 1 Calcined product: A mixture of 2 moles of zinc oxide and 1 mole of titanium oxide.
Calcium oxide source.

After adding calcium hydroxide and thoroughly mixing with wet method,
After removing the grain and drying it, it was heated in an electric furnace at 1200°C for 8 hours, and then finely pulverized.

Acidic metal phosphate: 5 parts by weight of primary aluminum phosphate and a mixture of primary aluminum phosphate and primary calcium phosphate in a weight ratio of 1:1. Dehydrated wire mesh 10 heated at 210°C for dehydration condensation. Part by weight and five parts by weight of dibasic calcium phosphate were mixed.

Divalent or higher valent metal salt of inorganic weak acid: 10 parts by weight of the above calcined product of hydrated calcium silicate, 20 parts by weight of acidic metal phosphate, i part by weight of hydrated calcium silicate, 20 M parts of water for 5 parts by weight of kaolin. In addition, after stirring and mixing in a glass fuse, the mixture was coated on an aluminum plate, dried to the touch, and then baked and hardened in an electric oven at 160°C for 30 minutes.

Example 2 In place of the hydrous calcium silicate in Example 1, 5 parts by weight of zirconium silicate was used.

Example 8 In place of the hydrous calcium silicate in Example 1, 5 parts by weight of calcium titanate was used.

Implementation Cartwheel 5 parts by weight of calcium titanate in place of the hydrated calcium silica in Example 1? In addition, in place of the fired product used in Example 1, 5 parts by weight of calcium oxide (calcium oxide source : Calcium hydroxide) was added and thoroughly mixed in a wet method, filtered, dried, heated in an electric oven at 1200°C for 8 hours, and heated to 0.

Using 10 parts by weight of the finely pulverized fired product, Example 1
5 parts by weight of calcium tungstate was used in place of the hydrated calcium silicate.

Example 6 1 part by weight of hydrated zinc silicate and 8 parts by weight of calcium titanate were used in place of the hydrated calcium silicate in Example 1. Example? .

In place of the hydrated calcium silicate in Example 1, 2 parts by weight of zinc zirconate R and 8 parts by weight of calcium titanate were used.

Example 8 In place of the acidic gold salt phosphate used in Example 1, a mixture of 10 parts by weight of monobasic aluminum phosphate and monobasic aluminum phosphate and monobasic calcium phosphate in a weight ratio of 1=1 was used. 10 parts by weight of dehydrated wire mesh heated at 210°C to undergo dehydration condensation, 51 parts by weight of dibasic calcium phosphate, and 25 parts by weight of acidic gold kite salt made from dibasic calcium phosphate were used, and a flexible plate was used in place of the aluminum plate. (Slate@) and cured at room temperature.

Example 9゜The fired product 1 of Example 5 was used instead of the fired product used in Example 1.
In addition, in place of the hydrated calcium silicate in Example 1, 0.5 parts by weight of zinc borate was used, and after drying to the touch, it was baked and hardened in an electric furnace at 180°C for 80 minutes. .

Example 10゜In place of the fired product used in Example 1, the fired product 101 of Example 5 was used, and in place of the hydrated calcium silicate of Example 1, 2.0% of zinc borate was used. Using parts by weight,
After being dry to the touch, it was baked and hardened in an electric oven at 180° C. for 80 minutes.

Example 11゜In place of the fired product used in Example 1, 5 i' parts of calcium oxide (calcium oxide source calcium dihydroxide) was added to 100 parts by weight of a mixture consisting of 1 mol of zinc oxide and 1 mol of titanium oxide. ), thoroughly mixed in a wet method, filtered and dried, heated in an electric P at 1200°C for 8 hours, then used 10 parts by weight of the finely ground calcined product, and added to hydrated calcium silicate. Instead, 1 part by weight of calcium borate was used, and after drying to the touch, it was baked and hardened in an electric oven at 180°C for 30 minutes.Example 12 In place of the fired product used in Example 1, Example 11.0 Parts by weight of the fired product IO were used, and 21 parts by weight of zinc molybdate was used in place of the hydrated calcium silicate of Example 1. After being dry to the touch, it was baked and hardened in an electric furnace at 180°C for 80 minutes.

Example 1f3゜In place of the acidic metal phosphate used in Example 1, 2 parts by weight of primary aluminum phosphate, 2 parts by weight of primary calcium phosphate, and a weight ratio of primary aluminum phosphate and primary calcium phosphate of 1 =1 mixture? 22 parts by weight of a machinable metal phosphate consisting of 10 parts by weight of a dehydrated wire mesh which had been dehydrated and condensed at 210°C and 21 parts by weight of calcium phosphate 1O were used, and in place of the aluminum plate. Apply it on the iron plate,
After being dry to the touch, it was baked and hardened in an electric oven at 180°C for 30 minutes.

Example 14゜In place of the acidic phosphorus salt used in Example 1, 22 parts by weight of the acidic phosphorus salt of Example 1B was used, and
Calcium zirconate 5N was used in place of the hydrated calcium silicate in Example 1, and was applied to an iron plate instead of an aluminum plate.

Pouch Example 15゜In place of the acidic metal phosphate used in Example 1, Example 18. using 22 parts by weight of acidic metal phosphate, and
In place of the hydrated calcium silicate in Example 1, 5 parts by weight of calcium stannate was used, and the coating was applied to an iron plate instead of an aluminum plate.

In place of the acidic metal phosphate used in Example 1 in Example 11, 22 parts by weight of the acidic metal phosphate of Example 18 was used, and in place of the baked product used in Example 1, Example 5 fired product IO
Weight section? In addition, 5 parts by weight of magnesium stannate was used in place of the hydrated calcium silicate in Example 1, and
It was applied to a steel plate instead of an aluminum plate.

Example 17 In place of the acidic metal phosphate used in Example 1, 22 parts by weight of the acidic metal II phosphate of Example 18 was used, and in place of the baked product used in Example 1.

Mixture 1 consisting of 1 mole of zinc oxide and 1 mole of titanium oxide
20 parts by weight of calcium oxide (calcium oxide source: calcium hydroxide) per 00 weight ITS? In addition, 10 parts by weight of the calcined product, which was added and thoroughly mixed in a wet method, filtered, dried, heated at 1200°C in an electric furnace for 8 hours, and then finely pulverized, was used. Instead, 8 parts by weight of zinc zirconate and 8 parts by weight of calcium stannate were used, and the coating was applied to an iron plate instead of an aluminum plate.

Comparative Example Example 1 was carried out in the same manner as in Example 1, except that hydrated calcium silicate was not used.

Comparative Example 2 In Example 8, it was coated on an aluminum plate without using hydrated calcium silicate, and after drying to the touch, it was heated at 160°C in an electric oven.
Bake hardening was performed for 80 minutes.

Comparative Example & Example IBK was carried out in the same manner as Example 1B without using hydrated calcium silicate.

Table 1 shows the coating film performance evaluation results for the samples obtained in the above Examples and Comparative Examples.

Paint film performance evaluation results Table 1 The evaluation method for each coating film performance is as follows.

1. Water resistance Test piece was treated with boiling water for 2 hours and then visually observed.

2. Flexibility Bend the test piece to 180°C with the vinyl coating outside.

After performing the same operation 22 times, the appearance of the coating film was visually observed.

Excellent: No cracks at all Good: No cracks Acceptable: Some cracks Not acceptable: Very cracks 8 Adhesion Judgment was made according to JIS K-5400 rice grain test method I/c.

4. Pencil temporary placement Judgment was made in accordance with the pencil side fitting test method of JISK-5400.

5. Test piece for decoration resistance After densifying tNN in air at 00° C. for 2 hours, the appearance of the coating film was determined by visual observation.

6. Pinhole The appearance of the coating film on the test piece was determined by visual observation.

Claims (1)

[Claims] (a) (i) zinc oxide; (ii) a titanium oxide source;
iii) A fired product obtained by heating a mixture consisting of at least one compound selected from the group consisting of a magnesium oxide source, a calcium oxide source, and a barium oxide source to a temperature of 600°C or higher, and @acidic metal phosphate at least 1 of salt
and (C) a divalent or higher valent metal salt of an inorganic weak acid as an essential component of at least a main element for forming a lid coating.