JP2001240773A - Water-glass cold cure vehicle composition and cold cure inorganic coating material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide cold cure inorganic coating materials comprising a metal modified glass fine powder/water-glass system which are different from the conventional organic resin coating materials, organoalkoxysilane based coating materials, and the general water-glass based coating materials. SOLUTION: The high functional inorganic coating materials can be obtained by adding an abrasive material, a metal salt or a metal hydroxide, and an acid to a glass fine powder to effect surface substitution reaction, reacting the reaction product with a water-glass or a modified water-glass to obtain a stable composite colloidal vehicle, and adding a pigment and an effective functional component to the vehicle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a metal-modified glass fine-silicate composite colloid, a metal fine powder, which is used for general buildings, ships, marine structures, tunnels, reservoirs, water purification plants, and air purification devices. Cuprous oxide, photooxidation catalyst titanium oxide, inorganic rust inhibitor (aluminum phosphate, zinc phosphate),
The present invention relates to a rust-proofing antifouling room-temperature-curable inorganic coating mainly containing a compound having antibacterial and antifungal functions.

[0002]

2. Description of the Related Art Inorganic paints using water glass have been developed as thermosetting paints, and then chemically cured or acid-treated.
It has been made into a paint as a mixed type with an organic polymer.

Many patents using silicides, metal oxides, polyphosphoric acids, metal powders and the like as water glass curing agents are known (Japanese Patent Application Laid-Open Nos. 47-42927 and 48-3).
No. 4935, JP-A-49-16690, JP-A-50-15122
No. 1, JP-A-50-2031, JP-B-50-25482 and JP-B-49-10813, U.S. Pat. S. P3,454,410, Br
t1, 342, 346), water resistance, room temperature (15-30 ° C.) curability, whitening phenomenon, etc., which are the essential drawbacks of water glass paints, have not been solved yet.

On the other hand, a coating paint using a hydrolyzed coating film of an organoalkoxysilane (methyl, ethyl silicate, etc.) has been developed (Japanese Patent Publication No. 2-26407).
No. 4, etc.), it is difficult to form a thick film, and it has not been generalized because of its high price.

[0005] Organic and organoalkoxysilane paints using titanium oxide as a photo-oxidation catalyst are available, but they are difficult to put into practical use due to the self-photolytic action of titanium oxide, and still have low pollution and high functionality. No inorganic paint has been developed.

[0006]

That is, water glass generally does not cure in a short period of time unless a heating and curing agent is used, but this is due to silicate condensation interference of alkali ions.

Therefore, in practice, heat treatment such as baking is predominant, and to a limited extent, hardeners composed of oxides, hydroxides, carbonates, sulfites and composites of polyvalent metals are used. I have.

[0008] However, these are generally not stable as paints, and are cured immediately after the addition of a curing agent, so that the pot life is short and the curing proceeds rapidly, so that a block condensate is formed and a stable coating film is formed. Difficult to get.

On the other hand, when metallic zinc is used as a curing agent, a stable coating film can be obtained, but it has not been used for general purposes because it is two-pack and has a high specific gravity of zinc.

Accordingly, an object of the present invention is to obtain a microporous film by developing a stable and water-resistant vehicle comprising a metal-modified glass fine powder-water glass and a modified water glass colloid.

Another object of the present invention is to efficiently disperse a rust-preventing agent, an anti-fouling agent or a photo-oxidation catalyst compound having an oxidizing ability in the above-mentioned vehicle, thereby making it possible to locate the active ingredient on the surface of the vehicle. An object of the present invention is to provide a highly functional inorganic paint which cannot be obtained by a coating film.

Still another object of the present invention is to provide a non-flammable, odorless, low-pollution inorganic coating which combines excellent room-temperature curability in which curing proceeds within a few hours in the drying process after application without a special curing agent. It is in.

[0013]

In order to achieve the above object, the present invention provides a method in which a glass abrasive and an appropriate amount of water are added to fine glass powder, and a metal salt or metal hydroxide and a trace amount of acid are added with stirring. In addition, a metal-modified glass fine powder composition in which the hydroxyl group on the surface of the obtained glass fine powder is partially substituted with a metal, and a silicate M ₂ O.nSiO ₂ (M: K, Na, Lin = 2 to 4) The present invention proposes a water-glass cold-curable vehicle composition containing a metal-modified glass fine powder-silicate composite colloid obtained by reacting an aqueous solution of the present invention with an aqueous solution.

The silicate M ₂ O.nSiO ₂ (M:
Examples of aqueous solutions of K, Na, Lin = 2 to 4) include phosphoric acid and phosphate, alum or metal salts such as chlorides, sulfates, nitrates such as zinc, aluminum, iron and zirconium;
Silicate M ₂ O.nSiO ₂ (M:
An aqueous solution of K, Na, Lin (2-4) can be used.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, since a silicate and a modified silicate easily polymerize and condense upon the evaporation of water to form a stable film, the silicate and the modified silicate serve as a stable reaction center serving as a base for polymerization. A composite colloid vehicle comprising a metal-modified glass fine powder composition and a silicate is obtained.

In the present invention, the metal that modifies the glass fine powder has a role of forming a stable colloid by bonding with oxygen bonded to silicate and silica of the modified silicate. That is, it is designed to be stabilized as an aqueous solution while binding to the metal-modified glass fine powder.

After coating, the composite colloid of the present invention starts condensation by evaporating water and forms a stable film. This film differs from a silicate alone film in that it has a stable condensation center. Has high water resistance.

In the present invention, glass fine particles having a particle size of 10.0 μm or less are used, and those having a particle size of more than 10 μm are not preferable because they settle.

As the glass abrasive, for example, cerium oxide or the like is used, and its addition amount is preferably 1 to 5% by weight, and if it exceeds this range, there is no glass polishing effect.

Further, the metal salt or metal hydroxide is expressed in terms of% by weight.
It is added so as to be 10 to 30%, but if it exceeds this range, there is no metal modifying effect.

Further, a silicate M ₂ O.nSiO ₂ (M: K, N
The aqueous solution of a, Lin = 2 to 4) is added so that the weight% becomes 10 to 60% with respect to the metal-modified glass fine powder composition. The powder-silicate composite colloid cannot be obtained.

Specific conditions for obtaining a metal-modified glass fine powder-silicate composite effective for the present invention are as follows: 1 to 5 parts by weight of cerium oxide as an abrasive is added to 100 parts by weight of glass fine powder; 10 to 30 parts by weight of a salt or metal hydroxide and 1 ml of 0.5 to 0.1 NHCl are added, and mixed polishing and surface reaction are performed for 1 to 24 hours.

The reaction product was washed once or twice with water, and water glass M ₂ O.nSiO ₂ (M: K, Na, Lin) was added to 1 part by weight of the reaction product.
= 2 to 4) were added, and the mixture was heated and reacted at 20 to 40 ° C for 0.5 to 2 hours to obtain a composite colloid vehicle.

Zeolite, talc, kaolin, diatomaceous earth, metal oxides and metal hydroxides (eg, cuprous oxide, titanium oxide, aluminum oxide, zinc oxide, rare earth oxide, One or more pigments such as chromium oxide, aluminum hydroxide, zinc hydroxide, etc.) and metal carbonates, etc., are screened according to their use and uniformly mixed to prevent rust and stain resistance and photo-oxidation. Can be obtained.

In this case, the preferred blending ratio of the above pigment to the composite colloid vehicle is 20 to 70% by weight.

The resulting composite colloid vehicle contains zinc,
When one or more of the pigments of aluminum and Fe are uniformly mixed at the time of use, a one-part, one-solid-phase, room-temperature-curable inorganic paint can be obtained.

In this case, the preferred blending ratio of the above pigment to the composite colloid vehicle is 40 to 90% by weight.

[0028]

Embodiments of the present invention will be described below. Example 1 2 parts by weight of cerium oxide was added to 100 parts by weight of glass fine powder adjusted to 1 to 10 μm, and 10 parts by weight of zinc chloride was added thereto, 0.1N
HCl (1 ml) was added and the mixed surface reaction was performed for 24 hours.

The reaction was washed twice with 100 ml of distilled water,
After drying at room temperature for 3 hours, 5 parts by weight of water glass Na ₂ O · 3.8SiO ₂ (No. 4 water glass) was added to 1 part by weight of the reaction dried product, and the mixture was reacted by heating at 30 ° C. for 2 hours. A colloid vehicle was obtained.

[0030]

## STR1 ## The above two reactions proceed as shown below.

Example 2 5 parts by weight of aluminum chloride and 2 ml of 0.1N HCl were added to 100 parts by weight of glass fine powder adjusted to 1 to 10 μm, and a mixed surface reaction was carried out for 10 hours.

The reaction was washed twice with 100 ml of distilled water,
After drying at room temperature for 3 hours, 5 parts by weight of water glass Na ₂ O · 3.8SiO ₂ (No. 4 water glass) was added to 1 part by weight of the reaction dried product, and the mixture was reacted by heating at 30 ° C. for 2 hours. A colloid vehicle was obtained.

Example 3 2 parts by weight of cerium oxide, 10 parts by weight of zinc hydroxide and 2 ml of 0.1N HCl were added to 100 parts by weight of glass fine powder adjusted to 1 to 10 μm, and a mixed surface reaction was carried out for 20 hours.

The reaction was washed twice with 100 ml of distilled water,
After drying at room temperature for 3 hours, 5 parts by weight of denatured water glass was added to 1 part by weight of the reaction dried product, and the mixture was heated and reacted at 25 ° C. for 2 hours to obtain a composite colloid vehicle.

The modified water glass used was prepared as follows. 6 L of silicate having a molar ratio (SiO ₂ / M ₂ O) of 4 was added to 6 L of water and heated. Then, 1 L of a 5% solution of aluminum alum was added and allowed to react. The mixture was concentrated by heating to 12 L and denatured. Water glass was used.

Example 4 A coating having the composition shown in Table 1 below was prepared in the composite colloid vehicle of Example 1, and applied to a blasted iron plate sample.
After drying for 12 hours, a salt spray rust prevention test was performed.

[0037]

【table 1】

The test results are shown in Tables 2 and 3. The test results show that the paint according to the present invention has excellent mechanical strength and rust prevention performance.

[0039]

[Table 2]

[0040]

[Table 3]

Example 5 A coating having the composition shown in Table 4 below was prepared from the composite colloid vehicle of Example 3, applied to a glass plate, and subjected to a photooxidation test and an antibacterial test. The curing time after application was 24 hours.

[0042]

[Table 4]

The test results are shown in Tables 5 and 6. From this test result, it is understood that the coating material according to the present invention has excellent photooxidation ability and antibacterial property.

[0044]

[Table 5]

[0045]

[Table 6]

Example 6 A paint having the composition shown in Table 7 below was prepared from the composite colloid vehicle of Example 2, applied to an FRP plate, and subjected to a marine antifouling performance test. An aqueous primer was used for application to the FRP plate. After the application, the mixture was allowed to stand for 12 hours and immersed in seawater for 8 months. The results are shown in Table 8 below.

[0047]

[Table 7]

[0048]

[Table 8]

From the results, it was found that the inorganic paint according to the present invention had an excellent antifouling effect in seawater.

[0050]

In summary, according to the present invention, rustproofing, antifouling performance or photooxidation performance is achieved by using a stable and water-resistant composite colloid vehicle composed of metal-modified glass fine powder-water glass and modified water glass colloid. It is possible to obtain an inorganic paint having high functionality that could not be obtained with an organic coating film such as

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Claims (4)

[Claims] 1. A glass abrasive and an appropriate amount of water are added to a glass fine powder, and a metal salt or a metal hydroxide and a trace amount of an acid are added with stirring to form a hydroxyl group on the surface of the glass fine powder with a metal. Metal-modified glass fine powder obtained by reacting a partially substituted metal-modified glass fine powder composition with an aqueous solution of silicate M ₂ O.nSiO ₂ (M: K, Na, Lin = 2 to 4) A water-glass cold-curing vehicle composition comprising a phosphate complex colloid as a main component. 2. A modified silicate M ₂ O.nSiO ₂ (M:
An aqueous solution of K, Na, Lin = 2-4) is used.
A water-glass cold-curing vehicle composition as described in the above. 3. The water-glass cold-curing vehicle composition according to claim 1 or 2, further comprising at least one pigment selected from the group consisting of zeolite, talc, kaolin, diatomaceous earth, metal oxides, metal hydroxides, and metal carbonates. A cold-setting inorganic paint obtained by adding the above. 4. A water glass cold-curable vehicle composition according to claim 1, wherein a pigment comprising zinc, aluminum, and Fe is used.
One-part, one-phase, room-temperature curing inorganic paint to which one or more kinds are added at the time of use.