JPS61295208A - Production of flaky metallic oxide - Google Patents

Abstract

PURPOSE:To produce the titled flaky metallic oxide with simple equipment inexpensively and safely by coating an aq. soln. of a metallic compd. on a smooth surface, drying the soln., releasing the obtained coated film from the smooth surface and baking the film. CONSTITUTION:An aq. soln. of a metallic compd. is coated on the smooth surface of a substrate of glass, metals, resins, etc., and the coated film is heated and dried at a temp. ranging from ordinary temp. to about 300 deg.C. The obtained coated film, preferably a cracked film, is released from the smooth surface and baked in the atmosphere at about 800-1,000 deg.C. The obtained flaky metallic oxide is crushed, as required, into an appropriate size. A metallic halide, a metallic acid halide, an alkoxy metallic halide, an acyloxy metallic halide, their condensates, etc., can be appropriately used as the metallic compd. Si, Al, Ti, Sn, In and Zr are suitably used as the metal and Cl is easy to use as the halogen.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing flaky metal oxides.

(Prior Art) Various flaky metal oxides have been known so far. For example, flaky titanium oxide, flaky alumina, etc. are mixed into paints and used to improve lubricity and gloss, or mixed into plastics and used for other purposes to improve mechanical properties. It has many uses.

A method in which a titanium compound is applied to a smooth substrate to form a film, and the substrate is melted or crushed to form flakes (Japanese Patent Publication No. 1980-
No. 4781) is known. However, the above method has drawbacks such as requiring the substrate to be melted, making the operation complicated, making it difficult to obtain a product with a uniform diameter, and making it extremely difficult to make the size uniform.

Another method is to apply an organic solvent solution of titanium alkoxide or titanium tetrachloride to a smooth surface, and then crack the glands formed by the action of water vapor to obtain flakes (U.S. Patent No. 2.941
．． (Specification No. 895, Specification No. 8.071,482)
has also been proposed. Although it is not possible to obtain flaky inorganic materials containing titanium compounds as the main component by these methods,
There were inconveniences such as not being able to collect everything as flakes.

In order to overcome the above-mentioned disadvantages, a method has been proposed in which a solution of a titanium compound in an organic solvent is applied to a heated substrate (Japanese Patent Publication No. 45-6424).However, in the case of this method, evaporation and boiling Therefore, extreme thickness unevenness tends to occur, and it is extremely difficult to control the thickness and size to be constant.

Furthermore, since all the conventional techniques use organic titanium compounds, the manufacturing cost is also high.

(Problems to be Solved by the Invention) An object of the present invention is to use inexpensive raw materials and water instead of an organic solvent as a solvent compared to the method for producing flaky metal oxides proposed in the past. The object of the present invention is to provide a method for producing flaky metal oxides that is highly economical and safe.

(Means for Solving the Problems) The present invention provides a method for producing flaky metal oxides by applying an aqueous solution of a metal compound to a substrate, peeling the coating film from the smooth surface after heating and drying, and baking it. be.

The method of the present invention will be described in more detail below.

In carrying out the method of the present invention, the aqueous solution of the metal compound preferably has film-forming properties.

Such film-forming properties can be achieved by dissolving a polymer compound of 211 or more bodies (for example, condensed phosphate, etc.) in water, or by associating water-soluble compounds in water and behaving like a polymer compound. can get.

However, even if it does not have film-forming ability, it may be any material that can be given a flaky shape by adding a known film-forming polymer such as polyol or ethyl cellulose.

Furthermore, the aqueous solution of a metal compound in the present invention includes cases where the solution reacts with water to form a different metal compound when dissolved in water.

For example, when titanium tetrachloride is dissolved in water, it is hydrolyzed to produce hydrochloric acid and titanic acid, and it essentially exists as a solution of titanic acid in hydrochloric acid, or in the case of an aqueous solution of aluminum chloride. be.

The metal of the metal compound of the present invention includes metals with two or more values,
Periodic table mb, ya, yb, wa
.

Metals belonging to group (1)a or group (2), more preferably one or more selected from aluminum, silicon, titanium, zirconium, indium, and tin.

Therefore, the metal compound may be a water-soluble compound of the above metals, and specifically, halides, sulfates,
Salts of inorganic acids such as nitrates, oxyhalides, oxysulfates, and oxynitrates, salts of organic carboxylic acids such as formates, acetates, and benzoates, water-soluble metal chelates, and derivatives thereof and the aforementioned Examples include oligomers and polymers (hereinafter simply referred to as condensates) formed by the condensation of metal compounds, including chlorides, oxychlorides, alkoxy metal chlorides, acyloxy metal chlorides, etc. These condensates and mixtures thereof are preferred.

Specifically, these compounds include silicon tetrachloride,
Silicon chlorides such as silicon oxychloride, silicon bromides such as silicon tetrabromide and silicon oxybromide, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monopropoxytrichlorosilane, dimethoxydichlorosilane,
Dibutoxydichlorosilane, triethoxymonochlorosilane, tripropoxymonochlorosilane, monomethoxytribromsilane, monoethoxytribromsilane, monopropoxytribromsilane, dimethoxydibromsilane, dibutoxydibromsilane, triethoxymonobromsilane , alkoxyhalogenosilanes such as tripropoxymonobromosilane, monoformyloxytrichlorosilane, monoacetoxytrichlorosilane, monopropionyloxytrichlorosilane, diformyloxydichlorosilane, dibutyryloxydichlorosilane, triformyloxymonochlorosilane, triacetoxymonochlorosilane, monoformyloxytribromosilane,
Acyloxyhalogenosilanes such as monoacetoxytribromsilane, monopropionyloxytribromsilane, diformyloxydibromsilane, dibutyryloxydibromsilane, triformyloxymonobromsilane, triacetoxymonobromsilane, silicon formate, Silicon compounds such as organic acid silicones such as silicon acetate and silicon benzoate, alkali silicates such as lithium silicate and sodium silicate, and condensates thereof; Aluminum chlorides such as aluminum chloride and indium oxychloride, aluminum bromide , aluminum bromides such as aluminum oxybromide, monomethoxydichloraluminum, monoethoxydichloraluminum, monopropoxydichloraluminum, jetoxymonochloraluminum, dipropoxymonochloraluminum,
Alkoxyhalogenoaluminum such as monomethoxydibromoaluminum, monoethoxydichloraluminum, monopropoxydibromoaluminum, jetoxymonobromoaluminum, dipropoxymonobromoaluminum, monoformyloxydichloraluminum,
Monoacetoxydichloraluminum, monopropionyloxydichloraluminum, diformyloxymonochloraluminum, diacetoxymonochloraluminum, monoformyloxydibromoaluminum, monoacetoxydibromoaluminum, monopropionyloxydibromoaluminum, diformyloxymonobromoaluminum , acyloxyhalogenoaluminiums such as diacetoxymonobromoaluminum, organic acid aluminums such as aluminum formate, aluminum acetate, and aluminum benzoate, and their condensates; titanium pentachloride, titanium tetrachloride, oxy Titanium chlorides such as titanium chloride, titanium bromides such as titanium tetrabromide, titanium oxybromide, monomethoxytrichlortitanium, monoethoxytrichlortitanium, monopropoxytrichlortitanium, dimethoxydichlortitanium, dibutoxydichlortitanium, Triethoxymonochlortitanium, tripropoxymonochlortitanium, monomethoxytribromotitanium, monoethoxytribromotitanium, monopropoxytribromotitanium, dimethoxydibromotitanium, dibutoxydibromotitanium, triethoxymonobromotitanium, tripropoxymonobromotitanium Alkoxyhalogenotitaniums such as monoformyloxytrichlortitanium, monoacetoxytrichlortitanium, monopropionyloxytrichlortitanium, diformyloxydichlortitanium, dibutyryloxydichlortitanium, triformyloxymonochlortitanium, triacetoxymonochlortitanium, mono Formyloxytribromo titanium, monoacetoxytribromo titanium, monopropionyloxytribromo titanium,
Diformyloxydibromo titanium, dibutyryloxydibromo titanium, triformyloxymonobromo titanium,
Titanium compounds such as acyloxyhalogenotitaniums such as triacetoxymonobromotitanium, organic acid titaniums such as titanium formate, titanium acetate, and titanium benzoate, and condensates thereof; tin dichloride, tin tetrachloride, and oxychloride. Tin chlorides such as tin, tin bromides such as tin tetrabromide, tin oxybromide, monomethoxytrichlortin, monoethoxytrichlortin, monopropoxytrichlortin, dimethoxydichlortin, dibutoxydichlortin, Ethoxymonochlortin, tripropoxymonochlortin, monomethoxytribromtin, monoethoxytribromtin, monopropoxytribromtin, dimethoxydibromtin, dibutoxydibromtin, triethoxymonobromtin,
Alkoxyhalogenotins such as tripropoxymonobromtin, monoformyloxytrichlortin, monoacetoxytrichlortin, monopropionyloxytrichlortin, diformyloxydichlortin, dibutyryloxydichlortin, triformyloxymonochlortin, trichlortin Acetoxymonochlortin, monoformyloxytribromtin, monoacetoxytribromtin, monopropionyloxytribromtin, diformyloxydibromtin, dibutyryloxydibromtin, triformyloxymonobromtin, triacetoxymonobromtin tin compounds such as acyloxyhalogenotins such as tin formate, tin acetate, tin organic acids such as tin benzoate, and condensates thereof; indium chlorides such as indium trichloride and indium oxychloride; Indium bromides such as indium chloride, indium oxybromide, monomethoxydichloroindium, monoethoxydichlorindium, monopropoxydichlorindium, jetoxymonochlorindium,
Alkoxyhalogenoindiums such as dipropoxymonochlorindium, monomethoxydibromoindium, monoethoxydibromoindium, monopropoxydibromoindium, jetoxymonobromoindium, dipropoxymonobromoindium, monoformyloxydichloroindium, monoacetoxy Dichlorindium, monopropionyloxydichlorindium, diformyloxymonochlorindium, diacetoxymonochlorindium, monoformyloxydibromoindium, monoacetoxydibromoindium, monopropionyloxydibromoindium, diformyloxymonobromoindium, dichloroindium Indium compounds such as acyloxyhalogenoindiums such as acetoxymonobromindium, organic acid indiums such as indium formate, indium acetate, and indium benzoate, and condensates thereof; zirconium chlorides such as zirconium tetrachloride and zirconium oxychloride. Zirconium bromides such as zirconium tetrabromide and zirconium oxybromide, monomethoxytrichlorozirconium, monoethoxytrichlorzirconium, monopropoxytrichlorzirconium, dimethoxydichlorozirconium, dibutoxydichlorozirconium, triethoxymonochlorzirconium, trichlorozirconium Alkoxyhalogenozirconiums such as propoxymonochlorozirconium, monomethoxytribromizirconium, monoethoxytribromizirconium, monopropoxytribromzirconium, dimethoxydibromzirconium, dibutoxydibromzirconium, triethoxymonobromzirconium, tripropoxymonobromzirconium, etc. , monoformyloxytrichlorozirconium, monoacetoxytrichlorzirconium, monopropionyloxytrichlorzirconium, diformyloxydichlorozirconium, dibutyryloxydichlorozirconium, triformyloxymonochlorzirconium, triacetoxymonochlorozirconium,
Acyloxy such as monoformyloxytribromizirconium, monoacetoxytribromzirconium, monopropionyloxytribromzirconium, diformyloxydibromzirconium, dibutyryloxydibromzirconium, triformyloxymonobromzirconium, triacetoxymonobromzirconium, etc. Organic acid zirconiums such as halogenozirconiums, zirconium formate, zirconium acetate, zirconium benzoate,
and their condensates; and mixtures of the above.

Among the above compounds, alkoxy metal chlorides and acyloxy metal chlorides can be easily obtained by reacting alcohols with metal chlorides and carboxylic acids with metal chlorides, respectively. for example,
If 1 mole of titanium tetrachloride and 1 mole of ethanol are mixed under non-aqueous conditions, they will easily react to produce monoethoxytrichloromethane, and 1 mole of silicon tetrachloride and 2 moles of acetic acid will be mixed under non-aqueous conditions. Then, acetoxychlorosilane containing diacetoxydichlorosilane as a main component is produced.

In the case of an alkoxy metal chloride, the molar ratio of the alcohol to be reacted to the chlorine in the metal chloride is preferably 1 or less. Even if alcohol is added in an amount equal to or more than chlorine, the metal chloride will no longer react, so the molar ratio is preferably 1 or less.

For exactly the same reason as mentioned above, in the case of an acyloxy metal chloride, the molar ratio of the carboxylic acid to be reacted with respect to the chlorine in the metal chloride is preferably 1 or less.

Any alcohol and carboxylic acid can be used for the reaction, but in consideration of solubility in water, alcohols and carboxylic acids having 4 or less carbon atoms are preferred.

A coating liquid can be obtained by dissolving one or more of the metal compounds detailed above in water.

A known coloring agent consisting of a compound such as iron, nickel, vanadium, chromium, or manganese may also be added to the coating solution.

The concentration of the metal compound in the coating solution varies depending on the type of metal compound and is not particularly limited, but if it is too dilute, it may not be flaky or it may have to be coated multiple times, which is not economical. On the other hand, if it is too thick, workability will decrease, so it is generally 2 to 80! The amount is preferably applied in % by weight from 6 to 50% by weight. Usually, the concentration of the coating liquid is determined depending on the desired film thickness of the metal oxide.

In carrying out the method of the invention, a coating solution is applied to a heated or unheated substrate.

As the substrate, glass, metal, resin, etc. can be used. It is preferable that the substrate surface be as smooth as possible.

Further, the substrate may be a flat plate, a roll, or a felt.

As a method for applying the coating liquid to the substrate, known coating methods such as a dipping method, a spray method, and a brush coating method can be employed.

For example, polymeric substances such as polyols and ethyl cellulose,
Nonionic or anionic surfactants may also be added.

In carrying out the method of the present invention, the coating liquid applied to the substrate is
It dries at room temperature to 800°C, causing cracks. As a drying method, it is convenient to heat the substrate itself using steam heating, electric heating, etc., or to heat the coated surface using an infrared heater or microwave.

According to the method of the present invention, thin pieces can be produced without using organic solvents, so there is no need for conventional organic solvent recovery equipment or explosion-proof equipment, and the equipment is greatly simplified, reducing equipment costs. Not only is it cheaper and safer, but the water-soluble metal compound used as the raw material is much cheaper than conventional metal alkoxides, so it has the advantage of being able to economically produce thin pieces. can be achieved.

In carrying out the method of the present invention, the thin film cracked on the substrate is peeled off with a scraper or the like and collected.

A flaky inorganic material can thereby be obtained.

The metal compound flakes recovered as described above have the functional groups that the starting metal compound had, such as halogen groups and alkoxy groups.

In particular, if halogen groups remain, there are disadvantages such as the tendency for the flakes to dissolve in water again, so it is necessary to sinter them and use them as chemically stable metal oxides.

The firing temperature is the temperature at which the metal compound becomes a metal oxide, and is 80°C.
The firing temperature is in the range of 0 to 1100°C, preferably 500 to 900°C, and the firing may normally be carried out in the atmosphere, but if necessary, a steam atmosphere or the like may be used.

The flaky metal oxide □ is crushed as appropriate depending on the purpose of use, but generally it has a length of about 1 to 100 μm and a thickness of about 0.5 μm.
It is used in a size of 01 to 10 μm, but is not limited to this.

(Effects of the Invention) The flaky inorganic material obtained by the method of the present invention is a nail polish enamel! Shiny pigments for leather products, self! @For car exterior metal painting, pearlescent buttons cast from unsaturated polyester resin, pigments for cosmetics, pearlescent pigments or extender pigments used as filling materials for plastics for food packaging, transparent tubes for sodium lamps, and condenser porcelain. It can be effectively applied to raw material powder and catalyst carrier for manufacturing ceramic products such as.

According to the method of the present invention described in detail above, in addition to having optical effects such as refractive index and gloss equivalent to conventionally known supported pigments,
It has the advantage of being able to produce flaky metal oxides at a lower cost and more safely.

The method of the present invention will be explained in more detail with reference to Examples below, but it is clear that the method of the present invention is not limited thereto. A coating solution was prepared by mixing with

A slide glass, which had been washed with a surfactant, washed with water and dried, was immersed in these liquids and pulled up at a speed of 7551/min. This was dried in an air bath at 90''C for 180 minutes, and the degree of flaking was measured.Then, the flakes were scraped onto a glass slide with a scraper, and the flakes were fired at 900''C for 80 minutes. Table 1 shows the size and thickness of the obtained flakes.

Note that the degree of flaking is expressed as a percentage of the area of the membrane that has become flaky after drying to the area of the membrane initially deposited on the slide glass.

From this, depending on the concentration of TiC, the obtained TiOx
It can be seen that the thickness and size of the flakes are different, and the degree of flaking is also different. In any of the examples, flakes are obtained, but in particular 20 to 40! Favorable results are obtained when m%.

Examples 7 to 12 A flake-forming solution was prepared by reacting 1419 g (0.1 mol) of TiC with 0.2 mol of the compound shown in Table 2 and then mixing it with 42 f of water. Using this liquid, a thin piece was obtained on a glass plate in the same manner as in Example 1. The obtained flakes were heated at 800°C.
, 5 hours, and then fired at 700° C. for 2 hours to obtain Ties flakes. The results are shown in Table 2. This shows that cyasyloxydichlorotitanium and dialkoxydichlorotitanium reacted with lower carboxylic acids such as formic acid and acetic acid and lower alcohols such as methanol and ethanol have a high exfoliation rate.

Example 18 SiCt417y (0.1 mol) was reacted with 6N acetic acid (0.1 mol) and then mixed with water 17f to prepare a flake forming solution. This liquid was applied to a slide glass in the same manner as in Example 1, and then dried in a microwave oven at 500W for 2 minutes to obtain a thin piece. As a result, the flaking rate was 90%. The obtained flakes were fired for 500080 minutes to give
g thin sections were obtained. The flakes had a thickness of 0.8μ and a size of 10μ.

Example 14 Ratio fi1.88, A12 (Js/C1 (0 weight ratio is 2
．． A flake forming solution was prepared by adding acetic acid to a basic aluminum chloride aqueous solution of No. 45 to adjust the pH to p) 18 to 5. This liquid was applied to a slide glass in the same manner as in Example 1, and then dried in an air bath at 120° C. for 80 minutes to obtain a thin piece. As a result, the flaking rate was 95%. The obtained flakes were treated at 850" for 6 hours while blowing water vapor into them, and then fired at 1000°C for 2 hours to obtain AI!08 flakes. The flakes had a thickness of 1.2 microns and a size of 80 microns.

Example 16 A compound obtained by reacting SnC1426,16' (0.1 mol) with 6.4 g (0.2 mol) of methanol and SbC
A compound obtained by reacting 1 m 1.14 f (0,005 mol) with ethanol 0.28 f (0.05 mol),
A flake forming liquid was prepared by mixing 490 g of water. After applying this solution thinly on a polyester film, heat it at 120°C.
20! pl! ] After drying, the flaky material was peeled off from the film. The flaky material was treated at 800°C for 6 hours and then fired at 600°C to obtain flaky tin oxide. When the electrical conductivity of the flaky tin oxide was measured, it was I x 10-'Ω100.

Example 16 A flake-forming liquid was prepared by mixing 22.21 m (0.1 mJl/) of InC with 609 g of water. This solution was thinly applied onto a slide glass in the same manner as in Example 1, and after drying with an air path at 120° C. for 2 minutes, the flaky material was peeled off from the glass. The flaky material was treated under steam at 800°C for 5 hours and then fired at 600''C to obtain flaky indium oxide.

When the conductivity of the flaky indium oxide was measured, it was 6.
It was X10Ω.

Example 17 ZrC142B, 8 f (0.1%) in formic acid 9.2
After reacting with f (0.2 mol), the mixture was mixed with 50 f of water to prepare a flake-forming liquid. This solution was applied to a slide glass in the same manner as in Example 1, and then heated in a microwave for 5 minutes.
It was dried for 2 minutes at 00W to obtain a thin section. As a result, the flaking rate was 100%. The obtained flakes were fired at 500°C for 80 minutes to obtain ZrOx flakes. The thin piece has a thickness of 0.8μ
The size was 50μ.

Claims (1)

[Scope of Claims] 1) A method for producing a flaky metal oxide, which comprises applying an aqueous solution of a metal compound onto a smooth surface, heating and drying the coating film, peeling it off from the smooth surface, and firing. 2) A patent claim characterized in that the metal compound is one or more selected from metal halides, metal acid halides, alkoxy metal halides, acyloxy metal halides, and condensates thereof. A method for producing a flaky metal oxide according to Scope 1. 3) As the metal of the metal compound, silicon, aluminum,
3. The method for producing a flaky metal oxide according to claim 2, characterized in that one or more selected from the group consisting of titanium, tin, indium, and zirconium are used. 4) The method for producing a flaky metal oxide according to claim 2, wherein the halogen is chlorine.