JPS62247834A - Production of flaked substance - Google Patents

Abstract

PURPOSE:To enhance the controllability of the thickness of the flake by coating a liq. metallic compd., etc., on a substrate having a smooth surface, regulating the thickness of the coated film to form a thin film, curing the thin film into a thin film substance, and then releasing the substance. CONSTITUTION:The raw liq. selected from a liq. metallic compd., a soln. of a metallic compd., and a sol of a metallic compd. is coated on a traveling substrate having a smooth surface, and then the thickness of the coated film is regulated to form a thin film. The thin film is then cured to form a flaky substance, which is released from the substrate to form the flaky substance. A roll, a sheet, a film, etc., can be used as the smooth substrate. Besides, the thickness of the coated film can be controlled by an air knife, a bar coater, a doctor blade, a torturing roll, a doctor roll. etc.

Description

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

More specifically, flaky metal compounds used as pigments, lubricants, and gloss improvers for paints and cosmetics, fillers for plastics, and raw materials for producing ceramics and inorganic crystals, such as flaky titanium oxide, flaky alumina, and flaky silica. Relating to a manufacturing method.

<Prior art> As a method for producing flakes, firstly, a titanium compound is applied to a smooth base material to form a film, and the base material is melted or crushed to form flakes (Japanese Patent Publication No. 30-4781). Publication No.)
It has been known.

The second method is to apply a solution of titanium alkoxide or titanium tetrachloride in an organic solvent to a smooth surface, and then crack the resulting film by the action of water vapor to obtain flakes (U.S. Patent No. 2,
94L895 and 3,071,482) have also been proposed.

Thirdly, 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. 45-642).
．． Publication No. 1).

Fourthly, drum flakers for producing resin flakes have been known.

This involves using a wooden roll to pump up the molten polymer from a undiluted solution hunt at the bottom of the roll, cooling the polymer on the roll by passing cooling water through the inside of the roll, and scraping it off with a scraper or the like.

<Problems to be Solved by the Invention> However, these methods have drawbacks, particularly in terms of controllability of the thickness of the flakes and productivity.

That is, in the first method mentioned above, it is necessary to melt the base material, the operation is complicated, and it is difficult to obtain a uniform size, and it is extremely difficult to make the size uniform. There were drawbacks.

The second and third methods involve manufacturing flaky inorganic materials in batches using glass plates or sheets of limited size, but this method is difficult to manufacture uniformly in large quantities. not enough.

In the fourth method, once the viscosity of the liquid is determined, the thickness of the flakes is determined by the speed of the rolls, so it is difficult to control the production amount separately from the thickness of the flakes. There's a problem.

That is, as the circumferential speed of the roll increases, the amount of liquid pumped up increases, and the thickness of the flakes increases.

For this reason, when it is desired to produce thin flakes, productivity is extremely reduced.

That is, an object of the present invention is to provide a method for producing a flaky inorganic material that is superior in controllability of flake thickness and mass production as compared to conventionally proposed production methods.

Means for Solving Problems> The present invention involves applying a stock solution selected from a liquid metal compound, a metal compound solution, and a metal compound sol onto a substrate having a smooth surface on which the coating is applied. The present invention provides a method for producing a flaky substance, which comprises controlling the thickness of the film to form a thin film, then solidifying the thin film to form a flaky substance, and peeling the flaky substance from the base material. be.

The present invention will be described in further detail below.

The stock solution used in the present invention is selected from a metal compound that is liquid itself, a solution of a metal compound dissolved in an appropriate solvent, and a metal compound sol.

For details, refer to the general formula MXnOm (where M is a metal element,
is one or more selected from an alkyl group, an alkoxy group, an acyloxy group, a hydroxyl group, or a halogen, 0 is oxygen, n and m are integers, and n1,2m is the valence of the metal element.

) or these polymers themselves or their solutions, and the other is a sol of metal oxides, metal hydroxides, metal sulfides, metal sulfates, organometallic polymers, etc.= 41 The metal of the metal compound of the present invention includes a divalent or higher valent metal,
Preferably, metals belonging to groups ma, IVa, or TVb of the periodic table are used, and more specifically, one or more metals selected from aluminum, silicon, titanium, zirconium, and tin are used.

The alkyl group of the metal compound of the present invention includes a methyl group,
Ethyl, butyl, pentyl, lauryl, etc. Alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, etc. Acyloxy groups include acetoxy, propionyloxy, butyryloxy, etc. Can be mentioned.

Such metal compounds include monoethyljethoxyaluminum, monomethyldibutoxyaluminum, monoethyljethoxyaluminum, dimethylmonomethoxyaluminum, diisopropylmonoethoxyaluminum, dimethylmonisopropoxyaluminum, diethylmonobentoxyaluminum pentate, etc. Alkoxyaluminums, trialkoxyaluminums such as trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, tripentoxyaluminum, monochlorodiacetoxyaluminum, monochlorodiisopropoxyaluminum, monochlordiacetoxyaluminum, dichloromono Alkoxyaluminum halides such as methoxyaluminum, dichloromonobutoxyaluminum, dibromomonomethoxyaluminum, aluminum halides such as aluminum trichloride, aluminum tribromide, monochlorodiethylaluminum, monochlorodiisopropylaluminum, monochlorodibutylaluminum, monochlorodiethyl Aluminum, monobromodimethylaluminum, monoiododiethylaluminum,
Alkylaluminum halides such as dichloromonoethylaluminum, dichloromonobutylaluminum, dichloromonoethylaluminum, etc., monobutyldiacetoxyaluminum, monomethyldipropionyloxyaluminum, monoisopropyldibutyryloxyaluminum, dimethylmonoacetoxyaluminum, dimethylmonopropionyloxy Alkylacyloxyaluminums such as aluminum, triacetoxyaluminums such as triacetoxyaluminum, tripropionyloxyaluminum, tributyrylochydialuminum, tripentanoyloxyaluminum, monochlorodiacetoxyaluminum, monobromodiacetoxyaluminum, dichloromonoiso Halogenated acyloxyaluminums such as propionyloxyaluminum and dibromomonoacetoxyaluminum, =7-alkoxy such as monomethoxydiacetoxyaluminum, monoethoxydipropionyloxyaluminum, dibutoxymonoacetoxyaluminum, and jetoxymonobutyryloxyaluminum Acyloxyaluminums, monomethyltrimethoxysilane, monobutyltrimethoxysilane, monomethyltriethoxysilane, monoethyltripentoxysilane, diethyldimethoxysilane, diisopropyljethoxysilane, tributylmonomethoxysilane, triethylmonopethoxysilane, Alkylalkoxysilanes such as isopropylmonoethoxysilane and triethylmonopentoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetrapentoxysilane; monochlorotrimethoxysilane; monocloxysilane,
Halogenated alkoxysilanes such as dichlorodibutoxysilane, diethyldimethoxysilane, trichloromonomethoxysilane, trichloromonopentoxysilane, tribromomonomethoxysilane, silicon halides such as silicon tetrachloride and silicon tetrabromide, monochlorotrimethyl halogenated alkylsilanes such as silane, monochlorotribentylsilane, monobromotrimedelsilane, monoiodotriethylsilane, dichlorodimethylsilane, dichlorodipentylsilane, trichloromonoethylsilane, trichloromonoisopropylsilane, tribromomonomethylsilane, Monomethyltriacetoxysilane, monomethyltripropionyloxysilane, monoisopropyltributyryloxysilane, diethyldiacetoxysilane, diethyldiprobionyloxysilane, trimethylmonoacetoxysilane, tributylmonacetoxysilane, triethylmonobutyryloxysilane, etc. Alkylacyloxysilanes, tetraacyloxysilanes such as tetraacetoxysilane, tetrapropionyloxysilane, tetrabutyryloxysilane, tetrapentanoyloxysilane, lyacetoxysilane, dichlorodiacetoxysilane, trichloromonoacetoxysilane, tribrome Halogenated acyloxysilanes such as monoacetoxysilane, monobutoxytriacetoxysilane, monoethoxytriprobionyloxysilane, monoisopropoxytributyryloxysilane, jetoxydiacetoxysilane,
Alkoxyacyloxysilanes such as diisoproboxydibutyrylogisilane, tributoxymonoacetoxysilane, monomethyltrimethoxytitanium, methyltrimethoxytitanium, monomethyltriacetoxytitanium, monoethyltribenxytitanium, diethyldimethoxytitanium , diisopropyljethoxytitanium, tributylmonoathoxytitanium, trimethylmonoethoxytitaniumsopropylmonoethoxytitanium, triethylmonobenoxytitanium, and other alkylalkoxytitaniums, tetrabutoxytitanium, tetraethoxytitanium, te1-lysoproboxytitanium, Tetraalkoxytitaniums such as tetrabutoxytitanium and tetrapentoxytitanium, monochlorotrimethoxytitanium, monochlorotriatoxytitanium, monobromotrimethoxytitanium, dichlorodibutoxytitanium, diiododiethoxytitanium=11-ram, trichloromono Halogenated acyloxytitaniums such as methoxytitanium, trichloromonopentoxytitanium, and tribromomonoatomoxytitanium, halogenated titaniums such as titanium tetrachloride and titanium tetrabromide, monochlorotrimethyltitanium, monochloro1-lipentyltitanium, monobromotrimethyltitanium,
Alkyl titanium halides such as monoiodotriethyl titanium, dichlorodimethyltitanium, dichlordimethyltitanium, trichlormonoethyltitanium, trichlormonoisopropyltitanium, tribromomonomethylticunilla 11, monomethyltriacetoxytitanium, monomethyltripropionyloxytitanium, Alkylacyloxytitaniums such as monoisopropyltributyryloxytitanium, diethyldiacetoxytitanium, diethyldipropionyloxytitanium, trimethylmonoacetoxytitanium, tributylmonoacetoxytitanium, triethylmonobutyryloxytitanium, tetraacetoxytitanium, tetrapropionyloxy Titanium, tetraacyloxytitaniums such as tetrabutyryloxytitanium, tetrapentanoyloxytitanium, monochlorotriacetoxytitanium, monochlorotributyryloxytitanium, monobromotriacetoxytitanium, dichlordiacetoxytitanium, trichlormonoacetoxytitanium, trichlorotriacetoxytitanium Halogenated acyloxytitaniums such as bromomonoacetoxytitanium, monobutoxytriacetoxytitanium, monoethoxytripropionyloxytitanium, monoisoprobogycitributyryloxytitanium, diethoxydiacetoxytitanium, diisopropoxydibutyryloxytitanium, and tripyryloxytitanium. Alkoxyacyloxytitaniums such as toxymonoacetoxytitanium, monomethyltrimethoxyzirconium, monobutyltrimethoxyzirconium, monomethyltriethoxyzirconium, monoethyltripentoxyzirconium, diethyldimethoxyzirconium, diisopropyljethoxyzirconium, tributylmonomethoxyzirconium, 1 - Alkylalkoxyzirconiums such as trimethylmonoethoxyzirconium, triisopropylmonoethoxyzirconium, and triethylmonobentoxyzirconium; tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxydidizirconium, tetrabutoxyzirconium, and tetrapentoxyzirconium; Alkoxy zirconiums, halogenated alkoxy such as monochlorotrimethoxyzirconium, monochlorotributoxyzirconium, monobromotrimethoxyzirconium, dichlordibutoxyzirconium, diethyldimethoxyzirconium, trichlormonomethoxyzirconium, trichlormonopentoxyzirconium, tribromomonomethoxyzirconium, etc. Zirconiums, halogenated zirconiums such as zirconium tetrachloride, zirconium tetrabromide, monochlorotrimethylzirconium, monochlorotripentylzirconium, monobromotrimethylzirconium, monoiodotriethylzirconium, dichlordimethylzirconium, dichlordimethylzirconium,
Halogenated alkylzirconiums such as trichlormonoethylzirconium, trichlormonoisopropylzirconium, tribromomonomethylzirconium, monomethyltriacetoxyzirconium, monomethyltripropionyloxyzirconium, monoisopropyltributyryloxyzirconium, diethyldiacetoxyzirconium, diethyldiacetoxyzirconium, etc. Alkylalkoxyzirconiums such as propionyloxyzirconium, trimethylmonoacetoxyzirconium, tributylmonoacetoxyzirconium, triethylmonobutyryloxyzirconium, tetraacetoxyzirconium, tetrapropionyloxyzirconium, tetrabutyryloxyzirconium, tetrapentanoyloxyzirconium, etc. Acyloxyzirconiums, halogenated acyloxyzirconiums such as monochlorotriacetoxyzirconium, monochlorotributyryloxyzirconium, monobromotriacetoxyzirconium, dichlordiacetoxyzirconium, trichlormonoacetoxyzirconium, tribromomonoacetoxyzirconium, monobutoxyzirconium, etc. Alkoxyacyloxyzirconiums such as acetoxyzirconium, monoethoxytripropionyloxyzirconium, monoisopropoxytributyryloxyzirconium, jetoxydiacetoxyzirconium, diisopropoxydibutyryloxyzirconium, tributoxymonoacetoxyzirconium, monomethyltrimethoxytin , monobutyltrimethoxytin, monomethyltriethoxytin, monoethyltripentoxytin, diethyldimethoxytin, diisopropyljethoxytin, tributylmonomethoxytin, trimethylmonoethoxytin, triisopropylmonoethoxytin, triethylmonopentoxytin, etc. alkylalkoxytins, tetramethoxytins, tetraethoxytins, tetraalkoxytins such as tetraisopropoxytin, tetrabutoxytin, tetrapentoxytin, monochlorotrimethoxytin, monochlor 1-ributoxytin, monobromotrimethoxytin, Alkoxytin halides such as dichlordibutoxytin, diiothodiethoxytin, trichlormonomethoxytin, l-lichlormonobentoxytin, tribromomonomethoxytin, halogenation of tin tetrachloride, tin tetrabromide, etc. Halogenation of tins, monochlorotrimethyltin, monochlorotripentyltin, monobromotrimethyltin, monoiodotriethyltin, dichlordimethyltin, dichlordimethyltin, trichlormonoethyltin, trichlormonoisopropyltin, tribromomonomethyltin, etc. Alkyltins, monomethyltriacetoxytin, monomethyltripropionyloxytin, monoisopropyltributyryloxytin, diethyldiacetoxytin, diethyldibrobionyloxytin, trimethylmonoacetoxytin, tributoxymonoacetoxytin, triethylmonobutyryloxytin Alkylacyloxytins such as tin, Te!・Tetraacyloxytins such as triacetoxytin, tetrapropionyloxytin, tetrabutyryloxytin, te1-raventanoyloxytin, monochlorotriacetoxytin, monochlor]・ributyryloxytin, monobromtri Acyloxytin halides such as acetoxytin, dichlordiacetoxytin, I-lichlormonoacetoxytin, tribromomonoacetoxytin, monobutoxytriacetoxytin, monoethoxytripropionyloxytin, monoisopropoxytributyryloxytin, Examples include alkoxyacyloxytins such as jetoxydiacetoxytin, diisopropoxydibutyryloxytin, tributoxymonoacetoxytin, and mixtures thereof.

Further, polymers of these metal compounds can be obtained by reacting metal compounds with water or carboxylic acid.

At this time, hydrochloric acid, sulfuric acid, caustic soda, ammonia, etc. may be used as a catalyst if necessary.

Examples of polymers include polyethoxyaluminoxane,
Poly(acetoxy-butoxy)siloxane, polyisopropoxytitanoxane, poly(butyl-ethoxy)
Examples include polymetalloxanes such as zirconoxane and poly(octyl-chlor)stanoxane.

Such metal compounds or polymers are liquid or solid at room temperature.

When used, it must be in liquid form, so if it is solid, it can be melted by heating or dissolved in an appropriate medium.

Furthermore, even if it is liquid at room temperature, it may be used by dissolving it in a solvent to adjust the concentration appropriately.

The solvent used varies depending on the type of metal compound, but
Water, alcohols such as methanol and ethanol, aliphatic hydrocarbons such as hexane, decane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, and mixtures thereof can be suitably used.

The concentration of the metal compound in the stock solution consisting of the metal compound solution varies depending on the type of metal compound and is not particularly limited, but if it is too dilute, a large amount of solvent will be dispersed, which is not economical.

On the other hand, if it is too concentrated, workability may decrease, so
It is generally used in an amount of about 2 to 80% by weight.

Regarding the metal compound sol, the metal compound forming the sol may be any compound that forms a sol in a suitable dispersion medium, such as metal oxides, metal hydroxides, metal sulfides, or metal chlorides. , metal salts such as metal sulfates, organometallic polymers, and the like.

The metal of the metal compound of the present invention includes a divalent or higher valent metal,
Preferably, metals belonging to the ma, rVa, or TVb groups of the periodic table are used, and more preferably one or more metals selected from aluminum, silicon, titanium, zirconium, and tin are used.

Specifically, polymers such as alumina, aluminum hydroxide, aluminum sulfide, aluminum chloride, aluminum oxychloride, basic aluminum chloride, polyaluminum chloride, aluminum sulfate, aluminum acetate, aluminum oxalate, and aluminum isopropoxide. Aluminum compounds such as polymers of aluminum alkoxides, polymers of aluminum alkyls such as polymers of triethylaluminum, polymers of alkoxysilanes such as polymers of silica, silicon oxychloride, silicon acetate, silicon oxalate, and tetraethylsilicate, silicon compounds such as polymers of alkylchlorosilanes such as polymers of dimethyldichlorosilane; polymers of titania, titanium hydroxide, titanium sulfide, titanium oxychloride, titanium sulfate, titanium acetate, titanium oxalate, and titanium isopropoxide; Polymers of titanium alkoxides such as, titanium compounds such as titanium acetylacetonate, polymers of zirconium oxide, zirconium hydroxide, zirconium sulfide, zirconium oxychloride, zirconium sulfate, zirconium acetate, zirconium oxalate, and zirconium isopropoxide. Zirconium alkoxide polymers, zirconium compounds such as zirconium acetylacetonate, tin oxide, tin hydroxide,
Polymers of tin alkoxides such as tin sulfide, tin chloride, tin oxychloride, basic tin chloride, tin sulfate, tin acetate, tin oxalate, polymers of tin isopropoxide, polymers of monophthyl trib and tin oxytin tin compounds such as alkylalkoxytin polymers,
etc.

Such metal compounds are liquid or solid at room temperature.

Since it must be a liquid sol when used, it is dispersed in a suitable dispersion medium such as water or an organic solvent.

The dispersion medium used varies depending on the type of metal compound, but water, alcohols such as methanol and ethanol, aliphatic hydrocarbons such as hexane, decane and cyclohexane,
Aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, and mixtures thereof can be suitably used.

The concentration of the metal compound sol varies depending on the type of metal compound and is not particularly limited, but if it is too dilute, a large amount of dispersion medium will be volatilized, which is not economical.

On the other hand, if it is too concentrated, workability may decrease, so
It is generally used in an amount of about 2 to 50% by weight.

Examples of aqueous commercially available sols include, for example, silica sol such as Ludox I (S-40 manufactured by DuPont), and alumina sol available under the trade name Alumina Sol 100 manufactured by Nissan Chemical Industries.

As an organic solvent dispersion system, methanol silica sol manufactured by Nissan Chemical Industries, Ltd. (trade name) is known.

As a method for preparing these sols, for example, silica
- When preparing helica sol, there are known methods such as making it from water glass by ion exchange, neutralizing water glass with acid, electrodialyzing water glass, and hydrolyzing ethyl silicate. There is.

In addition, when preparing an alumina sol, a method is well known in which a hydrolyzable compound such as aluminum acetate is hydrolyzed by means such as heating to form a sol. (Science of new industrial materials, silica and alumina (colloidal products), pp. 5-127. Chemical Handbook Applied Edition (revised 3rd edition), p. 132, edited by L1 Chemical Society).

If a more specific sol is desired, it can also be prepared by a known method described in the above-mentioned literature.

It is also effective to add a suitable pH adjuster, such as household hydrochloric acid or caustic soda, to stabilize the sol.

Furthermore, to make the thickness of the coating film uniform, these stock solutions are added with polymeric substances such as polyols and ethyl cellulose, high boiling point organic substances such as butyl cellosolve and glycerin, nonionic and anionic surfactants, etc. You can also do that.

! Alternatively, a known coloring agent consisting of a compound such as tL Ninogel, vanadium, chromium, or manganese may be added.

Specifically, the smooth base material referred to in the present invention preferably has a shape suitable for continuous production of rolls, belts, sheets, films, and the like.

There is no strict distinction between healds, sheets, and films, but they are classified into healds, sheets, and films in descending order of thickness.

A film with a thickness of 1 mm or less is usually called a film.

The material of the base material for rolls is usually a metal material.

When the stock solution used is strongly acidic and highly corrosive, the metal is coated with glass or polymer material, or a roll made of ceramic or polymer is used.

The belt uses a metal material or a polymer material.

For sheets and films, polymeric materials are used, especially polyester, polyamide, polyimide, polypropylene, etc.

When the base material is a soft Heald, C.I., film such as a polymeric material, it is stretched when running, so it must have strength to withstand the tension.

Furthermore, during the formation of the coating film, it is necessary to support the substrate with a device that holds it smooth, such as a backing roll.

To run on a smooth surface, rolls can be rotated, healds, sheets, and films can be circulated in an endless format with both ends connected, or a large number of rolls can be unrolled and run one after another. Adopted.

As the method and device for applying the undiluted solution to the smooth surface on which the vehicle is traveling, various well-known coating methods, coating methods, and devices used therefor can be used.

For example, there are methods such as a spray method, a brush method, and a method in which a strip of liquid is poured from a slit and placed on a smooth surface.

In addition, there is a method in which a running smooth surface, that is, a rotating roll surface, a running belt, sheet, or film is immersed in the stock solution contained in a container such as a hat.

In this case, if the running linear speed is high, the coating film will be thin, and if the linear velocity is low, the coating film will be thick.

This relationship between thickness and linear velocity may be determined in advance through a preliminary test.

In either method, a coating film is formed that is thicker than the thickness necessary for the flaky material of a predetermined thickness to be finally obtained.

Next, the excess coating film thickness is adjusted to the thickness of the liquid film commensurate with the predetermined thickness of the flaky material to be finally obtained.

This thickness adjustment method also uses methods and equipment that are part of well-known coating methods.

For example, there is a method of scraping off the excess using an air knife, bar coater, doctor blade, metering roll, doctor roll, etc.

The material of the bar coater, doctor blade, metering roll, doctor roll, etc. should preferably be one that has corrosion resistance against the stock solution, although it varies depending on the stock solution used.
Examples include ceramic materials such as glass and enamel, metal materials such as stainless steel and aluminum, and polymeric materials such as polyester and nylon.

The thickness of the liquid film itself can be determined by determining the relationship between the thickness of the liquid film and the final thickness of the flaky material in a preliminary test, and then setting the thickness of the liquid film each time based on the thickness of the flaky material required. good.

Note that it is also possible to perform a method in which pumping up the undiluted solution contained in a container such as a Hunt and forming a liquid film with an adjusted thickness in separate containers or locations.

For example, a roll is immersed in a container containing an undiluted solution and rotated to draw up the undiluted solution, and this is transferred as it is or one or more rolls in combination one after another.
It can also be applied by transfer to the last running smooth surface.

As the smooth base material travels, the liquid film formed on the smooth base material is moved to another location, and then solidified.

This solidification process is performed when the liquid film is a liquid metal compound.
This process involves thermal decomposition, calohydrolysis, oxidative decomposition, and condensation.

When the liquid film is a solution of a metal compound, the solvent is first volatilized and then subjected to thermal decomposition, hydrolysis, oxidative decomposition, etc. as described above.
This is a process of condensation.

In the case of a metal compound sol, the dispersion medium is first volatilized to form a gel. Then, if necessary, thermal decomposition, hydrolysis, oxidative decomposition, and condensation are performed.

Heating is used for these treatments.

It is preferable to perform this heating slowly so as not to form bubbles in the thin film.

As a specific method, the base material itself may be preheated, or if the base material is in the form of a roll, the roll may be heated by passing a heat medium through the inside of the roll.

Alternatively, a heating section may be provided and the liquid film of the stock solution may be directly heated using heated air, an electric or infrared heater, high frequency, or the like.

When the base material is in the form of a belt or film, the length of the heating section can be set arbitrarily, so that the solvent can be efficiently removed using heated air or the like.

Although the heating temperature cannot be determined unconditionally depending on the volatility of the solvent to be removed, generally room temperature to about 250°C is appropriate.

For example, in the case of a highly volatile solvent, it is sufficient to simply spray a gas at room temperature.

Hydrolysis, oxidative decomposition, and condensation proceed even with moisture and oxygen present in the air, but if necessary, water or steam may be added or an acid or alkali accelerator may be used.

Specifically, water vapor-containing gas (e.g., air), acid-containing gas, ammonia-containing gas,
It is brought into contact with water, an acid-containing solvent, etc. at room temperature to about 100°C.

The concentration of the gelling agent such as water, acid, alkali, etc. is adjusted as appropriate depending on the type of metal compound used, the target reaction rate, etc.

Compounds that solidify through thermal decomposition include metal alkoxides, and condensation occurs upon heating.

Examples of hydrolysis include metal chlorides and metal alkoxides that react with water and condense, and acids, alkalis, etc. may be added as catalysts.

Further, as an example of solidification with an acid or an alkali, there are metal compounds such as alkyl silicate that undergo condensation in the presence of a carboxylic acid.

Solidification causes the thin film to shrink in volume, causing minute cracks in the film and turning it into flakes.

The flaky material formed on the base material can be peeled off from the base material by mechanically scraping with a scraper, etc., by using ultrasonic waves, or by bending the base material if it is flexible. For example, a method of peeling it off by letting it peel off.

The thin flakes of the metal compound produced in the above manner are transparent and have high gloss, so they can be used as they are, but depending on the purpose, they can be heated to about 200 to 1100°C, preferably 500°C.
The product is calcined at a temperature of ~900°C.

This calcination mainly turns the metal compound into an oxide.

Further, the flaky inorganic material produced by the present invention has a thickness of about 0.
01 to 10 μm in length, but it is pulverized as appropriate depending on the purpose of use, and is generally used in a size of about 1 to 100 μm in length.

<Effects of the Invention> As described in detail below, according to the method of the present invention, a flake of any thickness can be formed by using a moving smooth surface and adjusting the thickness of the film of the stock solution of the metal compound on the surface. It is possible to mass produce.

The flaky inorganic substance obtained by the method of the present invention can be used as a gloss pigment for nail polish enamel leather products, for automotive exterior metal painting, pearlescent buttons cast from unsaturated polyester resin, pigments for cosmetics, fillers for plastics for food packaging, etc. It can be effectively applied to pearlescent pigments or extender pigments, raw material powders and catalyst carriers for manufacturing ceramic products such as transparent tubes for sodium lamps and condenser porcelain.

<Examples> 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.

Example 1 A homogeneous solution was prepared by dissolving 3 moles (1149 g) of zirconium tetrabutoxide and 2540 g of n-hexane, which was used as a stock solution.

I put this in the bat.

Free roll with a diameter of 30cm (non-driven free rotating roll)
A 33 cm wide polyvarnish film was passed over the top, which was run at a speed of 80 m/min by a separate drive.

A roll passed through this polyester film was immersed in this liquid at room temperature.

Next, nitrogen gas was jetted out at a linear velocity of 2 m/sec through a 1 mm wide slit placed close to the polyester film to which the stock solution had adhered, and was applied to the liquid film on the polyester film to evaporate the stock solution. The part was blown away.

The polyester film with the liquid film thickness adjusted in this way was passed horizontally through a 4 m long drying chamber in which nitrogen gas at 120°C was flowing down from above the film at a flow rate of 1 m/sec. A gelled film of zirconium tetrabutoxide was formed.

Furthermore, this polyester film was heated to a length of 4 m at 120°C.
The gel was passed horizontally through a chamber controlled to have a nitrogen gas atmosphere, where the zirconium tetrabutoxide polymer gel contracted in volume with the scattering of the dispersion medium and became minute flakes.

After the polyester film with the flakes attached thereto is once wound up, the film is immersed in an ultrasonic trichlene tank having a length of 1 m while being unwound to separate the flakes and the polyester film.

The peeled flakes were collected from the trichlene using a filter.

The polyester film is rolled up and reused.

The thus obtained flakes were fired at 750°C to obtain flaky zirconia having a thickness of 0.8 μm.

The production amount is 8kg/zirconia per 1m of roll width.
It was time.

Example 2 10 moles (2460 g) of tributoxyaluminum and 3020 g of butanol were mixed and dissolved, and 40 moles (900 g) of water were added thereto and reacted to produce a butanol sol of aluminum hydroxide, which was used as a stock solution.

Pump this into a nozzle with a gap of 1 mm and a width of 20 cm.
The liquid was fed at a rate of kg/hour.

With a gap of about Q, 5mm from the tip of the nozzle, a diameter of 40mm.
10 cm outside the free roll by a separate drive
A polyester film 50 cm wide and 3000 m long running at 0 m/min was passed through.

As a result, the stock solution becomes a thin film and is transferred onto the polyester film.

A roll (metering roll) rotating in the same direction at 8 m/min was installed close to the roll, and the thickness of the liquid film on the polyester film was adjusted to 8 turns.

This polyester film was coated with nitrogen at 100°C at a flow rate of 1
It was passed horizontally through a drying chamber with a length of 8 m flowing at m/s.

This removes the butanol from the stock solution, causing volumetric shrinkage and cracking, forming tin oxide flakes on the polyester film.

The polyester film with the flakes attached thereto was introduced into a 2 m long ultrasonic tri-clean tank to separate the flakes and the polyester film.

The peeled flakes were collected from the trichlene using a filter.

The polyester film is rolled up and reused.

The obtained flakes were fired at 1200°C and the size was 5-40.
A flaky alumina having a thickness of 1.5 μm was obtained.

The production amount of alumina per meter of polyester film width was 12 kg/hour.

Example 3 Tetraethyl orthosilicate was used as a stock solution.

This is pumped through a nozzle with a width of 20 cm and a gap of 1 mm to approx.
．． The liquid was fed at a rate of 8 kg/hour.

A diameter 8 mm heated to 130°C from the inside rotating at a circumferential speed of 3 m/min with a gap of approximately 0.5 mm from the tip of the nozzle.
A stainless steel roll with a diameter of 0 cm and a width of 20 cm was installed.

As a result, the stock solution was transferred onto the roll.

Air was blown out through a slit placed close to the roll and hit the liquid film on the roll to blow off a portion of the stock solution.

The thickness of the liquid film remaining on the roll was adjusted by adjusting the blowing line speed at this time.

Air at a temperature of 150° C. was allowed to flow against this liquid film portion at a flow rate of 1 m/sec.

This removed the water in the stock solution, causing volumetric shrinkage and cracking, resulting in silica flakes on the roll.

This flake was scraped off with a Swedish steel scraper.

The obtained flakes were fired at 900℃ and the size was 8-15μ.
, flaky silica with a thickness of 3 μm was obtained.

The production amount is 0.5 kg of silica per meter of roll width.
It was time.

Example 4 10 moles (2605 g) of tin tetrachloride were dissolved in 20 kg of water, and a solution of 40 moles (1600 g) of caustic soda dissolved in 10 kg of water was added dropwise to form a tin oxide sol. It was prepared and used as a stock solution.

Use a pump to apply this to a nozzle with a gap of 1 mm and a width of 20 cm.
．． The liquid was fed at a rate of 8 kg/hour.

A diameter 8 mm heated to 130°C from the inside rotating at a circumferential speed of 3 m/min with a gap of approximately 0.5 mm from the tip of the nozzle.
A stainless steel roll with a diameter of 0 cm and a width of 20 cm was installed.

As a result, the stock solution was transferred onto the roll.

Air was blown out from a slit installed close to the roll, and was applied to the liquid film on the roll to blow off a portion of the stock solution.

The thickness of the liquid film remaining on the roll was adjusted by adjusting the blowing line speed at this time.

Air at a temperature of 150°C flows at a flow rate of 1 m on the roll with this liquid film.
/ seconds.

This removed the water in the stock solution, causing volumetric shrinkage and cracking, resulting in tin oxide flakes on the roll.

The flakes were sown with a Sweden II scraper.

The obtained flakes were fired at 900°C and the size was 8-15.
A flaky tin oxide with a thickness of 3 μm was obtained.

The production amount is 1.2 kg of tin oxide per 1 m of roll width.
/ It was time.

Example 5 5 moles (2254 g) of mono-thousand tributoxytin were dissolved in 2750 g of toluene to prepare a stock solution.

This was placed in a hunt, and a roll (first roll) with a diameter of 10 cm and a width of 20 cm was immersed in this liquid at room temperature.
It was rotated at a circumferential speed of 1 minute.

Above this roll, a stainless steel endless belt with a width of 3 Q cm was brought into slight contact, running in the same direction at a circumferential speed of 20 m/min.

As a result, the stock solution on the first roll was stretched thin and transferred onto a stainless steel endless belt, and a bar coater with a gap of 100 μm was pressed against this endless heddle to adjust the thickness of the liquid film. .

The stainless steel endless heald whose thickness has been adjusted is passed horizontally through a 2 m long drying chamber which is heated with hot air at 150°C and into which siliceous steam is blown.

This removes toluene from the stock solution, and at the same time hydrolysis occurs, causing volumetric contraction and cracking.

As a result, a film of a compound mainly composed of poly(octylbutoxy)stanoxane solidified on the endless heald, contracted in volume, and became microscopic flakes.

This thin piece was scraped off with a scraper made of Econol resin, and the thin piece was separated using an endless heddle made of stainless steel.

The obtained flakes were calcined at 900 c to give size 3-15
A flaky tin oxide with a thickness of 3 μm was obtained.

=43= The production amount was 4 kg/hour as tin oxide per 1 m of roll width.

Example 6 286g of 1 mol (114g) of triethylaluminum
to tetrahydrofuran? The mixture was dissolved and reacted with 2 moles (120 g) of isopropanol to synthesize monoethyldiisopropoxyaluminum.

Furthermore, 0.25 mol (50 g) of lauric acid was reacted,
It was used as a stock solution.

This was placed in a vat, and a roll (first roll) with a diameter of 1Qcm and a width of 6Qcm was immersed in this liquid at room temperature.
It was rotated at a circumferential speed of 1 minute.

A stainless steel roll (second roll) with a diameter of 50 cm and a width of 20 cm heated to 130°C from the inside rotating in the same direction at a circumferential speed of 40 m/min was placed on three sides of this roll, and the roll gap was adjusted to 100 μ. It was installed.

As a result, the stock solution was transferred onto the second roll.

A bar coater with a gap of 75 μm was pressed against this second roll to adjust the thickness of the liquid film on the second roll.

This liquid film portion was coated with 15% water vapor on the second roll.
Nitrogen at 0°C was flowed at a flow rate of 1 m/sec.

This removed the tetrahydrofuran in the stock solution, and at the same time hydrolysis occurred, resulting in volumetric shrinkage and cracking, resulting in flakes of a polyaluminoxane-based compound on the second roll.

This flake was scraped off with a Swedish steel scraper.

The obtained flakes were fired at 900°C and the size was 5-25μ.
, flaky alumina with a thickness of 1 μm was obtained.

The production amount is 3.2 kg of alumina per 1 m of roll width.
/ It was time.

Example 7 Alumina sol (Alumina Sol 100, manufactured by Nichichi Kagaku Kogyo ■) was diluted with water so that the alumina concentration was 3%, and a stock solution was prepared.

This was placed in a vat, and a first roll having a diameter of 10 cm was immersed therein, and rotated at a circumferential speed of 20 m/min.

A rubber roll (second roll) having a diameter of 15 cm and rotating in the same direction at 20 m/min was placed above this roll so that it was almost in contact with the roll.

As a result, the stock solution was transferred onto the second roll.

Next, this second roll is run at a speed of 7 m/min with a width of 30 cm.
It was placed in slight contact with a stainless steel endless belt.

As a result, the stock solution on the second roll was stretched thin and transferred onto the stainless steel endless belt.

Next, air was blown out from a slit placed close to the stainless steel endless belt coated with the stock solution, and the air was blown against the liquid film on the roll to blow off a portion of the stock solution.

The thickness of the liquid film remaining on the roll was adjusted by adjusting the blowing line speed at this time.

Furthermore, it is passed horizontally through a 2 m long drying chamber heated to 150° C. by hot air.

Here, the water was removed and a film of alumina sol was formed on the stainless steel endless belt, which then contracted in volume and became a microfine flake.

The stainless steel endless belt with the flakes attached thereto was scraped off with a scraper made of Econol resin, and the flakes and the stainless steel endless belt were separated.

The flakes thus obtained were fired at 650° C. to obtain flaky alumina having a size of 8 to 50 μm and a thickness of about 2 μm.

The production amount is 1.2 kg of alumina per 1 m of roll width.
/ It was time.

148 completed

Claims (1)

[Claims] 1) A stock solution selected from a liquid metal compound, a metal compound solution, and a metal compound sol is once applied onto a base material having a smooth running surface, and then the thickness of the coating film is adjusted. 1. A method for producing a flaky substance, which comprises: forming a thin film, solidifying the thin film to form a flaky substance, and peeling the flaky substance from the base material. 2) The method for producing a flaky material according to claim 1, wherein the smooth base material is in the form of a roll, belt, sheet, or film. 3) The method for producing a flaky material according to claim 1, wherein the means for adjusting the thickness of the coating film is an air knife, a bar coater, a doctor blade, a metering roll, or a doctor roll.