JP2562875B2 - Manufacturing method of flaky material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a method for producing a flaky material. Various types of flaky substances have been conventionally known. For example,
Flaky titanium oxide, flaky alumina, etc. are mixed with paints and cosmetics to improve lubricity and gloss, or mixed with plastics as a filler to improve mechanical properties. It has a wide range of applications such as being used for purposes and as a raw material powder for ceramics and single crystals.

<Prior Art> As a method for manufacturing flakes, first, a method is used in which a titanium compound is attached to a smooth base material to form a film, and the base material is melted or crushed to form a flaky shape (Japanese Patent Publication No. Sho 30-4781). )It has been known.

Second, a method of applying titanium alkoxide or titanium tetrachloride in an organic solvent solution to a smooth surface and then cracking the film formed by the action of water vapor to obtain flakes (US Pat. No. 2,94,94).
Nos. 1,895 and 8,071,482 are also proposed.

Thirdly, a method of applying an organic solvent solution of a titanium compound to a high temperature heating substrate has also been proposed. (Japanese Patent Publication No. 45-6424
Issue).

Fourthly, a drum flaker for producing resin flakes has been conventionally known. This is a technique in which a single roll is used to pump up a polymer which is usually molten from a vat of undiluted solution at the bottom of the roll, cooling water is passed through the roll to cool the polymer on the roll, and the polymer is scraped 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 above-mentioned first method, it is necessary to dissolve the substrate, the operation is complicated, it is difficult to obtain a uniform size, and it is extremely difficult to make the sizes uniform. there were.

The second and third methods are batch-type methods for producing flaky inorganic materials using glass plates or sheets of limited size, and are not suitable as methods for producing a large quantity of uniform products.

In the fourth method, as will be described later, once the viscosity of the liquid is determined, the thickness of the flakes is determined by the speed of the roll, and therefore the production amount cannot be controlled separately from the thickness of the flakes. There is an essential problem. That is, as the peripheral speed of the roll increases, the amount of liquid pumped increases, and the thickness of the flakes becomes hot. For this reason, when it is desired to make thin slices, the productivity is extremely reduced.

An object of the present invention is to provide a method for producing a flaky inorganic substance which is excellent in controllability of the thickness of the flakes and mass productivity as compared with the conventionally proposed production methods.

<Means for Solving the Problem> The present invention regulates and supplies the liquid amount of a liquid onto a running smooth roll (hereinafter, sometimes referred to as a substrate) by using one or a plurality of rolls, Liquid metal compound on the substrate,
A controlled liquid film of a stock solution (hereinafter referred to as a stock solution) selected from a solution of a metal compound and a sol of a metal compound is formed, and then solidified to form a flaky material, and the flaky material is used as a base material. The present invention provides a method for producing a flaky material, which comprises further peeling.

 The present invention will be described in more detail below.

In the practice of the present invention, first, an undiluted solution was controlled on a substrate by using an apparatus capable of regulating and supplying a liquid amount of a liquid on a running smooth substrate and forming a liquid film of the liquid. As a method of forming a liquid film, a method of using an apparatus composed of one to a plurality of rolls can be mentioned.

In this method, put the stock solution in a container such as a vat,
While dipping the roll in the stock solution, rotate to pump the stock solution onto the roll. Then, the liquid film on the roll is transferred onto the running smooth base material. The amount of undiluted solution pumped up by the roll is determined by the peripheral speed of the roll. In the transfer to the base material, if the liquid amount is constant, the liquid film becomes thinner as the traveling linear velocity of the base material becomes higher, and the liquid film becomes thicker as the linear velocity becomes smaller.

It is known that these relationships are as shown in the following equation.

W = A · Vp ^m θ = K · Vp ^m / Vd where W is the pumping amount of the stock solution, V _p is the peripheral speed of the roll for pumping the stock solution, θ is the thickness of the liquid film, and Vd is the base material to be transferred. The traveling linear velocity, A, K, and m are constants.

V _p may be adjusted to an appropriate speed according to the production amount of flakes. It is usually in the range of about 1 to 100 m / min. Vd varies depending on the desired thickness of the slice and the production amount, and is usually 1 to 500 m.
The range is about / minute.

This method has good controllability of the film thickness, can easily obtain a thin piece of any thickness, has little variation in the thickness of the obtained thin piece, and controls the production amount by the speed of the roll that pumps the stock solution. It has a wide range of adjustment.

In this method, when the position of the roll for pumping the stock solution and the position of the moving smooth base material for transfer are apart, it is possible to place one or more rolls between the two and transfer the stock solution sequentially. is there.

In this case, the transfer amount can also be adjusted by adjusting the linear velocity and the gap between the rolls. Further, this makes it possible to transfer the liquid film more evenly onto the smooth base material.

As another method, there is a method in which an excessive amount of the stock solution is pumped up by a pumping roll, and then the excess liquid on the pumping roll is scraped off by a metering roll or the like to control the liquid amount and then transfer the liquid film onto the substrate. is there. Also in this case, a plurality of intermediate rolls having different peripheral speeds and one or a gap between the rolls may be installed between the first roll and the substrate. In this case, the amount of the stock solution supplied to the base material is determined by the rotation speed of the metering roll, the gap between the pumping roll and the like. Therefore, regarding the thickness of the liquid film on the base material, the liquid film becomes thinner as the linear velocity of the base material becomes higher, and the liquid film becomes thicker as the linear velocity becomes lower.

In this case, W cannot be simply expressed, but θ and Vd have an inversely proportional relationship, as in the above equation.

Since these methods have a method of controlling the liquid amount in addition to the peripheral speed of the roll, a wider adjustment is possible. Further, when the excess liquid is scraped off, the liquid film is smoothed.

Also in the case of this method, it is also possible to put a reverse roll between the pumping roll and the scraping portion, and between the scraping portion and the base material so as to transfer sequentially.

As another method, a gravure roll is used for the pumping roll or an intermediate roll from the pumping roll to the substrate, and the liquid amount is controlled by the density and depth of the gravure pattern, and then the liquid film is transferred onto the substrate. There is a way to do it.

In this case, if the volume of the concave portion of the gravure is D and the constant is C, then W = C · D · Vp θ = K · Vp / Vd.

In this method, since the amount of liquid is controlled by the depth of the density of the gravure pattern, there is an advantage that it is hardly affected by the viscosity of the liquid, the wettability between the roll and the liquid, and the like.

The material of the roll and the base material varies depending on the use conditions, but it is preferable that the material has corrosion resistance to the undiluted solution, and it also depends on the undiluted solution used. For example, ceramic materials such as glass and enamel, stainless steel, aluminum, and hard chrome plated steel Of metal material, polyester, nylon,
Polymer materials such as rubber may be used.

The material of the base material 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.

Any stock solution may be used as long as it forms a liquid film and becomes a thin piece by the subsequent solidification treatment.

The stock solution is selected from a metal compound which is itself liquid, a solution of the metal compound dissolved in a suitable solvent, and a metal compound sol.

Specifically, one is the general formula MXnOm (wherein M is a metal element, X is an alkyl group, an alkoxy group, an acyloxy group, a hydroxyl group or a halogen selected from 1
1 or 2 or more, O is oxygen, n and m are integers, and n + 2m is the valence of the metal element. ) Is a metal compound, a polymer itself or a solution thereof, and the other is a metal oxide, a metal hydroxide,
Examples of the sol include metal sulfides, metal nitrates, and organic metal polymers.

First, the general formula MXnOm (wherein M is a metal element, X is an alkyl group, an alkoxy group, an acyloxy group, a hydroxyl group or a halogen selected from 1
1 or 2 or more, O is oxygen, n and m are integers, and n + 2m is the valence of the metal element. ) The metal compound represented by or the polymer thereof will be described in more detail.

The metal of the above-mentioned metal compound is a metal having a valence of 2 or more, preferably a metal belonging to Group IIIa, IVa or IVb of the periodic table, and more preferably one or two selected from aluminum, silicon, titanium, zirconium and tin. The above metals are used.

Examples of the alkyl group of the metal compound of the present invention include a methyl group, an ethyl group, a butyl group, a pentyl group, a lauryl group and the like;
The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like; and the acyloxy group includes an acetoxy group, a propionyloxy group and a butyryloxy group.

Such metal compounds include monoethyldiethoxyaluminum, monomethyldibutoxyaluminum,
Monoethyldipentoxyaluminum, dimethylmonomethoxyaluminum, diisopropylmonoethoxyaluminum, dimethylmonoisopropoxyaluminum,
Alkylalkoxyaluminums such as diethylmonopentoxyaluminum; Trimethoxyaluminums, triethoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, tripentoxyaluminums and other trialkoxyaluminums; Monochlorodiethoxyaluminum, monochlorodiisopropoxyaluminum , Alkoxyaluminum halides such as monochlorodipentoxyaluminum, dichloromonomethoxyaluminum, dichloromonobutoxyaluminum and dibromomonomethoxyaluminum; Aluminum halides such as aluminum trichloride and aluminum tribromide; Monochlorodiethylaluminum and monochloro Diisopropyl aluminum, monochlorodibutyl aluminum, Alkyl aluminum halides such as nochlordipentylaluminum, monobromodimethylaluminum, monoiododiethylaluminum, dichloromonoethylaluminum, dichloromonobutylaluminum, diiodomonoethylaluminum; monobutyldiacetoxyaluminum, monomethyldipropionyloxyaluminum, Alkylacyloxyaluminums such as monoisopropyldibutyryloxyaluminum, dimethylmonoacetoxyaluminum, dimethylmonopropionyloxyaluminum; triacyloxyaluminums such as triacetoxyaluminum, tripropionyloxyaluminum, tributyryloxyaluminum and tripentanoyloxyaluminum. Kinds; Monochlorodiacetoxyl Halogenated acyloxyaluminums such as aluminum, monobromodiacetoxyaluminum, dichloromonoisopropionyloxyaluminum, dibromomonoacetoxyaluminum; monomethoxydiacetoxyaluminum, monoethoxydipropionyloxyaluminum, dibutoxymonoacetoxyaluminum, diethoxymonoaluminum. Alkoxyacyloxyaluminums such as butyryloxyaluminum; monomethyltrimethoxysilane, monobutyltrimethoxysilane, monomethyltriethoxysilane, monoethyltripentoxysilane, diethyldimethoxysilane,
Alkylalkoxysilanes such as diisopropyldiethoxysilane, tributylmonomethoxysilane, trimethylmonoethoxysilane, triisopropylmonoethoxysilane, triethylmonopentoxysilane; tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, Tetraalkoxysilanes such as tetrapentoxysilane; monochlorotrimethoxysilane, monochlorotributoxysilane, monobromotrimethoxysilane, dichlorodibutoxysilane, diiododiethoxysilane, trichloromonomethoxysilane, trichloromonopentoxysilane, trichlorosilane. Halogenated alkoxysilanes such as bromomonomethoxysilane; Silicon halides such as silicon tetrachloride and silicon tetrabromide; Monochloro Halogenated alkylsilanes such as trimethylsilane, monochlorotripentylsilane, monobromotrimethylsilane, monoiodotriethylsilane, dichlorodimethylsilane, dichlorodipentylsilane, trichloromonoethylsilane, trichloromonoisopropylsilane, tribromomonomethylsilane; Alkylacyloxy such as monomethyltriacetoxysilane, monomethyltripropionyloxysilane, monoisopropyltributyryloxysilane, diethyldiacetoxysilane, diethyldipropionyloxysilane, trimethylmonoacetoxysilane, tributylmonoacetoxysilane, triethylmonobutyryloxysilane Silanes; tetraacetoxysilane, tetrapropionyloxysilane, tetrabutyryloxysilane Tetraacyloxysilanes such as tetrapentanoyloxysilane, monochlorotriacetoxysilane, monochlorotributyryloxysilane, monobromotriacetoxysilane, dichlorodiacetoxysilane, trichloromonoacetoxysilane, tribromomonoacetoxysilane, etc. Halogenated acyloxysilanes; such as monobutoxytriacetoxysilane, monoethoxytripropionyloxysilane, monoisopropoxytributyryloxysilane, diethoxydiacetoxysilane, diisopropoxydibutyryloxysilane, tributoxymonoacetoxysilane Alkoxyacyloxysilanes; monomethyltrimethoxytitanium, monobutyltrimethoxytitanium, monomethyltriethoxytitanium, monoethyltripene Alkoxyalkoxytitaniums such as toxytitanium, diethyldimethoxytitanium, diisopropyldiethoxytitanium, tributylmonomethoxytitanium, trimethylmonoethoxytitanium, triisopropylmonoethoxytitanium, triethylmonopentoxytitanium; tetramethoxytitanium, tetraethoxytitanium, tetraiso Tetraalkoxytitaniums such as propoxytitanium, tetrabutoxytitanium and tetrapentoxytitanium; monochlorotrimethoxytitanium, monochlorotributoxytitanium, monobromotrimethoxytitanium, dichlorodibutoxytitanium, diiododiethoxytitanium, trichloromonomethoxytitanium,
Halogenated alkoxytitaniums such as trichlormonopentoxytitanium and tribrommonomethoxytitanium; Titanium halides such as titanium tetrachloride and titanium tetrabromide; Monochlorotrimethylpentanium, monochlorotripentyltitanium, monobromotrimethyltitanium,
Alkyl titanium halides such as monoiodotriethyltitanium, dichlorodimethyltitanium, dichlorodipentyltitanium, trichloromonoethyltitanium, trichloromonoisopropyltitanium, tribromomonomethyltitanium; monomethyltriacetoxytitanium, monomethyltripropionyloxytitanium, monoisopropyl Tributyryloxytitanium, diethyldiacetoxytitanium, diethyldipropionyloxytitanium,
Alkylacyloxytitaniums such as trimethylmonoacetoxytitanium, tributylmonoacetoxytitanium, triethylmonobutyryloxytitanium, etc .; Tetraacyloxytitanium such as tetraacetoxytitanium, tetrapropionyloxytitanium, tetrabutyryloxytitanium, tetrapentanoyloxytitanium, etc. Monochlorotriacetoxytitanium, monochlorotributyryloxytitanium, monobromotriacetoxytitanium, dichlorodiacetoxytitanium, trichloromonoacetoxytitanium, tribromomonoacetoxytitanium, and other halogenated acyloxytitaniums; monobutoxytriacetoxytitanium, Monoethoxytripropionyloxytitanium, monoisopropoxy Alkoxyacyloxytitaniums such as tyryloxytitanium, diethoxydiacetoxytitanium, diisopropoxydibutyryloxytitanium, tributoxymonoacetoxytitanium; monomethyltrimethoxyzirconium, monobutyltrimethoxyzirconium, monomethyltriethoxyzirconium, monoethyl. Alkylalkoxyzirconiums such as tripentoxyzirconium, diethyldimethoxyzirconium, diisopropyldiethoxyzirconium, tributylmonomethoxyzirconium, trimethylmonoethoxyzirconium, triisopropylmonoethoxyzirconium, triethylmonopentoxyzirconium; tetramethoxyzirconium, tetraethoxyzirconium, Tetraisopropoxyzirconi Tetraalkoxyzirconiums such as um, tetrabutoxyzirconium, tetrapentoxyzirconium; monochlorotrimethoxyzirconium, monochlorotributoxyzirconium, monobromotrimethoxyzirconium, dichlorodibutoxyzirconium, diiododiethoxyzirconium, trichloromonomethoxyzirconium, trichlor. Monopentoxy zirconium,
Tribrom monomethoxyzirconium and other halogenated alkoxy zirconium; Zirconium tetrachloride, zirconium tetrabromide and other halogenated zirconium; Monochlorotrimethyl zirconium, monochlorotripentyl zirconium, monobromotrimethyl zirconium, monoiodotriethyl zirconium, dichlorodimethyl Alkyl zirconium halides such as zirconium, dichlorodipentylzirconium, trichloromonoethylzirconium, trichloromonoisopropylzirconium, tribromomonomethylzirconium; monomethyltriacetoxyzirconium, monomethyltripropionyloxyzirconium, monoisopropyltributyryloxyzirconium, diethyldiethyl Acetoxy zirconium, diethyldi Alkylacyloxyzirconiums such as Ropionyloxyzirconium, Trimethylmonoacetoxyzirconium, Tributylmonoacetoxyzirconium, Triethylmonobutyryloxyzirconium; Tetraacetoxyzirconium, Tetrapropionyloxyzirconium, Tetrabutyryloxyzirconium, Tetrapentanoyloxyzirconium And other tetraacyloxyzirconiums; halogenated acyloxyzirconiums such as monochlorotriacetoxyzirconium, monochlorotributyryloxyzirconium, monobromotriacetoxyzirconium, dichlorodiacetoxyzirconium, trichloromonoacetoxyzirconium, tribromomonoacetoxyzirconium; Monobutoxytriacetoxy zirconium Alkoxyacyloxyzirconiums such as monoethoxytripropionyloxyzirconium, monoisopropoxytributyryloxyzirconium, diethoxydiacetoxyzirconium, diisopropoxydibutyryloxyzirconium, tributoxymonoacetoxyzirconium; monomethyltrimethoxytin, monobutyl Alkylalkoxy such as trimethoxytin, monomethyltriethoxytin, monoethyltripentoxytin, diethyldimethoxytin, diisopropyldiethoxytin, tributylmonomethoxytin, trimethylmonoethoxytin, triisopropylmonoethoxytin, triethylmonopentoxytin Tins; tetramethoxytin, tetraethoxytin, tetraisopropoxytin, tetrabutoxytin, tet Tetraalkoxytins such as pentoxytin; monochlorotrimethoxytin, monochlorotributoxytin, monobromotrimethoxytin, dichlorodibutoxytin, diiododiethoxytin, trichloromonomethoxytin, trichloromonopentoxytin, tribromomonomethoxy. Alkoxy tin halides such as tin; Tin halides such as tin tetrachloride and tin tetrabromide; Monochlorotrimethyltin, monochlorotripentyltin, monobromotrimethyltin, monoiodotriethyltin, dichlorodimethyltin, dichloro Alkyltin halides such as dipentyltin, trichloromonoethyltin, trichloromonoisopropyltin, tribromomonomethyltin; monomethyltriacetoxytin, monomethyltripropionyloxy Tin, monoisopropyl tributyl styryl oxy tin, diethyl diacetoxy tin, diethyl dipropionyl oxy tin, trimethyl mono acetoxy tin,
Alkylacyloxytins such as tributylmonoacetoxytin and triethylmonobutyryloxytin; tetraacyloxytins such as tetraacetoxytin, tetrapropionyloxytin, tetrabutyryloxytin and tetrapentanoyloxytin; monochlorotriacetoxy Halogenated acyloxytins such as tin, monochlorotributyryloxytin, monobromotriacetoxytin, dichlorodiacetoxytin, trichloromonoacetoxytin, tribromomonoacetoxytin; monobutoxytriacetoxytin, monoethoxytripropionyloxytin, Alkoxy reeds such as monoisopropoxytributyryloxytin, diethoxydiacetoxytin, diisopropoxydibutyryloxytin and tributoxymonoacetoxytin. Kishisuzu, and mixtures thereof.

Further, the polymer of these metal compounds can be obtained by reacting the metal compound with water or a carboxylic acid.
At this time, if necessary, hydrochloric acid, sulfuric acid, caustic soda, ammonia, etc. may be used as a catalyst. Examples of polymers include polyethoxyaluminoxane, poly (acetoxy-
Examples include polymetalloxane such as butoxy) siloxane, polyisopropoxytitanoxane, poly (butyl-ethoxy) zirconoxane, and poly (octyl-chloro) stannoxane.

Such metal compounds or polymers thereof are liquid or solid at room temperature. Since it must be a liquid at the time of use, when it is a solid, it is melted by heating or dissolved in an appropriate solvent. Further, even if it is a liquid at room temperature, it may be dissolved in a solvent and used in order to adjust the concentration appropriately.

The solvent to be used varies depending on the type of metal compound, but includes water, alcohols such as methanol and ethanol, aliphatic hydrocarbons such as hexane, decane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, and acetone. Ketones and mixed systems thereof can be preferably used.

The concentration of the metal compound in the undiluted solution varies depending on the kind of the metal compound and is not particularly limited, but if it is too dilute, the amount of the solvent to be scattered increases, which is not economical. On the other hand, if it is too thick, the workability may decrease, so it is generally used at about 2 to 80% by weight.

The metal compound forming the sol may be any as long as it becomes a sol in a suitable dispersion medium, for example, a metal oxide, a metal hydroxide, a metal sulfide, or a metal chloride,
Examples thereof include metal salts such as metal sulfates and organic metal polymers.

The metal of the above-mentioned metal compound is a metal having a valence of 2 or more, preferably a metal belonging to Group IIIa, IVa or IVb of the periodic table, and more preferably one or two selected from aluminum, silicon, titanium, zirconium and tin. The above metals are used. Specifically, aluminum such as alumina, aluminum hydroxide, aluminum sulfide, aluminum chloride, aluminum oxychloride, basic aluminum chloride, polyaluminum chloride, aluminum sulfate, aluminum acetate, aluminum oxalate, aluminum isopropoxide polymer. Aluminum compounds such as polymers of alkoxides, polymers of alkyl aluminums such as polymers of triethylaluminum,
Silicon compounds such as silica, polymers of alkoxysilanes such as silicon oxychloride, silicon acetate, silicon oxalate, polymers of tetraethyl silicate, polymers of alkylchlorosilanes such as polymers of dimethyldichlorosilane; titania, hydroxylation Titanium, titanium sulfide, titanium oxychloride, titanium sulfate, titanium acetate,
Polymers of titanium alkoxides, such as titanium oxalate, polymers of titanium isopropoxide,
Titanium compounds such as titanium acetylacetonate; zirconium oxide, zirconium hydroxide, zirconium sulfide, zirconium oxychloride, zirconium sulfate,
Polymers of zirconium alkoxides such as zirconium acetate, zirconium oxalate, zirconium isopropoxide polymers, zirconium compounds such as zirconium acetylacetonate; tin oxide, tin hydroxide, tin sulfide, tin chloride, tin oxychloride, basic Polymers of tin alkoxides such as tin chloride, tin sulfate, tin acetate, tin oxalate, tin isopropoxide polymers, tin compounds such as alkylalkoxytin polymers such as monooctyltributoxytin polymers, etc. Can be mentioned.

Such metal compounds are liquid or solid at room temperature.
Since it must be a liquid sol at the time of use, 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 alcohols such as water, methanol and ethanol; aliphatic or alicyclic hydrocarbons such as hexane, decane and cyclohexane; aromatic hydrocarbons such as toluene and xylene. Kinds; ketones such as acetone, and mixed systems thereof can be preferably used.

The concentration of the metal compound sol varies depending on the type of the metal compound and is not particularly limited, but if it is too dilute, the amount of the dispersion medium that volatilizes increases, which is not economical.
On the other hand, if it is too rich, workability may decrease, so
Generally, it is used at about 2 to 50% by weight.

 As a commercially available sol, for example, silica sol,
Ludox made by EI DuPont HS-40, Al
Alumina is the product name of Minasol manufactured by Nissan Chemical Industries, Ltd.
There are sol 100 etc. Nissan as an organic solvent dispersion system
Gaku Kogyo Co., Ltd. product name known as methanol silica sol
Have been.

As a method for preparing these sols, for example, when a silica sol is prepared, a method of making ion exchange from water glass, a method of neutralizing water glass with an acid, a method of electrodialyzing water glass, or a method of hydrolyzing ethyl silicate. A method of disassembling is known. Further, when preparing an alumina sol, a method of hydrolyzing a hydrolyzable compound such as aluminum acetate by means of heating or the like to form a sol is well known. (Science of new industrial materials, silica and alumina (colloid products), pp. 59-127
page. Applied Chemistry Handbook (revised 3rd edition), 132 pages, edited by The Chemical Society of Japan).

When a more specific sol is desired, it can be prepared by a known method described in the above-mentioned documents and the like.

Further, in order to stabilize the sol, it is effective to add an appropriate pH adjusting agent such as a small amount of hydrochloric acid or caustic soda.

Furthermore, in order to make the thickness of the coating film uniform, for example, high molecular substances such as polyol and ethyl cellulose, high boiling organic substances such as butyl cellosolve and glycerin, nonionic and anionic surfactants, etc. It can also be added.

Further, a known colorant composed of a compound such as iron, nickel, vanadium, chromium and manganese can also be added.

The liquid film formed on the smooth base material by traveling on the smooth base material is moved to another position and then solidified.

This solidification treatment is a treatment for performing thermal decomposition, hydrolysis, oxidative decomposition or condensation when the liquid film is a liquid metal compound. When the liquid film is a solution of a metal compound, it is a treatment of first performing thermal decomposition, hydrolysis, oxidative decomposition or condensation while volatilizing the solvent.

In the case of a metal compound sol, the dispersion medium is first volatilized to form a gel. Then, if necessary, it is a process of performing thermal decomposition, hydrolysis, oxidative decomposition or condensation.

These treatments involve heating. It is preferable that this heating is performed gently so that no bubbles are generated in the thin film.

As a specific method, a heating medium may be passed through the inside of the roll to heat the roll. Alternatively, a section for heating may be provided, and the liquid film of the stock solution may be directly heated by heated air, electric heat or infrared heater, high frequency, or the like.

The heating temperature cannot be generally stated depending on the volatility of the solvent or the like to be removed, but generally room temperature to 250 ° C. is suitable. For example, in the case of a highly volatile solvent or the like, it is sufficient to blow a gas at room temperature.

Hydrolysis, oxidative decomposition, or condensation proceeds even with water or oxygen existing in the air, but water or water vapor is added or an acid or alkali is used as an accelerator as necessary.

Specifically, from room temperature to about 250 ° C, steam-containing gas (such as air), acid-containing gas, ammonia-containing gas, normal temperature to
Contact with water, acid-containing solvent, etc. at about 100 ° C. The concentration of the gelling agent such as water, acid or alkali is appropriately adjusted depending on the kind of the metal compound used, the target reaction rate and the like.

As a compound that solidifies by thermal decomposition, there are metal alkoxides and the like, and condensation occurs by heating. Examples of hydrolysis include metal chlorides and metal alkoxides that react with water to condense, and acids, alkalis and the like may be added as catalysts. Further, as an example of solidifying with an acid or an alkali, there is a metal compound such as an alkyl silicate that causes condensation in the presence of a carboxylic acid.

The solidification causes the volume of the thin film to shrink, resulting in fine cracks in the film and thinning.

As a method of peeling the flaky material formed on the base material from the base material, a peeling method of mechanically scraping with a scraper, a peeling method using ultrasonic waves, or bending of the base material when the base material is flexible Examples of the method include peeling.

The thin piece of the metal compound produced as described above is transparent and has high gloss, so it can be used as it is, but it is calcined at a temperature of about 200 to 1100 ° C, preferably 500 to 900 ° C depending on the application. It is considered a product.

 By this calcination, the metal compound mainly becomes an oxide.

Further, the flaky inorganic substance produced in the present invention has a thickness of about 0.
Although a particle size of 01 to 10 μm is obtained, it is crushed as appropriate according to the purpose of use and generally used in a size of about 1 to 100 μm.

<Effects of the Invention> As described in detail above, by adjusting the supply amount of the stock solution by the method of the present invention and controlling the traveling linear velocity of the smooth base material, mass production of thin pieces of arbitrary thickness is achieved. Is possible.

The flaky inorganic substance obtained by the method of the present invention is used as a luster pigment for manicure enamel leather products, automobile exterior metal coating, pearlescent button cosmetic pigment by casting of unsaturated polyester resin, plastic filler for food packaging, etc. It can be effectively applied to a pearlescent pigment to be used, an extender pigment, a raw material powder for producing a ceramic product such as a light-transmitting tube for sodium lamps and condenser porcelain, and a catalyst carrier.

<Example> Hereinafter, the method of the present invention will be described in more detail with reference to Examples, but it is clear that the method of the present invention is not limited to these.

Example 4 Titanyl sulfate and sulfuric acid were mixed to obtain a titanium concentration of 0.25 mol /
A solution having a sulfuric acid concentration of 0.9 mol / 1 was prepared. While stirring this well, a 25 wt% caustic soda solution was mixed. pH6
The mixture was adjusted with a caustic soda solution so that the mixture was stirred for 24 hours.
The titania sol solution having a titania concentration of 1.4% by weight thus obtained was used as a stock solution.

This was placed in a vat, and a roll (first roll) having a diameter of 10 cm and a width of 60 cm was immersed in this liquid at room temperature and rotated at a peripheral speed of 10 m / min. A rubber roll (second roll) having a diameter of 30 cm rotating in the same direction at 10 m / min was installed above this roll so as to be almost in contact with it. As a result, the stock solution has been transferred onto the second roll. Next, a roll (third roll) with a diameter of 50 cm (third roll) heated by a heat medium from the inside rotating in the same direction at 24 m / min was placed slightly above the second roll. As a result, the stock solution on the second roll is thinly stretched and transferred onto the third roll.

Next, air at 150 ° C. was flown on the third roll to which the stock solution had adhered so that the flow rate was 1 m / sec. This removes the water in the stock solution, causes gelation, further volume contraction and cracking, and a titania flakes is formed on the third roll.
The flakes were scraped with a Swedish steel scraper.

The flakes thus obtained were fired at 650 ° C. to obtain flaky titania having a size of 8-40 μ and a thickness of about 1.5 μ.
The production amount was 3 kg / h as titania per 1 m roll width.

Example 9 5 mol (2254 g) of monooctyltributoxytin was added to
It was dissolved in 750 g of toluene to obtain a stock solution. This was placed in a vat, and a roll (first roll) having a diameter of 10 cm and a width of 20 cm was immersed in this solution at room temperature and rotated at a peripheral speed of 12 m / min. 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 that rotates in the same direction at a peripheral speed of 30 m / min is installed above this roll with the roll gap adjusted to 200 μ. did. As a result, the stock solution has been transferred onto the second roll.

Then, steam-containing nitrogen at 150 ° C. was flown onto the second roll to which the stock solution was adhered so that the flow rate was 1 m / sec. This removes the toluene in the stock solution, and at the same time causes hydrolysis, causing volume contraction and cracking, and a thin piece of a compound mainly containing poly (octylbutoxy) stannoxane is formed on the second roll. The flakes were scraped with a Swedish steel scraper.

The obtained flakes are baked at 900 ° C. to have a size of 3-15 μ,
A flaky tin oxide having a thickness of 3 μ was obtained. Production amount is roll width 1m
The amount of tin oxide was 6 kg / hour.

Example 10 Silica gel (Ludox HS-40, Ei Du
(Pon) is diluted with water so that the silica concentration becomes 8%.
Then it was made into a stock solution. Put this in a bat, diameter 10 cm, width 20
Immerse a cm roll (first roll) in this solution at room temperature,
It was rotated at a peripheral speed of 12 m / min. Close to this first roll
Roll (metering roll) that rotates in the same direction at 8 m / min.
Is installed to regulate the thickness of the liquid film on the first roll.
Was. Rotate above this roll in the same direction at a peripheral speed of 35 m / min.
A 50 cm diameter and 20 cm width heated to 100 ° C from inside.
Roll (second roll) made by
It was adjusted and installed. This ensures that the stock solution is on the second roll.
Has been transferred to.

Next, 120 ° C. air was flowed on the second roll having the stock solution attached thereto so that the flow rate was 1 m / sec. As a result, the water in the liquid film of the stock solution is removed, and a silica gel film is formed on the second roll. Further removal of water causes volume shrinkage and cracking, resulting in silica flakes. The flakes were scraped with a Swedish steel scraper.

The obtained flakes are baked at 600 ° C. to obtain a size of 3-15 μ,
Flake-shaped silica having a thickness of 1 μm was obtained. The production amount was 2.5 kg / hr of silica per 1 m of roll width.

Example 11 1 mol (114 g) of triethylaluminum was dissolved in 286 g of tetrahydrofuran, and 2 mol (120 g) of isopropanol was reacted with this to synthesize monoethyldiisopropoxyaluminum. Furthermore, lauric acid 0.25 mol (50
g) was reacted to give a stock solution.

This was placed in a vat, and a roll (first roll) having a diameter of 10 cm and a width of 20 cm was immersed in this liquid at room temperature and rotated at a peripheral speed of 20 m / min. A bar coater having a gap of 200 μ was pressed against this roll to regulate the amount of liquid lifted by the first roll. A stainless roll (second roll) with a diameter of 50 cm and a width of 20 cm heated to 130 ° C from the inside, which rotates in the same direction at a peripheral speed of 40 m / min, is placed above this roll with a roll gap of 100 μ.
It was adjusted and installed. As a result, the stock solution has been transferred onto the second roll.

Then, steam-containing nitrogen at 150 ° C. was flown onto the second roll to which the stock solution was adhered so that the flow rate was 1 m / sec. By this, tetrahydrofuran in the stock solution is removed, and at the same time, hydrolysis occurs, causing volume contraction and cracking, and a thin piece of a compound mainly containing polyaluminoxane is formed on the second roll. The flakes were scraped with a Swedish steel scraper.

The obtained flakes are fired at 900 ° C to obtain a size of 5-25μ,
A flaky alumina having a thickness of 1 μm was obtained. Production amount is roll width 1m
The amount of alumina was 3.2 kg / hour.

Example 12 A silica sol having a dispersion medium of methanol (trade name: methanol silica sol, manufactured by Nissan Chemical Industries, Ltd.) was adjusted to have a silica concentration of 5% to prepare a stock solution.

This was put in a vat, and a roll (first roll) having a diameter of 10 cm and a width of 20 cm was immersed in this liquid at room temperature and rotated at a peripheral speed of 18 m / min. A bar coater with a gap of 200 μ was pressed against this first roll to regulate the thickness of the liquid film on the first roll.
A stainless steel roll (second roll) with a diameter of 50 cm and a width of 20 cm heated to 100 ° C from the inside that rotates in the same direction at a peripheral speed of 50 m / min above this roll is installed with a roll gap of 100 μ did. As a result, the stock solution has been transferred onto the second roll.

Next, 120 ° C. air was flowed on the second roll having the stock solution attached thereto so that the flow rate was 1 m / sec. As a result, the water in the liquid film of the stock solution is removed, and a silica gel film is formed on the second roll. Further removal of water causes volume shrinkage and cracking, resulting in silica flakes. The flakes were scraped with a Swedish steel scraper.

 The obtained flakes were fired at 600 ° C.

As a result, flaky silica having a size of 3 to 25 μm and a thickness of 0.5 μm was obtained.

The production amount was 2 kg / hr of silica per 1 m of roll width.

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Claims (1)

(57) [Claims] 1. A liquid roll containing a liquid metal compound, a metal compound solution and a metal compound sol, the liquid amount of which is regulated and supplied by using one or a plurality of rolls on a running smooth roll. Formed into a controlled liquid film, and then subjected to a solidification treatment to form a flaky material, and peeling the flaky material from the roll, and a thickness of about 0.01 to 10 μm.
The method for producing a flaky material of m.