JPH0580403B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing flaky inorganic materials.
More specifically, a metal compound having an acyloxy group is applied onto a smooth surface, the coating film is hydrolyzed with water or steam, the hydrolyzed metal compound thin film is peeled off, and if necessary, it is baked. The present invention relates to a method for producing a flaky inorganic material by forming metal oxide flakes, the flaky inorganic material, and a cosmetic containing the same. Various kinds of flaky inorganic substances have been known so far. For example, flaky titanium oxide, flaky alumina, etc. are mixed into cosmetics and paints to improve lubricity and gloss, or mixed into plastics to improve mechanical properties and other purposes. used and has many uses. A titanium compound is attached to a smooth substrate to form a film.
A method is known in which the substrate is melted or crushed to form flakes (Japanese Patent Publication No. 4731/1983). 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. In addition, a method of applying an organic solvent solution of titanium alkoxide or titanium tetrachloride to a smooth surface and then cracking the film formed by the action of water vapor to obtain flakes (U.S. Pat. No. 2,941,895, U.S. Pat. No. 3,071,482) ) has also been proposed. By these methods,
Although it is possible to obtain flaky inorganic substances containing titanium compounds as the main component, it is not possible to recover all of them as flakes, and the flakes obtained in this way are irregular in size and shape. There were disadvantages such as the tendency to form irregular curls. In order to overcome the above disadvantages, a method has been proposed in which a solution of a titanium compound in an organic solvent is applied to a heated substrate at a high temperature. (Special Publication No. 45-6424). However, this method has drawbacks such as extreme thickness unevenness tends to occur due to evaporation and boiling, and it is extremely difficult to control the thickness and size to be constant. The purpose of the present invention is to provide high gloss that is superior in peelability, uniformity of flake size, controllability of flake size, smoothness of flakes, etc., compared to conventional methods for producing flaky inorganic materials. An object of the present invention is to provide a method for producing a flaky inorganic material having the following properties. That is, the present invention provides a method for producing a flaky inorganic material by applying an organic solvent solution of a metal compound to a substrate, hydrolyzing the coating film with water or steam, and peeling off the hydrolyzed metal compound thin film. It is an object of the present invention to provide a method for producing a flaky inorganic material, which is characterized in that a metal compound having an acyloxy group is used as a compound. The method of the present invention will be described in more detail below. The inorganic flakes according to the method of the present invention are produced by using a metal compound having an acyloxy group. In carrying out the method of the present invention, a metal compound having an acyloxy group has the general formula (RCOO)mMXn (where M is a metal element, R is a hydrocarbon group, and X is selected from an alkyl group, an alkoxy group, or a halogen). (where m+n is the valence of the metal element and m is a number satisfying 0.1<m<m+n) or a polymer thereof. Further, in the above-mentioned acyloxy group-containing metal compound, m in the general formula is 0.1 or more and m+n or less, preferably 0.2 to 2. If m is less than 0.1, the removability of the coating film, the uniformity of the size of the flakes, and the smoothness of the flakes will deteriorate, which is undesirable. By using this metal compound, a flaky metal oxide with excellent peelability, uniformity of flake size, controllability of flake size, and smoothness of flakes, which were the disadvantages of conventional skins, has been created. It can be manufactured easily and economically. The metal of the metal compound having an acyloxy group of the present invention is a divalent or higher valent metal, preferably a metal belonging to group b, a or b of the periodic table, more preferably aluminum, silicon, titanium,
One or more metals selected from zirconium and tin are used. Such metal compounds include monoacetoxydimethylaluminum, monoacetoxydiethylaluminum, monoacetoxydipropylaluminum, monopropionyloxydimethylaluminum, monopropionyloxydiethylaluminum, monobutyryloxydimethylaluminum, monohexanoyloxydimethylaluminum, Monoacyloxydialkyl aluminum such as monohexanoyloxydiethylaluminum, monohexanoyloxydipropylaluminum, monobenzoyloxydimethylaluminum, monobenzoyloxydiethylaluminum, monobenzoyloxydibutylaluminum, monoacetoxydiethoxyaluminum, monoacetoxydipropoxy Aluminum, monoacetoxydibutoxyaluminum, monoacetoxydipentoxyaluminum, monoacetoxydioctoxyaluminum, monopropionyloxydimethoxyaluminum, monopropionyloxydiethoxyaluminum, monopropionyloxydipropoxyaluminum, monopropionyloxydibutoxyaluminum, mono Butyryloxydimethoxyaluminum, monobutyryloxydiethoxyaluminum, monobutyryloxydipropoxyaluminum, monobutyryloxydipentoxyaluminum, monohexanoyloxydimethoxyaluminum, monohexanoyloxydiethoxyaluminum, monohexanoyloxy Monoacyloxydialkoxyaluminums such as dipropoxyaluminum, monobenzoyloxydimethoxyaluminum, monobenzoyloxydiethoxyaluminum, monobenzoyloxydibutoxyaluminum, monoacyloxyaluminum dihalides such as monoacetoxydichloraluminum, monoacetoxydibromoaluminum, etc. , diacetoxymonomethylaluminum, diacetoxymonoethylaluminum, diacetoxymonopropylaluminum, dipropionyloxymonomethylaluminum, dipropionyloxymonoethylaluminum, dibutyryloxymonomethylaluminum,
dihexanoyloxymonomethylaluminum,
dihexanoyloxymonoethylaluminum,
dihexanoyloxymonopropylaluminium, dibenzoyloxymonomethylaluminum,
Diacyloxymonoalkylaluminum such as dibenzoyloxymonoethylaluminum and dibenzoyloxymonobutylaluminum, diacetoxymonoethoxyaluminum, diacetoxymonopropoxyaluminum, diacetoxymonobutoxyaluminum, diacetoxymonopentoxyaluminum, diacetoxymono Octoxyaluminum, dipropionyloxymonomethoxyaluminum, dipropionyloxymonoethoxyaluminum, dipropionyloxymonopropoxyaluminum, dipropionyloxymonobutoxyaluminum, dibutyryloxymonomethoxyaluminum, dibutyryloxymonoethoxyaluminum, dibutyryloxydi Diacyloxymonoalkoxyaluminums such as pentoxyaluminum, dihexanoyloxydimethoxyaluminum, dihexanoyloxymonoethoxyaluminum, dihexanoyloxymonopropoxyaluminum, dibenzoyloxymonoethoxyaluminum, dibenzoyloxymonobutoxyaluminum, Acyloxy group-containing aluminum compounds such as diacyloxyaluminum monohalides such as acetoxymonochloraluminum and diacetoxymonobromoaluminum, or these together with alkylaluminums such as trimethylaluminum and triethylaluminum, trimethoxyaluminum, triethoxyaluminum, and tripropoxy Aluminum alkoxides such as aluminum, tobutoxyaluminum, tripentoxyaluminum,
Aluminum halides such as aluminum chloride and aluminum bromide, mixtures with aluminum carboxylates such as aluminum acetate, aluminum propionate, aluminum valerate, aluminum caproate, and aluminum benzoate, monoacetoxytrimethylsilane, monoacetoxytriethylsilane , monoacetoxytripropylsilane, monopropionyloxytrimethylsilane,
Monopropionyloxytriethylsilane, monobutyryloxytrimethylsilane, monohexanoyloxytrimethylsilane, monohexanoyloxytriethylsilane, monohexanoyloxytripropylsilane, monobenzoyloxytrimethylsilane, monobenzoyloxytriethylsilane, monobenzoyloxy Monoacyloxytrialkylsilanes such as tributylsilane,
Monoacetoxytriethoxysilane, monoacetoxytripropoxysilane, monoacetoxytributoxysilane, monoacetoxytripentoxysilane, monoacetoxytrioctoxysilane,
Monopropionyloxytrimethoxysilane, monopropionyloxytriethoxysilane, monopropionyloxytripropoxysilane, monopropionyloxytributoxysilane, monobutyryloxytrimethoxysilane, monobutyryloxytriethoxysilane, monobutyryloxytripropoxy Silane, monobutyryloxytripentoxysilane, monohexanoyloxytrimethoxysilane, monohexanoyloxytriethoxysilane, monohexanoyloxytripropoxysilane, monobenzoyloxytrimethoxysilane, monobenzoyloxytriethoxysilane, mono Monoacyloxytrialkoxysilanes such as benzoyloxytributoxysilane,
Monoacyloxysilane trihalides such as monoacetoxytrichlorosilane and monoacetoxytribromosilane, diacetoxydiethylsilane,
Diacyloxydialkylsilanes such as dipropionyloxydiethylsilane, dibutyryloxydimethylsilane, dihexanoyloxydiethylsilane, dibenzoyloxydiethylsilane, diacetoxydiethoxysilane, diacetoxydipentoxysilane, diacetoxydioctoxy Silane, diacyloxydialkoxysilanes such as dipropionyloxydiethoxysilane, dibutyryloxydimethoxysilane, dibutyryloxydipentoxysilane, dihexanoyloxydiethoxysilane, dibenzoyloxydiethoxysilane, diacetoxydichlor Silane, diacyloxysilane dihalides such as diacetoxydibromosilane, triacetoxymonomethylsilane, triacetoxymonoethylsilane, triacetoxymonopropylsilane, tripropionyloxymonomethylsilane, tripropionyloxymonoethylsilane, tributyryloxy Monomethylsilane, trihexanoyloxymonomethylsilane,
Triacyloxymonoalkylsilanes such as trihexanoyloxymonoethylsilane, trihexanoyloxymonopropylsilane, tribenzoyloxymonomethylsilane, tribenzoyloxymonoethylsilane, tribenzoyloxymonobutylsilane, triacetoxymonoethoxysilane, Triacetoxymonopropoxysilane, triacetoxymonobutoxysilane, triacetoxymonopentoxysilane, triacetoxymonoctoxysilane, tripropionyloxymonomethoxysilane, tripropionyloxymonoethoxysilane, cypropionyloxymonopropoxysilane, tripropionyloxy Monobutoxysilane, tributyryloxymonomethoxysilane,
Tributyryloxymonoethoxysilane, Tributyryloxytripentoxysilane, Trihexanoyloxytrimethoxysilane, Trihexanoyloxymonoethoxysilane, Trihexanoyloxymonopropoxysilane, Tribenzoyloxymonoethoxysilane, Tribenzoyl Acyloxy group-containing silane compounds such as triacyloxymonoalkoxysilanes such as oxymonobutoxysilane, triacyloxysilane monohalides such as triacetoxymonochlorosilane and triacetoxymonobromsilane, or together with these, tetramethylsilane, tetranitylsilane Alkyl silanes such as methyl silicate, ethyl silicate, propyl silicate, butyl silicate, alkyl silicates such as pentyl silicate, halogenated silanes such as silicon tetrachloride, silicon tetrabromide, silicon acetate, silicon propionate, valeric acid Silicon, mixtures with silicon carboxylates such as silicon caproate and silicon benzoate, monoacetoxytrimethyltitanium, monoacetoxytriethyltitanium, monoacetoxytripropyltitanium, monopropionyloxytrimethyltitanium, monopropionyloxytriethyltitanium, monobutyryl Monoacyloxytrialkyl titanium such as oxytrimethyltitanium, monohexanoyloxytrimethyltitanium, monohexanoyloxytriethyltitanium, monohexanoyloxytripropyltitanium, monobenzoyloxytrimethyltitanium, monobenzoyloxytriethyltitanium, monobenzoyloxytributyltitanium monoacetoxytriethoxytitanium, monoacetoxytripropoxytitanium, monoacetoxytributoxytitanium, monoacetoxytripentoxytitanium, monoacetoxytrioctoxytitanium, monopropionyloxytrimethoxytitanium, monopropionyloxytriethoxytitanium, monopropionyl Oxytripropoxytitanium, monopropionyloxytributoxytitanium, monobutyryloxytrimethoxytitanium, monobutyryloxytriethoxytitanium, monobutyryloxytripropoxytitanium, monobutyryloxytripentoxytitanium, monohexanoyloxytritanium Monoacyloxytrialkoxytitaniums such as methoxytitanium, monohexanoyloxytriethoxytitanium, monohexanoyloxytripropoxytitanium, monobenzoyloxytrimethoxytitanium, monobenzoyloxytriethoxytitanium, monobenzoyloxytributoxytitanium, monoacetoxy Monoacyloxytitanium trihalides such as trichlorotitanium and monoacetoxytribromotitanium, diacetoxydiethyltitanium, dipropionyloxydiethyltitanium, dibutyryloxydimethyltitanium,
Diacyloxydialkyl titaniums such as dihexanoyloxydiethyl titanium and dibenzoyloxydiethyl titanium, diacetoxydiethoxytitanium, diacetoxydipentoxytitanium, diacetoxydioctoxytitanium, dipropionyloxydiethoxytitanium, dibutyryloxy Diacyloxydialkoxytitaniums such as dimethoxytitanium, dibutyryloxydipentoxytitanium, dihexanoyloxydiethoxytitanium, dibenzoyloxydiethoxytitanium, diacyloxytitanium such as diacetoxydichlorotitanium, diacetoxydibromtitanium, etc. Dihalides, triacetoxymonomethyltitanium, triacetoxymonoethyltitanium, triacetoxymonopropyltitanium, tripropionyloxymonomethyltitanium, tripropionyloxymonoethyltitanium, tributyryloxymonomethyltitanium, trihexanoyloxymonomethyltitanium, trihexa Triacyloxymonoalkyltitaniums such as noyloxymonoethyltitanium, trihexanoyloxymonopropyltitanium, tribenzoyloxymonomethyltitanium, tribenzoyloxymonoethyltitanium, tribenzoyloxymonobutyltitanium, triacetoxymonoethoxytitanium, triacetoxy Monopropoxy titanium, triacetoxy monobutoxy titanium, triacetoxy monopentoxy titanium,
triacetoxymonooctoxytitanium, tripropionyloxymonomethoxytitanium, tripropionyloxymonoethoxytitanium,
Cypropionyloxymonopropoxytitanium, tripropionyloxymonobutoxytitanium, tributyryloxymonomethoxytitanium, tributyryloxymonoethoxytitanium, tributyryloxytripentoxytitanium, trihexanoyloxytrimethoxytitanium, trihexanoyl Triacyloxymonoalkoxytitaniums such as oxymonoethoxytitanium, trihexanoyloxymonopropoxytitanium, tribenzoyloxymonoethoxytitanium, tribenzoyloxymonobutoxytitanium, triacyloxytitaniums such as triacetoxymonochlorotitanium, triacetoxymonobromotitanium, etc. Acyloxy group-containing titanium compounds such as monohalides, or alkyl titaniums such as tetramethyl titanium, tetraethyl titanium, methyl titanate, ethyl titanate, propyl titanate,
Alkyl titanates such as butyl titanate and pentyl titanate, titanium halides such as titanium tetrachloride and titanium tetrabromide, titanium carboxylates such as titanium acetate, titanium propionate, titanium valerate, titanium caproate, and titanium benzoate, etc. mixture with, monoacetoxytrimethylzirconium, monoacetoxytriethylzirconium, monoacetoxytripropylzirconium, monopropionyloxytrimethylzirconium, monopropionyloxytriethylzirconium, monobutyryloxytrimethylzirconium, monohexanoyloxytrimethylzirconium, monohexanoyloxy triethylzirconium,
Monoacyloxytrialkylzirconiums such as monohexanoyloxytripropylzirconium, monobenzoyloxytrimethylzirconium, monobenzoyloxytriethylzirconium, monobenzoyloxytributylzirconium, monoacetoxytriethoxyzirconium, monoacetoxytripropoxyzirconium, monoacetoxytributoxy zirconium,
Monoacetoxytripentoxyzirconium, monoacetoxytrioctoxyzirconium, monopropionyloxytrimethoxyzirconium,
Monopropionyloxytriethoxyzirconium, monopropionyloxytripropoxyzirconium, monopropionyloxytributoxyzirconium, monobutyryloxytrimethoxyzirconium, monobutyryloxytriethoxyzirconium, monobutyryloxytripropoxyzirconium, monobutyryloxytrimethoxyzirconium Pentoxyzirconium, monohexanoyloxytrimethoxyzirconium, monohexanoyloxytriethoxyzirconium, monohexanoyloxytripropoxyzirconium, monobenzoyloxytrimethoxyzirconium, monobenzoyloxytriethoxyzirconium, monobenzoyloxytributoxyzirconium, etc. Monoacyloxytrialkoxyzirconiums, monoacyloxyzirconium trihalides such as monoacetoxytrichlorzirconium, monoacetoxytribromizirconium, diacetoxydiethylzirconium, dipropionyloxydiethylzirconium, dibutyryloxydimethylzirconium, dihexanoyloxydiethylzirconium, Diacyloxydialkylzirconiums such as dibenzoyloxydiethylzirconium, diacetoxydiethoxyzirconium, diacetoxydipentoxyzirconium, diacetoxydioctoxyzirconium, dipropionyloxydiethoxyzirconium, dibutyryloxydimethoxyzirconium, dibutyryloxyzirconia Diacyloxydialkoxyzirconiums such as pentoxyzirconium, dihexanoyloxydiethoxyzirconium and dibenzoyloxydiethoxyzirconium, diacyloxyzirconium halides such as diacetoxydichlorozirconium and diacetoxydibromzirconium, triacetoxymonomethylzirconium , triacetoxymonoethylzirconium, triacetoxymonopropylzirconium, tripropionyloxymonomethylzirconium, tripropionyloxymonoethylzirconium, tributyryloxymonomethylzirconium, trihexanoyloxymonomethylzirconium, trihexanoyloxymonoethylzirconium, trihexa Triacyloxymonoalkylzirconiums such as noyloxymonopropylzirconium, tribenzoylokimonomethylzirconium, tribenzoyloxymonoethylzirconium, tribenzoyloxymonobutylzirconium, triacetoxymonoethoxyzirconium, triacetoxymonopropoxyzirconium, triacetoxymonobutoxy Zirconium, triacetoxy monopentoxy zirconium, triacetoxy mono octoxy zirconium, tripropionyloxy monomethoxy zirconium, tripropionyloxy monoethoxy zirconium, cypropionyloxy monopropoxy zirconium, tripropionyloxy monobutoxy zirconium, tributyryloxy monomethoxy Zirconium, tributyryloxymonoethoxyzirconium, tributyryloxytripentoxyzirconium, trihexanoyloxytrimethoxyzirconium,
Triacyloxymonoalkoxyzirconiums such as trihexanoyloxymonoethoxyzirconium, trihexanoyloxymonopropoxyzirconium, tribenzoyloxymonoethoxyzirconium, tribenzoyloxymonobutoxyzirconium, triacetoxymonochlorozirconium, triacetoxymonobromzirconium, etc. Acyloxy group-containing zirconium compounds such as triacyloxyzirconium monohalides, or these together with tetramethylzirconium,
Alkylzirconiums such as tetraethylzirconium, alkylzirconates such as methylzirconate, ethylzirconate, propylzirconate, butylzirconate, pentylzirconate, zirconium halides such as zirconium tetrachloride and zirconium tetrabromide, acetic acid Zirconium, mixtures with zirconium carboxylates such as zirconium propionate, zirconium valerate, zirconium caproate, zirconium benzoate, etc., and monoacetoxytrimethyltin, monoacetoxytriethyltin, monoacetoxytripropyltin, monopropionyloxytrimethyltin, mono Propionyloxytriethyltin, monobutyryloxytrimethyltin, monohexanoyloxytrimethyltin, monohexanoyloxytriethyltin, monohexanoyloxytripropyltin, monobenzoyloxytrimethyltin, monobenzoyloxytriethyltin,
Monoacyloxytrialkyltins such as monobenzoyloxytributyltin, monoacetoxytriethoxytin, monoacetoxytripropoxytin, monoacetoxytributoxytin, monoacetoxytripentoxytin, monoacetoxytrioctoxytin, monopropionyloxytrimethoxy Tin, monopropionyloxytriethoxytin, monopropionyloxytripropoxytin, monopropionyloxytributoxytin, monobutyryloxytrimethoxytin,
Monobutyryloxytriethoxytin, monobutyryloxytripropoxytin, monobutyryloxytripentoxytin, monohexanoyloxytrimethoxytin, monohexanoyloxytriethoxytin, monohexanoyloxytripropoxytin, mono Monoacyloxytrialkoxytins such as benzoyloxytrimethoxytin, monobenzoyloxytriethoxytin, monobenzoyloxytributoxytin, monoacyloxytin trihalides such as monoacetoxytrichlortin, monoacetoxytribromtin, diacetoxydiethyl tin, diacyloxydialkyltins such as dipropionyloxydiethyltin, dibutyryloxydimethyltin, dihexanoyloxydiethyltin, dibenzoyloxydiethyltin, diacetoxydiethoxytin, diacetoxydipentoxytin, diacetoxydimethyltin Octoxytin, dipropionyloxydiethoxytin, dibutyryloxydimethoxytin,
Diacyloxydialkoxytins such as dibutyryloxydipentoxytin, dihexanoyloxydiethoxytin, dibenzoyloxydiethoxytin, diacyloxytin dihalides such as diacetoxydichlortin, diacetoxydibromtin, etc. , triacetoxymonomethyltin, triacetoxymonoethyltin, triacetoxymonopropyltin, tripropionyloxymonomethyltin, tripropionyloxymonoethyltin, tributyryloxymonomethyltin, trihexanoyloxymonomethyltin, trihexanoyloxymono Triacyloxymonoalkyltins such as ethyltin, trihexanoyloxymonopropyltin, tribenzoyloxymonomethyltin, tribenzoyloxymonoethyltin, tribenzoyloxymonobutyltin, triacetoxymonoethoxytin, triacetoxymonopropoxytin, Triacetoxymonobutoxytin, triacetoxymonopentoxytin, triacetoxymonoctoxytin, tripropionyloxymonomethoxytin, tripropionyloxymonoethoxytin, cypropionyloxymonopropoxytin, tripropionyloxymonobutoxytin, tributyl tin oxymonomethoxy, tributyryloxymonoethoxytin, tributyryloxytripentoxytin, trihexanoyloxytrimethoxytin, trihexanoyloxymonoethoxytin, trihexanoyloxymonopropoxytin, tribenzoyloxy Triacyloxymonoalkoxytins such as monoethoxytin and tribenzoyloxymonobutoxytin,
Acyloxy group-containing tin compounds such as triacyloxytin monohalides such as triacetoxymonochlortin and triacetoxymonobromtin, or these together with alkyltins such as tetramethyltin and tetraethyltin, methyl stannate, ethyl stannate, propyl Alkyl stannates such as stannate, butyl stannate, and pentyl stannate, tin halides such as tin tetrachloride and tin tetrabromide, tin acetate, tin propionate, tin valerate, tin caproate, and tin benzoate. Examples include mixtures with carboxylic acid tin and the like. These metal compounds are mixed in a proportion that satisfies m and n in the above general formula. Alternatively, polymers having acyloxy groups in side chains, such as poly(acetoxy-butoxy)siloxane, poly(propionyloxy-propoxy)titanoxane, poly(acetoxy-ethoxy)zirconoxane, poly(acetoxy-propoxy)stanoxane, poly(acetoxy-iso) Examples include polymetalloxanes such as propoxy)aluminoxane. Polymetalloxanes can also be produced by using acyloxyalkyl metals, acyloxyalkoxymetals, acyloxymetal halides, etc. as starting materials and condensing them, or by condensing these metals.
It can also be produced by reacting a polymetalloxane obtained by condensing an alkoxy metal or a metal halide with a carboxylic acid. Therefore, in the production of flaky inorganic substances, by using the above-mentioned specific acyloxy group-containing metal compound, it is possible to improve the removability of the coating film, the uniformity of the size of the flakes, the control of the size of the flakes, and the smoothness of the flakes. This makes it possible to produce flaky inorganic materials with improved and high gloss. In carrying out the method of the present invention, a coating solution is first prepared, and the preparation method may include mixing the acyloxy group-containing metal compound, other metal compounds, and an organic solvent in an appropriate ratio, or Aluminum halides such as aluminum chloride, alkoxyaluminum halides such as dichloromonoethoxyaluminum, aluminum alkoxides such as tripropoxyaluminum, aluminum compounds such as alkyl aluminum such as triethylaluminum, silicon halides such as silicon tetrachloride, trichloromonoethoxy Silicon compounds such as halogenated alkoxysilanes such as silane, alkyl silicates such as tetraethoxyorthosilicate, alkyl titaniums such as tetrapropoxytitanium, halogenated titaniums such as titanium tetrachloride, halogenated alkoxytitaniums such as trichlormonopropoxytitanium, tetra Titanium compounds such as alkyl titanates such as butyl titanate, zirconium halides such as zirconium tetrachloride, alkyl zirconiums such as tetraethyl zirconium, alkoxy zirconium halides such as trichloromonobutoxy zirconium, tetraalkyl zirconates such as tetrabutyl zirconate, etc. Zirconium compounds, tin halides such as tin tetrachloride and tin tetrabromide, alkyltin halides such as tetrabutyltin, alkyltin halides such as monochlorotributyltin, alkoxytin halides such as trichloromonooctoxytin, and alkyls such as tetrabutyl stannate. It may be prepared by adding and mixing a monocarboxylic acid having 1 to 10 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, etc. to a tin compound such as stannate, or an organic solvent solution thereof. . In carrying out the method of the present invention, any organic solvent can be used as long as it can dissolve the above-mentioned acyloxy group-containing metal compound as the organic solvent used for preparing the coating solution. Examples of such organic solvents include organic compounds with a boiling point of 150°C or less, such as hydrocarbons such as heptane, hexane, cyclohexane, benzene, and toluene, alcohols such as ethanol, propanol, and butanol, and oxygen-containing compounds such as acetone. . A known colorant 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 form into flakes, or it may have to be coated multiple times, making it economical. On the other hand, if it is too concentrated, workability will decrease, so it is generally 2 to 80% by weight, preferably 5%.
Applied at ~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 containing an acyl group-containing metal compound is applied to a heated or unheated substrate. Glass, metal, resin, etc. can be used as the substrate. 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. In order to make the thickness of the coating film uniform, for example, polymeric substances such as polyols and ethylcellulose, high-boiling substances such as butyl cellosolve and glycerin, nonionic or anionic surfactants, etc. may be added. In carrying out the method of the present invention, the coating solution applied to the substrate is exposed to a hydrolyzing agent such as air or water vapor-containing gas at room temperature to 250 DEG C., thereby hydrolyzing the coating film and causing cracks. The relative humidity in the hydrolyzing agent is generally between 20 and 95%, especially between 30 and 70%. A typical hydrolysis method is to apply a coating liquid onto a substrate in the atmosphere, and then heat the coated surface with an infrared heater or the like. Particularly in the case of a solvent with low volatility, heating is desirable. As a result, the solvent in the coating film evaporates, and at the same time or afterwards, the metal compound is hydrolyzed and cracks occur. According to the method of the present invention, flakes with excellent releasability are produced, and the size of the flakes produced by cracking is relatively uniform, so that the production yield can be high;
Moreover, the advantage that the size of the flakes can be controlled by the combination of the solvent and the acyloxy group can be achieved. In carrying out the method of the present invention, cracks in the thin film on the substrate are removed by peeling them off with a scraper or the like. A flaky inorganic material can thereby be obtained. The thin pieces of titanium, zirconium, etc. recovered as described above are transparent and have a high luster, so they can be used as they are, but depending on the purpose, about 200 pieces of
The product is calcined at a temperature of ~1100°C, preferably 500~900°C. The flaky inorganic material 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 and about 0.01 to 10 μm in thickness, but is not limited to this. 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, pearlescent pigments or extender pigments used as filling materials for plastics for food packaging, transparent tubes for titrium 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 also has excellent releasability, uniformity of flake size, and This method has the advantage of being able to produce flaky metal oxides with excellent controllability of thickness, smoothness of flakes, etc. 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 coating solution was prepared by adding each of the organic acids shown in Table 1 to a 40% by weight butanol solution of titanium tetrabutoxide in an amount equivalent to the amount of titanium in the solution, and then reacting at 70°C for 2 hours. . A slide glass, which had been washed with a surfactant, washed with water and dried, was immersed in these solutions and pulled up at a speed of 75 cm/min. This was dried in an air bath at 90°C for 30 minutes, and the degree of exfoliation was measured. Next, scrape off the thin piece onto the slide glass with a scrubber and remove the thin piece.
It was baked at 900°C for 30 minutes. The size of the obtained flakes,
The thickness is shown in Table 1. It should be noted that the degree of flaking is expressed as a percentage of the area that becomes flaky after drying to the area of the liquid film initially deposited on the slide glass. Example 2 48% by weight of titanium tetoisopropoxide
Acetic acid was added to the ethanol solution in the ratio shown in Table 2 relative to the titanium in the solution, and the mixture was mixed and stirred for 30 minutes. A thin piece was formed on a glass slide in the same manner as in Example 1. The results are shown in Table 2. The numbers in the table have the same meanings as above. Example 3 To a 15% by weight toluene solution of titanium tetraethoxide, propionic acid in an equimolar amount to the titanium contained was added and mixed for 1 hour, and then mixed at 5 rpm.
It adhered to a rotating stainless steel roll with a diameter of 20 cm, and after drying, the flakes were collected with a scraper. More than 90% of these flakes have a size of 7 μm ± 2 μm.
It was a fine flake with a thickness of 0.2 to 0.3 μm and a uniform grain size. When this was baked at 700°C for 30 minutes, transparent flakes with a size of about 5 μm were obtained. In the above experiment, all the same operations were performed except that propionic acid was not added, and the size was 5 μm.
-100 μm flakes were obtained. Even after firing, there were variations in size, so when we crushed them to adjust the particle size, about 20% of them turned into powder, and of the remaining 80%, 70% of the flakes were 3 μm to 8 μm in size. . Example 4 34 g of titanium tetrabutoxide was dissolved in isopropanol to make a solution with a concentration of 30% by weight, and 1.8 g of distilled water was added dropwise over 10 minutes to synthesize polytitanoxane. Next, the polytitanoxane solution was heated at 70° C. for 2 hours, and 7.4 g of propionic acid was added dropwise over 10 minutes to prepare a coating solution. A cleaned slide glass was immersed in the coating solution, pulled up at a speed of 75 cm/min, and then dried in an air bath at 90°C for 30 minutes. A glossy thin piece with a size of 50 to 80 μm and a thickness of 0.2 μm was obtained. It was done. The flaking rate was 100%. In the above experiment, all the same operations were performed except that propionic acid was not added, and the flaking rate was 80.
%, and the obtained flakes were curled,
It was inferior to Example 4. Example 5 An 8% by weight toluene solution of aluminum isopropoxide was prepared, and acetic acid was added thereto in the ratio shown in Table 3 relative to the aluminum in the solution. Approximately 1
After stirring for an hour, the cleaned glass slides were immersed and withdrawn at a speed of 75 cm/min. This was dried in an air bath at 90°C for 1 minute. The results are shown in Table 3. Example 6 A 30% by weight hexane solution of zirconium tetrabutoxide was prepared, and acetic acid was added to the solution in an equimolar amount to the zirconium in the solution.
The mixture was heated and stirred for a period of time to prepare a coating solution. A cleaned glass slide was immersed in this coating solution and pulled up at a rate of 75 cm/min, and then dried in an air bath at 90°C for 30 minutes.
A shiny flake of 100 μm and 1 μm thick was obtained. When this was fired at 1000℃, the size was 15 to 60μ.
It became a thin piece with a thickness of 0.6 μm. In the above experiment, all the same operations were performed except that acetic acid was not added, and the flaking rate was 30%, but the obtained flakes were curled and the size varied from 5 μm to 200 μm after firing. It was big. Example 7 12.32g of zirconium tetrachloride and 100g of ethanol
were mixed in a 300 ml flask and heated at 70°C for 2 hours to synthesize dichlorodiethoxyzirconium. After expelling hydrogen chloride from the reactants
After adding 6.0 g of acetic acid and heating at 70°C for an additional hour,
Cooled. Thereafter, thin pieces were obtained in the same manner as in Example 6. The size of the flakes was 20 to 60 μm and 0.4 μm thick after firing, and the flaking rate was 100%. In the above experiment, when all the operations were the same except that acetic acid was not added, the flaking rate was 10%, and the remainder was a whitish film. Example 8 To a 40% by weight ethanol solution of tetraethyl orthosilicate, formic acid with an amount twice the mole of Si in the solution was added, and after stirring and mixing at 70°C for 3 hours, a washed slide glass was immersed in this solution. . After this glass was pulled up at 75 cm/min, it was placed in an air bath.
It was dried at 90° C. for 30 minutes to obtain transparent flakes with a size of 50 to 400 μm and a thickness of 1 μm with a smooth surface. The flaking rate was 100%. This was baked at 450℃ for 30 minutes, and the size was 30-
A transparent thin piece of 250 μm and 0.7 μm thick was obtained. In the above experiment, when all the same operations were performed except that formic acid was not added, the slide glass turned pure white and no thin sections were obtained. Example 9 After dissolving 41.7 g of tetrabutoxytin in 300 g of a 1:1 mixed solvent of isopropanol/toluene,
12 g of acetic acid was added, and the mixture was heated and reacted at 70°C for 2 hours. After immersing the slide glass in this solution, 75cm/
When pulled up at a speed of 10 minutes and dried in an air bath at 90℃ for 30 minutes, the size was 100-500 μm and the thickness was 1 μm.
A thin section was obtained. Add this to antimony trichloride.
After being immersed in a wt% ethanol solution, it was dried again and then baked at 700°C for 1 hour to obtain bluish flakes with a size of 60-300 μm and a thickness of 0.7 μm. The specific resistance of the thin piece was 10Ω·cm. In the above experiment, when all the same operations were performed except that acetic acid was not added, the slide glass turned pure white and no thin sections were obtained. Example 10 19.0 g of titanium tetrachloride was added dropwise to 100 g of isopropanol in a 300 ml flask. After dropping, the mixture was heated to 70°C and stirred for 2 hours. As a result, 23.7 g of dichlorodiisopropoxytitanium and 7.3 g of hydrogen chloride are produced in the solution.
After adding 10.2 g of valeric acid to this solution and further reacting at 70°C for 2 hours, this solution was transferred to a beaker, and the washed slide glass was immersed in this solution.
When the film was pulled up at a rate of cm/min and then dried in an air bath at 90°C for 30 minutes, the flaking rate was 100%. When the flakes were collected and fired at 1000°C for 1 hour, highly glossy particles with a size of 50 μm to 150 μm and a thickness of 1.5 μm were obtained.

[Table] Comparing Experiment No. 1 and Nos. 2 to 5, the degree of flaking,
The effect of reacting with an organic acid is clear, both in terms of the variation in the size of the flakes. Also, from Experiment No. 6, it can be seen that the effect decreases when the number of carbon atoms is too large. Experiment No.
From the results of 2 to 5, it can be seen that by increasing the number of carbon atoms in the organic acid, the flakes become larger. Therefore, by changing the type of organic acid, it is possible to control the size of the flakes.

[Table] From the above results, the effect of adding acetic acid is already clear at 0.1 mol (relative to titanium). Also, it can be seen that the variation in the size of the flakes decreases as the amount of acetic acid added increases, but from experiment number 12, acetic acid cannot bind more than 4 moles to titanium, so even if more than this is added, It turns out that it is effectively meaningless.

[Table] From Table 3, it can be seen that when obtaining aluminum isopropoxide flakes, the number of moles of acetic acid relative to aluminum is preferably 1 or more. Example 11 and Comparative Example 7 Powder powder

[Table] Oxide flakes (A) are titanium oxide prepared in Example 3. In Comparative Example 7, aggregation occurred due to a small amount of added oil, but in Example 11, no aggregation occurred. In addition, as a result of the sensory test, Example 11 had better transparency than Comparative Example 7.
The spreadability was excellent, and the adhesion was the same. Example 12 and Comparative Example 8 Cake-shaped eyeshadow

【table】

[Table] The oxide flake (D) is made of titanium oxide made in Example 1, Experiment No. 2, and has high brightness. Example 12 and Comparative Example 8 were evaluated by sensory evaluation.
Although the spreadability, adhesion, and pearly feel were the same, Example 12 was superior in transparency, smoothness, and finish.

Claims (1)

[Claims] 1. Applying a liquid or organic solvent solution of a metal compound characterized by having an acyloxy group onto a smooth surface, hydrolyzing the coating film with water or steam,
A method for producing a flaky inorganic substance, which comprises peeling off the hydrolyzed metal compound thin film to form flakes. 2. Applying a liquid or organic solvent solution of a metal compound characterized by having an acyloxy group onto a smooth surface, and hydrolyzing the coating film with water or steam,
A method for producing a flaky inorganic substance, which comprises peeling off the hydrolyzed metal compound thin film and baking it to obtain a metal oxide flake. 3 Groups 3b and 4a of the periodic table as metals in metal compounds.
3. The method for producing a flaky inorganic material according to claim 1 or 2, characterized in that a metal selected from Group 4b or Group 4b is used. 4. Claim 1 or 2, characterized in that one or more selected from the group consisting of silicon, aluminum, titanium, tin, and zirconium is used as the metal of the metal compound.
A method for producing a flaky inorganic substance as described in Section 1. 5. The metal compound is a reaction product of one or more selected from metal chlorides, metal alkoxides, halogenated metal alkoxides, and polymetalloxanes which are condensates thereof, and an organic acid. A method for producing a flaky inorganic material according to claim 1 or 2. 6. Claim 1, wherein the acyloxy group is an acyloxy group having 1 to 10 carbon atoms.
A method for producing a flaky inorganic substance according to item 1 or 2. 7 Applying a liquid or organic solvent solution of a metal compound characterized by having an acyloxy group onto a smooth surface, hydrolyzing the coating film with water or steam,
A flaky inorganic substance produced by peeling off the hydrolyzed metal compound thin film. 8 Applying a liquid or organic solvent solution of a metal compound characterized by having an acyloxy group onto a smooth surface, hydrolyzing the coating film with water or steam,
A flaky inorganic material produced by peeling off the hydrolyzed metal compound thin film and firing it to form metal oxide flakes. 9 Applying a liquid or organic solvent solution of a metal compound characterized by having an acyloxy group onto a smooth surface, hydrolyzing the coating film with water or steam,
A cosmetic comprising a flaky inorganic material produced by peeling off the hydrolyzed metal compound thin film. 10 Applying a liquid or organic solvent solution of a metal compound characterized by having an acyloxy group onto a smooth surface, hydrolyzing the coating film with water or steam, and peeling off the hydrolyzed metal compound thin film,
A cosmetic comprising a flaky inorganic material produced by firing metal oxide flakes.