JP4583129B2 - Layered compound, method for producing the same, and hard film - Google Patents

Description

  The present invention relates to a layered compound, a method for producing the same, and a hard film. More specifically, the present invention includes a solid layered compound containing hafnium and / or zirconium, which is easy to transport, an efficient method for producing the same, and the layered compound. The present invention relates to a hard film formed from a coating layer and having high hardness and excellent hydrophobicity.

  As a typical inorganic layered compound, silicate or aluminosilicate which is a clay mineral has been known for a long time. In recent years, thin plate-like hydrous zirconia microcrystals and methods for producing the same have been known (see Patent Documents 1 and 2).

JP-A-62-223018

Japanese Patent Laid-Open No. 62-7629

The invention described in Patent Document 1
“A compound with a layered structure consisting of metal ions mainly composed of Zr and anions mainly composed of O. The main peak of the powder X-ray diffraction pattern in which the mutual position of Zr and O is similar to the ZrO ₂ crystal. A thin plate-like hydrous zirconia microcrystal characterized in that some of the crystals are crystals substantially in the same position as square or cubic ZrO ₂ , spread in a direction parallel to the layer surface, and have a thickness of 200 mm or less.
And “Heat treatment of acidic aqueous solution containing 0.1 to 1.0 g · atom / l of soluble zirconium salt as Zr and 0.2 to 2.0 g · atom / l of SO ₄ ^2- ion at a pH of 2 or less at 100 to 300 ° C. to first to produce a thin plate-like containing SO ₄ ^2-zirconia crystallites, lamellar hydrated zirconia crystallites of microcrystalline and removing substituting SO ₄ ^2-ions was aged in a basic aqueous solution Manufacturing method. "
It is.

In Patent Document 1,
“This invention is an additional invention of 1985 Patent Application No. 147238 (this patent application was published as Japanese Patent Application Laid-Open No. 62-7629, which is the above-mentioned Patent Document 2). The present invention relates to a thin plate-like hydrated zirconia microcrystal and a production method that are substantially the same in purpose and use and change to a more excellent thin plate-like zirconia crystallite by heating.
(See Patent Document 1, page 1, left column, line 20 to page 1, right column, line 4).

In addition, in Patent Document 1,
“The sheet-like hydrous zirconia crystallites of the present invention contain 0.1 to 1.0 g · atom / l of soluble zirconium salt as Zr and PH ² or less containing 0.2 to 2.0 g · atom / l of SO ₄ ^2- ion. First, a thin plate-like SO ₄ ^2- zirconia microcrystal is formed by heat treatment at 100 to 300 ° C., and the microcrystal is aged in a basic aqueous solution to remove SO ₄ ^2- ion by substitution. Obtainable."
(See the second page, upper left column, lines 9 to 15 of Patent Document 1).

The invention described in Patent Document 2
“1) A compound having a layered structure containing a metal ion mainly composed of Zr and SO ₄ ²⁻ ions having approximately 2/5 of the number of atoms, and having a hexagonal or trigonal crystal axis perpendicular to the layer surface, Is a crystal in which the mutual position of O and O is similar to the crystal of ZrO ₂ , and some of the main peaks of the powder X-ray diffraction pattern are substantially the same position as the tetragonal or cubic ZrO _2, and extend in parallel to the layer surface. A thin plate-like zirconia-based microcrystal having a thickness of 500 mm or less.

  2) A thin plate-like zirconia microcrystalline powder, characterized in that the powder particles are formed of dense or porous zirconia microcrystals having a thin plate shape having a thickness of 500 mm or less and a width direction of 5 times or more.

3) An acidic aqueous solution with a pH of 1.0 or less containing 0.1 to 1.5 g · atom / l of water-soluble zirconium salt as Zr and 0.3 to 3.0 g · atom / l of SO ₄ ^2- ion. A method for producing a thin plate-like zirconia-based microcrystal, which is heat-treated at 350 ° C.

4) An acidic aqueous solution having a pH of 1.0 or less and containing 0.1 to 1.5 g · atom / l of a soluble zirconium salt as Zr and 0.3 to 3.0 g · atom / l of SO ₄ ^2- ion is 110 to 350 A method for producing a thin plate-like zirconia fine crystal powder, which comprises synthesizing thin plate-like fine crystals by heat treatment at 0 ° C., and heat-desulfurizing the fine crystals to obtain thin plate-like fine particles of oxide. "
It is.

In claim 1 of Patent Document 1, there is a description of “a compound having a layered structure composed of a metal ion mainly composed of Zr and an anion mainly composed of O”. The “layered structure compound” disclosed in 1 is a structure in which a sulfate (anion) ion is coordinated to a Zr atom, and there is no disclosure of a compound having a layered structure other than such a structure, Since the invention described in Patent Document 1 has the same object and application as the invention of Patent Document 2, “a compound having a layered structure comprising a metal ion mainly composed of Zr and an anion mainly composed of O” "Is understood to be a compound having a layered structure composed of metal ions mainly composed of Zr and SO ₄ ^2- ions".

  The method for producing thin plate-like microcrystals described in Patent Document 1 is mixing sulfuric acid and a soluble zirconium salt, and no method other than the production method is disclosed.

  Moreover, the said patent document 1 does not have description about forming a hard film | membrane using the layered compound containing hafnium and / or zirconium, and a carbonyl group, and there is no description which suggests this.

  The invention described in Patent Document 2 has the same contents as the invention described in Patent Document 1.

  Unlike the inventions described in Patent Documents 1 and 2, this invention is formed from a solid hafnium and / or zirconium layered compound, an efficient production method thereof, and a coating layer containing the layered compound, which are easy to transport. It is an object of the present invention to provide a hard film having high hardness and excellent hydrophobicity.

The first means for solving the problems of the present invention is as follows:
(1) containing hafnium and / or zirconium and COO group is a layered compound, characterized by chromatic reflection peak at 2 [Theta] = 10 ° by X-ray diffraction (XRD) (CuKa line used).

The second means for solving the problems of the present invention is as follows:
(2) 100 parts by mass of hafnium hydroxide and / or zirconium hydroxide, 50 to 1000 parts by mass of water and 900 to 5000 parts by mass of carboxylic acid are mixed , heated to 50 to 100 ° C., and precipitates generated by heating are collected. a method of producing a layer compound according to claim 1, characterized in that.

The third means for solving the problems of the present invention is as follows:
(3) A hard film formed by irradiating the coating layer containing the layered compound of (1) with ultraviolet rays.

As a preferable aspect in the third means,
A hard film in which the coating layer contains a silane coupling agent and a hard film in which the coating layer contains an organic substance can be mentioned.

  According to the invention of the above (1), a solid layered compound containing hafnium and / or zirconium is provided, and this layered compound is easy to transport and can be used as a raw material for a hard film. A hard film can be easily formed.

  Moreover, according to the invention of (2), an efficient method for producing the hafnium and / or zirconium layered compound is provided.

  Further, according to the invention of (3) above, by irradiating the coating layer formed by coating the substrate with the aqueous solution containing the hafnium and / or zirconium layered compound, a glass substrate, a stainless steel substrate, or A hard film having a pencil hardness of 9H or more can be formed on a substrate such as a plastic substrate. This hard film is easier to implement on site by carrying the solid layered compound containing hafnium and / or zirconium to the site where the hard film is formed, preparing the coating solution on the site, and forming the coating layer. Can be formed.

  The layered compound of the present invention is a compound containing hafnium and / or zirconium and a carbonyl group.

  The layered compound according to the present invention is characterized by containing hafnium and / or a zirconium atom and a carbonyl group, and the hafnium ion and / or zirconium ion and an oxygen atom in the carbonyl group are coordinated. Presumed to be. The carbonyl group contained in the layered compound can be derived from a carboxylic acid represented by RCOOH (where R represents a hydrogen atom or a lower alkyl group).

When the layered compound is observed with a scanning electron microscope (SEM), it is observed as having a structure in which a large number of sheet-like materials are laminated. As a result of qualitative analysis by energy dispersive X-ray spectroscopy (EDS), this layered compound was confirmed to contain Hf (or Zr), C, and O. Moreover, since Cl and N were not observed, it became clear that Cl ⁻ ions and NH ₄ ⁺ ions were not contained.

Further, the layered compound was observed to have absorption based on COO groups by Fourier transform infrared absorption spectrum (FTIR spectrum). Moreover, according to X-ray diffraction (XRD), the layered compound has a reflection peak observed in the vicinity of 2θ = 10 ° (using CuK _α- ray), indicating that it has a layered structure. This layered compound is water-soluble. Therefore, the layered compound can be dissolved in an aqueous solvent such as water and a mixed solvent such as a lower water-soluble alcohol such as methyl alcohol and ethyl alcohol.

  Further, the layered compound according to the present invention may be a single layered compound of a compound containing hafnium and a carbonyl group or a compound containing zirconium and a carbonyl group, or a mixed layered compound of both. Good. There is no restriction | limiting in particular in the mixing ratio of both.

  In general, in forming a film such as a hard film by a wet method such as a sol-gel method, a sol is used as a coating solution. Generally, the solid content in the sol is 1 to 10% by mass, and the other component is a solvent such as alcohol. By applying the sol, the solvent is removed, and only a useful solid content remains to form a film. Therefore, when the sol is transported, the solvent that does not directly contribute to the formation of the film must be transported at the same time, which is reflected in the transportation cost. Moreover, the pot life of sol is at most one year, and further improvement is required.

  Since the layered compound of the present invention is solid and is only a component useful for the formation of a film, it is lighter than the sol and easy to carry, and can reduce transportation costs. In addition, the layered compound of the present invention is stable at room temperature and does not change its structure for at least one year. Therefore, a long life can be maintained as a material for forming the hard film. And since the layered compound of this invention is water-soluble, the preparation of the coating liquid used for formation of the said hard film is easy, and a hard film can be easily formed by field construction.

  The layered compound according to the present invention can be manufactured by the manufacturing method according to the present invention, that is, by mixing and heating hafnium hydroxide and / or zirconium hydroxide, water and carboxylic acid.

  Hafnium and / or zirconium hydroxide is obtained by mixing a salt solution containing a salt of hafnium and / or zirconium or an alkoxide solution containing an alkoxide of the above element with aqueous ammonia and / or amines. Can do.

  Examples of the hafnium or zirconium salt include halides, acetates, sulfates, carbonates, nitrates, and the like, and preferred salts are halides.

  As the hafnium halide, hafnium tetrachloride, hafnium tetrafluoride, hafnium tetrabromide, hafnium tetraiodide, and hafnium tetrachloride are preferable.

  Examples of the zirconium halide include zirconium tetrachloride, zirconium tetrafluoride, zirconium tetrabromide, zirconium tetraiodide, and zirconium dichloride oxide octahydrate.

  The hafnium or zirconium alkoxide is not particularly limited, but alkoxides having 5 or less carbon atoms, specifically, methoxide, ethoxide, propoxide, butoxide, and pentoxide are preferable.

  Examples of the solvent in the above-described salt solution or alkoxide solution include water and organic solvents such as alcohol, ketone, amine, and amide, and the solvent preferably used is water. When using an organic solvent, water-soluble organic solvents such as methanol, ethanol, butanol, isopropanol, vinyl alcohol, acetone, methyl ethyl ketone, and dioxane are preferred.

  The ammonia solution or amine mixed with the salt solution or alkoxide solution of the element contains ammonia and / or amines. Examples of the amines include primary amines, secondary amines, and tertiary amines.

  Although there is no restriction | limiting in the density | concentration of the hafnium chloride in the said hafnium chloride aqueous solution, Usually, 1-70 mass%, Preferably it is 1-50 mass%. Moreover, although there is no restriction | limiting in particular in the addition amount of the said ammonia water, It is preferable to set it as the quantity from which the pH of the said hafnium chloride aqueous solution will be 7-14.

  Zirconium hydroxide used in the method for producing a layered compound of the present invention is different from the production of hafnium hydroxide in particular, except that a zirconium compound such as zirconium chloride or zirconium chloride is used in place of the hafnium chloride. There is no. Alternatively, an aqueous solution of a mixture of hafnium chloride and zirconium chloride may be prepared, and a mixture of hafnium hydroxide and zirconium hydroxide may be produced in the same manner as described above. The mixing ratio of hafnium hydroxide and zirconium hydroxide is arbitrary.

  The layered compound of the present invention can be produced by adding water and a carboxylic acid to the hafnium hydroxide and / or zirconium hydroxide thus produced, mixing the mixture, and heating.

  Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, glycolic acid, lactic acid, glyceric acid, oxalic acid, and malonic acid. Among these, formic acid, acetic acid, oxalic acid, and malonic acid are preferable.

  The amount of water and carboxylic acid added is not particularly limited, but the amount of water added is usually 50 to 1000 parts by mass, preferably 100 to 600 parts by mass with respect to 100 parts by mass of hafnium hydroxide or zirconium hydroxide. The amount of carboxylic acid added is usually 900 parts by mass or more, preferably 900 to 5000 parts by mass.

  The heating conditions are usually from 50 to 100 ° C., preferably from 65 to 95 ° C., usually from 0.1 to 30 hours, preferably from 1 to 24 hours. The selected conditions can be adopted as appropriate.

  Since the hafnium hydroxide or zirconium hydroxide and carboxylic acid used in the production of the layered compound of the present invention are easily dissolved in water, the method for producing the layered compound of the present invention is complicated and does not involve many steps. Thus, the layered compound can be produced efficiently without taking any measures.

  The hard film of this invention can be formed by irradiating the coating layer containing the layered compound with ultraviolet rays.

  The hard film of the present invention is prepared by first preparing a coating solution for forming a coating layer, then coating the coating solution on a substrate to form the coating layer, and then irradiating the coating layer with ultraviolet rays. Formed by.

  The coating solution is prepared as an aqueous solution of a layered compound obtained by dissolving the layered compound in water. Although there is no restriction | limiting in the density | concentration of the layered compound in the aqueous solution of this layered compound, Usually, 1-40 mass%, Preferably you may be 1-20 mass%.

  The coating liquid preferably contains a silane coupling agent. This is because a coating layer formed by coating a coating solution containing a silane coupling agent on a substrate gives a hard film having excellent adhesion to the substrate. Moreover, it is preferable that the coating liquid contains an organic substance. This is because a hard film having excellent durability can be obtained. The silane coupling agent and the organic substance may each be contained alone in the coating solution, or both may be contained.

  Examples of the silane coupling agent include silane compounds having a functional group. Examples of the functional group include an amino group, a mercapto group, an epoxy group, a methacryloxyl group, an alkoxyl group, a glycidyl group, and a vinyl group. Can be mentioned.

Among such silane coupling agents, the general formula R ¹ _l X _m SiR ² _n (wherein R ¹ has an alkyl group, X has an alkoxy group or a halide ion, and R ² has an organic functional group) An alkyl group, l, m and n are each 0, 1, 2, 3 or 4 and l + m + n is 4.). The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 5 carbon atoms. The organic functional group bonded to the alkyl group represented by R ^2, -Y-Z (however, Y is a single bond or carbon atoms an alkylene bond 1 to 3, Z is a vinyl group, an epoxy group, glycidyl _{group, -X (CH 3) = CH} 2, -NH 2, -CH 2 Cl, -SH, glycidyloxy group, 1-methylvinyl carboxymethyl group, 2-amino - ethylamino group, 3,4-epoxycyclohexyl Group, etc.), particularly vinyl group, epoxy group, glycidyl group, 1-methylvinyl group, amino group, chloromethyl group, mercapto group, glycidyloxypropyl group, 1-methyl group. Preferred examples include -vinylcarbooxypropyl group, 2-amino-ethylaminopropyl group and the like.

  Specific examples of such silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, N β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl- γ-aminopropyl-aminopropyltrimethoxysilane, γ-chloropropylmethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-trihydroxysilylmethylphosphonate sodium salt, nitroclotris (methylene) triphosphonic acid, tris (trimethylsilyl) phosphate, tris (Trimethylsilyl) phosphite, diethyl phosphate ethyltriethoxysilane and the like can be mentioned.

  Moreover, as said organic substance, at least 1 type chosen from the photocurable monomer, the polymer which uses the said photocurable monomer as a structural unit, a tannin, and a koxib can be mentioned.

  Examples of the photocurable monomer include an ultraviolet curable monomer, and include (meth) acrylic acids such as acrylic acid, methacrylic acid and crotonic acid, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, Monofunctional acrylates such as 2-hydroxypropyl acrylate, tetrahydrofurfryl acrylate, 1,6-hexanediol monoacrylate and dicyclopentanediene acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 1,3- Butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, polyethylene glycol 400 Difunctional acrylates such as acrylate and tripropylene glycol diacrylate, trimethylol propane triacrylate, may be mentioned trifunctional or higher acrylate such as pentaerythritol triacrylate and dipentaerythritol hexaacrylate. Of these photocurable monomers, (meth) acrylic acids are preferred.

  Examples of the polymer having the photocurable monomer as a constitutional unit are obtained by polymerizing the (meth) acrylic acid, the monofunctional acrylate, the bifunctional acrylate, or the trifunctional or higher acrylate with ultraviolet irradiation. Poly (meth) acrylic acids or polyacrylates that can be used. Among these polymers, poly (meth) acrylic acids are preferable.

  Tannin is a substance that is contained in plants such as bark and seeds and produces polyhydric phenol carboxylic acid by hydrolysis. It is classified into hydrolyzable tannin that produces water-soluble gallic acid and the like by hydrolysis and condensed tannin that produces insoluble flovafenic acid and the like. The tannin used in the present invention may be any tannin. m-Galoyl gallic acid is also a kind of tannin and can be used similarly.

  Further, kakibib is a polymer of tannin, and for example, a liquid containing a high-molecular substance composed of oyster tannin collected from astringency can be cited. The molecular structure of this oyster tannin is Kagoshima University. Is presumed to have the following structure.

Although there is no particular limitation on the amount of monkey silane coupling agent and / or organic substance in the coating liquid, to Hafuniazoru 100 parts by weight of an HfO ₂ converted, is usually 50 to 5000 parts by weight, preferably 50 to 2,000 parts by weight It is said.

  Although there is no restriction | limiting in the material of the board | substrate with which the said coating liquid is apply | coated, Glass, a metal, or a plastic can be mentioned as a preferable material.

  Examples of the glass include quartz glass, 96% quartz glass, soda lime glass, soda lime glass, aluminoborosilicate glass, borosilicate glass, aluminosilicate glass, alkali-free glass, lead glass, and the like. .

  Examples of the metal include ordinary steel, structural constant alloy steel, high-tensile steel, heat-resistant steel, high-chromium heat-resistant steel, high-nickel-chromium heat-resistant steel and other alloy steel, stainless steel and other steel materials, and industrial use. Aluminum alloy such as pure aluminum, 5000 series alloy, Al-Mg series aluminum alloy, 6000 series aluminum alloy, copper alloy such as silver-filled copper, tin-filled copper, chromium copper, chromium-zirconium copper, zirconium copper, pure titanium, Examples thereof include titanium alloys such as a drag titanium alloy and a corrosion resistant titanium alloy.

  Examples of the plastic include polycarbonate, polyethylene, polypropylene, polyamide, polyacrylate, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polyphenylene sulfide, and polyimide.

  Furthermore, for example, on the surface of the plastic, on the surface of ceramics such as mullite porcelain, alumina porcelain, zircon porcelain, cordierite porcelain, steatite porcelain, and further on the surface of various metals such as steel and stainless steel, Examples thereof include materials plated with gold plating, nickel plating, chrome plating, and the like.

  The hard film of the present invention is formed by applying the coating solution on a substrate to form a coating layer, and irradiating the coating layer with ultraviolet rays. Prior to coating the coating solution on the substrate, It is preferable to clean the substrate surface. This is because by cleaning the substrate surface, a uniform coating layer can be formed without causing repelling.

  Examples of the cleaning means include a cleaning means using a detergent, particularly a neutral detergent, when the substrate is glass, and a metal surface using a degreasing agent when the substrate is metal. A means for degreasing the surface can be mentioned.

  As the degreasing agent, a degreasing agent containing a basic compound is suitable, and examples of the basic compound include sodium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, and sodium borate. Can do. Examples of the degreasing agent include commercially available alkaline cleaners such as cleaner E33 (trade name) commercially available from Atotech Japan Co., Ltd., die cleaner (trade name) commercially available from Daido Chemical Industries, Ltd., and Meltex. Cleaner S-61 (trade name), Enbond CA-S (trade name), Enbond Q-547 (trade name) and cleaner 160 (trade name), commercially available from Okuno Pharmaceutical Co., Ltd. Top Clean (trade name), Top Cleaner (trade name), A-screen (trade name), etc. can be easily obtained. These degreasing agents are used as a solution dissolved in a solvent, and water is usually used as the solvent. The concentration of the degreasing agent in the solution containing the degreasing agent is usually 0.1 to 60% by mass.

  Examples of the method for applying the coating solution onto the substrate include a dipping method in which the substrate is immersed in the coating solution and slowly lifting it, a casting method in which the coating solution is cast on a fixed substrate, and a coating solution. A continuous method in which the substrate is immersed in the coating solution from one end of the tank, and the substrate is taken out from the other end of the bath. The cloth solution is dropped on the rotating substrate, and the coating solution is applied onto the substrate by centrifugal force acting on the substrate. Examples thereof include a spinner method for casting, a spray method for spraying a coating liquid on a substrate, and a flow coating method.

  In this manner, the hard film of the present invention is formed by applying the coating liquid on the substrate to form a coating layer and irradiating the coating layer with ultraviolet rays. Examples of the light source used for ultraviolet irradiation include a high-pressure mercury lamp, a low-pressure mercury lamp, an excimer laser, and an Nd: YAG laser. By using these light sources, ultraviolet rays can be irradiated at low cost. The irradiation time is usually 1 minute to 1 hour.

  The hardness of the hard film (hafnia film and / or zirconia film) formed by irradiating the coating layer with ultraviolet rays can be evaluated by a pencil hardness method (JIS K 5400). The pencil hardness of the hard film of this invention is 9H or more.

  Further, the hydrophobicity of the hard film of the present invention can be evaluated by the contact angle of a water droplet measured using a contact angle meter. The contact angle of the hard film of this invention is 85 ° or more.

  Furthermore, the hard film of the present invention is a film that is transparent and free from cracks. Further, it was confirmed by an X-ray diffractometer that the hard film of the present invention was amorphous (amorphous).

  Attached to various equipment, equipment, machinery and equipment, such as automobile window glass, automobile painted surfaces, kitchen equipment, kitchen utensils, kitchen equipment, having high hardness and requiring or desired hydrophobic treatment By forming the hard film of the present invention on the surface of exhaust devices, bathing facilities, wash facilities, medical facilities, medical equipment, mirrors, glasses, etc., the hard film of the present invention fully functions. Will be fulfilled.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
16.3 g of hafnium chloride (HfCl ₄ ) was dissolved in 96 g of water under a nitrogen atmosphere. To the obtained solution, 27 ml of 29% ammonia water was added until pH 9.0, and the produced hafnium hydroxide precipitate was filtered, and the precipitate was washed with pure water until the filtrate became pH 7 or less. did. 41 g of pure water and 158 g of formic acid are added to the washed precipitate (sometimes referred to as a washed precipitate), and the heating temperature is adjusted to be within the temperature range of 80 to 90 ° C. for 5 hours. After stirring, the mixture was cooled to room temperature. The produced white precipitate was subjected to suction filtration and air-dried to obtain a hafnium-containing layered compound (Hf-1). An electron micrograph of the layered compound (Hf-1) is shown in FIG. 1, and an X-ray diffraction chart of the layered compound (Hf-1) is shown in FIG.

  The layered compound (Hf-1) thus obtained (2.5 g) was added to 22.5 g of pure water, and the mixture was stirred for 1 hour while adjusting the heating temperature so as to be in the temperature range of 55 to 60 ° C. An aqueous solution of compound (Hf-1) was prepared. On the other hand, a glass substrate made of soda lime glass was washed with a neutral detergent, rinsed with pure water, and then air-dried. The aqueous solution of the layered compound (Hf-1) was applied on the glass substrate by a spinner method. This coated sample was placed 9 cm below the light source, and irradiated with ultraviolet rays for 10 minutes using a 1 kw high-pressure mercury lamp (H1000L, manufactured by Toshiba Lighting & Technology Corp.) to form a hard film on the glass substrate.

  The hard film formed on the glass substrate was transparent, and no cracks were observed when observed with a 10-fold magnifier. The pencil hardness of the hard film was 9H or higher. In addition, the contact angle of the hard film with respect to water was measured by a contact angle meter (CA-D, manufactured by Kyowa Interface Science Co., Ltd.) (At this time, the glass substrate on which the hard film was formed was left indoors for 7 days. Measured later). The contact angle was 92 °. Furthermore, the structure of the hard film was examined using an X-ray diffractometer (RAD-2B, manufactured by Rigaku Corporation). Measurement was performed up to 2θ = 5 to 90 °, but no sharp reflection peak could be observed except for the glass halo pattern. From this, it was found that the hard film was amorphous.

(Example 2)
A hafnium-containing layered compound (Hf-2) was obtained in the same manner as in Example 1 except that the amount of formic acid used was 104 g.

  2.5 g of the layered compound (Hf-2) thus obtained was dissolved in 47.5 g of pure water at room temperature to prepare an aqueous solution of the layered compound (Hf-2). Using this aqueous solution of the layered compound (Hf-2), a hard film was formed in the same manner as in Example 1.

  The hard film formed on the glass substrate was transparent, and no cracks were observed when observed with a 10-fold magnifier. The pencil hardness of the hard film was 9H or higher. The contact angle measured in the same manner as in Example 1 was 89 °. Further, as in Example 1, it was found that the hard film was amorphous.

(Example 3)
Hafnium as in Example 1, except that 168 g of acetic acid was used instead of formic acid, and heating was carried out for 3 hours instead of heating for 5 hours while adjusting the heating temperature to be within the temperature range of 80 to 90 ° C. The contained layered compound (Hf-3) was obtained.

  A hard film was obtained in the same manner as in Example 1 except that 3.0 g of the layered compound (Hf-3) thus obtained was added to 21 g of pure water and non-alkali glass was used as the glass substrate. Formed.

  The hard film formed on the glass substrate was transparent, and no cracks were observed when observed with a 10-fold magnifier. The pencil hardness of the hard film was 9H or higher. The contact angle measured in the same manner as in Example 1 was 95 °. Furthermore, as in Example 1, it was found that this hard film was amorphous.

Example 4
The layered compound (Hf-3) (4.0 g) was added to 23 g of a mixed solvent of pure water and ethanol (pure water: ethanol = 1: 1 volume ratio) and stirred at 40 ° C. for 30 minutes. A hafnia-containing hard film was formed in the same manner as in Example 3 except that the irradiation was performed.

  The hard film formed on the glass substrate was transparent, and no cracks were observed when observed with a 10-fold magnifier. The pencil hardness of the hard film was 9H or higher. The contact angle measured in the same manner as in Example 1 was 96 °. Further, as in Example 1, it was found that the hafnia film was amorphous.

(Example 5)
After washing 300 g of the hafnium hydroxide obtained in Example 1, 300 g of pure water was added, 202.5 g of oxalic acid was used instead of 158 g of formic acid, and the temperature range was 80 to 90 ° C. A hafnium-containing layered compound (Hf-4) was obtained in the same manner as in Example 1 except that the mixture was heated and stirred for 4 hours while adjusting the heating temperature.

  Example 1 except that 2.5 g of the layered compound (Hf-4) thus obtained was added to 35 g of pure water and heated and stirred for 1.5 hours while adjusting the temperature to 50 to 60 ° C. In the same manner, a hard film was formed.

  The hard film formed on the glass substrate was transparent, and no cracks were observed when observed with a 10-fold magnifier. The pencil hardness of the hard film was 9H or higher. The contact angle measured in the same manner as in Example 1 was 90 °. Further, as in Example 1, it was found that the hafnia film was amorphous.

(Example 6)
16.4 g of chlorinated zirconium oxide (ZrCl ₂ O.8H ₂ O) was dissolved in 120 g of water. To the resulting solution, 25 ml of 29% aqueous ammonia was added to adjust the pH of the solution to 9.0, and the resulting zirconium hydroxide precipitate was filtered, and the precipitate was purified until the filtrate became pH 7 or lower. Washed with water. After adding 50 g of pure water and 143 g of formic acid to the precipitate after washing (sometimes referred to as washing precipitate), the mixture is heated and stirred for 2 hours while adjusting the temperature so that it falls within the temperature range of 80 to 90 ° C. And cooled to room temperature. The produced white precipitate was subjected to suction filtration and air-dried to obtain a zirconium-containing layered compound (Zr-1).

  3.0 g of the layered compound (Zr-1) thus obtained was added to 27 g of pure water, and the mixture was heated and stirred for 1 hour while adjusting the temperature to 50 to 60 ° C. to obtain the layered compound (Zr-1). An aqueous solution was prepared. On the other hand, a glass substrate made of soda lime glass was washed with a neutral detergent, rinsed with pure water, and then air-dried. This layered compound (Zr-1) aqueous solution was applied onto the glass substrate by a spinner method. This coated sample was placed 9 cm below the light source and irradiated with ultraviolet rays for 20 minutes with a 1 kW high-pressure mercury lamp (H1000L, manufactured by Toshiba Lighting & Technology Corp.) to form a hard film containing zirconia on the glass substrate.

  The hard film formed on the glass substrate was transparent, and no cracks were observed when observed with a 10-fold magnifier. The pencil hardness of the hard film was 9H or higher. Moreover, the contact angle with respect to the water of the hard film which left the glass substrate in which the hard film was formed in the room for 7 days was measured with the contact angle meter (CA-D, Kyowa Interface Science Co., Ltd.). As a measurement result, the contact angle was 95 °. Furthermore, the structure of the hard film was examined using an X-ray diffractometer (RAD-2B, manufactured by Rigaku Corporation). Measurement was performed up to 2θ = 5 to 90 °, but no sharp reflection peak could be observed except for the glass halo pattern. From this, it was found that the zirconia film was amorphous.

(Example 7)
Zirconium-containing layered compound (Zr-2) was obtained in the same manner as in Example 6 except that the amount of pure water used was 60 g, and 210 g of acetic acid was used instead of 143 g of formic acid.

  The addition of 3.0 g of layered compound (Zr-2) to 57 g of a mixed solvent of pure water and ethanol (pure water: ethanol = 1: 1 volume ratio), the use of alkali-free glass as the glass substrate, 15 A hard film was formed in the same manner as in Example 6 except that ultraviolet irradiation was performed for a minute.

  The hard film formed on the glass substrate was transparent, and no cracks were observed when observed with a 10-fold magnifier. The pencil hardness of the hard film was 9H or higher. Further, the contact angle measured in the same manner as in Example 6 was 98 °. Further, as in Example 6, it was found that the hard film was amorphous.

(Example 8)
5% ammonia water was added to the aqueous solution of the layered compound (Hf-1) prepared in Example 1 to adjust the pH to 7, and 1.33 g of a silane coupling agent [(3-glycidoxypropyl) trimethoxysilane]. And 3.3 g of acrylic acid were added and stirred to prepare a mixture. On the other hand, the stainless steel substrate (SUS 304) was degreased and then air-dried. On the stainless steel substrate, the mixture was applied by a spray method. This coated sample was placed 9 cm below the light source, and irradiated with ultraviolet rays for 10 minutes using a 1 kw high-pressure mercury lamp (H1000L, manufactured by Toshiba Lighting & Technology Corp.) to form a hard film on the stainless steel substrate.

  The hard film formed on the stainless steel substrate was transparent, and no cracks were observed when observed with a 10-fold magnifier. The pencil hardness of the hard film formed on the glass substrate was 9H or higher. Moreover, the contact angle with respect to the water of the hard film which left the glass substrate in which the hard film was formed in the room for 7 days was measured with a contact angle meter (CA-D, manufactured by Kyowa Interface Science Co., Ltd.). The stainless steel substrate on which the hard film was formed was left indoors and measured after 7 days). The contact angle was 87 °. Furthermore, the structure of the hard film was examined using an X-ray diffractometer (RAD-2B, manufactured by Rigaku Corporation). Measurement was performed up to 2θ = 5 to 90 °, but no sharp reflection peak could be observed except for the stainless steel halo pattern. From this, it was found that the hard film was amorphous.

Example 9
5% aqueous ammonia was added to the aqueous solution of the layered compound (Zr-1) prepared in Example 6 to adjust the pH to 7, and 1.6 g of a silane coupling agent [(3-glycidoxypropyl) trimethoxysilane]. And 4.2 g of acrylic acid were added and stirred to prepare a mixture. Using this mixed solution, a hard film (zirconia film) was formed in the same manner as in Example 6 except that ultraviolet irradiation was performed for 15 minutes.

  The hard film formed on the stainless steel substrate was transparent, and no cracks were observed when observed with a 10-fold magnifier. The pencil hardness of the hard film was 9H or higher. Further, the contact angle measured in the same manner as in Example 6 was 85 °. Further, as in Example 6, it was found that the zirconia film was amorphous.

FIG. 1 is an electron micrograph of the layered compound obtained in Example 1. FIG. 2 is an X-ray diffraction pattern of the layered compound obtained in Example 1.

Claims (5)

Containing hafnium and / or zirconium and COO group, layered compound, characterized by chromatic reflection peak at 2 [Theta] = 10 ° by X-ray diffraction (XRD) (CuKa line used). Mixing 100 parts by weight of hafnium hydroxide and / or zirconium hydroxide, 50 to 1000 parts by weight of water and 900 to 5000 parts by weight of carboxylic acid , heating to 50 to 100 ° C., and collecting precipitates produced by heating. The method for producing a layered compound according to claim 1.   A hard film formed by irradiating a coating layer containing the layered compound according to claim 1 with ultraviolet rays.   The hard film according to claim 3, wherein the coating layer contains a silane coupling agent.   The hard film according to claim 3, wherein the coating layer contains an organic substance.

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