JP2003301167A - Process for producing sol and method for water repellent treatment of base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for producing a sol, which can give a thin film excellent in water repellency and having higher hardness, and a method for the water repellent treatment of a base material, by which the sol can be cured under mild conditions and which comprises forming a cured thin film of the sol on a base material. <P>SOLUTION: The process for producing the sol comprises: mixing a salt solution or alkoxide solution of at least one element selected from groups 3 to 6 elements with at least one compound selected from the group consisting of aqueous ammonia, amines and quaternary ammonium compounds to give the hydroxide(s) of the element(s); and mixing the hydroxide(s) with water and/or an alcohol and nitric acid and/or an organic acid. The method for the water repellent treatment of the base material comprises applying the sol produced by the above process on the surface of the base material and curing it, alternatively comprises curing the sol produced by the above process and forming a thin film of the obtained cured material on the surface of the base material. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a sol and a method for treating a substrate with water repellency, and more specifically, a method for producing a sol which is excellent in water repellency and can give a thin film having higher hardness. And a method for treating water repellency of a substrate, which comprises curing a sol under mild conditions and forming a cured thin film obtained from the sol on the surface.

[0002]

2. Description of the Related Art In the modern living environment, water-repellent treatments such as anti-fog and anti-wet are desired, and there are many required equipments, devices and machines. These include, for example, window glass of automobiles, painted surfaces of automobiles, kitchen equipment, kitchen utensils, exhaust equipment attached to kitchen equipment, bathing equipment, washroom equipment, medical facilities, medical equipment, mirrors,
There are a wide variety of products such as eyeglasses, printed matter, leather goods, woodworking goods, paper, clothes, and cloth.

As a water-repellent treatment method for such equipment, devices, and machinery, for example, a thin film is formed by coating or chemical vapor-depositing a low-molecular fluorine compound, a fluororesin, or silicon on the surface of an automobile window glass. Then, a method of performing water repellent treatment is known. According to these methods, water repellency such that the contact angle of water droplets is 80 to 150 degrees can be realized.

However, in this conventional method, although water repellency can be imparted to some extent as described above, the hardness of the thin film to be formed is low and the equipment, device, and machine tool for performing the water repellency treatment. Since many of them come into contact with other machines and instruments, it is desired that they have high mechanical strength, especially higher hardness.

A silicone hard coat film, which is known as a cured film, is coated with a solution in which a silicon-containing polymer is dissolved on the surface of a substrate, dried, and then dried at 100 to 100%.
It was formed by heating (curing) to 300 ° C. Since this silicone hard film forms a cured film by heating at a relatively high temperature, when the base material is plastics, paper, wood, etc., yellowing or deterioration occurs and the silicone hard film There is also an inconvenience that the base material capable of forming is limited to a material capable of withstanding heat. Moreover, the hardness of the silicone hard film is about 3H in terms of pencil hardness. Therefore, there is a strong demand for a hard coat film that can be cured under mild conditions without selecting the material of the base material and that is hard and has excellent water repellency.

[0006]

In view of the above circumstances, the present invention provides a method for producing a sol which is excellent in water repellency and can give a thin film having a higher hardness, and the sol can be prepared under mild conditions. Can be cured,
It is an object of the present invention to provide a water repellent treatment method for a base material, which comprises forming a cured thin film obtained from the sol on the surface.

[0007]

In order to solve the above-mentioned problems, the inventor of the present invention has conducted extensive research by paying attention to an element as a raw material of a sol for giving a cured thin film and a treatment process of the element, and as a result, the present invention Came to complete.

That is, according to the present invention, firstly, a salt solution or an alkoxide solution of at least one element selected from Groups 3 to 6 of the periodic table, and aqueous ammonia, amines and a quaternary ammonium compound are used. A sol characterized by mixing with at least one selected from the group consisting of to obtain a hydroxide of the element, and mixing the hydroxide with water and / or alcohol and nitric acid and / or organic acid. A method of manufacturing the same is provided.

The first invention includes the sol manufacturing methods described in the following (1) to (5). (1) A method for producing a sol, which comprises a step of washing the hydroxide with water or alcohol before mixing the hydroxide with water and / or alcohol and nitric acid and / or organic acid. (2) A method for producing a sol, wherein the salt solution is an aqueous solution of a salt and the alkoxide solution is an aqueous solution of an alkoxide having 5 or less carbon atoms. (3) A method for producing a sol, wherein the alcohol used when mixing the hydroxide with water and / or alcohol and nitric acid and / or organic acid is an alcohol having 5 or less carbon atoms. (4) A method for producing a sol in which the alcohol used for the washing is an alcohol having 5 or less carbon atoms. (5) A method for producing a sol, wherein the organic acid is an organic acid having 20 or less carbon atoms.

According to the present invention, secondly, a method for treating water repellency of a substrate, characterized in that the sol produced by the method for producing a sol according to the first invention is applied to the surface of the substrate and cured. Will be provided.

The second aspect of the invention includes the water repellent treatment method for a substrate as described in (1) and (2) below. (1) A water repellent treatment method for a substrate, wherein the curing is performed by ultraviolet irradiation treatment or heat treatment. (2) A method for treating water repellency of a substrate, wherein the substrate is glass, metal, ceramics, plastics, paper, cloth, fiber, leather or wood.

According to the present invention, thirdly, the sol produced by the method for producing a sol according to the first invention is cured, and the obtained cured product is formed into a thin film on the surface of the substrate. A method for treating water repellent of a base material is provided.

The third invention includes the water repellent treatment method for a substrate as described in (1) and (2) below. (1) A water repellent treatment method for a substrate, wherein the curing is performed by ultraviolet irradiation treatment or heat treatment. (2) A method for treating water repellency of a substrate, wherein the substrate is glass, metal, ceramics, plastics, paper, cloth, fiber, leather or wood.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is, firstly, in Periodic Tables 3 to 3.
A salt solution or alkoxide solution of at least one element selected from Group 6 is mixed with aqueous ammonia and / or amines and a quaternary ammonium compound to obtain a hydroxide of the element, and the hydroxide Provided is a method for producing a sol, which comprises mixing water and / or alcohol and nitric acid and / or organic acid.

The element as a raw material component used in the first invention is not particularly limited as long as it is an element belonging to Groups 3 to 6 of the periodic table, but yttrium, zirconium, hafnium,
Lanthanum, niobium and tantalum are preferred. These elements are usually used alone, but two or more kinds may be used in combination.

Examples of salts of the above elements include halides, acetates, sulfates, carbonates, nitrates and the like.

The alkoxide of the above element is not particularly limited, but an alkoxide having 5 or less carbon atoms, specifically, methoxide, ethoxide, propoxide, butoxide, pentoxide is preferable.

In the first aspect of the invention, first, a salt solution or alkoxide solution of the above elements is prepared. Examples of the solvent used for preparing the salt solution or the alkoxide solution include water and organic solvents such as alcohols, ketones, amines and amides, and the solvent preferably used is water. When using an organic solvent, a water-soluble organic solvent such as methanol, ethanol, butanol, isopropanol, vinyl alcohol, acetone, methyl ethyl ketone or dioxane is preferable.

The concentration of the salt solution or alkoxide solution of the above-mentioned elements is not particularly limited, but is usually 1 to 70%, preferably 1 to 50% by mass. If it is less than 1%, the produced hydroxide will be fine particles and it will be difficult to filter, and if it exceeds 70%, aggregation of the hydroxide will be remarkable and filtration will be difficult, which is not preferable.

The conditions for preparing the above are not limited, but are usually 0 to 100 ° C., preferably 10 to
It is prepared by stirring and mixing at 50 ° C. The salt solution or alkoxide of the above element is rapidly dissolved in the above solvent.

Then, the thus prepared salt solution or alkoxide solution of the above element is mixed with aqueous ammonia to obtain a hydroxide of the above element. The amount of aqueous ammonia used is sufficient if the amount of hydroxide of the above-mentioned element is generated, but is usually 1 to 80% by mass, preferably 1 to 80% with respect to the salt solution or alkoxide solution of the above-mentioned element.
50%. If it is less than 1%, hydroxide may not be produced, and if it exceeds 80%, hydroxide and ammonia may be redissolved due to complex formation, which is not preferable.

The ammonia solution or amines to be mixed with the salt solution or alkoxide solution of the above elements contains at least one selected from the group consisting of aqueous ammonia, amines and quaternary ammonium compounds. Aqueous solution containing ammonia, that is, ammonia water, has a suitable concentration of ammonia of usually 1 to 29% by mass. Examples of the amines include primary amines, secondary amines, and tertiary amines. Examples of the primary amines include methylamine, ethylamine, propylamine, butylamine, 2-propenylamine, 2-methyl-2-propenylamine, 2-properoyloxyethylamine, 2- (2-methylproperoyloxy) ethylamine. As secondary amines, such as dimethylamine, diethylamine, dipropylamine, dibutylamine, di (2-propenyl) amine, di (2-methyl-2-propenyl) amine, 2-propenylamine, 2-methyl- As tertiary amines such as 2-propenylamine, 2-properoyloxyethylamine, 2- (2-methylproperoyloxy) ethylamine tacrylate), trimethylamine, triethylamine, tripropylamine, tributylamine, N, N- Dimethyl
2-properoyloxyethylamine, N, N-dimethyl-2- (2-methylproperoyloxy) ethylamine,
N, N-diethyl-2-properoyloxyethylamine, N, N-diethyl-2- (2-methylproperoyloxy) ethylamine, N, N-dimethyl-3-properoyloxypropylamine, N, N-dimethyl -3- (2
-Methylproperoyloxy) propylamine, N, N-
Diethyl-3-properoyloxypropylamine N, N
-Diethyl-3- (2-methylproperoyloxy) propylamine, N, N-dimethyl-3- (properoylamino) propylamine, N, N-dimethyl-3- (2-
Methylproperoylamino) propylamine, N, N-
Examples include diethyl-3- (properoylamino) propylamine and N, N-diethyl-3- (2-methylproperoylamino) propylamine. As the quaternary ammonium compound, tetraalkylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc., tetraalkylammonium hydroxide, tetramethylammonium iodide, tetraethylammonium iodide, etc. , Tetrapropylammonium iodide, tetrabutylammonium iodide, etc., tetraalkylammonium iodide, tetraarylammonium iodide, tetraarylammonium hydroxide and the like. As the amines, salts of the above primary amines to tertiary amines can also be used in the present invention. Such amines may be used as they are, or may be used as an amine-containing aqueous solution.

A salt solution or alkoxide solution of the above element is mixed with aqueous ammonia and / or amines,
The conditions for obtaining the hydroxide of the above element are not particularly limited, but are usually 0 to 70 ° C, preferably 0 to 40 ° C,
It can be obtained by stirring and mixing.

Subsequently, the hydroxide obtained is filtered off, and the hydroxide is mixed with water and / or alcohol and nitric acid and / or organic acid to produce the desired sol. In this case, there is no particular restriction on the order of mixing them.

For example, hydroxide and water and / or alcohol and nitric acid and / or organic acid may be mixed at once, hydroxide and water and / or alcohol are mixed, and then nitric acid and / or Alternatively, an organic acid may be mixed. Alternatively, the hydroxide may be mixed with nitric acid and / or an organic acid, and then water and / or alcohol may be mixed.

The amount of water and / or alcohol and nitric acid and / or organic acid to be mixed with the hydroxide may be any amount sufficient to peptize the hydroxide. 1 to 100 times by mass, preferably
It is 1 to 50 times. If it is less than 1 time, the concentration of metal ions becomes high, making it difficult to peptize, and if it exceeds 100 times,
The concentration of metal ions in the sol becomes low, which may make coating difficult, which is not preferable.

The sol includes, as its embodiment, a sol containing hafnia, a sol containing zirconia, and a sol containing hafnia and zirconia. That is, the sol containing hafnia and / or zirconia comprises a salt solution containing a salt of hafnium and / or zirconium or an alkoxide solution containing an alkoxide of the above element, and aqueous ammonia, amines and a quaternary ammonium compound. A hydroxide of the element is obtained by mixing with at least one selected from the group, and the hydroxide and water and / or
Alternatively, it can be prepared by a method having a substantial content of mixing an alcohol and an inorganic acid and / or an organic acid.

The alcohol used here is not particularly limited, but an alcohol having 5 or less carbon atoms is preferable. Specific examples include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-methylpropanol, 2-butanol, 2-methyl-2-propanol and the like.

The organic acid to be used is also not limited, but organic acids having 20 or less carbon atoms are preferable, such as formic acid, acetic acid, propionic acid, glycolic acid, lactic acid, glyceric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, Azelaic acid, 1,10-decanedicarboxylic acid, 1,4-tetradecanedicarboxylic acid and the like can be mentioned. Of these, formic acid and oxalic acid are particularly preferable.

There is no particular limitation on the mixing ratio in water and / or alcohol and nitric acid and / or organic acid, and when the total amount is 100 parts by mass, nitric acid and / or organic acid is usually added in an amount of 0.1 to 50. Parts by mass, preferably 1 to 20 parts by mass. If it is less than 0.1 parts by mass, the hydroxide will not be deflocculated, and if it exceeds 50 parts by mass, the nitric acid and / or organic acid used will damage the base material or cause alteration, and also at the time of application. The evaporation of nitric acid and / or organic acid may adversely affect the environment, which is not preferable.

There is no restriction on the mixing ratio of both when water and alcohol are used in combination, and there is no restriction on the mixing ratio of both when nitric acid and organic acid are used in combination, but usually the total amount of acid is When the amount is 100 parts by mass, nitric acid is 10 to 90 parts by mass, preferably 10 to 60 parts by mass.

In the first invention, as described above,
A salt solution or alkoxide solution of at least one element selected from Groups 3 to 6 of the periodic table is mixed with at least one selected from the group consisting of aqueous ammonia, amines and quaternary ammonium compounds, and An elemental hydroxide is obtained, the obtained hydroxide is filtered off, and this hydroxide is mixed with water and / or alcohol and nitric acid and / or organic acid to produce the desired sol. However, in this case, it is preferable to have a step of washing the hydroxide with water or alcohol before mixing the hydroxide with water and / or alcohol and nitric acid and / or organic acid.

The alcohol used for this washing is preferably an alcohol having 5 or less carbon atoms, specifically, methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-methylpropanol, 2-butanol, 2-Methyl-2-propanol etc. can be mentioned. This washing step is a step for adjusting the pH of the hydroxide and removing impurities and impurities attached to or contained in the hydroxide.

The method for producing a sol according to the first aspect of the invention is
Since it is a method that does not use an organic solvent or the like that pollutes the environment or harms the human body throughout the manufacturing process, it is an extremely safe and useful industrial manufacturing method of sol.

Secondly, the present invention provides a water repellent treatment method for a base material, characterized in that the sol produced by the sol production method according to the first invention is applied to the surface of the base material and cured. provide.

The sol used in the second invention is a sol manufactured by the sol manufacturing method according to the first invention.

There is no limitation on the applied substrate, and various materials can be adopted. For example, quartz glass, 96
% Quartz glass, soda lime glass, aluminoborosilicate glass, borosilicate glass, aluminosilicate glass and a base material formed of glass such as lead glass, and a base formed of plastics such as polycarbonate and polyethylene terephthalate Material, ordinary steel, structural constant alloy steel, high tensile strength steel, heat resistant steel, high chrome heat resistant steel, steel materials such as high nickel-chromium heat resistant steel and alloy steel and stainless steel, industrial pure aluminum, Fifty
00 series alloy, Al-Mg series aluminum alloy and 6
Aluminum alloys including 000 series aluminum alloys, various copper alloys including silver-containing copper, tin-containing copper, chromium copper, chromium / zirconium copper and zirconium copper,
Base material made of metallic material such as pure titanium, titanium alloy including drag titanium alloy and corrosion resistant titanium alloy, ceramic material such as mullite porcelain, alumina porcelain, zircon porcelain, cordierite porcelain and steatite porcelain And a coated metal substrate obtained by coating the surface of the substrate formed from the above metal-based material with any of enamel, glass lining and ceramic coating.

As the substrate formed of a glass material,
Examples include window glass of various structures including automobiles, rail vehicles, aircraft, and buildings such as houses, warehouses and buildings, and head-up displays for automobiles and aircraft, which require water repellency. .

As an example of the base material formed of a metal material, an exterior plate, for example, a power line, a building, a sash, and, for example, an outer plate of a rail car can be mentioned. Also,
Mention may also be made of metallic sundries, household substrates for kitchens, baths, toilets and the like.

Examples of the base material made of a ceramic material include insulators, insulators and ceramic styles, and roof tiles.

Examples of the coated metal substrate include various kinds of tanks, reaction tanks, brewing tanks and daily necessities such as cups, washbasins and vases.

Other examples of the above-mentioned base material include a coated surface in which a coating material is applied to the surface of metal or ceramic. Specific examples of the painted surface include the body surfaces of automobiles, railway vehicles, and aircraft.

Examples of the above-mentioned base material may further include outer walls of buildings such as concrete walls, terracotta tile walls, mortar walls, and plaster walls. Furthermore, the above-mentioned various base materials whose surfaces are plated can also be mentioned.

Examples of the base material include paper, cloth, fibers, leather,
Wood can also be mentioned. Among the various base materials described above, a base material formed of the above glass, a base material formed of the above plastics, paper and a composite base material thereof are mentioned as suitable base materials.

The method of applying the sol to the surface of the base material is, for example, a dipping method in which the base material is dipped in the sol and slowly pulled up, or a casting method in which the sol is cast on a fixed base material surface. Method, continuous method of immersing the base material in the sol from one end of the tank in which the sol is stored and taking out the base material from the other end of the tank, by dropping the sol on the rotating base material and by the centrifugal force acting on the base material. Examples thereof include a spinner method of casting a sol on a substrate, a spray method of spraying the sol on the surface of the substrate, and a flow coating method.

The amount of sol applied varies depending on the viscosity of the sol and other conditions. When a thin film having a desired thickness cannot be obtained by one application, the application can be repeated several times.
Further, in the case of curing by ultraviolet irradiation treatment, a plurality of thin films may be laminated by repeating coating and heating before and after ultraviolet irradiation.

Next, the sol applied to the surface of the base material is cured. This curing treatment may be performed by ultraviolet irradiation or heating.

When curing by ultraviolet irradiation treatment,
Ultraviolet irradiation can be performed after drying the base material coated with the sol, or ultraviolet irradiation can be performed immediately after coating. Further, the UV irradiation may be carried out at room temperature, and the temperature does not exceed 200 ° C., preferably 50 ° C.
It can also be performed while heating to 150 ° C. A very short irradiation time of 1 minute to 1 hour is sufficient. Moreover, the intensity of the ultraviolet rays to be irradiated is at most 200 mJ / c.
m ² , preferably 50 to 100 mJ / cm ² .

As described above, in the present invention, the ultraviolet irradiation conditions are mild, and for example, a plastic base material which does not yellow, deteriorates or deforms and which can withstand ultraviolet irradiation is used. The problem of having to make a choice can be eliminated.

A high-pressure mercury lamp or a low-pressure mercury lamp can be used as a light source of the ultraviolet rays to be irradiated. By using these mercury lamps, it is possible to inexpensively irradiate the ultraviolet rays having the above-mentioned intensity.

When the sol applied to the surface of the substrate is cured by heat treatment, the heat treatment condition is usually 50.
To 1000 ° C, preferably 50 to 600 ° C, 1 minute to 2
Time, preferably 10 minutes to 1 hour, but 50-4
It can also be cured under mild temperature conditions of 00 ° C. Therefore, even when the sol is cured by heat treatment, for example, the problem that a plastic substrate is not yellowed, altered or deformed and a heat-resistant substrate has to be specially selected is avoided. To be done. The heating means is not limited, and a means using an electric furnace, a means for blowing hot air, a means for standing in heated gas, and the like are adopted.

The thickness of the obtained cured thin film depends on the type of substrate,
Although it can be appropriately determined depending on the application target, it is usually selected from the range of 10 to 1000 nm.

The cured thin film thus formed on the surface of the substrate is non-crystalline (amorphous), has a pencil hardness of 7H or more, and has extremely high adhesion to the substrate. .

The thin film cured by UV irradiation or heating may be followed by a curing period. The curing period is at least 2 days, and if one week is expected, a cured thin film having a pencil hardness of 7H or more is obtained.

The cured thin film thus formed on the surface of the substrate becomes a thin film having excellent water repellency and practically useful and higher hardness. Here, the water repellency means the property of repelling water, and can be evaluated from the contact angle of a water drop by the contact angle method. The cured thin film according to the present invention has a contact angle of 8
The film has a water repellency of 0 degree or more.

The hardness is determined by the pencil hardness method (JIS K 5600-5-4).
The cured thin film according to the present invention has a hardness of 7H or higher. Further, the thin film according to the present invention is a film that is excellent in the property of easily removing stains such as adhered scales and the stain removing property. With this decontamination property, various contaminants can be adhered onto the thin film, and after a certain period of time, the contaminants can be removed by washing.

Thirdly, the present invention is characterized by curing the sol produced by the sol producing method according to the first invention,
Provided is a method for treating water repellency of a base material, which comprises forming the obtained cured product into a thin film on the surface of the base material.

The sol used in the third invention is a sol manufactured by the sol manufacturing method according to the first invention.
The curing treatment is the same as that described in the second invention.

The third aspect of the present invention is a method of curing the above sol, forming the obtained cured product into a thin film on the surface of a substrate, and subjecting the substrate to a water repellent treatment. This cured product is not only a thin film-shaped cured product formed by applying the sol to the surface of the substrate and then curing the sol, but also filling the sol in a predetermined mold and curing the filled sol. A cured product having a predetermined shape obtained by the above is included. Further, the applied base material is also as described in the second invention.

The water repellent treatment method for a substrate according to the third aspect of the invention is similar to the water repellent treatment method for a substrate according to the second aspect of the invention, in which the sol is applied to the surface of the substrate and then cured. A thin film-like cured product may be formed on the base material surface by means of the above, or a cured product formed in advance into a thin film form is mechanically connected to the base material surface by mechanical coupling means, for example, tacks, bolts, screws, etc. It may be bonded by physicochemical bonding means, for example various bonding means such as an adhesive. The thickness of the cured body formed in a thin film on the surface of the base material is also the same as in the second invention.

According to the water repellent treatment method for a base material of the third invention, the same effect as that of the second invention is obtained, and the cured thin film formed on the surface of the base material is excellent in water repellency and A thin film having a higher hardness which is practically useful.

As described above, the thin film according to the present invention, which is excellent in water repellency, has a higher hardness, and is excellent in stain removability, is required to undergo a water repellent treatment, and various equipments are required. , Equipment, machinery, for example, automobile window glass, automobile painted surface, kitchen equipment, kitchen utensils, exhaust equipment attached to kitchen equipment, bathing equipment, washroom equipment, medical facilities, medical equipment, mirrors, By forming it on the surface of spectacles, printed matter, clothing, paper, etc., its function is fully fulfilled.

[0063]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of sol I) 9.7 g (0.032 mol) of YCl ₃ .6H ₂ O was dissolved in 60 g of water. To this solution, 29% aqueous ammonia was added dropwise to adjust the pH to 9.0 to obtain a precipitate of yttrium hydroxide. Then, the obtained precipitate was separated by filtration and washed with pure water until the pH reached 7. The washed precipitate was placed in a beaker, 60 g of pure water was added, HCOOH formic acid was added dropwise until the pH reached 2, and the mixture was stirred at 70 ° C for 5 hours. Then, after cooling to room temperature, water for weight reduction was added to obtain Sol I.

[0065] Example 2 (Preparation of Sol _{II) ZrOCl 2 · 8H 2 O} 23.8g (0.074mol), was dissolved in water 200 g. To this solution, 29% aqueous ammonia was added dropwise to adjust the pH to 9.0 to obtain a precipitate of yttrium hydroxide. Then, the obtained precipitate was separated by filtration and washed with pure water until the pH reached 7. The washed precipitate was placed in a beaker, 200 g of pure water was added, 60% nitric acid was added dropwise until pH 1 and the mixture was stirred at 90 ° C for 2 hours. Then, after cooling to room temperature, water for weight reduction was added to obtain sol II.

Example 3 (Preparation of Sol III) Sol 3 was obtained in the same manner as in Example 2 except that the washed precipitate was placed in a beaker and 300 g of ethanol was added.

Example 4 (Preparation of Sol IV) The washed precipitate was placed in a beaker, 200 g of pure water was added, and the pH was adjusted.
Sol IV was obtained in the same manner as in Example 2 except that acetic acid was added dropwise until it became 1.5.

Example 5 (Preparation of Sol V) HfCl ₄ (5.44 g, 0.017 mol) under a nitrogen atmosphere was treated with 32 g of water (1.78 mol).
l) dissolved in. Aqueous ammonia (6.60 ml) was added dropwise to the solution to adjust the pH to 9.0 to obtain a hafnium hydroxide precipitate. Then, the precipitate obtained is filtered off and the pH is adjusted to 7 with pure water.
Washed until. The washed precipitate was placed in a beaker, 32 g of pure water was added, 1.10 g of nitric acid was added dropwise to adjust the pH to 1.0, and the mixture was stirred at 85 ° C. for 3 hours. Subsequently, formic acid HCOOH 3.96 g (0.
(086 mol) was added, and the mixture was stirred at 85 ° C. for 17 hours. Then, after cooling to room temperature, water for weight reduction was added to obtain Sol V.

Example 6 (Preparation of Sol VI) Example 5 except that the washed precipitate was placed in a beaker, 100 g of ethanol was added, and HCOOH formic acid was added until pH 1 was reached.
Sol VI was obtained in the same manner as in.

Example 7 (Preparation of Sol VII) 8.91 g (0.024 mol) of LaCl ₃ 7H ₂ O was dissolved in 70 g of water.
To this solution, 29% aqueous ammonia was added dropwise to adjust the pH to 9.0 to obtain a lanthanum hydroxide precipitate. Then, the obtained precipitate was separated by filtration and washed with pure water until the pH reached 7. The washed precipitate was placed in a beaker, 70 g of pure water was added, 60% nitric acid was added dropwise to adjust the pH to 1.0, and the mixture was stirred at 80 ° C. for 3 hours. Then, after cooling to room temperature, water for weight reduction was added to obtain sol VII.

Example 8 (Preparation of Sol VIII) Instead of LaCl ₃ 7H ₂ O, 5.35 g (0.02) of La (CH ₃ COO) ₃ 1.5H ₂ O
Sol VI in the same manner as in Example 7 except that 4 mol) was used.
I got II.

Example 9 (Preparation of sol IX) 5.44 g (0.017 mol) of HfCl ₄ in a nitrogen atmosphere under 32 g of water (1.78 mol)
l) dissolved in. To this solution, add a 1 molar solution of tetra-n-butylammonium hydroxide in methanol to drop the pH.
At 9.0, a hafnium hydroxide precipitate was obtained. Then
The obtained precipitate was separated by filtration and washed with pure water until the pH reached 7. The washed precipitate was placed in a beaker, 32 g of pure water was added, 60% nitric acid was added dropwise to adjust the pH to 0.5, and the mixture was stirred at 80 ° C. for 4 hours. Then, after cooling to room temperature, water for weight reduction was added to obtain sol IX.

[0073] Example 10 (Preparation of sol _{X) ZrOCl 2 · 8H 2 O} 23.8g (0.074mol), was dissolved in water 20g. A 10 wt% tetramethylammonium hydroxide aqueous solution was added dropwise to this solution to adjust the pH to 9.0, and a precipitate of zirconium hydroxide was obtained. Then, the obtained precipitate was separated by filtration and washed with pure water until the pH reached 7. The washed precipitate was placed in a beaker, 200 g of pure water was added, 60% nitric acid was added dropwise until pH 1 and the mixture was stirred at 85 ° C for 4 hours. Then, after cooling to room temperature, water for weight reduction was added to obtain sol X.

Example 11 (Preparation of sol XI) 5.44 g (0.017 mol) of HfCl _{4 was} added to 32 g of water (1.78 mol) under a nitrogen atmosphere.
l) dissolved in. Tri-n-butylamine was added dropwise to this solution to adjust the pH to 9.0 to obtain a hafnium hydroxide precipitate. Then, the precipitate obtained is filtered off and the pH is adjusted to 7 with pure water.
Washed until. The washed precipitate was placed in a beaker, 32 g of pure water was added, 60% nitric acid was added dropwise to adjust the pH to 1.5, and the mixture was stirred at 85 ° C. for 3 hours. Then, after cooling to room temperature, water for weight reduction was added to obtain sol XI.

Example 12 (Preparation of Sol XII) 8.91 g (0.024 mol) of LaCl ₃ 7H ₂ O was dissolved in 70 g of water.
Diethylamine was added dropwise to this solution to adjust the pH to 9.0 to obtain a lanthanum hydroxide precipitate. Then, the obtained precipitate was separated by filtration and washed with pure water until the pH reached 7. The washed precipitate was collected in a beaker, 70 g of pure water was added, 60% nitric acid was added dropwise to adjust the pH to 1.5, and the mixture was stirred at 85 ° C for 4 hours. Then, after cooling to room temperature, water for weight reduction was added to obtain sol XII.

Example 13 (Preparation of Sol XIII) 3.18 g (0.010 mol) of Nb (OC ₂ H ₅ ) ₅ was dissolved in 100 ml of 99.5% ethanol. 4 g of a 40% wt monomethylamine aqueous solution was added dropwise to this solution to obtain a niobium hydroxide precipitate. Then, the obtained precipitate was separated by filtration and washed with pure water until the pH reached 7. Place the washed precipitate in a beaker and add pure water 10
After adding 0 g, add 60% nitric acid dropwise to adjust the pH to 1.0, and
Stir for hours. Then, after cooling to room temperature, water for weight reduction was added to obtain sol XIII.

Example 14 (Preparation of sol XIV) 5.44 g (0.017 mol) of HfCl _{4 was} added to 32 g of water (1.78 mol) under a nitrogen atmosphere.
l) dissolved in. To this solution, 7.5 ml of 29% ammonia water
Was added dropwise to adjust the pH to 9.0 to obtain a hafnium hydroxide precipitate. Then, the precipitate obtained is filtered off and the pH is adjusted to 7 with pure water.
Washed until. Take the washed precipitate in a beaker, add 32 g of pure water, add 3 g of oxalic acid, and add 80-90
The mixture was stirred at ° C for 3 hours. Then, the mixture was cooled to room temperature and water for weight reduction was added to obtain sol XIV.

Example 15 (Preparation of Sol XV) Sol XV was obtained in the same manner as in Example 14 except that 6 g of oxalic acid was added.

Example 16 (Preparation of sol XVI) HfCl ₄ (5.44 g, 0.017 mol) was added under a nitrogen atmosphere to water (32 g, 1.78 mo).
l) dissolved in. To this solution, 7.5 ml of 29% ammonia water
Was added dropwise to adjust the pH to 9.0 to obtain a hafnium hydroxide precipitate. Then, the precipitate obtained is filtered off and the pH is adjusted to 7 with pure water.
Washed until. The washed precipitate was placed in a beaker, 32 g of pure water was added, 3.96 g of glutaric acid was added, and 60% nitric acid was added dropwise to adjust the pH to 0.1, followed by stirring at 80 to 90 ° C for 3 hours. Then, the mixture was cooled to room temperature, water for weight reduction was added, and sol XVI was obtained.

Example 17 (Preparation of sol XVII) Sol XVII was obtained in the same manner as in Example 16 except that 7.92 g of glutaric acid was added.

[0081] Example 18 (Preparation of sol _{XVIII) ZrOCl 2 · 8H 2 O} 23.8g (0.074mol), was dissolved in water 200 g. To this solution, 29% aqueous ammonia was added dropwise to adjust the pH to 9.0 to obtain a zirconium hydroxide precipitate. Then, the obtained precipitate was separated by filtration and washed with pure water until the pH reached 7. The washed precipitate was placed in a beaker, 200 g of pure water was added, 16.8 g of formic acid was added, and the mixture was stirred at 80 to 90 ° C for 3 hours.
Then, after cooling to room temperature, add water for weight reduction,
Sol XVIII was obtained.

Example 19 (Preparation of sol XIX) In place of 16.8 g of formic acid, 6.66 g of oxalic acid was added, except that
Sol XIX was obtained in the same manner as in Example 18.

Examples 20 to 38 33 mm × 33 mm non-alkali glass was thoroughly washed with a neutral detergent, rinsed with pure water, and then water drops were removed with an air gun.
It was immersed in 0% nitric acid for 15 hours and then dried in a clean environment at room temperature. 500 rpm for the first 5 seconds on this glass substrate
The sol I to XIX obtained in the above Examples 1 to 19 were respectively applied by spinner method under the condition of rotating at 2,000 rpm for the next 30 seconds to obtain a gel film.

The obtained gel film was irradiated with ultraviolet rays using an ultraviolet irradiation device. A high-pressure mercury lamp (H1000l Toshiba Litec) was used as a light source. The sample was placed 9 cm below the light source with an ultraviolet illuminance of 80 mW / cm ² and irradiated with two types of irradiation for 10 minutes and 30 minutes to form a cured thin film. The cured thin films formed from Sols I to VIII are referred to as cured thin films (1) to (8). Further, the gel film obtained by applying Sols IX to XIX was irradiated with ultraviolet rays for 10 minutes. The cured thin films formed from Sols IX to XIX are referred to as cured thin films (9) to (19).

Examples 27 to 34 33 mm × 33 mm non-alkali glass was thoroughly washed with a neutral detergent, rinsed with pure water, and then water droplets were removed with an air gun.
It was immersed in 0% nitric acid for 15 hours and then dried in a clean environment at room temperature. 500 rpm for the first 5 seconds on this glass substrate
The sols I to VIII obtained in the above Examples 1 to 8 were respectively applied by the spinner method under the condition of rotating at 2,000 rpm for the next 30 seconds to obtain gel films.

The obtained gel film was heated at 250 ° C. for 2 hours in an electric furnace.
Each was heated for a time to form a cured thin film. Sol I
~ VIII cured film formed from cured film (20) ~ (2
7).

[Evaluation] Water repellency (measurement of contact angle) Using the contact angle meter CA-D type (Kyowa Interface Science Co., Ltd.), the above cured thin films (1) to (19) and cured thin films (20) to ( The contact angle of 27) was measured. The results are shown in Tables 1 to 3.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

As shown in Tables 1 to 3, the contact angle is 80.
It was confirmed to be excellent in water repellency.

Hardness (Pencil Hardness Test) According to JIS K 5600-5-4, the above cured thin films (1) to (19)
And the pencil hardness of the cured thin films (20) to (27) was measured.
The results are shown in Tables 4-6.

The test method of the pencil hardness method is as follows. Apply a pencil with a hardness of 6B to 9H to the thin film at an angle of 45 ° C and load.
Pressed at 750g and pressed at least 3mm at a distance of 7mm. The surface of the thin film was visually inspected and the test was repeated with increasing hardness until two scars of at least 3 mm were formed.
The hardness of the hardest pencil that did not cause a scar was defined as the pencil hardness of the thin film.

[0094]

[Table 4]

[0095]

[Table 5]

[0096]

[Table 6]

As shown in Tables 4 to 6, the pencil hardness is 7
It was confirmed that it was H or more and was a thin film having high hardness.

[0098]

According to the present invention, a method for producing a sol which is excellent in water repellency and can give a thin film having higher hardness, and the sol can be cured even under mild conditions. Provided is a method for water-repellent treatment of a base material, which comprises forming a cured thin film on the surface, which is attached to a window glass of an automobile, a painted surface of an automobile, kitchen equipment called a system kitchen, kitchen utensils, kitchen equipment. Exhaust equipment, bathing equipment, washroom equipment, medical facilities, medical machinery, mirrors, glasses, etc. are desired, and various required equipment, devices, machinery design,
The contribution to the manufacturing field is extremely large.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C01G 33/00 C01G 33/00 C09D 1/00 C09D 1/00 185/00 185/00 F term (reference) 4G048 AA06 AA08 AB02 AC08 AD02 AD10 AE06 AE07 AE08 4G065 AA01 AA06 AA09 AB03X AB11X CA13 DA06 EA02 FA01 4G076 AA06 AA09 AB04 AB05 BA21 BB08 CA06 CA08 PC07 NA03 PC02 HA02 HA11 HA02 HA11 HA02 HA11 HA02 HA11 HA02 HA11 HA02 HA11 HA02 HA11 HA02 HA11 HA11 PC09 PC10

Claims (12)

[Claims] 1. A salt solution or alkoxide solution of at least one element selected from Groups 3 to 6 of the periodic table, and at least one selected from the group consisting of aqueous ammonia, amines and quaternary ammonium compounds. Is obtained to obtain a hydroxide of the element, and the hydroxide is mixed with water and / or alcohol and nitric acid and / or organic acid. 2. The sol according to claim 1, which has a step of washing the hydroxide with water or alcohol before mixing the hydroxide with water and / or alcohol and nitric acid and / or organic acid. Manufacturing method. 3. The method for producing a sol according to claim 1, wherein the salt solution is an aqueous solution of a salt, and the alkoxide solution is an aqueous solution of an alkoxide having 5 or less carbon atoms. 4. The alcohol used when mixing the hydroxide with water and / or alcohol and nitric acid and / or organic acid is an alcohol having 5 or less carbon atoms. The method for producing a sol according to 1. 5. The alcohol used for the washing has 5 carbon atoms.
The method for producing a sol according to claim 2, which is the following alcohol. 6. The method for producing a sol according to claim 1, wherein the organic acid is an organic acid having 20 or less carbon atoms. 7. A water repellent treatment method for a base material, which comprises applying the sol produced by the method for producing a sol according to any one of claims 1 to 6 to a surface of a base material and curing the sol. 8. The water repellent treatment method for a substrate according to claim 7, wherein the curing is performed by ultraviolet irradiation treatment or heat treatment. 9. The water repellent treatment method for a substrate according to claim 7, wherein the substrate is glass, metal, ceramics, plastics, paper, cloth, fiber, leather or wood. 10. A sol produced by the method for producing a sol according to any one of claims 1 to 6 is cured, and the obtained cured product is formed into a thin film on the surface of a substrate. Water repellent treatment method for a base material. 11. The water repellent treatment method for a substrate according to claim 10, wherein the curing is performed by ultraviolet irradiation treatment or heat treatment. 12. The water repellent treatment method for a substrate according to claim 10, wherein the substrate is glass, metal, ceramics, plastics, paper, cloth, fiber, leather or wood.