JP2003313499A - Hydrophilic coating composition, method for producing the same, and method for using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a hydrophilic coating material which can give a highly transparent film and can form a film having high adhesion to various substrates. <P>SOLUTION: A second liquid (liquid B) prepared by adding 0.01-10 wt.% water and 0.01-10 wt.% acid or alkali being a precipitation inhibitor to an alcoholic solvent is added dropwise to a first liquid (liquid A) prepared by adding 1-30 wt.% zirconium alkoxide to an alcoholic solvent to obtain the hydrophilic coating composition containing zirconium oxide (zirconia) as the principal component in the alcoholic solvent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrophilic coating composition used as an antifouling functional material and the like, as well as a method for producing and using the same.

[0002]

2. Description of the Related Art Photocatalytic coating materials such as titanium oxide are one of hydrophilic coating materials used as antifouling functional materials, but the photocatalytic coating film exhibits antifouling functions unless it is irradiated with ultraviolet rays. Can not do it. On the other hand, hydrophilic coating materials that can exhibit an antifouling function without being irradiated with ultraviolet rays have also been developed. For example, JP-A-2001-40294 discloses a zirconium compound such as zirconyl, zirconium nitrate, zirconium sulfate, and zirconium halide, a water-absorbing organic polymer such as polyvinyl alcohol, and a solvent such as water and a water-containing organic solvent. A coating composition comprising is disclosed. Further, as a photocatalyst coating material, Japanese Patent Application Laid-Open No.
As in JP-A-1-89752, a coating composition in which zirconia or the like is added to a photocatalyst such as titanium oxide is also known.

[0003]

However, in the conventional hydrophilic coating composition, the transparency is poor and not only the color and light transmittance of the substrate are impaired, but also the adhesive force to the substrate of various materials is obtained. There is a problem that a high-quality film cannot be formed. Further, in the case of a photocatalyst coating material such as titanium oxide, when the coating film is formed on the organic base material, the photocatalyst may decompose the organic compound to cause erosion of the base material.

The present invention has been made in view of the above points, and an object of the present invention is that hydrophilic coating can be performed at a low temperature and that a wide range of materials can be coated with high adhesion. Since the transparency is high, the design of the base material surface can be maintained without impairing the color and light transmittance of the base material, and the base material can be easily hydrophilized without irradiation of ultraviolet rays. To provide a protective coating composition and a method for producing and using the same. Also,
An object of the present invention is to easily hydrophilize a base material to prevent water droplets and dirt from adhering to the surface and to exhibit an excellent antifouling function, and moreover, an organic compound such as a photocatalyst. Hydrophilicity that can be used as an undercoat film for the production of photocatalytic coating film on organic base materials, without the action of decomposing water, easily adding a third component such as ultraviolet absorber, antibacterial agent, fungicide, etc. It is an object of the present invention to provide a coating composition and a method for producing and using the same.

[0005]

In order to achieve the above object, the hydrophilic coating composition of the present invention comprises zirconium-n-propoxide, zirconium tetramethoxide, zirconium ethoxide, zirconium isopropoxide and zirconium. A zirconium alkoxide selected from the group consisting of butoxide is a raw material, and zirconium oxide (zirconia) is contained in an alcohol solvent, and the content of zirconium atom as the zirconium oxide in the alcohol solvent is 0. 1 ~ 10wt
%, Preferably 0.5 to 7 wt%, more preferably 1 to 5
wt%, and more preferably 2-3 wt%. In this case, the particle diameter of the zirconium oxide (zirconia) in the hydrophilic coating composition is 0.5-10.
0 nm, preferably 5 to 50 nm, more preferably 10 to 3
It is 0 nm.

The method for producing the hydrophilic coating composition of the present invention is selected from the group consisting of zirconium-n-propoxide, zirconium tetramethoxide, zirconium ethoxide, zirconium isopropoxide and zirconium butoxide in an alcohol solvent. Zirconium alkoxide is 1 to 30 wt%, preferably 5 to 15
Water (0.01% to 10% by weight, preferably 0.1 to 5% by weight) in the alcohol-based solvent and the first liquid (A liquid) added by wt%
And 0.01 or more of an acid or an alkali that is a precipitation generation inhibitor.
10 wt%, preferably 0.02 to 8 wt%, more preferably 0.05 to 5 wt% is added to the second liquid (B liquid), and the zirconium oxide (zirconia) is the main component in the alcohol solvent. Is obtained as a hydrophilic coating composition.

Further, the method for producing the hydrophilic coating composition of the present invention comprises the step of adding zirconium-containing alcohol in an alcohol solvent.
The zirconium alkoxide selected from the group consisting of n-propoxide, zirconium tetramethoxide, zirconium ethoxide, zirconium isopropoxide and zirconium butoxide is 1 to 30% by weight, preferably 5%.
0.01 to 10 wt% of water in an alcohol solvent, preferably 0.1 to 10 wt% of the first liquid (liquid A)
5 wt% and an acid or alkali that is a precipitation formation inhibitor are added to 0.1.
A zirconium oxide (zirconia) is added to an alcohol solvent by dropping a second liquid (liquid B) mixed with 01 to 10 wt%, preferably 0.02 to 8 wt%, and more preferably 0.05 to 5 wt%. It is characterized by obtaining a hydrophilic coating composition containing as a main component.

The alcohol-based solvent used in the hydrophilic coating composition of the present invention and the method for producing the same is C _n.
Alcohol represented by the structural formula of H _{2n + 1} OH, for example, methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, ter-butyl alcohol, 1-pentanol, 2- Pentanol, 3-pentanol, etc. are used alone or in combination. As the precipitation generation inhibitor, acidic substances such as hydrochloric acid, nitric acid, sulfuric acid, oxalic acid and acetic acid may be used alone or in combination. When an alkali is used as the precipitation generation inhibitor, ammonia, amine compounds, etc. may be used alone or in combination. The acid or alkali that is the precipitation generation inhibitor is 0.0003 to 0.3 wt% in the composition, preferably 0.03 to 0.3 wt%.
03-0.3 wt%, more preferably 0.005-0.
1 wt% is included.

In the composition of the present invention and the method for producing the same, any one of an ester solvent such as ethyl acetate, an aromatic compound such as benzene, xylene and toluene, or a solvent in which a plurality of these compounds are combined is added and contained. You can Further, when the viscosity of the composition is, for example, 10 cp or less, a cellulose compound which is a thickener such as hydroxypropyl cellulose or 10 cp of acetylacetone or the like.
An organic substance having a higher viscosity may be added.

Further, in the composition of the present invention and the method for producing the same, Si, Al, Ti, Mn, Fe, Cu, Z
0.01 to 5% by weight of zirconium atom as the atomic weight of the element, such as halides of elements such as n, Y, Nb, Mo, Ag, and Sn, inorganic salts such as nitrates, and organometallic compounds such as alkoxides. , Preferably 0.0
It is also possible to add 2 to 1 wt%, more preferably 0.03 to 0.5 wt%. Further, as the antistatic agent, any of nonionic type such as poly (oxyethylene) alkylamine, anionic type such as alkylsulfonate and alkylbenzenesulfonate, cationic type such as quaternary ammonium chloride, and amphoteric type such as alkylbetaine type can be used. Alternatively, a substance obtained by combining a plurality of these substances may be added and contained.

Any one or a plurality of salicylic acid type compounds such as phenyl salicylate, benzophenone type compounds such as 2,4-dihydrobenzophenone, and ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate can be used. It is also possible to add and combine the combined substances. In addition, for the purpose of improving the growth suppressing function of bacteria, bacteria, fungi, etc., organic systems such as iodopropargyl derivatives, thiocyanato compounds, isothiazoline derivatives, etc., inorganic systems such as zeolite, silica gel, calcium phosphate, zirconium phosphate, etc., natural such as chitosan etc. It is also possible to add any of the materials or the like or a substance in which a plurality of these materials are combined to add them.

The method of using the hydrophilic coating composition of the present invention is as follows. The surface of a member (for example, a metal plate) made of a metal such as titanium, aluminum, stainless steel, iron, copper or a composite material of these metals, acrylic, urethane. Surface of organic coating such as epoxy, fluorine, fluorine or composite coating thereof, surface of resin such as acrylic resin, polycarbonate resin, vinyl chloride resin, polyolefin resin or combination thereof, or glass, tile It is characterized in that a coating film made of a hydrophilic coating composition is formed on the surface of a member made of gypsum, cement, concrete or the like or a member obtained by combining these members. That is, the hydrophilic coating composition of the present invention can be applied to a wide range of base materials.

The method of use of the present invention is one in which the hydrophilic coating composition is sprayed, brushed, roller-coated, dip-coated, spin coater-coated, bar coater-coated, or a combination thereof. After being immobilized on the surface of the base material, it is characterized by being dried at 50 to 200 ° C., preferably 90 to 140 ° C.
That is, the hydrophilic coating composition of the present invention can employ a coating method suitable for each substrate and can be coated at a low temperature.

As a method of using the present invention, a coating film of a hydrophilic coating composition can be formed on the surface of a substrate to reduce the adhesion of dirt to the surface of the substrate. That is, since the coating film according to the present invention has a hydrophilic function, it can be used for purposes such as antifouling. In addition, as a method of using the present invention, after forming a coating film of a hydrophilic coating composition as an undercoat layer on the surface of a substrate, a photocatalyst coating film can be formed as an overcoat layer on the surface of the coating film. That is, the hydrophilic coating composition of the present invention can also be used as an undercoating agent when applying a photocatalyst to an organic substrate, and in this case, by applying a photocatalyst coating film on the hydrophilic coating film. The organic base material can be protected from deterioration due to the influence of the photocatalytic function.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described. First, a method for producing a hydrophilic coating composition will be described. (1) In container 1, 1 part of zirconium alkoxide is added to an alcohol solvent represented by the structural formula of C _n H _{2n + 1} OH.
Mix 30 wt% and stir well (see Figure 1). The liquid prepared here is hereinafter referred to as liquid A. Examples of the zirconium alkoxide include zirconium-n-propoxide, zirconium tetramethoxide, zirconium ethoxide, zirconium isopropoxide, zirconium butoxide and the like. Examples of the alcohol solvent include isopropyl alcohol, isobutyl alcohol, methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, ter-.
Butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol and the like can be mentioned. Also here
In order to increase the viscosity and film thickness when applying the coating material, it is possible to add a thickener such as 0.01 to 3 wt% of hydroxypropyl cellulose or an organic substance such as 0.01 to 3 wt% of acetylacetone. is there.

(2) In a separate container 2, 0.01 to 10 wt% of water required for hydrolysis is mixed in an alcohol solvent, and an acid or an alkali which is a precipitation formation inhibitor is added in an amount of 0.
Mix 01 to 10 wt% and mix well (see FIG. 2). The solution prepared here is hereinafter referred to as solution B. Examples of the alcohol solvent include the alcohols described above, but it is not always necessary to use the same solvent as the liquid A.
As the precipitation generation inhibitor, an acidic substance such as hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, acetic acid, or an alkaline substance such as ammonia or an amine compound is used, and a precipitate is generated.
Adjust the pH of the solution to be acidic or alkaline with respect to the pH range. Further, here, in order to increase the viscosity and the film thickness when applying the coating material, 0.01 to 3 wt% of a thickener such as hydroxypropyl cellulose or 0.01 to 3 wt%
% Organic compounds such as acetylacetone may be added.

(3) The solution (solution B) in the container 2 is dropped into the solution (solution A) in the container 1 by using, for example, the metering pump 3, to cause a hydrolysis reaction in the container 1. To obtain zirconium oxide (zirconia) (see FIG. 3). In this case, the particle size of zirconia is, for example, 0.5 to 100 nm.
Is.

(4) The container 2 is placed in the solution (solution A) in the container 1.
After the solution (solution B) in (1) has been dropped, the hydrophilic coating composition obtained in the container 1 is transferred to the closed container 4 and stored. At this time, in the solution, fine zirconium oxide (zirconia) produced by the hydrolysis reaction, zirconium hydroxide produced in the course of the reaction, and a small amount of unreacted zirconium alkoxide coexist. Further, in this state, an alcohol solvent (container 5) may be added in order to suppress an excessive reaction in the coating liquid (see FIG. 4). Examples of the alcohol solvent include alcohols as described above, but it is not always necessary to use the same solvent as the liquid A or the liquid B.

The hydrophilic coating composition obtained as described above may contain various other components. For example, it is possible to add an ester solvent such as ethyl acetate, an aromatic compound such as benzene, xylene, or toluene, or a solvent obtained by combining a plurality thereof. In addition, Si, Al, Ti, Mn,
It is also possible to add halides of elements such as Fe, Cu, Zn, Y, Nb, Mo, Ag, and Sn, inorganic salts such as nitrates, and organometallic compounds such as alkoxides. Further, as an antistatic agent, a nonionic type such as poly (oxyethylene) alkylamine, an anionic type such as alkylsulfonate or alkylbenzenesulfonate,
It is also possible to add a cation-based compound such as a quaternary ammonium chloride, an amphoteric-based compound such as an alkyl betaine-type compound, or a substance obtained by combining a plurality thereof. In addition, salicylic acid compounds such as phenyl salicylate, 2,4-
It is also possible to add any one of benzophenone compounds such as dihydrobenzophenone, ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, or a combination thereof. In addition, for the purpose of improving the growth suppressing function of bacteria, bacteria, fungi, etc., organic systems such as iodopropargyl derivatives, thiocyanato compounds, isothiazoline derivatives, etc., inorganic systems such as zeolite, silica gel, calcium phosphate, zirconium phosphate, etc., natural such as chitosan etc. It is also possible to add any of the materials or the like, or a substance obtained by combining a plurality of these materials. These components are added to the solution A or / and the solution B in the process of producing the composition, or added to the obtained composition.

The resulting hydrophilic coating material should be applied onto a substrate by a coating method suitable for each substrate such as a spray method, a dip method, a brush coating method, a roller coating method, a spin coater method and a bar coater method. You can There are a wide range of materials for the base material that can be applied. For example, metals such as titanium, aluminum, stainless steel, iron, and copper, or composite materials of these metals, organic coating films such as acrylic, urethane, epoxy, and fluorine, or these Composite organic coating,
Examples thereof include resins such as acrylic resin, polycarbonate resin, vinyl chloride resin, and polyolefin resin, or resins in which these are combined, glass, tile, gypsum, cement, concrete, or the like, or materials in which these are combined.

After the hydrophilic coating material is applied to the substrate, it is dried at a temperature at which the alcohol solvent volatilizes. For example, when the solvent is isopropyl alcohol or isobutyl alcohol, each has a boiling point of 82.4 at normal pressure.
Dry at 0 ° C, 107.9 ° C or higher for 30 seconds or longer. The coating film thus obtained has a hydrophilic function and can be used for the purpose of antifouling and the like. This hydrophilic coating material can also be used as an undercoating agent when applying a photocatalyst to an organic substrate. In this case, by applying a photocatalyst coating film on the hydrophilic coating film, The material can be protected from deterioration due to the influence of the photocatalytic function.

[0022]

EXAMPLE An example of a method for preparing a hydrophilic coating composition will be shown as an example. Example 1 Zirconium-n-propoxide (11.7 wt%) was mixed in isopropyl alcohol and stirred sufficiently. The liquid prepared here is hereinafter referred to as liquid A. In another container,
Water was mixed with isopropyl alcohol in an amount of 0.5 wt% and 2N hydrochloric acid as a precipitation inhibitor was mixed in an amount of 1.1 wt%, and the mixture was sufficiently stirred. The solution prepared here is hereinafter referred to as solution B.
Solution B was slowly dropped into solution A, and a hydrolysis reaction was slowly generated to generate fine zirconium oxide (zirconia). After completion of dropping, the obtained composition was transferred to a closed container. At this time, isopropyl alcohol was added to suppress an excessive reaction in the coating liquid.

Example 2 Zirconium-n-propoxide (11.7 wt%) was mixed in isopropyl alcohol and sufficiently stirred (see FIG. 1). The liquid prepared here is hereinafter referred to as liquid A.
Further, here, 0.5 wt% of hydroxypropyl cellulose was added in order to increase the viscosity and the film thickness when applying the coating material. In a separate container, add 0.5 wt% of water in isopropyl alcohol and use 2 as a precipitation inhibitor.
1.1 wt% of N hydrochloric acid was mixed and sufficiently stirred (see FIG. 2). The solution prepared here is hereinafter referred to as solution B. Further, here, 0.5 wt% of hydroxypropyl cellulose was added in order to increase the viscosity and the film thickness when applying the coating material. Solution B is slowly dropped into solution A,
A hydrolysis reaction was gently generated to generate fine zirconium oxide (zirconia) (see FIG. 3). After completion of dropping, the obtained composition was transferred to a closed container. At this time, isopropyl alcohol was added to suppress excessive reaction in the coating liquid (see FIG. 4).

Example 3 13.8 wt% of zirconium tetramethoxide was mixed in isobutyl alcohol and stirred sufficiently (A
liquid). Further, here, in order to increase the viscosity and the film thickness when applying the coating material, 0.5 wt% acetylacetone was added. In a separate container, 0.5 wt% of water and 0.5 wt% of ammonia as a precipitation formation inhibitor were mixed in isobutyl alcohol and sufficiently stirred (Liquid B). Further, here, in order to increase the viscosity and the film thickness when applying the coating material, 0.5 wt% acetylacetone was added. Solution B was slowly dropped into solution A, and a hydrolysis reaction was slowly generated to generate fine zirconium oxide (zirconia). After completion of dropping, the obtained composition was transferred to a closed container. At this time, isobutyl alcohol was added to suppress an excessive reaction in the coating liquid.

Example 4 Zirconium ethoxide was mixed in isopropyl alcohol at 10.2 wt% and sufficiently stirred (Liquid A). In a separate container, add 0.5 wt of water in isopropyl alcohol.
%, 1.1 wt% of 2N hydrochloric acid as a precipitate formation inhibitor, and a small amount of ethyl acetate were mixed, and the mixture was sufficiently stirred (B
liquid). Solution B was slowly dropped into solution A, and a hydrolysis reaction was slowly generated to generate fine zirconium oxide (zirconia). After completion of dropping, the obtained composition was transferred to a closed container. At this time, isobutyl alcohol was added to suppress an excessive reaction in the coating liquid.

Example 5 12.3 wt% of zirconium isopropoxide was mixed in isobutyl alcohol and stirred sufficiently (A
liquid). In a separate container, add 0.5 wt% water in isopropyl alcohol and 1.1 wt% 2N hydrochloric acid as a precipitation inhibitor.
%, And a small amount of poly (oxyethylene) alkylamine (antistatic agent) was mixed and sufficiently stirred (B
liquid). Solution B was slowly dropped into solution A, and a hydrolysis reaction was slowly generated to generate fine zirconium oxide (zirconia). After completion of dropping, the obtained composition was transferred to a closed container. At this time, isopropyl alcohol was added to suppress an excessive reaction in the coating liquid.

Example 6 13.1 wt% zirconium butoxide was mixed in isopropyl alcohol and sufficiently stirred (solution A). In a separate container, add 0.5 wt% water in isobutyl alcohol.
%, 1.1 wt% of 2N hydrochloric acid as a precipitation inhibitor, a small amount of 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (ultraviolet absorber), and a small amount of iodopropargyl derivative (antibacterial / antifungal agent). ) Was mixed and sufficiently stirred (solution B). Solution B was slowly dropped into solution A, and a hydrolysis reaction was slowly generated to generate fine zirconium oxide (zirconia). After the dropping is completed,
The obtained composition was transferred to a closed container. At this time, isopropyl alcohol was added to suppress an excessive reaction in the coating liquid.

Next, the hydrophilic coating composition prepared in Example 2 was used to apply it to an acrylic substrate and a polycarbonate substrate, and the gloss value, color value, Ha
The results of measuring the ze value are shown in Table 1. The coating conditions were a dipping method and a pulling rate of 20 cm / min. Drying after coating was performed with a dryer at 90 ° C. for 1 minute. For comparison, the gloss value, the color value, and the Haze value of the acrylic substrate and the polycarbonate substrate which are not hydrophilically coated are measured.

[0029]

[Table 1]

The gloss value is 20 °, 60 °, using a Suga Tester HG-268 conforming to JIS K5400.
The 80 ° gloss was measured. Color value is JIS Z872
With Minolta CR-300 according to 2, the L ^* indicating lightness and the a ^* and b ^* indicating chromaticity were measured. The Haze value is
NDH-made by Nippon Denshoku Industries in accordance with JIS K7105
At 2000, the turbidity was measured.

As can be seen from the results in Table 1, both the acrylic substrate and the polycarbonate substrate show the gloss value, the color value and the Haze value which are almost the same as those of the untreated substrate even when the hydrophilic coating treatment is applied. In addition, the substrate subjected to the hydrophilic coating has a pencil hardness of 5H, showing a sufficient hardness (hardness). Further, in the hydrophilically coated substrate, no peeling of the coating layer was observed in the cross-cut test by sticking / peeling the adhesive tape, and sufficient adhesion was confirmed. And
It has been confirmed that the surface of the substrate which has been subjected to the hydrophilic coating treatment has been rendered hydrophilic by the hydrophilic coating treatment. Regarding the evaluation of hydrophilicity, after the test piece was made horizontal, 10 ml of water was sprayed, and water was spread over the entire surface of the test piece, and only when there was no water droplet was evaluated hydrophilicity development.

Further, using the hydrophilic coating composition prepared in Example 2, the antifouling performance of the test piece was evaluated by the antifouling evaluation test (for general use) proposed by the old civil engineering research institute. As the test piece, an aluminum substrate subjected to a hydrophilic coating treatment was used. The coating conditions are
The pulling rate was 40 cm / min by the dip method. Drying after coating is done at 1
It was carried out for a minute. As the simulated stain used in the test, carbon black (FW-200) dispersed in deionized water at 5 wt% was used. The suspension solution of carbon black, which becomes a simulated stain, was uniformly applied to the surface of the test piece by air spray. The test piece was dried at 60 ° C. for 1 hour and then left to cool to room temperature. The test piece to which the simulated dirt adhered was washed under running water by replacing the gauze in the order of vertical, horizontal, and vertical until washed. The washed test piece was wiped of water and then dried at room temperature for 3 hours.
The difference in brightness (Δ
L ^* ) was used to evaluate the antifouling performance. As a result, the L ^* test piece before the test 88.71, in L ^* of 86.81 for the test piece after the test, ΔL ^* = 86.81-88.71 = -
It was 1.90, and it was confirmed that there was sufficient antifouling performance.

Further, the hydrophilic coating composition prepared in Example 2 was used to evaluate the performance of the photocatalyst as an undercoat material. Using an acrylic plate (10 cm square) as a base material, a hydrophilic coating composition as an undercoat and a titanium oxide coating material (NS300C, manufactured by Nippon Soda Co., Ltd.), which is a photocatalyst, as the top coating, and the titanium oxide coating material only. Accelerated weathering resistance was compared with that of the coating amount by a metering weather meter. The hydrophilic coating composition and the photocatalyst coating material, which are the undercoat material, are applied under a pulling rate of 20 cm /
I went as min. Drying after coating was performed with a dryer at 90 ° C. for 1 minute. For the metering weather meter, A condition (UV intensity 0.75 kW / m ² , humidity 50% RH, temperature 63 ° C (black panel)), B condition (UV intensity 0.75 kW / m ² , water spray amount 200 cc / Minutes,
The test is carried out under two conditions of humidity 95% RH and temperature 38 ° C (dry bulb), and the test is repeated 50 times with one cycle consisting of A condition for 48 minutes and B condition for 12 minutes. Was carried out. As a result, peeling was not observed in the substrate coated with the hydrophilic coating composition, whereas peeling was observed in the substrate coated with only the photocatalyst.

[0034]

Since the present invention is configured as described above, it has the following effects. (1) The hydrophilic coating composition of the present invention can be applied to a wide range of base materials with high adhesion, and since it has high transparency, it does not impair the color and light transmittance of the base material. Also, the design of the surface of the base material can be maintained, and the base material can be easily made hydrophilic. Also, hydrophilic coatings are possible at low temperatures. (2) One of hydrophilic coating materials is a photocatalyst coating material, but the photocatalyst coating film needs to be irradiated with ultraviolet rays, whereas the coating film made based on the composition of the present invention is particularly irradiated with ultraviolet rays. Does not need (3) Since there is no action of decomposing an organic compound such as a photocatalyst, it is easy to add a third component such as an ultraviolet absorber, an antibacterial agent, a fungicide, an antistatic agent. (4) When the substrate is made hydrophilic by the coating film formed based on the composition of the present invention, water droplets and stains are less likely to adhere to the substrate, so that an excellent antifouling function is exhibited. (5) Since the coating film formed based on the composition of the present invention is an inorganic film and has no function of decomposing the hood and organic compounds, it is an undercoat film for forming a photocatalytic coating film on an organic substrate. It can also be used as, and can protect the organic base material from deterioration due to the influence of the photocatalytic function.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing a preparation process of a solution A in the embodiments and examples of the present invention.

FIG. 2 is a schematic explanatory diagram showing a process for preparing a liquid B in the embodiment and the examples of the present invention.

FIG. 3 is a schematic explanatory view showing a process of dropping the liquid B into the liquid A in the embodiments and examples of the present invention.

FIG. 4 is a schematic explanatory view showing a process of transferring the obtained hydrophilic coating composition to a closed container in the embodiments and examples of the present invention.

[Explanation of symbols]

1, 2, 5 containers 3 Fixed-quantity delivery pump 4 closed container

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Akihiro Murakami             1-1 Kawasaki-cho, Akashi-shi, Hyogo Kawasaki Heavy Industries             Akashi Factory Co., Ltd. (72) Inventor Kenjiro Shindo             1-1 Kawasaki-cho, Akashi-shi, Hyogo Kawasaki Heavy Industries             Akashi Factory Co., Ltd. (72) Inventor Tatsuya Imura             1-1 Kawasaki-cho, Akashi-shi, Hyogo Kawasaki Heavy Industries             Akashi Factory Co., Ltd. (72) Inventor Nobuo Suda             2-4-1 Hamamatsucho, Minato-ku, Tokyo Shigeru Kawasaki             Kogyo Co., Ltd. Tokyo headquarters (72) Inventor Seiji Terada             1-1 Kawasaki-cho, Akashi-shi, Hyogo Kawasaki Heavy Industries             Akashi Factory Co., Ltd. (72) Inventor Yoshito Aranishi             1-1 Kawasaki-cho, Akashi-shi, Hyogo Kawasaki Heavy Industries             Akashi Factory Co., Ltd. F-term (reference) 4J038 BA022 DM001 HA106 HA23                       HA246 HA306 JA03 JA17                       JA55 JB01 JC38 KA06 NA05                       NA06 NA20 PC02 PC03 PC04                       PC08

Claims (26)

[Claims] 1. Zirconium-n-propoxide, zirconium tetramethoxide, zirconium ethoxide,
A zirconium alkoxide selected from the group consisting of zirconium isopropoxide and zirconium butoxide is a raw material, and a zirconium oxide is contained in an alcohol solvent to contain a zirconium atom as the zirconium oxide in the alcohol solvent. The amount is 0.1
A hydrophilic coating composition, characterized in that it is 10 wt%. 2. Zirconium oxide having a particle size of 0.5 to
The hydrophilic coating composition according to claim 1, which has a thickness of 100 nm. 3. The alcohol solvent is an alcohol represented by the structural formula of C _n H _{2n + 1} OH, which is methanol, ethanol, 1-propanol, isopropyl alcohol,
1-butanol, 2-butanol, isobutyl alcohol, ter-butyl alcohol, 1-pentanol, 2
-The hydrophilic coating composition according to claim 1 or 2, which is at least one of pentanol and 3-pentanol. 4. The hydrophilic coating composition according to claim 1, wherein at least one of an ester solvent and an aromatic compound is contained in an alcohol solvent. 5. An acidic substance of at least any one of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid and acetic acid is added in an amount of 0.0003 to 0.3.
The hydrophilic coating composition according to any one of claims 1 to 4, wherein the hydrophilic coating composition contains wt%. 6. 0.0003 to 0.3 wt% of an alkaline substance of at least one of ammonia and amine compounds
% Of the hydrophilic coating composition according to any one of claims 1 to 4. 7. The hydrophilic coating composition according to claim 1, which contains at least one of a cellulose compound as a thickener and an organic substance having a high viscosity. 8. Si, Al, Ti, Mn, Fe, Cu,
A halide of at least one element of Zn, Y, Nb, Mo, Ag and Sn, an inorganic salt or / and an organometallic compound was contained in an amount of 0.01 to 5 wt% with respect to the zirconium atom as the atomic weight of the element. The hydrophilic coating composition according to claim 1. 9. A nonionic poly (oxyethylene) alkylamine, an anionic alkyl sulfonate, an alkylbenzene sulfonate, a cationic quaternary ammonium chloride and / or an amphoteric alkyl betaine type antistatic agent. Claim 1 containing
9. The hydrophilic coating composition according to any one of to 8. 10. An ultraviolet absorber containing at least one of salicylic acid-based phenyl salicylate, benzophenone-based 2,4-dihydrobenzophenone, and 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate. The hydrophilic coating composition according to any one of 1 to 9. 11. An organic iodopropargyl derivative, a thiocyanato compound and an isothiazoline derivative, an inorganic zeolite, silica gel, calcium phosphate and zirconium phosphate, and a natural material for the purpose of improving the growth inhibitory function of bacteria, bacteria, fungi and the like. The hydrophilic coating composition according to any one of claims 1 to 10, which contains at least one of the following chitosans. 12. Zirconium-n-propoxide, zirconium tetramethoxide, in an alcohol solvent,
1st to 30% by weight of zirconium alkoxide selected from the group consisting of zirconium ethoxide, zirconium isopropoxide and zirconium butoxide;
Water and 0.01 to 10 wt% of water in alcohol solvent
And 0.01 or more of an acid or an alkali that is a precipitation generation inhibitor.
A method for producing a hydrophilic coating composition, which comprises mixing with a second liquid added at 10 wt% to obtain a hydrophilic coating composition containing zirconium oxide as a main component in an alcohol solvent. 13. Zirconium-n-propoxide, zirconium tetramethoxide, in an alcoholic solvent,
A first mixture containing 1 to 30 wt% of a zirconium alkoxide selected from the group consisting of zirconium ethoxide, zirconium isopropoxide and zirconium butoxide.
0.01 to 10% by weight of water in alcohol solvent
And 0.01 or more of an acid or an alkali that is a precipitation generation inhibitor.
A method for producing a hydrophilic coating composition, characterized in that a hydrophilic coating composition containing zirconium oxide as a main component in an alcohol solvent is obtained by dropping a second liquid mixed with 10 wt%. 14. As the alcohol solvent, methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, ter-butyl alcohol, 1-pentanol, 2-pentanol and 3-pen. The method for producing a hydrophilic coating composition according to claim 12 or 13, wherein an alcohol represented by the structural formula of C _n H _{2n + 1} OH of at least one of the tanols is used. 15. The method for producing a hydrophilic coating composition according to claim 12, 13 or 14, wherein at least one of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid and acetic acid is used as an acid which is a precipitation formation inhibitor. 16. The method for producing a hydrophilic coating composition according to claim 12, 13 or 14, wherein at least one of ammonia and an amine compound is used as an alkali that is a precipitation formation inhibitor. 17. The method for producing a hydrophilic coating composition according to claim 12, wherein at least one of an ester solvent and an aromatic compound is added to the first liquid and / or the second liquid. . 18. The hydrophilic coating according to claim 12, wherein at least one of a cellulose compound as a thickener and an organic substance having a high viscosity is added to the first liquid and / or the second liquid. A method for producing a composition. 19. Si, Al, Ti, Mn, Fe, C
13. A halide of at least one element of u, Zn, Y, Nb, Mo, Ag and Sn, an inorganic salt or / and an organometallic compound is added to the first liquid or / and the second liquid. 19. The method for producing the hydrophilic coating composition according to any one of 18. 20. Nonionic poly (oxyethylene)
Alkyl amine, anionic alkyl sulfonate,
An alkylbenzene sulfonate, a cationic quaternary ammonium chloride and / or an amphoteric alkylbetaine type antistatic agent is added to the first liquid and / or the second liquid. A method for producing the hydrophilic coating composition described. 21. A salicylic acid-based phenyl salicylate, a benzophenone-based 2,4-dihydrobenzophenone, and / or 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate as a first liquid or a UV absorber. And / or is added to the second liquid.
21. The method for producing the hydrophilic coating composition according to any one of 2 to 20. 22. An organic iodopropargyl derivative, a thiocyanato compound and an isothiazoline derivative, an inorganic zeolite, silica gel, calcium phosphate and zirconium phosphate, and a natural material for the purpose of improving the growth inhibitory function of bacteria, bacteria, fungi, etc. 22. The method for producing a hydrophilic coating composition according to any one of claims 12 to 21, wherein at least one of the chitosan is added to the first liquid and / or the second liquid. 23. Titanium, aluminum, stainless steel,
The surface of a member made of any metal of iron and copper or a composite material of these metals, the surface of an organic coating film of any of acrylic, urethane, epoxy and fluorine or the surface of an organic coating film combining these, acrylic resin , Polycarbonate resin, vinyl chloride resin and polyolefin resin any resin or a surface of a composite resin thereof, or glass, tile, plaster, cement or concrete member or a surface of a composite member of these, A method for using a hydrophilic coating composition, which comprises forming a coating film of the hydrophilic coating composition according to any one of claims 1 to 11. 24. Any one of a spray method, a brush coating method, a roller coating method, a dipping method, a spin coater method and a bar coater method, or a combination of a plurality of the hydrophilic coating composition according to any one of claims 1 to 11. A method for using a hydrophilic coating composition, which comprises drying on 50 to 200 ° C. after being immobilized on the surface of a substrate by the above method. 25. A coating film of the hydrophilic coating composition according to claim 1 is formed on the surface of a substrate to reduce the adhesion of stains on the surface of the substrate.
A method for using the hydrophilic coating composition according to 3 or 24. 26. After forming a coating film of the hydrophilic coating composition according to any one of claims 1 to 11 on the surface of a substrate as an undercoat layer, a photocatalyst coating film is formed on the surface of the coating film as an overcoat layer. Use of the hydrophilic coating composition according to claim 23 or 24 to form.