JP2002302637A - Hydrophilic coated film-forming composition, process for preparing composite material using this and composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated film-forming composition which can form a coated film showing an excellent hydrophilicity, water-resistance durability and cleanability on a solid substrate at room or an elevated temperature, a composite material having the coated film and its preparation process. SOLUTION: The coated film-forming composition contains a reaction mixture obtained by mixing and reacting the raw materials which are (1) a Si-containing component, (2) a Zr-containing component, (3) an Al-containing component, (4) a Li-containing component and, if required, (6) an alkaline earth metal- containing component and (7) a Fe-containing component (provided that components (1)-(3) contains at least one alkoxide of Si, Zr or Al) with (5) a polyacrylic acid in water, and, if required, adding a divalent metal-containing compound and/or a compound containing iron with a valence other than 2. A coated film of the coated film-forming composition is formed on surfaces of various solid materials.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling, antifogging,
It is useful for antistatic, easy-to-clean, and improve slipperiness. Especially, it has both hydrophilicity and curability due to hydration reaction, long-lasting effect and excellent water-resistant durability. The present invention relates to a composition for use, a method for producing a composite material using the same, and a composite material.

[0002]

2. Description of the Related Art Conventional coating films having high hydrophilicity include titanium oxide-based photocatalyst systems, organic surfactant systems,
Coating films of inorganic water glass type and sol-gel type are known. The disadvantage of the photocatalytic coating film is that
A sufficient effect cannot be obtained in a dark place, and a disadvantage of a surfactant-based coating film is that it elutes in water and the effect is not maintained for a long time. Further, although the water glass-based coating film has high curability, it is formed by simple drying, and thus has a drawback of poor water resistance. Further, the sol-gel type coating film has a disadvantage that heating at a high temperature is required for curing, and a coating film having sufficient hydrophilicity and durability cannot be obtained by a low-temperature treatment.

For example, according to Kamiya et al. (Journal of the Aluminum Research Society, pp. 97-98, 1995), a coating film obtained by adding polyacrylic acid to sodium silicate is initially a hydrophilic film having a low contact angle. It has been shown that when it comes into contact with water, its hydrophilicity is reduced by the elution of sodium ions.

[0004]

SUMMARY OF THE INVENTION The present invention exhibits high hydrophilicity and self-curing properties by a hydration reaction, and can form a wall film excellent in water resistance and durability even at a low temperature, and can be formed at a high temperature. Another object of the present invention is to provide a composition for forming a hydrophilic member coating film for forming a wall film having more excellent durability, a method for producing a composite material using the same, and a composite material. That is, the present invention obtains excellent hydrophilicity by introducing a chemical bond with water by a hydration reaction, and at the same time, has a self-curing property, and is excellent in easy cleaning property, An object of the present invention is to provide a composition for forming a hydrophilic coating film having excellent water resistance and durability, a method for producing a composite material using the same, and a composite material.

[0005]

Means for Solving the Problems Formation of the hydrophilic coating film of the present invention
The composition for use comprises (1) a silicon alkoxide and a water-soluble salt.
A silicon-containing component comprising at least one selected from the group consisting of:
(2) Select from zirconium alkoxides and water-soluble salts
At least one zirconium-containing component
And (3) aluminum alkoxide and water-soluble salt
Aluminum-containing component comprising at least one selected from the group consisting of:
And (4) from at least one of the water-soluble salts of lithium.
And (5) polyacrylic acid
Are obtained by mixing and reacting
A reaction mixture containing the silicon-containing component (1),
Conium-containing component (2) and aluminum-containing component
(3) silicon alkoxide and zirconium alkoxide
Selected from co-oxides and alkoxides of aluminum
Characterized in that at least one kind is contained.
Things. In the composition for forming a hydrophilic coating film of the present invention
The silicon-containing component (1) contained in the raw material, zirconium
Component containing aluminum (2), component containing aluminum (3) and
And the content ratio of the lithium-containing component (4) is
O_Two , ZrO_Two , Al_Two O_Three And Li_Two To the absolute dry weight of O
Converted to 20-70 (SiO_Two ): 1 to 50 (ZrO
_Two ): 1 to 30 (Al_Two O_Three ): 5 to 30 (Li_Two O)
It is preferred that Composition for forming a hydrophilic coating film of the present invention
A silicon-containing component contained in the raw material
(1), zirconium-containing component (2), aluminum-containing
Compounding weight of component (3) and lithium-containing component (4)
With SiO_Two , ZrO_Two , Al_Two O_ThreeAnd Li_Two
 O, the total weight when converted to the absolute dry weight
The ratio of the combined dry weight of the lylic acid (5) is 100: 5 to 10
Preferably, the ratio is 0: 10,000. Hydrophilic of the present invention
In the composition for forming a functional coating film, the raw material contains the silicon-containing material.
Component (1), the zirconium-containing component (2),
Aluminum-containing component (3), the lithium-containing component
(6) 2 in addition to (4) and polyacrylic acid (5)
Divalent gold comprising at least one water-soluble salt of a divalent metal
Group-containing components, and (7) iron having a valence other than divalent.
Selected from iron-containing components comprising at least one water-soluble salt.
At least one member may be further included. Departure
The composition for forming a bright hydrophilic coating film, wherein the divalent metal
When the divalent metal of the component (6) is an alkaline earth metal,
And Zn, Cu (II), Fe (II), Ni (II), and
It is preferable to be selected from Mn (II). Hydrophilic of the present invention
In the composition for forming a functional coating film, the silicon-containing material in the raw material
The divalent metal-containing component (6) with respect to the component (1) and
Including the iron-containing component (7) having a valence other than divalent.
The ratio is SiO_Two , MO (where M is divalent
Represents a metal atom) and Fe_Two O_Three Converted to the absolute dry weight of
20-70 (SiO_Two ): 0 to 1000 (MO): 0
10 (Fe_Two O_Three ) Is preferable. Composition for forming a hydrophilic coating film of the present invention
In the product, the silicon synthesis component (1) in the raw material,
Zirconium-containing component (2), aluminum-containing component
(3), lithium-containing component (4), divalent metal-containing component
(6) and an iron-containing component having a valence other than divalent
The amount of (7) was changed to SiO_Two , ZrO_Two , Al_Two 
O_Three , Li_Two O, MO (where M represents a divalent metal atom)
And Fe_Two O_Three Total distribution when converted to absolute dry weight of
The ratio of the combined weight to the dry weight of polyacrylic acid (5) is
Preferably 100: 5 to 100: 100,000
New In the composition for forming a hydrophilic coating film of the present invention,
The amount of the polyacrylic acid in the raw material is based on the weight of water.
It is preferably 0.01 to 25%. Of the present invention
The method for producing a composite material is the method for forming a hydrophilic coating film of the present invention.
An aqueous coating solution containing the composition is applied to at least one surface of a solid substrate.
To form a hydrophilic coating film by solidifying the coating liquid layer.
That is to say. In the production method of the present invention,
The base material is metal material, ceramic, glass material, ceramic
Selected from at least one selected from materials and organic polymer materials
Preferably. The composite material of the present invention is a solid substrate
And the hydrophilic coating film of the present invention on at least one surface thereof.
An aqueous coating solution containing the composition for application is applied and solidified to form.
And a hydrophilic coating film. Composite material of the present invention
In the material, the solid substrate is a metal material, a ceramic material,
Select from glass material, ceramic material and organic polymer material
It is preferable that it is removed. In the composite material of the present invention,
In the hydrophilic coating film, components (1) to (5) of the raw materials and
The reaction product of water is formed and the silicon
Weight ratio of silicon, zirconium, aluminum and lithium
Are respectively SiO_Two , ZrO_Two , Al_TwoO_Three And Li_Two
 O When converted to absolute dry weight, 20-70 (SiO
_Two ): 1 to 50 (ZrO_Two ): 1 to 30 (Al_Two O
_Three ): 5 to 30 (Li_Two O) is preferred. Book
In the composite material of the invention, the raw material is the component (6) and
(7), in which case the hydrophilic
The components (1) to (5),
(6) and (7) and the reaction product of water is formed
And the silicon contained therein, the divalent metal,
The weight ratio to valence iron is SiO_Two , M
O (where M represents a divalent metal atom) and Fe_Two O_Three 
20 to 70 (SiO 2)_Two ):
1,000 (MO) or less: 10 (Fe_Two O_Three )
Preferably. In the composite material of the present invention, the parent material
Silicon, zirconium, aluminum contained in aqueous coatings
, And the lithium content, respectively,_Two , ZrO_Two ,
Al_Two O_ThreeAnd Li_Two When converted to absolute dry weight of O
Total weight and drying of polyacrylic acid of polyacrylic acid residue
The ratio to the weight when converted to the weight is 100: 5 to 10
Preferably, the ratio is 0: 10,000. Composite of the present invention
In the material, the raw material further comprises the components (6) and (7).
May be included, in this case, included in the hydrophilic coating film
Silicon, zirconium, aluminum, lithium,
Content of the metal having a valence of two and iron having a valence other than divalent,
SiO_Two , ZrO_Two , Al_Two O_Three Li_Two O, M
O (where M represents a divalent metal atom) and Fe_Two O_Three of
Total weight when converted to absolute dry weight and polyacrylic acid
Weight of the residue converted to polyacrylic acid dry weight
Is 100: 5 to 100: 100,000
Is preferred.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION A coating film (coating film) obtained from the composition for forming a hydrophilic coating film according to the present invention has both high hydrophilicity and self-curability obtained by a hydration reaction between its components. Have That is, the coating film obtained according to the present invention has a feature that it has a high self-curing property not found in a conventional hydrophilic coating film, and therefore has high water resistance and durability. .

[0007] The composition for forming a hydrophilic coating film of the present invention comprises:
(1) a silicon-containing component composed of at least one selected from alkoxides and water-soluble salts of silicon; (2) a zirconium-containing component composed of at least one selected from alkoxides and water-soluble salts of zirconium; A) an aluminum-containing component comprising at least one selected from aluminum alkoxides and water-soluble salts, provided that the silicon-containing component (1), the zirconium-containing component (2) and the aluminum-containing component (3) contain silicon; At least one selected from the group consisting of an alkoxide of zirconium, and an alkoxide of aluminum; and (4) a lithium-containing component comprising at least one water-soluble salt of lithium; and (5) polyacrylic acid. , Including a reaction mixture obtained by mixing and reacting raw materials consisting of Things.

[0008] In the coating film forming composition of the present invention, in addition to the components (1) to (5), the raw material thereof further comprises (6) at least one water-soluble salt of a divalent metal. It may further include at least one member selected from a metal-containing component and (7) an iron-containing component composed of at least one water-soluble salt of iron having a valence other than divalent.

In the method for producing a composite material of the present invention, an aqueous coating solution containing the composition for forming a hydrophilic coating film of the present invention is applied to at least one surface of a solid substrate, and the coating solution layer is solidified. , Forming a hydrophilic coating film. According to the method of the present invention, a composite material having a solid substrate and a hydrophilic coating film formed on at least one surface thereof is obtained.

The silicon-containing component (1) used as one component of the raw material of the composition for forming a coating film of the present invention is an alkoxide of silicon, preferably an alkoxide of silicon, for example, silicon methoxide, silicon ethoxide, silicon alkoxide. Propoxide, γ-glycidoxypropyltrimethoxysilane, and at least one water-soluble salt of silicon, for example, at least one selected from lithium, sodium, potassium, ammonium, and hydrofluoric acid salts of silicon. Including.

The zirconium-containing component (2) used as one component of the raw material of the coating film forming composition of the present invention includes zirconium alkoxide such as zirconium methoxide, zirconium ethoxide, zirconium tetrabutoxide, zirconium, and the like. , For example, at least one selected from zirconium hydrochloride, hydrofluoric acid, nitrate and the like.

The aluminum-containing component (3) contained as one component of the raw material of the composition for forming a coating film of the present invention includes alkoxides of aluminum, for example, aluminum methoxide, aluminum ethoxide, aluminum isobutoxide, and the like. It contains a water-soluble salt of aluminum, for example, at least one selected from nitrates, hydrochlorides and sulfates of aluminum.

The above-mentioned silicon-containing component (1), zirconium-containing component (2) and aluminum-containing component (3) include:
At least one selected from silicon alkoxides, zirconium alkoxides, and aluminum alkoxides must be contained.

The lithium-containing component (4) used as one component of the raw material of the composition for forming a coating film of the present invention is a water-soluble compound of lithium, for example, hydroxide or nitrate of lithium,
It is selected from acetate, citrate and the like.

The polyacrylic acid (5) used as one component of the raw material of the composition for forming a coating film of the present invention has no particular restrictions on the molecular weight, degree of polymerization, production method, etc. Those having a weight average molecular weight of 10,000 are preferred.

The raw material of the composition for forming a coating film of the present invention may contain, as necessary, a divalent metal-containing component (6).
And / or an iron-containing component having a valence other than divalent (7)
May be included, and the divalent metal-containing component (6)
Preferably an alkaline earth metal, ie, Ca, Sr, B
a, Ra, Be, and Mg, and Zn, Cu (II),
Water-soluble salts of divalent metals selected from Fe (II), Ni (II) and Mn (II), for example, at least one selected from hydrochloride, nitrate, sulfate, and organic acid salt And an iron-containing component having a valence other than divalent (7)
Contains a water-soluble iron salt having a valence other than divalent, for example, one or more selected from hydrochloride, nitrate, sulfate, and organic acid salt.

In the composition for forming a coating film of the present invention, the above components (1) to (4) and, if necessary, components (6) and (7)
And a raw material containing the component (5) (polyacrylic acid) in water or an organic solvent containing water, a reaction occurs between these components to form a reaction mixture. A coating solution prepared from the coating film forming composition of the present invention containing the reaction mixture is applied to the surface of a solid substrate, and the coating solution layer is solidified to form a coating film. This coating film contains an interaction mixture of components (1) to (5) and, if necessary, components (6) and (7). The role of each component present in the coating film will be described below.

The Si-containing component (1) (for example, Si
O ₂ ) is a basic constituent of the coating film. The Si-containing component (1) alone shows considerable hydrophilicity, but is not always practically sufficient. Further, the Si-containing component (1) in the coating film shows curability when heated alone to a high temperature. However, the Si-containing component (1) alone does not have sufficient water resistance and durability at low temperatures. However, when the Si-containing component (1) is combined with the Li-containing component (4) (eg, Li ₂ O) in the coating, the resulting coating exhibits excellent hydrophilicity and low temperature ( 40
(Approximately −100 ° C.). However, its curability is only manifested with drying, and the water resistance of the obtained cured product cannot be said to be sufficiently high for practical use. The lithium-containing component (4) in the coating film has an effect of accelerating the hydration reaction of the aluminum-containing component (3) (for example, Al ₂ O ₃ ). In addition, lithium component (4)
Has not only the effect of improving the hydrophilicity of the coating film, but also the effect of lifting oil adhering to the coating film, thereby improving the ease of cleaning of the coating film. Aluminum-containing component (3)
The function and effect of will be described later.

The polyacrylic acid component (5) acts as an organic binder in the coating film or is itself water-soluble and has low water resistance. The polyacrylic acid component (5) in the coating film slightly improves the water resistance of the coating film by being combined with the Si-containing component (1) and the Li-containing component, but this alone is still insufficient for practical use. Coating film (acrylic acid component (5) + Si-containing component (1) + L
The i-containing component (4) deteriorates when left in water. If this coating film is left in the air for a long period of time, its hydrophilicity is reduced. Therefore, the practical performance of the coating film composed of the polyacrylic acid component (5) + Si-containing component (1) + Li-containing component (4) is unsatisfactory.

The Al-containing component (3) is the same as the component (5) +
When added to the (1) + (4) -based coating film, the hydrophilicity, water resistance and durability of the obtained coating film are dramatically improved. The mechanism of this effect is not yet fully understood, but A
Aluminum ion generated from the l-containing component (3)
The above components (1), (4) and (5) are chemically bonded in a hydration reaction, and the resulting coating film is
This is because not only high hydrophilicity is exhibited, but also the curability itself is exhibited. The above components (1) + (3) +
The coating film formed by the system containing (4) + (5) is easily cured, exhibits improved water resistance and hydrophilicity, does not deteriorate even when left in water, and has a long Even if left in the air for a period, the hydrophilicity does not decrease. However, a coating film composed of the above four components (1) + (3) + (4) + (5) is not practically sufficient in alkali resistance.

The above four components (1) + (3) +
In the (4) + (5) system, the Zr-containing component (2) (for example, Zr
When O ₂ ) is added, the alkali resistance of the resulting coating film is significantly improved. This is because the Zr-containing component (2) is
This is considered to prevent the dissolution of the component (1) (eg, SiO2) by alkali.

The coating film formed by the composition of the present invention comprises:
In addition, Si reacts with each other and is contained as a reaction mixture.
Component (1), Zr component (2), Al component
(3), Li-containing component (4), and polyacrylic acid component
The effect of the present invention is exhibited by the interaction effect of (5).
I do. Inorganic component contained in the coating film forming composition of the present invention
(1) to (4), respectively, SiO_Two , ZrO_Two , Al
_Two O_Three And Li_Two The absolute dry weight ratio of the mixture when converted to O is
20-70 (SiO_Two ): 1 to 50 (ZrO_Two ): 1
30 (Al_Two O_Three ): 5 to 30 (Li_Two O)
And more preferably 50 to 60 (SiO 2 _Two ):
10-20 (ZrO_Two ): 10 to 20 (Al_Two O_Three ):
15-25 (Li _Two O). These inorganic components (1)
To (4) of the polyacrylic acid component (5) in total dry weight
The ratio to dry weight is 100: 5 to 100: 10,0
00, more preferably 100: 1.
00 to 100: 500.

In the composition for forming a coating film of the present invention, the ratio of the absolute dry weight in terms of SiO _{2 of the} Si-containing component (1) to the absolute dry weight is preferably 20 to 70%.
If it is less than 20%, the self-curing property of the resulting coating film may be insufficient, and if it exceeds 70%, the content of other components will be insufficient, and the desired effect will be obtained. May not be achieved. The ratio of the ZrO ₂ -based absolute dry weight of the Zr-containing component (2) to the absolute dry weight of the composition is as follows:
It is preferably 1 to 50%, and if it is less than 1%, sufficient alkali resistance of the coating film may not be ensured, and if it exceeds 50%, the self-curing property of the obtained coating film is poor. May be enough.

The ratio of the absolute dry weight in terms of Al ₂ O ₃ of the Al-containing component (3) to the absolute dry weight of the composition is 1 to 3.
It is preferably 0%, and if it is less than 1%, the water resistance, durability, and hydration of the resulting coating film may be insufficient, and if it exceeds 30%, it is obtained. The self-curing property of the coating film may be insufficient. The Li-containing component (4) promotes the effect of the Al-containing component (3). The ratio of the Li ₂ O-equivalent absolute dry weight of the Li-containing component to the absolute dry weight of the composition is preferably 5 to 30%, and if it is less than 5%, the hydrophilicity, water resistance, The durability may be insufficient, and if it exceeds 30%, the water resistance of the resulting coating film may be insufficient again.

In the coating film forming composition of the present invention, the ratio of the absolute dry weight of the polyacrylic acid component (5) to the total absolute dry weight of the inorganic components (1) to (4) is 5 to 10,000%.
When it is less than 5%, the self-curing property of the obtained coating film may be insufficient, and when it exceeds 10,000%, the self-curing property of the obtained coating film may be insufficient. May become insufficient again. If the self-curing property of the coating film is insufficient, its water resistance and durability will also be insufficient.

The Si-containing component (1), the Zr-containing component (2) and the Al-containing component (3) of the composition for forming a coating film of the present invention are each one selected from Si alkoxides, Zr alkoxides and Al alkoxides. It is necessary to include the above. The Si, Zr and / or Al alkoxide reacts with water and hydrolyzes to form an aqueous sol of an oxide or hydroxide of Si, Zr and / or Al. The oxide or hydroxide contained in this aqueous sol is made of ultrafine particles (particle size 10).
^-3 mm or less), it has high chemical reactivity with other components,
In addition, hydration reaction easily occurs, and the hydration property and self-curing property of the obtained coating film are significantly improved, and the transparency of the coating film is improved.

In the composition for forming a coating film of the present invention, Si
The component (1) preferably contains a Si alkoxide, for example, ethyl silicate. When an appropriate amount of water and an acid catalyst (polyacrylic acid) are added to the Si alkoxide, the Si alkoxide is hydrolyzed to generate an aqueous sol of SiO ₂ . Therefore, in the coating film forming composition of the present invention, SiO 2 is used as a reaction product of the raw material Si-containing component (1) and water.
Preferably, an aqueous sol of ₂ is included.

The raw material Zr-containing component (2) and the Al-containing component (3) of the coating film forming composition of the present invention are each water-soluble Z
It may contain an r salt and a water-soluble Al salt, but preferably contains an alkoxide and an Al alkoxide simultaneously with the Si-containing component (1). Zr alkoxide and A
The alkoxide is reacted with water and acrylic acid to form
It is hydrolyzed to produce a curable reaction product. The Li-containing component contains a water-soluble Li salt. It is preferable that the inorganic components (1) to (4) are each mixed as an aqueous dispersion.

As the polyacrylic acid used as the component (5) in the present invention, a commercially available product may be used as it is. Polyacrylic acid component (5), together with water, other inorganic components (1)
When (4) is mixed and contacted, a self-curing reaction is started. The reaction rate of this reaction is determined depending on the temperature and pH of the reaction system. Generally, the higher the reaction temperature and reaction pH, the higher the reaction rate. By utilizing this characteristic, the curing reaction of the composition-containing coating liquid layer can be controlled. For example, when a coating solution containing the composition of the present invention is applied to the surface of a solid substrate and the coating solution layer is solidified (cured) at room temperature, the pH value of the coating solution is increased to 7 or more. Accelerates curing. In this case, it is effective to minimize the water content in the coating liquid to form a coating film having high mechanical strength. If it is possible to heat the coating liquid layer, the coating liquid layer is heated, and the water is evaporated and removed to reduce the residual amount of water that causes a reduction in strength. Then, the coating liquid layer is cured by a self-curing reaction to form a coating film. In this case, if the pH value of the coating solution is excessively high, the curing reaction proceeds during heating for removing moisture, and air bubbles are taken in the coating film, which may lower the mechanical strength of the coating film. Therefore, in this case, it is preferable to set the pH value low so that the coating film hardens after moisture evaporation. Further, in order to adjust the curing speed and viscosity, a curing speed controlling inorganic compound such as a sodium salt, a potassium salt, an ammonium salt and / or an organic compound such as polyvinyl alcohol or alcohols is added to the coating solution. Is also good. Further, fine particles such as colloidal silica, alumina, and titanium dioxide may be added as an aggregate to the coating solution.

The divalent metal (hereinafter represented by M) -containing component (6) optionally contained in the coating film forming composition of the present invention contains at least one water-soluble salt of M (for example, nitrate). The component (6) plays a role in the strength of the film,
It is to improve durability and adhesion. The iron-containing component (7) having a valence other than divalent, which is contained as necessary, is one of water-soluble iron (other than II) salts (for example, nitrate).
The component (7) plays a role in improving the strength, durability and adhesion of the film. In the composition for forming a coating film of the present invention, the divalent metal (M) -containing component (6) and the non-divalent atom are based on the absolute dry weight of the Si-containing component (1) in the raw material in terms of SiO _2. The content ratio of the multivalent Fe-containing component (7) is SiO 2
₂ , MO (where M represents a divalent metal atom) and Fe
20-70 (SiO ₂ ): 0-1,000 (MO): 0 in terms of absolute dry weight of ₂ O ₃
-10 (Fe ₂ O ₃ ). Further, in the raw material, the silicon synthesis component (1), the zirconium-containing component (2), the aluminum-containing component (3), the lithium-containing component (4), the divalent metal-containing component (6), and other than divalent SiO ₂ amount of iron-containing component with a valence (7), respectively, ZrO
₂ , the total blended weight of Al ₂ O ₃ , Li ₂ O, MO (where M represents a divalent metal atom) and Fe ₂ O ₃ in terms of absolute dry weight, and polyacrylic acid (5) Is 1
The ratio is preferably from 00: 5 to 100: 100,000.

The Si-containing component (1) and the Zr-containing component (2) in the coating film formed using the coating film forming composition of the present invention.
And the network structure formed by the polyacrylic acid component (5) are chemically bonded via aluminum ions supplied from the Al-containing component (3) to form a coating film. It is considered to be self-curing. In this self-curing, the Li-containing component (4) promotes this reaction, and itself (eg, Li ₂ O) is also incorporated into the network structure formed by the curing reaction, attracting water molecules and coating the water. It is thought to promote the hydration of the membrane. The blending amount of polyacrylic acid in the raw material for the composition was 0.1 to the weight of water.
It is preferably in the range of 01 to 25% by weight, more preferably 1 to 10% by weight.

The composition for forming a hydrophilic coating film of the present invention may contain an organic solvent, a fungicide, an insecticide, a rust inhibitor and / or a coloring agent, if necessary, as long as the desired performance is not impaired. Alternatively, in order to impart antibacterial properties to the coating film, an antibacterial agent such as silver, for example, silver colloid, and a silver compound such as silver nitrate, silver lactate, etc. may be contained in the coating composition.

In the method for producing a composite material of the present invention, an aqueous coating solution containing the composition for forming a hydrophilic coating film of the present invention is applied on at least one surface of a solid substrate, and this coating solution layer is formed. Solidifies to form a hydrophilic coating. As aforementioned,
When the coating film is formed by natural drying at room temperature, the pH of the coating solution is preferably 1 to 7. When the coating film is formed by heating and solidifying, it is preferable to first remove the moisture by heating at 50 to 100 ° C. and then to cure by heating to 100 to 300 ° C. The weight of the solidified coating is not limited but is preferably generally is 0.1-5 g / m ^2, more preferably 1 to 2 g / m ^2. The type, shape, dimensions, etc. of the formal material of the solid substrate forming the coating film are not particularly limited as long as a coating film can be formed thereon, for example, metal materials, ceramics, glass materials,
A molding material containing at least one of a ceramic material, an organic polymer material, and the like, for example, a plate material, a bar material, a cotton material, and other molded products can be used as the base.

The composite material of the present invention is obtained by applying an aqueous coating solution containing the composition for forming a hydrophilic coating film of the present invention on at least one surface of a solid substrate and solidifying the same. And a functional coating film. The solid substrate contained in the composite material is as described above. In the hydrophilic coating film, a reaction product of components (1) to (5) of the raw material and water is formed, and the weight ratio of silicon, zirconium, aluminum, and lithium contained therein is SiO _2. , Z
When converted to absolute dry weight of rO ₂ , Al ₂ O ₃ and Li ₂ O, 20 to 70 (SiO ₂ ): 1 to 50 (ZrO ₂ ):
1~30 (Al ₂ O _3): is preferably 5~30 (Li ₂ O). Further, the raw material further contains an M-containing component (6) and a Fe-containing component (7) having a valence other than divalent,
In the hydrophilic coating film, components (1) to
(5) A reaction product of components (6) and (7) and water is formed, and the weight ratio of silicon, divalent metal, and non-divalent valent iron contained therein is: Each Si
O ₂ , MO (where M represents a divalent metal atom) and F
When converted to the absolute dry weight of e ₂ O ₃ , 20 to 70 (Si
O ₂ ): 1,000 (MO) or less: 10 (Fe ₂ O ₃ )
The following is preferred. Further, the total weight of silicon, zirconium, aluminum and lithium contained in the hydrophilic coating film as converted to the absolute dry weight of SiO ₂ , ZrO ₂ , Al ₂ O ₃ and Li ₂ O, respectively, and polyacrylic The ratio of the acid residue to the dry weight of polyacrylic acid is 100: 5 to 100: 10,000.
It is preferably 0. Further, the raw material is the component (6)
And (7), wherein the content of silicon, zirconium, aluminum, lithium, a divalent metal, and a nonvalent divalent iron contained in the hydrophilic coating film is set to Si, respectively.
The total weight of O ₂ , ZrO ₂ , Al ₂ O ₃ Li ₂ O, MO (where M represents a divalent metal atom) and Fe ₂ O ₃ , and the polyacrylic acid residue Of the weight when converted to the dry weight of polyacrylic acid,
The ratio is preferably from 100: 5 to 100: 100,000.

The coating film of the composite material obtained according to the present invention comprises:
Since it has hydrophilicity due to hydration and self-curing properties, it has excellent water resistance and durability, so the composite material of the present invention is useful for applications such as kitchens, home appliances, bicycles, textiles, building materials, etc. It is. As described above, since the coating film obtained in the present invention has hydrophilicity and self-curing property due to the hydration reaction, a film having excellent durability and water resistance can be obtained.

[0036]

The present invention will be described in detail with reference to the following examples. Example 1 The following composition: tetraethoxysilane 50 g zirconium tetrabutoxide 10 g aluminum isopropoxide 5 g lithium nitrate 10 g ethyl alcohol 20 g nitric acid 5 g water 20 g of an inorganic component-water reaction product-based dispersion having polyacrylic acid (weight average molecular weight) : 150,000) and stirred well, and then the pH value was adjusted to 4 by dropwise addition of a 1% aqueous sodium hydroxide solution. This mixture was applied as a coating liquid on one surface of an acrylic resin plate to a thickness of 10 μm,
It was left at room temperature and room temperature for drying and curing to form a hydratable coating film.

[0037] In each of Comparative Examples 1 to 5 Comparative Examples 1 to 5, from a mixture of Example 1,
A coating solution was prepared in which the above-mentioned tetraethoxysilane component, zirconium tetrabutoxide component, aluminum isopropoxide component, lithium nitrate component, and polyacrylic acid component were each omitted, and a coating film was formed in the same manner as in the example. did. The coating was at least dry and thus appeared to be cured.

The hydrophilic, and the hydrophilic and durability of the resulting coating films in Examples and Comparative Examples of the water durability test described above were measured by the following methods. For the hydrophilicity, the contact angle of a water droplet on the coating film was measured. In addition, durability was measured at 95 ° C.
Was immersed in hot water for 24 hours, immersed in 1N sodium hydroxide solution for 24 hours, or left in the air for one month, and then evaluated by measuring the contact angle again. Table 1 shows the results.

[0039]

[Table 1]

As is clear from Table 1, the coating film of the present invention has excellent durability, and as is clear from Comparative Examples 1 to 5, all of the components (1) to (5) cannot be omitted. Things.

Example 2 and Comparative Examples 6 to 10 In Examples 2 and Comparative Examples 6 to 10, the same coating liquids as in Example 1 and Comparative Examples 1 to 5 were prepared. However, the pH value was not adjusted by dropwise addition of a sodium hydroxide solution, but was diluted 1000 times with distilled water. 270 of each of these liquids
Spraying at a coating amount of 100 ml / m ² onto a glass plate heated to 0 ° C. to instantaneously evaporate water and at the same time, components (1) to
The reaction mixture of (5) was cured to form respective coating films. The hydrophilicity and durability of each of these coating films were measured in the same manner as in Example 1 and Comparative Examples 1 to 5. Table 2 shows the results.

[0042]

[Table 2]

As is clear from Table 2, the coating film on the glass plate of Example 2 according to the present invention showed excellent hydrophilicity even after the endurance load.

Example 3, Comparative Examples 11 to 15 In Examples 3 and 11 to 15, the coating solutions prepared in Example 1 and Comparative Examples 1 to 5 were prepared. However, instead of adjusting the pH value by dropping sodium hydroxide solution, 0.5
% Calcium hydroxide solution was added dropwise to adjust the pH to 3.
This mixed solution was applied to a stainless steel plate so that the thickness of the coating film became 1 μm. Further, it was heated at 180 ° C. for 10 minutes. The same hydrophilicity as above for these coating films,
A durability test was performed. Table 3 shows the results.

[0045]

[Table 3]

As is apparent from Table 3, the coating film on the stainless steel plate of Example 3 according to the present invention exhibited excellent hydrophilicity even after the endurance load.

Example 4 In the same manner as in Example 1, a hydratable coating film of the present invention was formed on an acrylic resin plate. 1 g of salad oil was dropped on the acrylic resin plate on which the hydratable coating film was formed.
Was immersed in water and the time required for the oil to float was measured, and an easy-cleaning test was performed. Table 4 shows the results.

Comparative Example 16 The same acrylic resin plate as used in Example 1 was used without forming a hydratable coating film thereon, and the same easy-cleaning test as in Example 4 was performed. Table 4 shows the results.

Example 5 A hydratable coating film of the present invention was formed on a glass plate in the same manner as in Example 2, and the same easy-to-clean test as in Example 4 was conducted. Table 4 shows the results.

Comparative Example 17 The same glass plate as that used in Example 2 was used without forming a hydratable coating film, and the same easy-cleaning test as in Example 4 was performed. Table 4 shows the results.

Example 6 A hydratable coating film of the present invention was formed on a stainless steel plate in the same manner as in Example 3, and the same easy-cleaning test as in Example 4 was performed. Table 4 shows the results.

Comparative Example 18 The same easy-to-clean test as in Example 4 was performed using the same stainless steel plate as used in Example 3 without forming a hydratable coating film. Table 4 shows the results.

[0053]

[Table 4]

Example 7 A coating solution having the following composition was prepared. Tetraethoxysilane 1 g Zirconium tetrabutoxide 0.4 g Aluminum isopropoxide 0.1 g Lithium hydroxide 0.5 g Zinc nitrate 3 g Nitric acid 5 g Water 70 g Polyacrylic acid 20 g 2 Propanol 500 g The above coating solution is coated on a galvanized steel sheet by dipping. Applied. When this was allowed to stand at room temperature for 24 hours, it was confirmed that the formed coating film having a thickness of 0.5 μm was cured so that it could not be removed even if it was rubbed strongly. The coated product was subjected to the same test as in Example 1. For comparison, the same test was performed on the galvanized steel sheet. Table 5 shows the results.

[0055]

[Table 5]

[0056] In addition Example 8 Example 7 further iron nitrate 0.1g coating solution of the composition according to (III), to prepare a coating liquid of Example 8. This coating solution was applied to the surfaces of a tin plate and an alumite plate using a roll coater, heated at 150 ° C. for 10 seconds, and cured and dried to form a coating film having a thickness of 1.0 μm. The adhesion between the obtained coating film and each of the tin plate and the alumite plate was good. The coated product and the tin plate and the alumite plate were subjected to the same test as in Example 1. Table 6 shows the results.

[0057]

[Table 6]

[0058]

According to the present invention, the problem of the durability of the hydrophilic film, which has been known as a problem which has been difficult to solve, has been solved. The water-based coating film of the present invention has excellent water resistance and durability and excellent easy-cleaning properties even when solidified by either high-temperature treatment or low-temperature treatment, and has various material types, dimensions, and shapes. Can be applied to materials.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CG131 HA246 HA276 HA436 JA23 JC38 MA08 MA10 NA05 NA06 PC02 PC03 PC08

Claims (16)

[Claims] 1. A silicon-containing component consisting of (1) at least one kind selected from silicon alkoxides and water-soluble salts, and (2) a zirconium-containing part consisting of at least one kind selected from zirconium alkoxides and water-soluble salts. A component; (3) an aluminum-containing component comprising at least one selected from alkoxides and water-soluble salts of aluminum; (4) a lithium-containing component comprising at least one water-soluble salt of lithium; Acrylic acid, a reaction mixture obtained by mixing and reacting raw materials consisting of water in water, provided that
The silicon-containing component (1) and the zirconium-containing component (2)
A composition for forming a hydrophilic coating film, wherein at least one selected from alkoxides of silicon, alkoxides of zirconium, and alkoxides of aluminum is contained in the aluminum-containing component (3). 2. The content ratio of the silicon-containing component (1), the zirconium-containing component (2), the aluminum-containing component (3) and the lithium-containing component (4) contained in the raw materials is SiO ₂ , ZrO ₂ , Al ₂ O ₃ and Li
In terms of ₂ O absolute dry weight, 20~70 (SiO _2): 1
_{~50 (ZrO 2): 1~30 (} Al 2 O 3): 5~3
It is 0 (Li ₂ O), the hydrophilic coating forming composition of claim 1. 3. The compounding weights of the silicon-containing component (1), the zirconium-containing component (2), the aluminum-containing component (3), and the lithium-containing component (4) contained in the raw materials are SiO ₂ and ZrO ₂ , respectively. , Al ₂ O ₃ and Li
The ratio of the total weight in terms of the absolute dry weight of ₂ O to the blended dry weight of polyacrylic acid (5) is 100: 5 to 10
The composition for forming a hydrophilic coating film according to claim 1, wherein the composition is 0: 10,000. 4. The method according to claim 1, wherein the raw material is the silicon-containing component (1),
(6) In addition to the zirconium-containing component (2), the aluminum-containing component (3), the lithium-containing component (4), and the polyacrylic acid (5), (6) at least one water-soluble salt of a divalent metal 2. The composition according to claim 1, further comprising at least one member selected from a divalent metal-containing component consisting of: and (7) an iron-containing component consisting of at least one water-soluble salt of iron having a valence other than divalent. The composition for forming a hydrophilic coating film according to the above. 5. The divalent metal of the divalent metal-containing component (6) is an alkaline earth metal and Zn, Cu (II), F
e (II), Ni (II), and Mn (II),
The composition for forming a hydrophilic coating film according to claim 4. 6. The silicon-containing component (1) in the raw material
The divalent metal-containing component (6) and other than the divalent
Content ratio of the iron-containing component (7) having a valence of
Respectively, SiO_Two , MO (where M represents a divalent metal atom)
And Fe _Two O_Three Converted to the absolute dry weight of 20-70 (SiO_Two ): 0 to 1000 (MO): 0
10 (Fe_Two O_Three The composition for forming a hydrophilic coating film according to claim 4 or 5, wherein
object. 7. The silicon synthesis component (1), the zirconium-containing component (2), the aluminum-containing component (3), the lithium-containing component (4) and the divalent metal-containing component (6) in the raw material. The amount of the iron-containing component (7) having a valence other than divalent is defined as SiO ₂ , ZrO ₂ , and Al, respectively.
₂ O ₃ , Li ₂ O, MO (where M represents a divalent metal atom) and the total blended weight of Fe ₂ O ₃ in terms of absolute dry weight, and the dry weight of polyacrylic acid (5) Is the ratio
5. The composition of claim 4, wherein the ratio is from 100: 5 to 100: 100,000.
7. The composition for forming a hydrophilic coating film according to any one of items 6 to 6. 8. The hydrophilic coating film according to claim 1, wherein the amount of the polyacrylic acid in the raw material is 0.01 to 25% based on the weight of water. Forming composition. 9. An aqueous coating solution containing the composition for forming a hydrophilic coating film according to claim 1 is applied to at least one surface of a solid substrate, and the coating solution layer is solidified. And producing a hydrophilic coating film. 10. The method according to claim 9, wherein the substrate is selected from one or more selected from a metal material, a ceramic, a glass material, a ceramic material, and an organic polymer material. 11. An aqueous coating solution containing the composition for forming a hydrophilic coating film according to any one of claims 1 to 8 on a solid substrate and at least one surface thereof, and formed by solidification. And a hydrophilic material. 12. The composite material according to claim 11, wherein the solid substrate is selected from a metal material, a ceramic material, a glass material, a ceramic material, and an organic polymer material. 13. A reaction product of the components (1) to (5) of the raw material and water is formed in the hydrophilic coating film,
The weight ratio of silicon, zirconium, aluminum and lithium contained therein is SiO ₂ , ZrO ₂ and A, respectively.
When converted to absolute dry weight of l ₂ O ₃ and Li ₂ O, 20
_{~70 (SiO 2): 1~50 (} ZrO 2): 1~30
(Al ₂ O _3): a 5~30 (Li ₂ O), the composite material according to claim 11. 14. The raw material further includes components (6) and (7), and in the hydrophilic coating film, the raw materials include components (1) to (5), components (6) and (7), and water. The reaction product is formed, the weight ratio of silicon contained therein, divalent metal and iron having a valence other than divalent is
When converted to the absolute dry weight of SiO ₂ , MO (where M represents a divalent metal atom) and Fe ₂ O ₃ , respectively, 20
_{~70 (SiO 2): 1000 (} MO) the following: 10 (F
e ₂ O ₃₎ or less, the composite material according to claim 13. 15. Silicon and jill contained in the hydrophilic coating film
Conium, aluminum and lithium content
Re SiO_Two , ZrO_Two , Al_Two O_Three And Li _Two O dryness
Total weight when converted to weight and polyacrylic acid residue
Ratio to weight when converted to dry weight of polyacrylic acid
Is from 100: 5 to 100: 10,000.
12. The composite material according to 11. 16. The raw material comprises components (6) and (7).
Silicon, zirconium contained in the hydrophilic coating film
Aluminum, lithium, divalent metals and other than divalent
The content of iron having a valence of_Two , Z
rO_Two , Al _Two O_Three , Li_Two O, MO (where M is divalent
Represents a metal atom) and Fe_Two O_Three Converted to absolute dry weight
When the total weight and polyacrylic acid residue polyacrylic
The ratio to the weight when converted to the acid dry weight is 100: 5.
12. The method of claim 11, wherein the ratio is -100 to 100,000.
Composite materials.