JP2002348542A - Coated article, coating liquid composition, and method for producing the coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an article coated with an organic-inorganic composite film having such high performances as durable even when used in the outdoors and highly hard, to provide a method for producing the article coated with the organic-inorganic composite film, capable of producing the article in excellent productivity, and to provide a coating liquid composition for producing the article coated with the organic-inorganic composite film. SOLUTION: This coated article comprises a substrate and the organic -inorganic composite film which covers the surface of the substrate, has a cation atom oxide capable of forming an oxide network, and is formed by substituting organic groups for a part of oxygen atoms of the oxide, wherein the organic- inorganic composite film contains an alkali metal oxide in an amount of 0.1-30% expressed in the number of the alkali metal atoms based on the total number of the cation atoms and the alkali metal atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an article coated with an organic-inorganic composite film, a composition for coating an organic-inorganic composite film, and an article coated with an organic-inorganic composite film formed on the surface of a substrate such as glass, ceramics, plastic or metal. It relates to a manufacturing method.

[0002]

2. Description of the Related Art A technique for modifying the surface of a substrate by providing an organic-inorganic composite film having an inorganic oxide and an organic group on the surface of a glass plate or other substrates is known.

Japanese Patent Application Laid-Open No. 4-338137 discloses a solution prepared by mixing a silicon alkoxide, a substituted silicon alkoxide in which an alkoxyl group is partially substituted with a fluoroalkyl group, an alcohol, water, and an acid (or base). A glass coated with a water-repellent organic-inorganic composite film by applying it to the surface and firing it is disclosed.

JP-A-8-239653 discloses that a mixture of a perfluoroalkylalkylsilane and a completely hydrolyzable silane (for example, tetrachlorosilane) is treated with a composition obtained by dissolving the mixture in a solvent, preferably a non-aqueous solvent. An organic-inorganic composite film-coated article having improved water repellency is disclosed.

JP-A-11-71682 discloses an article coated with a water-repellent organic-inorganic composite film treated with a composition obtained by dissolving a chlorosilyl group-containing compound and a fluoroalkyl group-containing silane compound in an alcoholic solvent. It has been disclosed.

[0006]

The organic-inorganic composite film in these techniques is a so-called sol-gel method in which a solution containing a hydrolyzable silane compound and a silane compound having a water-repellent group is applied to a substrate and dried. It has been produced by. In the sol-gel method, since the evaporation of the solvent proceeds in parallel with the formation of the oxide bond, when dried at 400 ° C. or less, fine pores are present in the film, and the hardness of the film is not high.
In order to make this nonporous and increase the hardness of the film, 500
Although calcination at ６００600 ° C. is indispensable, at such a temperature, an organic group such as a water-repellent group that contributes to surface modification is decomposed. Therefore, in the above-mentioned technique, drying or curing of the film is performed at a temperature of 250 ° C. or lower, and the obtained organic-inorganic composite film is obtained, for example, by a melting method, although the oxide is a main component. It did not result in a film having high hardness like oxides and ceramics to be obtained.

[0007] Such an organic-inorganic composite film-coated article, when used outdoors, for example, is easily scratched on the film surface due to exposure to a situation where sand is sprayed, and thus has improved properties. Will be lost. Further, the film is also damaged and peeled off by wiping the surface with a cloth or the like to remove the adhered dust, mud or sand. Further, even when dust or the like is not attached, small scratches are formed due to friction with a cloth or a brush made of hard fiber (for example, wiping the surface of an automobile window glass with a wiper or the like), thereby promoting deterioration of characteristics. Will be.

The present invention has been made in view of the above problems, and has been coated with an organic-inorganic composite film having high hardness, water repellency and other functions that can withstand outdoor use. It is an object to provide an article, a method for producing the coated article with excellent productivity, and a coating liquid composition for producing the coated article.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the hardness of the organic-inorganic composite film was reduced as compared with the case where the organic-inorganic composite film contained alkali metal ions. I found that it rises dramatically.

That is, the present invention comprises a substrate and an oxide of a cation atom capable of forming an oxide network coated on the surface of the substrate, wherein a part of oxygen of the oxide is substituted by an organic group. In a coated article comprising an organic-inorganic composite film comprising
The coated article, wherein the organic-inorganic composite film contains an alkali metal oxide in the number of alkali metal atoms, which is 0.1 to 30% of the total number of the alkali metal atoms and the cation atoms. is there.

In general, when forming an oxide film by a sol-gel method, a metal alkoxide, for example, an alkoxide of silicon (Si) is often used as a starting material. In the sol-gel method, volatilization of the solvent proceeds in parallel with the formation of a bond (siloxane bond) between a metal such as silicon (Si) and oxygen (O) by a dehydration condensation reaction, so that fine pores are present in the film. It becomes a porous silica film. Since the bond between silicon and oxygen is covalent, and silicon and oxygen are bonded with a large bond energy, a certain degree of siloxane bond forms a three-dimensional structure during the evaporation of the solvent, followed by a dehydration condensation reaction. Even when the reaction proceeds, the shrinkage of the structure is suppressed, and the solvent, the alcohol generated by the hydrolysis reaction, and the portion where the water generated by the dehydration condensation reaction volatilizes remain as pores, and silanol groups, alkoxyl groups , Water or alcohol will be present. The hardness of this porous silica film is not so high because of its porosity. When this film is heated at a temperature of 500 ° C. or higher, the pores of the film disappear and a nonporous silica film having high hardness is obtained. However, since a water-repellent organic group such as a fluoroalkyl group is decomposed at this heating temperature, the heating temperature of the film is set to a temperature at which the water-repellent organic group is not decomposed (for example, 300
C.), the pores of the film hardly disappear and the hardness of the film does not increase.

In the present invention, an alkali metal oxide is introduced into the organic-inorganic composite film. Since the alkali metal has a strong ionic character, it is dissolved in a coating solution for film formation and coexists with a hydrolyzable metal compound such as silicon alkoxide (for example, a silane compound). And exists in an ion state. Since the alkali metal (M) ion is monovalent, it reacts with a metal hydroxyl group (for example, a silanol group),
When the metal is, for example, silicon (Si), the metal is finally combined with oxygen (O) as shown in the following formula (1) inside the film to form “Si
−O-Si ”
^-+ M "to form a bond. Therefore, the skeleton of the organic-inorganic composite film into which the alkali metal oxide is introduced is more easily deformed by heat than the skeleton of the film not containing the alkali metal oxide. As a result, according to the present invention, the skeleton is deformed by drying or heating at a temperature lower than the decomposition temperature (250 to 300 ° C.) of the organic group contained in the organic-inorganic composite film, and many pores disappear, so that the film is Is densified, and a film with extremely high hardness is obtained.

Embedded image ≡Si—O ^{− +} M (M is an alkali metal) (1)

The organic-inorganic composite film of the present invention may contain an alkaline earth metal oxide. Alkaline earth metals, like alkali metals, have a strong ionic character. By containing an alkaline earth metal oxide,
The wear resistance of the film can be further increased without impairing the low-temperature curing characteristics due to the introduction of the alkali metal. The organic-inorganic composite film of the present invention contains an organic group as described later, and the organic group is present at a higher density on the surface than inside the organic-inorganic composite film. By adding the alkaline earth metal oxide, the density of the organic group on the film surface can be further increased, and as a result, the function of the organic group can be further enhanced. For example, when the organic group is a water-repellent group, the contact angle of the film can be further increased by adding an alkaline earth metal oxide, and the rolling properties of water droplets can be further improved.

In the present invention, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr) are used as the alkali metal. so,
Li and Cs are preferably used because of their ready availability and high solubility in both water and alcohol. As the alkaline earth metal, calcium (Ca), magnesium (Mg), strontium (Sr), barium (Ba), radium (Ra) and beryllium (Be) are used.
Due to the availability, high solubility in both water and alcohol, and lack of toxicity, Ca
And Mg are preferably used.

If the content of the alkali metal oxide in the organic-inorganic composite film is too small, the effect of low-temperature curability cannot be obtained, and if it is too large, the film segregates and becomes inhomogeneous, and the hardness of the film becomes low. Since the content is reduced, this content is represented by the number of alkali metal atoms, the cation atoms constituting the oxide forming the network of the organic-inorganic composite film, the alkali metal atoms and the alkaline earth metal atoms described below. It is 0.1 to 30%, preferably 1 to 25% of the total number.

If the content of the alkaline earth metal oxide in the organic-inorganic composite film is too large, it segregates and becomes inhomogeneous and the hardness of the film decreases. Expressed in terms of the number of metal atoms, it is preferably 0 to 30% of the total number of cation atoms constituting the network-forming inorganic oxide of the organic-inorganic composite film, the total number of the alkali metal atoms and the alkaline earth metal atoms, It is more preferably 0.1 to 30%, and further preferably 1 to 25%. However, the total content of the alkali metal oxide and the alkaline earth metal oxide is represented by the total number of the alkali metal atom and the alkaline earth metal atom, and the cation atom, the alkali metal atom and the alkaline earth metal It is preferably 50% or less of the total number of atoms.

The organic-inorganic composite film of the present invention has an oxide of a cation atom capable of forming an oxide network. The cation atoms include silicon, titanium, zirconium, aluminum, germanium, tantalum, tin, antimony, cerium, lanthanum, tungsten, indium,
Boron and the like can be given. Among them, silicon is preferably used because agglomerates and crystals are relatively unlikely to be formed during film formation and a film without cracks is easily obtained.

The organic-inorganic composite film of the present invention has an oxide of a cation atom capable of forming an oxide network, and a part of oxygen of the oxide is substituted with an organic group. The organic group is not particularly limited, but is preferably a monovalent organic group, for example, an alkyl group such as a methyl group, an ethyl group, and an isopropyl group, a phenyl group, a vinyl group, an aminopropyl group, an acrylic group, and an epoxy group. Group, polyether group,
Further, there may be mentioned a fluoroalkyl group and a chloroalkyl group in which part or all of hydrogen of hydrocarbon is substituted with fluorine or chlorine. Among these, for example, an alkyl group and a fluoroalkyl group can impart water repellency to the film, a methyl group can impart low friction to the film, and an aminopropyl group and a polyether group can impart hydrophilicity to the surface. Can be given.

In the organic-inorganic composite film, these organic groups are
It exists in a form bonded to a cation atom (eg, silicon atom) of an inorganic oxide (eg, SiO ₂ ) forming the network. If the content of the organic group is too small, the film does not contribute to the modification of the substrate surface and does not perform a predetermined function, and if the content is too large, the strength of the film decreases. In the organic-inorganic composite film, the total number of the cation atoms of the inorganic oxide forming the network, the total number of the alkali metal atoms and the total number of the alkaline earth metal atoms is 0.001 or more and less than 2 times. Is preferred. More preferably, it is 0.01 to 1 times. The organic groups may be uniformly distributed in the thickness direction of the film, or may be a gradient composition film whose concentration changes from the interface side with the substrate toward the outer surface. For example, to have a water-repellent function,
It is more preferable that the number of alkyl groups and / or fluoroalkyl groups contained in the film be 50 to 100% of the total number of organic groups, resulting in a water-repellent film having high durability in combination with the film hardness.

As described above, according to the present invention, by containing an alkali metal ion, or an alkali metal ion and an alkaline earth metal ion, drying or heating at a temperature lower than the decomposition temperature of an organic group contributing to surface modification can be performed. A film having a high hardness that was not obtained before can be obtained, and as a result,
The durability performance of the organic-inorganic composite film has been dramatically improved.

Such low-temperature curability can be controlled, for example, by controlling the refractive index of the film in addition to the property of modification by an organic group.
Even if a transition metal ion or the like is further introduced into the film for the purpose of further adding a function of controlling the visible light transmittance, it is not hindered. That is, the coexistence of a metal ion exhibiting a desired function and an alkali metal oxide (or both of an alkali metal oxide and an alkaline earth metal oxide) enables drying or heating at a temperature of 300 ° C. or less, In addition, a composite functional film having high hardness and having both the property of modifying by an organic group and the function of a metal ion can be obtained. For example, a colored organic-inorganic composite film can be obtained by adding cobalt oxide, iron oxide, nickel oxide, and copper oxide.

Further, regarding organic molecules such as organic dyes,
Although it is possible to include the same in the composite film, it is preferable that the content of organic molecules other than the organic group is 5% by weight or less based on the weight of the film. This is because if added in excess of this, the low-temperature curability may be impaired.

If the thickness of the film is too large, the hardness of the film tends to decrease, and if it is too small, the effect of surface modification cannot be obtained. Therefore, the film thickness is preferably 5 to 200 n
m, more preferably 5 to 100 nm, even more preferably 5 to 50 nm.

The present invention also relates to (A) an organometallic compound having a non-hydrolyzable organic group, (B) an acid, and (C) an alkali metal compound, and if necessary, (D) complete condensation polymerization. A coating composition comprising a compound which is capable of being hydrolyzed and polycondensed, and (E) an alkaline earth metal compound.

In the component (A), the number of cation atoms excluding the organic group is the same as that of the components (A), (C) and (D).
It is preferred that the content is 0.1 to 99.8% with respect to the total number of cation atoms of the component and the component (E) (excluding the cation atoms in the organic group; the same applies to the following description). , 1.0 to 90%. The component (C) is such that the number of alkali metal atoms is equal to the total number of cation atoms excluding the organic groups of the components (A), (C), (D) and (E). It is preferably contained so as to be 0.1 to 30%, more preferably 1 to 25%. The component (D) is a component that further strengthens the bond between the film and the substrate. The component (D) is such that the number of cation atoms excluding the organic group is the same as the total number of the cation atoms excluding the organic group of the components (A), (C), (D) and (E). Thus, the content is preferably 0 to 99.7%, more preferably 1 to 88%. In the component (E), the number of alkali metal atoms is equal to the component (A), the component (C),
It is preferably contained in an amount of 0.1 to 30%, and more preferably 1 to 25%, based on the total number of cation atoms excluding the organic groups of the component (D) and the component (E). More preferably, it is performed.

Although the component (D) in the present invention is not an essential component, the component (D) can be dissolved in an alcohol which is a general solvent, and is a compound or a compound which can be completely hydrolyzed and polycondensed. Compounds capable of polycondensation can be widely used. The completely hydrolyzable and polycondensable compound is a compound in which a hydrolyzable group is bonded to a cation atom, and is a compound in which the number of hydrolyzable groups is equal to the valence of the cation atom. The compound capable of being completely polycondensed is a compound in which a hydroxyl group is bonded to a cation atom, and is a compound in which the number of hydroxyl groups is equal to the valence of the cation atom.
As the component (D), for example, a cation atom capable of forming an oxide network (silicon, titanium, zirconium, aluminum, germanium, tantalum, gallium, tin, antimony, cerium, lanthanum, tungsten, indium, scandium, yttrium, boron, etc. )) Alkoxides, hydroxides, chlorides, nitrates and the like. Titanium, zirconium, aluminum, and alkoxides such as boron, very high reactivity, if it is difficult to obtain a homogeneous solution by adding only this,
It may be added by chelating with a β-diketone such as acetylacetone. In the case of a compound that is insoluble in alcohol but soluble in water, water may be added as needed. More specifically, as the component (D),
Silicon tetraalkoxides such as tetramethoxysilane and tetraethoxysilane, titanium tetraalkoxides such as titanium tetraisopropoxide and titanium tetrabutoxide, zirconium tetraalkoxides such as zirconium tetraisopropoxide, zirconium tetraethoxide and zirconium tetrabutoxide, H ₃ BO ₃ , ZrOC
l ₂ , ZrO (NO ₃ ) ₂ , AlCl ₃ , GeCl ₄ , TaCl ₅ , GaCl ₃ , InC
_{l 3, ScCl 3, YCl 3} , LaCl 3, CeCl 3, Al (NO 3) 3, Ga (N
O ₃ ) ₃ , In (NO ₃ ) ₃ , SbCl ₃ , WCl ₆ , Sc (NO ₃ ) ₃ , Y (NO ₃ ) ₃ , La
Compounds such as (NO ₃ ) ₃ and Ce (NO ₃ ) ₃ have high solubility in water and alcohol and can be suitably used.

As the alkali metal compound as the component (C), for example, alkali metals (lithium, sodium, potassium,
Rubidium, cesium, and francium) chlorides, nitrates, and the like are used. More specifically, LiCl, NaCl, KC
Metal compounds such as l, RbCl, CsCl, and FrCl have high solubility in water and alcohol and can be suitably used.

The alkaline earth metal compound as the component (E) is not an essential component. However, as the component (E), for example, an alkaline earth metal (beryllium, magnesium, calcium, Strontium, barium, radium) chlorides, nitrates and the like are used. More specifically, BeCl ₂ , MgCl ₂ , Mg (N
O ₃ ) ₂ , CaCl ₂ , Ca (NO ₃ ) ₂ , SrCl ₂ , BaCl ₂ , RaCl ₂ , Ba (N
Metal compounds such as O ₃ ) ₂ have high solubility in water and alcohol and can be suitably used.

In the present invention, examples of the organometallic compound having a non-hydrolyzable organic group as the component (A) include metal compounds among the compounds described as the component (D), ie, silicon, titanium and zirconium. , Aluminum, germanium, tantalum, tin, antimony, cerium, lanthanum, tungsten and indium, a compound in which a part of the anion is substituted by a non-hydrolyzable organic group can be preferably used. All of these metals are cation atoms capable of forming an oxide network.
The non-hydrolyzable organic group is not particularly limited, but may be a methyl group, an ethyl group, an alkyl group such as an isopropyl group, a phenyl group, a vinyl group, an aminopropyl group, an acrylic group, an epoxy group, or Examples thereof include a fluoroalkyl group and a chloroalkyl group in which a part or all of hydrogen of a hydrocarbon is substituted. These organic groups remain in the organic-inorganic composite film, and impart functionalities such as water repellency, low friction, and hydrophilicity to the film. Such an organosilicon compound having a non-decomposable organic group can be particularly preferably used because it is obtained as a relatively stable compound.

For example, silane compounds having an alkyl group include CH ₃ (CH ₂ ) ₁₈ SiCl ₃ and CH ₃ (CH ₂ )
₁₆ SiCl ₃ , CH ₃ (CH ₂ ) ₂ SiCl ₃ , CH ₃ CH ₂ Si
Cl ₃ , (CH ₃ CH ₂ ) ₂ SiCl ₂ , (CH ₃ CH ₂ ) ₃ Si
Cl, CH ₃ SiCl ₃ , (CH ₃ ) ₂ SiCl ₂ , (CH ₃ )
Alkyl-containing chlorosilanes such as ₃ SiCl; CH ₃
(CH ₂ ) ₁₈ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₆ Si
(OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₈ Si (OCH ₃ ) ₃ , CH
₃ (CH ₂ ) ₇ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₂ Si (O
CH ₃ ) ₃ , CH ₃ CH ₂ Si (OCH ₃ ) ₃ , (CH ₃ C
H ₂ ) ₂ Si (OCH ₃ ) ₂ , (CH ₃ CH ₂ ) ₃ SiOCH ₃ ,
CH ₃ Si (OCH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ ,
(CH ₃ ) ₃ SiOCH ₃ , CH ₃ (CH ₂ ) ₁₈ Si (OC ₂ H
₅ ) ₃ , CH ₃ (CH ₂ ) ₁₆ Si (OC ₂ H ₅ ) ₃ , CH ₃ (C
H ₂ ) ₈ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₇ Si (OC _{2
H 5) 3, CH 3 (} CH 2) 2 Si (OC 2 H 5) 3, CH 3 CH
₂ Si (OC ₂ H ₅ ) ₃ , (CH ₃ CH ₂ ) ₂ Si (OC
_{2 H 5) 2, (CH} 3 CH 2) 3 SiOC 2 H 5, CH 3 Si (O
_{C 2 H 5) 3, (} CH 3) 2 Si (OC 2 H 5) 2, (CH 3) 3
Alkoxy silanes containing alkyl groups such as SiOC ₂ H ₅ , CH ₃ O (Si (CH ₃ ) ₂ O) _n CH ₃ , where n
Is a methoxyl polydimethylsiloxane having a terminal such as 2-2000), HO (Si (CH ₃ ) ₂ O) _n H, and a silanol polydimethylsiloxane having a terminal such as n (where n is 2 to 2000).

Examples of the silane compound having a fluoroalkyl group include CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ SiC
l ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (C
F ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₃ (CH ₂ )
₂ SiCl ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ SiCl ₃ , CF
Fluoroalkyl group-containing trichlorosilane such as ₃ (CH ₂ ) ₂ SiCl ₃ ; CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (O
CH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC
_{H 3) 3, CF 3 (} CF 2) 5 (CH 2) 2 Si (OCH 3) 3,
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ C
F ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si
And a fluoroalkyl group-containing trialkoxysilane such as (OCH ₃ ) ₃ .

By using these fluoroalkyl group-containing silane compounds, a water repellent function can be imparted to the substrate surface, but trichlorosilane containing a fluoroalkyl group having 10 or more fluorine atoms, By using trialkoxysilane or the like, a film having both excellent water repellency and durability can be obtained.
In particular, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (heptadecafluorodecyltrimethoxysilane) and
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ (Heptadecafluorodecyltrichlorosilane) Can be preferably used.

The acid which is the component (B) in the coating composition of the present invention is not particularly limited, but the one which evaporates during drying and is less likely to remain on the film, the higher the hardness of the film. It is preferable because it is possible. For example, hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid, formic acid, trifluoroacetic acid and the like can be mentioned.
Among them, hydrochloric acid, which has a high degree of ionization and volatility and is relatively safe in handling, is particularly preferred. It is preferable that the component (B) is contained in an amount of 0.001 to 3N.

As the solvent in the present invention, a solvent having a boiling point at atmospheric pressure of 150 ° C. or less can be used widely. For example, hydrocarbons such as hexane, toluene, and cyclohexane, halogenated hydrocarbons such as methyl chloride, carbon tetrachloride, and trichloroethylene; ketones such as acetone and methyl ethyl ketone; nitrogen-containing compounds such as diethylamine; and ethyl acetate. Esters and alcohols can be used. Among them, alcohol solvents are preferably used and include, for example, methanol, ethanol, 1-propanol, 2-propanol, butyl alcohol, amyl alcohol and the like. Among them, methanol, ethanol, 1- Chain-type saturated monohydric alcohols having 3 or less carbon atoms, such as propanol and 2-propanol, are more preferably used because of their high evaporation rate at room temperature.

The alcohol may contain water of 0% by weight or more and 50% by weight or less. Commercially available special grade alcohols usually contain 0.2% by weight or more of water, but in the present invention, they can be preferably used without dewatering or other treatments leading to increased costs.
When the metal raw material is added, the metal compound may be dissolved in water and added in advance, or another solvent may be added to control the drying speed or the viscosity of the liquid.
Also in that case, the amount of the above-mentioned chain-type saturated monohydric alcohol having 3 or less carbon atoms is preferably 10% by weight or more based on the amount of the solvent. If the amount is less than this, a homogeneous and transparent film may not be obtained.

In the coating composition (coating solution) containing the components (A) to (E), the components (A) and (D) are mixed with the catalyst (B) and a small amount of water in the solvent. , A hydrolysis reaction and a dehydration condensation reaction proceed.
When a large amount of water is present in the coating liquid, the hydrolysis reaction and dehydration condensation reaction of the components (A) and (D) are accelerated, the pot life of the coating liquid is shortened, and drying after coating the coating liquid is performed. In this case, unevenness of the film thickness tends to occur. Therefore, in order to prolong the pot life of the solution and eliminate unevenness in film thickness upon drying after coating, it is preferable that the concentration of water in the coating solution be as low as possible. 0.2% by weight for commercial alcohols
Since the above water is contained, in the present invention, this water alone is sufficient. However, when water is separately added, the concentration of water in the coating liquid is 0 to 5% by weight. Is more preferable, and more preferably 0 to 2% by weight. Even when the concentration of water in the coating liquid is zero, the hydrolysis reaction is not hindered because the water in the air is absorbed by the coating film after being applied to the substrate.

The coating method in the present invention is not particularly limited, and examples thereof include dip coating, flow coating, curtain coating, spin coating, spray coating, bar coating, roll coating, and brush coating.

The coating in the present invention is carried out in an atmosphere having a relative humidity of 40% or less at 0 to 40 ° C., for example, at room temperature. Drying after application is performed in an atmosphere having a relative humidity of 40% or less at 0 to 40 ° C., for example, at room temperature for 10 seconds to 20 minutes. Then, if necessary, at a temperature higher than room temperature and equal to or lower than 300 ° C. for 30 seconds to
You may heat for 10 minutes. Therefore, a high-hardness film having functionality unique to the organic group can be obtained without decomposition of the organic group constituting the film. When the functional organic group is a water-repellent group, when heated to a temperature higher than room temperature and 300 ° C. or less after the above-mentioned coating, the resulting film tends to have reduced water droplet rolling properties and ultraviolet light resistance. Is preferably dried.

As the substrate in the present invention, a transparent or opaque plate-like body, a rod-like body, and other various shapes such as glass, ceramics, plastic, and metal can be used. When the surface of the substrate has few hydrophilic groups, the surface is preliminarily treated with an oxygen-containing plasma or corona atmosphere to make the surface hydrophilic, or the substrate surface is near 200 to 300 nm in an oxygen-containing atmosphere. It is preferable to perform a surface treatment after irradiating an ultraviolet ray having the following wavelength to perform the hydrophilic treatment.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below with reference to examples. Example 1 Heptadecafluorodecyltrimethoxysilane (CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(Shin-Etsu Silicone, hereinafter sometimes referred to as "FAS")
0.2 g of tetraethoxysilane (Si (OCH ₂ C
H _{3) 4,} manufactured by Shin-Etsu Silicone, hereinafter sometimes referred to as "TEOS") 0.6 g, lithium chloride 0.00947g and concentrated hydrochloric acid (35 wt%) 2 g of ethanol (water content 0.35 wt%) 999. It was added to 19 g with stirring to hydrolyze FAS and TEOS to obtain a coating solution. F which is a metal compound in the coating liquid
Table 1 shows the mole fractions of the contents of AS, TEOS and lithium chloride, with the total amount of them as 100 mol%. This coating solution was washed with a glass substrate (3.4 mm × 150 × 150) of a soda-lime silicate glass composition.
mm) at a relative humidity of 30% and a room temperature (20 ° C.) by a flow coating method.
(0 ° C.) for about 1 minute to obtain an organic-inorganic composite film-coated glass plate coated with a water-repellent film having a thickness of about 40 nm. The molar fraction of alkali metal atoms to the total of cation atoms (silicon) and alkali metal atoms (lithium) constituting the inorganic oxide of the obtained organic-inorganic composite film was as shown in Table 1.

With respect to the obtained glass plate coated with an organic-inorganic composite film having a water-repellent function, the contact angle of water was measured with a contact angle meter (CA-
DT, manufactured by Kyowa Interface Science Co., Ltd.), and measured as a static contact angle with a water droplet having a weight of 2 mg. The larger the value of the contact angle, the better the static water repellency. As a measure of the ability of water droplets to roll on the surface of a coated glass plate having water repellency (rolling property of water droplets), a 50 μl water droplet was placed on the surface of a horizontally disposed coated glass plate, and the glass plate was gradually inclined. Then, the inclination angle (critical inclination angle) of the glass plate when the water droplet placed on the surface started rolling was measured. The smaller the critical inclination angle is, the more excellent the dynamic water repellent performance is, for example, it indicates that raindrops attached to the windshield window of a running automobile are easily scattered and the driver's view is not obstructed. .

Further, the hardness of the film was evaluated by applying a commercial Taber abrasion test to a glass plate coated with an organic-inorganic composite film 100 times under a load of 250 g for 100 times.
This was done by measuring the static contact angle with a water drop weighing mg.

Table 2 shows the contact angles of the organic-inorganic composite film having a water-repellent function and the contact angles before and after the Taber abrasion test. The obtained film had a large contact angle of 108 degrees before the Taber test, a contact angle of 90 degrees after the Taber test, a small decrease in the contact angle before and after the Taber test, and a very high film hardness. Was. The rolling property of the water droplet was 8 degrees in terms of a critical inclination angle.

Examples 2 to 10 The water-repellent function was carried out in the same manner as in Example 1 except that the raw materials of the metal compounds and the component ratios in the coating liquid of Example 1 were changed as shown in Table 1. Was obtained. The thickness of the organic-inorganic composite film was in the range of 5 to 50 nm in all of Examples 2 to 10. The composition of the cations of the obtained film, that is, the moles of alkali metal atoms or alkaline earth metal atoms with respect to the total of the cation atoms, alkali metal atoms and alkaline earth metal atoms constituting the inorganic oxide network of the organic-inorganic composite film. The fractions were as shown in Table 1. Table 2 shows the measurement results in the same manner as in Example 1.

Each of the obtained films was a film having a large contact angle before the Taber test, a small decrease in the contact angle after the Taber test, and a high hardness. A comparison between Example 3 containing no alkaline earth metal oxide and Example 4 in which part of the alkali metal oxide of Example 3 was replaced with an alkaline earth metal oxide showed a comparison with Example 3. It can be seen that Example 4 is more excellent in abrasion resistance and rolling properties of water droplets.

[Comparative Examples 1 to 5] The water-repellent function was carried out in the same manner as in Example 1 except that the raw materials of the metal compound and the amount of addition thereof in the coating liquid of Example 1 were changed as shown in Table 1. Was obtained.
The composition of the cations in the obtained membrane was as shown in Table 1. Table 2 shows the measurement results in the same manner as in Example 1.

Although the obtained film had a large contact angle before the Taber test, the contact angle after the Taber test was greatly reduced, the water repellency was almost lost, and the film hardness was very low.

Example 11 In the coating solution of Example 1, the metal compound having a non-reactive organic group was silanol-terminated polydimethylsiloxane (manufactured by Gelest,
An organic-inorganic composite film-coated glass having a low friction function was obtained in the same manner as in Example 1 except that the raw material of the metal compound and the amount of addition thereof were changed as shown in Table 1 using an average molecular weight of 4200). Was. However, the component ratio and each mole fraction are based on the terminal silanol polydimethylsiloxane (average molecular weight of 42
00) is represented by the number of moles converted to SiO ₂ . The composition of the cations in the obtained membrane was as shown in Table 1.

Further, a surface measuring device “HEID” manufactured by Shinto Scientific Co., Ltd.
Using "ON-14", the coefficient of kinetic friction between the paper and the film surface was measured, and it was found that a very low frictional resistance surface having a friction coefficient of 0.1 or less was obtained. The resulting membrane is
As shown in Table 2, the contact angle before the Taber test was large, the decrease in the contact angle after the Taber test was small, and the film was high in hardness. When the coefficient of friction was measured after the Taber test, the coefficient of friction was a very small value of 0.1 or less as in the case of the Taber test.

Comparative Example 6 The procedure of Example 9 was repeated except that the amounts of LiCl and MgCl ₂ .6H ₂ O used in the coating solution of Example 9 were both zero and DMS and TEOS were changed as shown in Table 1. In the same manner as in Example 9, an organic-inorganic composite film-coated glass having a low friction function was obtained. Although the obtained film has a large contact angle before the Taber test, the decrease in the contact angle after the Taber test is large, and almost no water repellency is lost.
The film hardness was very low.

Also, the kinetic friction coefficient between the paper and the film surface was measured before and after the Taber test in the same manner as in Example 9, and the friction coefficient before the Taber test was 0.1 or less. Although obtained, the coefficient of friction after the Taber test increased to 0.5.

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[Table 1] 原料 Metal compound raw materials Component ratio Alkali metal alkaline earth metal (Molar ratio) Species content Species content (mol%) (mol%) ──────────────────────────────── ─── Example 1 FAS / TEOS / LiCl 10/83/7 Li 7-0 2 FAS / TEOS / CsCl 5/87/8 Cs 8-0 3 FAS / TEOS / LiCl 10/80/10 Li 10-0 4 FAS / TEOS / LiCl / MgCl ₂・ 6H ₂ O 10/80/7/3 Li 7 Mg 3 5 FAS / LiCl / CaCl ₂・ 2H ₂ O 98/1/1 Li 1 Ca 16 FAS / CsCl / MgCl _{2 · 6H 2 O 50/25/25 Cs 25} Mg 25 7 FAS / TEOS / CsCl / CaCl 2 · 6H 2 O 10/88/1/1 Cs 1 Ca 1 8 FAS / ZrOCl 2 · 8H 2 O / KCl 10 / 80/10 K 10-0 9 FAS / H ₃ BO ₃ / NaCl / CaCl ₂・ 2H ₂ O 50/40/5/5 Na 5 Ca 5 10 FAS / LiCl 95/5 Li 5-0 11 DMS / TEOS / LiCl / MgCl ₂・ 6H ₂ O 1/89/7/3 Li 7 Mg 3 Comparative example 1 FAS 100-0-0 2 FAS / TEOS 10/90-0-0 3 FAS / TEOS / LiCl 10/50 / 40 Li 40 - 0 4 FAS / TEOS / CsCl / MgCl 2 · 6 H ₂ O 5/15/40/40 Cs 40 Mg 405 FAS / TEOS / CaCl ₂・ 6H ₂ O 10/80/10-0 Ca 106 DMS / TEOS 1/99-0-0 ───── ─────────────────────────────── * FAS: F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , TEOS: Si (OC ₂ H ₅ ) ₄ , DMS: Silanol-terminated polydimethylsiloxane (average molecular weight 4,200)

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[Table 2] 接触 Contact angle before wear test (degree) Wear test Post contact angle (degree) Critical tilt angle (degree) ──────────────────────────────────── Example 1 108 90 8 Example 2 108 95 7 Example 3 108 85 6 Example 4 108 89 4 Example 5 108 91 6 Example 6 108 96 6 Example 7 108 985 Example 8 108 92 8 Example 9 108 90 8 Example 10 107 88 9 Example 11 100 88 4 Comparative Example 1 108 60 10 Comparative Example 2 108 73 9 Comparative Example 3 108 75 10 Comparative Example 4 108 78 12 Comparative Example 5 108 76 13 Comparative Example 6 100 78 10 ──────────────────────────── ─────

[0054]

According to the present invention as described above,
By adding an alkali metal ion to the organic-inorganic composite film, an organic-inorganic composite film having significantly improved hardness can be obtained. Further, by containing an alkaline earth metal ion together with an alkali metal ion, the hardness of the film can be further increased and the functionality of the organic group can be further increased.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4D075 BB24Z BB56Z BB93Z BB99Z CA36 DB01 DB13 DB14 DB31 EA07 EB16 EB42 EC02 EC30 4J038 AA011 AA012 DF022 DL031 DL032 DM021 DM022 GA02 GA09 GA12 GA16 HA156 HA176 HA186 HA06 HA11 NA07 NA11 PA18 PA19

Claims (17)

[Claims] 1. A substrate and a surface of the substrate coated on the substrate.
A coated article comprising an organic-inorganic composite film having an oxide of a cation atom capable of forming an oxide network and substituting a part of oxygen of the oxide with an organic group, wherein the organic-inorganic composite film is an alkali metal oxide. A coated article characterized in that the product contains 0.1 to 30% of the total number of the alkali metal atoms and the cation atoms, expressed in terms of the number of alkali metal atoms. 2. The organic-inorganic composite film further expresses an alkaline earth metal oxide by the number of alkaline earth metal atoms,
The coated article according to claim 1, wherein the coated article contains 0.1 to 30% of the total number of the alkali metal atom, the alkaline earth metal atom and the cation atom. 3. The organic-inorganic composite film, wherein the organic group is
In terms of the number, the total number of the alkali metal atoms, the alkaline earth metal atoms, and the cation atoms is 0.
The coated article according to claim 1, which contains 001 times or more and less than 2 times. 4. A method according to claim 1, wherein 50 to 100% of the total number of the organic groups is
The coated article according to any one of claims 1 to 3, which is an alkyl group and / or a fluoroalkyl group. 5. The coated article according to claim 1, wherein the oxide of a cation atom capable of forming the oxide network is a silicon oxide. 6. An organic metal compound (A) having a non-hydrolyzable organic group and capable of hydrolysis and polycondensation, (B) an acid, and (C) an alkali metal compound, and if necessary, (D) A) a coating composition comprising a compound capable of being completely polycondensed or capable of being hydrolyzed and polycondensed, and (E) an alkaline earth metal compound. 7. The number of alkali metal atoms of the component (C) is equal to the total number of cation atoms excluding the organic groups of the components (A), (C), (D) and (E). The coating composition according to claim 6, which is contained in an amount of 0.1 to 30%. 8. The number of cation atoms excluding the organic group of the component (D) is less than the number of cation atoms excluding the organic group of the components (A), (C), (D) and (E). The coating composition according to claim 6, which is contained in an amount of 0 to 99.8% based on the total amount of the components. 9. The number of the alkaline earth metal atoms of the component (E) is less than the number of cation atoms excluding the organic groups of the components (A), (C), (D) and (E). The coating composition according to claim 6, which is contained in an amount of 0.1 to 30% based on the total. 10. The component (A), the component (C), and the component (D).
The number of cation atoms excluding the organic group of the component (A) is 0.1 to 99.8% relative to the total number of cation atoms excluding the organic group of the component and the component (E), and the component (C) Is 0.1 to 30%, and the number of cation atoms excluding the organic group of the component (D) is 0 to 99.7.
%, And the number of alkaline earth metal atoms in the component (E) is 0.1 to 30%, respectively. Further, the component (B) is 0.001 to 3N, and water is 0 to 5% by weight. ,
The coating composition according to claim 6, which contains each. 11. The coating composition according to claim 6, wherein the coating composition contains a solvent having a boiling point at atmospheric pressure of 150 ° C. or lower. 12. The coating composition according to claim 11, wherein the solvent is an alcohol. 13. The coating composition according to claim 6, wherein the component (A) is a trialkoxysilane containing a fluoroalkyl group. 14. A method for producing a coated article, comprising applying the coating composition according to any one of claims 6 to 13 to a substrate surface and drying. 15. The method according to claim 14, wherein the drying is performed at room temperature.
A method for producing the coated article according to the above. 16. The method according to claim 14, wherein the drying is performed in an atmosphere having a relative humidity of 40% or less. 17. The method for producing a coated article according to claim 14, wherein heating after the drying is performed at a temperature higher than room temperature and equal to or lower than 300 ° C.