JP2002206059A - Organic-inorganic composite gradient material and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organic-inorganic composite gradient material having a component gradient structure in which the content of a metal component is continuously changed in the thickness direction of the material and capable of well suppressing deterioration with oxygen, light, heat, photocatalyst oxidation, etc. SOLUTION: This organic-inorganic composite gradient material includes a composite in which an organic polymer is chemically bound to a metal oxide compound and has a gradient structure in which the content of the metal component is continuously changed from the surface of the material in the depth direction and the content of a stabilizer for the polymer is substantially zero in the surface layer of the material and is continuously increasing in the depth direction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organic-inorganic composite gradient material and its use. More specifically, the present invention has a component gradient structure in which the content of the metal component changes continuously in the thickness direction of the material, and the content of the polymer stabilizer contained therein is substantially zero in the surface layer. It has a slope structure that continuously increases in the depth direction, and oxygen,
Light, heat, organic-inorganic composite gradient material useful for various applications as a functional material, capable of favorably suppressing deterioration due to photocatalytic oxidation and the like, a coating agent for forming a film comprising the gradient material, particularly an organic base material The present invention relates to a coating agent used for an intermediate film interposed between a photocatalytic active material layer and a structure having a coating made of the gradient material on the surface.

[0002]

2. Description of the Related Art In recent years, with the diversification of requirements concerning the performance and functions of organic polymer materials, it has become difficult to satisfy with a single polymer compound, and different materials having different properties are added to the polymer compound. Compounding is being done.
For example, physical property modification by dispersing a reinforcing material in an organic polymer material is widely performed, and specifically, an organic or inorganic material such as carbon fiber, glass fiber, metal fiber, ceramic fiber, and aramid fiber. A fibrous substance or a powdered inorganic filler such as calcium carbonate, silica, alumina or the like is added and uniformly dispersed.

[0003] In addition, studies are being actively conducted to develop new functions by mixing different types of polymer compounds, compatibilizing them via a compatibilizer in some cases, and forming a polymer alloy. On the other hand, recently, a functionally graded material, which is a composite material whose properties are completely different between the front and the back, has been attracting attention by gradually changing the composition of the material.For example, a metal-ceramic composite gradient function that has both the heat resistance of ceramics and the strength of metal Materials have been developed as airframe materials for supersonic aircraft.

[0004] Such functionally graded materials are classified into inorganic graded materials, organic graded materials and organic-inorganic composite graded materials, and a plurality of materials, for example, a plurality of different kinds of inorganic materials, a plurality of different kinds of organic materials. By mixing each other or one or more organic materials and one or more inorganic materials, and controlling the distribution density, orientation, etc., depending on the location, the physical properties of a plurality of component materials can be expressed.
It is expected to be used in the aviation, automotive, electronics, medical, energy, and radiation and electromagnetic shielding fields.

[0005] The present inventors have previously proposed various uses as a novel functional material, for example, a coating film, an adhesive between an organic material and an inorganic or metal material, and a coating material between an organic substrate and a photocatalytic coating film. The composition is continuous in the thickness direction, which is useful for applications such as an intermediate film that prevents deterioration of the organic base material and an intermediate film that improves the adhesion between the organic base material and the inorganic or metal material layer. -Graded organic-inorganic composite gradient material (Japanese Patent Application No.
-264592).

This organic-inorganic composite gradient material is an organic-inorganic composite material containing a chemical bond of an organic polymer compound and a metal compound, and the content of the metal compound is increased in the thickness direction of the material. It has a component gradient structure that changes continuously,
It is a novel material that is extremely useful for the various applications described above.

By the way, it is known that an organic polymer compound is deteriorated by oxygen, ozone, light (such as ultraviolet rays) and the like.
For example, antioxidants, antiozonants, ultraviolet absorbers,
Various polymer stabilizers such as a light stabilizer and a metal deactivator are added. In order for such a stabilizer to function effectively, it is necessary that the stabilizer is homogeneously distributed with respect to the organic polymer compound.

However, when these polymer stabilizers are simply added to the organic-inorganic composite gradient material,
When a coating film is formed on an organic substrate using this material, the surface layer portion of the coating film is substantially free of the organic polymer compound component (substantially only a metal component) and comes into contact with the organic substrate. Although the portion which is substantially composed of only the organic polymer compound component (substantially the metal component becomes 0), the polymer stabilizer is substantially uniformly distributed in the coating film. Therefore, in the depth direction of the coating film, the ratio of the polymer stabilizer to the organic polymer compound component changes, and in the surface layer portion, the ratio becomes extremely large, but in the portion in contact with the organic base material. The above ratio becomes smaller. As a result, there arises a problem that the function as a stabilizer is not effectively exhibited.

When the organic-inorganic composite gradient material is used for an intermediate film interposed between an organic base material and a photocatalytic active material layer, the photocatalytic active material layer is irradiated with light such as ultraviolet rays. As the organic-inorganic composite gradient material, a material having particularly excellent weather resistance is required.

As described above, when an organic-inorganic composite gradient material simply added with a polymer stabilizer is used as an intermediate film of a photocatalytically active material, a high surface layer portion of the intermediate film in contact with the photocatalytically active material layer is formed. Due to the presence of the molecular stabilizer, it is easily oxidatively degraded by the oxidizing action of the photocatalytically active material, and there is also a problem that the effectiveness of the stabilizer is inevitably lost.

[0011]

SUMMARY OF THE INVENTION Under such circumstances, the present invention has a component gradient structure in which the content of a metal component changes continuously in the thickness direction of a material, and oxygen,
An object of the present invention is to provide an organic-inorganic composite gradient material which can favorably suppress deterioration due to light, heat, photocatalytic oxidation and the like and is useful for various uses as a functional material, and its use.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, they have found that a polymer stabilizer is contained and its content is substantially zero in the surface layer of the material.
However, they have found that a composite gradient material having a gradient structure that continuously increases in the depth direction can be adapted to the purpose, and based on this finding, completed the present invention.

That is, the present invention provides (1) a composite in which an organic polymer compound and a metal oxide compound are chemically bonded, and the content of the metal component is continuous from the surface of the material in the depth direction. An organic-inorganic composite gradient material having a component gradient structure that gradually changes, including a polymer stabilizer,
The content of the polymer stabilizer is substantially 0 in the surface layer of the material.
An organic-inorganic composite gradient material having a gradient structure that continuously increases in the depth direction, (2)
A coating agent characterized in that a coating composed of the organic-inorganic composite gradient material is formed on a substrate; and (3) a structure having a coating composed of the organic-inorganic composite gradient material. To provide.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The organic-inorganic composite gradient material of the present invention is an organic-inorganic composite material including a composite obtained by chemically bonding an organic polymer compound and a metal oxide compound, preferably the composite , Having a component gradient structure in which the content of a metal component in the material continuously changes in the depth direction from the material surface. The content of the polymer stabilizer contained in the material is substantially zero in the surface layer of the material, and has a tilted structure that continuously increases in the depth direction.

[0015] Such a composition gradient structure is confirmed, for example, by sputtering the surface of a coating film of an organic-inorganic composite gradient material provided on a substrate made of an organic material, and shaving the film. It can be carried out by measuring the content of carbon atoms and metal atoms on the surface and the specific atoms in the polymer stabilizer component by X-ray photoelectron spectroscopy or the like.
Specifically, FIG. 1A shows an organic-inorganic composite material (as a metal atom, having a thickness of 70 nm) provided on a polycarbonate plate in Example 1 described later.
FIG. 1 (b) is a graph showing the relationship between the sputtering time and the contents of carbon atoms, silicon atoms, and nitrogen atoms in the ultraviolet absorber component in a coating film comprising silicon atoms and titanium atoms). FIG. 2 is an enlarged graph showing the relationship between the sputtering time and the nitrogen atom content in FIG. 1A. As can be seen from this figure, the surface of the coating film before sputtering is almost 100% with titania and silica. However, as the film is eroded by sputtering, the content of titanium atoms and silica atoms continuously decreases, and the content of carbon atoms increases. Appears, and from the point when the sputtering time exceeds 35 minutes, the film surface contains almost only organic components. On the other hand, the surface of the coating film before sputtering is substantially free of nitrogen atoms, but the content of nitrogen atoms continuously increases as the film is scraped by sputtering.

That is, in this graded material, the content of the metal component composed of two substantially homogeneous mixed metal oxide compounds in the material is gradually reduced from the surface toward the substrate, and the ultraviolet absorption It is shown that the content of the agent component is almost 0 on the surface, and gradually increases from the surface toward the substrate. In the case where the polymer stabilizer component does not have a specific atom (atom other than the atoms contained in other components), the film is cut by sputtering,
The content of the polymer stabilizer component itself on the membrane surface over time may be measured by other analytical means.

The content of the metal component in such a gradient material is not particularly limited, but is usually 5 to 98% by weight, preferably 20 to 98% by weight, and particularly preferably 50 to 90% by weight in terms of metal oxide. % By weight. The degree of polymerization and the molecular weight of the organic polymer compound are not particularly limited as long as they can form a film, and may be appropriately selected according to the type of the polymer compound, desired coating film properties, and the like.
The content of the polymer stabilizer component is not particularly limited, but is usually 0.01 to 50 mol%, and preferably 0.1 to 50 mol%.
-30 mol%, particularly preferably 1-20 mol%. The polymer stabilizer is not particularly limited, but preferably includes, for example, an antioxidant, an ultraviolet absorber, a light stabilizer and the like, and these may be contained alone or in combination of two or more. They may be included in combination.

The kind of the metal component in the composite gradient material of the present invention is not particularly limited. For example, a metal oxide compound containing a metal atom selected from a silicon atom, a titanium atom, a zirconium atom and an aluminum atom is preferable. . The metal oxide-based compound may be contained alone or as a mixture of two or more kinds, and may be contained in the form of a composite metal oxide having two or more kinds of metal atoms. You may.

In the gradient material of the present invention, it is preferable that the stabilizer for polymer is chemically bonded to an organic polymer compound in the material so that the stabilizer itself has a gradient structure. Further, the gradient material of the present invention has a thickness of 0.0
1-5 μm, especially 0.01-. Those having a range of 1.0 μm are preferred from the viewpoints of gradient and coating film performance. An organic-inorganic composite gradient material in which a polymer stabilizer component is chemically bonded to an organic polymer compound in such a composite gradient material can be efficiently produced by the following method.

First, (A) and (a) an ethylenically unsaturated unit having a metal-containing group capable of bonding to a metal oxide by hydrolysis (hereinafter sometimes referred to as a hydrolyzable metal-containing group) in a molecule. Polymer, (b) a metal-free ethylenically unsaturated monomer, and (c) a polymerizable polymer having an ethylenically unsaturated group, a polymerizable stabilizer component comprising A coating liquid containing an organic polymer compound having a bonded hydrolyzable metal-containing group and (B) one obtained by hydrolyzing one or more metal-containing compounds capable of forming a metal oxide by hydrolysis. After preparation, a coating film composed of the coating liquid is formed on an organic substrate, and then subjected to a heat-drying treatment, whereby the organic-inorganic composite gradient material of the present invention is obtained.

The ethylenically unsaturated monomer having a hydrolyzable metal-containing group (A) or (a) is a compound represented by the following general formula (II):

[0022]

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(Wherein R ³ is a hydrogen atom or a methyl group;
A is an alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, and R ⁴ is a hydrolyzable group or a non-hydrolyzable group, at least one of which is hydrolyzed by (B)
It must be a hydrolyzable group capable of components chemically bonded, and when R ⁴ is plural, each R ⁴ may be the mutually the same or different, M ² is silicon, titanium, zirconium, a metal atom such as aluminum, k is the valence of the metal atom M ^2. )).

In the general formula (II), examples of the hydrolyzable group of R ⁴ which can be chemically bonded to the component (B) by hydrolysis include, for example, a halogen atom such as an alkoxyl group, an isocyanate group, a chlorine atom, an oxy group. Halogen group,
An acetylacetonate group, a hydroxyl group and the like are mentioned. On the other hand, as the non-hydrolyzable group which does not chemically bond to the component (B), for example, a lower alkyl group is preferably mentioned.

Examples of the metal-containing group represented by -M ² R ⁴ _k-1 in the general formula (II) include, for example, trimethoxysilyl, triethoxysilyl, tri-n-propoxysilyl, triisopropoxy Silyl group, tri-n-butoxysilyl group, triisobutoxysilyl group, tri-se
c-butoxysilyl group, tri-tert-butoxysilyl group, trichlorosilyl group, dimethylmethoxysilyl group,
Methyldimethoxysilyl group, dimethylchlorosilyl group,
Methyldichlorosilyl group, triisocyanatosilyl group,
Such as methyldiisocyanatosilyl group, trimethoxy titanium group, triethoxy titanium group, tri-n-propoxy titanium group, triisopropoxy titanium group, tri-n-butoxy titanium group, triisobutoxy titanium group, tri-sec- Butoxy titanium group,
Tri-tert-butoxytitanium group, trichlorotitanium group, further, trimethoxyzirconium group, triethoxyzirconium group, tri-n-propoxyzirconium group, triisopropoxyzirconium group, tri-
n-butoxyzirconium group, triisobutoxyzirconium group, tri-sec-butoxyzirconium group, tri-tert-butoxyzirconium group, trichlorozirconium group, and further, dimethoxyaluminum group, diethoxyaluminum group, di-n-propoxy Examples include an aluminum group, a diisopropoxyaluminum group, a di-n-butoxyaluminum group, a diisobutoxyaluminum group, a di-sec-butoxyaluminum group, a di-tert-butoxyaluminum group, and a trichloroaluminum group. One type of the ethylenically unsaturated monomer as the component (a) may be used alone, or two or more types may be used in combination.

On the other hand, the metal-free ethylenically unsaturated monomer as the component (b) includes, for example, a compound represented by the general formula (II)
I)

[0027]

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(Wherein R ⁵ is a hydrogen atom or a methyl group,
X is a monovalent organic group. An ethylenically unsaturated monomer represented by the formula (III-a):

[0029]

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(Wherein R ⁵ is the same as described above, and R ⁶ represents a hydrocarbon group), or an ethylenically unsaturated monomer represented by the above formula (III-a) General formula (III-b) as an ethylenically unsaturated monomer and an adhesion improver optionally added

[0031]

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(Wherein R ⁷ is a hydrogen atom or a methyl group;
R ⁸ represents an epoxy group, a hydroxyl group, a mercapto group, an amino group,
It represents a halogen atom or a hydrocarbon group having an ether bond. )) And a mixture with the ethylenically unsaturated monomer represented by the formula (1).

In the ethylenically unsaturated monomer represented by the general formula (III-a), the hydrocarbon group represented by R ⁶ is a linear or branched alkyl group having 1 to 10 carbon atoms. A cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups, a pentyl group, a hexyl group, an octyl group, and a decyl group. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cyclooctyl group.
Examples of the aryl group of 0 include a phenyl group, a tolyl group,
Examples of the aralkyl group having 7 to 10 carbon atoms such as a xylyl group, a naphthyl group, and a methylnaphthyl group include a benzyl group, a methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

Examples of the ethylenically unsaturated monomer represented by the general formula (III-a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. , Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth)
Acrylate and the like. These may be used alone or in combination of two or more.

The hydrocarbon group having at ethylenically unsaturated monomer represented by the general formula (III-b), an epoxy group represented by R ^8, a hydroxyl group, a mercapto group, an amino group, a halogen atom or an ether bond Preferred examples thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Can be. As the halogen atom of the above substituent,
A chlorine atom and a bromine atom are preferable, and the amino group may be any of a free amino group, a monoalkyl-substituted amino group, and a dialkyl-substituted amino group. Specific examples of the hydrocarbon group include the same groups as those exemplified in the description of R6 in Formula (III-a).

Examples of the ethylenically unsaturated monomer represented by formula (III-b) include glycidyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate, 2- (3,4 -Epoxycyclohexyl) ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-mercaptoethyl (meth) acrylate, 3
-Mercaptopropyl (meth) acrylate, 2-mercaptopropyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth)
Acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate,
4-dimethylaminobenzyl (meth) acrylate, 2
-Chloroethyl (meth) acrylate, 2-bromoethyl (meth) acrylate and the like can be preferably mentioned. In addition, as the ethylenically unsaturated monomer represented by the general formula (III), styrene, α-methylstyrene, α-acetoxystyrene, m-, o- or p-bromostyrene, m- , O- or p-chlorostyrene, m-, o- or p-vinylphenol, 1-
Alternatively, 2-vinylnaphthalene or the like can be used. These may be used alone or in combination of two or more.

When the ethylenically unsaturated monomer represented by the general formula (III-a) and the ethylenically unsaturated monomer represented by the general formula (III-b) are used in combination, It is preferred to use the latter ethylenically unsaturated monomer in a proportion of 1 to 100 mol% with respect to the ethylenically unsaturated monomer.

Further, as the stabilizer for the polymerizable polymer having an ethylenically unsaturated group as the component (c), for example, an antioxidant, an ultraviolet absorber, a light stabilizer and the like having an ethylenically unsaturated group can be used. Are preferred. The structure of these compounds is not particularly limited as long as it has an ethylenically unsaturated group in the molecule,
For example, those having the following structures can be used.

Specific examples of the antioxidant having an ethylenically unsaturated group include structural formulas (A) and (B)

[0040]

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And the like. The compound of the structural formula (A) is a commercially available product “Sumilyzer GS”
[Sumitomo Chemical Industries, Ltd., trade name].

Specific examples of the ultraviolet absorber having an ethylenically unsaturated group include a compound represented by the following general formula (C):

[0043]

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(Wherein R ⁹ represents an alkylene group and R ¹⁰ represents a hydrogen atom or a methyl group);
Structural formula (D)

[0045]

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And the like.
You. In the general formula (C), R ⁹Is an ethylene group,
R¹⁰Is a methyl group, a commercially available product "RUVA-
93 "[Otsuka Chemical Co., Ltd., trade name]
Can be.

Further, specific examples of the light stabilizer having an ethylenically unsaturated group include structural formulas (E) and (F).

[0048]

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And the like. In addition, the compound of the above structural formula (E) is a commercially available product “ADK STAB LA-82” [trade name, manufactured by Asahi Denka Kogyo Co., Ltd.]
The compound of the structural formula (F) can be obtained as a commercial product “ADK STAB LA-87” (trade name, manufactured by Asahi Denka Kogyo KK).

The ethylenically unsaturated monomer having a hydrolyzable metal-containing group of the component (a), the metal-free ethylenically unsaturated monomer of the component (b), and the ethylenically unsaturated monomer of the component (c) By subjecting a polymerizable polymer stabilizer having a saturated group to radical copolymerization in the presence of a radical polymerization initiator, a hydrolyzable metal-containing polymer stabilizer component (A) is chemically bonded. An organic polymer compound having a group is obtained.

In this case, the component (c) is usually 0.01 to 50 mol%, preferably 0.05 to 20 mol%, more preferably 0.05 to 20 mol%, based on the total amount of the components (a) and (b). Is used at a ratio of 0.5 to 10 mol%.

On the other hand, the metal-containing compound (hydrolyzable metal-containing compound) capable of forming a metal oxide by hydrolysis of the component (B) is represented by the following general formula (I): R ¹ _mn M ¹ R ² _n . (I) (wherein R ¹ is a non-hydrolyzable group, R ² is a hydrolyzable group,
M ¹ represents a metal atom, m is a valence of the metal atom M,
n is an integer satisfying the relationship 0 <n ≦ m. Or a condensation oligomer thereof.

[0053] the general formula (I), when R ¹ is more than one, a plurality of R ¹ may be the same or different and when R ² is plural, R ² is a same Or different. Preferred examples of the non-hydrolysable group represented by R ¹ include an alkyl group, an aryl group, and an alkenyl group, and examples of the hydrolysable group represented by R ² include an alkoxyl group, an isocyanate group, and a chlorine atom. A halogen atom, an oxyhalogen group,
An acetylacetonate group is exemplified. Also, M ¹
As the metal atom represented by, for example, silicon, titanium,
Zirconium, aluminum and the like can be mentioned.

Examples of the compound represented by the general formula (I) or a condensation oligomer thereof include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, Isobutoxysilane, tetra-sec
-Butoxysilane, tetra-tert-butoxysilane and the like, and the corresponding tetraalkoxytitanium and tetraalkoxyzirconium, furthermore, trimethoxyaluminum, triethoxyaluminum, tri-
Metal alkoxides such as n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, triisobutoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, or metal alkoxide oligomers, for example, commercially available alkoxy Examples of the silane oligomer include “methyl silicate 51” and “ethyl silicate 40” (both are trade names manufactured by Colcoat), and further include tetraisocyanatosilane, methyltriisocyanatosilane, tetrachlorosilane, and methyltrichlorosilane. As the component (B), a metal alkoxide is preferable. In the present invention, one kind of the hydrolyzable metal-containing compound may be used alone, or two or more kinds thereof may be used in combination.

In the present invention, alcohols, ketones,
In a suitable polar solvent such as ether, the above (A)
A mixture of the organic polymer compound as the component and at least one hydrolyzable metal-containing compound as the component (B) is prepared by using an acid such as hydrochloric acid, sulfuric acid, or nitric acid, or a cation exchange resin as a solid acid. Hydrolysis treatment at a temperature of 100 ° C., preferably 20 to 60 ° C., and in the case of using a solid acid, after removing it, further, if necessary, distilling off or adding a solvent and suitable for coating. The viscosity is adjusted to prepare a coating solution. If the temperature is too low, hydrolysis does not proceed, while if it is too high, the hydrolysis / polymerization reaction proceeds too quickly, making control difficult, and as a result, the gradient of the resulting gradient coating film may be reduced. (B)
A polar solvent solution containing a metal-containing compound as a component may be prepared in advance, an acid may be added to the solution to advance a hydrolysis reaction, and this may be mixed with the component (A), followed by hydrolysis.

Depending on the type of the inorganic component, even after the preparation of the coating solution, hydrolysis and polycondensation may gradually progress and the coating conditions may fluctuate. Therefore, a solid dehydrating agent insoluble in the coating solution may be used. For example, addition of anhydrous magnesium sulfate or the like can prevent a decrease in pot life. In this case, the coating liquid is used for coating after removing the dehydrating agent.

Next, using the coating solution thus obtained, the thickness of the dried coating film on the organic substrate is usually 0.01 to 0.01.
5 μm, preferably 0.01 to
Dip coating method, spin coating method, so as to be in the range of 1.0 μm, more preferably 0.02 to 0.7 μm.
A coating film is formed by a known means such as a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, and a known drying treatment, for example, at about 40 to 150 ° C. By heating and drying at a temperature, the organic-inorganic composite gradient material of the present invention can be obtained.

As the organic substrate, for example, acrylic resin such as polymethyl methacrylate, polystyrene or A
Styrene resins such as BS resin, olefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as 6-nylon and 6,6-nylon, polyvinyl chloride resins, Examples of the base material include polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins, polyimide resins, and cellulose resins such as cellulose acetate.

These organic base materials can be subjected to a surface treatment by an oxidation method or a concavo-convex method, if desired, in order to improve the adhesion with the gradient material of the present invention. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet method), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and examples of the unevenness method include a sand blast method and a solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of the base material.

In the present invention, the organic substrate is coated on the surface of a substrate made of a material other than the organic material, for example, a metal material, a glass or ceramic material, or other various inorganic or metal materials. Those having a membrane are also included.

In the thus obtained organic-inorganic composite gradient material of the present invention, the surface layer contains almost 100% of the metal component in the material, but gradually decreases in the direction of the base material. It becomes almost 0% near the base material. The content of the polymer stabilizer is substantially zero in the surface layer, and has a tilted structure that continuously increases in the direction of the base material.

The present invention also provides a coating agent for forming a coating comprising the organic-inorganic composite gradient material on a substrate.

As the coating agent, (A)
An organic polymer compound having a hydrolyzable metal-containing group to which a polymer stabilizer component is chemically bonded, and (B)
A coating solution containing a component obtained by hydrolyzing at least one kind of hydrolyzable metal-containing compound as a component can be used.

This coating agent can be used for the following purposes. First, it is used for application as a coating film.
Since the organic-inorganic composite gradient material has excellent adhesiveness to an organic substrate and the surface of a coating film has the property of a metal oxide, for example, a coating layer made of the material is provided on various plastic films. Thereby, it is possible to obtain a hard coat film having excellent scratch resistance and heat resistance, as well as good adhesion.

Next, it is used for application as an adhesive.
As described above, the graded material of the present invention has excellent adhesion to an organic base material and has excellent adhesion to an inorganic or metal material because its surface is a metal oxide compound. Therefore, it is suitable as an adhesive between an organic material and an inorganic or metal material.

Further, it is used as an intermediate film interposed between an organic base material and a coat layer containing at least an inorganic or metallic material. When a coating layer containing an inorganic or metal material is formed on an organic substrate, generally, the adhesion between the organic substrate and the coating layer is insufficient, the durability is poor, and peeling over time, Alternatively, there is a problem that the film is easily peeled off by heat or moisture.

By using the gradient material of the present invention as an intermediate film and interposing it between the organic substrate and the coat layer containing an inorganic or metallic material, the intermediate film has a gradient as described above. From the excellent adhesion to the organic substrate, and also excellent adhesion to the coating layer containing an inorganic or metal-based material provided thereon, as a result, the inorganic or metal-based material on the organic substrate Can be formed with extremely good adhesion.

In the present invention, the thickness of the interlayer is usually 0.01 to 5 μm, preferably 0.01 to 1.0 μm.
m, more preferably in the range of 0.02 to 0.7 μm.

The coat layer containing the inorganic or metal material is not particularly limited, and various coat layers can be formed. For example, (1) a photocatalytic active material layer,
(2) an inorganic or metallic conductive material layer, (3) a hard coat layer containing an inorganic or metallic material, (4) an inorganic or metallic optical recording material layer or an inorganic or metallic dielectric layer, etc. Are preferred.

Next, the coat layer containing each inorganic or metal material will be described. (1) Photocatalytic active material layer: When a coat layer of a photocatalytic active material such as titanium dioxide is provided on the surface of an organic base material, the photocatalytic action causes a problem that the organic base material is deteriorated in a short time. Therefore, it has been attempted to provide a coating layer of a photocatalytically active material such as titanium dioxide on an organic substrate via an inorganic binder which is hardly deteriorated by photocatalysis. However, there is a problem that the inorganic binder has insufficient adhesion to an organic base material and is inferior in durability.

When the gradient material of the present invention is used as an intermediate film and is interposed between the organic substrate and the coat layer of the photocatalytically active material, the adhesion to the organic substrate is excellent, and the surface is almost metal oxide-based. Since it is a compound, it has good adhesion to the coat layer of the photocatalytically active material, and the intermediate film is not easily degraded by the photocatalytic action, so that the organic base material can be sufficiently protected.

When an ultraviolet absorber or a light stabilizer is used as a stabilizer for a polymer in the gradient material of the present invention, the content of the ultraviolet absorber or the light stabilizer has a gradient structure, and the surface layer portion in contact with the photocatalytic active material layer of the interlayer film. Since the content of the ultraviolet absorber or light stabilizer is substantially 0, the ultraviolet absorber or light stabilizer is hardly oxidized and deteriorated by the oxidizing action of the photocatalytically active material, so that the weather resistance is remarkably excellent. And an intermediate film having good durability.

Further, the gradient material of the present invention can be interposed between a metal base material having an organic coating film on its surface and the photocatalytic active material layer as an intermediate film. This intermediate film has excellent adhesion with the organic coating film, and also has good adhesion with the coating layer of the photocatalytic active material, as well as the above-mentioned organic base material. It is hardly deteriorated and can sufficiently protect the organic coating film. Such a use is particularly useful when a photocatalytically active material layer is provided on a steel sheet for automobiles having an organic coating film on the surface.

Examples of the metal base material having an organic coating film on its surface include metal base materials such as cold-rolled steel sheets, galvanized steel sheets, aluminum / zinc alloy-plated steel sheets, stainless steel sheets, aluminum sheets, and aluminum alloy sheets. An organic coating film can be used. When the gradient material of the present invention is used as such an intermediate film, it is particularly effective when the coating layer of the photocatalytically active material provided thereon is titanium dioxide having a high photocatalytic ability.

(2) Inorganic or metallic conductive material layer:
Organic substrates having a conductive material layer on the surface, particularly plastic films, are used for electroluminescence devices (EL devices), liquid crystal display devices (LCD devices), solar cells, etc., and further include electromagnetic wave shielding films and antistatic films. It is used as Examples of the conductive material used in such applications include metal oxides such as indium oxide, tin oxide, zinc oxide, cadmium oxide, and ITO (indium tin oxide); gold, platinum, silver, nickel, aluminum, and copper. Inorganic or metallic conductive materials such as metals as described above are used. And these inorganic or metallic conductive materials are usually formed on an organic substrate such as a plastic film by a known means such as a vacuum deposition method, a sputtering method, and an ion plating method.
It is formed as a thin film having a thickness of about 50 to 2000 angstroms.

The inorganic or metallic conductive material layer formed in this way has insufficient adhesion to the organic base material. By interposing between the inorganic or metal-based conductive material layer, the adhesion between the organic base and the inorganic or metal-based conductive material layer can be improved. Further, even when a transparent conductive film is required, transparency is hardly impaired by interposing the intermediate film made of the gradient material of the present invention.

(3) Hard coat layer containing inorganic or metallic material: A hard coat film having a good surface hardness and excellent scratch resistance and abrasion resistance is, for example, a vehicle,
It is widely used for attaching surfaces such as window glass of buildings and plastic boards for windows, and for protecting CRT displays and flat panel displays.

On the other hand, plastic lenses have been rapidly spread in recent years because they are lighter in weight and more excellent in safety, workability, fashionability and the like than glass lenses. However, this plastic lens has a drawback that it is easily damaged as compared with a glass lens, and therefore, its surface is coated with a hard coat layer.

Examples of the material for the hard coat layer provided on such a hard coat film or a plastic lens include a mixture of alkyltrihydroxysilane and its partial condensate, colloidal silica and a silicon-modified acrylic resin, and organotrialkoxysilane. Inorganic or metallic materials such as a mixture of a hydrolysis condensate, a mixture of an alkoxysilane hydrolysis condensate and colloidal silica, a zirconium, a metal selected from aluminum and titanium and a chelate compound and a silicon-modified acrylic resin. Hard coating agents are frequently used.

To form a hard coat layer on an organic substrate such as a plastic film or a plastic lens,
The hard coat agent containing the inorganic or metal-based material, using a known method such as a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, a gravure coat method, a spray coat method, or the like. A method of applying the composition on an organic substrate so that the dry film thickness is about 1 to 30 μm and performing a drying treatment is usually used.

The thus formed hard coat layer containing an inorganic or metal material has insufficient adhesion to an organic base material. By interposing the hard coat layer between the organic base material and the hard coat layer containing an inorganic or metallic material, the adhesion between the organic base material and the hard coat layer containing an inorganic or metallic material can be improved. Further, in the plastic lens, even if an intermediate film made of the inclined material of the present invention is interposed, it hardly causes a decrease in the transparency of the plastic lens or the generation of interference fringes.

(4) Inorganic or metallic optical recording material layer or inorganic or metallic dielectric layer: In recent years, it has characteristics such as rewritable, high density, large capacity storage capacity, and non-contact with the recording / reproducing head. Uses a phase change from a magneto-optical disk or crystal to amorphous using an optical recording medium that records information using the magnetization reversal of the magnetic film using the heat energy of a semiconductor laser beam or the like and uses the magneto-optical effect to read. Phase change disks have been developed and are now in practical use.

Such an optical recording medium is generally formed by forming an optical recording material layer, a dielectric layer, a metal reflection layer, an organic protective layer on a light-transmitting resin substrate (organic substrate), for example, a substrate such as polycarbonate or polymethyl methacrylate. It has a structure in which layers are sequentially laminated, and a dielectric underlayer may be provided between the substrate and the optical recording material layer in some cases.

The optical recording material layer provided on the substrate includes, for example, Tb-Fe, Tb-Fe-Co, Dy-Fe-C
o, inorganic magneto-optical recording materials such as Tb-Dy-Fe-Co, or TeOx, Te-Ge, Sn-Te-
Ge, Bi-Te-Ge, Sb-Te-Ge, Pb-S
An inorganic phase change recording material such as n-Te or Tl-In-Se is used. If desired, the dielectric underlayer provided between the substrate and the optical recording material layer may include, for example, S
Inorganic materials such as iN, SiO, SiO ₂ and Ta ₂ O ₅ are used. The inorganic optical recording material layer and the dielectric underlayer are usually formed by a known means such as a vacuum evaporation method, a sputtering method, and an ion plating method.

Since the inorganic or metallic optical recording material layer or the inorganic dielectric underlayer formed as described above has insufficient adhesion to the translucent resin substrate, the gradient material of the present invention is not used. As an intermediate film, by interposing between a light-transmitting resin substrate and the optical recording material layer or the dielectric underlayer,
Adhesion between the substrate and the optical recording material layer or the dielectric underlayer can be improved.

[0086] Other coating layers containing inorganic or metallic materials include titanium oxide, zinc oxide, indium oxide, tin oxide, zinc sulfide, and antimony-doped tin oxide (AT
O), an inorganic infrared absorbing layer such as tin-doped indium oxide (ITO), and a magnetic layer on which metal is deposited.

The present invention further provides a structure having a coating made of the above-mentioned organic-inorganic composite gradient material. As such a structure, for example, an organic substrate having a coat layer containing at least an inorganic or metal material, with the organic-inorganic composite gradient material of the present invention interposed as an intermediate film,
Alternatively, the organic-inorganic composite gradient material of the present invention is interposed as an intermediate film, and has a photocatalytically active material layer, such as a metal base material provided with an organic coating film on its surface. An article having a coat layer interposed as a film and containing at least an inorganic or metal material can be given.

As a specific example of the article, a coat layer containing at least an inorganic or metal material is composed of (1) a photocatalytic active material layer, (2) an inorganic or metal conductive material layer, and (3)
A hard coat layer containing an inorganic or metal material, and
(4) An inorganic or metallic optical recording material layer or an inorganic or metallic dielectric layer can be preferably exemplified. As the above structure, a structure having a photocatalytically active material layer on an organic base material via a coating made of an organic-inorganic composite gradient material is particularly preferable.

[0089]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The properties of the films formed in each example were determined according to the methods described below. (1) Gradient Argon sputtering (4 kV) using an XPS apparatus “PHI-5600” (manufactured by ULVAC-PHI, Inc.)
Was performed at intervals of 3 minutes to scrape the film, and the content of carbon atoms, metal atoms and nitrogen atoms on the film surface was measured by X-ray photoelectron spectroscopy to examine the gradient.

(2) Weather Resistance A sample having a photocatalyst layer was subjected to a weather resistance acceleration test for a predetermined time using a sunshine weather meter [“Sunshine Weather Meter S300” manufactured by Suga Test Instruments Co., Ltd.]. For samples after the weathering test, JIS K
Haze value [Nippon Denshoku Industries Co., Ltd. N
DH2000 used], yellowing degree [manufactured by Shimadzu Corporation]
UV-2100]], and compared with those before the test. In addition, the adhesion of the coating film was evaluated by a cross-cut peeling test based on JIS K5400.

Example 1 (1) Preparation of Organic Component 11.4 g (0.11) of methyl methacrylate (MMA)
4 mol), 1.41 g (0.00568 mol) of 3-methacryloxypropyltrimethoxysilane (MPTMS),
1.83 g (0.00568 mol) of polymerizable ultraviolet absorber "RUVA-93" (manufactured by Otsuka Chemical Co., Ltd.) and 2,2'-azobisisobutyronitrile (AIBN)
0.205 g (0.00125 mol) was mixed,
For 7 hours to obtain an organic component. In this case, the molar ratio of the polymerizable ultraviolet absorber component was 4.7 with respect to 100 acrylic monomers.

(2) Preparation of Inorganic Component Liquid 60 g of tetraethoxysilane (TEOS) (0.288)
Mol), 75 g of ethanol (1.63 mol), 1 mol /
0.35 ml of aqueous nitric acid solution (HNO
₃ 3.5 × 10 ⁻⁴ mol) and 40 g of water (2.22)
Mol) were mixed and hydrolyzed / condensed for 48 hours to obtain an inorganic component liquid A.

On the other hand, titanium tetraisopropoxide (T
TIP) 60 g (0.208 mol), ethanol 75 g
(1.63 mol), concentrated nitric acid 0.8 g (8.41 × 10
^-3 mol) and 3.8 g (0.211 mol) of water were mixed and hydrolyzed / condensed for 4 hours to obtain an inorganic component liquid B.

(3) Preparation of Coating Solution and Evaluation of Film In a solution prepared by dissolving 2.0 g of the organic component obtained in the above (1) in 500 ml of methyl ethyl ketone, 400 ml of ethyl cellosolve and the solution of the above (2) were used. 20 ml of the obtained inorganic component liquid A and the inorganic component liquid B8
0 ml was added to prepare a coating solution.

Next, the above coating solution was spray-coated on a polycarbonate plate (trade name: EC100U, manufactured by Tsutsunaka Plastics Co., Ltd.), dried by heating in an oven at 80 ° C. for 12 hours, and dried to a thickness of 0.07 μm. -An inorganic composite gradient film was formed.

The gradient of this film was measured, and the relationship between the sputtering time and the contents of titanium, silicon, carbon and nitrogen atoms was shown in FIG. 1 (a) as a graph. An enlarged graph of the relationship with the content is shown in FIG. 1 (a) and 1 (b), the film surface is occupied by the inorganic components of titania and silica, but its content decreases toward the substrate side, and instead contains carbon atoms (organic components). It was confirmed that at the same time as the rate increased, the content of nitrogen atoms (UV absorber components) also increased.

Further, the substrate coated with the gradient film was spray-coated with a photocatalyst coating solution [NSC-200C manufactured by Nippon Soda Co., Ltd.] diluted 10-fold by weight with isopropanol. Heat and cure in an oven at 80 ° C for 1 hour.
A photocatalyst layer of 05 μm was obtained. The obtained sample was subjected to a 900-hour weathering acceleration test using a sunshine weather meter. Table 1 shows the results.

Example 2 (1) Preparation of Organic Component 11.4 g (0.114 mol) of MMA, MPTMS
1.41 g (0.00568 mol), 14.7 g (0.045) of the polymerizable ultraviolet absorber "RUVA-93" (supra)
6 mol) and 0.271 g (0.00165 mol) of AIBN were mixed and subjected to a radical polymerization reaction at 70 ° C. for 7 hours to obtain an organic component. At this time, the polymerizable ultraviolet absorber component is
The molar ratio was 38.1 based on 100 acrylic monomers. (2) Preparation of inorganic component liquid In the same manner as in Example 1 (2), an inorganic component liquid A and an inorganic component liquid B were prepared. (3) Preparation of coating liquid and evaluation of film Same as Example 1 (3) using the organic component liquid obtained in (1) and the inorganic component liquid A and the inorganic component liquid B obtained in (2). To prepare a coating liquid, and an organic-inorganic composite gradient film was further formed.

The gradient of this film was measured, and the relationship between the sputtering time and the contents of titanium, silicon, carbon and nitrogen atoms is shown in the graph of FIG. 2 (a). FIG. 2B shows an enlarged graph of the relationship with the content. 2 (a) and 2 (b), the film surface is occupied by the inorganic components of titania and silica, but its content decreases toward the substrate side, and instead contains carbon atoms (organic components). It was confirmed that at the same time as the rate increased, the content of nitrogen atoms (UV absorber components) also increased. Further, a weather resistance acceleration test was performed in the same manner as in Example 1 (3). Table 1 shows the results.

Example 3 (1) Preparation of Organic Component 11.4 g (0.114 mol) of MMA, MPTMS
1.41 g (0.00568 mol), 1.83 g (0.005 g) of the polymerizable ultraviolet absorber "RUVA-93" (supra)
68 mol), polymerizable hindered amine light stabilizer “LA
-82 "[made by Asahi Denka Kogyo KK] 1.36 g (0.00
568 mol) and AIBN 0.215 g (0.00
131 mol) and subjected to a radical polymerization reaction at 70 ° C. for 7 hours to obtain an organic component. At this time, the polymerizable ultraviolet absorber component and the polymerizable hindered amine light stabilizer component are:
The molar ratio was 4.7 with respect to 100 acrylic monomers. (2) Preparation of inorganic component liquid In the same manner as in Example 1 (2), an inorganic component liquid A and an inorganic component liquid B were prepared. (3) Preparation of coating liquid and evaluation of film Same as Example 1 (3) using the organic component liquid obtained in (1) and the inorganic component liquid A and the inorganic component liquid B obtained in (2). To prepare a coating liquid, and an organic-inorganic composite gradient film was further formed.

The gradient of this film was measured, and the relationship between the sputtering time and the contents of titanium, silicon, carbon and nitrogen atoms is shown in the graph of FIG. 3 (a). FIG. 3B shows an enlarged graph of the relationship with the content. 3 (a) and 3 (b), the film surface is occupied by the inorganic components of titania and silica, but its content decreases toward the substrate side, and instead contains carbon atoms (organic components). It was confirmed that the content of nitrogen atoms (UV absorber component and light stabilizer component) also increased at the same time as the rate increased. Further, a weather resistance acceleration test was performed in the same manner as in Example 1 (3). Table 1 shows the results.

Example 4 (1) Preparation of Organic Component An organic component was prepared in the same manner as in Example 1 (1). (2) Preparation of inorganic component liquid In the same manner as in Example 1 (2), an inorganic component liquid A and an inorganic component liquid B were prepared. (3) Preparation of coating liquid and evaluation of film Same as Example 1 (3) using the organic component liquid obtained in (1) and the inorganic component liquid A and the inorganic component liquid B obtained in (2). To prepare a coating solution.

Next, a polyethylene terephthalate film [trade name: HB-3, manufactured by Teijin Limited] was used.
The coating solution was coated with a Meyer bar having a thickness of 2 mm, and dried in an oven at 80 ° C for 12 hours to form an organic-inorganic composite gradient film having a thickness of 0.07 µm.

The gradient of this film was measured, and the relationship between the sputtering time and the contents of titanium, silicon, carbon and nitrogen atoms is shown in the graph of FIG. 4 (a). FIG. 4B shows an enlarged graph of the relationship with the content rate. 4 (a) and 4 (b), the film surface is occupied by the inorganic components of titania and silica, but the content decreases toward the substrate side, and instead, the content of carbon atoms (organic components) It was confirmed that at the same time as the rate increased, the content of nitrogen atoms (UV absorber components) also increased.

Further, the substrate coated with the gradient film was coated with a photocatalyst coating solution (described above) using a Meyer bar having a wire diameter of 0.1 mm, and was cured by heating in an oven at 80 ° C. for 1 hour. A photocatalyst layer of 0.05 μm was obtained. The obtained sample was subjected to a weathering acceleration test for 600 hours using a sunshine weather meter. Table 1 shows the results.

Comparative Example 1 (1) Preparation of Organic Component 11.4 g of MMA without using a polymerizable ultraviolet absorber
(0.114 mol), 1.41 g of MPTMS (0.0
0568 mol), and 0.20 g (0.0
And a radical polymerization reaction at 70 ° C. for 7 hours to prepare an organic component. (2) Preparation of inorganic component liquid In the same manner as in Example 1 (2), an inorganic component liquid A and an inorganic component liquid B were prepared. (3) Preparation of coating liquid and evaluation of film Same as Example 1 (3) using the organic component liquid obtained in (1) and the inorganic component liquid A and the inorganic component liquid B obtained in (2). To prepare a coating liquid, and an organic-inorganic composite gradient film was further formed.

The gradient of this film was measured, and the relationship between the sputtering time and the contents of titanium, silicon, carbon and nitrogen atoms is shown in the graph of FIG. 5 (a). An enlarged graph of the relationship with the content is shown in FIG. 5 (a) and 5 (b), the film surface is occupied by the inorganic components of titania and silica, but the content decreases toward the substrate side, and instead contains carbon atoms (organic components). It was confirmed that the rate increased. However, no nitrogen atom was confirmed. Further, a weather resistance acceleration test was performed in the same manner as in Example 1 (3). Table 1 shows the results.

Comparative Example 2 (1) Preparation of Organic Component Copolymerization was performed in the same manner as in Comparative Example 1 (1) without using a polymerizable ultraviolet absorber to prepare an organic component. (2) Preparation of inorganic component liquid In the same manner as in Comparative Example 1 (2), an inorganic component liquid A and an inorganic component liquid B were prepared. (3) Preparation of Coating Solution and Evaluation of Film 1.4 g of the organic component obtained in (1) above, 0.65 g of a benzotriazole-based UV absorber [trade name: Tinuvin 328, manufactured by Ciba Specialty Chemicals] .0
(0186 mol) in 500 ml of methyl ethyl ketone, 400 ml of ethyl cellosolve, 20 ml of the inorganic component liquid A and 80 ml of the inorganic component liquid B obtained in the above (2) were added to prepare a coating liquid.

Next, this coating solution was used to prepare Example 1 (3).
An organic-inorganic composite gradient film was formed in the same manner as described above. The gradient of this film was measured, and the relationship between the sputtering time and the contents of titanium, silicon, carbon, and nitrogen atoms was graphically shown in FIG. FIG. 6B shows an enlarged graph of the relationship. 6 (a) and 6 (b), the film surface is occupied by the inorganic components of titania and silica, but its content decreases toward the substrate side, and instead contains carbon atoms (organic components). It was confirmed that the rate increased. However, nitrogen atoms were uniformly detected from the entire coating film. Further, a weather resistance acceleration test was performed in the same manner as in Example 1 (3). Table 1 shows the results.

Comparative Example 3 (1) Preparation of Organic Component Copolymerization was conducted in the same manner as in Comparative Example 2 (1) without using a polymerizable ultraviolet absorber to prepare an organic component. (2) Preparation of inorganic component liquid In the same manner as in Comparative Example 2 (2), an inorganic component liquid A and an inorganic component liquid B were prepared. (3) Preparation of coating liquid and evaluation of film Same as Comparative Example 2 (3) using the organic component liquid obtained in (1) and the inorganic component liquid A and the inorganic component liquid B obtained in (2). To prepare a coating solution.

Next, the organic compound was prepared in the same manner as in Example 4 (3).
An inorganic composite gradient film was formed. The gradient of this film was measured, and the sputtering time and titanium atom, silicon atom,
Fig. 7 (a) shows the relationship with the content of carbon atoms and nitrogen atoms.
FIG. 7B shows an enlarged graph of the relationship between the sputtering time and the nitrogen atom content. 7 (a) and 7 (b), the film surface is occupied by the inorganic components of titania and silica, but its content decreases toward the substrate side, and instead contains carbon atoms (organic components). It was confirmed that the rate increased. However,
Nitrogen atoms were detected uniformly throughout the coating. Further, a weather resistance acceleration test was performed in the same manner as in Example 4 (3). Table 1 shows the results.

Example 5 (1) Preparation of Organic Component 11.4 g (0.114 mol) of MMA, MPTMS
1.41 g (0.00568 mol), 22.1 g (0.068) of polymerizable ultraviolet absorber "RUVA-93" (supra)
4 mol) and 0.308 g (0.00188 mol) of AIBN were mixed and subjected to a radical polymerization reaction at 70 ° C. for 7 hours to obtain an organic component. At this time, the polymerizable ultraviolet absorber component is
The molar ratio was 57.2 based on 100 acrylic monomers. (2) Preparation of inorganic component liquid In the same manner as in Example 1 (2), an inorganic component liquid A and an inorganic component liquid B were prepared. (3) Preparation of coating liquid and evaluation of film Same as Example 1 (3) using the organic component liquid obtained in (1) and the inorganic component liquid A and the inorganic component liquid B obtained in (2). To prepare a coating liquid, and an organic-inorganic composite gradient film was further formed.

The gradient of this film was measured, and the relationship between the sputtering time and the contents of titanium, silicon, carbon and nitrogen atoms is shown in the graph of FIG. 8 (a). FIG. 8B shows an enlarged graph of the relationship with the content rate. 8 (a) and 8 (b), the film surface is occupied by the inorganic components of titania and silica, but the content decreases toward the substrate side, and instead, the content of carbon atoms (organic components) It was confirmed that at the same time as the rate increased, the content of nitrogen atoms (UV absorber components) also increased. Since the content of the ultraviolet absorber component in this gradient film was too large and the adhesion to the substrate was insufficient, the weather resistance promotion test was not performed.

[0114]

[Table 1]

[0115]

According to the organic-inorganic composite gradient material of the present invention, the content of the polymer stabilizer contained therein is substantially 0 in the surface layer, and the gradient increases continuously in the depth direction. Having a structure, it can favorably suppress deterioration due to oxygen, light, heat, photocatalytic oxidation and the like, and is useful as a functional material. In particular, when used as an intermediate film of a photocatalytically active material,
The durability against the oxidizing power of the photocatalytically active material is increased, and the reliability in long-term light exposure is improved.

[Brief description of the drawings]

FIG. 1 is a graph (a) showing the relationship between the sputtering time and the content of carbon, silicon, titanium and nitrogen atoms in the organic-inorganic composite gradient film obtained in Example 1, and the sputtering time and nitrogen. It is an enlarged graph (b) which shows a relationship with the content rate of an atom.

FIG. 2 is a graph (a) showing the relationship between the sputtering time and the content of carbon, silicon, titanium and nitrogen atoms in the organic-inorganic composite gradient film obtained in Example 2; It is an enlarged graph (b) which shows a relationship with the content rate of an atom.

FIG. 3 is a graph (a) showing the relationship between the sputtering time and the content of carbon, silicon, titanium and nitrogen atoms in the organic-inorganic composite gradient film obtained in Example 3, and the sputtering time and nitrogen. It is an enlarged graph (b) which shows a relationship with the content rate of an atom.

FIG. 4 is a graph (a) showing the relationship between the sputtering time and the content of carbon, silicon, titanium and nitrogen atoms in the organic-inorganic composite gradient film obtained in Example 4, and the sputtering time and nitrogen. It is an enlarged graph (b) which shows a relationship with the content rate of an atom.

FIG. 5 is a graph (a) showing the relationship between the sputtering time and the content of carbon, silicon, titanium and nitrogen atoms in the organic-inorganic composite gradient film obtained in Comparative Example 1, and the sputtering time and nitrogen. It is an enlarged graph (b) which shows a relationship with the content rate of an atom.

FIG. 6 is a graph (a) showing the relationship between the sputtering time and the content of carbon, silicon, titanium and nitrogen atoms in the organic-inorganic composite gradient film obtained in Comparative Example 2, and the sputtering time and nitrogen. It is an enlarged graph (b) which shows a relationship with the content rate of an atom.

FIG. 7 is a graph (a) showing the relationship between the sputtering time and the content of carbon, silicon, titanium and nitrogen atoms in the organic-inorganic composite gradient film obtained in Comparative Example 3, and the sputtering time and nitrogen. It is an enlarged graph (b) which shows a relationship with the content rate of an atom.

8 is a graph (a) showing the relationship between the sputtering time and the content of carbon, silicon, titanium and nitrogen atoms in the organic-inorganic composite gradient film obtained in Example 5, and FIG. It is an enlarged graph (b) which shows a relationship with the content rate of an atom.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09D 201/02 C09D 201/02 // C08F 230/04 C08F 230/04 C08G 81/02 C08G 81/02 ( 72) Inventor Norihiro Nakayama 2-1-1, Yabuta Nishi, Gifu City, Gifu Prefecture Ube Nitto Kasei Co., Ltd. F-term (reference) 4F100 AA17A AH06 AH08A AK01A AK02A AK25 AK45 AL01A AR00C AT00B BA02 BA03 BA07 BA10A BA07A CA05A JL00 JL08C 4J002 BG051 EC076 EX046 FD206 GT00 4J031 AA12 AA27 AB02 AC01 AD01 AF12 4J038 CG141 CH081 CL001 4J100 AL03Q AL08P AL08Q AL08R BA02Q BA03Q BA29Q BA52Q BA78P BA93P BA94P BA95Q BB00Q BC01Q

Claims (10)

[Claims] 1. A component gradient structure including a complex in which an organic polymer compound and a metal oxide compound are chemically bonded, and wherein the content of a metal component continuously changes from the surface of the material in the depth direction. An organic-inorganic composite gradient material having a polymer stabilizer, and the content of the polymer stabilizer is substantially 0 in the surface layer of the material, and continuously in the depth direction. An organic-inorganic composite gradient material characterized by having an increasing gradient structure. 2. The organic-inorganic composite gradient material according to claim 1, wherein the polymer stabilizer is chemically bonded to an organic polymer compound in the material. 3. A complex in which an organic polymer compound and a metal oxide compound are chemically bonded to each other, wherein (A) and (a) an ethylenic compound having a metal-containing group capable of bonding to a metal oxide by hydrolysis in a molecule. In a molecule obtained by copolymerizing an unsaturated monomer, (b) an ethylenically unsaturated monomer containing no metal, and (c) a stabilizer for a polymerizable polymer having an ethylenically unsaturated group, An organic polymer compound having a metal-containing group capable of bonding to a metal oxide by decomposition and chemically bonding a polymer stabilizer, and (B) one or more metals capable of forming a metal oxide by hydrolysis The organic-inorganic composite gradient material according to claim 2, which is obtained by hydrolyzing a contained compound. 4. The organic-inorganic composite gradient material according to claim 3, wherein component (c) is used in a proportion of 0.01 to 50 mol% based on the total amount of component (a) and component (b). 5. The organic-inorganic composite gradient according to claim 1, wherein the polymer stabilizer is at least one selected from an antioxidant, an ultraviolet absorber and a light stabilizer. material. Wherein (B) the metal-containing compound capable of forming a metal oxide by hydrolysis of components of the general formula _{^{(I) R 1 m-n}} M 1 R 2 n ... (I) (R 1 in the formula Is a non-hydrolyzable group, R ² is a hydrolyzable group,
M ¹ represents a metal atom, m is a valence of the metal atom M,
n is an integer satisfying the relationship 0 <n ≦ m. 6. The organic-inorganic composite gradient material according to claim 3, which is a compound represented by the formula (1) or a condensation oligomer thereof. 7. The method according to claim 1, wherein the thickness is 0.01 to 5 μm.
7. The organic-inorganic composite gradient material according to any one of items 6 to 6. 8. A coating agent, wherein a coating comprising the organic-inorganic composite gradient material according to claim 1 is formed on a substrate. 9. A structure having a coating made of the organic-inorganic composite gradient material according to claim 1. Description: 10. The structure according to claim 9, wherein a photocatalytically active material layer is provided on the organic substrate with a coating made of an organic-inorganic composite gradient material interposed therebetween.