JP2001310943A - Organic/inorganic functionally gradient material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic/inorganic functionally gradient composite material, which has various application as functional material, has good adhesion with organic matrix, and has continuous gradient change of its composition in a direction of thickness. SOLUTION: The organic/inorganic functionally gradient composite material contains a chemically bonded compound obtained from an organic polymer and a metallic oxide. The composite material has a component having continuously gradient structure wherein the content of the metallic compound as a component is continuously changed from the surface of the material in the direction of the depth. The organic polymer used is obtained from a) ethylenic unsaturated monomer having a hydrolysable metal containing group, b) (meth) acrylic acid ester of a hydrocarbon group having a specific functional group, and c) (meth)acrylic acid ester of a hydrocarbon group having no functional group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an organic-inorganic composite gradient material and its use. More specifically, the present invention relates to an organic-inorganic composite material containing a chemical bond of an organic polymer compound and a metal oxide compound, wherein the content of the metal oxide compound is in the thickness direction of the material. An organic-inorganic composite gradient material having a continuously changing component gradient structure, having excellent adhesion to an organic substrate, and being useful as a functional material for various applications, a coating agent for forming a film comprising the gradient material, and The present invention relates to 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.

[0003] For example, the modification of physical properties by dispersing a reinforcing material in an organic polymer material is widely performed, and specifically, organic fibers such as carbon fiber, glass fiber, metal fiber, ceramic fiber, and aramid fiber are used. And inorganic fibrous substances, or powdered inorganic fillers such as calcium carbonate, silica, and alumina are added and uniformly dispersed. In addition, studies are being actively conducted to mix new polymer compounds, optionally compatibilize them via a compatibilizer, and form a polymer alloy, thereby expressing new functions. 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.

On the other hand, a layer composed of various inorganic or metallic materials, for example, a photocatalytically active material, a conductive material, a hard coat agent, an optical recording material, a magnetic powder, an infrared absorbing material, etc., is provided on a plastic substrate. Production of conductive materials is widely performed.

When such an inorganic or metal material layer is provided on a plastic substrate, the adhesion to the substrate is generally insufficient. For example, an inorganic primer layer is provided on a plastic substrate. A method of forming an inorganic or metal material layer thereon is often used. However, in this method, although the adhesion between the inorganic primer layer and the inorganic or metal material layer is good, the adhesion between the plastic substrate and the inorganic primer layer is not always sufficient, Inferior or poor adhesion over time. Therefore, development of a technique for forming an inorganic or metal material layer on a plastic substrate with good adhesion has been desired.

[0007] Under such circumstances, the present inventors have:
Previously, various applications as a new functional material, such as coatings, adhesives between organic materials and inorganic or metal materials, provided between the organic substrate and the photocatalytic coating, the deterioration of the organic substrate An organic-inorganic composite gradient material whose composition continuously changes in the thickness direction, which is useful for applications such as an intermediate film for preventing or an intermediate film for improving the adhesion between an organic base material and an inorganic or metallic material layer. (Japanese Patent Application No. 11-264592).

The 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. However, since the gradient material is formed by utilizing the ability of the polymer portion to adsorb to the base material, depending on the type of the base material, the adhesion to the base material may not always be sufficient. there were.

[0009]

SUMMARY OF THE INVENTION Under such circumstances, the present invention has a component gradient structure in which the content of a metal oxide-based compound changes continuously in the thickness direction of the material, An object of the present invention is to provide an organic-inorganic composite gradient material which is extremely excellent in adhesion to a substrate and is useful as a functional material for various uses, and its use.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a complex comprising an organic polymer compound and a metal oxide compound is chemically bonded. An organic compound having a component gradient structure in which the metal oxide compound continuously changes in the depth direction from the surface of the material.
An inorganic composite gradient material, wherein, as the organic polymer compound, an ethylenically unsaturated monomer having a metal-containing group capable of binding to a metal oxide by hydrolysis in a molecule, and a specific structure of a metal-free ( It has been found that the object can be achieved by using a product obtained by copolymerizing (meth) acrylic acid ester, and the present invention has been completed based on this finding.

That is, the present invention provides (1) a complex in which an organic polymer compound and a metal oxide compound are chemically bonded, and wherein the metal oxide compound extends in a depth direction from the surface of the material. Organic having continuously changing component gradient structure
An inorganic composite gradient material, wherein as the organic polymer compound, (a) an ethylenically unsaturated monomer having a metal-containing group capable of bonding to a metal oxide by hydrolysis in a molecule;
(B) General formula (I) containing no metal

[0012]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² represents an epoxy group, a halogen atom or a hydrocarbon group having an ether bond. )) And (c) a metal-free general formula (II)

[0014]

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(Wherein R ³ is a hydrogen atom or a methyl group,
R ⁴ represents a hydrocarbon group. (2) an organic-inorganic composite gradient material characterized by using a product obtained by copolymerizing an ethylenically unsaturated monomer represented by the following formula (2): A coating agent characterized by being formed on a substrate, and (3) the organic compound
A structure having a coating made of an inorganic composite gradient material.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The organic-inorganic composite gradient material of the present invention is an organic-inorganic composite material containing a composite obtained by chemically bonding an organic polymer compound and a metal oxide compound, preferably the composite An organic-inorganic composite material comprising a body,
It has a component gradient structure in which the content of the metal oxide compound in the material changes continuously from the material surface in the depth direction.

Such a composition gradient structure can be 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 to form a film over time. It can be performed by measuring the content of carbon atoms and metal atoms on the surface by X-ray photoelectron spectroscopy or the like. Specifically, FIG. 1 shows that in Example 1 described later, a thickness of 0.09 μm provided on a polyethylene terephthalate film was used.
FIG. 3 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms in a coating film made of an organic-inorganic composite material (including silicon atoms as metal atoms). The surface of the coating film before sputtering is occupied by almost 100% of silicon atoms. However, as the film is abraded by sputtering, the content of silicon atoms on the film surface decreases, and carbon atoms are removed. The content increases and almost only carbon atoms are present on the substrate surface. That is, in this graded material,
It is shown that the content of the metal oxide compound in the material gradually decreases from the surface toward the substrate.

The organic-inorganic composite gradient material of the present invention is characterized in that it contains a composite in which a metal oxide compound is chemically bonded to an organic polymer compound. Can be easily formed by the method described in (1).

The metal oxide compound in the gradient material of the present invention is preferably one that can be formed by a sol-gel method. Such a metal oxide compound is selected from, for example, silicon, titanium, zirconium and aluminum. Oxide compounds of the metal to be used. These metal oxide-based compounds may contain one kind of metal, or may contain two or more kinds of metals.

The content of the metal oxide compound in the gradient material of the present invention is not particularly limited, but is usually 5 to 98% by weight, preferably 20 to 98% by weight in terms of metal oxide.
It is in the range of 98% by weight, particularly preferably 50-95% 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.

Further, the graded material of the present invention preferably has a thickness of 5 μm or less, particularly in the range of 0.01 to 1.0 μm, from the viewpoint of the gradient and the coating film performance.

Such an organic-inorganic composite gradient material can be efficiently produced by the following method. First, (A) an organic polymer compound 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, and (B) a metal by hydrolysis. A coating compound is prepared by mixing a polymer obtained by subjecting a metal compound capable of forming an oxide (hereinafter, sometimes referred to as a hydrolyzable metal compound) to a hydrolysis treatment.

The metal (A) is a metal-containing group capable of bonding to a metal oxide by hydrolysis in the organic polymer compound, and the metal (B) is a metal compound capable of forming a metal oxide by hydrolysis. As, for example, silicon,
Preferable examples include at least one selected from titanium, zirconium and aluminum.

In the present invention, the organic polymer compound having a metal-containing group capable of binding to a metal oxide by hydrolysis in the molecule as the component (A) includes, in the present invention, (a) An ethylenically unsaturated monomer having a metal-containing group capable of binding to an oxide, (b) a metal-free general formula (I)

[0025]

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(Wherein R ¹ is a hydrogen atom or a methyl group;
R ² represents an epoxy group, a halogen atom or a hydrocarbon group having an ether bond. )) And (c) a metal-free general formula (II)

[0027]

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(Wherein R ³ is a hydrogen atom or a methyl group,
R ⁴ represents a hydrocarbon group. The compound obtained by copolymerizing the ethylenically unsaturated monomer represented by the formula (1) is used.

In the ethylenically unsaturated monomer of the component (a), examples of the metal-containing group capable of bonding to a metal oxide by hydrolysis include, for example, a compound represented by the following general formula (III) -M ¹ R ⁵ _n-1 . III) wherein R ⁵ is a hydrolysable or non-hydrolysable group, at least one of which is hydrolyzed
(B) must be a component chemically bonded may hydrolyzable group, and when R ⁵ is plural, each R ⁵ may be the identical to each other, be different Well, M
¹ is silicon, titanium, zirconium, a metal atom such as aluminum, n represents a valence of the metal atom M ^1. )).

In the general formula (III), examples of the hydrolyzable group of R ⁵ which can be chemically bonded to the component (B) by hydrolysis include, for example, a halogen atom such as an alkoxyl group and a chlorine atom, an oxyhalogen group, An acetylacetonate group and the like are mentioned. On the other hand, as the non-hydrolyzable group not chemically bonded to the component (B), for example, a lower alkyl group is preferably mentioned.

The metal-containing group represented by the general formula (III) includes, for example, trimethoxysilyl, triethoxysilyl, tri-n-propoxysilyl, triisopropoxysilyl, tri-n-butoxy Silyl group, triisobutoxysilyl group, tri-sec-butoxysilyl group, tri-tert-butoxysilyl group, trichlorosilyl group, dimethylmethoxysilyl group, methyldimethoxysilyl group, dimethylchlorosilyl group, methyldichlorosilyl group, tritrisilyl group Methoxy 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-butoxy Titanium group, trichlorotitanium group Furthermore, trimethoxy zirconium based, triethoxy zirconium based, tri -
n-propoxy zirconium group, triisopropoxy zirconium group, tri-n-butoxy zirconium group, triisobutoxy zirconium group, tri-sec-butoxy zirconium group, tri-tert-butoxy zirconium group, trichloro zirconium group, or even, Dimethoxyaluminum group, diethoxyaluminum group, di-
Examples thereof include an n-propoxyaluminum 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.

Examples of the ethylenically unsaturated monomer having a metal-containing group capable of binding to a metal oxide by hydrolysis in the molecule as the component (a) include, for example, those represented by the general formula (IV):

[0033]

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(Wherein R ⁶ 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 ⁵ , M ¹ and n are the same as described above. And (meth) acrylic acid esters having an alkyl group containing a metal-containing group represented by formula (1) as an ester component.
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.

In the ethylenically unsaturated monomer represented by the general formula (I) of the component (b), the epoxy group represented by R ² , the halogen atom or the hydrocarbon group having an ether bond has a carbon number of Preferable examples 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. As the halogen atom of the above substituent, a chlorine atom and a bromine atom are preferable.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, various butyl, pentyl, hexyl, octyl, decyl and the like. Is mentioned. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group,
Examples of the aryl group having 6 to 10 carbon atoms such as cyclooctyl group include phenyl group, tolyl group, xylyl group, naphthyl group, and methylnaphthyl group, and examples of the aralkyl group having 7 to 10 carbon atoms. Examples 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 (I) include glycidyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate, 2- (3,4-epoxy) Cyclohexyl) ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-bromoethyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

In the ethylenically unsaturated monomer represented by the general formula (II) of the component (c), the hydrocarbon group represented by R ⁴ may be a linear or branched C 1-10 hydrocarbon group. An alkyl group, a cycloalkyl group having 3 to 10 carbon atoms,
Preferred are an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms. Specific examples of these hydrocarbon groups include those represented by R in the aforementioned general formula (I).
^The same groups as those exemplified in the description of ² can be given.

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

The organic polymer compound having a metal-containing group capable of being bonded to a metal oxide by hydrolysis in the molecule as the component (A) includes the components (a), (b) and (c).
The components can be obtained by a conventionally known method, for example, by radical copolymerization in the presence of a radical polymerization initiator. At this time, the component (b) is preferably used in a proportion of 1 to 100 mol% with respect to the component (c).

The metal compound (hydrolyzable metal compound) which can form a metal oxide by hydrolysis as the component (B) is, for example, a compound represented by the following general formula (V): M ² R ⁷ _m (V) , R ⁷ are a hydrolyzable group or a non-hydrolyzable group, at least two of which are hydrolyzable groups, and at least one is a hydrolyzable group capable of chemically bonding to the component (A) by hydrolysis. A plurality of R ^{7 s} may be the same or different; M ² is a metal atom such as silicon, titanium, zirconium and aluminum; and m is the valence of the metal atom M ² Is a metal compound represented by the following formula:

Examples of the hydrolyzable group of R ⁷ in the general formula (V) include an alkoxyl group, a halogen atom such as a chlorine atom, an oxyhalogen group, an acetylacetonate group and an isocyanate group. Preferred examples of the non-hydrolyzable group include a lower alkyl group, an aryl group, and an alkenyl group.

As the hydrolyzable metal compound, an oligomer derived from the metal compound represented by the general formula (V) or a mixture of a plurality of metal compounds represented by the general formula (V) is used. be able to. The above general formula (V)
As the metal compound represented by, a metal alkoxide is particularly preferable.

Examples of the metal alkoxide include tetramethoxysilane, tetraethoxysilane, tetra-n
-Propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraisocyanate silane, methyltrimethoxysilane, methyltriethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltriisocyanatesilane, phenyltriisocyanatesilane, etc. Corresponding to tetraalkoxytitanium, trialkoxytitanium, dialkoxytitanium and tetraalkoxyzirconium, trialkoxyzirconium, Turkey carboxymethyl zirconium,
Further, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, triisobutoxyaluminum, tri-sec-
Metal alkoxides such as butoxyaluminum and tri-tert-butoxyaluminum, or metal alkoxide oligomers, for example, commercially available alkoxysilane oligomers “methyl silicate 51”, “ethyl silicate 40” (all trade names manufactured by Colcoat Co., Ltd.), “ MS
-51 "and" MS-56 "(all manufactured by Mitsubishi Chemical Corporation). These may be used alone or in combination of two or more.

In the present invention, when a metal alkoxide is used as the component (B), the polymer compound of the component (A) and the metal compound of the component (B) are dissolved in an appropriate polar solvent such as alcohol, ketone or ether. The mixture of alkoxides is prepared by using an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid or a cation exchange resin as a solid acid, usually from 0 to 6%.
Hydrolysis at a temperature of 0 ° C., preferably 20 to 40 ° C., and in the case of using a solid acid, after removing it, and further, if necessary, distilling off or adding a solvent, which is suitable for coating. The viscosity is adjusted to prepare a coating solution. If the temperature is too low, the hydrolysis does not proceed, while if it is too high, the hydrolysis proceeds too much, and the gradient of the resulting gradient coating film may be reduced.

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, for example, anhydrous By adding magnesium sulfate or the like, a decrease in pot life can be prevented. In this case, the coating solution is used for coating after removing the dehydrating agent.

Next, using the coating solution thus obtained, a dried coating film, usually having a thickness of 5
μm or less, particularly for an intermediate film,
Dip coating method, spin coating method, spray coating method, bar coating method, knife coating method, roll coating method, blade coating method, so as to be in a range of from 1.0 to 1.0 μm, more preferably from 0.02 to 0.7 μm. The organic-inorganic composite gradient material of the present invention is obtained by forming a coating film by a known means such as a die coating method and a gravure coating method, and performing a known drying treatment, for example, heating and drying at a temperature of about 40 to 150 ° C. Can be

In the present invention, the hydrolyzable metal-containing group in the polymer compound of component (A) is subjected to hydrolysis treatment of a mixture of the component (A) and the hydrolyzable metal compound of component (B). Is hydrolyzed, and the hydrolyzable metal compound (B) is also hydrolyzed and partially polymerized. next,
By applying this coating solution to a substrate made of an organic material (sometimes referred to as an organic base material), a flexible polymer chain portion in the polymer compound of the component (A) is adsorbed on the substrate, and The hydrolyzed portion of the metal-containing group in the side chain is located away from the substrate. By heat-drying this coating film, the hydrolysis of the metal-containing group in the side chain further progresses, and the hydrolysis and polymerization of the hydrolyzable metal compound as the component (B) further progresses. The polymer compound and the metal oxide compound are formed by condensation (chemical bond) between the reactive group generated by the hydrolysis of the side chain, for example, the silanol group and the hydrolysis of the component (B) and the polymer. A chemically bonded complex forms. Therefore, the composite gradient material of the present invention is disclosed in JP-A-8-2834.
It is fundamentally different from the gradient composite described in JP-A-25.

In the composite gradient material of the present invention formed on the organic substrate in this manner, the content of the metal oxide compound in the material is almost 100% on the surface, but it is successive in the direction of the substrate. It decreases and becomes almost 0% near the substrate. That is, the composite gradient material of the present invention is generally composed of a film-like material formed on an organic substrate, and the surface of the film-like material that is in contact with the organic substrate is an organic polymer compound. The other open system surface is a metal oxide compound.

In the present invention, since the composite gradient material is formed by the above-described mechanism, the time required for the polymer chain portion to be adsorbed on the substrate made of an organic material after the formation of the coating film is a general time. It is important to maintain the liquid state for at least several seconds.

As the soluble solvent for the organic component and the soluble solvent for the inorganic component to be used, different solvents are usually used, and they need to have miscibility. In addition, in application by a coating machine or a spray method, etc., in order to obtain a good inclined structure without unevenness in thickness, in order to cause adsorption of a polymer compound before inorganic components condense with each other. Preferably, the evaporation point of the inorganic component-soluble solvent is higher than that of the organic component-soluble solvent. Note that a single solvent can be used as long as it can dissolve both the organic component and the inorganic component.

The substrate made of an organic material is not particularly limited. For example, an acrylic resin such as polymethyl methacrylate, a styrene-based resin such as polystyrene or ABS resin,
Olefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, 6-nylon and 6,
Substrates made of polyamide resins such as 6-nylon, polyvinyl chloride resins, polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins, polyimide resins, and cellulose resins such as cellulose acetate can be exemplified.

These substrates can be subjected to a surface treatment by an oxidation method, a roughening method, or the like, if desired, in order to further improve the adhesion to 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 substrate.

The substrate made of an organic material in the present invention may be made of a material other than an organic material, for example, a metal material, a glass or ceramic material, or a substrate made of various inorganic or metal materials. Those having a system coating film are also included.

The thus-obtained organic-inorganic composite gradient material of the present invention has excellent adhesiveness to an organic base material, has the above-mentioned excellent gradient, and (1) a substrate and an inorganic material. The inclination of the film can be arbitrarily and easily controlled by the property of relieving stress due to thermal contraction or physical expansion and contraction of the film, (2) the refractive index changes continuously, and (3) the mixing ratio of inorganic and organic components. (4) It is useful for various uses as a new functional material because it has properties such as the ability to control the surface structure during film formation by the form of the inorganic component.

The present invention also provides a coating agent for forming a coating comprising the organic-inorganic composite gradient material on a substrate. Examples of the coating agent include (A) an organic polymer compound having a metal-containing group capable of bonding to a metal oxide by hydrolysis in a molecule, and (B) a metal compound capable of forming a metal oxide by hydrolysis. And those comprising a coating solution obtained by subjecting a mixture of the above to hydrolysis treatment.

This coating film 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 5 μm or less, preferably 0.0 μm.
1 to 1.0 μm, more preferably 0.02 to 0.7 μm
Range.

The coating layer containing the inorganic or metal material is not particularly limited, and various coating 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 base material and the coat layer of the photocatalytically active material, the adhesion to the organic base material 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.

Further, the gradient material of the present invention can be interposed as an intermediate film between a metal base having an organic coating film on its surface and the photocatalytic active material layer. This intermediate film has excellent adhesion with an organic coating film, and has good adhesion with a coating layer of a photocatalytically active material, as well as the organic base material, and is hardly deteriorated by a photocatalytic action. The coating film can be sufficiently protected. 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.

Since the inorganic or metallic conductive material layer thus formed has insufficient adhesion to the organic substrate, the gradient material of the present invention is used as an intermediate film and the organic substrate and 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, etc. 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 of 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 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 reflective 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.

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.

[0080]

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 adhesion of the gradient film was evaluated according to the following method. (1) Adhesion I According to JIS K5400, a cross cut tape method was performed. 1 mm on the coating surface of each test piece with a rotary cutter
After 100 squares of squares are squared and Nichiban Cellotape (registered trademark) is pressed, 30,000 mm / mi
A 90 degree peel test was performed at a speed of n. The adhesion was evaluated by counting the presence or absence of peeling out of 100 squares.

(2) Adhesion II In the above (1), the adhesion was measured in the same manner as (1) except that the peeling test was performed at a speed of 500 mm / min instead of the speed of 30,000 mm / min. An evaluation was performed.

Example 1 20.0 g (0.2 mol) of methyl methacrylate, 2.48 g of γ-methacryloxypropyltrimethoxysilane
(0.01 mol) and glycidyl methacrylate
To 2 g (0.1 mol) of the mixed solution, 0.3 g (0.0018 mol) of 2,2'-azobisisobutyronitrile was added and stirred to obtain a homogeneous solution. When the solution was reacted at 75 ° C. for 3 hours with stirring, a polymer having a number average molecular weight in terms of polystyrene of 120,000 by gel permeation chromatography (GPC) was obtained.

On the other hand, 120 g of tetraethoxysilane
(0.58 mol) in 100 g of ethanol was added to 10 g of a 1 mol / liter nitric acid aqueous solution and 73 g of water.
g and 50 g of ethanol were slowly added dropwise while stirring. This solution was stirred at room temperature for 5 hours to obtain an inorganic component solution.

Next, 0.1 g of the above polymer was dissolved in 50 ml of methyl isobutyl ketone, and 10 ml of the inorganic component solution was added to this solution.
The solution diluted in milliliter was added with slow stirring to prepare a coating solution. This coating liquid was applied on a polyethylene terephthalate (hereinafter abbreviated as PET) film “T-60” (manufactured by Toray Industries, Inc., thickness: 50 μm) using a bar coater (wire diameter: 0.1 mm). Drying was performed in an oven at 80 ° C. for 24 hours. The thickness of the formed film was 0.07 μm.

The XPS device “PHI-5600” is applied to this film.
Using [ULVAC-PHI Co., Ltd.], the film was shaved by argon sputtering (4 kV), the content of carbon atoms and silicon atoms on the film surface was measured by X-ray photoelectron spectroscopy, and the gradient was measured. Examined. FIG. 1 is a graph showing the relationship between the sputtering time (related to the film depth) and the contents of carbon atoms and silicon atoms. From this figure, it can be seen that the film has a gradient.

The obtained film was immersed in 0.005 mol / liter ammonia water for 10 minutes, and then dried at room temperature for 2 hours to promote the condensation of the inorganic components and to densify. For this film, adhesion I and
II was evaluated. As a result, both adhesion I and II were 100
/ 100, indicating high adhesion.

Comparative Example 1 In Example 1, glycidyl methacrylate was not used, and the amount of methyl methacrylate was 30.0 g (0.3
Mol), polymerization was carried out in the same manner as in Example 1.
10,000 polymers were obtained. Hereinafter, the same operation as in Example 1 was performed to form a film on the PET film, and the gradient and the adhesion I and II were evaluated. FIG. 2 is a graph showing the relationship between the sputtering time and the contents of carbon atoms and silicon atoms. From this figure, it can be seen that the film has a gradient. The adhesions I and II were 0/100, 9 respectively.
4/100, and the adhesion was considerably inferior to Example 1.

Example 2 A coating solution prepared in Example 1 was coated on a polycarbonate sheet “Iupilon” (manufactured by Mitsubishi Engineering-Plastics Corporation, thickness 400 μm) with a bar coater (wire diameter 0.1 m).
m) and dried in an oven at 80 ° C. for 24 hours. The thickness of the formed film was 0.08 μm.
Hereinafter, in the same manner as in Example 1, the gradient and the adhesion I and II of the film were evaluated. FIG. 3 is a graph showing the relationship between the sputtering time and the contents of carbon atoms and silicon atoms. From this figure, it can be seen that the film has a gradient. Adhesion I and II were both 100/100, indicating high adhesion.

Then, a mixed gas of argon and oxygen (volume ratio: 99:90) was formed on the film thus obtained by using an oxide target composed of 90% by weight of indium oxide and 10% by weight of stannic oxide. 1) Under an atmosphere, a transparent conductive film having a thickness of 200 nm was formed using a DC magnetron sputtering apparatus (Shimadzu Corporation, HS-720) to produce a sheet with a transparent conductive film. This was also evaluated for adhesion I and II in the same manner. As a result, both were 100/100, indicating high adhesion.

Comparative Example 2 The procedure of Example 2 was repeated, except that the coating liquid prepared in Comparative Example 1 was used instead of the coating liquid prepared in Example 1, and the same operation as in Example 2 was carried out. A sheet with a conductive film was produced. The evaluation results of the adhesiveness of the gradient film before the formation of the conductive film were 100/100 for both the adhesiveness I and II, but after the formation of the conductive film, the adhesiveness I and II were 5/100 and 100, respectively.
/ 100, which was inferior to Example 2 in adhesiveness.

Comparative Example 3 Polymerization was carried out in the same manner as in Example 1 except that methyl methacrylate was not used and the amount of glycidyl methacrylate was changed to 42.6 g (0.3 mol). Performed to obtain a polymer. This polymer was insoluble in organic solvents and could not be used as a coating liquid.

Example 3 In Example 1, 14.2 g of glycidyl methacrylate was used.
Polymerization was carried out in the same manner as in Example 1 except that 2.97 g (0.02 mol) of 2-chloroethyl methacrylate was used instead of (0.1 mol), and the number average molecular weight in terms of polystyrene by GPC method was reduced. 80,000 polymers were obtained. Hereinafter, the same operation as in Example 1 was performed to form a film having a thickness of 0.07 μm on the PET film.
II was evaluated. FIG. 4 is a graph showing the relationship between the sputtering time and the contents of carbon atoms and silicon atoms. From this figure, it can be seen that the film has a gradient. The adhesiveness I and II are both 100/100,
High adhesion was shown.

Example 4 The coating liquid prepared in Example 1 was applied to a PET film “T
-60 "[manufactured by Toray Industries, Inc., 250 μm thick] with a spray gun" w-88 series "[manufactured by Iwata Corporation].
Coating was performed under the conditions of an air pressure of 0.2 MPa and an operation speed of 15 m / min, followed by drying in an oven at 80 ° C. for 24 hours to obtain a film having a thickness of 0.08 μm. This film was evaluated for gradient and adhesion I and II in the same manner as in Example 1. FIG. 5 is a graph showing the relationship between the sputtering time and the contents of carbon atoms and silicon atoms. From this figure, it can be seen that the film has a gradient. The adhesiveness I and II were both 100/100, indicating high adhesiveness.

[0095]

The organic-inorganic composite gradient material of the present invention is an organic-inorganic composite material containing a chemical bond of an organic polymer compound and a metal oxide compound. It has a component gradient structure in which the content continuously changes in the thickness direction of the material, and has excellent adhesion to organic substrates, and is used as a novel functional material for various applications, especially as a coating agent, for coatings and organic materials. It is suitable for an adhesive between an organic or inorganic or metallic material and an intermediate film interposed between an organic substrate and a coat layer containing an inorganic or metallic material.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms in an organic-inorganic composite film obtained in Example 1.

FIG. 2 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms in the organic-inorganic composite film obtained in Comparative Example 1.

FIG. 3 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms in the organic-inorganic composite film obtained in Example 2.

FIG. 4 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms in the organic-inorganic composite film obtained in Example 3.

FIG. 5 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms in the organic-inorganic composite film obtained in Example 4.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tadashi Koike 2-1-1, Yabuta Nishi, Gifu City, Gifu Prefecture Inside Ube Nitto Kasei Co., Ltd. (72) Norihiro Nakayama 2-1-1, Yabuta Nishi, Gifu City, Gifu Prefecture No. Ube Nitto Kasei Co., Ltd.

Claims (7)

[Claims] 1. A component gradient comprising a complex in which an organic polymer compound and a metal oxide compound are chemically bonded, wherein the metal oxide compound continuously changes from the surface of the material in the depth direction. An organic-inorganic composite gradient material having a structure, wherein as the organic polymer compound, (a) an ethylenically unsaturated monomer having a metal-containing group capable of bonding to a metal oxide by hydrolysis in a molecule, b) metal-free general formula (I) (Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an epoxy group, a halogen atom or a hydrocarbon group having an ether bond) and a metal (c) represented by the following formula: Not including general formula (II) (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrocarbon group.) A copolymer obtained by copolymerizing an ethylenically unsaturated monomer represented by the formula: Organic-inorganic composite gradient material. 2. The organic-inorganic composite gradient material according to claim 1, which has a thickness of 5 μm or less. 3. The organic-inorganic composite gradient material according to claim 1, wherein the metal oxide compound is obtained by hydrolytic polycondensation of a metal alkoxide. 4. Component (b) is added to component (c) in an amount of 1 to 1
The organic-inorganic composite gradient material according to claim 1, 2 or 3, which is copolymerized by using at a ratio of 00 mol%. 5. A film composed of a film formed on an organic substrate, and the surface of the film in contact with the organic substrate is substantially an organic polymer compound component, and the other The organic-inorganic composite gradient material according to any one of claims 1 to 4, wherein the open system surface is a metal oxide-based compound component. 6. A coating agent, wherein a coating comprising the organic-inorganic composite gradient material according to claim 1 is formed on a substrate. 7. A structure comprising a coating made of the organic-inorganic composite gradient material according to any one of claims 1 to 5.