JP2001240796A - Organic/inorganic hybrid-inorganic composite gradient material and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic/inorganic composite gradient material which has a component-gradient structure wherein the content of inorganic components continuously changes in the direction of the thickness of the material, generates little crack and may be formed on the surface of any kind of a substrate. SOLUTION: The organic/inorganic hybrid-inorganic composite gradient material having a component-gradient structure wherein the content of inorganic components continuously changes in the direction of the depth from the surface of the material, is formed using a coating liquid containing (a) tetraisocyanate silane and (b) an organosilicon compound of formula (I): R1nSi(OR2)4-n, wherein R1 is a (un) saturated non-hydrolyzable organic group; R2 is a 1-6C alkyl group; and n is an integer of 1-3 and/or its hydrolysate/condensate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organic-inorganic hybrid-inorganic composite gradient material and its use. More specifically, the present invention has a component gradient structure in which the content of the inorganic component changes continuously and relatively slowly in the thickness direction of the material, has good flexibility, and has a large film thickness. Organic-inorganic hybrid that is hardly cracked or cracked, and can be formed on the surface of any type of substrate regardless of the type of the substrate, and is useful as a functional material for various applications.
The present invention relates to an inorganic composite gradient material, a coating agent for forming a film composed of the gradient material, and a structure having a film composed 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. 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 in which the composition of the material is changed little by little and which has completely different properties between the front and back sides, has attracted attention. For example, metal-ceramics having both the heat resistance of ceramics and the strength of metals Composite functionally graded 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. However, since the gradient material is formed by utilizing the ability of the polymer portion to adsorb to the base material, the base material is limited to a material whose surface is at least made of an organic material.
When the thickness of the gradient material is large, cracks and the like may occur.

[0007]

SUMMARY OF THE INVENTION Under such circumstances, the present invention has a component gradient structure in which the content of an inorganic component continuously changes in the thickness direction of a material, and has good flexibility. Organic-inorganic useful for various applications as a functional material that can be formed on the surface irrespective of the type of the base material, without causing cracks and cracks even when the film thickness is large. It is an object of the present invention to provide a composite gradient material and its use.

[0008]

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 tetraisocyanatosilane, an organosilicon compound having a specific structure, a partial hydrolyzate thereof, and a hydrolyzate thereof have been obtained. By using a coating liquid containing an oligomer that is a decomposition condensate, an organic-inorganic hybrid-inorganic composite gradient material can be formed on the surface of the substrate regardless of the type of the substrate, and this has a gradient structure. The present inventors have found that they are relatively gentle, have good flexibility, and are unlikely to cause cracks and cracks even when the film thickness is large, and have completed the present invention based on this finding.

That is, the present invention provides (1) a component gradient structure in which the content of an inorganic component in a material continuously changes from the surface of the material in the depth direction, and (a) tetraisocyanatosilane and , (B) general formula (I) R ¹ nSi (OR ² ) _4-n (I) (wherein, R ¹ is a saturated or unsaturated, non-hydrolyzable organic group, and R ² is a C 1 to C 6) alkyl group, n is an integer of 1 to 3, when R ¹ is a plurality, the plurality of R ¹ may be the same with or different from each other, if the OR ² there is a plurality, the plurality of OR ² are mutually They may be the same or different.)
An organic-inorganic hybrid formed using a coating liquid containing at least one selected from the group consisting of an organosilicon compound represented by the following formula, a partial hydrolyzate of the compound, and an oligomer that is a condensate thereof: Inorganic composite gradient material,
(2) a coating agent characterized by forming a film made of the above-mentioned organic-inorganic hybrid-inorganic composite gradient material on a substrate; and (3) the above-mentioned organic-inorganic hybrid-
A structure having a coating made of an inorganic composite gradient material.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Organic-Inorganic Hybrid of the Present Invention
The inorganic composite gradient material has a component gradient structure in which the content of the inorganic component in the material changes continuously from the surface of the material in the depth direction, and the intermediate layer contains an organic-inorganic hybrid. The surface layer is substantially composed of silicon oxide, and has a feature that the content of the inorganic component relatively gradually decreases as approaching the substrate and the content of the organic compound component increases.

[0011] Such a gradient component structure is confirmed, for example, by sputtering the surface of the coating film of the organic-inorganic hybrid-inorganic composite gradient material provided on the substrate and shaving the film, and with time. It can be carried out by measuring the content of carbon atoms and metal atoms by X-ray photoelectron spectroscopy or the like. Specifically, FIG. 1 shows that in Example 1 described later, a thickness of 0.12 μm provided on a polyethylene terephthalate film was used.
FIG. 4 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 hybrid-inorganic composite material (including silicon atoms as metal atoms). In addition, the surface of the coating film before sputtering is occupied by nearly 90% of silicon atoms. When the sputtering time exceeds about 35 minutes after the content of carbon atoms increases, the film surface becomes almost only carbon atoms.

That is, it is shown that in this graded material, the content of the inorganic component in the material is gradually reduced from the surface toward the substrate. In the organic-inorganic hybrid-inorganic composite gradient material of the present invention having such a component gradient structure, the content of the inorganic component is not particularly limited, but the silicon atom content in all elements is usually 1 to 4.
The range is 5% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 35% by weight. Further, the gradient material of the present invention has a thickness of 5 μm or less, particularly 0.01 to 1.0.
Those having a size in the range of μm are preferred from the viewpoint of the gradient and the coating film performance.

Such an organic-inorganic hybrid-inorganic composite gradient material can be efficiently produced by the following method. First, (a) tetraisocyanatosilane and (b) a general formula (I) R ¹ nSi (OR ² ) _4-n ... (I) (wherein, R ¹ is a saturated or unsaturated non-hydrolysable organic compound) group, R ² is an alkyl group having 1 to 6 carbon atoms, n is an integer of 1 to 3, when R ¹ is a plurality, the plurality of R ¹ may be the same with or different from each other, OR ² is more In some cases, the plurality of OR ² may be the same or different.)
A coating liquid containing at least one selected from the group consisting of an organosilicon compound represented by the formula (1), a partial hydrolyzate of the compound and an oligomer which is a condensate thereof is prepared.

In the organosilicon compound represented by the general formula (I), the saturated or unsaturated non-hydrolysable organic group represented by R ¹ includes, for example, an alkyl group having 1 to 20 carbon atoms, A) an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms having an acryloyloxy group or an epoxy group. Here, the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and the alkyl group may be any of linear, branched and cyclic. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, cyclopentyl. Group, cyclohexyl group and the like. As the alkyl group having 1 to 20 carbon atoms having a (meth) acryloyloxy group or an epoxy group, the alkyl group having 1 to 1 carbon atoms having the above substituent
An alkyl group of 0 is preferable, and this alkyl group may be linear, branched, or cyclic. Examples of the alkyl group having the substituent include a γ-acryloyloxypropyl group, a γ-methacryloyloxypropyl group, a γ-glycidoxypropyl group, and a 3,4-epoxycyclohexyl group. The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, and the alkenyl group may be linear, branched,
Any of a ring shape may be sufficient. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a hexenyl group, an octenyl group and the like. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. The aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.

On the other hand, the alkyl group having 1 to 6 carbon atoms represented by R ² may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group and an n-propyl group. Group, isopropyl group, n-butyl group, isobutyl group,
sec-butyl group, tert-butyl group, pentyl group,
Examples include a hexyl group, a cyclopentyl group, and a cyclohexyl group.

N is an integer of 1 to 3; when there are a plurality of R ^{1 s} , each R ¹ may be the same or different, and when there are a plurality of OR ² , ² may be the same or different.

Examples of the organosilicon compound represented by the general formula (I) include, for example, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane , Vinyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane and the like.

In the present invention, as the above-mentioned component (b), these organosilicon compounds may be used, a partial hydrolyzate thereof may be used, and an oligomer which is a hydrolytic condensate thereof may be used. Is also good. Alternatively, a mixture thereof can be used.

The content ratio of the component (a) and the component (b) in the coating liquid has a desired component gradient structure,
From the viewpoint that a graded material having good flexibility and hardly causing cracks and cracks can be formed, the molar ratio is preferably 10%.
0:10 to 100: 500, more preferably 100: 2
0 to 100: 450, more preferably 100: 30 to
It is selected in the range of 100: 400.

An organic solvent is usually used for the coating liquid,
The organic solvent is not particularly limited as long as it can dissolve the components (a) and (b) and is inert to them. Such solvents include, for example, hexane, heptane, aliphatic hydrocarbon solvents such as octane, toluene, aromatic hydrocarbon solvents such as xylene, ethyl acetate, butyl acetate, ester solvents such as cellosolve acetate, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone can be exemplified. These solvents may be used alone or as a mixture of two or more.

The above-mentioned components (a) and (b) are added to these solvents at predetermined ratios, respectively, and are uniformly dissolved to obtain a coating liquid for forming a gradient material according to the present invention. The solid content concentration in this coating liquid may be any concentration so that the coating liquid has a viscosity that allows coating.
There is no particular limitation.

Next, using the coating liquid thus obtained, the thickness of the dried coating film on the substrate is usually 5 μm or less, particularly 0.01 to 1. 0μ
m, more preferably in the range of 0.02 to 0.7 μm, dip coating, spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, A coating film is formed by a known means such as a gravure coating method, and if necessary, a known drying treatment, for example, a heat drying treatment at a temperature of about 30 to 150 ° C., and further curing by humidification at a humidity of 80% or more. Thus, the organic-inorganic hybrid-inorganic composite gradient material of the present invention is obtained.

Although the reason why the inclined structure is formed is not always clear, it is presumed that the reason is as follows. After applying the coating solution to the substrate, first, highly reactive tetraisocyanatosilane reacts with moisture in the air on the surface of the coating solution to form a silica film on the surface, and the solvent is further volatilized. At the same time, the tetraisocyanatosilane forms a siloxane network due to the moisture in the air.
At that time, the amounts of the solvent and the organosilicon compound are increased from the side closer to the substrate of the coating film, and a gradient distribution is generated. further,
When moisture or the like infiltrates, the organosilicon compound is hydrolyzed and polycondensed by the catalytic action of ammonia produced as a result of the reaction between tetraisocyanatosilane and moisture, and chemically bonds in the siloxane network, Be fixed. Finally, the target organic-inorganic hybrid-inorganic composite gradient material is formed by evaporating the residual solvent by drying.

The substrate is not particularly limited, and a substrate made of glass, ceramics, metal, an organic polymer compound or the like can be used. Examples of the substrate made of the organic polymer compound include acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene and ABS resin, olefin resins such as polyethylene and polypropylene, and polyester resins such as polyethylene terephthalate and polyethylene naphthalate. Resins, polyamide resins such as 6-nylon and 6,6-nylon, polyvinyl chloride resins, polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins, polyimide resins, cellulose resins such as cellulose acetate, etc. Substrates.

The substrate made of these organic polymer compounds can be subjected to a surface treatment by an oxidation method or a concavo-convex method, 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 the like.
Examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of the base material.

Examples of the substrate made of metal include substrates made of aluminum, brass, stainless steel, magnesium alloy, iron, copper and the like. As for these metal substrates, those subjected to a known surface treatment may be used. Further, a composite material of these metal materials on the surface of a different kind of base material (polymer material, other inorganic material, ceramic material) can also be used.

In the thus obtained organic-inorganic hybrid-inorganic composite gradient material of the present invention, the surface layer is almost composed of silicon oxide, and the content of the inorganic component decreases relatively gradually as the material approaches the substrate. And a graded structure in which the content of the organic compound component increases.

That is, the organic-inorganic hybrid-inorganic composite gradient material of the present invention generally comprises a film-like material formed on a substrate, and substantially has a surface in contact with the substrate of the film-like material. Is a component containing an organic-inorganic hybrid and an inorganic oxide, and the other open surface is an inorganic oxide component. In addition, since the intermediate layer is composed of a component containing an organic-inorganic hybrid and an inorganic oxide and has good flexibility, cracks and cracks are unlikely to occur even when the film thickness is large.

The present invention also relates to the organic-inorganic hybrid
Another object of the present invention is to provide a coating agent for forming a coating made of an inorganic composite gradient material on a substrate. Examples of the coating agent include: (a) tetraisocyanatosilane; (b) an organosilicon compound represented by the general formula (I); a partial hydrolyzate of the compound; and an oligomer which is a condensate thereof. What consists of a coating liquid containing at least one selected is used.

This coating agent can be used for the following applications. First, it is used for application as a coating film.
The organic-inorganic hybrid-inorganic composite gradient material has excellent adhesiveness to a substrate, and the surface of the coating film has the property of silicon oxide, so that, for example, a coating layer made of the material is provided on various plastic films. This makes it possible to obtain a hard coat film having excellent scratch resistance, heat resistance, and the like and good adhesion.

Further, by providing a coat layer made of the above-mentioned material on a metal substrate, scratch resistance, weather resistance, corrosion resistance,
Stain resistance can be imparted.

Next, it is used for use as an adhesive.
The gradient material of the present invention has excellent adhesion to the substrate as described above, and also has excellent adhesion to inorganic or metal materials because the surface is a silicon oxide. Therefore,
It is suitable as an adhesive between various materials and an inorganic or metal material.

Further, it is used for 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 coating 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 intermediate film is usually 5 μm or less, preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.7 μm. 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, and (2) an inorganic or metal conductive material. Preferred examples include a layer, (3) a hard coat layer containing an inorganic or metallic material, and (4) an inorganic or metallic optical recording material layer or an inorganic or metallic dielectric layer.

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 adhesiveness to the organic substrate is excellent, and the surface is substantially made of silicon oxide. Therefore, the adhesiveness between the photocatalytically active material and the coat layer is good, and the intermediate film is not easily deteriorated 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 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 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.

Since the thus formed hard coat layer containing an inorganic or metallic material has insufficient adhesion to an organic substrate, the hard coat layer containing the gradient material of the present invention is used as an intermediate film to form an organic substrate. 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 features such as rewritable, high-density, large-capacity storage capacity, and non-contact with a 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 light-transmitting 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 hybrid-inorganic composite gradient material. As such a structure, for example, various substrates having a coating layer containing at least an inorganic or metal material and an organic-inorganic hybrid-inorganic composite gradient material of the present invention interposed as an intermediate film, or the composite gradient An article having a coating layer containing at least an inorganic or metal material with a material interposed therebetween as an intermediate film 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 photocatalytically 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.

[0054]

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 following methods. (1) Gradient Argon sputtering (4 kV) using an XPS apparatus “PHI-5600” (manufactured by ULVAC-PHI, Inc.)
Was applied at 3 minute intervals to scrape the film, and the content of carbon atoms and silicon atoms (or aluminum atoms in the case of an aluminum film) on the film surface was measured by X-ray photoelectron spectroscopy to examine the inclination.

(2) Surface water contact angle The surface water contact angle was measured using a contact angle meter “G-1” (manufactured by Elma Sales Co., Ltd.).

(3) Flexibility Using a stainless steel rod having a diameter of 6 mm, bending the coated surface to the outside, holding it for 10 seconds, observing the bent portion with a scanning electron microscope (SEM), and cracking or peeling. Was checked and the flexibility was evaluated according to the following criteria. ：: No cracking or peeling occurred. ×: Cracking is observed.

Example 1 In a 100 ml plastic container, 1.75 g of γ-methacryloxypropyltrimethoxysilane (0.
007 mol) and 1.38 g of tetraisocyanatosilane
(0.007 mol), and 50 ml of toluene was added thereto to prepare a uniform coating solution. Next, polyethylene terephthalate having a thickness of 0.188 mm (hereinafter, referred to as polyethylene terephthalate)
Abbreviated as PET. ) Film "Lumirror T-60"
On the [Toray Industries, Ltd.], apply the above coating solution with a wire diameter of 0.125 m.
m, coated with a stainless steel bar around which a stainless steel wire is wound.
A μm film was formed. Table 1 shows the evaluation of the surface water contact angle and the flexibility of this film.
2 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms.

Example 2 Example 1 was the same as Example 1 except that a 0.1 mm-thick aluminum film (hereinafter abbreviated as aluminum film) was used as the substrate instead of the PET film.
In the same manner as in the above, a film having a thickness of 0.12 μm was formed. The evaluation of the surface water contact angle and flexibility of this film is shown in Table 1, and the inclination is shown in FIG. 2 in a graph showing the relationship between the sputtering time and the content of carbon, silicon and aluminum atoms. Show.

Example 3 In Example 1, an aluminum film having a thickness of 0.1 μm was used as a substrate instead of a PET film, and a spray gun “w-88 series” [Anest Iwata Co., Ltd.
A film having a thickness of 0.14 μm was formed in the same manner as in Example 1 except that the coating was performed at an air pressure of 0.2 MPa. The evaluation of the surface water contact angle and flexibility of this film is shown in Table 1, and the inclination is shown in FIG. 3 in a graph showing the relationship between the sputtering time and the content of carbon, silicon and aluminum atoms. Show.

Example 4 A 100 ml plastic container was charged with 2.4 g (0.0121 mol) of phenyltrimethoxysilane, and 0.22 ml of 1 mol / l nitric acid (water: 0.0122 mol) was added thereto. The mixture was slowly added with stirring, and stirred for 5 hours to partially hydrolyze. Next, to this solution, a solution in which 2.8 g (0.0143 mol) of tetraisocyanatosilane was dissolved in 50 ml of ethyl acetate was added to prepare a uniform coating solution.

Next, the above coating liquid was sprayed on an aluminum film having a thickness of 0.1 mm using a spray gun “w-88 series”.
Air pressure 0.2MP by [Anest Iwata Co., Ltd.]
After coating in a, the film was heated and dried at 80 ° C. overnight to form a film having a thickness of 0.14 μm. The evaluation of the surface water contact angle and flexibility of this film is shown in Table 1, and the inclination is shown in FIG. 4 in a graph showing the relationship between the sputtering time and the content of carbon, silicon and aluminum atoms. Show.

COMPARATIVE EXAMPLE 1 A 100 ml plastic container was charged with 2.76 g (0.0141 mol) of tetraisocyanatosilane.
To this, 50 ml of toluene was added to prepare a uniform coating solution. Next, the above coating solution was coated on a 0.188 mm-thick PET film "Lumirror T60" (manufactured by Toray Industries, Inc.) using a stainless steel bar around which a stainless steel wire having a wire diameter of 0.125 mm was wound. For one night to form a film having a thickness of 0.13 μm. The evaluation of the surface water contact angle and flexibility of this film is shown in Table 1, and the inclination is shown in FIG. 5 in a graph showing the relationship between the sputtering time and the content of carbon, silicon and aluminum atoms. Show.

Comparative Example 2 In Comparative Example 1, an aluminum film having a thickness of 0.1 μm was used as a substrate instead of a PET film, and a spray gun “w-88 series” [Anest Iwata Co., Ltd.]
A film having a thickness of 0.14 μm was formed in the same manner as in Comparative Example 1 except that the coating was performed at an air pressure of 0.2 MPa. The evaluation of the surface water contact angle and the flexibility of this film is shown in Table 1, and the inclination is shown in FIG. 6 in a graph showing the relationship between the sputtering time and the content of carbon, silicon and aluminum atoms. Show.

[0065]

[Table 1]

As can be seen from Table 1, cracks and peeling were not observed in the films of Examples 1 to 4 in the evaluation test of the flexibility. However, in each of Comparative Examples 1 and 2, cracks occurred. confirmed. Further, Examples 1 to 4 and Comparative Example 1,
Sample No. 2 has a surface water contact angle of 38 to 42 °, which is the same level as that of silica, and it can be seen that the film surface is substantially silica. Furthermore, it can be seen from FIGS. 1 to 6 that the films of Examples 1 to 4 have a gently inclined structure. On the other hand, it can be seen that Comparative Example 1 has a substantially two-layer structure, while Comparative Example 2 has a substantially single-layer structure, and none of them has a tilted structure.

[0067]

The organic-inorganic hybrid-inorganic composite gradient material of the present invention has a component gradient structure in which the content of the inorganic component changes continuously and relatively slowly in the thickness direction of the material, and has good flexibility. It has a property and is hard to generate cracks and cracks even when the film thickness becomes large. Further, it can be formed on the surface of the substrate regardless of the kind of the substrate, and is useful for various uses as a functional 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, silicon and aluminum atoms in the organic-inorganic composite film obtained in Example 2.

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

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

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 Comparative Example 1.

FIG. 6 is a graph showing the relationship between the sputtering time and the content of carbon atoms, silicon atoms and aluminum atoms in the organic-inorganic composite film obtained in Comparative Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C09J 1/00 C09J 1/00 175/04 175/04 (72) Inventor Eisuke Tachibana Gifu City, Gifu Prefecture 2-1-1 Yabuta Nishi Ube Nitto Kasei Co., Ltd. F-term (reference) 4F100 AA00C AH06B AH06K AK42A AK52B AK52K AT00A BA03 BA07 BA10B BA10C GB07 GB31 GB32 GB41 GB66 JB04 JD08 JK14 YY00B4CA01CA01 CA01 LB01 4J038 AA011 DG181 DG291 HA441 MA09 NA03 NA05 NA11 NA12 NA14 4J040 AA011 EF171 EF311 HA301 JA09 LA06 MA01 MA02

Claims (6)

[Claims] 1. A component gradient structure in which the content of an inorganic component in a material continuously changes in the depth direction from the surface of the material,
And (a) tetraisocyanatosilane and (b) a general formula (I) R ¹ nSi (OR ² ) _4-n ... (I) (wherein, R ¹ is a saturated or unsaturated, non-hydrolysable organic group. , R ² is an alkyl group having 1 to 6 carbon atoms, n is an integer of 1 to 3, when R ¹ is a plurality, the plurality of R ¹ may be the same with or different from each other, OR ² there are a plurality of In this case, a plurality of OR ² may be the same or different.)
An organic-inorganic hybrid formed using a coating liquid containing at least one selected from the group consisting of an organosilicon compound represented by the following formula, a partial hydrolyzate of the compound, and an oligomer that is a condensate thereof: Inorganic composite gradient material. 2. The gradient organic-inorganic hybrid-inorganic composite material according to claim 1, which has a thickness of 5 μm or less. 3. The organic-inorganic hybrid-inorganic composite according to claim 1, wherein the coating liquid contains the component (a) and the component (b) in a molar ratio of 100: 10 to 100: 500. Graded material. 4. A film comprising a film formed on a substrate, and a surface of the film which is in contact with the substrate is a component containing an organic-inorganic hybrid and an inorganic oxide, The organic-inorganic hybrid-inorganic composite gradient material according to claim 1, 2 or 3, wherein the other open system surface is an inorganic oxide component. 5. A coating agent, wherein a coating comprising the organic-inorganic hybrid-inorganic composite gradient material according to any one of claims 1 to 4 is formed on a substrate. 6. A structure comprising a coating comprising the organic-inorganic hybrid-inorganic composite gradient material according to any one of claims 1 to 4.