JP2003291251A - Composite material and method for manufacturing the material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite material which shows outstanding gas barrier properties, and high flexure resistance and Gelbo resistance. <P>SOLUTION: A metallic film and/or a metallic oxide film with a thickness of b1 are formed on at least one, of the main surfaces of a support, which has a maximum height of 100 nm or less and is smooth, is formed so that the relationship of b1>a (a is a maximum height of the smooth surface) is satisfied. Alternatively, a metallic film and/or a metallic compound film which have a thickness of b2 and b3 respectively, are formed on both main surfaces of said support so that the relationship of (b2+b3)>a is satisfied. Consequently, it is possible to obtain the composite material with improved gas barrier properties. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite material having a gas barrier property which can be used as a packaging material, an outer packaging material for a vacuum heat insulating material, a sealing film for an organic EL element, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, composite materials (or highly functional thin films)
The technological development of is remarkable, and its application fields are diverse. As an example of the composite material, a composite material having a gas barrier property (hereinafter, also simply referred to as “gas barrier composite material”) is known. The gas-barrier composite material is a material having a gas-barrier property formed by forming a dense gas barrier layer on the surface of a support such as a plastic film by vapor deposition or the like.

As a gas barrier composite material, a composite material is known in which an aluminum layer is formed as a gas barrier layer on the surface of a plastic film. Due to its low production cost, this composite material is mainly used in the field of food packaging.

As another gas barrier composite material, a composite material is known in which a vinylidene chloride or ethylene-vinyl alcohol copolymer layer is formed as a gas barrier layer on the surface of a plastic film by a wet coating method.
This composite material is characterized by being inexpensive, highly flexible, and transparent, and is mainly used in the field of food packaging.

As yet another gas barrier composite material,
As a gas barrier layer on the surface of the plastic film,
It is known that a thin film of an inorganic oxide such as silicon oxide or aluminum oxide is formed. This composite material has excellent transparency and is used as a transparent packaging material for packaging foods, pharmaceuticals, and electronic parts.

As described above, these gas barrier composite materials are used not only as a packaging material for foods or the like, but also as an outer packaging material for a vacuum heat insulating material and a sealing film for an organic EL element.

[0007] The vacuum heat insulating material is a heat insulating material formed by vacuum-packing a porous core material having open cells with an outer packaging material having gas barrier properties. The vacuum heat insulating material is one in which the internal vacuum layer exhibits heat insulating properties. Since the vacuum heat insulating material exhibits excellent heat insulating performance even when thin, it is useful as a heat insulating material for refrigerators and houses. In addition, the sealing film of the organic EL element is provided for the purpose of preventing alteration of the materials forming the organic material layer (including the organic light emitting layer), the anode and the cathode.

[0008]

The gas barrier properties required for the gas barrier composite material differ depending on the application. For example, gas barrier composite materials may be used as vacuum insulation materials and organic E
When used as a constituent element of an L element, higher gas barrier properties are required as compared with when used as a food packaging material.

Further, the disadvantage caused by the low gas barrier property of the composite material depends on the application. For example, in order to store an object in a specific gas atmosphere, the object may be packaged with a gas barrier composite material and a gas having a specific composition may be enclosed. In that case, if the gas barrier property of the composite material is small, the composition of the internal gas may change over time, which may adversely affect the object to be packaged.

When the gas barrier composite material is used as an outer packaging material for a vacuum heat insulating material, if the gas barrier property of the composite material is small, the internal pressure increases with time. As a result, the heat insulating performance of the vacuum heat insulating material deteriorates.

When the gas barrier composite material is used as a sealing film for an organic EL element, if the gas barrier property of the composite material is small, moisture (water vapor) in the atmosphere diffuses into the organic material layer with the passage of time and becomes organic. Material deteriorates. As a result, a non-light emitting area is generated. Occurrence of non-emission area
The life of the device is shortened, and when the device is used as a display panel, the image quality is deteriorated.

[0012] As described above, the gas barrier property of the gas barrier composite material affects the quality of the product manufactured by using it, and therefore it is desirable that the gas barrier property is as high as possible, and it is desirable that it does not change over a long period of time. for that reason,
In any of the fields, composite materials with further improved gas barrier properties are required.

The gas barrier property can be improved by increasing the thickness of the gas barrier layer such as aluminum formed on the surface of the plastic film. However, when the thickness of the gas barrier layer is increased, the flexibility of the composite material as a whole is reduced. If the bending resistance of the composite material is low, it may hinder processes such as laminating, bag making, and printing. Further, when the thickness of the gas barrier layer is increased, cracks are easily generated in the layer, and the gelbo resistance of the composite material is deteriorated. Composite materials with low gelbo resistance have the disadvantages of poor workability and limited shape.

Further, it is required for the gas barrier composite material that the gas barrier property does not deteriorate even at high temperature, that is, the retort property. A composite material in which the gas barrier layer is vinylidene chloride or an ethylene-vinyl alcohol copolymer tends to have a reduced gas barrier property when subjected to a high temperature treatment or when exposed to a high temperature atmosphere. Do not meet.

The gas barrier properties of a composite material using a layer of silicon oxide or aluminum oxide as a gas barrier layer do not deteriorate even after being subjected to high temperature treatment. However, its gas barrier property is generally inferior to that of a composite material having an aluminum layer as a gas barrier layer. Further, the cost required for forming the silicon oxide layer tends to be high. In contrast, a layer of aluminum oxide can be formed at a lower cost than a layer of silicon oxide. However, composite materials having a layer of aluminum oxide generally have poor flex resistance. This is because aluminum oxide is brittle.

As described above, the gas barrier composite material is required to have more excellent gas barrier properties and bending resistance. Further, the gas barrier composite material is required to have retort properties, flex resistance and gelbo resistance. Moreover, there is also a need to manufacture such composite materials at lower costs. In particular, since the development of vacuum heat insulating materials and organic EL devices is rapidly progressing, there is an urgent need to develop a composite material having high gas barrier properties suitable for them. The present invention has been made in view of such circumstances, and an object of the present invention is to provide a composite material having more excellent gas barrier properties.

[0017]

In order to solve the above-mentioned problems, as a result of studies by the present inventors, the gas barrier property of the composite material is such that the surface smoothness of the support forming the gas barrier layer is enhanced and the gas barrier layer The inventors have found that the thickness can be improved by appropriately selecting the thickness according to the roughness of the surface of the support, and have completed the present invention. The present invention will be described below.

In the present specification including the following description, with respect to the constitution of the composite material, the “surface” of each film (or layer) constituting the composite material means a surface exposed when each film is formed. That is, the surface of each membrane farther from the support is meant. With respect to the constitution of the composite material, the term "on" of each film constituting the composite material means "on the surface far from the support" of each film unless otherwise specified. Therefore, for example, "on the XX membrane" means "at a position adjacent to the surface of the XX membrane remote from the support". Further, the “main surface” refers to the two facing sheet-like members.
The two broad surfaces are sometimes called simply "surfaces".

The first composite material according to the present invention is a composite material having a gas barrier property, in which a metal and / or metal compound film having a thickness b1 is formed on one main surface of a support. And the maximum height of the main surface of the support on which the metal and / or metal compound film is formed is 1
A smooth surface having a thickness of 00 nm or less, the maximum height a of the smooth surface and the thickness b1 of the metal and / or metal compound film
Are composite materials satisfying the relationship of b1> a.

In the composite material of the present invention, at least one main surface of the support is a smooth surface having a maximum height of 100 nm or less, and a metal and / or a metal as a gas barrier layer is formed on the smooth surface. It is characterized in that the compound film is formed so that the thickness b1 thereof is larger than the maximum height a of the smooth surface. Due to this feature, the number of pinhole-like defects generated in the metal and / or metal compound film can be reduced. Therefore, the composite material of the present invention has a high gas barrier property and is high over a long period of time. The gas barrier property is maintained.

Here, the "gas barrier property" refers to the property of the composite material impeding the permeation of various gases. Gas permeation is hindered by the composite material of the present invention, for example, CO _{2,
N 2, O 2, H 2} , He, and an _{H 2} O.

The support constituting the composite material of the present invention comprises 2
A sheet-like member having two main surfaces, and at least one of the main surfaces is a smooth surface having a maximum height of 100 nm or less. That is, at least one surface of the support constituting the composite material of the present invention does not have high protrusions, and minute protrusions are present. In this specification, a surface having a maximum height of 100 nm or less may be simply referred to as “smooth surface”. As long as at least one main surface is such a smooth surface, the smoothness of the other main surface is not particularly limited. The other major surface may be, for example, a rough surface with a maximum height exceeding 100 nm. Preferably, the two major surfaces of the support are both smooth surfaces. The support is preferably an organic polymer film.

In the present specification, "maximum height" means J
The maximum height Ry defined in IS B0601. The maximum height is one of the parameters representing the surface roughness. The maximum height can be measured according to JIS B0601, for example, using an atomic force microscope.
As the atomic force microscope, for example, SPI3800 manufactured by Seiko Instruments Inc. is used.

In the composite material of the present invention, metal and / or
Alternatively, the metal compound film acts as a gas barrier layer. The term "metal and / or metal compound film" includes a metal film, a metal compound film, and a film composed of a metal and a metal compound (including a film in which a metal film and a metal compound film are laminated). Used to include. The term "metal and / or metal compound film" is used in consideration of the fact that a film formed as a metal film may inevitably include its oxide or the like (that is, a metal compound). Membrane-formed composite materials are also used to indicate that they are within the scope of the invention. Metal compounds include metal oxides such as aluminum oxide and silicon oxide, metal oxynitrides such as silicon oxynitride, and metal nitrides such as silicon nitride. Note that in the context of the present invention, silicon is included in "metal".

When the metal and / or metal compound film is formed on the surface of the support by a vapor deposition method, particularly a physical vapor deposition method,
If the protrusions are present on the surface of the support, the metal and / or the metal compound tends to be insufficiently attached to the shadowed portions of the protrusions. This insufficient adhesion becomes more remarkable as the height of the protrusion increases. The portion where the metal and / or the metal compound is insufficiently adhered becomes a pinhole-like defect portion, which deteriorates the gas barrier property of the composite material. Since the composite material of the present invention has a film of a metal and / or a metal compound formed on a smooth surface of a support, the generation of pinhole-like defects due to high protrusions is effectively suppressed, It is considered that this improves the gas barrier property.

Even on the smooth surface of the support, the adhesion of the metal and / or the metal compound tends to be insufficient in the shadow of the fine protrusions. In order to suppress this insufficient adhesion, in the composite material of the present invention, the thickness b1 of the metal and / or metal compound film is made larger than the maximum height a of the smooth surface. It is considered that suppressing insufficient adhesion suppresses the generation of defective portions, thereby ensuring higher gas barrier properties. Thus, with a support having a smaller maximum smooth surface height, the film thickness of the metal and / or metal compound can be smaller. By reducing the thickness of the metal and / or metal compound film, the bending resistance of the entire composite material is improved. If the thickness of the metal and / or metal compound film is small, cracks are less likely to occur and the gelbo resistance is improved.

As used herein, the thickness of a metal and / or metal compound film is the horizontal distance from the mean line of the surface of the support on which it is formed to the surface of the metal and / or metal compound film. Equivalent to. Here, the average line of the surface is the average line m defined in JIS B0601.
Equivalent to. Therefore, when the relationship of b1> a is satisfied, the metal and / or metal compound film covers the highest protrusion.

The composite material of the present invention preferably has an amorphous carbon film on the surface of the metal and / or metal compound film. The amorphous carbon film is formed by plasma CVD as described later.
When formed by the method, the surface of the metal and / or metal compound film is uniformly and densely coated. Therefore, the composite material in which the amorphous carbon film is provided on the surface of the metal and / or metal compound film has a further improved gas barrier property.

Alternatively, the amorphous carbon film is made of metal and / or
Alternatively, it may be located between the metal compound membrane and the support.
That is, the amorphous carbon film may be formed on the smooth surface of the support, and the metal and / or metal compound film may be formed thereon. In that case, the amorphous carbon film uniformly and densely covers the surface of the support, and even when defects such as pinholes or cracks occur in the film of metal and / or metal compound formed thereon. , Effectively suppress gas permeation.

The amorphous carbon film may be formed on the smooth surface of the support and the surface of the metal and / or metal compound film. That is, the composite material of the present invention may have a structure in which two amorphous carbon films sandwich a film of a metal and / or a metal compound. The composite material having such a structure has a higher gas barrier property.

In the second composite material according to the present invention, a metal and / or metal compound film having a thickness b2 is formed on one main surface of the support, and the other main surface has a thickness of b2. b
A composite material having a gas barrier property in which a metal and / or metal compound film of 3 is formed, and the maximum height of at least one main surface of the support is 100 nm.
A smooth surface having a maximum height a of the smooth surface of
And the film thicknesses b2 and b3 of the metal and / or the metal compound are composite materials satisfying the relationship of (b2 + b3)> a. This composite material has a metal and / or metal compound film formed on two main surfaces (that is, both surfaces) of a support. The support and the film of the metal and / or the metal compound constituting the composite material are as described above with respect to the first composite material.

This composite material is characterized in that the combined thickness (b2 + b3) of the metal and / or metal compound films formed on both surfaces of the support is larger than the maximum height a of the smooth surface. Therefore, in this composite material, the thickness of the metal and / or metal compound film formed on the smooth surface does not necessarily need to be larger than the maximum height a of the smooth surface.

The metal and / or metal compound films formed on both sides of the support may be the same or different. Also, b2 = b3 may be satisfied, or b2 ≠ b3 may be satisfied.

It is considered that this composite material exhibits a high gas barrier property by the metal and / or metal compound films formed on both sides of the support complementing each other with the defective portions formed in the film. That is, even if a defect such as a pinhole occurs in the film of one metal and / or metal compound, the gas barrier property in the defect is decreased because the other metal and / or metal compound facing each other with the support interposed therebetween. It is thought to be suppressed by the membrane. The condition under which the supplementary effect is effectively obtained is (b2 + b3)> a.

The second composite material also preferably has an amorphous carbon film. The amorphous carbon film is located on the surface of the film of at least one metal and / or metal compound or between the film of at least one metal and / or metal compound and the support. For example, the amorphous carbon film may be formed only on the surface of one metal and / or metal compound film, or may be formed on the surface of both metal and / or metal compound films. The amorphous carbon film may be located only between one metal and / or metal compound film and the support, or it may be located between both metal and / or metal compound films and the support. You may let me.
Alternatively, the amorphous carbon film may be formed so as to sandwich the film of one metal and / or metal compound. Alternatively,
The amorphous carbon film is located on the surface of the film of one metal and / or metal compound and the other metal and / or
Alternatively, it may be located between the metal compound membrane and the support. Alternatively, the amorphous carbon film may be formed so as to sandwich the film of one metal and / or the metal compound and be formed on the surface of the film of the other metal and / or the metal compound.

In the first composite material according to the present invention, a support having at least one main surface which is a smooth surface having a maximum height of 100 nm or less is prepared, and the smooth surface is provided with a metal. And / or a metal compound film is formed so that the thickness b1 thereof is b1> a (a is the maximum height of the smooth surface). The metal and / or metal compound film is preferably formed by a vacuum deposition method.

In the second composite material according to the present invention, at least one main surface is prepared as a smooth surface having a maximum height of 100 nm or less, and one main surface of the support is prepared. A metal and / or metal compound film having a thickness b2 on the other main surface, and a metal and / or metal compound film having a thickness b3 on the other main surface, (b2 + b3)> a (a is the maximum height of the smooth surface). Is manufactured according to a manufacturing method including: The metal and / or metal compound film is preferably formed by a vacuum deposition method.

The vacuum heat insulating material according to the present invention is a vacuum heat insulating material in which a porous core material is vacuum-packaged with an outer packaging material, and the first or second composite material of the present invention is used as the outer packaging material. Is. The composite material of the present invention maintains the vacuum state inside the vacuum heat insulating material for a long period of time, and contributes to extending the life of the vacuum heat insulating material.

The organic EL device according to the present invention includes a substrate, an anode, an organic material layer including an organic light emitting layer, a cathode, and a sealing film, and the anode, the organic material layer and the sealing film are provided between the substrate and the sealing film. An organic EL element in which a cathode is located, which uses the above-mentioned first or second composite material of the present invention as a sealing film.
The composite material of the present invention protects the organic material layer and the like from moisture and oxygen in the atmosphere, and contributes to extending the life of the organic EL element.

Another organic EL element according to the present invention is a substrate,
An organic EL device including an anode, an organic material layer including an organic light emitting layer, a cathode, and a sealing film, wherein the anode, the organic material layer, and the cathode are located between the substrate and the sealing film. Both of the stop films are the above-mentioned first or second composite materials of the present invention. Due to such characteristics, the organic EL element has high flexibility.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. FIG. 1 schematically shows a cross section of an example of the first composite material (100) of the present invention, and FIG. 2 schematically shows a cross section of an example of the second composite material (200) of the present invention. In FIGS. 1 and 2, reference numerals 102 and 202 denote supports,
Reference numerals 104, 204 and 206 all indicate films of metal and / or metal compound.

The support constituting the composite material of the present invention is a support in which at least one main surface is a smooth surface.
As described above, in the present specification, the smooth surface refers to a surface having fine protrusions but having a maximum height not exceeding 100 nm.

The support is preferably an organic polymer film. The organic polymer film is formed by forming an organic polymer into a sheet by a method such as a melt extrusion method, a hot melt method, or a laminating method, stretching the film in the longitudinal direction and / or the width direction as necessary, and then cooling and It can be obtained by applying heat fixation or the like. As the organic polymer, polyethylene (PE) (including low density polyethylene (LDPE) and high density polyethylene (HDPE)), polypropylene (PP), polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), nylon, etc. Polyamide (PA), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol (PV
A), polyamideimide, polyimide, polyetherimide, polysulfone, polycarbonate, ethylene-vinyl alcohol copolymer (EVOH), ethylene-vinyl acetate copolymer, polyvinyl acetate, polystyrene, AB
Examples thereof include S resin, polystyrene-ABS resin, acrylic resin, methacrylic resin, unsaturated polyester, urethane resin, fluororesin such as Teflon (registered trademark), and silicone resin. The organic polymer film may consist of one organic polymer selected from these organic polymers, or 2 selected from these organic polymers.
It may consist of a mixture of the above resins. The organic polymer film may be composed of a copolymer of a monomer forming the exemplified organic polymer and another monomer. The organic polymer film may be a laminate of two or more organic polymer films.

The organic polymer film may contain additives for improving the properties of the film. The additives are specifically ultraviolet absorbers, antistatic agents, plasticizers, lubricants, colorants, extreme pressure agents, rust preventives, and the like.

The organic polymer film constituting the composite material of the present invention is PE, PP, PET, PEN, PA (polyamide), PVA (polyvinyl alcohol) or EVO.
It is preferably made of H (ethylene-vinyl alcohol copolymer), and PET, PVA, EVOH, P
More preferably, it consists of E or PP.
The material of the film is selected in consideration of the gas barrier property of the film itself and the cost required for manufacturing the film. For example, a film made of EVOH is preferably used because it has a high gas barrier property itself. However, since the manufacturing cost is high, a PET film or the like is preferably used when an inexpensive composite material is required.

When the support is an organic polymer film,
The surface usually has protrusions. The protrusions are usually intentionally formed in order to ensure the running property during film production. The protrusions are formed by fixing fine particles of silicon oxide or alumina on the surface of the film with an appropriate binder, or by forming an organic polymer (synthetic resin) containing such fine particles into a film. .

Protrusions may also be inadvertently formed during film manufacture. Factors that form such protrusions include the composition of the film, the type and amount of additives in the film, the drying temperature during film formation, the degree of crystallinity of the polymer in the film, and the formation of oligomers.

The maximum height a of the smooth surface of the film is 10
It is preferably 0 nm or less, more preferably 80 nm or less. The average surface roughness of the smooth surface is 10
It is preferably not more than nm, more preferably not more than 5 nm.

The average surface roughness is an extension of the arithmetic average roughness Ra defined in JIS B0601 so that it can be applied to a measurement surface having a predetermined area. Therefore, the average surface roughness can be said to be a value obtained by averaging the absolute values of the deviations from the reference surface to the designated surface, and can be obtained by the following formula.

[Equation 1] (Where a and b are the lengths of two sides of the measurement surface, S is the area of the measurement surface, f (x, y) is the height in the measurement surface, and Z0
Indicates the height of the reference surface)

Here, the measurement surface means a surface which is an object of roughness measurement, and is, for example, a surface of 30 μm × 30 μm.
The reference plane is, when the average value of the height of the designated surface is Z0,
A plane expressed by Z = Z0. Average surface roughness can also be measured with an atomic force microscope.

The organic polymer film used in the present invention is
It is necessary to control and manufacture the surface shape so that at least one surface has a smooth surface. Therefore, if the protrusions are intentionally formed using fine particles, the diameter is 30 nm.
It is preferable to use the following fine particles having a diameter of 3 to 2
It is more preferable to use fine particles of 0 nm. In addition, in order to suppress the formation of unintended protrusions during film production, it is necessary to appropriately select the composition of the material of the organic polymer film. For example, when the above-mentioned additive is added, it is preferable to reduce the amount of the additive.

The thickness of the organic polymer film used in the present invention is preferably 3 to 500 μm, and 5 to 30.
The thickness is more preferably 0 μm, particularly preferably 3 to 100 μm.

Organic polymeric films suitable for constructing the composite material of the present invention are commercially available. For example, an organic polymer film available as a base film of a vapor deposition tape for recording has a smooth surface on the side where a magnetic layer (recording layer) is formed, and is suitable for constituting the composite material of the present invention.

The support may be a sheet-shaped member other than the organic polymer film. For example, a substrate made of soda glass, hard glass, Pyrex (registered trademark) glass, or the like may be used as the support.

Next, the specific form of the metal and / or metal compound film constituting the composite material of the present invention will be described. The meaning of “film of metal and / or metal compound” is
As described above. In the composite material of the present invention, the metal and / or metal compound film is formed for the purpose of improving the gas barrier property of the support, and is formed on one or both main surfaces of the support. When the metal and / or metal compound film is formed only on one main surface of the support as in FIG. 1, the main surface on which the metal and / or metal compound film is formed is a smooth surface.

As the "metal" constituting the "metal and / or metal compound film", aluminum, silicon, calcium, titanium, chromium, manganese, iron, cobalt,
Examples include nickel, copper, zinc, zirconium, silver, indium and tin. The metal film may be a film composed of one metal selected from these metals, or 2
It may be a film formed by mixing the above metals, or may be a film formed by an alloy of two or more metals.

The "metal compound" constituting the "metal and / or metal compound film" is an oxide of the above metal,
Examples thereof include nitrides and oxynitrides. "The metal compound film may be a film composed of one metal compound selected from these, or a film composed of a mixture of two or more metal compounds selected from these, or a compound of an alloy of two or more metals. May be a membrane consisting of

The metal and / or metal compound film is preferably any one of an aluminum film, an aluminum oxide film and a silicon oxide film. Of these, the aluminum film usually inevitably contains aluminum oxide (AlO _x ). The ratio of aluminum and aluminum oxide differs depending on the conditions for forming the aluminum film. Further, the aluminum film may contain oxygen which is not combined with aluminum.

Metal oxides such as aluminum oxide and silicon oxide are characterized by being transparent, insulating and excellent in storage stability under high temperature and high humidity.
Therefore, a composite material having a film of a metal oxide formed as a film of a metal and / or a metal compound utilizes these characteristics, and for example, a packaging material (eg, an infusion bag) whose contents are required to be visible. It is preferably used for.

As shown in FIG. 1, when the metal and / or metal compound film (104) is formed only on one main surface of the support (102), the thickness b1 is the maximum of the main surface. It is set to be larger than the height a, that is, b1> a. However, if the thickness of the metal and / or metal compound film is too large, bending resistance and workability may deteriorate, and cracks may occur. Therefore, b1 is preferably 1 μm or less, more preferably 500 nm or less, and particularly preferably 100 nm or less. Even if b1> a, sufficient gas barrier properties may not be obtained if the metal and / or metal compound film is too small. Therefore, b1 is
The thickness is preferably 5 nm or more, more preferably 10 nm or more.

As shown in FIG. 2, the metal and / or metal compound film (204, 206) is attached to the support (202).
When it is formed on both main surfaces to have the thicknesses of b2 and b3, respectively, the combined thickness (b2 + b3) of b2 and b3 should be larger than the maximum height a of the smooth surface of the support. To do. As long as this condition is satisfied, b2 and b3 are not particularly limited. b
Each of 2 and b3 is preferably in the range of 5 nm to 1 μm, more preferably in the range of 10 to 500 nm, and particularly preferably in the range of 10 to 200 nm.
(B2 + b3) is preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 500 nm, and particularly preferably in the range of 20 to 300 nm. b
The reason why the preferable ranges of 2, b3 and (b2 + b3) are these is as described above in relation to b1.

As a method for forming a film of a metal and / or a metal compound, there are a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method and an ion plating method, and a CVD (chemical vapor deposition) method. The film of the metal and / or the metal compound is preferably formed by the PVD method from the viewpoint of productivity.

Among the PVD methods, the vacuum deposition method uses a lump of metal or a lump of a metal compound as an evaporation material, and heats this under a vacuum to evaporate, and the evaporated metal or metal compound is used as a substrate (of the present invention). It is a method of forming a thin film by adhering and depositing it on the surface of a support of a composite material). Resistance heating, high frequency induction heating, and electron beam are available as heating methods for evaporation materials. Of these, the electron beam method is the most preferable. The reason is that the film formed by using the electron beam method has a higher gas barrier property than the film formed by using the resistance heating method and the high frequency induction heating method, and does not corrode even when stored under high temperature and high humidity. There are few generations and the electron beam method is excellent in mass productivity. The vacuum vapor deposition may be performed under any conditions as long as the object of the present invention is not impaired. For example, a bias may be applied to the support or an electron beam may be irradiated during the vapor deposition. The temperature of the support may be raised or the support may be cooled during vapor deposition.

When forming a film containing a metal compound, the film may be formed by a reactive vapor deposition method. For example, if a metal is used as an evaporation material and oxygen vapor is introduced into the metal vapor and vacuum vapor deposition is performed so as to react the two, a metal oxide film is formed. Examples of metal oxides that can be formed by the reactive vapor deposition method include aluminum oxide and silicon oxide.

Next, the amorphous carbon film will be described. An example of a composite material having an amorphous carbon film is shown in FIGS. FIG. 3 shows a composite material (300) having a metal and / or metal compound film (104) formed on a smooth surface of a support and an amorphous carbon film (106) formed on the surface thereof. FIG. 4 shows an amorphous carbon film (10) between a support (102) and a film (104) of metal and / or metal compound.
6) shows a composite material (400) in which is located. 3 and 4, the same reference numerals as those used in FIG.
Represents the same element as they represent.

The amorphous carbon film is a film containing carbon, hydrogen and oxygen, and the bonding modes of atoms are diamond bond (SP ³ bond) and graphite bond (SP ^2).
(Bonds) and further partially contains bonds between carbon and hydrogen. It is considered that this bond between carbon and hydrogen imparts a polymer property to the amorphous carbon film and makes the amorphous carbon film a dense layer.

The thickness of the amorphous carbon film is preferably 1 to 1000 nm, more preferably 3 to 500 nm, particularly preferably 5 to 100 nm. When the amorphous carbon film is positioned so as to sandwich the metal and / or metal compound film, the thickness of each amorphous carbon film is preferably within the above range.

The amorphous carbon film is formed by PV deposition such as vacuum deposition.
It is preferably formed on the surface of the metal and / or metal compound film formed by the D method. When a thin film is formed by the PVD method, defects such as pinholes are more likely to occur in the film, as compared with the CVD method. The amorphous carbon film densely covers such a defect portion and effectively suppresses the deterioration of the gas barrier property in the defect portion.

The amorphous carbon film may be formed by a conventional method for forming an amorphous carbon film. Specifically, the plasma CV is used.
It is formed by the D method or the sputtering method. Since the amorphous carbon film formed by the plasma CVD method has fewer defects than the amorphous carbon film formed by the sputtering method, it has a high gas barrier property and the degree of deterioration even when stored under high temperature and high humidity. Is small. The plasma CVD method is also excellent in productivity. Therefore, the amorphous carbon film is preferably formed by the plasma CVD method.

When the amorphous carbon film forming the composite material of the present invention is formed by the plasma CVD method, the source gas is conventionally used when forming the amorphous carbon film by the plasma CVD method. The gas that is present. Source gases are methane, ethane, propane, butane, pentane, hexane,
Hydrocarbon gas selected from ethylene, propylene, butylene, toluene, benzene, etc., hydrogen gas,
It is a mixture of reaction accelerating gases selected from nitrogen gas, argon, helium gas and the like. The exemplified hydrocarbon-based gas may be used alone or in combination of two or more. The same applies to the reaction promoting gas.

The formation of the carbon film by the plasma CVD method is as follows.
Specifically, it is carried out by introducing a source gas into the reaction vessel and generating plasma of a hydrocarbon-based gas inside the reaction vessel while maintaining the pressure inside the vessel at 1 to 100 Pa. Plasma may be generated, for example, by generating an electric discharge in a reaction vessel. During the formation of the carbon film, the hydrocarbon-based gas and the reaction accelerating gas may be introduced into the reaction vessel at a predetermined flow rate and mixed in the reaction vessel. By changing the ratio of the supply amount (eg, flow rate) of the reaction-promoting gas to the supply amount (eg, flow rate) of the hydrocarbon-based gas, the ratio of other atoms (eg, hydrogen, oxygen or nitrogen) to carbon in the carbon film can be changed. Can be changed.

When plasma is generated by electric discharge, the electric discharge type may be either an external electrode type or an internal electrode type, and the discharge frequency can be experimentally determined. The properties of the amorphous carbon film can be changed by changing the voltage applied during discharge. Generally, when the voltage is high, the hardness of the film increases, and when the voltage is low, the hardness of the film tends to decrease. Also, the properties of the film can be changed by changing the pressure of the source gas.

The plasma is generated by a method in which electrons are resonated by a microwave and a magnetic field to convert the source gas into plasma, that is, electron cyclotron resonance (Electron Cyclotron Res.
onance; ECR).

When the amorphous carbon film constituting the composite material of the present invention is formed by the sputtering method, graphite, diamond or the like is used as the target. Sputter evaporation may be performed by bombarding a target with an ion beam, or may be performed by making an inert gas into plasma and bombarding the target with ions in the plasma. The inert gas is, for example, nitrogen, argon or helium. The inert gas may be present in the sputtering apparatus in the form of a mixed gas with the above hydrocarbon-based gas. The mixed gas is, for example, a mixed gas of nitrogen and methane, a mixed gas of argon and methane, or a mixed gas of helium and methane.

The amorphous carbon film may also be formed when a metal and / or metal compound film is formed on both main surfaces of the support. In that case, various forms are assumed as described above. Some of them are illustrated in FIGS. 5, the same reference numerals as those used in FIG. 2 represent the same elements as those shown in FIG.

In FIG. 5A, an amorphous carbon film (2) is formed on the surface of one metal and / or metal compound film (204).
08) formed composite material (500a). FIG. 5B shows an amorphous carbon film (208, 2) formed on the surface of both metal and / or metal compound films (204, 206).
It is the composite material (500b) which formed 10). FIG. 5C shows a composite material (500c) in which one metal and / or metal compound film (204) is sandwiched between two amorphous carbon films (208, 212). FIG. 5 (d)
Is a film of one metal and / or metal compound (20
An amorphous carbon film (208) is formed on the surface of 4), and an amorphous carbon film (214) is located between the other metal and / or metal compound film (206) and the support (202). It is a composite material (500d).

As shown in FIG. 5, in a composite material in which a film of metal and / or metal compound is formed on both main surfaces of a support, when one main surface of the support is "rough",
The amorphous carbon film is preferably formed on the surface of the metal and / or metal compound film formed on the “rough” main surface of the support or on the “rough” main surface of the support. This is because when the amorphous carbon film is formed on the "rough" main surface side of the support, the gas barrier property of the composite material is further improved.

The composite material of the present invention preferably has a metal and / or metal compound film, and in the case of having an amorphous carbon film, preferably maintains the gas barrier performance of the amorphous carbon film for a long period of time. The outermost layer is formed of an organic polymer film. That is, it is preferable to form an organic polymer film on the surface of the metal and / or metal compound film, and when an amorphous carbon film is formed on the surface of the metal and / or metal compound film, It is preferable to form an organic polymer film on the surface of the amorphous carbon film. Alternatively, the organic polymer film may be formed on the surface of the support on the side where the metal and / or metal compound film is not formed. In either case, the surface of the organic polymer film becomes the exposed surface of the composite material.

The organic polymer film is a metal film (for example, Al
It is particularly preferable to form on the surface of the metal film or on the surface of the amorphous carbon film formed on the surface of the metal film, because it effectively suppresses the generation of rust in the film. Rust occurs when metal changes into hydroxide or the like under the influence of atmospheric moisture and various gases. The part where rust is generated also becomes a defective part of the film,
Reduces gas barrier properties. Since the organic polymer film exhibits water repellency or moisture impermeability, it suppresses the generation of rust and therefore keeps the gas barrier property of the composite material good for a long time.

6A and 6B illustrate a composite material having an organic polymer film. 6, the same reference numerals as those used in FIG. 1 represent the same elements as those shown in FIG. FIG. 6A shows the support (10
A metal and / or metal compound film (104) is formed on the smooth surface of 2), and an organic polymer film (10) is formed on the surface.
8) is the formed composite material (600a). In FIG. 6B, a metal and / or metal compound film (104) and an amorphous carbon film (1) are formed on a smooth surface of a support (102).
06) and the organic polymer film (108) are the composite material (600b) formed in this order.

In the composite material in which the metal and / or metal compound film is formed on the two main surfaces of the support, it is preferable that at least one surface of the composite material is the surface of the organic polymer film. It is more preferable that the surface of is the surface of the organic polymer film. That is, the organic polymer film is preferably formed on the surface of at least one metal and / or metal compound film, and more preferably formed on the surface of both metal and / or metal compound films. preferable. When the amorphous carbon film is formed on the surface of the metal and / or metal compound film, the organic polymer film is formed on the surface of the amorphous carbon film.

The organic polymer film is a film made of an organic polymer. Examples of the organic polymer include those exemplified as the organic polymer suitable for forming the support, higher fatty acids such as stearic acid, and fluorine-based lubricants such as perfluoropolyether. The organic polymer film may contain an extreme pressure agent, an anticorrosive agent, and the like in addition to these organic polymers.

The organic polymer film is formed by an organic vapor deposition method or a wet coating method. In the wet coating method, an organic polymer is dissolved and / or dispersed in an appropriate solvent, if necessary, together with an extreme pressure agent to prepare a coating solution, and the coating solution is applied to the surface of a metal and / or metal compound film. It is a method of forming a film by coating on a substrate and then evaporating the solvent. The coating liquid is
When the amorphous carbon film is formed on the metal and / or metal compound film, it is applied to the surface of the amorphous carbon film. The solvent used when preparing the coating liquid is selected according to the organic polymer. For example, when an ethylene-vinyl alcohol copolymer film is formed as an organic polymer film, a mixed solvent of alcohol and water is used as the solvent.

The thickness of the organic polymer film is preferably 1 to
It is in the range of 1000 nm, and more preferably 2 to 50.
It is in the range of 0 nm, particularly preferably in the range of 3 to 100 nm.

The preferred embodiments of the present invention have been exemplified above. As still another form of the present invention, there is a form in which a film of a metal and / or a metal compound and an amorphous carbon film are repeatedly laminated in this order on the surface of a support.
That is, when the metal and / or metal compound film is M and the amorphous carbon film is C, M / C / M is formed on the surface of the support.
The composite material of the present invention also includes a laminated body of / C ... In such composite materials,
The combined thickness of the films of each metal and / or metal compound is required to be larger than the maximum height a of the smooth surface. In the stack, each metal and / or metal compound film may be made of the same material or different materials. Further, in the laminated body, the thickness of each metal and / or metal compound film may be the same or different from each other. The same applies to the thickness of each amorphous carbon film.

The composite material of the present invention can be used as it is as a gas barrier sheet. The composite material of the present invention may be used by laminating or coating additional polymeric films or lamina.

Furthermore, in the process of producing the composite material of the present invention, when a metal and / or metal compound film or an amorphous carbon film is formed on the surface of the support by vapor deposition, a pretreatment for vapor deposition is performed. Good. The vapor deposition pretreatment is performed in order to remove the influence of gas and impurities that may be present in the support. Examples of such treatment include vacuum discharge treatment such as plasma treatment and glow treatment, heat treatment with heating rolls and lamps, and irradiation treatment with ions and electrons.

The composite material of the present invention shows an excellent gas barrier property, and a metal and / or metal compound film is formed by b1.
Since it can be made thin as long as> a is satisfied,
It is also excellent in flex resistance and gelbo resistance. Therefore, the composite material of the present invention is suitable for various applications, in particular:
It is preferably used as an outer packaging material of a vacuum heat insulating material and a sealing film of an organic EL element. Hereinafter, a vacuum heat insulating material and an organic EL element using the composite material of the present invention will be described.

The vacuum heat insulating material is obtained by completely covering a porous core material (for example, foam) having open cells with the composite material of the present invention, and then covering the inside with the composite material (that is,
It is formed by decompressing the inside of the bubbles of the other-porous core material) to bring it into a substantially vacuum state. Such a structure can be used as a heat insulating material, preferably as a high-performance heat insulating material, because the vacuum layer formed therein can exhibit high heat insulating properties.
It is considered that the high degree of heat insulation depends on how high the degree of vacuum of the vacuum layer can be increased, and the durability of heat insulation depends on how long the degree of vacuum of the vacuum layer can be maintained. It is considered that each of them corresponds to the high gas barrier property of the composite material. That is, when the gas barrier property of the composite material is high, it is considered that the vacuum degree of the vacuum layer can be made higher and the vacuum degree of the vacuum layer can be maintained for a longer period of time, so that a higher performance heat insulating material can be configured. It is possible to Since the composite material of the present invention has an excellent gas barrier property, the vacuum heat insulating material constituted by using it has higher heat insulating performance.

In the organic EL device, an anode, an organic material layer including an organic light emitting layer, and a cathode are formed in this order on a substrate, and then the composite material of the present invention is placed on the cathode as a sealing film. can get. The substrate is generally a glass substrate, the anode is indium tin oxide (ITO), and the cathode is alkali metal or alkaline earth metal. The organic material layer has a two-layer structure including a hole transport layer and a light emitting layer, a two layer structure including a light emitting layer and an electron transport layer, and a hole transport layer, a light emitting layer and an electron transport layer. Some have a three-layer structure. When the organic El element is sealed using a composite material in which a film of a metal and / or a metal compound is formed only on the smooth surface of the support, the composite material has a metal and / or metal compound film inside and It may be arranged on either side. Preferably,
The film of metal and / or metal compound is arranged on the inside. When the metal and / or metal compound film is located outside, the composite material may be deteriorated due to the influence of the outside air or the like, which may also deteriorate the organic material.

The composite material of the present invention can also be used as a substrate of an organic EL device. In that case, an anode is formed on the surface of the composite material of the present invention, an organic material layer and a cathode are formed thereon, and the composite material of the present invention is disposed on the cathode as a sealing film to form an organic EL device. It is formed. This organic EL
The device has a structure in which an anode, an organic material layer and a cathode are sandwiched between the composite material of the present invention. The substrate and the sealing film may be the same composite material or different composite materials. When the composite material of the present invention is used as a substrate, the composite material needs to be transparent, and thus all the constituent elements of the composite material need to be transparent. Therefore, the support of the composite material constituting the substrate is preferably a highly transparent polyethylene film or polyester film, and the metal and / or metal compound film is preferably made of silicon oxide or aluminum oxide. . When both the substrate and the sealing film are a composite material having an organic polymer film as a support, the obtained organic EL element has flexibility and is useful as, for example, a flexible display.

[0092]

EXAMPLES The present invention will now be described in more detail with reference to examples. These examples are only one aspect of the present invention,
The invention is in no way limited by these examples.

In the following Examples and Comparative Examples, the maximum height and average surface roughness of the smooth surface of the support, and the thickness of each film (metal and / or metal compound film and amorphous carbon film) Was calculated as follows.

(1) Maximum height of smooth surface and average surface roughness The maximum height was determined by using an atomic force microscope (Seiko Denshi Kogyo, trade name: SPI3800), and JIS B 060 was used.
It asked according to 1. Average surface roughness is 30 μm × 30 μm
The square was used as a measurement surface, and the measurement was performed using the same AFM.

(2) Thickness of Metal and / or Metal Compound Film When an Al film is formed as a metal and / or metal compound film: For the Al film, a scanning microscope (SE) is used.
The relationship between the thickness and the surface resistance measured by observation according to M) and the relationship between the thickness and the amount of transmitted light were obtained in advance. Applying the relationship obtained, from the surface resistance and the amount of transmitted light, Al
The film thickness was determined. When aluminum oxide or silicon oxide was formed as a film of a metal and / or a metal compound: A cross section was observed by SEM for measurement.

(3) Thickness of amorphous carbon film The cross section was observed by SEM and measured.

Example 1 As a support, a polyethylene having a thickness of 12 μm, in which the maximum height of one main surface (smooth surface) was 50 nm and the average surface roughness of the main surface was 3.9 nm. Terephthalate (PET) film (Toray Industries, Inc.)
Prepared). An Al film was formed on the surface (that is, a smooth surface) of this PET film by using the apparatus shown in FIG. 7 to obtain a composite material.

During the formation of the Al film, the cooling rotary drum (70
The set temperature of the refrigerant for cooling 3) was -20 ° C. PE
The T film (701) was set on the feed shaft (702), the line speed at the time of vapor deposition was set to 50 m / min, and the film was wound on the winding shaft (704). The vacuum deposition was carried out by irradiating the Al (706) in the ceramic crucible (705) with an electron beam (707) from an electron gun to dissolve and evaporate Al and attach it to the support from below. At this time, the spread of the metal vapor flow is shielded (708, 709).
And the solid angle (ω) is set to 38 °. The thickness of the Al film was 80 nm.

Example 2 Using the same PET film as used in Example 1, an Al film having a thickness of 80 nm was formed on the smooth surface of the film by the vacuum evaporation method in the same manner as in Example 1. After forming the Al film, an amorphous carbon film was formed on the surface of the Al film by the plasma CVD method using the apparatus shown in FIG. 8 to obtain a composite material.

During the formation of the amorphous carbon film, the set temperature of the cooling medium for cooling the cooling rotary drum (803) was 20 ° C.
The PET film (801) having an Al film was set on the feed shaft (802), the line speed was set to 10 m / min, and the film was wound on the winding shaft (804). Plasma CVD uses methane gas (80) in a box (805).
6) and hydrogen gas (807) were introduced, and while vacuum evacuation, voltage was applied to form a plasma atmosphere. The thickness of the amorphous carbon film was 20 nm.

Example 3 Using the same PET film as used in Example 1, an Al film having a thickness of 80 nm was formed on the smooth surface of the film by the vacuum deposition method in the same manner as in Example 1. Further, an amorphous carbon film having a thickness of 20 nm was formed on the surface of the Al film in the same manner as in Example 2.

An organic polymer film was formed on the surface of the amorphous carbon film. The organic polymer film is made of isopropyl alcohol (I
A coating solution (concentration 1000 ppm) prepared by dissolving perfluoropolyether in (PA) was applied by a reverse roll coater, and then IPA was evaporated to form. The finally obtained organic polymer film had a thickness of 5 nm.

(Example 4) Using the same film as the PET film used in Example 1, an Al film having a thickness of 50 nm was formed on the smooth surface of the film in the same manner as in Example 1 by a vacuum deposition method. Further, on the other main surface of the PET film, in the same manner as in Example 1, 50 nm thick Al
The film was formed by a vacuum evaporation method to obtain a composite material. Each A
The thickness of the l film was made smaller than that of the Al film formed in Example 1 by reducing the electric power applied to the electron gun.

Example 5 Using the same PET film as used in Example 1, an Al film having a thickness of 50 nm was formed on both main surfaces of the film in the same manner as in Example 4 by vacuum deposition. Formed. A 20 nm-thick amorphous carbon film was formed on the surface of the Al film formed on the smooth surface of the PET film in the same manner as in Example 2 to obtain a composite material.

Example 6 The same film as the PET film used in Example 1 was used, and an Al film having a thickness of 50 nm was formed on both main surfaces of the film in the same manner as in Example 4 by a vacuum deposition method. Formed. An amorphous carbon film having a thickness of 20 nm was formed on the surface of the Al film formed on the smooth surface of the PET film in the same manner as in Example 2.

Further, an organic polymer film was formed on the surface of the amorphous carbon film to obtain a composite material. The organic polymer film was prepared by dissolving ethylene-vinyl alcohol copolymer (EVOH) in a mixed solvent of alcohol and water (concentration 2000 ppm), and then coating the solution with a reverse roll coater and then evaporating the solvent. Formed. EV finally obtained
The thickness of the OH film was 5 nm.

(Example 7) As a support, one main surface (smooth surface) had a maximum height of 50 nm, and the main surface had an average surface roughness of 4.2 nm. A vinyl alcohol copolymer (EVOH) film (manufactured by Kuraray Co., Ltd.) was prepared. An Al film having a thickness of 80 nm was formed on the surface (that is, a smooth surface) of the EVOH film in the same manner as in Example 1 to obtain a composite material.

Example 8 EVOH used in Example 7
A composite material was obtained by forming an Al film with a thickness of 50 nm on both main surfaces of the film in the same manner as in Example 4 except that the same film as the film was used as the support.

(Example 9) The same film as the EVOH film used in Example 7 was prepared as a support. Using the apparatus shown in FIG. 1, while introducing oxygen gas into the vacuum vapor deposition apparatus, Al was evaporated and adhered to the support. Thereby, a composite material having a 100 nm-thick aluminum oxide film formed on a smooth surface was obtained. Cooling temperature of the cooling drum, set temperature, line speed and solid angle (ω)
Was the same as in Example 1.

Example 10 As the support, the same EVOH film used in Example 7 was prepared.
Using the apparatus shown in FIG. 7, a silicon oxide film having a thickness of 100 nm was formed by vacuum vapor deposition to obtain a composite material. The silicon oxide film was formed by placing silicon oxide in the crucible (705) and irradiating it with an electron beam. The set temperature, line speed, and solid angle (ω) of the cooling medium for cooling the cooling rotary drum were the same as in Example 1.

Comparative Example 1 As a support, a 12 μm-thick PET film (manufactured by Toray Industries, Inc.) having a maximum height of one main surface of 300 nm and an average surface roughness of 10.0 nm was prepared. . On this surface of this PET film, Example 1
In the same manner as above, a 100 nm thick Al film was formed to obtain a composite material. The thickness of the Al film was made larger than that of the Al film formed in Example 1 by increasing the input power of the electron gun.

(Comparative Example 2) As a support, one of the main surfaces has a maximum height of 200 nm and an average surface roughness of 8.5 nm.
An EVOH film (manufactured by Kuraray Co., Ltd.) having a thickness of 12 μm was prepared. An Al film having a thickness of 100 nm was formed on the surface of this EVOH film in the same manner as in Example 1 to obtain a composite material. The thickness of the Al film was made larger than that of the Al film formed in Example 1 by increasing the input power of the electron gun.

(Comparative Example 3) EVOH used in Comparative Example 2
Using the same film as the film, an Al film having a thickness of 250 nm was formed in the same manner as in Example 1 on the main surface having the maximum height and the plane roughness of 200 nm and 8.5 nm, respectively. Obtained. The thickness of the Al film was made larger than that of the Al film formed in Example 1 by increasing the input power of the electron gun.

Table 1 shows the distribution of the fine projections present on the surface of the PET film used in Example 1 and the PET film used in Comparative Example 1. The distribution of the fine projections was examined by defining a ground level (valley bottom line) with the surface of the support 30 μm × 30 μm as a measurement range, and slicing the surface in order from the ground level every 10 nm. From this table, it can be seen that the surface smoothness of the PET film used in the examples is high.

[0115]

[Table 1]

In each of the examples and comparative examples, after forming a film of a metal and / or a metal compound and then visually observing the surface, pinhole-like defects were observed in the Al film formed in each comparative example. No such defects were observed in the Al film, aluminum oxide film and silicon oxide film formed in the examples. Further, when observed in detail with a 100 × optical microscope, several pinhole-shaped defects were observed in the visual field in the Al film formed in each comparative example. In the Al film and the like formed in each example, the number of defective portions observed in the visual field was 1 or 0, and this was the same even if the observation location was changed. The number of defects such as the Al film formed in each of the examples and comparative examples tended to increase as the maximum height of the surface of the support increased and the thickness of the Al film decreased.

In each of the above Examples and Comparative Examples, the thickness of the Al film was adjusted by the input power of the electron gun. The thickness of the Al film can also be adjusted by increasing or decreasing the line speed. Similarly, the thickness of the amorphous carbon film can be adjusted by adjusting the line speed, the discharge current, the gas pressure and the like.

The gas barrier properties, durability and storability of the composite materials obtained in the respective examples and comparative examples were evaluated as follows. (1) Gas barrier properties All the composite materials have high gas barrier properties, and evaluation cannot be performed when oxygen gas is used. Therefore, the gas barrier properties were evaluated using CO ₂ gas. The evaluation was performed by setting the composite material as a sample between the CO ₂ gas and the vacuum layer, and measuring the CO ₂ gas that permeated the composite material and diffused into the vacuum layer with a gas mass spectrometer. Here, the gas permeation amount measured for the composite material obtained in Example 1 is set to 1, and the relative value to that is shown as the gas barrier performance.

(2) Durability and storability (corrosion resistance) The composite material was placed in an environment of a temperature of 60 ° C. and a relative humidity of 90% for 10 days.
After standing for a day, the surface condition of the composite material was observed to evaluate the degree of corrosion of the composite material. The evaluation criteria are as follows. X: Rust is generated, and more than half of the generated rust forms transparent spots. Δ: Rust is generated, but transparent spots are not formed. ◯: A little rust is generated, but there is no problem in practical use. A: No rust is observed.

The evaluation results are shown in Table 2 together with the constitution of the composite material.
Shown in.

[0121]

[Table 2]

From Table 2, when Example 1 and Comparative Example 1 in which the smoothness of the film surface is different, the gas barrier property is higher even though the composite material of Comparative Example has a larger Al film thickness. The composite material of the example is higher. It is considered that this is because the film used in Example 1 had high surface smoothness, and thus the generation of pinhole-like defects in the Al film formed thereon was suppressed. The same applies when comparing Example 7 and Comparative Example 2. Comparative Example 3 is A
The gas barrier property is higher than that of Comparative Example 2 and is equivalent to that of Examples 9 and 10 because the 1 film is thick and the thickness is larger than the maximum height of the surface. However, Comparative Example 3 is inferior in durability and storability. It is considered that this is because the support used in Comparative Example 3 had a large thickness of the Al film, and thus defects such as cracks were likely to occur after the film was formed. That is, it is considered that in the composite material of Comparative Example 3, a defective portion was generated later due to an external force applied during the test work, and corrosion progressed at the defective portion.

Comparing Example 1 and Example 7, Example 7 was superior in gas barrier property despite the fact that the Al film had the same thickness. Similarly, when comparing Example 4 and Example 8, Example 8 was superior in gas barrier property. From this result, it is understood that the gas barrier property of the film itself against CO ₂ gas is higher in the EVOH film than in the PET film.

The composite materials of Examples 4, 5, 6 and 8 in which Al films were formed on both main surfaces of the support all showed excellent gas barrier properties. It is considered that this is because, even if a defect exists in one Al film, the other Al film secures the gas barrier property on the opposite side of the defect.

The gas barrier properties of Examples 9 and 10 in which a metal oxide film was formed were lower than the gas barrier properties of Example 7 in which a metal film was formed, but Comparative Example 2 in which a metal film of the same thickness was formed. Is better than that. This is
The metal oxide film originally has a lower gas barrier property than the metal film, but by applying the present invention, even when the metal oxide film is used as the gas barrier layer, it is equal to or higher than the conventional one. It shows that a gas barrier property can be achieved. Further, the composite material having the metal oxide film formed thereon has an advantage of excellent durability and storage stability.

Comparing Example 2 and Example 1, Example 2 showed superior gas barrier properties. Similarly, when comparing Example 4 and Example 5, the gas barrier property is similar to that of Example 5.
Was better. This indicates that the amorphous carbon film contributes to the improvement of the gas barrier property.

Comparing Example 2 and Example 3, Example 3 showed better durability and storability even though the thickness of the support and the Al film was the same. Similarly, when comparing Example 5 and Example 6, Example 6 was superior in durability and storability. from this result,
It can be seen that the organic polymer film contributes to the improvement of durability and storability of the composite material.

[0128]

As described above, according to the present invention, 1) a metal and / or metal compound film is formed on the smooth surface of at least one main surface of the support, and the thickness b1 thereof is A composite material, characterized in that it is greater than the maximum height a of the smooth surface, and 2) a metal having a thickness of b2 and b3 respectively on both main surfaces of the support, at least one of which is a smooth surface and And / or a metal compound film is formed, and (b2 + b3) is larger than the maximum height a of the smooth surface. Due to these characteristics, the composite material of the present invention exhibits superior gas barrier properties to the conventional composite materials.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing an example of a composite material of the present invention.

FIG. 2 is a cross-sectional view schematically showing an example of the composite material of the present invention.

FIG. 3 is a cross-sectional view schematically showing an example of the composite material of the present invention.

FIG. 4 is a cross-sectional view schematically showing an example of the composite material of the present invention.

5 (a) to 5 (d) are cross-sectional views each schematically showing an example of the composite material of the present invention.

6 (a) and 6 (b) are cross-sectional views each schematically showing an example of the composite material of the present invention.

FIG. 7 is a schematic view showing an apparatus for forming a film of a metal and / or a metal compound.

FIG. 8 is a schematic view showing an apparatus for forming an amorphous carbon film.

[Explanation of symbols]

100, 200, 300, 400, 500a, 500
b, 500c, 500d ... composite material, 102, 20
2 ... Support, 104, 204, 206 ... Metal and /
Or a metal compound film, 106, 208, 210, 21
2, 214 ... amorphous carbon film, 108 ... organic polymer film,
701 ... Film, 702 ... Feed shaft, 703 ... Cooling rotary drum, 704 ... Winding shaft, 705 ... Crucible, 70
6 ... Evaporation material, 707 ... Electron beam, 708, 70
9 ... Shielding plate, 801 ... Film having Al film, 80
2 ... Feed shaft, 803 ... Cooling rotary drum, 804 ... Take-up shaft, 805 ... Box, 806 ... Methane gas, 80
7 ... Hydrogen gas.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C23C 14/08 C23C 14/08 A 4K030 14/10 14/10 14/14 14/14 B 16/26 16 / 26 H05B 33/02 H05B 33/02 33/04 33/04 33/14 33/14 A // C08L 101: 00 C08L 101: 00 F term (reference) 3E067 AA11 AB99 BA12A BB14A BB26A CA04 CA18 FA01 FB11 FC01 GA13 GA14 3K007 AB11 AB12 AB13 BA07 BB01 CA06 DB03 FA02 4F006 AA12 AA13 AA19 AA35 AA38 AB73 AB74 BA05 CA07 DA01 4F100 AA01B AA37C AB01B AK01A AK01D AK42B JAJ AJBJJAJJ15J15JE15J16JE15J16JE15J61D16E61C61D06E61C61D16E61C61D06HE666E16HBJBAEBAH AA25 BA03 BA44 BA46 BA62 BC00 BD00 CA01 CA02 4K030 BA27 BB05 CA07 CA12 FA01 HA04 LA01 LA11

Claims (25)

[Claims] 1. A composite material having a gas barrier property in which a film of a metal and / or a metal compound having a thickness b1 is formed on one main surface of a support, the composite material comprising a metal and / or a metal compound. The main surface of the support on which the film is formed is a smooth surface having a maximum height of 100 nm or less, and the maximum height a of the smooth surface and the thickness b1 of the metal and / or metal compound film. Is a composite material satisfying the relationship of b1> a. 2. The composite material according to claim 1, wherein an amorphous carbon film is formed on the surface of the metal and / or metal compound film. 3. The composite material according to claim 1, wherein an amorphous carbon film is located between the metal and / or metal compound film and the support. 4. The composite material according to claim 1, wherein at least one surface of the composite material is a surface of an organic polymer film. 5. A metal and / or metal compound having a thickness of b2 is formed on one main surface of the support, and a metal and / or metal compound having a thickness of b3 is formed on the other main surface. A composite material having a gas barrier property, in which at least one main surface of a support is
A smooth surface with a maximum height of 100 nm or less,
The maximum height a of the smooth surface and the thicknesses b2 and b3 of the metal and / or metal compound film are (b2 + b3)> a
Material that satisfies the relationship of. 6. The composite material according to claim 5, wherein an amorphous carbon film is formed on the surface of at least one metal and / or metal compound film. 7. A composite material according to claim 5, wherein an amorphous carbon film is located between at least one metal and / or metal compound film and the support. 8. The composite material according to claim 5, wherein at least one surface of the composite material is a surface of an organic polymer film. 9. The composite material according to claim 1, wherein the support is an organic polymer film. 10. A support having at least one main surface which is a smooth surface having a maximum height of 100 nm or less is prepared, and a metal and / or metal compound film is provided on the smooth surface.
A method for producing a composite material having a gas barrier property, which comprises forming such that its thickness b1 is b1> a (a is the maximum height of the smooth surface). 11. A support having at least one main surface that is a smooth surface having a maximum height of 100 nm or less, and a metal and / or a metal having a thickness b2 on one main surface of the support. A metal compound film, and a metal and / or metal compound film having a thickness b3 on the other main surface are formed as (b2 + b3)> a (a
Is the maximum height of the smooth surface), and a method for producing a composite material having a gas barrier property. 12. The manufacturing method according to claim 10, wherein the metal and / or metal compound film is formed by a vacuum deposition method. 13. The manufacturing method according to claim 10, further comprising forming an amorphous carbon film on the surface of the metal and / or metal compound film. 14. An amorphous carbon film is formed on the main surface of a support on which a metal and / or metal compound film is formed, and a metal and / or metal compound film is formed on the surface of the amorphous carbon film. The manufacturing method according to claim 10 or claim 13. 15. The manufacturing method according to claim 11, further comprising forming an amorphous carbon film on the surface of one or both of the metal and / or metal compound films. 16. The method according to claim 1, further comprising forming an amorphous carbon film on one main surface of the support and forming a film of one metal and / or metal compound on the surface of the amorphous carbon film.
The manufacturing method according to claim 1 or claim 15. 17. A method comprising forming an amorphous carbon film on both main surfaces of a support and forming a film of both metals and / or metal compounds on the surface of the amorphous carbon film.
The manufacturing method according to claim 1 or claim 15. 18. The manufacturing method according to claim 13, wherein the amorphous carbon film is formed by a plasma CVD method. 19. The method according to claim 10, further comprising forming an organic polymer film on the surface of the metal and / or metal compound film by a wet coating method or a vapor deposition method. 20. The method according to claim 13, further comprising forming an organic polymer film on the surface of the amorphous carbon film by a wet coating method or a vapor deposition method. 21. The method according to claim 11, further comprising forming an organic polymer film on the surface of one or both of the metal and / or metal compound film by a wet coating method or a vapor deposition method. 22. The method according to claim 15, further comprising forming an organic polymer film on the surface of one or both of the amorphous carbon films by a wet coating method or a vapor deposition method. 23. A vacuum heat insulating material obtained by vacuum-packing a porous core material having open cells with an outer packaging material, wherein the outer packaging material is the composite material according to any one of claims 1 to 9. Insulation. 24. An organic EL device including a substrate, an anode, an organic material layer including an organic light emitting layer, a cathode, and a sealing film, wherein the anode, the organic material layer, and the cathode are located between the substrate and the sealing film. An organic EL element, wherein the sealing film is the composite material according to any one of claims 1 to 9. 25. An organic EL device including a substrate, an anode, an organic material layer including an organic light emitting layer, a cathode, and a sealing film, and the anode, the organic material layer, and the cathode being located between the substrate and the sealing film. An organic EL device, wherein both the substrate and the sealing film are the composite material according to any one of claims 1 to 9.