JP2003276115A - Laminate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which can be used for various applications due to a smooth surface and which can improve gas barrier properties by use together with a vapor deposited film of an inorganic oxide. <P>SOLUTION: The laminate comprises a base, and a resin thin film layer laminated on at least one surface of the base and made of a resin. In this laminate, the thin film layer has a temperature at an equilibrium vapor pressure of 10<SP>-3</SP>Torr of a range of 60 to 500°C, and is formed by polymerizing a vinyl polymerizable monomer which is not thermally decomposed at its temperature. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminate having a surface smoothed by forming a resin thin film on a substrate.

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging foods, non-foods, pharmaceuticals, etc., contain oxygen, water vapor, which permeate the packaging materials in order to suppress alteration of the contents and retain their functions and properties. In addition, it is necessary to prevent the influence of a gas that modifies the contents, and it is required to have a gas barrier property for blocking these gases.

Therefore, conventionally, a metal foil made of a metal such as aluminum, a metal vapor-deposited film thereof, polyvinyl alcohol, ethylene-
Resin films of vinyl alcohol copolymers, polyvinylidene chloride, polyacrylonitrile, etc. and those coated with these resins have been generally used as packaging materials for gas barrier layers.

However, a packaging material using a metal foil made of a metal such as aluminum or a metal vapor-deposited film thereof has excellent gas barrier properties, but it is not possible to see through the packaging material to confirm the contents. There was a problem that it had to be treated as an incombustible material at the time of disposal and that a metal detector could not be used at the time of inspection. In addition, gas barrier resin films and films coated with them have a high temperature-humidity dependency and cannot maintain a high level of gas barrier properties.In addition, polyvinylidene chloride, polyacrylonitrile, etc. can be used as raw materials of harmful substances when discarded or incinerated. There is such a problem.

Further, in the field of electronic devices, conventionally, inorganic materials such as Si wafer and glass have been widely used as substrates for electronic devices. However, in recent years, polymer substrates have been desired for various reasons such as weight reduction of products, flexibility of substrates, cost reduction, and handling characteristics. However, the polymer material has a problem that the gas permeability is significantly higher than that of an inorganic material such as glass.

Therefore, when a polymer substrate is used as a substrate for an electronic device, there is a problem that the device is oxidized and deteriorated by oxygen penetrating and diffusing into the electronic device through the polymer substrate. However, there is a problem that the required degree of vacuum in the electronic device cannot be maintained.

For example, in Japanese Unexamined Patent Publication Nos. 2-251429 and 6-124785, a polymer film is used as a substrate of an organic electroluminescence device. However, in the case of these organic EL elements, since the organic film is deteriorated by oxygen and water vapor penetrating into the organic EL element through the polymer film which is the substrate, the light emitting property becomes insufficient, and There may be problems such as concern about durability.

That is, as described above, a polymer having a sufficient gas barrier property in various fields and capable of ensuring a good quality of a gas barrier object by the gas barrier property and having an excellent gas barrier property. The film has not been established.

One of the problems in forming a vapor deposition film of an inorganic oxide such as a silicon oxide film on such a polymer film as a gas barrier film is the problem of smoothness of the polymer film surface. is there. Generally, there are fine irregularities on a polymer film, and when an inorganic oxide is formed on this by a vacuum film formation method, defects due to the film formation on the fine irregularities are found in the vapor deposition film. It has been pointed out that there is a problem that the gas barrier property is generated and the gas barrier property is deteriorated.

Further, for example, in an organic EL device,
When the surface on which the light emitting layer is formed has no flatness, there is a disadvantage that a black spot occurs, and thus various functional elements are required to have a smooth surface. In particular, in the case of forming a functional element on a polymer film for imparting flexibility, unevenness on the resin film becomes a problem, and means for smoothing such unevenness is required. It was

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and can be used for various purposes because of its smooth surface. In addition, it can be used together with a vapor deposited film of an inorganic oxide. Its main purpose is to provide a laminate that can improve gas barrier properties by using it.

[0012]

In order to achieve the above-mentioned object, the present invention, as set forth in claim 1, comprises a base material and at least one surface of the base material, which has a surface average roughness of 4 or less.
A resin thin film layer made of a resin having a thickness of not more than nm is provided. According to the present invention, since the surface average roughness is 4 nm or less as described above, even when it is used in various applications where smoothness is required, such as a substrate of an organic EL element, a black spot is generated. No trouble occurs. Further, by vapor-depositing an inorganic oxide on such a smooth surface, a uniform vapor-deposition layer with few defects can be deposited, so that a gas barrier film having a higher gas barrier property can be obtained.

In the invention described in claim 1, as described in claim 2, the temperature at which the resin thin film layer has an equilibrium vapor pressure of 10 ⁻³ Torr is 60 ° C. to 50 ° C.
It is preferable that the resin thin film layer is formed by polymerizing a vinyl polymerizable monomer which is in the range of 0 ° C. and is not thermally decomposed at that temperature. This is because it is possible to form a resin thin film layer having higher smoothness by using such a compound as a raw material.

The present invention also has a base material and a resin thin film layer made of a resin laminated on at least one surface of the base material, as described in claim 3, wherein the resin thin film layer has an equilibrium vapor pressure. Is 10 ⁻³ Torr at a temperature of 60 ° C. to 500 ° C.
There is provided a laminate, which is a resin thin film layer formed by polymerizing a vinyl polymerizable monomer which is in the range of 0 ° C. and does not undergo thermal decomposition at that temperature. According to the present invention, since the resin thin film layer is formed by using such a material, it is possible to form an extremely smooth surface, which is used as a substrate of a functional element having various functions. be able to.

In the invention described in claim 2 or 3, it is preferable that the resin thin film layer is formed in vacuum as described in claim 4. This is because a more uniform and smooth resin thin film layer can be formed by the dry film forming method.

In the invention described in any one of claims 2 to 4, as described in claim 5, the vinyl polymerizable monomer is contained at room temperature and atmospheric pressure (23 degrees, 1 atm). It is preferable that the solid state is). This is because such a vinyl-polymerizable monomer is preferable in the production process when forming the resin thin film layer.

In the invention described in any one of claims 2 to 5, as described in claim 6, the vinyl polymerizable monomer contains 5 to 5 carbon atoms.
It is preferable to have 50 alkyl groups or fluorinated alkyl groups as a substituent. The resin thin film layer obtained by polymerizing the vinyl polymerizable monomer having such a substituent has water repellency on the surface, so that the application requiring water repellency on the surface and the reduction of surface contamination are required. This is because it can be suitably used for various purposes, for example, for improving the gas barrier property when used together with a vapor deposition film of an inorganic oxide.

In the invention described in any one of claims 2 to 5, as described in claim 7, the vinyl polymerizable monomer is a (meth) acrylate monomer. preferable. Since the (meth) acrylate monomer is easy to introduce a substituent, it becomes possible to easily introduce a substituent required for imparting properties required for the resin thin film layer, such as water repellency. This is because it is possible to easily design the characteristics of the resin thin film layer.

In the invention described in claim 7, as described in claim 8, it is preferable that the (meth) acrylate monomer is a fluorinated alkyl (meth) acrylate monomer. By using such a material as the raw material of the resin thin film layer, it becomes possible to impart various properties such as water repellency and antifouling property while having a smooth surface, and to apply it to various applications. Is possible.

In the invention described in any one of claims 1 to 8, as described in claim 9, the contact angle with water on the surface of the resin thin film layer is 70 ° or more. The measurement temperature is preferably 23 ° C. This is because it is preferable to have such a water repellency in a water repellency application, for example, in a case where the gas barrier property is required when used together with an inorganic oxide vapor deposition layer.

In the invention described in any one of claims 1 to 9, as described in claim 10, the resin thin film layer has a thickness of 5 to 2000.
It is preferably in the range of nm. When the film thickness is smaller than the above range, it is difficult to obtain smoothness by forming a resin thin film layer, and in order to obtain smoothness, there is not much need to exceed the above upper limit. is there.

In the invention described in any one of claims 1 to 10, as described in claim 11, a vapor deposition layer made of an inorganic oxide is formed on the substrate. Even if the resin thin film layer is formed on the resin thin film layer, the resin thin film layer is formed on the base material and the inorganic oxide is formed on the resin thin film layer. The vapor deposition layer may be laminated. Since the resin thin film layer relaxes the stress of the vapor deposition layer and suppresses the defects of the vapor deposition layer due to the deformation when used together with the vapor deposition film of the inorganic oxide as described above, a highly flexible gas barrier film can be obtained. This is because it can be used as a gas barrier laminate having improved gas barrier properties.

In the invention described in claim 11 or claim 12, as described in claim 13, the vapor deposition layer and the resin thin film layer are laminated within a range of 2 to 10 layers. It is preferable. By laminating, the resin thin film layer relieves the stress of the vapor deposition layer and suppresses the defects of the vapor deposition layer due to deformation, so that a gas barrier film having high flexibility is obtained, and thus the gas barrier property is improved. .

In the invention described in any one of claims 11 to 13, claim 1
As described in 4, the outermost layer is preferably the resin thin film layer. By thus forming the resin thin film layer as the outermost layer, it becomes possible to improve the smoothness of the surface, and the application requiring both the characteristics of the surface smoothness and the gas barrier property, for example, the application such as the substrate of the organic EL element. This is because it can be used favorably.

In the invention described in any one of claims 11 to 14, claim 15
As described in, the vapor deposition layer made of the above inorganic oxide,
It is preferably a vapor deposition layer made of silicon oxide or silicon oxynitride. This is because these vapor deposition layers have excellent gas barrier properties.

In the invention described in any one of claims 11 to 14, claim 16
The film thickness of the vapor deposition layer is 5 to 500 n
It is preferably within the range of m. If the film thickness is thinner than the above range, there may be a problem in gas barrier properties, while if the film thickness is thicker than the above range, problems such as easy cracking of the deposited film may occur. Because there is.

In the invention described in any one of claims 11 to 15, claim 17
As described above, it is preferable that the substrate is a resin film. This is because, for example, flexible gas barrier films and the like are required in various packaging materials and various image display devices, and in such a case, a resin film is used as a base material.

In the invention described in any one of claims 11 to 17, claim 18
And the oxygen permeability of the laminate is 1.0 c.
c / m ² / day or less, and a water vapor transmission rate of 1.0
It is preferably g / m ² / day or less. By setting the oxygen permeability and the water vapor permeability within the above ranges, almost no oxygen and water vapor that cause a change in the quality of the contents are permeated, so that it can be preferably used in applications requiring high gas barrier properties. Because.

The present invention is also as described in claim 19.
As a raw material, the equilibrium vapor pressure is 10 ^-3Become Torr
The temperature is within the range of 60 ° C to 500 ° C, and the temperature is
The vinyl polymerizable monomer that does not thermally decompose in
The film forming process of forming a film on a substrate in a vacuum
The resulting monomer is irradiated with actinic radiation to polymerize,
And a polymerization step of forming a resin thin film layer.
A method of manufacturing a laminated body is provided.

According to the present invention, since a resin thin film layer having an extremely smooth surface can be formed on a substrate, for example, a vapor deposition film having few defects can be formed by laminating a vapor deposition film of an inorganic oxide thereon. Therefore, it is possible to produce a laminate having advantages such as being able to improve gas barrier properties.

In the present invention, the equilibrium vapor pressure is 10 ⁻³ To as a raw material as described in claim 20.
A vinyl polymerizable monomer having a temperature of rr within the range of 60 ° C. to 500 ° C. and not thermally decomposed at that temperature is used, and this is film-formed on a base material by a vapor deposition method assisting ions in vacuum. Provided is a method for producing a laminate, which comprises a resin thin film layer forming step of polymerizing to form a resin thin film layer. According to the present invention, since the resin thin film layer is formed by using the ion-assisted method, it has a smooth surface, and the degree of polymerization of the resin in the formed resin thin film layer is high, and the physical properties are good. It is possible to form a simple resin thin film layer.

In the invention described in claim 20, as described in claim 21, there is a post-treatment step of performing post-treatment by irradiating the formed resin thin film layer with an actinic radiation. It is preferable. By performing such a post-treatment step, the degree of polymerization in the resin thin film layer can be further improved, and the physical properties of the resin in the resin thin film layer can be improved.

In the invention described in any one of claims 19 to 21, claim 22
The method according to claim 23, which has a vapor deposition step of depositing an inorganic oxide by a vacuum film-forming method after the step of forming the resin thin film layer on the substrate as described in As described above, the deposition step of depositing the inorganic oxide on the substrate by the vacuum deposition method may be performed, and then the step of forming the resin thin film layer may be performed.

When the resin thin film layer is formed first, since the vapor deposition film of the inorganic oxide is deposited on the smoothed resin thin film layer surface, it is possible to reduce the occurrence of defects in the vapor deposition film. This is because, as a result, the gas barrier property can be improved. Therefore, when a vapor deposition film made of an inorganic oxide is formed first and then a resin thin film is formed, the gas barrier having an extremely smooth outermost layer. This is because a laminated body having a property can be obtained, and therefore, a laminated body which is required to have gas barrier properties and surface smoothness and which can be suitably used for, for example, a substrate of an organic EL element can be manufactured. Further, since the resin thin film layer relieves the stress of the vapor deposition layer and suppresses the defects of the vapor deposition layer due to deformation, it becomes possible to obtain a gas barrier film having high flexibility.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION First, a laminated body included in the present invention will be described, and then a manufacturing method of the laminated body included in the present invention will be described.

A. Laminated body The laminated body of the present invention has a base material and a specific resin thin film layer made of a resin formed on at least one surface of the base material. Hereinafter, the specific resin thin film layer which is a characteristic portion of such a laminated body of the present invention will be described first, and then the substrate and other configurations will be described.

1. Resin thin film layer The resin thin film layer in the present invention has characteristics in terms of material and form.

First, in terms of materials, the equilibrium vapor pressure is 10 ⁻³ as a raw material for forming the resin thin film layer in the laminate.
The point is that the temperature of Torr is in the range of 60 ° C. to 500 ° C., and a vinyl polymerizable monomer that does not undergo thermal decomposition at that temperature is used.

In the present invention, since the resin thin film layer is formed by using such a vinyl-polymerizable monomer, it is possible to obtain a laminate having extremely excellent surface smoothness. Hereinafter, such a resin thin film layer will be described as a first embodiment.

On the other hand, in terms of morphology, the surface average roughness of the resin thin film layer is 4 nm or less.
In the present invention, since the surface is extremely uneven as described above, it is possible to form a gas barrier film having a good gas barrier property by forming an inorganic oxide film on the surface of the resin thin film layer. A laminated body having the advantage of can be obtained. Hereinafter, such a resin thin film layer will be described as a second embodiment.

(1) First Embodiment In this embodiment, the resin thin film layer formed on the substrate is
The temperature at which the equilibrium vapor pressure is 10 ⁻³ Torr is 60 ° C. to 5 ° C.
00 ° C, preferably 80 ° C to 450 ° C, especially 100 ° C to
It is formed by polymerizing a vinyl-polymerizable monomer which is in the range of 400 ° C. and is not thermally decomposed at that temperature.

In the present embodiment, the method for producing this resin thin film layer is not particularly limited, and a wet method may be used, but generally, in a vacuum, the monomer is gradually evaporated and this is used. It is preferably produced by a method of depositing and polymerizing on a substrate or a vapor deposition layer. In order to use such a manufacturing method, it is preferable to use the above-mentioned materials. Specifically, a monomer having a temperature higher than the above range is likely to be difficult to vaporize at a temperature at which it is not thermally decomposed, and a monomer having a temperature lower than the above range should be gradually evaporated in the above-mentioned production method. However, even if it evaporates, it will evaporate again when it is deposited on the base material, and there is a problem such as poor fixability.

Another characteristic of such a material is that the vinyl polymerizable monomer is at room temperature and normal pressure (23 degrees, 1 atm).
It is preferable that the solid state is. As also described above, when forming a film in a vacuum, in order to evaporate gradually by heating in a vacuum and deposit on a substrate,
This is because the use of raw materials that are in a solid state at room temperature and atmospheric pressure facilitates handling.

The molecular weight of such a vinyl-polymerizable monomer is 50 or more and 1000 or less, and particularly 10
Those within the range of 0 to 800 are preferably used. This is because those having such an average molecular weight are easy to handle during the vacuum film formation as described above.

The vinyl-polymerizable monomer used in the present invention is a molecule having a carbon-carbon double bond capable of radical polymerization and has an equilibrium vapor pressure of 10 ⁻³ Torr.
There is no particular limitation as long as the temperature at which it falls within the above range, and various materials can be selected according to the characteristics of the resin thin film layer obtained.

Specifically, for example, in order to improve the water repellency of the surface, it is preferable that the above vinyl polymerizable monomer has a hydrophobic group, and specifically, it has 5 carbon atoms.
Those having an alkyl group or a fluorinated alkyl group having a carbon number of 50 to 50, preferably 10 to 30 as a substituent are suitably used.

In this embodiment, various kinds of substituents can be easily added to the vinyl-polymerizable monomer, that is, a substituent capable of imparting characteristics to the resin thin film layer to be obtained. Preferably there is.
Further, it is preferable that the resin thin film layer has good polymerizability. From this point of view, in the present embodiment, the vinyl polymerizable monomer is preferably a (meth) acrylate monomer. The (meth) acrylate monomer is a concept including an acrylate monomer and a methacrylate monomer.

Examples of the (meth) acrylate monomer that can be used in this embodiment include octadecyl acrylate, octadecyl methacrylate, stearyl acrylate, stearyl methacrylate, hexadecyl acrylate, and hexadecyl methacrylate. .

Further, in the present embodiment, among them, a fluoroalkyl (meth) acrylate monomer can be preferably used. This is due to the following reasons.

That is, by using such a fluorinated alkyl (meth) acrylate, the water repellency of the surface of the obtained resin thin film layer can be greatly improved. Therefore, by laminating it with a vapor deposition film of an inorganic oxide as described below, a laminate having improved gas barrier properties can be obtained.

Further, since a smooth film containing fluorine is formed on the surface of the base material, a protective film for surface modification of a material requiring a thermally and chemically stable surface, high water repellency,
Protective film for surface modification of materials that require resistance to surface contamination, insulating film for high-speed electronic devices that requires low dielectric constant and high resistivity, and optics that requires low refractive index and high transmittance. This is because it is possible to obtain a laminate having a wide range of applicability to applications such as surface coating of devices and clad layers of waveguide devices.

Specific examples of the fluorinated alkyl (meth) acrylate that can be used in the present invention include eicosafluoroundecyl acrylate,
Eicosafluoroundecyl methacrylate, hexadecafluorononyl acrylate, hexadecafluorononyl methacrylate, hexadecafluoro-9-
(Trifluoromethyl) decyl acrylate and hexadecafluoro-9- (trifluoromethyl) decyl methacrylate can be used, and eicosafluoroundecyl acrylate is particularly preferably used.

In the present embodiment, it can be said that the resin thin film layer preferably has water repellency as a characteristic. This water repellency is used in combination with the vapor-deposited film of an inorganic oxide having a gas barrier property as described above. For example, when it is desired to impart a gas barrier property when a polymer film is used as a substrate, By forming the resin thin film layer having water repellency on the surface, the gas barrier property can be greatly improved.

Also, by forming a resin thin film layer having water repellency on a hydrophilic substrate such as glass and removing it in a pattern, it is possible to form patterns having different wettability. This is because it is possible to form various functional elements such as color filters by applying coating liquids for forming various functional elements along the wettability.

As a measure of such water repellency, the contact angle with water on the surface of the resin thin film layer is 70 ° or more, especially 8
It is preferably within the range of 0 ° to 130 ° (measurement temperature 23 ° C). This is because it is preferable to have water repellency of this level for use in the above-mentioned applications.

The method of measuring the contact angle with water is as follows.
It is a value obtained by using a contact angle measuring device (model number CA-Z) manufactured by Kyowa Interface Science Co., Ltd. That is, one drop (a fixed amount) of pure water is dropped on the surface of the object to be measured, and after a certain time has passed,
A method of observing a water drop shape using a microscope or a CCD camera and physically determining a contact angle is used, and the contact angle with water measured by this method is taken as the contact angle with water in the present invention.

In the present invention, the film thickness of the resin thin film layer formed on such a base material depends on the intended use, the type of base material, the type of monomer used for forming the resin thin film layer, the resin thin film layer. Although it is largely different depending on the forming method and the like, it is generally in the range of 5 to 2000 nm, and particularly preferably in the range of 10 nm to 1000 nm. When the film thickness is smaller than the above range, it may be difficult to obtain smoothness by forming the resin thin film layer, and in order to obtain smoothness, it is necessary to exceed the above upper limit. This is because there is a possibility that problems in terms of material cost and production efficiency may occur.

The method of forming such a resin thin film layer is not particularly limited, and it may be formed by using a wet method, for example. However, a wet method such as a spray method or a spin coat method has a drawback that it is difficult to obtain smoothness at a molecular level (nm level), and a solvent is used, so that it is not suitable for electronic device applications. . In the present invention, it is preferable that the film is formed in vacuum from the viewpoint that a uniform film can be obtained and surface smoothness can be obtained relatively easily. In the present invention, a method of gradually evaporating the vinyl polymerizable monomer in a vacuum and vapor depositing it on the substrate is particularly preferable, in which the vinyl polymerizable monomer as described above can be used, for example, Japanese Patent No. 2996516. Vapor deposition methods in vacuum other than the flash vapor deposition method used in US Pat. This is because in the case of the flash evaporation method, since the raw material is a liquid, a post-treatment for curing the formed film is necessary, and when the treatment is not performed sufficiently, a liquid monomer exists and is insufficient. This is because there is a problem in that smoothness cannot be obtained, and in that case, the vapor pressure of the monomer is high, which itself deteriorates the characteristics of the electronic device.

(2) Second Embodiment The second embodiment of the resin thin film layer used in the present invention is a resin thin film layer made of a resin having a surface average roughness of 4 nm or less, and particularly 3 nm or less. Since the surface of the resin thin film layer of the present embodiment is such an extremely smooth surface that has never been seen in the past, for example, by forming an inorganic oxide on the surface of the resin thin film layer, a gas barrier film having a good gas barrier property is obtained. In addition, it can be used for various applications such as application as a base material of a recording medium that requires smoothness.

The surface average roughness value in this embodiment is the atomic force microscope (S) manufactured by Seiko Instruments.
TM), 100μM scan range, 135sec
The value determined by the condition of / frame is used.

The resin thin film layer made of such a resin is not particularly limited, but the materials described in the first embodiment can be used. The suitable material, characteristics, film thickness, etc. of the resin thin film layer of the present embodiment are the same as those of the first embodiment, so description thereof will be omitted here.

2. Substrate The substrate used in the present invention may be an organic substance such as resin or an inorganic substance such as glass, and may be transparent or opaque depending on the application to be used. Good. However, it is preferable that the base material be a plastic material and a transparent film in consideration of the application such as a packaging material and a substrate of an image display device such as an organic EL element.

Examples of such resinous film base materials are polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polystyrene films, polyethylene sulfone films, polyamide films. , Polyvinyl chloride film,
Examples thereof include a polycarbonate film, a polyacrylonitrile film, and a polyimide film.

The substrate may be stretched or unstretched,
Further, those having mechanical strength and dimensional stability are preferable. Among them, polyethylene terephthalate arbitrarily stretched in the biaxial direction is preferably used in packaging. Further, a polyether sulfone film has good solvent resistance and a polycarbonate film has good heat resistance, and is preferably used in electronic device applications. A thin film is formed by coating various well-known additives and stabilizers such as an antistatic agent, an ultraviolet protective agent, a plasticizer, and a lubricant on the surface of the base material on which the resin thin film layer is provided or on the opposite surface. May be.

Further, in order to improve the adhesion with the resin thin film layer or the vapor deposition film of inorganic oxide described later, corona treatment, low temperature plasma treatment, ion bombardment treatment, chemical treatment as the pretreatment of the surface of the base material, You may give a solvent treatment.

The thickness of the base material is not particularly limited in the case of packaging use, and in consideration of suitability as a packaging material, a film obtained by laminating films having different properties other than a single film can be used. However, considering the workability in the case of forming a resin thin film layer or a vapor deposition layer made of an inorganic oxide described later, the range of 3 to 400 μm is preferable for practical use, and the range of 6 to 30 μm is particularly preferable.

In the case of electronic device use, it may be an alternative to a glass substrate under the present circumstances, and in order to match the post-process equipment manufactured with the glass substrate specification, a relatively thick range of 100 to 800 μm, especially 100 to 800 μm. 400μ
The range of m is preferable, but as the technology advances, it is expected that the weight and flexibility of the substrate will be reduced, and the cost will be reduced.
It is considered that the range is 0 μm.

In consideration of mass productivity, it is desirable to use a continuous film having a long length so that the above layers can be continuously formed.

3. Inorganic oxide vapor deposition layer In the present invention, in addition to the resin thin film layer, an inorganic oxide vapor deposition film may be formed on the above-mentioned substrate. This is because a laminated body having high gas barrier properties can be obtained by forming a vapor deposition film made of an inorganic oxide and laminating it on the resin thin film layer in this manner.

In the present invention, a resin thin film layer may be formed on a substrate, and a vapor deposition layer made of an inorganic oxide may be formed on the surface of the resin thin film layer. Further, a vapor deposition layer made of an inorganic oxide may be formed on the substrate. May be formed, and the resin thin film layer may be formed thereon.

When the resin thin film layer is first formed on the substrate, since the vapor deposition layer made of an inorganic oxide is formed on the resin thin film layer having an extremely smooth surface, the vapor deposition layer may have unevenness of the base. Since no defect due to this occurs, there is an advantage that an extremely good gas barrier property can be obtained.

On the other hand, when the resin thin film layer is formed on the vapor deposition layer made of an inorganic oxide, the surface can be smoothed.
Even when the light emitting layer or the like of the element is formed, it is possible to reduce the possibility of causing a defect such as a dark spot.

In the present invention, it is preferable to repeatedly stack the resin thin film layer and the vapor deposition layer made of an inorganic oxide. Specifically, from the viewpoint of gas barrier properties, it is preferable that the vapor deposition layer is laminated at least twice, so that it is preferable to laminate within the range of 2 to 10 layers, particularly within the range of 2 to 6 layers. When the amount is less than the above range, it is not preferable because it may not be possible to obtain sufficient gas barrier properties although it depends on the gas barrier properties of the vapor deposition layer, and the gas barrier properties are improved even when laminated over the above range. However, it is not preferable because there is a possibility that a demerit accompanying the increase of the overall film thickness, for example, the occurrence of cracks may occur.

In the present invention, for the purpose of imparting smoothness to the base material, first, a resin thin film layer is formed on the base material, and then a vapor deposition layer made of an inorganic oxide and a resin thin film layer are formed in this order. A laminated body in which the outermost surface is a resin thin film layer after being laminated once is preferable. By forming a resin thin film layer on a substrate, it becomes possible to form a vapor deposition film composed of an inorganic oxide on a smooth surface, the gas barrier property is improved, and by further forming a resin thin film layer on the outermost surface. This is because it becomes possible to smooth the surface of the laminate, which is preferable when used as a substrate of an organic EL element or the like.

In the present invention, when the resin thin film layer is formed together with the inorganic oxide vapor deposition layer, the resin thin film layer is preferably a water repellent layer. By forming a layer having water repellency on the surface of the inorganic oxide layer in this manner, the gas barrier property can be further improved.

The vapor deposition layer made of such an inorganic oxide is
There is no particular limitation as long as it is transparent and has a gas barrier property against oxygen, water vapor and the like. Specifically, aluminum oxide, silicon oxide, silicon oxynitride, a mixture thereof, or the like can be given. In the present invention, from the viewpoint of having a high gas barrier property,
It is preferable to use silicon oxide or silicon oxynitride.

Optimum conditions for the film thickness of the vapor deposition layer made of such an inorganic oxide vary depending on the type and composition of the inorganic compound used, but it is generally desirable to be in the range of 5 to 500 nm, and especially 10 to 200 nm. It is preferably within the range. If the film thickness is smaller than the above range, a uniform film may not be obtained, and the function as a gas barrier material may not be sufficiently fulfilled, which is not preferable. Further, if the film thickness exceeds the above range, it may not be possible to maintain flexibility in the thin film, and it is not preferable because cracks may occur in the thin film due to external factors such as bending and pulling after the film formation. .

In the present invention, when the resin thin film layer and the vapor deposition layer made of an inorganic oxide are formed on the substrate, the oxygen permeability of such a laminate is 1 cc /
m ² / day or less, particularly preferably 0.5 cc /
m ² / day or less and a water vapor transmission rate of 1 g / m ²
/ Day or less, particularly preferably 0.5 g / m ² /
It is preferably not more than day. By setting the oxygen permeability and the water vapor permeability within the above ranges, almost no oxygen and water vapor that cause a change in the quality of the contents are permeated, so that it can be preferably used in applications requiring high gas barrier properties. Because. The above value is
It is a value when a resin, particularly a plastic film, is used as the base material.

B. Method for Manufacturing Laminated Body Next, a method for manufacturing a laminated body included in the present invention will be described. The method for manufacturing this laminated body can be roughly classified into two modes depending on whether or not an ion-assisted vapor deposition method is used. Hereinafter, the case where the ion-assisted vapor deposition method is not used (third embodiment) will be described first, and then the case where the ion-assisted vapor deposition method is used (fourth embodiment) will be described.

1. Third Embodiment In this embodiment, as a raw material, the equilibrium vapor pressure is 10 ⁻³ To.
a film forming step of forming a film on a substrate in a vacuum, using a vinyl polymerizable monomer having a temperature of rr within the range of 60 ° C. to 500 ° C. and not thermally decomposing at that temperature;
A method for producing a laminate, comprising a step of polymerizing the formed monomer by irradiating it with an actinic radiation to form a resin thin film layer.

Here, the vinyl-polymerizable monomer is the same as that described in the above-mentioned section "A. Laminated body", and therefore the description thereof is omitted here.

First, in the film forming step, such a vinyl polymerizable monomer is heated and vaporized in a high vacuum,
This is a step of depositing / forming a film on a base material. Next, a polymerization step of forming a resin thin film layer by irradiating the vinyl polymerizable monomer formed on the substrate with an actinic radiation to polymerize the vinyl polymerizable monomer is performed. The actinic radiation used here is not particularly limited as long as it can polymerize a vinyl-polymerizable monomer, but is usually an electron beam, an ultraviolet ray,
Gamma rays and the like are preferably used.

In the present invention, a vapor deposition step of forming a vapor deposition layer made of an inorganic oxide may be performed before or after performing the step of forming the resin thin film layer on such a base material. This vapor deposition step can be formed by various vacuum vapor deposition methods that are usually performed. However, when a base material that is susceptible to thermal damage such as a resin is used, the sputtering method is used. It is preferable to select a vacuum film forming method such as an ion plating method, a plasma vapor deposition method (CVD) or the like that does not cause thermal damage to the substrate. By performing such a vapor deposition process, a laminate having a gas barrier property can be obtained.

The matters such as the kind of the inorganic oxide and the film thickness of the vapor deposition film, and the matters concerning the obtained laminated body having a gas barrier property are the same as those described in the above "A. Laminated body". Therefore, the description is omitted here.

2. Fourth Embodiment In this embodiment, as a raw material, the equilibrium vapor pressure is 10 ⁻³ To.
A vinyl polymerizable monomer having a temperature of rr within the range of 60 ° C. to 500 ° C. and not thermally decomposed at that temperature is used, and this is film-formed on a base material by a vapor deposition method assisting ions in vacuum. A method for producing a laminate, which comprises a resin thin film layer forming step of polymerizing to form a resin thin film layer.

Here, the vinyl-polymerizable monomer is the same as that described in the above section "A. Laminated body", and therefore the description thereof is omitted here.

The feature of this embodiment is that this vinyl-polymerizable monomer is formed into a film and polymerized on a substrate in vacuum by using an ion-assisted vapor deposition method. Here, the ion-assisted vapor deposition method used in the present invention is a method of ionizing and vaporizing a part of a film forming material by using electrons or plasma for film formation and the like, and a typical example thereof is , Ionization deposition method, ion plating method, ion assisted deposition method, plasma polymerization method, plasma CVD method and the like. Specifically, as the ionizer, a thermoelectron generator consisting of a grid-shaped anode surrounding the passage area of the vapor deposition material and a tungsten filament-shaped cathode arranged outside it is used, and the tungsten filament is electrically heated to generate thermoelectrons. Then, an electron extraction voltage is applied to the anode to irradiate the evaporation material with the hot electrons, thereby ionizing the material.

By using such an ion-assisted vapor deposition method, the adhesion between the base material and the resin thin film layer formed on the base material is improved, and the polymerization of the vinyl polymerizable monomer is promoted. A resin thin film layer having high properties can be obtained.

In the vapor deposition method using the above-mentioned ions, it can be said that the electron acceleration voltage is preferably in the range of 30 to 300V. In addition, current, per deposition area 1cm ^2, 0.
01 to 10 mA is a preferable range. If both the accelerating voltage and the current are lower than the above range, it is not preferable because the progress of the polymerization may be slowed. If the accelerating voltage and the current are over the above range, carbonization may progress, or decomposition may result in a complicated structure. It is not preferable because it may occur.

In this embodiment, after the resin thin film layer forming step of forming the resin thin film layer by the ion assisted vapor deposition method as described above, a post-treatment step of further irradiating with an active irradiation ray may be performed. This is because it is possible to complete the polymerization of the vinyl polymerizable monomer by performing such a post-treatment process. Note that the active irradiation line used here is the same as that described in the third embodiment, so description thereof will be omitted here.

Also in this embodiment, the step of forming a vapor deposition film made of an inorganic oxide by the vacuum film forming method as in the third embodiment is performed before the resin thin film layer forming step.
Alternatively, it may be performed later. Since this point is the same as the third embodiment, the description thereof is omitted here.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, has substantially the same configuration as the technical idea described in the scope of the claims of the present invention, and has any similar effect to the present invention. It is included in the technical scope of the invention.

[0093]

EXAMPLES The laminate of the present invention will be specifically described below with reference to examples. The present invention is not limited to the examples below.

Example 1 As a base material, a thickness of 100 μm
The biaxially stretched polyethylene naphthalate (PEN) film was prepared. The degree of vacuum in the chamber is 4.0 × 10
^The pressure was reduced to ^-3 Pa. Electric power having a frequency of 90 kHz (input power 300 W) was applied to the electrodes. Hexamethyldisiloxane (HMDSO), oxygen gas, and helium gas were introduced in predetermined amounts. Vacuum degree at that time is 30 Pa
Control was performed to form a silicon oxide thin film of 100 nm by plasma vapor deposition (CVD method).

Next, the vacuum degree of the vacuum evaporation system using ions shown in FIG. 1 was reduced to 2 × 10 ⁻³ Pa. After that, the stainless steel crucible 1 was heated to 100 ° C. to evaporate the acrylate compound 2 as the evaporation material. At that time, a current of 3 A is applied to the tungsten filament 3
And apply an electron extraction voltage of 50 V to the anode 4 and
A 0 mA thermoelectron was generated in the vacuum chamber. Thus, the resin thin film layer 5 having a thickness of 200 nm was formed on the base material 6 to obtain the laminate of the present invention.

Table 1 shows the results evaluated by the following evaluation methods.
Put together.

(Silicon oxide film forming conditions) Introduced gas ratio: hexamethyldisiloxane: oxygen gas: helium = 1
0:30:30 (sccm) (Acrylate film formation conditions) Acrylate compound: n-octadecyl acrylate Evaporation temperature: 100 ° C. Film formation rate: 20 nm / min Ionization filament current: 3 A Electron emission current: 10 mA Electron extraction voltage: 50 V Ionization anodic potential: 50 V Substrate potential: 0 V [Comparative Example 1] A laminate was obtained in the same manner as in Example 1 except that the resin thin film layer was not provided. Table 1 summarizes the results evaluated by the following evaluation methods.

[0098]

[Table 1]

(Evaluation method) Oxygen permeability: Oxygen gas permeability measuring device (manufactured by MOCON:
OX-TRAN2 / 20) was used and the measurement was performed at 23 ° C. and 90% Rh. -Water vapor permeability: Water vapor permeability measuring device (MOCON:
PERMATRAN 3/31), 37.8 ° C 10
It was measured under the condition of 0% Rh. -Surface smoothness: measured with an atomic force microscope (Nanopics manufactured by Seiko Instruments) under the conditions of 100 μM scan range and 135 sec / frame, and the average roughness Ra, the maximum height difference Rmax, and the mean square roughness Rms are measured. I asked. -Surface wettability: The contact angle with water was determined using a contact angle measuring device.・ Organic film confirmation: Infrared spectroscopic analyzer (FT-6 manufactured by JASCO Corporation)
10) was used, and the equipped ATR (total reflection) measuring device was attached to measure the infrared absorption spectrum of the thin film surface.

[Embodiment 2] As a vapor deposition material, 1H, 1H, 1H-E
It was evaporated with icosafluoroundecyl acrylate at a temperature of 100 ° C. A glass substrate on which aluminum was vapor-deposited was used as a substrate material, and the substrate temperature was kept at -20 ° C.

When vapor deposition was performed while irradiating electrons with energy of 50 eV and current amount of 5 mA, a thin film was grown at a rate of 0.45 nm / min. When the infrared absorption spectrum of this film was compared with that of the monomer, the peak of stretching vibration of the vinyl group at 1416 cm ⁻¹ shifted to the high frequency side. This shows that a vinyl polymer having the basic molecular structure of the monomer material was obtained.

The contact angle of water on the surface of the resin thin film layer thus obtained was 87 °.

[Example 3] A resin thin film layer was formed on a substrate in the same manner as in Example 2 except that the electron current was set to 30 mA. A fluoropolymer thin film could be obtained at a film forming rate of 1.1 nm / min.

[0104]

According to the present invention, the resin thin film layer is formed by using the specific vinyl polymerizable monomer.
An extremely smooth surface can be obtained, which brings about an effect that it can be used as a substrate of functional elements having various functions.

[0105]

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of an ion-assisted vapor deposition method in the present invention.

[Explanation of symbols]

1 ... crucible 2 ... Evaporation material 3 ... Tungsten filament 4 ... Anode 5 ... Resin thin film layer 6 ... Base material

Continued front page    F-term (reference) 4F100 AA01D AA01E AA20D AA20E                       AK01A AK01B AK01C AK21B                       AK21C AK25B AK25C AK42                       AT00A BA02 BA03 BA04                       BA05 BA06 BA07 BA08 BA10B                       BA10C BA10D BA10E BA13                       DD07B DD07C EH66 EH662                       EJ24 EJ242 EJ52 EJ522                       GB23 GB66 JD03 JM02B                       JM02C JM02D JM02E YY00B                       YY00C

Claims (23)

[Claims] 1. A laminate comprising: a base material; and a resin thin film layer formed on at least one surface of the base material and made of a resin having a surface average roughness of 4 nm or less. 2. The equilibrium vapor pressure of the resin thin film layer is 10
^The resin thin film layer is formed by polymerizing a vinyl polymerizable monomer that has a temperature of ⁻³ Torr of 60 ° C. to 500 ° C. and is not thermally decomposed at that temperature. The laminate described. 3. A base material and a resin thin film layer made of a resin laminated on at least one surface of the base material, wherein the resin thin film layer has a temperature at which the equilibrium vapor pressure is 10 ⁻³ Torr of 60 ° C. A resin thin film layer formed by polymerizing a vinyl polymerizable monomer that does not undergo thermal decomposition at a temperature in the range of 500 ° C. and is a resin thin film layer. 4. The laminate according to claim 2 or 3, wherein the resin thin film layer is formed in vacuum. 5. The laminate according to any one of claims 2 to 4, wherein the vinyl-polymerizable monomer is in a solid state at room temperature and normal pressure (23 ° C, 1 atm). . 6. The vinyl polymerizable monomer has 5 carbon atoms.
The laminated body according to any one of claims 2 to 5, which has ˜50 alkyl groups or fluorinated alkyl groups as a substituent. 7. The vinyl-polymerizable monomer is (meth)
An acrylate monomer, characterized in that
The laminated body according to any one of claims 1 to 6. 8. The (meth) acrylate monomer is
The laminate according to claim 7, which is a fluorinated alkyl (meth) acrylate monomer. 9. The contact angle with water on the surface of the resin thin film layer is 70 ° or more (measurement temperature 23 ° C.), according to any one of claims 1 to 8. Laminate. 10. The film thickness of the resin thin film layer is from 5 to 200.
It is in the range of 0 nm, The laminated body in any one of Claim 1 to Claim 9 characterized by the above-mentioned. 11. The vapor deposition layer made of an inorganic oxide is formed on the base material, and the resin thin film layer is further formed on the base material. The laminated body according to. 12. The method according to claim 1, wherein the resin thin film layer is formed on the base material, and a vapor deposition layer made of an inorganic oxide is further laminated thereon. The laminated body according to. 13. The vapor deposition layer and the resin thin film layer are 2
It laminated | stacked within the range of a layer-10 layer, The laminated body of Claim 11 or Claim 12 characterized by the above-mentioned. 14. The laminate according to claim 11, wherein the outermost layer is the resin thin film layer. 15. The layered structure according to claim 11, wherein the vapor deposition layer made of the inorganic oxide is a vapor deposition layer made of silicon oxide or silicon oxynitride. body. 16. The thickness of the vapor deposition layer is 5 to 500 nm.
The laminated body according to any one of claims 11 to 15, wherein the laminated body is within the range. 17. The laminated body according to claim 11, wherein the base material is a resin film. 18. The oxygen permeability of the laminate is 1.0 cc.
/ M ² / day or less, and water vapor transmission rate is 1.0 g
/ M ² / day or less, 11.
The laminated body according to any one of claims 1 to 17. 19. A raw material having an equilibrium vapor pressure of 10 ⁻³ T.
the temperature of orr is in the range of 60 ° C to 500 ° C,
And using a vinyl polymerizable monomer that is not thermally decomposed at that temperature, a film forming step of forming a film on a base material in a vacuum, the monomer formed is irradiated with actinic radiation to polymerize, And a polymerization step of forming a resin thin film layer. 20. As a raw material, the equilibrium vapor pressure is 10 ⁻³ T.
the temperature of orr is in the range of 60 ° C to 500 ° C,
In addition, a resin thin film layer forming step of forming a resin thin film layer by using a vinyl polymerizable monomer that does not thermally decompose at that temperature and forming a resin thin film layer on a substrate by using an ion assisted vapor deposition method in vacuum A method for producing a laminate, which comprises: 21. The resin thin film layer further formed,
The method for producing a laminate according to claim 20, further comprising a post-treatment step of performing post-treatment by irradiating with actinic radiation. 22. The method according to claim 19, further comprising a vapor deposition step of depositing an inorganic oxide by a vacuum deposition method after performing the step of forming the resin thin film layer on a base material. The method for producing a laminate according to claim 1. 23. The vapor deposition step of vapor depositing an inorganic oxide on a substrate by a vacuum film forming method, and then the step of forming the resin thin film layer is performed. A method for producing a laminate according to any one of claims.