WO2015146323A1

WO2015146323A1 - Functional film and method for producing functional film

Info

Publication number: WO2015146323A1
Application number: PCT/JP2015/053618
Authority: WO
Inventors: 友和関; 英二郎岩瀬
Original assignee: 富士フイルム株式会社
Priority date: 2014-03-27
Filing date: 2015-02-10
Publication date: 2015-10-01
Also published as: JP2015189047A; JP6042840B2

Abstract

The present invention addresses the problem of providing: a low-cost functional film which is free from damage on an inorganic layer or the like and stably exhibits an aimed performance; and a method for producing this functional film. The problem is solved by a functional film wherein: the retardation value of a gas barrier supporting body is 300 nm or less; the lowermost layer and the uppermost layer of an organic-inorganic laminate are inorganic layers; the difference between the linear expansion coefficient of the gas barrier supporting body and the linear expansion coefficient of a backside protective film is 0-80 ppm/°C; the melting point of a frontside protective film is 80-170°C; the adhesive force between the gas barrier supporting body and an adhesive layer is from 0.01 N/25 mm to 0.15 N/25 mm; and the adhesive force between the frontside protective film and an inorganic layer is from 0.02 N/25 mm to 0.06 N/25 mm.

Description

Functional film and method for producing functional film

The present invention relates to a functional film having a laminated structure of an organic layer and an inorganic layer, and a method for producing the functional film.

Gas barrier films such as optical elements, display devices such as liquid crystal displays and organic EL displays, various semiconductor devices, parts and components that require moisture resistance in various devices such as solar cells, and packaging materials for packaging food and electronic components Has been.
The gas barrier film generally has a configuration in which a plastic film such as a polyethylene terephthalate (PET) film is used as a support (substrate) and a gas barrier layer that exhibits gas barrier properties is formed thereon. Moreover, as a gas barrier layer used for a gas barrier film, the layer which consists of various inorganic compounds, such as a silicon nitride, silicon oxide, aluminum oxide, is known, for example.

In such a gas barrier film, as a configuration for obtaining higher gas barrier performance, an organic / organic layer having a laminated structure in which an organic layer made of an organic compound and an inorganic layer made of an inorganic compound are alternately laminated on a support. An inorganic laminated gas barrier film (hereinafter also referred to as a laminated gas barrier film) is known.
In the laminated gas barrier film, the inorganic layer mainly exhibits gas barrier properties. In a laminated gas barrier film, an inorganic layer is formed on an organic layer serving as a base, whereby the formation surface of the inorganic layer is smoothed by the organic layer, and the inorganic layer is formed on the organic layer having good smoothness. Form. Thereby, the uniform inorganic layer without a crack, a crack, etc. is formed, and the outstanding gas barrier performance is acquired. Moreover, more excellent gas barrier performance can be obtained by repeatedly including a plurality of laminated structures of the organic layer and the inorganic layer.

A so-called roll-to-roll (hereinafter also referred to as RtoR) is known as a method for producing such a laminated gas barrier film. RtoR means that a support is fed from a support roll formed by winding a long support in a roll shape, and the support, that is, the film-forming material is conveyed in the longitudinal direction, while an organic layer or an inorganic is applied to the support. This is a manufacturing method in which a layer is formed and a support on which an organic layer or an inorganic layer is formed is wound into a roll.
By using RtoR, an organic layer or an inorganic layer can be continuously formed while transporting a long support, so that a laminated gas barrier film can be produced with very high productivity.

As described above, in the laminated gas barrier film, it is the inorganic layer that mainly exhibits gas barrier properties. Therefore, when the inorganic layer is damaged, the gas barrier performance is significantly lowered.
In the laminated gas barrier film, the organic layer functions as a base layer for appropriately forming the inorganic layer. Accordingly, when the organic layer is damaged, a proper inorganic layer cannot be formed, and the gas barrier performance is also greatly reduced.

On the other hand, in the laminated gas barrier film, it is advantageous that the support is thin in consideration of optical characteristics, weight, cost, and the like.
However, the thin support has a weak self-supporting property (so-called stiffness), and is liable to be bent during the transport by RtoR. If the support on which the organic layer or the inorganic layer is formed is bent during conveyance, the previously formed organic layer or inorganic layer is damaged.

In addition, in RtoR, it may be unavoidable that a pair of conveying rollers, a guide roller, or the like is in contact with an organic layer or an inorganic layer. However, the organic layer or the inorganic layer may be damaged by the contact of the roller.
In order to eliminate such inconvenience, in the production of a laminated gas barrier film using RtoR, a so-called stepped roller having a large end portion diameter is used to sandwich and convey only the end portion of the support. It is known to use contact transport.
However, when the stiffness of the support is weak, it becomes increasingly difficult to carry out proper conveyance by such non-contact conveyance.

In order to eliminate such inconveniences, Patent Document 1 and Patent Document 2 describe that an organic layer or an inorganic layer is formed by RtoR using a support in which a laminate film is attached to a non-formation surface of an organic film or an inorganic film. A method for producing a gas barrier film for forming a layer is described.
According to this method, by attaching a protective material to the back surface of the support, the support, or the self-supporting property of the laminate including the support, can be secured, and when a thin support is used, Even when non-contact conveyance is used, the organic layer and the inorganic layer can be appropriately formed by RtoR without causing the support to be bent.

In addition, in order to prevent the inorganic layer on the surface from coming into contact with the guide roller or the like and damaging the inorganic layer during handling in RtoR manufacturing or winding around a roll, the surface of the deposited inorganic layer is protected. A film is also pasted (Patent Document 3).

JP 2011-149057 A JP 2011-167967 A JP 2012-192738 A

By the way, in recent years, it has been considered to use an organic / inorganic laminated gas barrier film for a top emission type organic EL device used for a mobile phone, a display, or the like.
In a laminated gas barrier film used for such applications, it is necessary to use a support having a low retardation value and high optical transparency, such as a cycloolefin copolymer (COC) film. In terms of optical properties of the gas barrier film, the support is preferably thin.

However, a laminated gas barrier film using such a COC film or the like as a support cannot be manufactured inexpensively and appropriately by RtoR using the protective material described above.

That is, in the production of a laminated gas barrier film using a protective material, the protective material does not become a part of the product, but is finally peeled off and discarded. Therefore, an inexpensive polyethylene terephthalate (PET) film or the like is used as the protective material.

On the other hand, in the case of a laminated gas barrier film, a vapor phase film forming method such as plasma CVD is used to form a normal inorganic layer. For the formation of the organic layer, an application method is used in which a coating containing an organic material that becomes the organic layer is applied, dried, and cured.
That is, in the production of a laminated gas barrier film, the support and the protective material are exposed to heat by a vapor deposition method such as plasma CVD in the formation of the inorganic layer, and in the formation of the organic layer, Exposed to heat during drying. Furthermore, in the formation of the organic layer, heating may be performed when the coating film is cured.

However, a film having excellent optical characteristics such as a COC film and a PET film are completely different in thermal expansion / shrinkage and thermal characteristics such as Tg. Therefore, both films show different deformations in processes involving heating.
In the production of a laminated gas barrier film by RtoR, when a film having different thermal characteristics is used between the support and the protective material as described above, there is a stress due to conveyance, bending due to a change in the conveyance route, etc. Due to the different deformations of the two films in the process involving, peeling of the support and the protective material, wrinkles and breakage of the support, and the like cause damage to the inorganic layer.
Moreover, it is difficult to completely adhere between the support and the protective material, and bubbles exist between the support and the protective material. For this reason, in the process involving heating, the bubbles expand, and the support and the protective material are peeled off, and the support is wrinkled or broken.

The problem caused by the difference in the thermal characteristics between the support and the protective material does not occur if the support and the protective material are made of the same material, that is, the same thermal characteristics are used.
However, a film having excellent optical properties such as a COC film is very expensive as compared with a PET film or the like. Further, as described above, the protective material is a material that is finally discarded. Therefore, when a film having excellent optical properties such as a COC film is used as the support, the cost of the laminated gas barrier film becomes very high if a protective material is used from the same material.
Further, even if the same material is used for the support and the protective material, peeling due to air bubbles existing between the support and the protective material, wrinkles and breakage of the support cannot be suppressed.

Of the films having excellent optical properties, the COC film has low adhesion to the organic layer. Therefore, even if an organic layer is laminated on a support as an underlayer of the inorganic layer, peeling occurs between the support and the organic layer due to stress due to transport or bending due to change of the transport path, etc. As a result, the inorganic layer is damaged.

By the way, when an organic / inorganic laminated type gas barrier film is used for a top emission type organic EL device or the like, an adhesive is used on a passivation film having a gas barrier property covering an organic EL material as a light emitting element. Laminate the gas barrier film.

In such an organic EL device, examples of the passivation film forming material include inorganic materials such as silicon nitride, silicon oxide, and silicon oxynitride that exhibit gas barrier properties.
Therefore, from the viewpoint of adhesiveness, in the organic / inorganic laminated type gas barrier film used for organic EL devices and the like, the uppermost layer is an inorganic layer, the inorganic layer and the passivation film face each other, and the inorganic materials are bonded to each other. It is preferable to laminate via an adhesive.

Here, as described above, since the inorganic layer is brittle and easily broken, a protective film for protecting the inorganic layer is attached to the uppermost inorganic layer of the produced gas barrier film. When such a gas barrier film is incorporated into an organic EL device or the like, the protective film is peeled off to expose the inorganic layer, and is adhered onto the passivation film.
Here, when the protective film and the inorganic layer are attached via an adhesive, when the protective film is peeled off, the adhesive remains on the inorganic layer, and adhesion between the passivation film and the inorganic layer is achieved. May interfere.

An object of the present invention is to solve such problems of the prior art, and in an organic / inorganic laminated functional film formed by alternately forming an organic layer and an inorganic layer, the organic layer and the inorganic layer Provided with a functional film that stably exhibits the target performance at a low cost and without damage to the inorganic layer, even when heating is involved in the formation of the film, and a method for producing the functional film There is to do.

As a result of intensive research aimed at achieving the above-mentioned problems, the present inventors have found that in a functional film in which an organic-inorganic laminate is laminated on a gas barrier support having a low retardation value and excellent optical properties, the lowermost layer and the lowest layer of the organic-inorganic laminate. The upper layer is an inorganic layer, the difference between the coefficient of linear expansion of the gas barrier support and the coefficient of linear expansion of the back surface protective film is within a predetermined range, the melting point of the protective film is within a predetermined range, and the adhesive strength between the gas barrier support and the adhesive layer By using a functional film that defines the adhesive strength between the protective film and the uppermost inorganic layer, the organic layer and the inorganic layer can be formed at a low cost, even when heating is involved in the formation of the organic layer and the inorganic layer. The present invention has been completed by finding that the intended performance is stably exhibited without any damage.
That is, this invention provides the functional film of the following structures, and its manufacturing method.

(1) The gas barrier support, the organic / inorganic laminate formed on the gas barrier support by alternately laminating the inorganic layer and the organic layer, and the surface of the gas barrier support on which the organic / inorganic laminate is formed ( Having a pressure-sensitive adhesive layer attached to the opposite surface), a back surface protective film attached to the pressure-sensitive adhesive layer, and a protective film laminated on the organic-inorganic laminate,
The retardation value of the gas barrier support is 300 nm or less,
The organic-inorganic laminate has one or more organic layers and two or more inorganic layers, and the bottom layer on the gas barrier support side and the top layer on the surface protective film side are inorganic layers,
The difference between the coefficient of linear expansion of the gas barrier support and the coefficient of linear expansion of the back surface protective film is 0 to 80 ppm / ° C.
The melting point of the surface protective film is 80 to 170 ° C.,
The adhesive strength of the gas barrier support and the adhesive layer at 25 ° C. is 0.01 N / 25 mm to 0.15 N / 25 mm,
A functional film in which the adhesive strength at 25 ° C. between the surface protective film and the uppermost inorganic layer of the organic-inorganic laminate is 0.02 N / 25 mm to 0.06 N / 25 mm.
(2) The function according to (1), wherein the first mixed layer is provided between the gas barrier support and the lowermost inorganic layer of the organic-inorganic laminate, and the thickness of the first mixed layer is 1 nm to 20 nm. Sex film.
(3) The organic-inorganic laminate has a second mixed layer between the organic layer and the inorganic layer laminated on the organic layer, and the thickness of the second mixed layer is 1 nm to 20 nm (1 ) Or the functional film according to (2).
(4) The functional film according to any one of (1) to (3), wherein the adhesive force between the adhesive layer and the back surface protective film at 25 ° C. is 0.05 N / 25 mm to 0.20 N / 25 mm.
(5) The thickness of the gas barrier support is 20 μm to 120 μm, the thickness of one organic layer of the organic-inorganic laminate is 0.5 μm to 5 μm, and the thickness of one inorganic layer is 10 nm to 200 nm. The thickness of the adhesive layer is 15 μm to 250 μm, the thickness of the back surface protective film is 12 μm to 100 μm, and the thickness of the surface protective film is 20 μm to 100 μm. Functional film.
(6) The functional film according to any one of (1) to (5), wherein the glass transition temperature of the gas barrier support is 130 ° C. or higher, and the glass transition temperature of the back surface protective film is 70 ° C. or higher.
(7) The adhesive strength between the gas barrier support and the adhesive layer at 100 ° C. is 0.03 N / 25 mm to 0.14 N / 25 mm, and the adhesive strength at 200 ° C. is 0.04 N / 25 mm to 0.13 N / 25 mm. The adhesive strength between the adhesive layer and the back surface protective film at 100 ° C. is 0.07 N / 25 mm to 0.19 N / 25 mm, and the adhesive strength at 200 ° C. is 0.08 N / 25 mm to 0.18 N / 25 mm (1 ) To (6).
(8) The functional film according to any one of (1) to (7), wherein the back surface protective film has a friction coefficient of 0.6 or less.
(9) The functional film according to any one of (1) to (8), wherein the Young's modulus of the surface protective film is ¼ or less of the Young's modulus of the gas barrier support and the Young's modulus of the back surface protective film.
(10) The pressure-sensitive adhesive layer is made of a pressure-sensitive adhesive material in which the alkyl group portion of the alkyl acrylate monomer has 3 to 10 carbon atoms, or further contains an alkyl methacrylate monomer, and has a temperature of 25 ° C. to 150 ° C. and a UV irradiation amount of 100 mJ. The functional film according to any one of (1) to (9), wherein the volume shrinkage due to crosslinking is 3% or less when crosslinked under the conditions of / cm ² to 1000 mJ / cm ² .
(11) A long laminate having a gas barrier support, an adhesive layer attached to the gas barrier support, and a back surface protective film attached to the adhesive layer, and a gas barrier support of the elongated laminate A step of producing a composite having an inorganic layer and an organic layer laminated alternately on the surface, and the surface opposite to the back surface protective film is an organic layer;
A film forming step of forming the uppermost inorganic layer by vapor phase growth on the organic layer on the surface while transporting the composite in the longitudinal direction;
A surface protective film attaching step for attaching a surface protective film on the uppermost inorganic layer formed in the film forming step;
The film forming step and the surface protective film attaching step are continuously performed under the same pressure and temperature environment,
The retardation value of the gas barrier support is 300 nm or less,
The difference between the coefficient of linear expansion of the gas barrier support and the coefficient of linear expansion of the back surface protective film is 0 to 80 ppm / ° C.
The melting point of the surface protective film is 80 to 170 ° C.,
A method for producing a functional film, wherein an adhesive force between a gas barrier support and an adhesive layer at 25 ° C. is 0.01 N / 25 mm to 0.15 N / 25 mm.
(12) The step of producing the composite includes an application step of applying a composition to be an organic layer on the inorganic layer, and a drying step of drying the applied composition of the long laminate in which the inorganic layer is laminated. The method for producing a functional film according to (11), wherein the temperature of the composite is 70 ° C. or higher in the drying step.
(13) The step of producing the composite includes an application step of applying a composition to be an organic layer on the inorganic layer, and a drying step of drying the applied composition of the long laminate in which the inorganic layer is laminated. And a curing step of forming an organic layer by irradiating the dried composition with ultraviolet irradiation, and in the curing step, the composite is heated from the back surface protective film side so that the temperature becomes 30 ° C. or higher. The method for producing a functional film according to (11) or (12), wherein ultraviolet irradiation is performed.

According to the present invention, in the organic / inorganic laminated functional film in which the organic layer and the inorganic layer are alternately laminated, even when heating is involved in the formation of the organic layer and the inorganic layer, By using an inexpensive protective material, it is possible to manufacture a functional film having the desired performance without damage to the inorganic layer or the like at a low cost.

1 (A) and 1 (B) are diagrams conceptually showing an example of the functional film of the present invention, and FIG. 1 (C) shows an adhesive layer and a back surface protective film from the functional film of the present invention. It is a figure which shows notionally an example of the state which peeled the surface protection film. It is a figure which shows notionally an example of the manufacturing apparatus which enforces the manufacturing method of the functional film of this invention, Comprising: FIG. 2 (A) is a film-forming apparatus of an inorganic layer, FIG.2 (B) is film-forming of an organic layer Device.

Hereinafter, the functional film of the present invention and the method for producing the functional film will be described in detail based on the preferred embodiments shown in the accompanying drawings.

FIG. 1A conceptually shows an example in which the functional film of the present invention is used as a gas barrier film.

In addition, the functional film of this invention is not limited to a gas barrier film. That is, the present invention can be used in various known functional films such as various optical films such as a filter that transmits light of a specific wavelength and an antireflection film.
In the organic / inorganic laminated functional film like the functional film of the present invention, it is the inorganic layer that mainly exhibits the intended function. Therefore, the functional film of the present invention may be configured by selecting an inorganic layer that exhibits a desired function such as light transmittance at a specific wavelength.

However, according to the present invention, a functional film having an inorganic layer free from defects such as cracks and cracks can be obtained by having an adhesive layer and a protective material described later. Moreover, the functional film excellent in the optical characteristic is obtained by selecting the thing which consists of a material excellent in optical characteristics, such as a low retardation value, as a support body.
Therefore, the present invention is more suitably used for a gas barrier film that often requires high optical properties and has a large performance deterioration due to damage to the inorganic layer.

The gas barrier film according to the functional film of the present invention is an organic / inorganic laminate obtained by alternately laminating inorganic layers 14 and organic layers 16 on the front surface (main surface) of the gas barrier support 12. It has the above-mentioned organic / inorganic laminated type gas barrier film. Note that in FIG. 1A, only the inorganic layer 14 is hatched in order to clarify the configuration.
A gas barrier film 10a shown in FIG. 1 (A) has a gas barrier support 12 having an inorganic layer 14 on the surface, an organic layer 16 thereon, and a second inorganic layer 14 thereon. The inorganic layer 14 and the organic layer 16 of the support 12 are alternately formed, and a total of three layers of two inorganic layers 14 and one organic layer 16 are laminated. The two inorganic layers 14 and the one organic layer 16 constitute an organic / inorganic laminate 28 in the present invention.
An adhesive layer 20 is attached to the back surface of the gas barrier support 12, that is, the reverse surface (the opposite surface) of the formation surface of the inorganic layer 14 and the organic layer 16. A film 24 is attached. The gas barrier support 12, the adhesive layer 20, and the back surface protective film 24 constitute a laminate 26 in the present invention.
Furthermore, the surface protective film 18 is stuck on the organic / inorganic laminate 28, that is, on the second inorganic layer 14.

In addition, in the gas barrier film 10a shown to FIG. 1 (A), although the organic inorganic laminated body 28 was set as the structure which laminated | stacked the inorganic layer 14 and the organic layer 16 alternately in total in this order, the gas barrier of this invention The film is not limited to this.
For example, as in the gas barrier film 100 shown in FIG. 1B, the organic / inorganic laminate 28 is formed on the second inorganic layer 14, the second organic layer 16, and the third inorganic layer. 14 may be configured to have a total of five layers of three inorganic layers 14 and two organic layers 16 laminated. Alternatively, the organic / inorganic laminate 28 may have a total of seven or more layers in which the inorganic layers 14 and the organic layers 16 are alternately laminated.
As will be described later, the organic layer 16 functions as a base layer for properly forming the inorganic layer 14, and the more the number of layers of the combination of the base organic layer 16 and the inorganic layer 14, the better. A gas barrier film having gas barrier properties can be obtained.

In the organic / inorganic laminate 28, the lowermost layer on the gas barrier support 12 side and the uppermost layer on the surface protective film 18 side are both inorganic layers 14.
This will be described in detail later.

As described above, the gas barrier film 10 a of the present invention has the organic-inorganic laminate 28 in which the inorganic layers 14 and the organic layers 16 are alternately laminated on the gas barrier support 12. Further, an adhesive layer 20 and a back surface protective film 24 are provided on the back surface of the gas barrier support 12. A surface protective film 18 is provided on the organic / inorganic laminate 28.
Here, the adhesive layer 20, the back surface protective film 24, and the surface protective film 18 are finally peeled off, and the inorganic layer 14 and the organic layer 16 are formed on the surface of the gas barrier support 12 as shown in FIG. It is set as the gas barrier film 10b which has only alternately. In this regard, the same applies to the gas barrier film 100 shown in FIG.

In the gas barrier film 10a of the present invention, the gas barrier support 12 is a sheet-like material having a retardation value (Retardation) of 300 nm or less (hereinafter also referred to as a low retardation film).
By using a low retardation film having a retardation value of 300 nm or less as the gas barrier support 12, a gas barrier film excellent in optical properties can be obtained. Thereby, for example, when the gas barrier film of the present invention is used for an organic EL device or the like, it is possible to prevent a decrease in light contrast and a decrease in visibility due to reflection of external light.
Considering this point, the retardation value of the gas barrier support 12 is preferably 200 nm or less, and more preferably 150 nm or less.
Furthermore, in the present invention, for the same reason, the gas barrier support 12 preferably has a total light transmittance of 85% or more.

Specifically, the gas barrier support 12 is made of a plastic (polymer material) such as polycarbonate (PC), cycloolefin polymer (COP), cycloolefin copolymer (COC), triacetyl cellulose (TAC), or transparent polyimide. A plastic film is preferably exemplified.
The gas barrier support 12 has various functions such as a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, a light shielding layer, a planarization layer, a buffer layer, and a stress relaxation layer on the surface of such a plastic film. The layer (film | membrane) for obtaining may be formed.

In the present invention, the thickness of the gas barrier support 12 is preferably 20 to 120 μm.
By setting the thickness of the gas barrier support 12 to 20 μm or more, it is possible to suppress an increase in curling due to the formation of the inorganic layer 14 and the organic layer 16, and this makes it easy to wind up as a roll. 10a, or the gas barrier film 10b from which the pressure-sensitive adhesive layer 20, the back surface protective film 24 and the surface protective film 18 have been peeled off.
Further, by setting the thickness of the gas barrier support 12 to 120 μm or less, a gas barrier film 10b with good optical characteristics can be obtained, and a thin gas barrier film 10a (10b) can be obtained. 10a (10b) is obtained, a lightweight gas barrier film 10a (10b) is obtained, and a product using the gas barrier film 10b (such as an organic EL device) is preferable in terms of reduction in weight and thickness.
Considering the above points, the thickness of the gas barrier support 12 is more preferably 20 to 75 μm.

In addition, the gas barrier support 12 preferably has a glass transition temperature (Tg) of 130 ° C. or higher, and more preferably 140 ° C. or higher.
As described above, the inorganic layer 14 and the organic layer 16 are formed on the surface of the gas barrier support 12. Here, the inorganic layer 14 is usually formed by a vapor deposition method such as plasma CVD, and the organic layer 16 is formed by an application method in which a coating containing an organic compound that becomes the organic layer 16 is applied, dried and cured. Is done. That is, in the gas barrier film 10 a, the inorganic layer 14 and the organic layer 16 are formed by a method that involves heating the gas barrier support 12.
On the other hand, by using a gas barrier support 12 having a Tg of 130 ° C. or higher, thermal damage of the gas barrier support 12 due to heating in the formation of the inorganic layer 14 and the organic layer 16 can be prevented. Furthermore, it is preferable also from the point that the thermal damage of the gas barrier support 12 in the heating process in the manufacture of a product using the gas barrier film 10b from which the adhesive layer 20, the back surface protective film 24 and the surface protective film 18 are peeled can be prevented.

Further, the gas barrier support 12 has a difference in linear expansion coefficient from the back surface protective film 24 of 0 to 80 ppm / ° C.
By setting the difference between the linear expansion coefficient of the gas barrier support 12 and the linear expansion coefficient of the back surface protective film 24 to 0 to 80 ppm / ° C., the gas barrier support 12 is heated by the formation of the inorganic layer 14 and the organic layer 16 described above. And the back surface protective film 24 can be suitably prevented from peeling or deforming.
This point will be described in detail later.

As described above, in the gas barrier film 10a of the present invention, the organic / inorganic laminate in which the inorganic layers 14 and the organic layers 16 are alternately formed is laminated on the gas barrier support 12.
The inorganic layer 14 is a layer made of an inorganic compound. In the gas barrier film 10a, the inorganic layer 14 mainly exhibits the target gas barrier property.

The material for forming the inorganic layer 14 is not limited, and various layers made of an inorganic compound that exhibits gas barrier properties can be used.
Specifically, metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metal carbides such as aluminum carbide; silicon oxide, Silicon oxides such as silicon oxynitride, silicon oxycarbide, silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; mixtures of two or more of these; and Inorganic compounds such as these hydrogen-containing materials are preferably exemplified.
In particular, silicon nitride, silicon oxide, silicon oxynitride, and aluminum oxide are suitably used for the gas barrier film because they are highly transparent and can exhibit excellent gas barrier properties. Of these, silicon nitride is particularly suitable for its excellent gas barrier properties and high transparency.

In the present invention, the thickness of the inorganic layer 14 is preferably 10 to 200 nm.
By setting the thickness of the inorganic layer 14 to 10 nm or more, the inorganic layer 14 that stably expresses sufficient gas barrier performance can be formed. Further, the inorganic layer 14 is generally brittle, and if it is too thick, there is a possibility that cracks, cracks, peeling, etc. may occur. However, if the thickness of the inorganic layer 14 is 200 nm or less, cracks will occur. Can be prevented.
In consideration of such points, the thickness of the inorganic layer 14 is preferably 15 to 100 nm, and more preferably 20 to 75 nm.

In addition, when it has the some inorganic layer 14 like the gas barrier film 10a shown to FIG. 1 (A), the thickness of each inorganic layer 14 may be the same, or may mutually differ.
Similarly, in the case of having a plurality of inorganic layers 14 as in the gas barrier film 10a, the forming material of each inorganic layer 14 may be the same or different. However, in consideration of productivity, production cost, etc., it is preferable to form all the inorganic layers 14 with the same material.

In the gas barrier film 10 of the present invention, the inorganic layer 14 may be formed (film formation) by a known inorganic layer forming method according to the forming material.
Specifically, plasma CVD such as CCP-CVD and ICP-CVD, sputtering such as magnetron sputtering and reactive sputtering, and vapor deposition methods (vapor deposition) such as vacuum deposition are preferably exemplified.

Here, as shown to FIG. 1 (A), in the gas barrier film 10a concerning the functional film of this invention, the inorganic layer 14 is formed in the surface of the gas barrier support body 12. As shown in FIG.
As described above, when the gas barrier support has a low retardation value, the adhesion between the gas barrier support and the organic layer is low. Even if formed, peeling occurs between the support and the organic layer due to stress due to conveyance, bending due to a change in the conveyance path, and the like, resulting in damage to the inorganic layer.

On the other hand, in the present invention, the inorganic layer 14 is formed on the surface of the gas barrier support 12. That is, the lowermost layer of the organic / inorganic laminate 28 is the inorganic layer 14. Thereby, even when the gas barrier support 12 having a low retardation value with excellent optical properties is used, the adhesion between the gas barrier support 12 and the organic / inorganic laminate 28 is improved, and peeling is prevented. Can prevent damage.
In addition, the inorganic layer 14 formed on the surface of the gas barrier support 12 not only exhibits gas barrier properties but also functions as a protective layer for the gas barrier support 12.

As described above, the organic layer 16 is formed by a coating method using a paint containing an organic compound. This paint includes methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) organic solvents.
However, the plastic film used as the gas barrier support 12 may have low resistance to the organic solvent, and the plastic film may be dissolved depending on the combination of the plastic film and the organic solvent. In particular, the low retardation film as described above has low resistance to organic solvents and often dissolves. That is, when the organic layer 16 is formed on the surface of the gas barrier support 12, the surface of the gas barrier support 12 may be dissolved depending on the combination of the forming material of the gas barrier support 12 and the organic solvent contained in the paint. .
When such dissolution of the gas barrier support 12 occurs, the retardation value of the gas barrier support 12 changes, the light transmittance decreases, the haze increases, and the optical characteristics of the gas barrier film are greatly reduced. Resulting in.

On the other hand, like the gas barrier film 10a shown in FIG. 1A, the inorganic layer 14 is formed on the surface of the gas barrier support 12, and the organic layers 16 and the inorganic layers 14 are alternately laminated thereon. Thereby, the inorganic layer 14 acts as a protective layer against the organic solvent contained in the coating material forming the organic layer 16.
Therefore, even when the resistance of the gas barrier support 12 to the organic solvent is low, it is possible to prevent the gas barrier support 12 from being dissolved by the paint and to maintain the optical characteristics of the gas barrier support 12, and to provide a gas barrier film having excellent optical characteristics. Obtainable.

Here, in the configuration having the inorganic layer 14 on the surface of the gas barrier support 12 as in the gas barrier film 10 a shown in FIG. 1A, the gas barrier support 12 is interposed between the inorganic layer 14 and the gas barrier support 12. You may have an area | region like a mixed layer in which the formation component and the formation component of the inorganic layer 14 were mixed. The mixed layer between the inorganic layer 14 and the gas barrier support 12 is the first mixed layer in the present invention.
By having such a mixed layer between the gas barrier support 12 and the inorganic layer 14, the adhesion between the inorganic layer 14 and the gas barrier support 12 can be improved, the strength of the gas barrier film 10a can be improved, and the gas barrier support It is also possible to prevent a decrease in gas barrier properties due to the peeling of the inorganic layer 14 from the body 12.

Similarly, a component in which the organic layer 16 is formed and a component in which the inorganic layer 14 is formed are mixed between the organic layer 16 serving as a base layer and the inorganic layer 14 formed on the surface of the organic layer 16. It may have a region such as a layer. The mixed layer between the organic layer 16 and the inorganic layer 14 is the second mixed layer in the present invention.
By having such a mixed layer between the organic layer 16 and the inorganic layer 14, the adhesiveness between the inorganic layer 14 and the organic layer 16 can be improved, the strength of the gas barrier film 10a can be improved, and the organic layer 16 It is also possible to prevent the gas barrier property from being lowered due to the peeling of the inorganic layer 14 from the substrate.

The thicknesses of the first mixed layer and the second mixed layer are not particularly limited, but the adhesion between the gas barrier support 12 and the inorganic layer 14, the adhesion between the organic layer 16 and the inorganic layer 14, and the strength. From the viewpoint of production efficiency, the thickness of the first mixed layer and the second mixed layer is preferably 1 nm to 20 nm.
The mixed layer is a layer containing a component derived from the gas barrier support 12 or the organic layer 16 and a component derived from the inorganic layer 14. Therefore, the position where the component derived from the inorganic layer 14 disappears is the boundary between the gas barrier support 12 or the organic layer 16 and the mixed layer, and the position where the component derived from the gas barrier support 12 or the organic layer 16 disappears, It is a boundary between the inorganic layer 14 and the mixed layer.

As described above, the inorganic layer 14 is formed by a vapor deposition method such as plasma CVD. By adjusting the deposition conditions, the presence or absence of the mixed layer, the thickness of the mixed layer, and the like can be adjusted. .
For example, when the inorganic layer 14 is formed by plasma CVD, the mixed layer is formed by a method of adjusting the plasma intensity generated by adjusting input power or the like, a method of adjusting a bias applied when the inorganic layer 14 is formed, or the like. The presence or absence, the thickness of the mixed layer, etc. can be adjusted.

On the other hand, as described above, in the gas barrier film according to the functional film of the present invention, the uppermost layer of the organic-inorganic laminate 28 is the inorganic layer 14.
Thus, by making the uppermost layer of the organic / inorganic laminate 28 the inorganic layer 14, it is possible to prevent outgas emission due to the organic layer 16. Therefore, in the configuration in which the uppermost layer of the organic / inorganic laminate 28 is the inorganic layer 14, for example, a device that is easily affected by unnecessary gas components such as an organic EL device needs to be disposed on the organic / inorganic laminate 28 side. In some cases.
Further, by using the inorganic layer 14 as the uppermost layer of the organic / inorganic laminate 28, when the gas barrier film 10a is used for a top emission type organic EL device or the like, the passivation film made of an inorganic material of the organic EL device and the uppermost layer are used. The upper inorganic layer 14 can be faced and bonded. That is, since the same inorganic materials are bonded to each other with an adhesive, the adhesion between the passivation film and the inorganic layer 14 can be improved, moisture and gas can be prevented from entering, and the organic EL material which is a light emitting element of the organic EL device Deterioration can be prevented.

The organic layer 16 is a layer made of an organic compound, and is basically a cross-linked (polymerized) organic compound that becomes the organic layer 16.
As described above, the organic layer 16 functions as a base layer for properly forming the inorganic layer 14 that exhibits gas barrier properties. By having such a base organic layer 16, the surface on which the inorganic layer 14 is formed can be flattened and made uniform to be in a state suitable for the formation of the inorganic layer 14.
In the laminated type gas barrier film in which the underlying organic layer 16 and the inorganic layer 14 are laminated, it is possible to form the appropriate inorganic layer 14 on the entire surface of the film without gaps, and to have excellent gas barrier properties. A gas barrier film can be obtained.

In the gas barrier film 10a, the material for forming the organic layer 16 is not limited, and various known organic compounds can be used.
Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, or polysiloxane, etc. An organic silicon compound film is preferably exemplified. A plurality of these may be used in combination.

Among them, the organic layer 16 composed of a polymer of a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group is preferable in terms of excellent glass transition temperature and strength.

In particular, in addition to the above strength, the glass transition temperature is 120 ° C., mainly composed of acrylate and / or methacrylate monomers and oligomer polymers, in terms of low refractive index, high transparency and excellent optical properties. The above acrylic resin and methacrylic resin are preferably exemplified as the organic layer 16.
Among them, dipropylene glycol di (meth) acrylate (DPGDA), 1,9-nonanediol di (meth) acrylate (A-NOD-N), 1,6 hexanediol diacrylate (A-HD-N), Bifunctional or higher acrylate and / or methacrylate monomers such as trimethylolpropane tri (meth) acrylate (TMPTA), (modified) bisphenol A di (meth) acrylate, dipentaerythritol hexa (meth) acrylate (DPHA), etc. An acrylic resin and a methacrylic resin mainly composed of a polymer are preferably exemplified. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.

By forming the organic layer 16 with an acrylic resin or a methacrylic resin, particularly an acrylic resin or a methacrylic resin having two or more functions, the inorganic layer 14 can be formed on a base having a high three-dimensional crosslink density. Can be formed.

The thickness of the organic layer 16 is preferably 0.5 to 5 μm.
By setting the thickness of the organic layer 16 to 0.5 μm or more, the entire surface of the inorganic layer 14 can be reliably covered with the organic layer 16, and the surface of the organic layer 16, that is, the formation surface of the inorganic layer 14 can be planarized.
In addition, by setting the thickness of the organic layer 16 to 5 μm or less, occurrence of problems such as cracks in the organic layer 16 and curling of the gas barrier film 10a due to the organic layer 16 being too thick is suitably suppressed. be able to.
Considering the above points, the thickness of the organic layer 16 is more preferably 1 to 3 μm.

In addition, when it has the some organic layer 16 like the gas barrier film 100 shown in FIG.1 (B), the thickness of each organic layer 16 may be the same, or may mutually differ.
Similarly, in the case of having a plurality of organic layers 16 as in the gas barrier film 100, the forming material of each organic layer 16 may be the same or different. However, in consideration of productivity, production cost, etc., it is preferable to form all the organic layers 16 with the same material.

In the present invention, the organic layer 16 is basically formed by a coating method.
That is, when the organic layer 16 is formed, first, monomers, dimers, trimers, oligomers and the like as the organic compound that becomes the organic layer 16, and further, a polymerization initiator, a silane coupling agent, a surfactant, and an increasing viscosity agent The paint which dissolves etc. in the organic solvent is adjusted. Next, this paint is applied to the surface of the inorganic layer 14 and dried. After drying, an organic compound is polymerized by ultraviolet irradiation, electron beam irradiation, heating, or the like to form the organic layer 16.

In the gas barrier film 10 a of the present invention, the adhesive layer 20 is attached to the back surface of the gas barrier support 12, and the back surface protective film 24 is attached to the adhesive layer 20.
As described above, the gas barrier support 12, the adhesive layer 20, and the back surface protective film 24 constitute the laminate 26 in the present invention.

As in the examples described in Patent Document 1 and Patent Document 2 described above, the back surface protective film 24 is weak in the stiffness of the gas barrier support 12 and is formed in each layer by roll-to-roll (hereinafter also referred to as RtoR). When proper conveyance is difficult, the gas barrier support 12 is supported from the back side to ensure self-supporting property and enable stable conveyance without bending or formation of wrinkles.
Here, as described above, in the gas barrier film 10 a of the present invention, the back surface protective film 24 has thermal characteristics different from those of the gas barrier support 12. Specifically, the difference between the linear expansion coefficient of the gas barrier support 12 and the linear expansion coefficient of the back surface protective film 24 is 0 to 80 ppm / ° C.
Further, in the gas barrier film 10a of the present invention, the adhesive strength between the adhesive layer 20 and the gas barrier support 12 at 25 ° C. is 0.01 to 0.15 N / 25 mm.
Preferably, the adhesive force between the adhesive layer 20 and the back surface protective film 24 at 25 ° C. is 0.05 to 0.20 N / 25 mm.
In the present invention, the adhesive strength between the gas barrier support 12 and the adhesive layer 20, the adhesive strength between the adhesive layer 20 and the back surface protective film 24, the linear expansion coefficient of the gas barrier support and the linear expansion of the back surface protective film are as described above. Specify the difference from the coefficient.
Thereby, even when an expensive gas barrier support 12 such as a COC film is used, the gas barrier film 10a having the inorganic layer 14 free from damage such as cracks and cracks is realized without increasing the cost.

As described above, in the gas barrier film 10a of the present invention, in order to realize excellent optical properties, the gas barrier support 12 has a retardation value composed of PC, COP, COC, TAC, transparent polyimide, and the like as low as 300 nm or less. A retardation film is used. Further, the gas barrier support 12 preferably has a total light transmittance of 85% or more.
On the other hand, since the back surface protective film 24 is finally peeled off and discarded, it is preferable to use an inexpensive film such as a PET film.

However, a low retardation film such as a COC film and a PET film or the like, for example, have a large difference in Tg, one of which thermally expands and the other thermally contracts, and the thermal expansion / contraction rate differs greatly. Characteristic, that is, linear expansion coefficient is different.
When the laminated body 26 having the gas barrier support 12 and the back surface protective film 24 having different thermal characteristics is used to form the inorganic layer 14 or the organic layer 16 on the surface of the gas barrier support 12 by RtoR, the inorganic layer 14 The gas barrier support 12 and the back surface protective film 24 show completely different deformations due to heat caused by plasma or the like when forming the organic layer 16, or heat caused by drying when the organic layer 16 is formed. Since there is also a bend or the like, this causes peeling of the gas barrier support 12 and the back surface protective film 24, wrinkles or breakage of the gas barrier support 12 and the like. Further, due to peeling of the gas barrier support 12 and the back surface protective film 24, wrinkles of the gas barrier support 12, etc., the proper inorganic layer 14 cannot be formed, and further, the previously formed inorganic layer 14 is damaged. , Gas barrier properties are reduced.

If a film made of the same material as that of the gas barrier support 12 is used as the back surface protection film 24, a problem caused by a difference in thermal characteristics between the back surface protection film 24 and the gas barrier support body 12 does not occur.
However, since a film having high optical properties such as a low retardation film such as a COC film is expensive, when a film having high optical properties such as a low retardation film is used as a rear surface protective film to be finally discarded, a gas barrier is used. The cost of the film becomes very high.
In addition, even if the same material is used for the gas barrier support and the back surface protective film, peeling due to air bubbles existing between the gas barrier support and the back surface protective film, wrinkles and breakage of the gas barrier support are suppressed. I can't.

In contrast, in the gas barrier film 10a of the present invention, the difference between the linear expansion coefficient of the gas barrier support 12 and the linear expansion coefficient of the back surface protective film 24 is set to 0 to 80 ppm / ° C., and the adhesive layer 20 and the gas barrier support 12 The adhesive strength at 25 ° C. is set to 0.01 to 0.15 N / 25 mm. That is, the difference in thermal characteristics between the gas barrier support 12 and the back surface protective film 24 is within a predetermined range, and the adhesive layer 20 and the gas barrier support 12 are attached with very weak force.
Therefore, when the gas barrier support 12 and the back surface protective film 24 exhibit different deformations due to heating during the formation of the inorganic layer 14 or the organic layer 16 by RtoR, the adhesive layer 20 and the gas barrier support 12 having a weak adhesion force are It peels and then repeats being stuck again by tension.
By repeating this peeling and sticking, different deformations of the gas barrier support 12 and the back surface protective film 24 are absorbed. Moreover, even if the bubble between the gas barrier support 12 and the back surface protective film 24 expands, the bubble is released when it is once peeled off.
As a result, there is no peeling of the gas barrier support 12 and the back surface protective film 24 due to the different deformations of the two or bubbles existing between them, wrinkles of the gas barrier support 12, etc., and the inorganic layer resulting from this 14 and the formation of an inappropriate inorganic layer 14 can be prevented.

Also preferably, the adhesive strength of the adhesive layer 20 and the back surface protective film 24 at 25 ° C. is 0.05 to 0.20 N / 25 mm. Thereby, when the gas barrier support 12 and the back surface protective film 24 show different deformations due to heating, peeling and sticking are repeatedly generated between the adhesive layer 20 and the back surface protective film 24, and the gas barrier support body. The mutually different deformations of 12 and the back surface protective film 24 are absorbed.

In the present invention, the back surface protective film 24 has a difference in linear expansion coefficient from that of the gas barrier support 12 within a predetermined range, and the adhesive strength between the gas barrier support 12 and the back surface protective film 24 and the adhesive layer 20 is within the above range. It is said. Thereby, in manufacture of the gas barrier film by RtoR, conveyance can be stabilized by the back surface protective film 24. Further, even when an expensive low retardation film such as a COC film is used as the gas barrier support 12 in order to obtain a gas barrier film 10a having excellent optical properties, the back surface protection of an inexpensive one such as a PET film is possible. The film 24 can be used.
Further, as described above, the gas barrier film 10a is finally the gas barrier film 10b from which the adhesive layer 20 and the back surface protective film 24 have been peeled off. Here, in this invention, since the adhesive force of the adhesion layer 20 and the gas barrier support body 12 is weak, the adhesion layer 20 can also be easily peeled by peeling the back surface protective film 24, and also the inorganic layer 14 is damaged. It is possible to perform the peeling without performing, and to prevent the adhesive layer 20 from remaining on the gas barrier support 12.
In particular, according to the present invention, it is possible to prevent the adhesive layer 20 from remaining on the gas barrier support 12, and therefore, by using a film having excellent optical properties such as a low retardation film as the gas barrier support 12, the optical properties are excellent. The gas barrier film 10b can be obtained, and can be suitably used as a gas barrier film used for a top emission type organic EL device used for a mobile phone or a display.

In the gas barrier film 10a of the present invention, if the adhesive force between the adhesive layer 20 and the gas barrier support 12 is less than 0.01 N / 25 mm, sufficient adhesive force between the adhesive layer 20 and the gas barrier support 12 cannot be obtained, or the adhesive layer 20 and the gas barrier support 12 may unnecessarily peel off.
If the adhesive force between the adhesive layer 20 and the gas barrier support 12 exceeds 0.15 N / 25 mm, the inorganic layer 14 may be damaged when the back surface protective film 24 or the like is peeled off. Further, when the back surface protective film 24 or the like is peeled off, the adhesive layer 20 remains on the gas barrier support 12, that is, an adhesive residue is generated, or peeling and sticking between the adhesive layer 20 and the gas barrier support 12 are performed. In some cases, the repetition does not occur, and different deformations of the gas barrier support 12 and the back surface protective film 24 cannot be absorbed. Furthermore, inconveniences such as inability to open bubbles present between the adhesive layer 20 and the gas barrier support 12 may occur.
Considering the above points, the adhesive force between the adhesive layer 20 and the gas barrier support 12 is 0.01 to 0.15 N / 25 mm.

In the gas barrier film 10a of the present invention, if the adhesive force between the adhesive layer 20 and the back surface protective film 24 is less than 0.05 N / 25 mm, sufficient adhesive force between the adhesive layer 20 and the back surface protective film 24 cannot be obtained. There is a possibility that inconveniences such as adhesive residue on the gas barrier support side occur.
If the adhesive force between the adhesive layer 20 and the back surface protective film 24 exceeds 0.20 N / 25 mm, the inorganic layer 14 may be damaged when the back surface protective film 24 or the like is peeled off. Further, there is a case where peeling and sticking are not repeated between the pressure-sensitive adhesive layer 20 and the back surface protective film 24, and different deformations of the gas barrier support 12 and the back surface protective film 24 cannot be absorbed. Furthermore, inconveniences such as inability to open bubbles present between the adhesive layer 20 and the back surface protective film 24 may occur.
Considering the above points, the adhesive strength between the adhesive layer 20 and the back surface protective film 24 is preferably 0.05 to 0.20 N / 25 mm.
In addition, in this invention, in order to peel the adhesive layer 20 by peeling the back surface protective film 24 together, the adhesive force of the adhesive layer 20 and the back surface protective film 24 is the pressure sensitive adhesive layer 20 and the gas barrier support 12. It is preferable that it is larger than the adhesive strength.

In the gas barrier film 10a of the present invention, the pressure-sensitive adhesive force between the pressure-sensitive adhesive layer 20 and the gas-barrier support 12 is 0.01 to 0.15 N / 25 mm, and the pressure-sensitive adhesive strength between the pressure-sensitive adhesive layer 20 and the back surface protective film 24 is 0. As a method for adjusting the thickness to 0.05 to 0.20 N / 25 mm, known methods that are performed using various adhesives and adhesive tapes can be used.
Hereinafter, the adhesive strength in the above range is also referred to as slight adhesion.

In the present invention, the pressure-sensitive adhesive layer 20 may be made of various adhesives that can obtain the above-mentioned pressure-sensitive adhesive force depending on the gas barrier support 12 and the back surface protective film 24.
Examples of the material of the pressure-sensitive adhesive layer 20 include acrylic resin adhesives, epoxy resin adhesives, urethane resin adhesives, vinyl resin adhesives, rubber adhesives, and the like.

Specifically, the adhesive layer 20 is preferably made of a material having 3 to 10 carbon atoms in the alkyl group portion of the alkyl acrylate monomer. Alternatively, it is preferable to further contain an alkyl methacrylate monomer. Thus, the use of a material having a long-chain alkyl group moiety as the material of the adhesive layer 20 is preferable in that the volume shrinkage when cured is as low as 3% or less, and the adhesiveness is low.

The thickness of the adhesive layer 20 is preferably 15 to 250 μm.
By setting the thickness of the pressure-sensitive adhesive layer 20 to 15 μm or more, different deformations of the gas barrier support 12 and the back surface protective film 24 due to repeated peeling and sticking of the pressure-sensitive adhesive layer 20 and the gas barrier support 12 described above are sufficiently obtained. More preferably, the gas barrier support 12 and the back surface protective film 24 can be peeled off, the gas barrier support 12 can be wrinkled or broken, and the inorganic layer 14 can be prevented from being damaged.
On the other hand, by setting the thickness of the pressure-sensitive adhesive layer 20 to 250 μm or less, it is possible to prevent the thermal conductivity from being lowered with respect to cooling from the back surface when the inorganic layer 14 described later is formed. This is preferable in that the gas barrier property of the layer 14 can be improved.
Considering the above points, the thickness of the adhesive layer 20 is more preferably 25 to 150 μm.

What is necessary is just to form such an adhesion layer 20 by the well-known method according to the adhesive agent etc. to utilize.
As an example, a method of forming by applying an adhesive and a method of forming using an adhesive tape (adhesive tape) are exemplified.
Moreover, when using said alkyl acrylate monomer, after apply | coating the coating liquid used as the material of the adhesion layer 20, it superposes | polymerizes (crosslinks) by UV hardening and forms. Further, it is preferable that the volumetric shrinkage due to polymerization (crosslinking) is 3% or less when UV-cured under conditions of a temperature of 25 ° C. to 150 ° C. and a UV irradiation amount of 100 mJ / cm ² to 1000 mJ / cm ² .

On the other hand, if the difference in linear expansion coefficient from the gas barrier support 12 is 0 to 80 ppm / ° C., the back surface protective film 24 can be a sheet-like material made of various materials, particularly various plastic films. Is available.
As described above, the gas barrier film 10a of the present invention has the RtoR by the back surface protective film 24 as described above by setting the difference in the linear expansion coefficient between the gas barrier support 12 and the back surface protective film 24 in such a range. When using a film having excellent optical properties such as a low retardation film such as a COC film, an inexpensive PET film should be used as the back surface protective film 24 while stabilizing the transportation of the gas barrier support 12 in Therefore, the gas barrier film 10a which is inexpensive and does not damage the inorganic layer 14 is realized.
In addition, as described above, in the present invention, even if there is a slight difference in the linear expansion coefficient between the back surface protective film 24 and the gas barrier support 12, the back surface protective film 24 can be sufficiently absorbed. It can be more suitably applied when the difference in coefficient of linear expansion from the gas barrier support 12 is 10 ppm to 80 ppm / ° C. If the difference in linear expansion coefficient is less than 10 ppm, the selection range of the material is narrowed, and the same material as the gas barrier support 12 may have to be selected. In particular, when an expensive optical film is used for the back surface protective film, the cost becomes twice or more. Further, when the difference in linear expansion coefficient exceeds 80 ppm, deformation itself due to heat in the film forming process becomes large, and a high-quality inorganic film cannot be obtained. In addition, when the produced gas barrier film is incorporated into various devices or used, deformation due to heat increases, and a desired gas barrier property may not be exhibited.

As described above, the back surface protective film 24 is finally peeled off and discarded. Therefore, it is preferable to use a low-cost material.
Specifically, a plastic film made of PET, PP or the like is preferably exemplified.

In the present invention, the thickness of the back surface protective film 24 is preferably 12 to 100 μm.
By setting the thickness of the back surface protective film 24 to 12 μm or more, the effect of providing the back surface protective film 24 is sufficiently exerted, and the gas barrier support 12 (laminated body 26) is formed when forming the inorganic layer 14 or the like by RtoR. ) Is preferable in that stable conveyance is possible.
Moreover, the thermal deformation amount of the back surface protective film 24 in the case of formation of the inorganic layer 14 grade | etc., Can be reduced by making the thickness of the back surface protective film 24 into 100 micrometers or less. Moreover, it can prevent that thermal conductivity falls with respect to the cooling from the back surface in the case of formation of the inorganic layer 14 mentioned later. Furthermore, the lightweight gas barrier film 10a is obtained.
Considering the above points, the thickness of the back surface protective film 24 is more preferably 25 to 75 μm.

In the present invention, the thickness ratio between the gas barrier support 12 and the back surface protective film 24 is preferably 0.1 to 5 as the ratio of “back surface protective film 24 / gas barrier support 12”.
By setting the ratio of the thicknesses of the gas barrier support 12 and the back surface protective film 24 within this range, the inorganic layer 14 and the organic layer 14 are formed due to the difference in thermal characteristics between the gas barrier support 12 and the back surface protective film 24. It is preferable in that the stress that the back surface protective film 24 gives to the inorganic layer 14 or the like during formation of the layer 16 or the like can be reduced, and higher gas barrier properties can be obtained.

Moreover, it is preferable that the glass transition temperature (Tg) of the back surface protective film 24 is 70 degreeC or more, and it is more preferable that it is 80 degreeC or more.
As described above, the gas barrier film 10a is protected from the back surface by heating during the formation of the inorganic layer 14 and the organic layer 16 by setting the Tg of the back surface protective film 24 to 70 ° C. or higher, like the gas barrier support 12 described above. The film 24 is preferable in that heat damage and dissolution of the film 24 can be prevented.

The water vapor transmission rate (WVTR) of the back surface protective film 24 is preferably 0.1 to 10 [g / (m ² · day)].
As described above, in the present invention, the gas barrier support 12 having a low retardation value with excellent optical characteristics is used. Such a gas barrier support 12 may have a high water vapor transmission rate. Further, as described above, the inorganic layer 14 is formed directly on the gas barrier support 12 from the viewpoint of adhesion.
For this reason, water vapor, oxygen or the like that has passed through the gas barrier support reaches the lowermost inorganic layer, and there is a possibility that adhesion may be reduced or gas barrier properties may be reduced due to oxidation of the inorganic layer.

In contrast, by setting the water vapor transmission rate of the back surface protective film 24 to 0.1 to 10 [g / (m ² · day)], it is possible that water vapor, oxygen, or the like reaches the lowermost inorganic layer. It can prevent and it can prevent that adhesiveness and gas-barrier property fall.
In the present invention, the water vapor transmission rate (WVTR) is a value measured based on a moisture permeability test method (cup method) of moisture-proof packaging material of JIS Z0208.

Moreover, it is preferable that the friction coefficient of the surface by which the back surface protective film 24 is exposed is 0.6 or less.
By setting the coefficient of friction of the back surface protective film 24 to 0.6 or less, the friction between the back surface protective film 24 and the guide roller or the like during transport by RtoR is reduced, and the laminate 26 is transported with a low transport force. Can do. Thereby, generation | occurrence | production of peeling of the gas barrier support body 12 and the back surface protective film 24, wrinkles, etc. of the gas barrier support body 12 can be prevented more suitably.
In addition, in this invention, let the friction coefficient of the back surface protective film 24 be a friction coefficient of back surface protective films measured based on JISK7125.

Here, the adhesive strength of the adhesive layer 20 and the gas barrier support 12 at 100 ° C. is preferably 0.03 to 0.14 N / 25 mm, and the adhesive strength at 200 ° C. is 0.04 to 0.13 N / 25 mm. It is preferably 25 mm.
The adhesive strength between the adhesive layer 20 and the back surface protective film 24 at 100 ° C. is preferably 0.07 to 0.19 N / 25 mm, and the adhesive strength at 200 ° C. is 0.08 to 0.18 N / 25 mm. Is preferred.

By setting the adhesive strength of the adhesive layer 20, the gas barrier support 12 and the back surface protective film 24 at a high temperature within the above range, the adhesive strength is increased by heating during the formation of the inorganic layer 14 and the organic layer 16 by RtoR. The difference in deformation due to heat between the gas barrier support 12 and the back surface protective film 24 is prevented by repeating peeling and sticking between the adhesive layer 20 and the gas barrier support 12 and / or the back surface protective film 24. It is possible to more suitably prevent the gas barrier support 12 and the back surface protective film 24 from peeling off, wrinkles of the gas barrier support 12 and the like due to the different deformations.

In the gas barrier film 10a of the present invention, a surface protective film 18 is attached to the surface of the organic-inorganic laminate 28 of the gas barrier support 12. That is, the surface protective film 18 is stuck on the surface of the uppermost inorganic layer 14 of the organic-inorganic laminate 28.

The inorganic layer 14 is hard and brittle because it is dense. Therefore, it is easily damaged when it receives an impact directly from the outside. As described above, the inorganic layer 14 mainly exhibits gas barrier properties in the gas barrier film 10a of the present invention. Therefore, when the inorganic layer 14 is damaged, the gas barrier property is lowered.
On the other hand, by sticking the surface protective film 18 on the uppermost inorganic layer 14, the inorganic layer 14 is protected and damage to the inorganic layer 14 is prevented.

In the present invention, the adhesive strength between the surface protective film 18 and the uppermost inorganic layer 14 at 25 ° C. is 0.02 N / 25 mm to 0.06 N / 25 mm.
As described above, when the gas barrier film 10a is used in various apparatuses such as an organic EL device, the surface protective film 18 is peeled from the inorganic layer 14. Therefore, if the adhesive force between the surface protective film and the inorganic layer is strong, the inorganic layer may be damaged when the surface protective film is peeled off.
On the other hand, by making the adhesive force between the surface protective film 18 and the uppermost inorganic layer 14 in the above range, the surface protective film 18 can be peeled without damaging the inorganic layer 14, and optical characteristics and A gas barrier film excellent in gas barrier properties can be used in an apparatus such as an organic EL device.

The material of the surface protective film 18 has a melting point (melting point) of 80 ° C. to 170 ° C.
As described above, when the gas barrier film 10a is used in various apparatuses such as an organic EL device, the surface protective film 18 is used in a peeled state like the gas barrier film 10b. For example, when a gas barrier film is incorporated into an organic EL device, the inorganic material of the uppermost inorganic layer of the gas barrier film and the passivation film of the organic EL device are bonded together with an adhesive.
Here, the adhesive for favorably bonding the inorganic materials and the adhesive suitably used for adhering the surface protective film are made of different materials. Therefore, when the surface protective film and the uppermost inorganic layer are bonded via an adhesive, the adhesive remains on the inorganic layer, and the function of the adhesive that bonds the inorganic layer and the passivation film is inhibited. This causes inconveniences such as

Therefore, in the present invention, the surface protective film 18 is stuck directly on the uppermost inorganic layer 14 without using an adhesive.
Here, thermocompression bonding is used as a method of attaching the surface protective film without using an adhesive. Therefore, even when heat is applied to the surface protective film by thermocompression bonding, problems such as peeling due to a difference in thermal characteristics between the back surface protective film and the gas barrier support may occur.
On the other hand, in the present invention, the melting point of the material of the surface protective film 18 is set to 80 ° C. to 170 ° C. Thereby, thermocompression bonding can be performed at a relatively low temperature, and problems caused by a difference in thermal characteristics between the back surface protective film and the gas barrier support can be suitably reduced.

Further, by setting the melting point of the material of the surface protection film 18 to 80 ° C. to 170 ° C., immediately after forming the inorganic layer 14, the surface is formed by thermocompression using heat generated when the inorganic layer 14 is formed. The protective film 18 can be stuck.

The material of the surface protective film 18 is not particularly limited as long as the glass transition temperature satisfies the above range. Specifically, polyethylene (PE), polypropylene (PP), or the like can be suitably used as the material for the surface protective film 18. In particular, low-density polyethylene is suitably used as the material for the surface protective film 18.

The thickness of the surface protection film 18 is preferably 20 μm to 100 μm.
By making the thickness of the surface protective film 18 20 μm or more, it is preferable in that the effect of protecting the uppermost inorganic layer 14 is sufficiently exhibited, and the gas barrier film 10a can be stably conveyed by RtoR. .
In addition, the thickness of the surface protective film 18 is preferably 100 μm or less, so that a lightweight gas barrier film 10a can be obtained, and the roll diameter when wound with RtoR can be reduced.
Further, from the viewpoint of protecting the inorganic layer 14 and reducing the weight, the thickness of the surface protective film 18 is preferably 30 μm to 70 μm.

The Young's modulus of the surface protective film 18 is preferably ¼ or less of the Young's modulus of the gas barrier support 12 and the Young's modulus of the back surface protective film 24.
By reducing the Young's modulus of the surface protective film 18, the peelability of the surface protective film 18 can be improved, the wrinkles at the time of winding can be reduced, and the step difference at the end due to the difference in the formation width of each layer can be transferred. This is preferable in that it can be reduced.

The water vapor permeability of the surface protective film 18 is preferably 0.5 to 25 [g / (m ² · day)].
By setting the water vapor transmission rate of the surface protective film 18 to 0.5 to 25 [g / (m ² · day)], it is possible to prevent water vapor, oxygen, and the like from reaching the uppermost inorganic layer, and to have a gas barrier property. It can be prevented from lowering.

Next, production of the functional film of the present invention will be described.
2A and 2B conceptually show an example of a production apparatus for producing the gas barrier film 10a of the present invention.
This manufacturing apparatus includes an inorganic film forming apparatus 32 that forms the inorganic layer 14 and an organic film forming apparatus 30 that forms the organic layer 16.
FIG. 2A shows an inorganic film forming apparatus 32, and FIG. 2B shows an organic film forming apparatus 30.

Both the inorganic film forming apparatus 32 shown in FIG. 2A and the organic film forming apparatus 30 shown in FIG. 2B send out the forming material from a roll formed by winding a long forming material. The above-mentioned RtoR (Roll to Roll) is performed in which each layer is formed (film formation) while the forming material is conveyed in the longitudinal direction, and the forming material on which each layer is formed is wound again in a roll shape. ).
Such RtoR enables high-productivity and efficient production of the gas barrier film 10a.

Here, the manufacturing apparatus shown in FIG. 2 (A) and FIG. 2 (B) attaches the adhesive layer 20 to the back surface of the long gas barrier support 12 as shown in FIG. The inorganic layer 14 and the organic layer are formed on the surface of the gas barrier support 12 of the laminate 26 formed by sticking the back surface protective film 24 to the adhesive layer 20, that is, on the opposite surface (opposite surface) of the adhesive layer 20. 16 are alternately formed to manufacture the gas barrier film 10a and the like.
Therefore, in the inorganic film forming apparatus 32 shown in FIG. 2A, the film forming material Za is a long laminate 26 and a surface in which one or more layers are formed on the surface of the laminate 26. Is the material of the organic layer 16.
On the other hand, in the organic film forming apparatus shown in FIG. 2B, the film forming material Zb is the material of the inorganic layer 14 having one or more layers formed on the surface of the stacked body 26 and the surface thereof.

The inorganic film forming apparatus 32 is an apparatus for forming the inorganic layer 14 on the surface of the film forming material Za by a vapor phase growth method, and includes a supply chamber 56, a film forming chamber 58, and a winding chamber 60.
In addition to the illustrated members, the inorganic film forming apparatus 32 conveys a long material to be formed such as a conveying roller pair, a guide member that regulates the position of the film forming material Za in the width direction, and various sensors. However, various members provided in a known apparatus that performs film formation by a vapor deposition method may be included.

The supply chamber 56 includes a rotation shaft 64, a guide roller 68, and a vacuum exhaust unit 70.
In the supply chamber 56, a material roll 61, which is a laminated body 26 in which the laminated body 26, the organic layer 16, and the like are formed and wound with a long film-forming material Za, is loaded on a rotating shaft 64.
When the material roll 61 is loaded on the rotating shaft 64, the film forming material Za passes through a predetermined conveyance path from the supply chamber 56 to the winding shaft 92 of the winding chamber 60 through the film forming chamber 58. Passed. The inorganic film forming apparatus 32 that uses RtoR synchronizes the feeding of the film forming material Za from the material roll 61 and the winding of the film forming material Za with the inorganic layer formed on the winding shaft 92. Thus, an inorganic layer is continuously formed on the film forming material Za in the film forming chamber 58 while transporting the film forming material Za in the longitudinal direction.

In the supply chamber 56, the rotating shaft 64 is rotated clockwise in the drawing by a driving source (not shown), the film forming material Za is fed from the material roll 61, and a predetermined path is guided by the guide roller 68, so that the partition wall 72. From the slit 72 a formed in the step S, the film is sent to the film formation chamber 58.

In the illustrated example, the inorganic film forming apparatus 32 is provided with a vacuum evacuation unit 74 in the supply chamber 56 and a vacuum evacuation unit 76 in the winding chamber 60, respectively, as a preferred embodiment. In the inorganic film forming apparatus 32, during the film formation, the pressure in the supply chamber 56 and the take-up chamber 60 is adjusted according to the pressure in the film forming chamber 58 described later, that is, the film forming pressure, by the respective vacuum exhaust means. Maintain a predetermined pressure. As a result, the pressure in the adjacent chamber is prevented from affecting the pressure in the film forming chamber 58.
The vacuum evacuation means 70 is not particularly limited, and various known vacuum evacuation means used in a vacuum film formation apparatus such as a vacuum pump such as a turbo pump, a mechanical booster pump, a dry pump, and a rotary pump, Is available. In this regard, the same applies to the other vacuum exhaust means 74 and 76 described later.

The film forming chamber 58 is for forming an inorganic layer on the surface of the stacked body 26 or the organic layer 16 that is the film forming material Za by a vapor phase growth method. In the illustrated example, the film forming chamber 58 includes a drum 80, a film forming unit 82, the vacuum exhaust unit 74 described above, and guide

rollers

84a and 84b.
In addition, a film roll 87 for supplying a surface protective film F for protecting the deposited inorganic layer 14 is also disposed in the film forming chamber 58.

The film forming material Za conveyed to the film forming chamber 58 is guided to a predetermined path by the guide roller 84a and is wound around a predetermined position of the drum 80. The film forming material Za is transported in the longitudinal direction while being positioned at a predetermined position by the drum 80, and the inorganic layer 14 is continuously formed.

The vacuum evacuation means 74 evacuates the inside of the film forming chamber 58 to obtain a degree of vacuum corresponding to the formation of the inorganic layer 14.

The drum 80 is a cylindrical member that rotates in the counterclockwise direction around the center line.
The film forming material Za supplied from the supply chamber 56 and guided to a predetermined path by the guide roller 84a and wound around a predetermined position of the drum 80 is wound around a predetermined area of the peripheral surface of the drum 80, and the drum The inorganic layer 14 is formed on the surface by the film forming means 82 while being transported along a predetermined transport path while being supported / guided by 80.
Note that the drum 80 may include temperature adjusting means, and the laminate 26 may be cooled, for example, during the formation of the inorganic layer 14.

The film forming means 82 forms the inorganic layer 14 on the surface of the film forming material Za by a vapor phase growth method.
In the production method of the present invention, the inorganic layer 14 may be formed by a known vapor deposition method such as the formation method described in the above-mentioned patent document. Therefore, the film forming method in the film forming means 82 is not particularly limited, and any known film forming method such as CVD, plasma CVD, sputtering, vacuum deposition, ion plating, etc. can be used.

Therefore, the film forming means 82 is composed of various members according to the vapor phase growth method to be performed.
For example, if the film forming chamber 58 is for depositing the inorganic layer 14 by ICP-CVD (inductively coupled plasma CVD), the film forming means 82 may include an induction coil for forming an induction magnetic field, It has gas supply means for supplying the reaction gas to the membrane region.
If the film forming chamber 58 is for depositing the inorganic layer 14 by the CCP-CVD method (capacitive coupling type plasma CVD), the film forming means 82 is hollow and has a large number of small surfaces on the surface facing the drum 62. A high-frequency electrode having a hole and connected to a reaction gas supply source, a shower electrode acting as a reaction gas supply means, and the like are configured.
If the film forming chamber 58 forms the inorganic layer 14 by vacuum deposition, the film forming means 82 heats the crucible filling the film forming material, the shutter for shielding the crucible, and the film forming material in the crucible. It has a heating means and the like.
Further, if the film forming chamber 58 is for depositing the inorganic layer 14 by sputtering, the film forming means 82 includes a target holding means, a high frequency electrode, a gas supply means, and the like.

The formation conditions of the inorganic layer 14, such as temperature and pressure, may be appropriately set according to the type of the film forming unit 82, the target film thickness, film forming rate, and the like.
For example, when the inorganic layer 14 is formed by the CCP-CVD method, the pressure in the film formation chamber 58 is preferably 20 Pa to 200 Pa, and the temperature is preferably 0 ° C. to 80 ° C. When the inorganic layer 14 is formed by ICP-CVD, the pressure in the film formation chamber 58 is preferably 0.1 Pa to 10 Pa and the temperature is preferably 0 ° C. to 80 ° C.

The film forming material Za on which the inorganic layer 14 is formed and the surface protective film F is adhered while being supported / conveyed by the drum 80 is guided to a predetermined path by the guide roller 84b, and is formed in the partition 75. From 75a, it is conveyed to the winding chamber 60.

Here, as described above, the film forming chamber 58 includes the film roll 87 for supplying the surface protective film F for protecting the formed inorganic layer 14.
The film roll 87 is formed by winding the surface protective film F in a roll shape. The film roll 87 is supported by a rotating shaft 86 that is rotated by a drive source (not shown), and rotates in synchronization with the transport of the film forming material Za to send out the surface protective film F. The surface protection film F is brought into contact with the surface of the inorganic layer 14 by the guide roller 84b and is laminated / adhered to the film forming material Za. That is, in the film forming chamber 58, the guide roller 84b also functions as a sticking roller for the surface protective film F to the film forming material Za.

In addition, when the inorganic layer 14 formed in the film formation chamber 58 becomes the uppermost inorganic layer 14, the surface protective film F stuck on the inorganic layer 14 is a gas barrier film shown in FIG. It is the surface protection film 18 in 10a.
In addition, when the inorganic layer 14 formed in the film forming chamber 58 is an inorganic layer 14 other than the uppermost inorganic layer 14, the surface protective film F adhered on the inorganic layer 14 has an organic composition described later. The surface protective film F is peeled off when the organic layer 16 is formed in the membrane device 30.

Thus, in the method for producing a functional film of the present invention, the surface protective film F is applied in the film forming chamber 58 immediately after the inorganic layer 14 is formed. That is, the step of forming the inorganic layer 14 and the step of attaching the surface protective film F that protects the inorganic layer 14 are continuously performed under the same pressure and temperature environment.
By performing the film forming step and the surface protective film attaching step continuously under the same pressure and temperature environment, the surface protective film F can be thermocompression bonded using the heat applied in the film forming step. it can. Further, in the attaching step, the surface protective film F is attached continuously under the same pressure as the film forming step, that is, under vacuum, and therefore, between the surface protective film F and the inorganic layer 14. It is possible to reduce the mixing of bubbles.

Note that the pressure and temperature in the attaching process, that is, the pressure and temperature in the film forming chamber 58 may be set as appropriate according to the film forming method performed in the film forming process.
Moreover, in the sticking process, you may have a heating means to heat the surface protection film F and / or the film-forming material Za. For example, the guide roller 84b that acts as a sticking roller for the surface protective film F may have a heating means.

Further, in the illustrated example, the guide roller 84b disposed at the position closest to the drum 80 on the downstream side of the drum 80 and the film forming means 82 is an adhesive roller for attaching the surface protective film F. However, the present invention is not limited to this, and the second and subsequent guide rollers from the drum 80 may be used as the adhering rollers.
However, from the viewpoint of protecting the inorganic layer 14, the surface protection film F may be attached before the film forming material Za on which the inorganic layer 14 is formed by the film forming unit 82 comes into contact with another guide roller or the like. preferable. Therefore, it is preferable that the guide roller 84b disposed at a position closest to the drum 80 is a sticking roller.

In the illustrated example, the adhering step is performed in the film forming chamber 58 which is the same chamber as the film forming step. However, the present invention is not limited to this, and the adhering step is the film forming chamber 58. It is good also as a structure performed in a different chamber. For example, a configuration in which the sticking process is performed in the winding chamber 60 may be adopted, or a chamber for performing the sticking process may be provided between the film forming chamber 58 and the winding chamber 60. Note that in the case where the attaching step is performed in a chamber other than the film formation chamber 58, the temperature and pressure in this chamber may be set to be the same as the temperature and pressure in the film formation chamber.

Moreover, in the inorganic film-forming apparatus 32 of the example of illustration, although it was set as the structure which sticks the surface protection film F also to inorganic layers 14 other than the uppermost inorganic layer 14, it is not limited to this, It becomes the uppermost layer. The surface protective film F may be attached only to the inorganic layer 14.

Moreover, as the surface protective film F stuck to inorganic layers 14 other than the uppermost inorganic layer 14, the same plastic film as the surface protective film 18 can be used, and it is the same material as the surface protective film 18. May be different materials.

In the illustrated example, the winding chamber 60 includes a guide roller 90, a winding shaft 92, and the above-described vacuum exhaust means 76.
The film-formed film forming material Za that has been transported to the winding chamber 60 is wound into a roll shape by a winding shaft 92 to form the inorganic layer 14 and the surface protective film F is adhered thereto. The material roll 93 is formed by winding the material Za. This material roll 93 is supplied to the organic film forming apparatus 30, or is supplied to the next step as a material roll 93 formed by winding the gas barrier film 10a, which is a functional film of the present invention.

The organic film forming apparatus 30 shown in FIG. 2 (B) applies a coating material to be the organic layer 16 while transporting a long film-forming material Zb in the longitudinal direction, and after drying, coats the coating film by light irradiation. This is an apparatus for forming an organic layer 16 by crosslinking (polymerizing) the contained organic compound and curing it.
In the illustrated example, the organic film forming apparatus 30 includes, as an example, a coating unit 36, a drying unit 38, a light irradiation unit 40, a rotating shaft 42, a winding shaft 46, and a pair of conveying

rollers

48 and 50. . The organic film forming apparatus 30 also includes a winding shaft 44 that peels off and winds up the surface protective film F attached by the inorganic film forming apparatus 32 that forms the inorganic layer 14.
In addition to the illustrated members, the organic film forming apparatus 30 performs film formation by coating while conveying a long material to be formed such as a pair of transport rollers, a guide member for the material to be deposited Zb, and various sensors. You may have the various members provided in a well-known apparatus.

In the organic film forming apparatus 30, a material roll 93 formed by winding a long film-forming material Zb that is the stacked body 26 on which the stacked body 26, the inorganic layer 14, and the like are formed is loaded on the rotating shaft 42.
When the material roll 93 is loaded on the rotating shaft 42, the film forming material Zb is pulled out from the material roll 61, passes through the conveying roller pair 48, and passes under the coating unit 36, the drying unit 38, and the light irradiation unit 40. Then, it passes through a predetermined conveying path that reaches the winding shaft 46 through the conveying roller pair 50.

In the organic film forming apparatus 30 using RtoR, the film forming material Za from the material roll 61 is fed out and the film forming material Zb on which the organic layer is formed on the winding shaft 46 is synchronously performed. Thus, while the long film-forming material Zb is transported in the longitudinal direction along a predetermined transport path, the coating material 36 is applied with the coating material that is an organic layer, the drying device 38 is used to dry the coating material, and the light irradiation device 40 is used. The organic layer is formed by curing.

In addition, when the film-forming material Zb is a material after the inorganic layer 14 is formed, the surface protection film F is adhered to the surface of the inorganic layer 14, so that the transport by the transport roller pair 48 is performed. And the surface protection film F is peeled from the film-forming material Zb by winding by the winding shaft 44 that rotates in synchronization with this conveyance. That is, in the organic film forming apparatus 30, the transport roller pair 48 also functions as a peeling roller for the surface protective film F.

The coating means 36 applies a paint for forming the organic layer 16 prepared in advance on the surface of the film forming material Zb.
This paint is obtained by dissolving an organic compound such as a monomer, which becomes the organic layer 16 by crosslinking and polymerizing in an organic solvent, in the organic solvent. Further, preferably, the coating material contains a silane coupling agent in order to improve the adhesion of the organic layer 16. Furthermore, necessary components such as a surfactant, a polymerization initiator, and an increasing viscosity agent may be appropriately added to this paint.

There is no particular limitation on the method of applying the coating material to the film forming material Zb in the applying means 36.
Therefore, the application of the paint is all known coating methods such as die coating, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, etc. Is available.
Above all, because the coating can be applied in a non-contact manner, the surface of the film-forming material Zb is not damaged, and the bead formation is excellent in the embedding of the surface of the film-forming material Zb, etc. Are preferably used.

As described above, the film forming material Zb is then transported to the drying unit 38 and the coating applied by the coating unit 36 is dried.
The method of drying the paint by the drying means 38 is not limited, and before the film-forming material Zb reaches the light irradiation means 40, the paint is dried and the organic solvent is removed to allow crosslinking (polymerization). Any known drying means can be used as long as it can be brought into a stable state. Various known methods can be used. As an example, heat drying with a heater, heat drying with warm air, and the like are exemplified.

The drying temperature is preferably set to 70 ° C. or higher so that the temperature of the film forming material Zb at the time of drying in the drying means 38 is 70 ° C. or higher.
When the coating material containing the silane coupling agent is used, the adhesion between the organic layer 16 and the inorganic layer 14 is further improved by drying the coating material with the film-forming material Zb at a temperature of 70 ° C. or higher. preferable.

Next, the film forming material Zb is transported to the light irradiation means 40. The light irradiation means 40 irradiates the coating material applied by the application means 36 and dried by the drying means 38 with ultraviolet rays or visible light, and crosslinks (polymerizes) an organic compound such as a monomer contained in the coating material to cure it. The organic layer 16 is used.
At the time of curing of the coating film by the light irradiation means 40, the light irradiation area by the light irradiation means 40 in the film forming material Zb may be made an inert atmosphere by nitrogen substitution or the like, if necessary. Further, if necessary, a temperature of the film forming material Zb, that is, the coating film, may be adjusted at the time of curing by using a backup roller or the like that contacts the back surface.

Deposition during curing so that the temperature of the film-forming material Zb when the coating film is cured by the light irradiation means 40 is preferably 30 ° C. or higher (more preferably 50 ° C. or higher, more preferably 60 ° C. or higher). The heating temperature of the film material Zb is preferably 30 ° C. or higher (more preferably 50 ° C. or higher, more preferably 60 ° C. or higher).
By setting the temperature of the film-forming material Zb in the curing step within the above range, it is preferable in that the crosslinking (polymerization) density can be increased and the hardness and scratch resistance of the organic layer can be improved.

In the present invention, the crosslinking (polymerization) of the organic compound that becomes the organic layer is not limited to photopolymerization. That is, various methods according to the organic compound used as the organic layer 16 can be used for crosslinking of the organic compound, such as heat polymerization, electron beam polymerization, and plasma polymerization.
In the present invention, as described above, since an acrylic resin such as an acrylic resin or a methacrylic resin is preferably used as the organic layer 16, photopolymerization is preferably used.

The film-forming material Zb on which the organic layer 16 has been formed in this manner is nipped and conveyed by the conveyance roller pair 50 to reach the take-up shaft 46, and is taken up again in a roll shape by the take-up shaft 46. The material roll 61 is formed by winding the film forming material Zb on which the layer 16 is formed.
The material roll 61 is supplied to the inorganic film forming apparatus 32 as a material roll 61 formed by winding the film forming material Zb on which the organic layer 16 is formed.

Hereinafter, in the manufacturing apparatus shown in FIGS. 2 (A) and 2 (B), the action in producing the gas barrier film 10a in which two inorganic layers 14 and one organic layer 16 shown in FIG. 1 (A) are formed. By explaining the above, the production method of the present invention will be described in more detail.
In addition, when producing the gas barrier film 100 shown in FIG. 1 (B) and the gas barrier film having other layer configurations, depending on the number of inorganic layers 14 and the number of organic layers 16 to be formed, and the layer configuration, The formation of the similar inorganic layer 14 and organic layer 16 may be repeated.

First, the adhesive layer 20 is formed on the long gas barrier support 12, and the long laminate 26 is produced by attaching the back surface protective film 24 to the adhesive layer 20.
For example, the laminate 26 may be applied to a long sheet-like material such as a feeding means for a long sheet-like material from a material roll or a laminating roller in a known organic layer deposition apparatus shown in FIG. Manufactured by a known method using RtoR, such as a method using an apparatus incorporating a means for laminating a long sheet-like material, to produce a long laminate sheet obtained by sticking two sheet-like materials with an adhesive layer do it. In addition, in the production of the laminate 26, when drying and curing of the adhesive layer 20 are not necessary, a drying part and a curing part of the adhesive layer 20 (paint) are unnecessary.

The laminated body 26 may be formed by forming a laminated body in which the adhesive layer 20 is attached to the back surface protective film 24 and attaching the gas barrier support 12 to the adhesive layer 20 of the laminated body. Or the laminated body 26 may form the laminated body which affixed the adhesion layer 20 on the gas barrier support body 12, and may affix the back surface protective film 24 on the adhesion layer 20 of this laminated body. Here, in the present invention, since a low retardation film is used as the gas barrier support 12, a method of forming a laminate in which the adhesive layer 20 is adhered to the back surface protective film 24 and laminating the gas barrier support 12 thereon is provided. It is preferably used.

When a roll formed by winding such a laminated body 26 is produced, this roll is loaded as a material roll 61 onto the rotation shaft 64 of the supply chamber 56 of the inorganic film forming apparatus 32.
When the material roll 61 is loaded on the rotating shaft 64, the film forming material Za is drawn out and passed through a predetermined path from the supply chamber 56 through the film forming chamber 58 to the winding shaft 92 of the winding chamber 60. The

The film formation material Za sent out from the material roll 61 is guided by the guide roller 68 and conveyed to the film formation chamber 58.
The film forming material Za transferred to the film forming chamber 58 is guided by the guide roller 84a, wound around the drum 80, supported by the drum 80, and transferred through a predetermined path by the film forming means 82. For example, the first inorganic layer 14 is formed by CCP-CVD. Then, the surface protection film F sent out from the film roll 87 is stuck on the first inorganic layer 14.
Note that the inorganic layer 14 may be formed by a known vapor deposition method according to the inorganic layer 14 to be formed. Therefore, the process gas to be used, the film formation conditions, and the like may be set / selected as appropriate according to the inorganic layer 14 to be formed, the film thickness, and the like.

The film forming material Zb on which the inorganic layer 14 is formed is guided by the guide roller 84b and conveyed to the winding chamber 60.
The film forming material Zb transported to the winding chamber 60 is guided to the winding shaft 92 by the guide roller 90, wound in a roll shape by the winding shaft 92, and used as a material roll 93.

A material roll 93 formed by winding the laminated body 26 on which the first inorganic layer 14 is formed is loaded on the rotating shaft 42 of the organic film forming apparatus 30.
When the material roll 93 is loaded on the rotating shaft 42, the laminate 26 formed with the first inorganic layer 14 that is the film-forming material Zb is pulled out of the material roll 93, passes through the conveying roller pair 48, It passes through the coating means 36, the drying means 38, and the light irradiation means 40, passes through a pair of transport rollers 50, and reaches a take-up shaft 46.

The film-forming material Zb drawn from the material roll 93 is peeled off from the surface protection film F by the transport roller pair 48 and then transported to the coating means 36, and the coating material to be the organic layer 16 is applied to the surface. As described above, the paint to be the organic layer 16 is obtained by dissolving an organic compound such as a monomer, a silan coupling agent, a polymerization initiator, and the like in an organic solvent according to the organic layer 16 to be formed.
The film-forming material Zb to which the coating material to be the organic layer 16 is applied is then heated by the drying means 38 to remove the organic solvent and dry the coating material.

The film-forming material Zb from which the coating material has been dried is then irradiated with ultraviolet rays or the like by the light irradiation unit, and the organic compound is polymerized and cured to form the first organic layer 16. If necessary, the organic compound that becomes the organic layer 16 may be cured in an inert atmosphere such as a nitrogen atmosphere. Further, the laminated body 26 may be heated when the organic compound to be the organic layer 16 is cured.

The film-forming material Zb on which the first organic layer 16 is formed is conveyed by the conveying roller pair 50 and wound in a roll shape by the take-up shaft 46, and the inorganic layer 14 and the organic layer 16 are layered one by one. The material roll 61 formed by winding the formed laminate 26 is supplied again to the inorganic film forming apparatus 32 shown in FIG.

The material roll 61 formed by winding the laminated body 26 in which the inorganic layer 14 and the organic layer 16 are formed one by one is loaded on the rotating shaft 64 of the inorganic film forming apparatus 32 in the same manner as described above. The layered body 26 in which the inorganic layer 14 and the organic layer 16 are formed is pulled out as a film forming material Za and passed through the take-up shaft 92, and the second layer is formed on the first organic layer 16. The inorganic layer 14 is formed, and further, the surface protective film 18 is adhered, and the organic / inorganic laminate 28 and the surface protective film 18 including the inorganic layer 14, the organic layer 16, and the inorganic layer 14 are formed. The gas barrier film 10a shown in FIG.
The gas barrier film 10a is wound around a winding shaft 92 in a roll shape, and is shipped or stored as a product as a material roll 93 around which the gas barrier film 10a is wound, or is supplied to the next step or the like.

Here, in the present invention, as described above, since the rear surface protective film 24 is provided, even when the gas barrier support 12 is thin and weak, the formation of the inorganic layer 14 and the organic layer 16 by RtoR is stable. The film forming materials Za and Zb can be conveyed.
Further, as described above, in the laminate 26, the adhesive layer 20 and the gas barrier support 12 are slightly adhered, and further, the difference between the linear expansion coefficient of the gas barrier support 12 and the linear expansion coefficient of the back surface protective film 24 is different. 0 to 80 ppm / ° C. Therefore, it is heated by the formation of the inorganic layer 14 and also heated to dry the paint in the formation of the organic layer 16, and the gas barrier support 12 and the back surface protective film 24 are deformed differently, or bubbles existing between the layers Since the adhesive layer 20 and the back surface protective film 24 repeat peeling and sticking even if the gas expands, the gas barrier film 10a causes peeling of the gas barrier support 12 and back surface protective film 24, wrinkles of the gas barrier support 12 and the like. This prevents damage to the inorganic layer 14 due to this.

Further, in the present invention, as described above, since the surface protective film 18 is provided, the inorganic layer 14 can be prevented from being damaged. Further, since the surface protective film 18 and the inorganic layer 14 are slightly adhesive, damage to the inorganic layer 14 when the surface protective film 18 is peeled can be prevented. Further, since the melting point of the surface protective film 18 is 80 to 170 ° C., it can be thermocompression bonded at a low temperature, and problems caused by the adhesive remaining can be prevented.

As mentioned above, although the functional film of this invention and the manufacturing method of a functional film were demonstrated in detail, this invention is not limited to the said Example, In the range which does not deviate from the summary of this invention, various improvement and change Of course, you may do.

Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.
[Example 1]
As the gas barrier support 12, a long COC film (F1 film, manufactured by Gunze Co., Ltd.) having a width of 1000 mm and a thickness of 50 μm was prepared. The gas barrier support 12 has a linear expansion coefficient (CTE) of 65 ppm / ° C. and a retardation value (Re) of 5 nm. The Young's modulus is 3 GPa. Furthermore, water vapor transmission rate (WVTR) is ^{1 [g / (m 2 ·} day)].
Moreover, as the back surface protective film 24, a long PET film (Lumirror, manufactured by Toray Industries, Inc.) having a width of 1000 mm and a thickness of 50 μm was prepared. The back surface protective film 24 has a linear expansion coefficient (CTE) of 15 ppm / ° C. and a friction coefficient (μ) of 0.6. The Young's modulus is 4.5 GPa. The water vapor transmission rate (WVTR) is 3 [g / (m ² · day)].
Further, as the surface protective film 18 or the surface protective film F, a long low density polyethylene film (LDPE) (SUNYTECT PAC-2, manufactured by Sanei Kaken Co., Ltd.) having a width of 1000 mm and a thickness of 50 μm was prepared. The surface protective film has a melting point Tm of 108 ° C. The Young's modulus is 0.3 GPa. The water vapor transmission rate (WVTR) is 20 [g / (m ² · day)].
It is.

An acrylic resin adhesive (adhesive material) containing an alkyl acrylate monomer having 3 to 10 carbon atoms in the alkyl group portion was applied to one surface of the back surface protective film 24 as the adhesive layer 20. This adhesive was obtained by preparing in the same manner as the pressure-sensitive adhesive coating solution described in Example 1 of JP-A-2008-38103.
The adhesive was applied so that the cured adhesive layer 20 had a thickness of 50 μm.

Next, the adhesive was irradiated with ultraviolet rays to be in a semi-cured state. A gas barrier support 12 (COC film) was adhered to the semi-cured adhesive to produce a laminate 26 composed of the gas barrier support 12, the adhesive layer 20, and the back surface protective film 24.
In addition, the above process was performed using the well-known apparatus by RtoR which has an application | coating means and hardening | curing means of an adhesive agent, and the lamination | stacking means of a elongate sheet-like material.
When the adhesive strength between the gas barrier support 12 and the back surface protective film 24 and the adhesive layer 20 of the laminate 26 was measured according to JIS Z0237 using a peeling tester, the gas barrier support 12 and the adhesive layer 20 The adhesive force (25 ° C.) was 0.025 N / 25 mm, and the adhesive force (25 ° C.) between the back surface protective film 24 and the adhesive layer 20 was 0.1 N / 25 mm.

A material roll 61 formed by winding the laminated body 26 (film formation material Za) is loaded on the rotating shaft 64 of the inorganic film forming apparatus 32 shown in FIG. An inorganic layer 14 having a thickness of 25 nm was formed on the surface of the support 12 (the surface opposite to the surface on which the pressure-sensitive adhesive layer 20 was formed), and the surface protective film F was attached by thermocompression bonding.

Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ), and hydrogen gas (H ₂ ) were used as the film forming gas. The supply amounts were 100 sccm for silane gas, 200 sccm for ammonia gas, 500 sccm for nitrogen gas, and 500 sccm for hydrogen gas. The film forming pressure was 50 Pa.
The shower film-forming electrode was supplied with 3000 W of plasma excitation power at a frequency of 13.5 MHz from a high-frequency power source. Further, 500 W bias power was supplied to the drum 80 from a bias power source. During the film formation, the temperature of the drum 80 was adjusted to 20 ° C.

When the formation of the inorganic layer 14 was completed, purified air was introduced into the supply chamber 56, the film formation chamber 58, and the winding chamber 60 to release the atmosphere.
Next, the material roll 93 formed by winding the laminated body 26 on which the inorganic layer 14 was formed was taken out from the winding chamber 60.
When the cross-section of the laminate 26 on which the inorganic layer 14 was formed was measured by SEM, the thickness of the mixed layer formed by mixing the forming component of the gas barrier support 12 and the forming component of the inorganic layer 14 was 5 nm.

A material roll 93 formed by winding the laminate 26 (film formation material Zb) on which the inorganic layer 14 is formed is loaded on the rotating shaft 42 of the organic film forming apparatus 30 shown in FIG. An organic layer 16 having a thickness of 3 μm was formed on the surface.
The coating material for forming the organic layer 16 is MEK (methyl ethyl ketone) added with TMPTA (manufactured by Daicel Cytec), photopolymerization initiator (Irg189 manufactured by Ciba Chemicals), and silane coupling agent (KBM5103 manufactured by Shin-Etsu Silicone). And prepared. That is, the organic layer 16 is a layer formed by polymerizing TMPTA.
The addition amount of the photopolymerization initiator was 2% by mass in the concentration excluding the organic solvent, and the addition amount of the silane coupling agent was 10% by mass in the concentration excluding the organic solvent (that is, TMPTA in the solid content was 88%). mass%). Moreover, the solid content concentration of the paint obtained by diluting the components blended in these ratios with MEK was 15% by mass (that is, MEK was 85% by mass).

The coating means 36 used a die coater. The drying means 38 used the apparatus which blows off the drying wind from a nozzle, and drying was performed at 80 degreeC. Further, the light irradiation means 40 was irradiated with ultraviolet rays to carry out polymerization. The curing with ultraviolet rays was performed while heating the gas barrier support 12 to 80 ° C. from the back side so that the irradiation amount of the ultraviolet rays was about 500 mJ / cm ² in terms of the integrated irradiation amount.

Next, a material roll 61 formed by winding the laminate 26 in which the organic layer 16 is formed on the inorganic layer 14 is loaded again into the inorganic film forming apparatus 32 shown in FIG. The inorganic layer 14 having a thickness of 50 nm is formed, and the surface protective film 18 is attached by thermocompression bonding, and the inorganic layer 14 is formed on the surface of the laminate 26 composed of the gas barrier support 12, the adhesive layer 20, and the back protective film 24. A gas barrier film 10a shown in FIG. 1 (A) formed by forming an organic / inorganic laminate 28 composed of the organic layer 16 and the inorganic layer 14 and the surface protective film 18 was produced.
When the adhesive strength (25 ° C.) between the surface protective film 18 and the uppermost inorganic layer 14 of the gas barrier film 10a was measured according to JIS Z0237 using a peel tester, the adhesive strength was 0.04 N / 25 mm. Met. Moreover, when the cross section of the gas barrier film 10a was measured by SEM, the formation component of the organic layer 16 and the formation component of the inorganic layer 14 existing between the organic layer 16 and the inorganic layer 14 formed on the organic layer 16 The thickness of the mixed layer formed by mixing was 5 nm.

[Examples 2 to 4]
Example 2 except that the thickness of the back surface protective film 24 was 38 μm;
Except for the thickness of the back surface protective film 24 being 75 μm (Example 3);
A gas barrier film 10a shown in FIG. 1A was produced in the same manner as in Example 1 except that the thickness of the back surface protective film 24 was changed to 20 μm (Example 4).

[Examples 5 to 8]
Except for the thickness of the gas barrier support 12 being 25 μm (Example 5);
Example 6 except that the thickness of the gas barrier support 12 is 25 μm and the thickness of the back surface protective film 24 is 75 μm;
Except for the thickness of the gas barrier support 12 being 100 μm (Example 7);
A gas barrier film 10a shown in FIG. 1A is produced in the same manner as in Example 1 except that the thickness of the gas barrier support 12 is 100 μm and the thickness of the back surface protective film 24 is 38 μm (Example 8). did.

[Examples 9 to 10]
Except for changing the thickness of the surface protective film 18 to 25 μm (Example 9);
A gas barrier film 10a shown in FIG. 1A was produced in the same manner as in Example 1 except that the thickness of the surface protective film 18 was changed to 75 μm (Example 10).

[Examples 11 to 15]
Except for changing the thickness of the adhesive layer 20 to 25 μm (Example 11);
Except for changing the thickness of the adhesive layer 20 to 75 μm (Example 12);
Except for changing the thickness of the adhesive layer 20 to 100 μm (Example 13);
Except for changing the thickness of the adhesive layer 20 to 150 μm (Example 14);
A gas barrier film 10a shown in FIG. 1A was produced in the same manner as in Example 1 except that the thickness of the adhesive layer 20 was changed to 200 μm (Example 15).

[Examples 16 to 18]
Except for changing the back surface protective film 24 to a PEN film having a thickness of 50 μm and a linear expansion coefficient of 13 ppm / ° C. (Teonex manufactured by Teijin DuPont Films) (Example 16);
Except for changing the back surface protective film 24 to a PI film having a thickness of 50 μm and a linear expansion coefficient of 27 ppm / ° C. (Kapton manufactured by Toray DuPont) (Example 17);
The back protective film 24 is changed to a PI film (Kapton manufactured by Toray DuPont) with a thickness of 50 μm and a linear expansion coefficient of 27 ppm / ° C., and the gas barrier support 12 has a thickness of 50 μm, a linear expansion coefficient of 77 ppm / ° C., and a retardation value of 148 nm. A gas barrier film 10a shown in FIG. 1 (A) was produced in the same manner as in Example 1 except that the PC film was changed to S148 (manufactured by Teijin Limited) (Example 18).

[Examples 19 to 23]
Except for changing the conditions for forming the adhesive layer 20 so that the adhesive strength with the gas barrier support 12 is 0.01 (Example 19);
Except for changing the conditions for forming the adhesive layer 20 so that the adhesive strength with the gas barrier support 12 is 0.05 (Example 20);
The conditions for forming the adhesive layer 20 were changed, and the adhesive strength with the gas barrier support 12 was changed to 0.15 (Example 21);
Except for changing the conditions at the time of forming the adhesive layer 20 so that the adhesive strength with the back surface protective film 24 is 0.05 (Example 22);
Except for changing the conditions for forming the adhesive layer 20 and setting the adhesive strength with the back surface protective film 24 to 0.20 (Example 23); The gas barrier film 10a shown in FIG.

[Examples 24 to 25]
Except for changing the conditions at the time of thermocompression bonding the surface protective film 18 to make the adhesive strength with the inorganic layer 14 0.02 (Example 24);
Except for changing the conditions for thermocompression bonding of the surface protective film 18 and setting the adhesive strength with the inorganic layer 14 to 0.06 (Example 25); The gas barrier film 10a shown in FIG.

[Example 26]
Except that the surface of the back surface protective film 24 opposite to the surface on which the adhesive layer 20 is formed is subjected to corona treatment to roughen the surface roughness and the friction coefficient is 0.4 (Example 26). In the same manner as in Example 1, a gas barrier film 10a shown in FIG.

[Example 27]
Example 27 is the same as Example 1 except that the surface protective film 18 is changed to a PP film (SUNYTECT PAC-3 manufactured by Sanei Kaken Co., Ltd.) having a thickness of 50 μm, a melting point Tm of 165 ° C., and a Young's modulus of 0.6. A gas barrier film 10a shown in FIG.

[Examples 28 to 31]
The temperature of the drum 80 was changed to 5 ° C., and the thickness of the mixed layer between the gas barrier support 12 and the inorganic layer 14 was changed to 1 nm (Example 28);
The temperature of the drum 80 was changed to 60 ° C., and the thickness of the mixed layer between the gas barrier support 12 and the inorganic layer 14 was 20 nm (Example 29);
The temperature of the drum 80 was changed to 5 ° C., and the thickness of the mixed layer between the organic layer 16 and the inorganic layer 14 was changed to 1 nm (Example 30);
The temperature of the drum 80 was changed to 60 ° C., and the mixed layer between the organic layer 16 and the inorganic layer 14 was changed to 20 nm (Example 31); The gas barrier film 10a shown in FIG.

[Examples 32 to 35]
Change the conditions when forming the adhesive layer 20,
The adhesive strength between the gas barrier support and the adhesive layer at 100 ° C. is 0.03 N / 25 mm.
Except for the adhesive force of the adhesive layer and the back surface protective film at 100 ° C. being 0.07 N / 25 mm (Example 32);
Change the conditions when forming the adhesive layer 20,
Adhesive strength of the gas barrier support and adhesive layer at 100 ° C. is 0.14 N / 25 mm
Except for the adhesive force of the adhesive layer and the back surface protective film at 100 ° C. being 0.19 N / 25 mm (Example 33);
Change the conditions when forming the adhesive layer 20,
The adhesive strength between the gas barrier support and the adhesive layer at 200 ° C. is 0.04 N / 25 mm.
Except that the adhesive force between the adhesive layer and the back surface protective film at 200 ° C. was 0.08 N / 25 mm (Example 34);
Change the conditions when forming the adhesive layer 20,
The adhesive strength between the gas barrier support and the adhesive layer at 200 ° C. is 0.13 N / 25 mm.
The gas barrier film shown in FIG. 1 (A) was the same as Example 1 except that the adhesive force between the adhesive layer and the back surface protective film at 200 ° C. was 0.18 N / 25 mm (Example 35). 10a was produced.

[Comparative Example 1]
A gas barrier film was produced in the same manner as in Example 1 except that the back surface protective film and the adhesive layer were not provided.

[Comparative Example 2]
A gas barrier film was produced in the same manner as in Example 1 except that the surface protective film was not provided.

[Comparative Examples 3 to 4]
Other than changing the conditions for forming the adhesive layer to set the adhesive strength with the gas barrier support to 2 (Comparative Example 3);
A gas barrier film was produced in the same manner as in Example 1, except that the conditions for forming the adhesive layer were changed so that the adhesive strength with the gas barrier support was 0.005 (Comparative Example 4).

[Comparative Examples 5 to 6]
Other than changing the conditions at the time of thermocompression bonding the surface protective film, the adhesive strength with the inorganic layer was 0.2 (Comparative Example 5);
A gas barrier film was produced in the same manner as in Example 1, except that the conditions for thermocompression bonding of the surface protective film were changed so that the adhesive strength with the inorganic layer was 0.001 (Comparative Example 6).

[Comparative Example 7]
A gas barrier film was produced in the same manner as in Example 1 except that the organic / inorganic laminate was configured in the order of an organic layer, an inorganic layer, and an organic layer from the gas barrier support side (Comparative Example 7).

[Comparative Example 8]
A gas barrier film was prepared in the same manner as in Example 1 except that the back protective film was changed to a PE film (SUNYTECT PAC-2 manufactured by Sanei Kaken Co., Ltd.) having a thickness of 50 μm and a linear expansion coefficient of 160 ppm / ° C. Produced.

[Comparative Example 9]
1A except that the surface protective film was changed to a PET film (Lumirror manufactured by Toray Industries, Inc.) having a thickness of 50 μm, a melting point of 260 ° C. and a Young's modulus of 5.5 (Comparative Example 9). The gas barrier film 10a shown in FIG.

[Evaluation]
Regarding the gas barrier films of Examples 1 to 35 and Comparative Examples 1 to 9 produced in this way, the deformability of the gas barrier film before peeling the surface protective film and the back surface protective film (hereinafter referred to as “deformability before peeling”). Gas barrier property of the gas barrier film before peeling the surface protective film and peeling the back surface protective film (hereinafter also referred to as “barrier property before peeling”), the gas barrier film after peeling the back surface protective film and the surface protective film The gas barrier property of the gas barrier film after peeling the back surface protective film and the surface protective film (hereinafter also referred to as “barrier property after peeling”) was evaluated. .

<Deformability of gas barrier film (deformability before peeling)>
In an arbitrarily selected 1 m ² region, the deformability of the produced gas barrier film was evaluated by visual confirmation.
“AAA” when no deformation is observed;
When a slight deformation can be confirmed at one place, “AA”;
“A” when slight deformation can be confirmed in 2 to 3 places;
“B” when slight deformation can be confirmed in 4 to 5 places;
"C" when the deformation is seen but not a problem in practice;
“D” when there is a large deformation and cannot be used in practice.
The case where there was a large deformation on the entire surface and it could not be used practically was evaluated as “E”;

<Gas barrier property before peeling (barrier property before peeling)>
The surface protective film was peeled from the produced gas barrier film, and the water vapor transmission rate [g / (m ² · day)] was measured by the calcium corrosion method (method described in JP-A-2005-283561). The conditions for the constant temperature and humidity treatment were a temperature of 40 ° C. and a humidity of 90% RH.
Anything less than 7 × 10 ^-6 [g / (m ² · day)] is “AAA”;
AA above 7 × 10 ^-6 [g / (m ² · day)] and less than 9 × 10 ^-6 [g / (m ² · day)];
9 × 10 ⁻⁶ [g / (m ² · day)] or more and less than 3 × 10 ⁻⁵ [g / (m ² · day)] “A”;
3 x 10 ^-5 [g / (m ² · day)] or more and less than 5 x 10 ^-5 [g / (m ² · day)] "B";
“C” for items of 5 × 10 ⁻⁵ [g / (m ² · day)] or more and less than 9 × 10 ⁻⁵ [g / (m ² · day)];
9 × 10 ⁻⁵ [g / (m ² · day)] or more and less than 3 × 10 ⁻⁴ [g / (m ² · day)] “D”;
3 × 10 ⁻⁴ [g / (m ² · day)] or more was evaluated as “E”;

<Deformability after peeling>
After peeling off the surface protective film from the gas barrier film, the back protective film (and the adhesive layer) was further peeled off to obtain a gas barrier film comprising a gas barrier support and an organic / inorganic laminate.
About this gas barrier film, the deformation | transformation property after peeling of a back surface protective film and a surface protective film was evaluated by confirming the deformation | transformation of a gas barrier support body, and the residual of the adhesion layer to a gas barrier support body visually. When the peelability is poor, the gas barrier support is easily deformed and the adhesive layer remains on the gas barrier support.
“A” when the gas barrier support is not deformed even if it is peeled, and there is no residual adhesive layer on the gas barrier support;
“B” when the gas barrier support is deformed and / or at least one of the adhesive layer remaining on the gas barrier support is slightly generated by peeling;
A case where at least one of deformation of the gas barrier support and remaining of the adhesive layer on the gas barrier support is intermittently generated in the peeling direction due to peeling, “C”;
A case where at least one of deformation of the gas barrier support and remaining of the adhesive layer on the gas barrier support is continuously generated in the peeling direction due to peeling and cannot be used practically;
The case where any one of the cases where the gas barrier support could not be peeled, the gas barrier support was broken, and the entire adhesive layer remained was evaluated as “E”.

<Gas barrier properties after peeling (barrier properties after peeling)>
Similarly to the gas barrier property before peeling, the water vapor permeability [g / (m ² · day)] of the gas barrier film from which the back surface protective film and the surface protective film were peeled was measured and evaluated in the same manner.
The configurations of Examples 1 to 27 and Comparative Examples 1 to 9 are shown in Table 1 below, and the results are shown in Tables 2 to 4 below.

As shown in Tables 1 to 4 above, the gas barrier film of the present invention is 9 × 10 ⁻⁵ [g / (m ² · day) before and after peeling of the back surface protective film 24 and the surface protective film 18. It has an excellent gas barrier property of less than
In Example 21, since the adhesive force between the gas barrier support 12 and the adhesive layer 20 is slightly higher than that of the other examples, repeated peeling and sticking between the gas barrier support 12 and the adhesive layer 20 are performed. It is considered that the inorganic layer 14 is slightly damaged due to this, and the gas barrier property is slightly decreased.
In Example 22, the adhesive strength between the back surface protective film 24 and the adhesive layer 20 is slightly lower than in the other examples. Therefore, after the back surface protective film 24 is peeled off, the adhesive layer remains on the gas barrier support 12 side. Occurred intermittently.

On the other hand, Comparative Example 1 in which the back surface protective film and the adhesive layer are not provided does not have the back surface protective film, and thus has no self-supporting property and poor sliding property. Therefore, nicks and wrinkles were generated by the transport of RtoR, and cracks in the gas barrier support occurred. As a result, the gas barrier property was lowered.
Further, in Comparative Example 2 that does not have the surface protective film 18, the inorganic layer directly touches the guide roller during conveyance with RtoR. As a result, the inorganic layer was cracked and the gas barrier property was lowered.
Further, in Comparative Example 3 in which the adhesive strength between the gas barrier support and the adhesive layer is 2 N / 25 mm, the adhesive strength is too high, so that peeling and sticking are repeated between the gas barrier support 12 and the adhesive layer 20. Therefore, deformation cannot be suppressed. As a result, wrinkles were generated and gas barrier properties were lowered.
Further, in Comparative Example 4 in which the adhesive strength between the gas barrier support and the adhesive layer is 0.005 N / 25 mm, the adhesive strength is too weak, so that it peels off during the transport of RtoR, resulting in the inorganic layer. Cracks, cracks, etc. occurred in the gas and the gas barrier properties were lowered.
In Comparative Example 5 in which the adhesive strength between the surface protective film and the inorganic layer is 0.2 N / 25 mm, the adhesive strength of the surface protective film is too high. Part was observed to remain on the inorganic layer. Moreover, since the adhesive force was too high, the surface inorganic film was damaged at the time of peeling. As a result, the gas barrier properties were lowered.
Further, in Comparative Example 6 in which the adhesive strength between the surface protective film and the inorganic layer is 0.001 N / 25 mm, the adhesive strength of the surface protective film is too low, so that it peels off during the transport of RtoR. As a result, cracks and cracks were generated in the inorganic layer, and the gas barrier properties were lowered.
Further, in Comparative Example 7 in which the lowermost layer and the uppermost layer were organic layers, the adhesion between the lowermost organic layer and the gas barrier support was low, and an appropriate organic / inorganic laminate could not be formed.
Further, in Comparative Example 8 in which the difference between the coefficient of linear expansion of the gas barrier support and the coefficient of linear expansion of the back surface protective film is 95 ppm, the back surface protective film melts with heat and breaks during transportation. As a result, cracks and cracks were generated in the inorganic layer, and the gas barrier properties were lowered.
Further, in Comparative Example 9 where the melting point of the surface protective film is 260 ° C., the adhesion between the surface protective film and the inorganic layer is low, and the surface is peeled off during transportation, and the inorganic layer is damaged by contact with the guide roller or the like. , Gas barrier properties decreased.

Next, in the examples, the gas barrier properties immediately after the production and the gas barrier properties after a lapse of a predetermined time were measured, and durability was evaluated.

[Examples 36 to 37]
Except for changing the gas barrier support 12 to a COP film (ARTON manufactured by JSR) having a thickness of 50 μm and a water vapor transmission rate of 100 [g / (m ² · day)] (Example 36);
Except for changing the gas barrier support 12 to a TAC film having a thickness of 50 μm and a water vapor transmission rate of 600 [g / (m ² · day)] (Fuji Film, Fuji Tac) (Example 37); Similarly, a gas barrier film 10a shown in FIG.

[Examples 38 to 39]
Except for changing the back surface protective film 24 to a PEN film having a thickness of 50 μm and a water vapor transmission rate of 2 [g / (m ² · day)] (Teonex manufactured by Teijin DuPont Films) (Example 38);
Except that the back surface protective film 24 was changed to a PC film (S148, manufactured by Teijin Limited) having a thickness of 50 μm and a water vapor transmission rate of 100 [g / (m ² · day)] (Example 39); Thus, a gas barrier film 10a shown in FIG.

[Examples 40 to 41]
Except for changing the surface protective film 18 to a PP film (SUNYTECT PAC-3 manufactured by Sanei Kaken Co., Ltd.) having a thickness of 50 μm and a water vapor transmission rate of 10 [g / (m ² · day)] (Example 40);
Example 41 is the same as Example 1 except that the surface protection film 18 is changed to a PET + PE composite film (Panabrid, manufactured by Panac) having a thickness of 50 μm and a water vapor transmission rate of 3 [g / (m ² · day)]. Thus, a gas barrier film 10a shown in FIG.

[Example 42]
The gas barrier support 12 is changed to a COP film (ARTON manufactured by JSR) having a thickness of 50 μm and a water vapor transmission rate of 100 [g / (m ² · day)], and the back protective film 24 is changed to a thickness of 50 μm and a water vapor transmission rate of 100 [ g / (m ² · day)] A gas barrier film 10a shown in FIG. 1A was produced in the same manner as in Example 1 except that it was changed to a PC film (S148 manufactured by Teijin Ltd.) (Example 42). .

[Evaluation]
<Durability>
For the gas barrier films of Examples 1 and 36 to 42 produced in this manner, the water vapor transmission rate [g / (m ² · day)] immediately after production, and the environment of 85 ° C. and 85% humidity for 1000 hours. Durability was evaluated by measuring water vapor permeability [g / (m ² · day)] after standing.
In any case, the water vapor permeability was measured by peeling off the surface protective film 18 and the back surface protective film 24 immediately before the measurement. That is, after leaving the surface protective film 18 and the back surface protective film 24 in an environment of a temperature of 85 ° C. and a humidity of 85% for 1000 hours without peeling, the surface protective film 18 and the back surface protective film 24 are peeled to increase the water vapor transmission rate. It was measured.

In the same manner as described above, the water vapor permeability [g / (m ² · day)] of the produced gas barrier film was measured by a calcium corrosion method (a method described in JP-A-2005-283561). The conditions for the constant temperature and humidity treatment were a temperature of 40 ° C. and a humidity of 90% RH.
Evaluation is the ratio of water vapor permeability [g / (m ² · day)] after leaving for 1000 hours to water vapor permeability [g / (m ² · day)] immediately after production,
More than 85% "A";
“B” for 55% or more and less than 85%;
30% or more and less than 55% "C";
Those less than 30% were evaluated as “D”.
The results are shown in Table 5 below.

As shown in Table 5 above, the water vapor transmission rate of the back protective film is 0.1 to 10 [g / (m ² · day)], and the water vapor transmission rate of the surface protective film is 0.5 to 25 [g. It can be seen that Examples 1, 36 to 38, 40, and 41, which are / (m ² · day)], have high gas barrier properties after being left for 1000 hours and are excellent in durability.
Further, from the comparison between Example 1 and Example 39 and the comparison between Example 36 and Example 42, when the water vapor transmission rate of the back surface protective film exceeds 25 [g / (m ² · day)]. It can be seen that the gas barrier property after leaving for 1000 hours is slightly lowered and the durability is slightly lowered.
From the above results, the effects of the present invention are clear.

It can be suitably used as a protective film for organic EL devices.

10a, 10b, 100 Gas barrier film 12 Gas barrier support 14 Inorganic layer 16 Organic layer 18 Surface protective film 20 Adhesive layer 24 Back surface protective film 26 Laminated body 28 Organic / inorganic laminated body 30 Organic film forming apparatus 32 Inorganic film forming apparatus 36 Coating means 38 Drying means 40 Light irradiation means 42, 64, 86 Rotating

shaft

44, 46, 92

Winding shaft

48, 50 Conveying roller pair 56 Supply chamber 58 Film forming chamber 60

Winding chamber

61, 93

Material roll

68, 84a, 84b, 90

Guide rollers

70, 74, 76 Vacuum exhaust means 72, 75

Partitions

72a, 75a Slit 80 Drum 82 Film forming means 87 Film roll

Claims

A gas barrier support, an organic / inorganic laminate formed by alternately laminating inorganic layers and organic layers and formed on the gas barrier support, and a surface of the gas barrier support on which the organic / inorganic laminate is formed are opposite to each other. Having an adhesive layer to be attached, a back surface protective film to be attached to the adhesive layer, and a surface protective film to be laminated on the organic-inorganic laminate;
The retardation value of the gas barrier support is 300 nm or less,
The organic-inorganic laminate has one or more organic layers and two or more inorganic layers, and the bottom layer on the gas barrier support side and the top layer on the surface protective film side are inorganic layers,
The difference between the coefficient of linear expansion of the gas barrier support and the coefficient of linear expansion of the back surface protective film is 0 to 80 ppm / ° C.
The melting point of the surface protective film is 80 to 170 ° C .;
The adhesive strength of the gas barrier support and the adhesive layer at 25 ° C. is 0.01 N / 25 mm to 0.15 N / 25 mm,
A functional film, wherein an adhesive force at 25 ° C. between the surface protective film and the inorganic layer of the uppermost layer of the organic-inorganic laminate is 0.02 N / 25 mm to 0.06 N / 25 mm.
Having a first mixed layer between the gas barrier support and the lowermost inorganic layer of the organic-inorganic laminate,
The functional film according to claim 1, wherein the thickness of the first mixed layer is 1 nm to 20 nm.
In the organic-inorganic laminate, a second mixed layer is provided between the organic layer and the inorganic layer laminated on the organic layer,
The functional film according to claim 1, wherein the thickness of the second mixed layer is 1 nm to 20 nm.
The functional film according to any one of claims 1 to 3, wherein an adhesive force of the adhesive layer and the back surface protective film at 25 ° C is 0.05 N / 25 mm to 0.20 N / 25 mm.
The gas barrier support has a thickness of 20 μm to 120 μm,
The thickness of one organic layer of the organic-inorganic laminate is 0.5 μm to 5 μm, and the thickness of one inorganic layer is 10 nm to 200 nm,
The adhesive layer has a thickness of 15 μm to 250 μm;
The back protective film has a thickness of 12 μm to 100 μm;
The functional film according to any one of claims 1 to 4, wherein the surface protective film has a thickness of 20 袖 m to 100 袖 m.
The glass transition temperature of the gas barrier support is 130 ° C. or higher,
The functional film according to any one of claims 1 to 5, wherein the back surface protective film has a glass transition temperature of 70 ° C or higher.
The gas barrier support and the adhesive layer have an adhesive strength at 100 ° C. of 0.03 N / 25 mm to 0.14 N / 25 mm, and an adhesive strength at 200 ° C. of 0.04 N / 25 mm to 0.13 N / 25 mm,
The adhesive strength between the adhesive layer and the back surface protective film at 100 ° C. is 0.07 N / 25 mm to 0.19 N / 25 mm, and the adhesive strength at 200 ° C. is 0.08 N / 25 mm to 0.18 N / 25 mm. Item 7. The functional film according to any one of Items 1 to 6.
The functional film according to any one of claims 1 to 7, wherein a friction coefficient of the back surface protective film is 0.6 or less.
The functional film according to any one of claims 1 to 8, wherein the Young's modulus of the surface protective film is ¼ or less of the Young's modulus of the gas barrier support and the Young's modulus of the back surface protective film.
The pressure-sensitive adhesive layer is made of a pressure-sensitive adhesive material containing an alkyl group part of an alkyl acrylate monomer having 3 to 10 carbon atoms, and has a temperature of 25 ° C. to 150 ° C. and a UV irradiation amount of 100 mJ / cm 2 to 1000 mJ / cm 2 . The functional film according to any one of Claims 1 to 9, wherein the volume shrinkage due to crosslinking is 3% or less when crosslinked with.
A long laminate having a gas barrier support, an adhesive layer attached to the gas barrier support, a back surface protective film attached to the adhesive layer, and a gas barrier support of the elongated laminate A step of producing a composite having an inorganic layer and an organic layer alternately laminated on the surface, and the surface opposite to the back surface protective film is an organic layer;
A film forming step of forming an uppermost inorganic layer by vapor phase growth on the organic layer on the surface while transporting the composite in the longitudinal direction;
A surface protective film attaching step for attaching a surface protective film on the uppermost inorganic layer formed in the film forming step;
The film forming step and the surface protective film attaching step are continuously performed under the same pressure and temperature environment,
The retardation value of the gas barrier support is 300 nm or less,
The difference between the coefficient of linear expansion of the gas barrier support and the coefficient of linear expansion of the back surface protective film is 0 to 80 ppm / ° C.
The melting point of the surface protective film is 80 to 170 ° C .;
A method for producing a functional film, wherein an adhesive force of the gas barrier support and the adhesive layer at 25 ° C. is 0.01 N / 25 mm to 0.15 N / 25 mm.
The step of producing the composite includes an application step of applying a composition to be an organic layer on the inorganic layer of the long laminate in which the inorganic layer is laminated,
A drying step of drying the applied composition,
The method for producing a functional film according to claim 11, wherein the temperature of the composite is 70 ° C. or higher in the drying step.
The step of producing the composite includes an application step of applying a composition to be an organic layer on the inorganic layer of the long laminate in which the inorganic layer is laminated,
A drying step of drying the applied composition;
A curing step of curing the dried composition by irradiation with ultraviolet rays to form the organic layer,
The method for producing a functional film according to claim 11 or 12, wherein in the curing step, the composite is irradiated with ultraviolet rays while being heated from the back surface protective film side so that the temperature becomes 30 ° C or higher.