WO2015198701A1

WO2015198701A1 - Method for producing functional film

Info

Publication number: WO2015198701A1
Application number: PCT/JP2015/062137
Authority: WO
Inventors: 望月　佳彦; 藤縄　淳
Original assignee: 富士フイルム株式会社
Priority date: 2014-06-27
Filing date: 2015-04-21
Publication date: 2015-12-30
Also published as: JPWO2015198701A1

Abstract

Provided is a method for producing a functional film, which is capable of preventing decrease of adhesion between an inorganic layer, from which a protective film has been separated, and a layer formed on the inorganic layer. This method for producing a functional film comprises: a substrate preparation step for preparing a substrate that has a surface formed of an organic material; a film formation step for forming an inorganic layer, which has a composition ratio of carbon of 5% or less, on the substrate by plasma CVD in a vacuum; an inactivation step for inactivating a dangling bond of the formed inorganic layer; and a bonding step for removably bonding a protective film, which is formed of a plastic film, onto the inorganic layer after the inactivation step.

Description

Method for producing functional film

The present invention relates to a method for producing a functional film having an inorganic layer.

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 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 forming an inorganic layer made of these inorganic compounds, thin film formation by a vacuum film forming method such as sputtering or plasma CVD (chemical vapor deposition) is used.

Further, in such a gas barrier film, as a configuration that can obtain higher gas barrier performance, the support has 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. Organic / inorganic laminated gas barrier films (hereinafter also referred to as laminated gas barrier films) are known.
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.

Here, as a method for enabling the production of a functional film with high productivity and production efficiency, this substrate is sent out from a substrate roll formed by winding a long substrate into a roll shape and conveyed in the longitudinal direction. An apparatus for forming a film by so-called roll-to-roll (hereinafter also referred to as RtoR) is known, in which an inorganic layer is formed while the formed substrate is wound into a roll. .
In particular, when manufacturing a laminated gas barrier film in which a plurality of layers as described above are laminated, by using RtoR, an organic layer and an inorganic layer are continuously formed while transporting a long substrate. Therefore, a gas barrier film can be produced with very high productivity.

In the production of such a functional film, an inorganic layer formed on the surface of the substrate due to conveyance by a pair of conveyance rollers, contact with other members, etc. after forming the inorganic layer on the surface of the substrate If the film is damaged, there is a possibility that a functional film having the intended performance cannot be manufactured.
In particular, in the RtoR apparatus described above, the inorganic layer formed on the substrate and the back surface of the substrate are in sliding contact with each other when the substrate is wound after the inorganic layer is formed.
Moreover, in order to manufacture a high quality product, it is preferable to keep the surface of the inorganic layer clean.

Therefore, in the production of a functional film such as a gas barrier film, in order to protect the inorganic layer, a protective film is attached to the surface of the inorganic layer to protect the inorganic layer.
That is, after film formation of the inorganic layer, a protective film is attached to the surface of the inorganic layer, and the substrate is transported to the site where the next treatment is performed with the substrate and protective film having the inorganic layer formed on the surface. Alternatively, the substrate with the protective film attached is wound up into a roll once and loaded into a substrate processing apparatus such as a film forming apparatus or a surface processing apparatus for performing the next processing and immediately before performing the next processing. The protective film is peeled off and the substrate surface is treated.

For example, in Patent Document 1, when a laminated gas barrier film is manufactured by RtoR, an inorganic layer on the surface is prevented from being damaged by contact with a guide roller or the like after the formation of the inorganic layer. It describes that a protective film is stuck on the surface of an inorganic layer immediately after forming a film, and this protective film is peeled off immediately before forming an organic layer to protect the inorganic layer.

Moreover, as a form using a protective film, even when supplying a functional film that uses the outermost layer as an inorganic layer, in order to protect the inorganic layer, a peelable protective film is attached to the inorganic layer. It is possible to provide.

For example, when the gas barrier film is used for a top emission type organic EL device, the gas barrier film is laminated on the passivation film having a gas barrier property covering the organic EL material as the light emitting element by using an adhesive. By doing so, deterioration of the organic EL material can be suitably prevented.
Here, as a material for forming the passivation film, inorganic materials such as silicon nitride, silicon oxide, and silicon oxynitride that exhibit gas barrier properties are used.
Therefore, from the viewpoint of adhesiveness, in a gas barrier film used for an organic EL device or the like, the inorganic layer and the passivation film are opposed to each other with the uppermost layer being an inorganic layer, and the inorganic materials are laminated via an adhesive. It is preferable.
However, if the outermost layer of the gas barrier film is an inorganic layer, the inorganic layer is easily damaged, and the target barrier performance may not be obtained. Therefore, when supplying such a gas barrier film, in order to prevent damage to the inorganic layer, it is necessary to supply the protective film on the outermost inorganic layer.

As described above, even in a functional film in which the outermost layer is used as an inorganic layer, in order to protect the inorganic layer, it is conceivable to supply a peelable protective film attached to the inorganic layer.

JP 2012-192738 A

However, the adhesion between the inorganic layer and the layer formed on the inorganic layer is reduced when another layer such as an organic layer or an adhesive layer is formed on the inorganic layer after the protective film on the inorganic layer is peeled off. There was a problem to do.
According to the study by the present inventors, the components of the protective film remain on the surface of the inorganic layer after the protective film is peeled off, and are formed on the inorganic layer and the inorganic layer due to the presence of the transferred component. It was found that the adhesion with the layer was inhibited.
Further, it has been found that such a problem occurs when a denser inorganic layer is formed by plasma CVD, or when the conveyance speed is improved to improve manufacturing efficiency.

A general protective film is designed so that it can be easily peeled off by adhering with an intermolecular force acting between the adhesive layer of the protective film and the counterpart member.
However, according to the study by the present inventors, when a dense inorganic layer is formed in a vacuum by plasma CVD that can form a dense inorganic layer, and a protective film is applied immediately after that, It was found that the components of the protective film were transferred to the surface of the inorganic layer after peeling off the protective film. Immediately after forming a high density inorganic layer by plasma CVD in vacuum, the surface activity of the inorganic layer is very high, and there are many unbonded hands, so it is chemically bonded to the components of the protective film. It is estimated that the phenomenon will occur.
In particular, it is considered that more dangling bonds are generated when a dense inorganic layer is formed by increasing the applied voltage. In vacuum, since there is almost no partner binding to the generated unbonded hands, it is considered that many unbonded hands remain until the protective film is attached. Moreover, since the time from the formation of the inorganic layer to the attachment of the protective film is shortened when the conveyance speed is high, the activity of the surface of the formed inorganic layer does not decrease during the attachment of the protective film, and more unbonded hands. Is considered to remain. Therefore, it is considered that the phenomenon that the component of the protective film and the inorganic layer are chemically bonded easily occurs.
In this way, when the chemically bonded inorganic layer and the protective film are peeled off, they are peeled off while breaking the chemical bonds in the protective film. Therefore, it is considered that the components of the protective film are transferred and remain on the surface of the inorganic layer after the protective film is peeled off.

An object of the present invention is to solve such problems of the prior art, and it is possible to prevent a decrease in adhesion between the inorganic layer after the protective film is peeled off and the layer formed on the inorganic layer. It is providing the manufacturing method of a functional film.

As a result of earnest research to achieve the above-mentioned problems, the present inventor has obtained a substrate preparation step of preparing a substrate having a surface made of an organic material, and a carbon composition ratio of 5% on the substrate by plasma CVD in a vacuum. A film forming step for forming the following inorganic layer, an inactivation step for deactivating the dangling bonds of the formed inorganic layer, and a protective film made of a plastic film after the deactivation step on the inorganic layer In addition, it has been found that by having a sticking step for sticking in a peelable manner, it is possible to prevent a decrease in adhesion between the inorganic layer after peeling the protective film and the layer formed on the inorganic layer, The present invention has been completed.
That is, this invention provides the manufacturing method of the functional film of the following structures.

(1) a substrate preparation step of preparing a substrate having a surface made of an organic material;
A film forming step of forming an inorganic layer having a carbon composition ratio of 5% or less on the substrate by plasma CVD in vacuum;
An inactivation step for inactivating dangling bonds of the deposited inorganic layer;
The manufacturing method of a functional film which has the sticking process of sticking the protective film which consists of a plastic film on an inorganic layer so that peeling is possible after an inactivation process.
(2) The method for producing a functional film according to (1), wherein the inactivation step leaves an interval of 15 seconds or more between the film formation step and the sticking step.
(3) The method for producing a functional film according to (1), wherein the inactivation step cools the substrate.
(4) The material according to any one of (1) to (3), wherein the material of the inorganic layer formed in the film forming step is a combination of elements selected from the group consisting of Si, Al, O, N, and H. A method for producing a functional film.
(5) Furthermore, after the sticking step, a peeling step for peeling the protective film,
The method for producing a functional film according to any one of (1) to (4), further comprising an organic layer forming step of forming an organic layer on the surface of the inorganic layer on the side where the protective film is peeled after the peeling step.
(6) The method for producing a functional film according to (5), wherein the organic layer forming step is further repeated from the film forming step to form two or more inorganic layers and one or more organic layers.
(7) The substrate preparation step prepares a substrate roll formed by winding a long substrate,
The function according to any one of (1) to (6), wherein a long substrate is fed from a substrate roll and conveyed in the longitudinal direction of the substrate while performing a film forming step, an inactivation step, and a pasting step For producing a conductive film.

According to such this invention, the manufacturing method of the functional film which can prevent the fall of the adhesiveness of the inorganic layer after peeling a protective film and the layer formed on this inorganic layer can be provided. .

BRIEF DESCRIPTION OF THE DRAWINGS 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. 1 (A) is a film-forming apparatus of an inorganic layer, FIG.1 (B) is film-forming of an organic layer. Device. It is a figure which shows notionally an example of the stepped roller of the film-forming apparatus shown to FIG. 1 (A). It is a figure which shows notionally another example of the film-forming apparatus of the inorganic layer which enforces the manufacturing method of the functional film of this invention. 4 (A) to 4 (C) are cross-sectional views showing an enlarged part of the functional film for explaining the method for producing the functional film of the present invention. FIG. 5A to FIG. 5C are cross-sectional views showing an enlarged part of the functional film for explaining the method for producing the functional film of the present invention.

Hereinafter, preferred embodiments of the method for producing a functional film of the present invention will be described in detail.

In the method for producing a functional film of the present invention, the surface of an inorganic layer formed on a substrate is inactivated, and then a protective film is attached on the inorganic layer.
Specifically, the production method of the present invention includes:
A substrate preparation step of preparing a substrate having a surface made of an organic material;
A film forming process for forming an inorganic layer having a carbon composition ratio of 5% or less on a substrate by plasma CVD in a vacuum;
An inactivation step of inactivating dangling bonds of the deposited inorganic layer, and
After the inactivation step, there is a sticking step of sticking a protective film made of a plastic film on the inorganic layer in a peelable manner.

Furthermore, the production method of the present invention has, as a preferred aspect,
After the sticking step, a peeling step for peeling the protective film,
An organic layer forming step of forming an organic layer on the surface of the inorganic layer on the side where the protective film is peeled off.
Hereafter, each process of the manufacturing method of this invention is explained in full detail using an example of the manufacturing apparatus which enforces the manufacturing method of this invention.

FIG. 1 (A) and FIG. 1 (B) are diagrams conceptually showing an example of a production apparatus for carrying out the functional film production method of the present invention. 4 (A) to 4 (C) and FIGS. 5 (A) to 5 (C) are enlarged views of a part of the functional film for explaining the method for producing the functional film of the present invention. FIG.
In the following description, an example in which the method for producing a functional film is used for the method for producing a gas barrier film will be described.

In addition, the manufacturing method of the functional film of this invention is not limited to the manufacturing method of a gas barrier film. That is, this invention can be utilized as a manufacturing method of well-known functional films, such as various optical films, such as a filter which permeate | transmits the light of a specific wavelength, and an antireflection film.
In the functional film having an inorganic layer produced by the method for producing a functional film of the present invention, it is the inorganic layer that mainly exhibits the intended function. Therefore, what is necessary is just to comprise the manufacturing method of the functional film of this invention according to the inorganic layer which expresses the target functions, such as the light transmittance of a specific wavelength.

Of the functional films, the gas barrier film greatly affects the barrier performance when the inorganic layer is in contact with other members and cracks. Therefore, in order to protect the formed inorganic layer, it is necessary to stick a protective film with the first guide roller after the film formation. However, when a high-density inorganic layer is formed in order to improve the barrier performance, the transfer of components during peeling of the protective film is likely to occur.
On the other hand, according to the present invention, as will be described later, even when a high-density inorganic layer is formed in vacuum by plasma CVD capable of forming a dense film and then a protective film is adhered, It can prevent that the component of a protective film transfers to the surface of the inorganic layer after peeling a film.
Therefore, the present invention is more suitably used for a gas barrier film that is formed at a high density and has a high gas barrier property.

1A and 1B are respectively an inorganic film forming apparatus 32 that performs a film forming process, an inactivation process, and an attaching process, and an organic that performs a peeling process and an organic layer forming process. This is a film forming apparatus 30.

Both the inorganic film forming apparatus 32 shown in FIG. 1A and the organic film forming apparatus 30 shown in FIG. 1B 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 can produce an efficient functional film with high productivity.

Here, the manufacturing apparatus shown in FIG. 1 (A) and FIG. 1 (B) has an inorganic layer 14 and an organic layer 16 alternately on the surface of a long substrate 12 as shown in FIG. 4 (C). The formed gas barrier film 10c and the like are manufactured.
Accordingly, in the inorganic film forming apparatus 32 shown in FIG. 1A, the film forming material Za is the long substrate 12 and one or more layers formed on the surface of the substrate 12, and the surface is organic. It is the material of the layer 16.
On the other hand, in the organic film forming apparatus shown in FIG. 1B, the film forming material Zb is formed by forming one or more layers on the surface of the substrate 12, and the surface is the inorganic layer 14, and the inorganic layer on this surface. 14 is a material in which a protective film 18 is attached to 14.

The production method of the present invention is not limited to the production of a functional film such as a gas barrier film by RtoR using a long substrate, but a so-called single wafer type composition using a cut sheet substrate. A functional film may be produced using a membrane method.
In the production method of the present invention, a plurality of organic layers 16 and / or inorganic layers 14 may be alternately formed. In that case, the formation method may be the same or different in each layer.

In the present invention, the substrate 12 is not particularly limited as long as the surface is made of various organic materials such as a polymer material and a resin material.
Various materials can be used for the substrate 12 as long as the surface is formed of an organic material and an inorganic layer can be formed by plasma CVD. Specifically, the substrate 12 made of a polymer material such as polyethylene terephthalate (PET), polyethylene naphthalate, polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, polyacrylate, polymethacrylate, It is exemplified as a suitable example.
In the present invention, the substrate 12 is a film-like object such as a long film or a cut sheet-like film.

Furthermore, the substrate 12 has a plastic film, an article made of an organic material, a metal film or a glass plate, various metal articles as a main body, and a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, An organic layer made of an organic material for obtaining various functions, such as a light shielding layer, a planarizing layer, a buffer layer, and a stress relaxation layer, may be formed.
In this case, these functional layers are not limited to one layer, and a substrate in which a plurality of functional layers are formed may be used as the substrate 12.

An inorganic film forming apparatus 32 shown in FIG. 1A is an apparatus for forming the inorganic layer 14 by plasma CVD as an example of a manufacturing apparatus that performs the method for manufacturing a functional film of the present invention.
The inorganic film forming apparatus 32 is an apparatus for forming the inorganic layer 14 on the surface of the film formation material Za by a vapor deposition method. The inorganic film forming apparatus 32 includes a vacuum chamber 52 and an unwinding chamber 54 formed in the vacuum chamber 52. The film forming chamber 56 and the drum 80 are included.
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 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. Then, the inorganic layer 14 is formed in the film formation chamber 56 while the long film formation material Za is conveyed in the longitudinal direction while being wound around the drum 80. After a predetermined time has elapsed, in the unwinding chamber 54, a protective film is attached to the surface of the inorganic layer 14, wound around the winding shaft 92, and wound into a roll.

The drum 80 is a cylindrical member that rotates in the clockwise direction in the drawing around a rotation axis that passes through the center of the drum 80 and is parallel to a direction perpendicular to the paper surface.
The drum 80 conveys in a longitudinal direction a film forming material Za guided by a guide roller 84a of an unwinding chamber 54, which will be described later, around a predetermined area on the peripheral surface and held in a predetermined position. Then, after being transferred into the film forming chamber 56, it is sent to the stepped roller 84 b in the unwinding chamber 54.

Here, the drum 80 also functions as a counter electrode of a film forming electrode 82 of the film forming chamber 56 described later, and is grounded. That is, the drum 80 and the film forming electrode 82 constitute an electrode pair.

If necessary, the drum 80 may be connected to a bias power source for applying a bias voltage to the drum 80. Alternatively, the ground and the bias power supply may be connected to be switchable.
As the bias power source, all known power sources such as a high frequency power source and a pulse power source for applying a bias voltage, which are used in various film forming apparatuses, can be used.
Further, the drum 80 may include a temperature adjusting means, and the film forming material Za may be cooled, for example, during the film formation of the inorganic layer 14.

The unwinding chamber 54 is a region in the vacuum chamber 52 other than the film forming chamber 56 described later. That is, the unwind chamber 54 is formed by the inner wall surface of the vacuum chamber 52, the peripheral surface of the drum 80, and the

partition walls

60a and 60b extending from the inner wall surface of the vacuum chamber 52 to the vicinity of the peripheral surface of the drum 80. Space.
Here, the leading ends of the

partition walls

60a and 60b on the drum 80 side are close to the peripheral surface of the drum 80 to a position where they do not come into contact with the film forming material Za to be conveyed, and the unwind chamber 54, the film forming chamber 56, Are separated in a substantially airtight manner.

Such an unwinding chamber 54 includes the winding shaft 92, the

guide rollers

68, 84a, 90a and 90b, the stepped roller 84b, the rotating shaft 64, the rotating shaft 86, and the vacuum exhaust means 70. Have.

The rotating shaft 64 is loaded with a material roll 61 around which a long film-forming material Za is wound. The

guide rollers

68 and 84a are ordinary guide rollers that guide the film forming material Za on the upstream side of the drum 80 in the transport path of the film forming material Za. Further, the stepped roller 84 b is a normal stepped roller that guides the film forming material Za on the downstream side of the drum 80. The

guide rollers

90a and 90b are ordinary guide rollers that guide the film forming material Za on the downstream side of the stepped roller 84b. The take-up shaft 92 is a known elongate take-up shaft for taking up the film-forming material Za having the inorganic layer formed thereon.
The guide roller 90b also functions as a sticking roller for sticking the protective film 18 on the deposited inorganic layer 14. In the following description, the guide roller 90b is also referred to as a sticking roller 90b. The sticking roller 90b will be described in detail later.

Here, as shown in FIG. 2, the stepped roller 84 b is a so-called stepped roller in which the diameter of the end portion is larger than the diameter of the other region. The stepped roller 84b conveys the film forming material Za while guiding it without contacting the inorganic layer 14 formed on the film forming material Za.
A stepped roller 84b is disposed between the drum 80 and the adhering roller 90b, and the film forming material Za separated from the drum 80 is conveyed by using the stepped roller 84b, whereby the adhering from the film forming chamber 56 is performed. The conveying distance to the landing roller 90b can be increased. That is, the time from the formation of the inorganic layer 14 to the attachment of the protective film 18 can be increased.

In the present invention, reducing the activity of the surface of the inorganic layer 14 when the protective film 18 is adhered by setting the time from the formation of the inorganic layer 14 to the adhesion of the protective film 18 to 15 seconds or more. Can do. Therefore, since the protective film 18 is attached to the inorganic layer 14 having a low surface activity, that is, the inorganic layer 14 having a reduced number of dangling bonds on the surface, the inorganic layer and the components of the protective film are chemically treated. Binding can be suppressed.
Thus, the process of leaving a time interval of 15 seconds or more from the film formation to the attachment of the protective film is an inactivation process in the present invention.

Here, the time from film formation to sticking in the inactivation step is preferably 25 seconds or more. Thereby, the activity of the inorganic layer 14 surface can be reduced more suitably.

In the illustrated example, one stepped roller 84b is disposed between the drum 80 and the adhering roller 90b. However, the present invention is not limited to this. Accordingly, two or more stepped rollers may be arranged. Note that a stepped roller may be disposed as a guide roller that contacts the surface on which the inorganic layer 14 of the film formation material Za is formed, and the surface on the side on which the inorganic layer 14 of the film formation material Za is formed. A normal guide roller may be used as the guide roller in contact with the opposite surface.
Further, in the illustrated example, by using the stepped roller 84b, the time from the formation of the inorganic layer 14 to the attachment of the protective film 18 is set to 15 seconds or more, but is not limited thereto. As long as the time from non-deposition to sticking can be set to 15 seconds or more, a configuration without using a stepped roller may be used.

In the illustrated example, a material roll 61 formed by winding a long film-forming material Za in a roll shape is mounted on a rotating shaft 64. When the material roll 61 is mounted on the rotary shaft 64, the film forming material Za passes through the

guide rollers

68 and 84a, the drum 80, the stepped roller 84b, the guide roller 90a, and the sticking roller 90b. A predetermined path to the winding shaft 92 is passed.
In the inorganic film forming apparatus 32, the film forming material Za from the material roll 61 is sent out and the film forming material Za with the inorganic layer formed on the winding shaft 92 is synchronously wound. The film forming material Za and the protective film 18 are continuously attached while the film forming material Za is transported in the longitudinal direction along a predetermined transport path.

The rotating shaft 86 is loaded with a film roll 87 formed by winding a protective film 18 for protecting the deposited inorganic layer 14 in a roll shape, and rotates in synchronization with the conveyance of the film forming material Za to protect it. The film 18 is sent out. The rotating shaft 86 is rotated by a driving source (not shown).

The protective film 18 sent out from the film roll 87 is brought into contact with the surface of the inorganic layer 14 by the adhering roller 90b, and is laminated / adhered to the film forming material Za.
The sticking roller 90b may have a heating means.
Here, as above-mentioned, sticking of the protective film 18 is performed after an inactivation process. Thereby, since the protective film 18 is stuck to the inorganic layer 14 in a state where the surface activity is low, that is, the inorganic layer 14 in a state where the number of dangling bonds on the surface is reduced, the inorganic layer and the components of the protective film are bonded. It is possible to suppress chemical bonding.
This will be described in detail later.

In the sticking step, the inorganic layer 14 can be protected by sticking the protective film 18 to the surface of the inorganic layer 14 in a peelable manner.
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, in the gas barrier film produced by the production method of the present invention, it is the inorganic layer 14 that mainly exhibits gas barrier properties. Therefore, when the inorganic layer 14 is damaged, the gas barrier property is lowered.
On the other hand, by sticking the protective film 18 to the surface of the inorganic layer 14, handling in the inorganic film forming apparatus after the inorganic layer 14 is formed, winding of the film forming material on which the inorganic layer 14 is formed, It is possible to prevent the inorganic layer 14 from being damaged when handling to the organic film forming apparatus, transporting with the organic film forming apparatus, or when the uppermost layer is supplied as a gas barrier film of the inorganic layer 14. Moreover, handling of the substrate 12 on which the inorganic layer 14 is formed becomes easy, that is, workability can be improved.

The protective film 18 is not particularly limited, and various known plastic films used for protecting the inorganic layer 14 formed by a vapor deposition method, such as a low density polyethylene film, can be used.

Moreover, the thickness of the protective film 18 will not be specifically limited if it is the thickness which can prevent the crack of the inorganic layer 14, etc.
In addition, from the viewpoint of preventing cracking of the inorganic layer 14, the thickness of the protective film 18 is preferably 20 μm or more. Moreover, 100 micrometers or less are preferable from viewpoints, such as flexibility of a gas barrier film, size reduction and weight reduction, and the ease of winding in a roll form.

The vacuum exhaust means 70 is a vacuum pump for reducing the pressure in the unwind chamber 54 to a predetermined degree of vacuum. The vacuum evacuation means 70 makes the inside of the unwinding chamber 54 a pressure that does not affect the pressure in the film forming chamber 56.
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 other vacuum exhaust means 74 described later.

A film forming chamber 56 is disposed downstream of the unwind chamber 54 in the transport direction of the film forming material Za.
The film forming chamber 56 is a part where a film forming process is performed by plasma CVD, and an inorganic layer is formed on the surface of the substrate 12 or the organic layer 16 which is the film forming material Za by a vapor deposition method.
The film forming chamber 56 is a space formed by an inner wall surface of the vacuum chamber 52, a peripheral surface of the drum 80, and

partition walls

60 a and 60 b extending from the inner wall surface of the vacuum chamber 52 to the vicinity of the peripheral surface of the drum 80. It is.

In the inorganic film forming apparatus 32, the film forming chamber 56 forms a film on the surface of the film forming material Za by CCP (Capacitively Coupled Plasma) -CVD as an example. And a high-frequency power source 83 and a vacuum exhaust means 74.
The film forming material Za wound around a predetermined position of the drum 80 and transported to the film forming chamber 56 is transported in the longitudinal direction while being positioned at the predetermined position by the drum 80 to continuously form the inorganic layer 14. The

The film forming electrode 82 constitutes an electrode pair together with the drum 80 when the inorganic film forming apparatus 32 forms a film by CCP-CVD. The film forming electrode 82 is a known film forming electrode used in a vacuum film forming apparatus such as plasma CVD. For example, a so-called shower electrode is used as the film forming electrode 82. The shower electrode has a hollow, substantially rectangular parallelepiped shape, and is disposed with the discharge surface, which is one maximum surface, facing the peripheral surface of the drum 80, and the discharge surface, which is the surface facing the drum 80, has many through holes. Is formed entirely.
The film formation electrode 82 generates plasma for film formation between the discharge surface and the peripheral surface of the drum 80 forming the electrode pair, thereby forming a film formation region.

A source gas is supplied to a film forming region between the film forming electrode 82 and the drum 80 by a source gas supply unit (not shown).
For example, when the film-forming electrode 82 is a shower electrode, the source gas supply means supplies the source gas into the shower electrode. A large number of through holes are formed on the surface of the shower electrode facing the drum 80. Therefore, the source gas supplied to the shower electrode is introduced between the film forming electrode 82 and the drum 80 from this through hole.

As the source gas, a known reaction gas corresponding to the inorganic layer 14 to be formed may be used. For example, when a silicon nitride film used as a gas barrier film or the like is formed as the inorganic layer 14, silane gas and ammonia gas and / or nitrogen gas may be used. Similarly, a silicon oxide film is formed. If present, silane gas and oxygen gas may be used as the source gas.
If necessary, various gases such as an inert gas such as helium gas, neon gas, argon gas, krypton gas, xenon gas, and radon gas, hydrogen gas, and the like may be used in combination with the source gas.

The vacuum evacuation means 74 is for evacuating the inside of the film forming chamber 56 to obtain a degree of vacuum corresponding to the formation of the inorganic layer 14.

In the illustrated example, the film formation chamber 56 is configured to form an inorganic layer by CCP-CVD. However, the present invention is not limited to this, and a known plasma such as ICP-CVD (inductively coupled plasma CVD) is used. CVD is available.

Therefore, the inside of the film forming chamber 56 is composed of various members according to the vapor deposition method to be performed.
For example, if the film forming chamber 56 forms the inorganic layer 14 by the ICP-CVD method, an induction coil for forming an induction magnetic field and a gas supply means for supplying a reaction gas to the film forming region And so on.

Note that the formation conditions of the inorganic layer 14, such as temperature and pressure, may be appropriately set according to the film formation method, the target film thickness, film formation 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 56 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 56 is preferably 0.1 Pa to 10 Pa and the temperature is preferably 0 ° C. to 80 ° C.

The inorganic layer 14 formed in the film formation chamber 56 is a layer made of an inorganic compound not containing carbon.

There are no limitations on the material for forming the inorganic layer 14, and various layers made of an inorganic compound exhibiting gas barrier properties with a carbon composition ratio of 5% or less 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; silicon such as silicon oxide and silicon oxynitride Inorganic compounds such as oxides; silicon nitrides such as silicon nitride; hydrides thereof; mixtures of two or more of these; and hydrogen-containing substances thereof are preferably exemplified.
In particular, an inorganic compound composed of a combination of elements selected from the group consisting of Si, Al, O, N, and H is suitable. Among these, 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.

Here, in the present invention, the inorganic layer 14 may contain 5% or less of carbon as an unavoidable impurity. Or in order to express a predetermined function, you may contain 5% or less of carbon.
That is, the inorganic layer 14 may not contain carbon, but may contain carbon as an inevitable impurity derived from the material used as the raw material of the inorganic layer. For example, when a silicon compound is used as the inorganic layer, carbon can be contained in the inorganic layer derived from an organic silane such as Si (OCH ₃ ) _{4 as} a raw material.
The composition ratio of carbon in the inorganic layer was determined by measuring the number of atoms of Si, Al, O, N, and C in the inorganic layer 14 by XPS measurement (X-ray photoelectron spectroscopy measurement). And calculated as the ratio of C atoms.

The thickness of the inorganic layer 14 to be formed is not particularly limited, but 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, the present invention can be suitably used when the dense inorganic layer 14 is formed in order to develop a high gas barrier property.
Specifically, when the material for forming the inorganic layer 14 is silicon oxide, the film density of the inorganic layer is preferably 1.8 to 2.2 g / cm ^{3. In} the case of silicon nitride, the film of the inorganic layer is preferable. The density is preferably 2.1 to 2.5 g / cm ^{3. In} the case of silicon oxynitride, the film density of the inorganic layer is preferably 2.0 to 2.4 g / cm ³ . In this case, the film density of the inorganic layer is preferably 2.7 to 3.2 g / cm ³ .

As described above, after the inorganic layer 14 is formed in the film forming chamber 56, after a time interval of 15 seconds or more, the protective film 18 is attached by the attaching roller 90b.

Here, as described above, the inorganic layer immediately after being formed at a high density in a vacuum by plasma CVD has a high surface activity, and it is presumed that many dangling bonds exist. In particular, when a dense inorganic layer is formed by increasing the applied power or the like, the number of atoms constituting the inorganic layer increases, and it is considered that more dangling bonds are generated. At this time, in the atmosphere, it is considered that the dangling bonds react with elements in the atmosphere and deactivate, but in vacuum, there is no bonding partner, so it is considered that more dangling bonds remain. In addition, even when the conveyance speed is increased to improve production efficiency, the time from the formation of the inorganic layer to the attachment of the protective film is shortened, so the surface activity of the inorganic layer is reduced when the protective film is attached. It is thought that more unbonded hands remain.
Therefore, when a protective film is stuck on the highly active inorganic layer, it is estimated that this unbonded hand and the component of a protective film will couple | bond chemically.
When the chemically bonded inorganic layer and the protective film are peeled off, the chemical bond in the protective film is peeled off, and the protective film components are transferred and remain on the surface of the inorganic layer after the protective film is peeled off. Conceivable.
Therefore, when the protective film is peeled off and another layer is formed on the inorganic layer, the protective film components remain on the surface of the inorganic layer, and the presence of the transferred components causes the inorganic layer and the inorganic layer to remain on the surface. There was a problem that the adhesion with the formed layer was hindered.

On the other hand, in the present invention, by performing an inactivation step with a time interval of 15 seconds or more from the formation of the inorganic layer 14 to the attachment of the protective film, the surface of the inorganic layer 14 is not present. The bond is inactivated, and the surface activity of the inorganic layer 14 is reduced. Thereby, in order to form a dense inorganic layer, a protective film 18 for protecting the inorganic layer 14 is pasted even when the applied power is increased or the conveyance speed is increased to improve the production efficiency. When it does, it can suppress that the inorganic layer and the component of a protective film couple | bond together chemically.
Therefore, when the protective film is peeled off to form another layer on the inorganic layer, it is possible to prevent the components of the protective film from remaining on the surface of the inorganic layer, and between the inorganic layer and the layer formed on the inorganic layer. Adhesion can be improved.

Among the functional films, the gas barrier film has a possibility that the barrier performance is greatly deteriorated when the inorganic layer is in contact with other members and cracks even a little, and the influence on the contact with the surface of the inorganic layer is great. Therefore, it is necessary to protect the inorganic layer formed by attaching a protective film with the first guide roller immediately after the film formation and before contacting the other members.
On the other hand, since a gas barrier film requires high gas barrier performance, it is necessary to form a particularly dense inorganic layer. In order to form a dense inorganic layer, it is necessary to increase the applied power. Therefore, in the production of a gas barrier film, the surface of the inorganic layer after film formation is in a very high activity state.
Therefore, in the production of the gas barrier film, chemical bonds between the unbonded hands on the surface of the inorganic layer and the components of the protective film are likely to occur, and the components are easily transferred when the protective film is peeled.
Therefore, the method for producing a functional film of the present invention is more suitably used for a method for producing a gas barrier film that is formed at a high density and has a high gas barrier property.

In the unwinding chamber 54, the protective film 18 is attached and the material roll 93 wound in a roll shape is supplied to the organic film forming apparatus 30, or the gas barrier film 10a shown in FIG. The material roll 93 that is rotated is supplied to the next process.

The organic film forming apparatus 30 shown in FIG. 1 (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 and curing an organic compound contained therein.
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 has a take-up shaft 44 that peels off and winds up the protective film 18 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 in which the inorganic layer 14 or the like is formed on the substrate 12 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 93, passes through the conveying roller pair 48, passes through 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 Zb is fed out from the material roll 93 and the film forming material Zb on which the organic layer is formed on the take-up 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, since the protective film 18 is attached to the surface of the inorganic layer 14, the conveyance by the conveyance roller pair 48, And the protective film 18 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 protective film 18.
That is, the organic film forming apparatus 30 performs an organic layer forming process after the peeling process.

The organic layer 16 formed in the organic layer forming step is a layer made of an organic compound, and is basically a cross-linked organic compound that becomes the organic layer 16.

In the production method of the present invention, 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.

The thickness of the organic layer 16 formed in the organic layer forming step is not particularly limited, but is preferably 0.1 to 50 μm.
By setting the thickness of the organic layer 16 to 0.1 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 50 μm or less, it is possible to suitably suppress the 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. be able to.
Considering the above points, the thickness of the organic layer 16 is more preferably 0.15 to 5 μm.

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, a dimer, a trimer, or an oligomer, 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 material 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 so that crosslinking is possible. Any known drying means can be used if possible. As an example, heat drying with a heater, heat drying with warm air, and the like are exemplified.

The temperature of the film formation material Zb at the time of drying in the drying means 38 is preferably 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.

The film formation material Zb is then 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, or crosslinks an organic compound such as a monomer contained in the coating material by heating or the like. The organic layer 16 is cured.

Here, as described above, in the present invention, after the inorganic layer 14 is formed, the protective film 18 is adhered after reducing the activity of the surface of the inorganic layer 14 with a time interval of 15 seconds or more. Therefore, when the protective film 18 is peeled off in order to form the organic layer 16 on the inorganic layer 14, the remaining components of the protective film 18 can be reduced. Therefore, the adhesion between the inorganic layer 14 and the organic layer 16 formed on the inorganic layer 14 can be improved.
In particular, when the coating material that forms the organic layer 16 contains a silane coupling agent, if the component of the protective film 18 such as carbon remains on the surface of the inorganic layer 14, the silane coupling agent The effect of improving the adhesion due to may not be obtained, and the adhesion between the inorganic layer 14 and the organic layer 16 may be reduced.
On the other hand, in this invention, since the residual of the component of the protective film 18 to the inorganic layer 14 surface at the time of peeling off the protective film 18 can be reduced, the effect of improving the adhesion by the silane coupling agent can be sufficiently expressed. And the adhesion between the inorganic layer 14 and the organic layer 16 can be improved.

When the coating film is cured 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.

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, and 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 density can be increased and the hardness and scratch resistance of the organic layer can be improved.

In the present invention, the crosslinking 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, or is shipped or stored as a product, or the next process or the like. To be supplied.

Hereinafter, in the manufacturing apparatus shown in FIGS. 1 (A) and 1 (B), a gas barrier film in which two inorganic layers 14 and one organic layer 16 shown in FIG. 5 (A) are formed and a protective film 18 is laminated. The production method of the present invention will be described in more detail by explaining the action when producing 10d.
In addition, when producing a gas barrier film having other layer configuration such as the gas barrier film 10a shown in FIG. 4A, 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, as a preparation process, a material roll 61 formed by winding the substrate 12 is prepared.
In the inorganic film forming apparatus 32, when the material roll 61 formed by winding the substrate 12 is loaded on the rotating shaft 64, the substrate 12 as the film forming material Za is drawn out, and the film forming chamber 56 is extracted from the unwind chamber 54. Through a predetermined path to the take-up shaft 92 of the unwind chamber 54.

The film formation material Za sent out from the material roll 61 is guided by the

guide rollers

68 and 84a, wound around the drum 80, supported by the drum 80, and conveyed to the film formation chamber 56 while being conveyed through a predetermined path. Is done.
The film forming material Za transferred to the film forming chamber 56 is supported by the drum 80 and transferred through a predetermined path as a film forming process, and the first inorganic layer 14 is formed by, for example, CCP-CVD. It is formed.

The film forming material Za on which the inorganic layer 14 is formed is conveyed to the unwinding chamber 54 as an inactivation step, separated from the drum 80, and guided to the stepped roller 84b and the guide roller 90a to be a sticking roller. Up to 90b. At this time, the time required for conveyance from the film forming chamber 56 to the sticking roller 90b is set to 15 seconds or more, and the dangling bonds on the surface of the inorganic layer 14 are inactivated.

The protective film 18 sent out from the film roll 87 is stuck to the film-forming material Za conveyed to the sticking roller 90b as the sticking step on the first inorganic layer 14 (FIG. 4 ( A)).

The film forming material Za to which the protective film 18 is attached, that is, the film forming material Zb, is wound into a roll shape by the take-up shaft 92 to form a material roll 93.

Next, a material roll 93 formed by winding the substrate 12 on which the first inorganic layer 14 is formed and the protective film 18 is laminated 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 substrate 12 on which the first inorganic layer 14 that is the film formation material Zb is formed is pulled out of the material roll 93 and applied through the conveying roller pair 48. It passes through the means 36, the drying means 38, and the light irradiation means 40, passes through a pair of transport rollers 50, and passes through a predetermined transport path to the winding shaft 46.

The film forming material Zb drawn from the material roll 93 is subjected to the organic layer forming step after the protective film 18 is peeled off by the transport roller pair 48 (see FIG. 4B) as a peeling step. That is, the film-forming material Zb from which the protective film 18 has been peeled is 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 paint 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 (FIG. 4C). reference). 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 substrate 12 may be heated when the organic compound that becomes 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. A material roll 61 formed by winding the formed substrate 12 is supplied again to the inorganic film forming apparatus 32 shown in FIG.

The material roll 61 formed by winding the substrate 12 on 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 as described above. The substrate 12 on which the inorganic layer 14 and the organic layer 16 are formed is drawn out as a film forming material Za and passed through the take-up shaft 92, and the second inorganic layer 14 is formed on the first organic layer 16. After the inactivation step, the protective film 18 was further stuck, and the organic / inorganic laminate composed of the inorganic layer 14, the organic layer 16, and the inorganic layer 14 and the protective film 18 were laminated. The gas barrier film 10d shown in FIG.
The gas barrier film 10d is wound around the 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 10d is wound, or is supplied to the next step or the like. For example, the material roll 93 may be further supplied to the organic film forming apparatus 30, the protective film 18 may be peeled off (FIG. 5B), and the organic layer 16 may be formed (FIG. 5C).

Here, in the present invention, as described above, after the inorganic layer 14 is formed, after the dangling bonds on the surface of the inorganic layer 14 are inactivated by a time interval of 15 seconds or longer, the bonding roller 90b is used. Since the protective film 18 is adhered, the remaining of the components of the protective film 18 when the protective film 18 is peeled from the inorganic layer 14 can be reduced, and the organic layer formed on the inorganic layer 14 and the inorganic layer 14. Adhesion with 16 can be improved.

In the above-described embodiment, after the inorganic layer 14 is formed, the dangling bonds on the surface of the inorganic layer 14 are deactivated with a time interval of 15 seconds or more. However, the present invention is not limited to this. .
FIG. 3 is an example of an inorganic film forming apparatus for carrying out another example of the inactivation step in the present invention.
The inorganic film forming apparatus 110 shown in FIG. 3 has the same configuration as the inorganic film forming apparatus 32 shown in FIG. 1A except that it has a sticking roller 114 instead of the stepped roller 84b. The same reference numerals are given to the components, and detailed description thereof is omitted.

The inorganic film forming apparatus 110 includes a vacuum chamber 52, an unwinding chamber 112 formed in the vacuum chamber 52, a film forming chamber 56, and a drum 80.
The unwinding chamber 112 is a region other than the film forming chamber 56 in the vacuum chamber 52. The unwinding chamber 112 has a winding shaft 92, guide

rollers

68, 84 a and 90, a sticking roller 114, a rotating shaft 64, a rotating shaft 86, and a vacuum exhaust means 70.

The adhering roller 114 is an adhering roller that is disposed downstream of the drum 80 and adheres the protective film 18 onto the inorganic layer 14 that has been formed. Here, the sticking roller 114 is cooled to 15 ° C. or less by a cooling means (not shown).
By cooling the sticking roller 114 to 15 ° C. or lower, the substrate 12 is sufficiently cooled when the protective film 18 is stuck to the film forming material Za.

The bonding roller 114 is cooled to 10 ° C. or lower to sufficiently cool the substrate 12 when the protective film 18 is bonded to the film forming material Za, thereby inactivating the unbonded hands on the surface of the inorganic layer 14. can do. Thereby, when the protective film 18 is stuck, it can suppress that an inorganic layer and the component of a protective film couple | bond together chemically.
Therefore, when the protective film is peeled off to form another layer on the inorganic layer, it is possible to prevent the components of the protective film from remaining on the surface of the inorganic layer, and between the inorganic layer and the layer formed on the inorganic layer. Adhesion can be improved.

Here, the temperature of the substrate 12 when the protective film 18 is stuck is preferably 15 ° C. or less, and more preferably 10 ° C. or less. Thereby, the activity of the inorganic layer 14 surface can be reduced more suitably.

In the example shown in FIG. 3, the adhering roller 114 is cooled. However, the present invention is not limited to this, and a guide roller is disposed between the drum 80 and the adhering roller 114, and this guide roller is used. It is good also as a structure which cools and the board | substrate 12 is cooled. Alternatively, a known cooling means such as a device for blowing cold air is disposed between the drum 80 and the sticking roller 114 to cool the substrate 12 and inactivate the unbonded hands on the surface of the inorganic layer 14. Also good.

Further, the deactivation step may be a combination of a configuration in which the time from the formation of the inorganic layer 14 to the attachment of the protective film 18 is 15 seconds or more and a configuration in which the substrate 12 is cooled. In other words, in the inorganic film forming apparatus 32 shown in FIG. 1A, the substrate 12 may be cooled by cooling the sticking roller 90b.

As mentioned above, although the manufacturing method of the functional film of this invention was demonstrated in detail, this invention is not limited to the said embodiment, Even if various improvements and changes are performed in the range which does not deviate from the summary of this invention. Of course it is good.

Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.
[Example 1]
(Board preparation process)
The substrate 12 was prepared by forming an organic layer made of acrylate on the surface of a long PET film having a width of 1000 mm and a thickness of 100 μm (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.). This organic layer is formed on a long PET film by the same method as the method for forming the organic layer 16 by the organic film forming apparatus 30.
A material roll 61 formed by winding a substrate 12 to be a film forming material Za is loaded on the rotation shaft of the inorganic film forming apparatus 32 shown in FIG. 1A, and the film forming material Za is placed on a predetermined transport path. The following film formation process, inactivation process, and sticking process were performed while being inserted and conveyed.

(Film formation process)
First, the inorganic layer 14 made of silicon nitride having a thickness of 50 nm was formed on the surface of the substrate 12 transferred to the film formation chamber 56.

Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), and hydrogen gas (H ₂ ) were used as source gases supplied to the film forming chamber 56. As for the supply amount, the flow rate converted to the volume at 0 ° C. and 0.1013 MPa was 100 mL / min for silane gas, 400 mL / min for ammonia gas, and 1000 mL / min for hydrogen gas. In addition, about the flow volume, the following description is the flow volume converted into the volume in 0 degreeC and 0.1013 MPa similarly.
The film forming pressure was 50 Pa.
A plasma excitation power of 2 kW at a frequency of 13.5 MHz was supplied from the high frequency power supply 83 to the film forming electrode 82.
The composition ratio of carbon in the deposited inorganic layer 14 was measured by XPS and found to be 1% or less.

(Inactivation process)
Between the drum 80 and the adhering roller 90b, one stepped roller 84b and one guide roller 90a are arranged, and the time until the film is transferred from the film forming chamber 56 to the adhering roller 90b, that is, The time from the formation of the inorganic layer to the attachment of the protective film was 60 seconds.

(Attaching process)
Next, the protective film 18 was stuck to the film forming material Za by the sticking roller 90b.
As the protective film 18, a long polyethylene film having a width of 1000 mm and a thickness of 50 μm (SUNYTECT PAC-2, manufactured by Sanei Kaken Co., Ltd.) was used.

After the film-forming material Za having a predetermined length is subjected to a film-forming process, an inactivation process, and a sticking process, when the winding around the winding shaft 92 is completed, the unwind chamber 54 and the film-forming chamber 56 are finished. Cleaned dry air was introduced to open the atmosphere.
Next, a material roll 93 (see FIG. 4A) formed by winding the substrate 12 on which the inorganic layer 14 was formed and the protective film 18 was attached was taken out from the unwind chamber 54.

(Peeling process)
The substrate 12 on which the inorganic layer 14 is formed and the protective film 18 is adhered, that is, the material roll 93 formed by winding the film forming material Zb, is rotated on the rotating shaft 42 of the organic film forming apparatus 30 shown in FIG. Each process was carried out while being transported through a predetermined transport path.
First, the protective film 18 of the film forming material Zb was peeled off by the conveying roller pair 48 and the winding shaft 44.

(Organic layer formation process)
After the peeling step, the organic layer 16 having a thickness of 3 μm is formed on the surface of the inorganic layer 14 by the coating unit 36, the drying unit 38, and the light irradiation unit 40, and the gas barrier film 10c shown in FIG. did.

The paint for forming the organic layer 16 is MEK (methyl ethyl ketone), TMPTA (manufactured by Daicel Cytec Co., Ltd.), photopolymerization initiator (Irg189 manufactured by Ciba Chemicals Co., Ltd.), silane coupling agent (Shin-Etsu Chemical Co., Ltd., Shin-Etsu). Silicone KBM5103) was added to prepare. 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 a 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 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 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 carried out while heating the substrate 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.

[Example 2]
A gas barrier film was produced in the same manner as in Example 1 except that the treatment conditions in the film formation step were changed as follows and the time of the inactivation step was changed to 16 seconds.

Two film formation chambers 56 are arranged in series in the transport direction, and the supply amount of the raw material gas in each film formation chamber is 250 mL / min for silane gas, 1000 mL / min for ammonia gas, and 2500 mL / min for hydrogen gas.
The plasma excitation power supplied to the film forming electrode 82 was 5 kW.
The composition ratio of carbon in the deposited inorganic layer 14 was measured by XPS and found to be 1% or less.

[Example 3]
Between the drum 80 and the adhering roller 90b, two stepped rollers 84b and two guide rollers 90a are arranged, and in the inactivation process, until the film is transferred from the film forming chamber 56 to the adhering roller 90b. A gas barrier film was produced in the same manner as in Example 2 except that the time was set to 25 seconds.

[Example 4]
In the deactivation process, instead of the configuration in which the stepped roller 84b is arranged and the time from the film formation process to the bonding process is set to 15 seconds or more, the bonding roller is cooled to cool the substrate 12. Except for the above, a gas barrier film was produced in the same manner as in Example 1.
That is, in Example 4, instead of the inorganic film forming apparatus 32 shown in FIG. 1 (A), the inorganic film forming apparatus 110 shown in FIG. It was.
The cooling temperature of the sticking roller 114 was 10 ° C.

[Example 5]
A gas barrier film was produced in the same manner as in Example 4 except that the cooling temperature of the sticking roller 114 was 0 ° C.

[Example 6]
A gas barrier film was produced in the same manner as in Example 5 except that the processing conditions in the film forming step were changed as follows.

[Example 7]
A gas barrier film was produced in the same manner as in Example 6 except that the cooling temperature of the sticking roller 114 was −15 ° C.

[Comparative Example 1]
Except that the stepped roller is not arranged and the inactivation step is not performed, that is, except that the time from the film formation chamber to the sticking roller is 12 seconds, the same as in Example 1, A gas barrier film was prepared.

[Comparative Example 2]
Two film forming chambers 56 are arranged in series in the conveying direction, no stepped roller is arranged, and the inactivation process is not performed, that is, the time from the film forming chamber to the adhering roller is 6 seconds. A gas barrier film was produced in the same manner as in Example 1 except that.

[Comparative Example 3]
Except that the stepped roller is not arranged and the inactivation step is not performed, that is, except that the time from the film formation chamber to the sticking roller is 2 seconds, the same as in Example 2, A gas barrier film was prepared.

[Comparative Example 4]
A gas barrier film was produced in the same manner as in Example 2 except that the stepped roller was not disposed, the inactivation step was not performed, and the sticking step was not performed.

[Evaluation]
With respect to the produced gas barrier films of Examples 1 to 7 and Comparative Examples 1 to 4, the adhesion of the organic layer formed on the inorganic layer was evaluated. Further, the water vapor permeability of the gas barrier film was measured to evaluate the barrier property.

<Adhesion>
After peeling off the protective film 18, the gas barrier film 10 c having the organic layer 16 formed on the inorganic layer 14 was subjected to a cross-cut test to evaluate the adhesion between the inorganic layer 14 and the organic layer 16. The cross-cut test is based on JIS-K5600, and the organic layer 16 is 1 mm wide, cut, and peeled off with an adhesive tape (Cello Tape (registered trademark) CT-24 manufactured by Nichiban Co., Ltd.). The residual mass was measured and the adhesion was evaluated.

<Gas barrier properties>
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.
The configuration and evaluation results of each example and comparative example are shown in Table 1 below.

As shown in Table 1 above, it can be seen that all of the gas barrier films of Examples 1 to 7 produced by the method for producing a functional film of the present invention exhibit good adhesion. Moreover, since a protective film is stuck immediately after film-forming of an inorganic layer and an inorganic layer is protected with a protective film until just before forming an organic layer on an inorganic layer, a crack etc. of an inorganic layer can be prevented suitably. Therefore, it turns out that it has a high gas barrier property.

On the other hand, it can be seen that Comparative Examples 1 to 3 in which the protective film was stuck without performing the inactivation step decreased the adhesion with the organic layer formed on the inorganic layer after the protective film was peeled off.
On the other hand, it can be seen that Comparative Example 4 in which the protective film is not attached cannot prevent the inorganic layer from being cracked, and thus the gas barrier property is 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 to 10f Gas barrier film 12 Substrate 14 Inorganic layer 16 Organic layer 18 Protective film 30 Organic

film forming apparatus

32, 110 Inorganic film forming apparatus 36 Application means 38 Drying means 40 Light irradiation means 42, 64, 86

Rotating shafts

44, 46, 92

Winding shaft

48, 50 Conveying roller pair 52

Vacuum chamber

54, 112 Unwinding chamber 56

Film forming chamber

60a,

60b Partition wall

61, 93

Material roll

68, 84a, 90,

90a Guide roller

70, 74 Vacuum exhaust means 80 Drum 82 Composition Membrane electrode 83 High frequency power supply 84b Stepped roller 87

Film roll

90b, 114 Adhesive roller

Claims

A substrate preparation step of preparing a substrate having a surface made of an organic material;
A film forming step of forming an inorganic layer having a carbon composition ratio of 5% or less on the substrate by plasma CVD in vacuum;
An inactivation step of inactivating dangling bonds of the inorganic layer formed;
The manufacturing method of a functional film which has the sticking process of sticking the protective film which consists of a plastic film on the said inorganic layer so that peeling is possible after the said inactivation process.
The method for producing a functional film according to claim 1, wherein the inactivation step is an interval of 15 seconds or more between the film formation step and the sticking step.
The method for producing a functional film according to claim 1, wherein the inactivation step cools the substrate.
The function according to any one of claims 1 to 3, wherein a material of the inorganic layer formed in the film forming step is a combination of elements selected from the group consisting of Si, Al, O, N, and H. For producing a conductive film.
Furthermore, after the sticking step, a peeling step for peeling the protective film,
The functional film according to any one of claims 1 to 4, further comprising an organic layer forming step of forming an organic layer on a surface of the inorganic layer on the side where the protective film is peeled off, after the peeling step. Production method.
Furthermore, the said organic layer formation process is repeated from the said film-forming process, The manufacturing method of the functional film of Claim 5 which forms two or more said inorganic layers and one or more said organic layers.
The substrate preparation step is to prepare a substrate roll formed by winding the long substrate.
7. The film forming step, the deactivation step, and the adhering step are performed while the long substrate is sent out from the substrate roll and conveyed in the longitudinal direction of the substrate. 2. A method for producing a functional film according to item 1.