JP5788825B2 - Method for producing functional film - Google Patents

Description

  The present invention relates to an organic / inorganic laminated functional film in which an organic layer and an inorganic layer are formed on a substrate, and a method for producing the functional film.

Various functional films such as gas barrier films, protective films, optical films such as optical filters and antireflection films, etc. in various devices such as optical elements, display devices such as liquid crystal displays and organic EL displays, semiconductor devices, thin film solar cells, etc. (Functional sheet) is used.
As an example of such a functional film, a plastic film such as a polyethylene terephthalate (PET) film is used as a substrate, and an inorganic layer (a layer made of an inorganic compound) that exhibits a desired function is formed thereon. It has the composition which becomes.

For example, in the case of a gas barrier film, a gas barrier film is known in which a layer (film) made of silicon nitride or silicon oxynitride charcoal that exhibits gas barrier properties is formed on the surface of a plastic film.
In addition, as a configuration for obtaining a higher gas barrier property, an organic layer made of an organic compound is provided as a base layer (undercoat layer) on the surface of the substrate, and the organic layer is made of an inorganic compound that exhibits gas barrier properties. An organic / inorganic laminated type gas barrier film having an inorganic layer is known. Furthermore, it is also known that higher gas barrier properties can be obtained by having a plurality of laminated structures of an organic layer and an inorganic layer.

In such an organic / inorganic laminated type (hereinafter also simply referred to as a laminated type) functional film, when another member such as a film or a device is bonded to the uppermost inorganic layer, the surface of the inorganic layer is It is preferable to have a certain degree of surface roughness.
For example, in an organic EL element or a solar cell, a gas barrier film may be attached to the surface as a protective layer. Here, in these applications, an adhesive may not be used due to the characteristics of the apparatus. When a laminated gas barrier film is used for such an application, the surface of the inorganic layer of the gas barrier film must be a certain level or more in order to obtain physical adhesion performance with the bonding surface of a member such as an organic EL element. It is necessary to have a surface roughness of

In addition, in a laminated functional film, an adhesive can be used when another member is bonded to the uppermost inorganic layer, or a layer having excellent adhesion such as an organic layer is formed on the uppermost inorganic layer. In some cases, a film is formed.
However, even in such applications, it is preferable that the surface of the inorganic layer has a certain degree of surface roughness because high adhesion can be obtained.

Therefore, it is known that in a laminated functional film, after forming an inorganic layer, the surface of the inorganic layer is roughened to ensure adhesion with other members.
For example, in Patent Document 1, in order to ensure adhesion of an organic layer when forming an organic layer as a protective layer on an inorganic layer in a laminated gas barrier film, prior to the formation of the organic layer. The surface roughness Ra is set to 10 to 100 nm by roughening the surface of the inorganic layer.
Examples of the method for roughening the inorganic layer include reverse sputtering, dry etching, wet etching, and the like.

JP 2010-247369 A

  As shown in Patent Document 1, in the laminated functional film, when the uppermost inorganic layer is roughened to give a certain level of surface roughness, Adhesion can be improved when a certain layer is formed on the inorganic layer.

However, the roughening of the surface of the inorganic layer is a treatment that damages the inorganic layer. For this reason, when the surface roughening treatment of the inorganic layer is performed, the performance of the inorganic layer is deteriorated, and the target performance may not be obtained.
Moreover, the thickness of an inorganic layer may become thin depending on the degree of roughening. Also in this case, naturally, the performance of the inorganic layer is reduced as compared with the deposited inorganic layer, and the intended performance cannot be obtained.

In addition, in the laminated functional film, when the roughening treatment of the inorganic layer is performed, the surface roughness of the inorganic layer may become too large.
Thus, when the surface roughness of the inorganic layer becomes too large, the performance of the functional film may be deteriorated due to the surface roughness of the inorganic layer.

  An object of the present invention is to solve the above-described problems of the prior art, and an organic layer as a base layer is formed on a substrate, and an inorganic layer that expresses a target function is formed thereon. In the organic / inorganic laminated type functional film, a function capable of obtaining high adhesion and stably obtaining the desired performance when the inorganic layer and another member are adhered. It is providing the functional film and the manufacturing method of this functional film.

  In order to solve the above problems, the functional film of the present invention is a combination of an organic layer on a substrate and an inorganic layer formed on the organic layer and made of an inorganic compound containing at least silicon and nitrogen. The surface roughness Ra of the uppermost inorganic layer is 3 nm or less, and the surface roughness Ra of the organic layer below the uppermost inorganic layer is 1 nm or more. Provide functional film.

In such a functional film of the present invention, the uppermost inorganic layer preferably has a surface roughness Ra of 1 nm or more.
Moreover, it is preferable that the surface roughness Ra of the organic layer under the uppermost inorganic layer is 2 nm or less.
Moreover, it is preferable that the surface is an inorganic layer.
Moreover, it is preferable that the thickness of an inorganic layer is 15-200 nm.
Furthermore, it is preferable that the thickness of the organic layer is 0.5 to 5 μm.

  Also, the method for producing a functional film of the present invention comprises forming an organic layer on the surface of a substrate, and an inorganic compound containing at least silicon and nitrogen by plasma CVD containing ammonia gas as a source gas on the organic layer. The inorganic layer is formed, and the inorganic layer is formed while controlling the etching of the organic layer by plasma so that the surface roughness Ra of the organic layer is 1 nm or more. A method for producing a film is provided.

In such a method for producing a functional film of the present invention, it is preferable to use a long substrate and form the inorganic layer while transporting the substrate in the longitudinal direction.
In addition, it is preferable that the etching of the organic layer is controlled in the upstream portion in the substrate transport direction in the film formation region of the inorganic layer.
Furthermore, after the inorganic layer deposition is stabilized, the substrate transport and deposition are stopped, the surface of the substrate in the deposition region is analyzed, and the substrate transport is performed on the entire substrate in the width direction of the substrate. It is preferable to control the etching of the organic layer so that the measurement result when the most upstream position in the direction is detected and the surface roughness Ra of the most upstream position is measured is 1 nm or more.

According to the present invention, in the organic / inorganic laminated functional film in which the organic layer and the inorganic layer are alternately laminated, the uppermost inorganic layer has an appropriate surface roughness. High adhesion can be obtained when adhering to this member or when depositing another layer on the inorganic layer. Moreover, the surface roughness of the inorganic layer is not formed by roughening the surface of the inorganic layer, but is formed by the lower organic layer having an appropriate surface roughness, so that the inorganic layer has sufficient target performance. A high-performance functional film that can be easily developed is obtained.
Moreover, according to the manufacturing method of the functional film of this invention, such a high performance functional film can be manufactured stably.

(A)-(C) are figures which show notionally an example of the gas barrier film using the functional film of this invention. (A) And (B) is a figure which shows notionally an example of the manufacturing apparatus which enforces the manufacturing method of the functional film of this invention, (A) is a film-forming apparatus of an organic layer, (B) is an inorganic layer The film forming apparatus.

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

FIG. 1A conceptually shows an example of a gas barrier film using the functional film of the present invention.
A gas barrier film 10a shown in FIG. 1A basically has a support Z such as a plastic film, which will be described later, as a substrate, and has an organic layer 12 on the surface (surface) of the support Z. An inorganic layer 14 made of an inorganic compound containing silicon and nitrogen such as silicon nitride or silicon oxynitride is formed thereon.

In addition, the functional film of the present invention is a combination of an organic layer and an inorganic layer made of an inorganic compound containing silicon and nitrogen thereon (a laminated structure of an inorganic layer and an organic layer below it). The structure shown in FIG. 1A is not limited as long as it has one or more, and various layer structures can be used.
For example, as a configuration in which higher gas barrier performance is obtained, an intermediate organic layer 12a is provided on a support Z, and an intermediate inorganic layer 14a is provided thereon, as in a gas barrier film 10b shown in FIG. Further, a four-layer configuration may be employed in which the organic layer 12 is provided thereon and the inorganic layer 14 is provided thereon. Alternatively, as in the gas barrier film 10c shown in FIG. 1 (C), the first intermediate organic layer 12a is provided on the support Z, and the first intermediate inorganic layer 14a is provided thereon. 6 having a second intermediate organic layer 12a, a second intermediate inorganic layer 14a thereon, an organic layer 12 thereon, and an inorganic layer 14 thereon, or Further, it may be a constitution having a repetition of a laminated constitution of organic layers / inorganic layers.
Moreover, the structure which has the protective organic layer for protecting the inorganic layer 14 on the uppermost inorganic layer 14 as needed may be sufficient.

As will be described in detail later, in the gas barrier film (functional film) of the present invention, the inorganic layer 14 which is the uppermost inorganic layer has a surface roughness Ra (arithmetic average roughness Ra) of 3 nm or less. The surface roughness Ra of the lower organic layer 12 is 14 nm or more. Further, the surface roughness of the inorganic layer 14 is not obtained by the surface roughening treatment of the inorganic layer 14, but is realized by having an appropriate surface roughness Ra of the underlying organic layer 12 of 1 nm or more. .
By having such a configuration, the gas barrier film of the present invention has excellent gas barrier properties (performance) that sufficiently expresses the adhesion with other members of the surface of the inorganic layer 14 and the performance of the inorganic layer 14. To achieve both.

In the gas barrier film of the present invention, each of the layers other than the uppermost inorganic layer 14 and the organic layer 12 below the uppermost inorganic layer 14 may satisfy the surface roughness condition.
That is, in the gas barrier film shown in FIG. 1 (B) or FIG. 1 (C), one or more layers of the intermediate organic layer 12a or the surface roughness Ra of all layers may be 1 nm or more. One or more layers or all layers of 14a may have a surface roughness Ra of 3 nm or less.
In consideration of the adhesion between the layers and the gas barrier performance of the intermediate inorganic layer 14a, it is preferable that both the intermediate organic layer 12a and the intermediate inorganic layer 14a satisfy the above-mentioned surface roughness conditions.

Moreover, this gas barrier film 10a (10b and 10c) can be manufactured with the manufacturing method of the functional film of this invention.
As will be described in detail later, in the method for producing a functional film of the present invention, basically, an organic layer 12 is formed on the surface of a substrate, and a plasma CVD is performed by plasma CVD using a source gas containing ammonia gas thereon. The inorganic layer 14 is formed while the etching of the organic layer 12 is controlled.

That is, in the production method of the present invention, as an example, a support Z such as a plastic film is used as a substrate, an organic layer 12 is formed on the surface, and an inorganic layer 14 is formed thereon by plasma CVD. The gas barrier film 10a (functional film) of the present invention having the organic layer 12 and the inorganic layer 14 as shown in 1 (A) is produced.
As another example, in the production method of the present invention, one or more combinations of the intermediate organic layer 12a and the intermediate inorganic layer 14a formed on the support Z are used as a substrate, and the organic layer is formed thereon. 12 may be formed, and the inorganic layer 14 may be formed thereon by plasma CVD. For example, in the production method of the present invention, a substrate in which the intermediate organic layer 12a and the intermediate inorganic layer 14a are formed on the support Z is used as a substrate, the organic layer 12 is formed thereon, and the inorganic layer is formed thereon. 14 may be formed to produce a four-layer gas barrier film such as the gas barrier film 10c shown in FIG.

In the present invention, the intermediate organic layer 12a and the intermediate inorganic layer 14a may also be formed by the manufacturing method of the present invention.
That is, the production method of the present invention may produce the functional film of the present invention using the functional film of the present invention as a substrate.

Moreover, the functional film of the present 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 an optical filter and an antireflection film. However, as will be described later, according to the present invention, it is possible to produce a functional film having an appropriate surface roughness with which the inorganic layer 14 can ensure high adhesion without performing the roughening treatment of the inorganic layer 14. Therefore, the present invention is suitably used for a gas barrier film in which performance deterioration due to damage or the like of the inorganic layer 14 is large.

In the gas barrier film of the present invention, the support (substrate (base material)) Z is not particularly limited, and various known sheet-like materials that are used as a support for functional films such as a gas barrier film, Is available.
Preferably, the sheet-like support Z is long and flexible so that the organic layer 12 and the inorganic layer 14 can be formed by roll-to-roll described later. A web-like support Z) is used.

Specific examples of the support Z include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, polyacrylate, and polymethacrylate. Suitable examples include plastic films made of various plastics (polymer materials).
In the present invention, 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 are provided on the surface of such a plastic film. A substrate on which a layer (film) for obtaining is formed may be used as the support Z (substrate).

The gas barrier film 10 a has an organic layer 12 on the support Z.
The organic layer 12 is a layer made of an organic compound (a layer (film) containing an organic compound as a main component) and is basically a crosslinked (polymerized) monomer and / or oligomer. The organic layer 12 functions as a base layer for properly forming an inorganic layer 14 that exhibits a target function such as gas barrier properties, which will be described later.
By having such an organic layer 12, the surface of the organic layer 12 can be flattened by embedding irregularities on the surface of the support Z, foreign matters attached to the surface of the support Z, and the like. By flattening the surface of the organic layer, areas where the inorganic compound that becomes the inorganic layer 14 is difficult to deposit, such as irregularities on the surface of the support Z and shadows of foreign matter, are eliminated, and the entire surface of the organic layer 12 is appropriately formed. The inorganic layer 14 can be formed.

Although there is no limitation in the thickness of the organic layer 12, it is preferable to set it as 0.5-5 micrometers.
By setting the thickness of the organic layer 12 to 0.5 μm or more, the surface of the organic layer 12 is flattened by suitably embedding irregularities on the surface of the support Z and foreign matters attached to the surface of the support Z. it can.
In addition, by setting the thickness of the organic layer 12 to 5 μm or less, the occurrence of problems such as cracks in the organic layer 12 and curling of the gas barrier film 10a caused by the organic layer 12 being too thick is suitably suppressed. be able to.
Considering the above points, the thickness of the organic layer 12 is more preferably 1 to 3 μm.

In the gas barrier film 10 of the present invention, the material for forming the organic layer 12 is not limited, and various known organic compounds (resins / polymer 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 organosilicon compound is preferably exemplified.

Among them, the organic layer 12 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 Tg and strength.
In particular, in addition to the above Tg and strength, acrylic resin and methacrylic resin mainly composed of acrylate and / or methacrylate monomer or oligomer polymer in terms of low refractive index and excellent optical properties are organic layers. 12 is preferably exemplified.
Among them, in particular, dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), etc. Acrylic resins and methacrylic resins mainly composed of a polymer of acrylate and / or methacrylate monomers or oligomers are preferably exemplified.

Such an organic layer 12 may be formed (formed) by a known method.
For example, a coating material containing an organic solvent, an organic compound that becomes the organic layer 12, a surfactant, and the like is prepared, and this coating material is applied, dried, and then cross-linked.

Note that the above description regarding the organic layer 12 is the same for the intermediate organic layer 12a shown in FIGS. 1B and 1C (and the protective organic layer on the inorganic layer 14).
Further, in the gas barrier film of the present invention, when the intermediate organic layer 12a is provided or when the protective organic layer is provided on the uppermost inorganic layer 14, the thickness of the organic layer 12, the intermediate organic layer 12a, and the protective organic layer. They may be the same or different. Moreover, when it has the some intermediate | middle organic layer 12a, each thickness may be the same or different.

Here, in the gas barrier film 10a of the present invention, the organic layer 12 has a surface roughness Ra of 1 nm or more.
This will be described in detail later.

The gas barrier film 10 a has an inorganic layer 14 on the organic layer 12.
The inorganic layer 14 is a layer made of an inorganic compound containing silicon and nitrogen (a layer (film) containing an inorganic compound containing silicon and nitrogen as a main component).

As will be described in detail later, in the manufacturing method of the present invention, the inorganic layer 14 is formed by plasma CVD using a source gas containing ammonia gas. When the inorganic layer 14 is formed, the organic layer 12 is etched by plasma (mainly ammonia plasma).
In the present invention, the surface roughness Ra of the organic layer 12 is set to 1 nm or more by controlling the etching of the organic layer 12 during the formation of the inorganic layer 14. Further, the surface roughness Ra of the lower organic layer 12 is used to provide the inorganic layer 14 with an appropriate surface roughness Ra of 3 nm or less by using irregularities of 1 nm or more.

  In the gas barrier film 10a, the inorganic layer 14 mainly exhibits gas barrier properties. That is, in the functional film of the present invention, the inorganic layer 14 mainly expresses the intended function such as gas barrier properties.

The material for forming the inorganic layer 14 is not particularly limited, and various inorganic compounds containing silicon and nitrogen can be used.
Specific examples include silicon nitride, silicon oxynitride, silicon nitride carbide, silicon oxynitride carbide, and the like. Among them, silicon nitride is preferably exemplified in that a high-performance inorganic layer 14 having a dense and high gas barrier property can be obtained, film formation can be performed at a low temperature, and optical characteristics can be controlled by structure control. .

In the present invention, the thickness of the inorganic layer 14 is preferably 15 to 200 nm.
If the thickness of the inorganic layer 14 is 15 nm or less, it may be difficult to obtain a desired gas barrier property stably. In addition, inorganic compounds containing silicon and nitrogen are hard and brittle. For this reason, if the thickness of the inorganic layer 14 exceeds 200 nm, it tends to naturally cause cracks, cracks, peeling, etc., and it may be difficult to stably obtain the desired gas barrier properties (target performance). .
In consideration of such points, the thickness of the inorganic layer 14 is more preferably 15 to 100 nm, and particularly preferably 20 to 75 nm.

In addition, the description regarding the above inorganic layer 14 is the same also regarding the intermediate | middle inorganic layer 14a shown to FIG. 1 (B) and (C).
Moreover, in the gas barrier film of this invention, when it has the intermediate inorganic layer 14a, the thickness of the inorganic layer 14 and the intermediate inorganic layer 14a may be the same or different. Furthermore, when it has the some intermediate | middle inorganic layer 14a, each thickness may be same or different. In addition, the layer sandwiched between the intermediate organic layers 12 may be a layer made of an inorganic compound not containing nitrogen and / or silicon.

Here, in the gas barrier film 10a of the present invention, the inorganic layer 14 which is the uppermost inorganic layer has a surface roughness Ra of 3 nm or less. Moreover, the organic layer 12 under the inorganic layer 14 has a surface roughness Ra of 1 nm or more.
By having such a configuration, the present invention realizes both cohesion of the surface of the inorganic layer 14 and high gas barrier properties due to the inorganic layer 14.

As described above, in order to obtain sufficient adhesion, for example, when a laminated gas barrier film in which organic layers and inorganic layers are alternately laminated is attached to an organic EL element as a protective layer, It is necessary that the surface of the inorganic layer serving as the sticking surface has an appropriate surface roughness.
In the case of such applications, conventionally, a surface roughening treatment of an inorganic layer (inorganic layer surface) such as reverse sputtering has been performed in order to impart surface roughness to the inorganic layer. However, if the roughening treatment of the inorganic layer is performed, the performance of the inorganic layer is deteriorated, and the target gas barrier film property cannot be obtained. In addition, the surface roughness may become too large, which may cause the performance of the inorganic layer to deteriorate.

On the other hand, in the present invention, the surface of the inorganic layer 14 is not roughened by the surface roughness Ra of the organic layer 12 by setting the surface roughness Ra of the organic layer 12 to 1 nm or more. In addition, the surface roughness Ra gives a surface roughness of 3 nm or less.
Therefore, according to the present invention, the surface of the inorganic layer 14 has an appropriate surface roughness. Therefore, when a certain member such as a film or an organic EL element is attached to the surface of the inorganic layer 14, or the organic layer 12. Even when a certain layer such as a protective organic layer is formed on the inorganic layer 14, sufficient adhesion can be obtained between the inorganic layer 14 and these layers. In addition, since the inorganic layer 14 is not roughened to give surface roughness, the performance inherent to the deposited inorganic layer 14 can be appropriately maintained after ensuring the adhesion of the surface of the inorganic layer 14. Demonstrates high gas barrier film properties.

In the gas barrier film 10a of the present invention, the surface roughness Ra of the inorganic layer 14 is 3 nm or less.
If the surface roughness Ra of the inorganic layer 14 exceeds 3 nm, the surface roughness is too large and the inorganic layer 14 cannot exhibit sufficient gas barrier properties.
Considering the above points, the surface roughness Ra of the inorganic layer 14 is preferably 2 nm or less.

In addition, the surface roughness Ra of the inorganic layer 14 is preferably 1 nm or more, and particularly preferably 1.5 nm or more.
By setting the surface roughness Ra of the inorganic layer 14 to 1 nm or more, preferable results can be obtained in that the adhesion of the surface of the inorganic layer 14 can be stably and sufficiently secured.

On the other hand, in the gas barrier film 10a of the present invention, the surface roughness Ra of the organic layer 12 serving as the lower layer (underlayer) of the inorganic layer 14 (the surface roughness Ra of the film formation surface of the inorganic layer 14) is 1 nm or more.
When the surface roughness Ra of the organic layer 12 is less than 1 nm, a sufficient surface roughness cannot be imparted to the surface of the inorganic layer 14, and sufficient adhesion between the inorganic layer 14 and the organic layer 12 is obtained. Inconvenience such as not being possible.
Considering the above points, the surface roughness Ra of the organic layer 12 is preferably 1.2 nm or more.

There is no particular limitation on the upper limit of the surface roughness Ra of the organic layer 12.
However, if the surface roughness of the organic layer 12 is too large, the surface roughness of the inorganic layer 14 becomes excessively large and the inorganic layer 14 cannot properly cover the entire surface of the organic layer 12, and the gas barrier property deteriorates. There is a high possibility that inconveniences such as a high possibility of occurrence will occur.
Therefore, the surface roughness Ra of the organic layer 12 is preferably 2 nm or less, particularly preferably 1.5 nm or less.

Here, in the gas barrier film 10a of the present invention, the surface roughness Ra of the organic layer 12 is often difficult to measure directly.
In the present invention, when it is difficult to directly measure the surface roughness Ra of the organic layer, the surface roughness Ra of the organic layer 12 may be measured (knowledge) as follows.

In the manufacturing method of the present invention, the inorganic layer 14 made of an inorganic compound containing silicon and nitrogen is formed on the surface of the organic layer 12 by plasma CVD using a source gas containing ammonia gas.
In the production method of the present invention, preferably, an inorganic layer is formed on the organic layer 12 by using a roll-to-roll (hereinafter referred to as RtoR) as shown in FIG. 14 is formed. Specifically, RtoR is a roll formed by winding a flexible long substrate (flexible web-shaped substrate) such as a flexible long support Z, In this film forming method, a substrate is sent out, a film is formed while the substrate is conveyed in the longitudinal direction, and the film-formed substrate is wound again in a roll shape.

When the inorganic layer 14 is formed on the organic layer 12 by plasma CVD, the organic layer 12 is etched by plasma together with the formation of the inorganic layer 14 (deposition of the inorganic compound). As a result, the surface of the organic layer 12 is etched. However, it becomes rough.
In the manufacturing method of the present invention using a source gas containing ammonia gas, this etching is mainly performed by ammonia plasma. As will be described in detail later, in the present invention, the surface roughness Ra of the organic layer 12 is set to 1 nm or more by controlling the etching of the organic layer 12 when forming the inorganic layer 14 by using this etching by plasma. And
Therefore, as described above, in the manufacturing method of the present invention, the surface roughness Ra of the organic layer 12 is 1 nm or more, and a roughening process such as an etching process or a blasting process of the organic layer 12 is performed. Don't do it.

In the formation of the inorganic layer 14 on the surface of the organic layer 12, initially, the etching of the organic layer 12 by plasma frequently occurs, and gradually, the amount of deposition of the inorganic compound increases and the etching decreases. When the film formation time elapses, film formation of the inorganic layer 14 covering the entire surface with the inorganic compound is started.
Therefore, in RtoR in which film formation is performed while the substrate is being transported, in the film formation region (in the example shown in FIG. 2, the region where the shower electrode 80 and the drum 68 (support Zo) face each other), the substrate transport direction. The organic layer 12 is often etched on the upstream side, and the deposition amount of the inorganic compound gradually increases and the etching decreases toward the downstream, and the inorganic compound covers the entire surface at a certain position in the transport direction. Formation of the layer 14 is started.
The etching of the organic layer 12 inevitably forms a region (organic / inorganic mixed region) where the forming material of the organic layer 12 and the forming material of the inorganic layer 14 are mixed under the inorganic layer 14. Sometimes it is done. In the present invention, this mixed region is also regarded as the organic layer 12.

Utilizing this, when the inorganic layer 14 is formed on the surface of the organic layer 12 by RtoR, after the formation of the inorganic layer 14 is sufficiently stabilized, the conveyance and film formation of the substrate are stopped to form the film. By analyzing the surface of the substrate located in the region, the surface roughness of the organic layer 12 can be measured.
That is, when the transport and film formation of the substrate are stopped, the surface of the substrate located in the film formation region has a large amount of etching of the organic layer 12 on the upstream side, and the deposition amount of the inorganic compound is small. The amount of deposition of the inorganic compound gradually increases and the etching decreases, and the downstream side from a certain position in the transport direction becomes the inorganic layer 14 covering the entire surface with the inorganic compound.
Therefore, after the film formation of the inorganic layer 14 is stabilized, the conveyance and film formation of the substrate are stopped, the surface of the substrate located in the film formation region is analyzed using an analysis means such as ESCA or SIMS, and the width direction of the substrate The most upstream position in the transport direction in which the entire region (in the direction orthogonal to the transport direction) becomes the inorganic layer 14 is detected, and the surface roughness Ra is measured at this position. Thereby, the surface roughness Ra of the surface of the organic layer 12, that is, the film formation surface of the inorganic layer 14 can be measured (the surface roughness Ra at this position is defined as the surface roughness Ra of the organic layer 12).

Here, the position where the entire region in the width direction of the substrate becomes the inorganic layer 14 is, in other words, the position where the entire region in the width direction of the substrate is only the component derived from the inorganic layer 14.
Furthermore, in other words, the position where the entire region in the width direction of the substrate becomes the inorganic layer 14 is a position where the component derived only from the organic layer 12 disappears in the entire region in the width direction of the substrate.

In addition, by using this method, the surface roughness Ra of the organic layer 12 is also measured when the inorganic layer 14 is formed on the organic layer 12 by a batch-type film forming method that does not transport the substrate. it can.
That is, the inorganic layer 14 of the gas barrier film 10a of the present invention is analyzed in the depth direction using ESCA or the like, and the shallowest component in which only the organic layer 12 is detected corresponding to the entire surface of the inorganic layer 14 is detected. The position (the position farthest from the substrate) is detected. From the depth of the position and the film formation rate of the inorganic layer 14, the film formation time from the start of film formation of the inorganic layer 14 to the position of this depth is calculated.
Next, the inorganic layer 14 is formed until the calculated film formation time in exactly the same manner as the formation of the inorganic layer 14 in the analyzed gas barrier film 10a. By measuring the surface roughness Ra of the surface, the surface roughness Ra of the surface of the organic layer 12 can be measured.

In FIG. 2, an example of the manufacturing apparatus which manufactures the above-mentioned gas barrier film 10a with the manufacturing method of the functional film of this invention is shown notionally.
This manufacturing apparatus has an organic film forming apparatus 30 for forming the organic layer 12 and an inorganic film forming apparatus 32 for forming the inorganic layer 14 for carrying out the manufacturing method of the present invention.
2A shows the organic film forming apparatus 30, and FIG. 2B shows the inorganic film forming apparatus 32. 2 illustrates the production of the gas barrier film 10a shown in FIG. 1A, which has the organic layer 12 on the support Z and the inorganic layer 14 thereon.

Both the organic film forming apparatus 30 and the inorganic film forming apparatus 32 shown in FIG. 2 are apparatuses that perform film formation using the above-described RtoR.
Such RtoR can produce the gas barrier film 10a (functional film) with high productivity and high efficiency.

The production method of the present invention is not limited to the production of a functional film such as a gas barrier film using RtoR using a long support Z, but a so-called single wafer type using a cut sheet substrate. A functional film may be manufactured using a (batch type) film formation method.
However, even when the surface roughness Ra of the organic layer 12 cannot be directly measured, as described above, the surface roughness of the organic layer 12 can be easily measured when the manufacturing method using RtoR is used. That is, by using RtoR, it is possible to manufacture the gas barrier film 10a that fully exhibits the features of the present invention. Therefore, in the present invention, it is preferable to manufacture the gas barrier film 10a and the like by RtoR.

  Even when a cut sheet substrate is used, the method for forming the organic layer 12 and the inorganic layer 14, and the intermediate organic layer 12a, the protective organic layer, and the intermediate inorganic layer 14a are basically described below. This is the same as the manufacturing method using RtoR.

The organic film forming apparatus 30 shown in FIG. 2 (A) applies a paint to be the organic layer 12 while transporting a long support Z (substrate) in the longitudinal direction, and after drying, coats the film by light irradiation. Is an apparatus for forming a film of the organic layer 12 by crosslinking and curing the organic compound contained therein.
As an example, the organic film forming apparatus 30 includes a coating unit 36, a drying unit 38, a light irradiation unit 40, a rotating shaft 42, a winding shaft 46, and conveyance roller pairs 48 and 50.
In addition to the illustrated members, the organic film forming apparatus 30 performs film formation by coating while conveying a long film forming material such as a pair of conveying rollers, a guide member such as a support Z, and various sensors. You may have the various members provided in a well-known apparatus.

In the organic film forming apparatus 30, a support roll ZR formed by winding a long support Z is loaded on the rotary shaft 42.
When the support roll ZR is loaded on the rotating shaft 42, the support Z is pulled out from the support roll ZR, passes through the conveying roller pair 48, and passes under the coating means 36, the drying means 38, and the light irradiation means 40. Then, the paper is passed through a predetermined transport path that passes through the pair of transport rollers 50 and reaches the take-up shaft 46.

In the organic film forming apparatus 30, the feeding of the support Z from the support roll ZR and the winding of the support Zo on which the organic layer 12 is formed on the winding shaft 46 are performed in synchronization. Thus, while the long support Z is transported in the longitudinal direction along a predetermined transport path, the coating material 36 is applied with the coating material that becomes the organic layer 12, the drying device 38 is used to dry the coating material, and the light irradiation device 40 is used to dry the coating material. By curing, the organic layer 12 is formed.
As described above, the organic layer 12 is formed by embedding irregularities on the surface of the support Z, foreign matters attached to the surface of the support Z, etc. to flatten the surface of the organic layer 12, and the inorganic layer 14 is deposited. It is provided to eliminate difficult parts.

The coating means 36 is for applying a coating material prepared in advance to form the organic layer 12 on the surface of the support Z.
This paint is obtained by dissolving or dispersing an organic compound (monomer / oligomer) that becomes the organic layer 12 by crosslinking and polymerization in an organic solvent. In addition, various additives necessary for forming the organic layer 12, such as a surfactant (surface modifier), a silane coupling agent, a polymerization initiator (crosslinking agent), and the like are appropriately added to this coating material. The

Various types of organic compounds that can be crosslinked (polymerized) to form the organic layer 12 can be used.
Among them, as described in the description of the material for forming the organic layer 12, a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group is preferable, and in particular, monomers of acrylate and / or methacrylate. Among these, acrylate and / or methacrylate monomers and oligomers having 2 or more functional groups, particularly 3 or more functional groups, are particularly preferable.

The coating material for forming the organic layer 12 may be prepared by a known method by dissolving (dispersing) such an organic compound, a surfactant, or the like in the organic solvent in a known method.
There are no particular limitations on the organic solvent used in the preparation of the paint, and examples of the organic solvent used for forming the organic layer in the organic / inorganic laminated functional film such as methyl ethyl ketone (MEK), cyclohexanone, isopropyl alcohol, and acetone. Various types are available.

  There is no limitation on the viscosity of the coating material, and the viscosity may be appropriately set so that the coating material can be applied to the entire surface of the support Z according to the components contained in the coating material, the coating method, and the like. That is, the viscosity of the coating material may be a viscosity that wets the entire surface of the support Z with the coating material, including foreign matters and irregularities.

In the coating means 36, the coating method for the support Z is not particularly limited.
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.
In particular, since the coating can be applied in a non-contact manner, the coated surface (in particular, the inorganic layer surface when forming a plurality of organic layers 12) is not damaged, and irregularities and foreign matter on the surface of the support Z are formed by the formation of beads (liquid reservoir). For example, the die coating method is suitably used because of its excellent embedding property.

  The coating amount of the coating is not limited, and the coating can be applied to the entire surface of the support Z according to the viscosity of the coating, the content of the organic compound in the coating, and the coating method. The coating amount according to the thickness of the organic layer 12 may be set as appropriate.

As described above, the support Z is then transported to the drying means 38, and the paint applied by the applying means 36 is dried.
The method for drying the paint by the drying means 38 is not limited, and the paint can be dried (the organic solvent is removed) before the support Z reaches the light irradiation means 40 so that it can be crosslinked. For example, all known drying means can be used. As an example, heat drying with a heater, heat drying with warm air, and the like are exemplified.

The support Z is then transported to the light irradiation means 40. The light irradiation means 40 irradiates the coating material applied by the coating means 36 and dried by the drying means 38 with ultraviolet rays (UV light), visible light or the like to crosslink organic compounds (monomers or oligomers of organic compounds) contained in the coating material. (Polymerization) is cured to form the organic layer 12.
Here, when the coating film is cured by the light irradiation means 40, the light irradiation area by the light irradiation means 40 in the support Z is set to an inert atmosphere (oxygen-free atmosphere) by nitrogen substitution or the like as necessary. Also good. Moreover, you may make it adjust the temperature of the support body Z, ie, a coating film, at the time of hardening using a backup roller etc. which contact | abut to a back surface as needed.

In the present invention, the crosslinking of the organic compound that becomes the organic layer 12 is not limited to photopolymerization. That is, various methods according to the organic compound used as the organic layer 12, such as heat polymerization, electron beam polymerization, and plasma polymerization, can be used for crosslinking of the organic compound.
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 12, photopolymerization is preferably used.

  The support Z thus formed with the organic layer 12 (hereinafter, the support Z with the organic layer 12 formed is referred to as “support Zo”) is nipped and conveyed by the conveyance roller pair 50 and wound up. The shaft 46 reaches the shaft 46, and is wound again into a roll shape by the winding shaft 46 to obtain a roll ZoR formed by winding the support Zo.

This roll ZoR is supplied to the inorganic film forming apparatus 32 shown in FIG.
That is, in the example shown in FIG. 2, the inorganic film forming apparatus 32 forms the inorganic layer 14 on the support Zo on which the organic layer 12 is formed on the support Z, and FIG. The gas barrier film 10a which is an example of the functional film of this invention shown in FIG.
As described above, the inorganic film forming apparatus 32 forms the inorganic layer 14 made of an inorganic compound containing silicon and nitrogen on the surface of the organic layer 12 by plasma CVD using ammonia gas as a source gas. The inorganic film forming device 32 forms the inorganic layer 14 while controlling the etching of the organic layer 12 by plasma.

The inorganic film forming apparatus 32 shown in FIG. 2B basically includes a vacuum chamber 60, an unwinding chamber 62 and a film forming chamber 64 in the vacuum chamber 60, and a drum 68. The
In FIG. 2B, a part of the shower electrode 80 disposed in the film formation chamber 64 is shown in cross section. In addition to the members shown in the drawing, the inorganic film forming apparatus 32 is known to perform film formation by a vapor deposition method while conveying a long film-forming material such as a pair of conveying rollers, a guide member, and various sensors. You may have the various members provided in an apparatus.

In the inorganic film forming apparatus 32, a roll ZoR obtained by winding the support Zo is loaded into the unwind chamber 62.
The support Zo is pulled out from the roll ZoR in the unwinding chamber 62 and is transported in the longitudinal direction while being wound around the drum 68, and the inorganic layer 14 is formed in the film forming chamber 64, and then the winding is again performed. It is transported to the take-out chamber 62 and wound (rolled).

The drum 68 is a cylindrical member that rotates counterclockwise in the drawing around the center line.
The drum 68 wraps a support Zo guided by a guide roller 76a of an unwind chamber 62, which will be described later, on a predetermined path, and conveys the support Zo in a longitudinal direction while holding the support Zo at a predetermined position. The film is transferred into the film forming chamber 64 and sent again to the guide roller 76 b in the unwinding chamber 62.

Here, the drum 68 also functions as a counter electrode of a shower electrode 80 (film formation electrode) of the film formation chamber 64 described later. That is, in the illustrated inorganic film forming apparatus 32, the drum 68 and the shower electrode 80 constitute an electrode pair.
Therefore, in the illustrated example, the drum 68 is grounded. However, the present invention is not limited to this, and a bias power source for applying a bias to the drum 68 may be connected to the drum 68 as necessary. Alternatively, the connection between the ground and the bias power source may 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, which are used in various film forming apparatuses, can be used.

The drum 68 may also serve as temperature adjusting means for the support Zo (that is, the film forming temperature) during film formation. Therefore, it is preferable that the drum 68 includes a temperature adjusting means.
The temperature adjusting means of the drum 68 is not particularly limited, and various temperature adjusting means such as a temperature adjusting means for circulating a refrigerant or the like, a cooling means using a Peltier element or the like can be used.

As described above, the vacuum chamber 60 includes the unwinding chamber 62 and the film forming chamber 64. In the illustrated example, the unwinding chamber 62 and the film forming chamber 64 are arranged in the vertical direction (vertical direction) with the unwinding chamber 62 facing upward.
The unwinding chamber 62 and the film forming chamber 64 are (substantially) hermetically separated by the drum 68 and the partition walls 70 a and 70 b extending from the inner wall surface 60 a on the side surface side of the vacuum chamber 60 to the vicinity of the peripheral surface of the drum 68. Is done.
In order to suitably separate the unwinding chamber 62 and the film forming chamber 64, the tips of the partition walls 70a and 70b (the end opposite to the inner wall surface of the vacuum chamber 60) may not contact the transported support Zo. It is preferable to be close to the peripheral surface of the drum 68 to a certain position.

  The unwinding chamber 62 includes a rotating shaft 72, a winding shaft 74, guide rollers 76a and 76b, and a vacuum exhaust means 78.

The rotating shaft 72 is a known object that rotates while supporting the roll ZoR. The take-up shaft 74 is a known elongate take-up shaft for taking up the film-formed support Zo.
Furthermore, the guide rollers 76a and 76b are normal guide rollers that guide the support body Zo along a predetermined transport path.

The roll ZoR is attached to the rotation shaft 72.
When the roll ZoR is mounted on the rotating shaft 72, the support Zo passes through a predetermined path (inserted) through the guide roller 76a, the drum 68, and the guide roller 76b to the winding shaft 74. )
In the inorganic film forming apparatus 32, the feeding of the support Zo from the roll ZoR and the winding of the film-formed support Zo on the take-up shaft 74 are performed in synchronization with each other to form a long support Zo in a predetermined manner. The film is formed in the film forming chamber 64 while being transported in the longitudinal direction along the transport path.

The vacuum exhaust means 78 is for depressurizing the inside of the unwinding chamber 62 to a predetermined degree of vacuum.
In the inorganic film forming apparatus 32, the evacuation unit 78 is also provided in the unwinding chamber 62, and the inside of the unwinding chamber 62 is maintained at a predetermined degree of vacuum, whereby the pressure in the unwinding chamber 62 is reduced in the film forming chamber 64. This prevents the formation of the layer 14 from being affected.

In the present invention, the vacuum exhaust means 78 is not particularly limited, and vacuum pumps such as turbo pumps, mechanical booster pumps, rotary pumps, and dry pumps, further auxiliary means such as cryocoils, the degree of ultimate vacuum and the amount of exhaust. Various known (vacuum) evacuation means used in a vacuum film forming apparatus using an adjusting means or the like can be used.
In this regard, the same applies to the vacuum exhaust means 92 described later.

As described above, in the inorganic film forming apparatus 32, the film forming chamber 64 is provided under the unwinding chamber 62 (under the partition walls 70 a and 70 b).
The film forming chamber 64 includes a shower electrode 80, a source gas supply unit 86, a high frequency power source 84, and a vacuum exhaust unit 90. Further, an exhaust means 82 is disposed immediately upstream of the shower electrode 80. In this film forming chamber 64, as an example, the inorganic layer 14 is formed on the surface of the support Zo, that is, on the organic layer 12 by CCP-CVD (Capacitively Coupled Plasma).

The shower electrode 80 is a film forming electrode, and constitutes an electrode pair in CCP-CVD together with the drum 68 (counter electrode) described above.
In the illustrated example, the shower electrode 80 has, for example, a substantially rectangular parallelepiped shape made of aluminum and having a maximum surface facing the peripheral surface of the drum 68. Moreover, the shower electrode 80 is a curved surface shape so that the opposing surface with the drum 68 may become a parallel surface spaced apart from the surrounding surface of the drum 68 as a preferable aspect.

A hollow portion 80 a is formed inside the shower electrode 80.
A number of gas supply holes 80b for supplying the raw material gas are formed from the hollow portion 80a to the surface facing the drum 68 (support Zo). In the shower electrode 80, the gas supply hole 80 b is formed entirely on the surface facing the drum 68.

In the present invention, as the shower electrode 80, a known shower electrode (shower plate) used in an apparatus for performing film formation by plasma CVD or the like can be used.
Further, the surface of the shower electrode 80 facing the drum 68 may be roughened by forming a sprayed film, blasting or the like in order to prevent the deposited film from being peeled off.

The source gas supply unit 86 is a known gas supply unit used in a plasma CVD apparatus for supplying source gas (process gas / film formation gas). In the present invention, an inorganic layer 14 made of an inorganic compound containing silicon and nitrogen such as silicon nitride is formed on the surface of the organic layer 12 using a source gas containing ammonia gas.
The source gas supply unit 86 supplies source gas to the hollow portion 80 a of the shower electrode 80. Therefore, the source gas flows into the gas supply hole 80b from the hollow portion 80a, and is supplied from the gas supply hole 80b between the shower electrode 80 and the drum 68 (support Zo), that is, between the electrode pair in CCP-CVD. The

The high-frequency power supply 90 is also a known high-frequency power supply used in a plasma CVD apparatus.
The high frequency power supply 90 supplies plasma excitation power (film formation power) to the shower electrode 80 (electrode body 82) that is a film formation electrode.

In addition, the manufacturing method of this invention is not limited to using such a shower electrode.
That is, the inorganic layer 14 is formed by CCP-CVD using a deposition electrode that does not have a source gas supply function and a nozzle for supplying source gas between the deposition electrode and the support Zo. May be.

  In the film forming chamber 64, the source gas is supplied from the source gas supply unit 86 to the hollow portion 80a of the shower electrode 80, and the source gas is discharged from the gas supply hole 80b communicating with the hollow portion 80a. The source gas is supplied between the drum 68 (support Zo) and the plasma excitation power is supplied from the high frequency power source 84 to the shower electrode 80, whereby the surface of the support Zo (organic layer 12) is formed by CCP-CVD. An inorganic layer 14 is formed.

Here, in the illustrated inorganic film forming apparatus 32, the exhaust means 82 is disposed immediately upstream of the shower electrode 80 in the film forming chamber 64. The exhaust means 82 has a function of adjusting the exhaust amount as a preferred mode.
The exhaust means 82 exhausts the source gas from a film formation region, that is, a region where the shower electrode 80 and the drum 68 (support Zo) face each other. In the apparatus of the illustrated example, the exhaust means 82 for exhausting the source gas in the film formation region from the upstream side is provided, so that the plasma has a long residence time in the plasma and a high radical concentration on the upstream side of the film formation region. In contact with the surface of the layer 12, etching of the organic layer 12 by plasma (mainly ammonia plasma) is promoted. Further, by adjusting the exhaust amount by the exhaust means 82, the strength of etching by plasma can be controlled.

In the present invention, the surface roughness Ra of the organic layer 12 is set to 1 μm or more by forming the inorganic layer 14 on the surface of the organic layer 12 while controlling the etching by using the etching by plasma as described above. And the inorganic layer 14 is formed into a film on the surface of this organic layer 12, and the gas barrier film 10a of this invention is produced.
As described above, in the film formation of the inorganic layer 14 using RtoR, after the film formation of the inorganic layer 14 is stabilized, the conveyance and film formation of the substrate are stopped, the substrate surface in the film formation region is analyzed, and the width direction The surface roughness Ra of the organic layer 12 can be measured by detecting the most upstream position where the entire region is the inorganic layer 14 and measuring the surface roughness Ra of the most upstream position.
Accordingly, in the film forming chamber 64 of the inorganic film forming apparatus 32, the exhaust is performed so that the surface roughness Ra of the support Zo is 1 nm or more at the most upstream position where the entire width direction is the inorganic layer 14. The inorganic layer 14 is formed by setting the exhaust amount by the means 82. Thereby, the etching by plasma is controlled, and the inorganic layer 14 having an appropriate surface roughness due to the irregularities on the surface of the organic layer 12 is formed on the organic layer 12 having a surface roughness Ra of 1 nm or more. it can.

  The exhaust means 82 is not limited, and there is a known thing that can suck gas under reduced pressure, such as a fan whose strength can be adjusted, an exhaust port whose flow rate can be branched from the exhaust pipe of the vacuum pump 92 (78). Various types are available.

In the present invention, the method of controlling the etching of the organic layer 12 when forming the inorganic layer 14 is not limited to the exhaust means 82 for exhausting the source gas in the film formation region from the upstream side as shown in the example, Various methods for partially adjusting the plasma intensity in the film formation region can be used.
As an example, a method of partially widening or narrowing the gap between the electrodes is exemplified in order to reduce the dielectric breakdown voltage for plasma discharge only partly in the transport direction and to make an electrode configuration in which power is efficiently input. Is done. Similarly, a method in which the pressure is partially increased or decreased in order to reduce the dielectric breakdown voltage for plasma discharge in a part of the transport direction and to make an electrode configuration in which power is efficiently input is also exemplified.
In addition, a method of partially adjusting the supply amount and / or supply ratio of the source gas (mainly ammonia gas provided for etching) in the transport direction is also exemplified. Furthermore, a method of partially increasing or decreasing the intensity of plasma excitation power and / or bias power in the transport direction is also exemplified.
In addition to this, in order to enhance the action of chemical etching, the inorganic layer 14 is formed (subjected to plasma) while locally heating the film in the transport direction, or the source gas is locally applied in the transport direction. Examples of the method of heating are as follows.
Such etching control is preferably performed at the upstream portion of the film formation region (upstream side from the center in the transport direction), and particularly preferably at the most upstream portion of the film formation region.

When the inorganic layer 14 is formed on the organic layer 12 by plasma CVD, generally, the higher the etching rate, the larger the surface roughness of the organic layer 12. Similarly, when the inorganic layer 14 is formed on the organic layer 12 by plasma CVD, generally, the longer the etching time (the longer it takes to form the inorganic layer 14), the more organic The surface roughness of the layer 12 is increased.
Therefore, the etching of the organic layer 12 when the inorganic layer 14 is formed may be controlled by controlling the etching rate and the etching time.
Etching control by etching rate and etching time is, for example, by knowing the relationship between the etching rate and etching time and the surface roughness Ra of the organic layer 12 by simulation and experiment, and creating a calibration curve showing the relationship between the two. In addition, the calibration curve may be used.

In the manufacturing method of the present invention, the film formation conditions of the inorganic layer 14 such as the supply amount of the source gas, plasma excitation power, and film formation pressure are not limited. That is, the film formation conditions are appropriately set according to the thickness of the inorganic layer 14, the kind of the inorganic layer 14 to be formed, the target film formation speed, the film thickness of the inorganic layer 14, the source gas used, and the like. That's fine.
Moreover, there is no limitation also on the source gas to be used. If ammonia gas is included, a known source gas may be used according to the kind of the inorganic layer 14 to be formed. For example, when silicon nitride is formed as the inorganic layer 14, the raw material gas is a combination of silane gas, ammonia gas, and hydrogen gas, and a combination of silane gas, ammonia gas, and nitrogen gas (inert gas). A known source gas such as a combination of silane gas, ammonia gas, hydrogen gas, and nitrogen gas may be used.

In the production method of the present invention, the control of the surface roughness Ra of the inorganic layer 14 is performed by a known method such as adjustment of plasma electromotive force, adjustment of raw material gas amount, adjustment of film forming pressure, adjustment of raw material gas composition, etc. Can be done.
In the production method of the present invention, the surface roughness Ra of the inorganic layer 14 may be controlled as necessary according to the surface roughness of the organic layer 12 or the like.

  The support Zo, that is, the gas barrier film 10a on which the inorganic layer 14 has been formed in the film formation chamber 64, is again conveyed to the unwind chamber 62, guided to the guide roller 76b, and conveyed to the take-up shaft 74. It is wound and supplied to the next step as a roll 10aR formed by winding the gas barrier film 10a.

In addition, in the manufacturing method of the functional film of this invention, the film-forming method of the inorganic layer 14 is not limited to CCP-CVD of the example of illustration.
That is, as the method for forming the inorganic layer 14, various known plasma CVD methods such as ICP (Inductively Coupled Plasma) -CVD and microwave CVD can be used.

Hereinafter, the operation of the inorganic film forming apparatus 32 will be described.
As described above, when the roll roll ZoR formed by winding the support Zo formed by forming the organic layer 12 on the support Z is loaded on the rotating shaft 72, the support Zo is pulled out from the roll ZoR. Then, it passes through a predetermined conveying path that reaches the winding shaft 74 through the guide roller 76a, the drum 68, and the guide roller 76b.

When the support Zo is inserted, the vacuum chamber 60 is closed, and the vacuum exhaust means 78 and 62 are driven to start exhausting each chamber.
When the unwind chamber 62 and the film forming chamber 64 are evacuated to a predetermined vacuum level or less, the source gas supply unit 86 is then driven to supply the source gas to the film forming chamber 64.

  When the pressures in all the chambers are stabilized at the predetermined pressure, the drum 68 and the like are started to rotate, the conveyance of the support Zo is started, and the high frequency power supply 84 is further driven to convey the support Zo in the longitudinal direction. At the same time, film formation of the inorganic layer 14 on the support Zo in the film formation chamber 64 is started, and the inorganic layer 14 is continuously formed on the long support Zo.

When the inorganic layer 14 is formed, the organic layer 12 is etched to roughen the organic layer 12. Here, in the film forming chamber 64, the exhaust means 82 is set so that the surface roughness Ra of the organic layer 12 is 1 nm or more at the most upstream position where the entire width direction in the film forming region is the inorganic layer 14. The etching amount of the organic layer 12 is controlled by adjusting the exhaust amount.
If necessary, the film formation conditions of the inorganic layer 14 are adjusted so that the surface roughness Ra of the inorganic layer 14 is 3 nm or less, and preferably 1 nm or more.
Accordingly, the surface of the inorganic layer 14 is excellent in adhesion, and the inorganic layer 14 is formed by forming the inorganic layer 14 having a surface roughness of 2 nm or less on the organic layer 12 having a surface roughness Ra of 1 nm or more. A high-performance gas barrier film 10a that exhibits the target gas barrier properties can be suitably produced.

As shown in FIG. 1B, in the case of manufacturing the gas barrier film 10b having a four-layer structure, the same organic layer and inorganic layer are formed twice, and the intermediate layer is formed on the support Z. The organic layer 12a is formed, the intermediate inorganic layer 14a is formed thereon, the organic layer 12 is formed thereon, and the inorganic layer 14 is formed thereon. At this time, when the intermediate inorganic layer 14a is formed, the etching control of the intermediate organic layer 12a by the exhaust means 82 or the like may or may not be performed.
Further, as shown in FIG. 1C, a gas barrier film 10c having a six-layer structure and a gas barrier film having a larger number of layers are also formed with the same number of layers (organic / inorganic). It can be manufactured by repeating according to the number of repetitions of the lamination.
When forming the protective organic layer as the uppermost layer, after the uppermost inorganic layer 14 is formed, the roll is loaded again into the organic film forming apparatus 30 to form the protective organic layer. That's fine.

  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 a functional film, a gas barrier film 10a having an organic layer 12 and an inorganic layer 14 on the surface of a support Z as shown in FIG.

  As the support Z, a long PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) having a width of 1000 mm and a thickness of 100 μm was used.

An organic compound was charged into an organic solvent and stirred to prepare a coating material for the organic layer 12.
As the organic compound, TMPTA (manufactured by Daicel-Cytec) was used. MEK was used as the organic solvent. A surfactant (BYK378 manufactured by BYK Japan) and a photopolymerization initiator (Irg184 manufactured by Ciba Chemicals) were added to the paint.
The amount of the organic compound excluding the organic solvent in the paint (the amount of the organic compound in the solid content) was 97% by weight.

The support roll ZR formed by winding the support Z is loaded on the rotating shaft 42 of the organic film forming apparatus 30 shown in FIG. 2A, and the prepared paint is applied to the surface of the support Z by the applying means 36. It was coated / dried, crosslinked / cured by the light irradiation means 40, and a roll ZoR formed by winding the support Z (support Zo) on which the organic layer 12 was formed was obtained.
The coating means 36 used a die coater. The coating amount was set so that the dry film thickness was 2 μm. That is, the film thickness of the organic layer 12 is approximately 2 μm.
The drying means 38 used hot air. As the light irradiation means 40, an ultraviolet irradiation device was used.

  Next, the roll ZoR is loaded into the inorganic film forming apparatus 32 shown in FIG. 2 (B), and the surface of the support Zo on which the organic layer 12 is formed is nitrided to a thickness of 40 nm as the inorganic layer 14 by CCP-CVD. A roll 10aR formed by forming a silicon film and winding a gas barrier film 10a having an inorganic layer 14 formed on the organic layer 12 was produced.

The drum 68 is made of stainless steel and has a diameter of 1000 mm. The drum 68 incorporates temperature adjusting means.
The high frequency power source 86 is a high frequency power source having a frequency of 13.5 MHz, and the plasma excitation power supplied to the shower electrode 80 is 2 kW.

Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), and hydrogen gas (H ₂ ) were used as the film forming gas. The supply amount was 50 sccm for silane gas, 100 sccm for ammonia gas, and 150 sccm for hydrogen gas. The film forming pressure was 100 Pa.

Prior to the production of the gas barrier film 10a to be an actual product, an inorganic layer is formed on the surface of the support Zo in the same manner as the formation of the inorganic layer 14, and after the film formation is stabilized, the support Zo is transported. The film formation was stopped, and the surface of the support Zo was analyzed by ESCA to detect the most upstream position where the entire region in the width direction was an inorganic layer.
Next, the detected surface roughness Ra at the most upstream position, that is, the surface roughness Ra of the organic layer 12 was measured. The surface roughness Ra was measured using SPA 500 manufactured by SII Nanotechnology Inc. with a measurement range of 10 μm.
Such measurement was performed by changing the exhaust amount by the exhaust unit 82 in various ways, and the exhaust by the exhaust unit 82 was adjusted so that the surface roughness Ra of the organic layer 12 was 1.1 nm.

  The surface roughness Ra of the inorganic layer 14 of the produced gas barrier film 10a was 1.3 nm. In addition, the surface roughness of the inorganic layer 14 was measured similarly to the previous.

<Example 2>
A gas barrier film 10a was produced in the same manner as in Example 1 except that the exhaust amount by the exhaust unit 82 was adjusted so that the surface roughness Ra of the organic layer 12 was 1.9 nm.
Moreover, it was 2.5 nm when the surface roughness Ra of the inorganic layer 14 of the produced gas barrier film 10a was measured similarly.

<Example 3>
The same as in Example 1 except that the exhaust amount by the exhaust means 82 is adjusted and the temperature of the support Zo is locally adjusted in the transport direction so that the surface roughness Ra of the organic layer 12 is 1.2 nm. Thus, a gas barrier film 10a was produced.
The temperature of the support Zo was adjusted by adjusting the temperature of the drum 68.
Moreover, it was 2.7 nm when surface roughness Ra of the inorganic layer 14 of the produced gas barrier film 10a was measured similarly.

<Comparative Example 1>
The same as in Example 1 except that the exhaust amount by the exhaust unit 82 is adjusted and the temperature of the support Zo is locally adjusted in the transport direction so that the surface roughness Ra of the organic layer 12 is 0.4 nm. Thus, a gas barrier film was produced.
The temperature of the support Zo was adjusted by adjusting the temperature of the drum 68.
Moreover, when the surface roughness Ra of the inorganic layer 14 of the produced gas barrier film was measured similarly, it was 3.8 nm.

<Comparative Example 2>
A gas barrier film was produced in the same manner as in Example 1 except that the exhaust amount by the exhaust unit 82 was adjusted so that the surface roughness Ra of the organic layer 12 was 2.3 nm.
Moreover, when the surface roughness Ra of the inorganic layer 14 of the produced gas barrier film was similarly measured, it was 3.2 nm.

<Comparative Example 3>
A gas barrier film was produced in the same manner as in Example 1 except that the exhaust amount by the exhaust unit 82 was adjusted so that the surface roughness Ra of the organic layer 12 was 0.1 nm.
Moreover, it was 0.5 nm when surface roughness Ra of the inorganic layer 14 of the gas barrier film produced similarly was measured.

[Adhesion test]
50 parts by weight of MEK, 49 parts by weight of DPCA (manufactured by Nippon Kayaku Co., Ltd.) and 1 part by weight of a photopolymerization initiator (Ilquagua manufactured by Ciba Geigy) were mixed and stirred to prepare a paint.
This paint is applied to the surface of the inorganic layer of the produced gas barrier film, dried in a drying chamber set at 80 ° C., and then irradiated with 2000 mJ / cm ² of ultraviolet light to form a hard coat layer having a thickness of 50 μm. A film was formed.
One surface of a double-sided adhesive tape (“No. 502” manufactured by Nitto Denko Corporation) was attached to the surface of this hard coat layer and cut to 50 mm × 300 mm, and then left for 1 hour in an atmosphere of 23 ° C. and 50% RH. .
After leaving, the double-sided pressure-sensitive adhesive tape was peeled off in the direction of 180 degrees under the same atmosphere as when left using an Instron type tensile tester under the condition of a tensile speed of 300 mm / min.
The case where no peeling of the hard coat layer occurred on the entire surface was evaluated as “excellent”, and the case where some peeling was observed was evaluated as “impossible”.

[Measurement of gas barrier properties]
About each produced gas barrier film, water-vapor-permeation rate [g / (m < ² > * day)] was measured by the calcium corrosion method (method described in Unexamined-Japanese-Patent No. 2005-283561).
as a result,
Example 1 is less than 1 × 10 ⁻⁴ [g / (m ² · day)],
Example 2 is less than 1 × 10 ⁻⁴ [g / (m ² · day)],
Example 3 is less than 1 × 10 ⁻⁴ [g / (m ² · day)],
Comparative Example 1 is 5 × 10 ⁻² [g / (m ² · day)],
Comparative Example 2 is 2 × 10 ⁻³ [g / (m ² · day)],
Comparative Example 3 is less than 1 × 10 ⁻⁴ [g / (m ² · day)],
Met.

[Comprehensive evaluation]
“Excellent” means that the water vapor transmission rate is less than 1 × 10 ⁻⁴ [g / (m ² · day)] and the result of the adhesion test is “Excellent”;
“Good” if the water vapor transmission rate is less than 1 × 10 ⁻⁴ [g / (m ² · day)] and the result of the adhesion test is “impossible”;
Regardless of the result of the adhesion test, a water vapor permeability of 1 × 10 ⁻⁴ [g / (m ² · day)] was evaluated as “impossible”;
The results are shown in the table below.

As shown in the above table, each of the gas barrier films of the present invention in which the surface roughness Ra of the organic layer is 1 nm or more and the surface roughness Ra of the inorganic layer is 3 nm or less is the surface roughness of the inorganic layer. Both high adhesion and excellent gas barrier properties are achieved.
In contrast, Comparative Example 1 in which the surface roughness of the organic layer is too small and the surface roughness of the inorganic layer is too large, and Comparative Example 2 in which the surface roughness of the inorganic layer is too large have good adhesion. Low gas barrier properties. Further, Comparative Example 3 in which the surface roughness of both the organic layer and the inorganic layer is too small has high gas barrier properties but has insufficient adhesion.
From the above results, the effects of the present invention are clear.

  It can use suitably for functional films, such as a gas barrier film used for a solar cell, an organic EL display, etc., and its manufacture.

10a, 10b, 10c Gas barrier film 12 Organic layer 14 Inorganic layer 12a Intermediate organic layer 14c Intermediate inorganic layer 30 Organic film forming apparatus 32 Inorganic film forming apparatus 36 Coating means 38 Drying means 40 Light irradiation means 42, 72 Rotating shafts 46, 74 Spindle 48, 50 Conveying roller pair 60 Vacuum chamber 62 Unwind chamber 64 Film forming chamber 68 Drum 70a, 70b Partition wall 76a, 76b Guide roller 78, 92 Vacuum exhaust means 80 Shower electrode 82 Exhaust means 86 Source gas supply section 90 High frequency power supply

Claims (6)

An organic layer is formed on the surface of the substrate, and an inorganic layer made of an inorganic compound containing at least silicon and nitrogen is formed on the organic layer by plasma CVD containing ammonia gas as a source gas.
In the formation of the inorganic layer, the etching of the organic layer by plasma is controlled so that the surface roughness Ra of the organic layer is 1 nm or more , and the surface roughness Ra of the inorganic layer is 3 nm or less. A method for producing a functional film, characterized in that The method for producing a functional film according to claim 1 , wherein the inorganic layer is formed while a long substrate is used and the substrate is conveyed in the longitudinal direction. The method for producing a functional film according to claim 2 , wherein the etching of the organic layer is controlled in an upstream portion in the substrate transport direction in the film formation region of the inorganic layer. After the formation of the inorganic layer is stabilized, the conveyance and film formation of the substrate are stopped, the surface of the substrate in the film formation region is analyzed, and the inorganic layer is formed over the entire width direction of the substrate. detecting the most upstream position of the substrate conveying direction in which, as a measurement result at the time of measuring the surface roughness Ra of the upstream-most position is greater than or equal to 1 nm, to claim 2 or 3 controlling the etching of the organic layer The manufacturing method of the functional film of description. The method for producing a functional film according to any one of claims 2 to 4, wherein the etching of the organic layer is controlled by an evacuation unit disposed upstream of a film formation region of the inorganic layer. Control of the etching of the organic layer,
A method of partially adjusting a gap between electrodes of a pair of electrodes for performing film formation by plasma CVD in a transport direction of the substrate;
A method of partially adjusting the pressure in the film formation region of the inorganic layer in the transport direction of the substrate;
A method of partially adjusting at least one of the supply amount and the supply ratio of the ammonia gas in the film formation region of the inorganic layer in the transport direction of the substrate;
A method of partially adjusting at least one of the intensity of plasma excitation power and the intensity of bias power for film formation by plasma CVD in the transport direction of the substrate;
A method of locally heating the substrate in a transport direction of the substrate in a film formation region of the inorganic layer; and
The production of the functional film according to any one of claims 2 to 5, wherein the raw material gas is locally heated in the transport direction of the substrate in the film formation region of the inorganic layer by one or more methods. Method.