JP5723732B2 - Functional film and method for producing functional film - Google Patents

Description

  The present invention relates to a functional film such as a gas barrier film and a method for producing the functional film.

Gas barrier films such as optical elements, display devices such as liquid crystal displays and organic EL displays, various semiconductor devices, parts and components that require moisture resistance in various devices such as solar cells, and packaging materials for packaging food and electronic components Has been.
The gas barrier film generally has a structure in which a plastic film such as a polyethylene terephthalate (PET) film is used as a support (substrate) and a film (gas barrier film) that exhibits gas barrier properties is formed thereon.

Various inorganic films (films made of inorganic compounds) are known as films exhibiting gas barrier properties.
Specifically, inorganic films such as silicon nitride, silicon oxide, silicon oxynitride, and aluminum oxide are used for the gas barrier film.

Here, the inorganic film used for the gas barrier film is required to have excellent adhesion to the support (lower layer).
Moreover, if there are defects such as cracks or peeling in the inorganic film, the gas barrier properties are greatly reduced. Therefore, in order to obtain high gas barrier performance, the inorganic film formed on the gas barrier film is required to have no (small) cracks, peeling, defective portions, and the like.
In order to satisfy such requirements, various proposals have been made for gas barrier films formed by forming an inorganic film having gas barrier properties.

For example, Patent Document 1 describes a gas barrier film in which silicon oxynitride is formed as an inorganic film having gas barrier properties on a support (synthetic resin sheet), and the density distribution of the inorganic film is adjusted. Has been.
Specifically, in Patent Document 1, the density of the inorganic film (silicon oxynitride film) near the interface on the support side is A, and the density of the region excluding the vicinity of the interface is B, and the inorganic film is 0.905. There is described a gas barrier film that is a single deposited layer having a relationship of ≦ A / B <1.000 and continuous in the film thickness direction.

Japanese Patent No. 4533138

In the gas barrier film described in Patent Document 1, the structure of the inorganic film is not simple because the inorganic film has the above-described density distribution, that is, there are portions having different densities inside the inorganic film. It ’s complicated.
The gas barrier film described in Patent Document 1 exhibits a function of hindering the permeation of water vapor due to the complicated internal structure of the inorganic film, and exhibits a high gas barrier property.

However, in the inorganic film formed by forming a high density region after such a low density region is formed, depending on the film thickness and the composition of the inorganic film, the entire film may be formed when the required film thickness is formed. The stress balance is easily lost, and the film is likely to crack or peel off.
This tendency becomes higher as the dense inorganic film with high gas barrier property is obtained.

In addition, when a crack or defect occurs in the film during the formation of the inorganic film, the crack or defect often grows as it is.
In this case, large cracks and defects remain in the formed inorganic film, and the gas barrier performance is greatly deteriorated.

  An object of the present invention is to solve the above-mentioned problems of the prior art, and in a functional film such as a gas barrier film formed by forming an inorganic film on a support such as a plastic film, the support and the inorganic film Functionality capable of significantly reducing cracks, delamination and defects in the inorganic film, and also significantly reducing damage to the support when forming the inorganic film. It is providing the manufacturing method which can manufacture a film and such a highly efficient functional film suitably.

  In order to achieve the above object, the functional film of the present invention is a functional film having a support and an inorganic film formed on the support, wherein the inorganic film includes the region B, and A functional film comprising a region A having a lower density and thinner than the region B, and further having one or more laminated structures of a region B, a region A, and a region B laminated in the thickness direction. provide.

In such a functional film of the present invention, it is preferable that the inorganic film further has one or more laminated structures of a region A, a region B, and a region A laminated in the thickness direction.
Further, when the density of the region A is a and the density of the region B is b, it is preferable that “0.6 <a / b <1” is satisfied.
The inorganic film preferably contains silicon and nitrogen.
Moreover, it is preferable that the thickness of the laminated structure of the region B, the region A, and the region B is 10 to 200 nm.
Moreover, it is preferable that the thickness of the laminated structure of the region A, the region B, and the region A is 5 to 100 nm.
Furthermore, it is preferable that the inorganic film has gas barrier properties.

  In addition, the method for producing a functional film of the present invention includes forming the same inorganic film by a plurality of film forming means using plasma CVD arranged in the transport direction of the support while transporting the support. In the film forming means continuous in the body transport direction, the downstream control means for controlling the gas flow from the downstream side of the film forming area of the upstream film forming means to the outside of the film forming area, and the downstream film forming means A method for producing a functional film, wherein the inorganic film is formed using at least one of upstream control means for controlling a gas flow from the upstream side of the film forming region to the outside of the film forming region. provide.

In such a method for producing a functional film of the present invention, the inorganic film is formed by using a control means for controlling the gas flow from the upstream side of the film forming area of the uppermost film forming means to the outside of the film forming area. Preferably.
In addition, it is preferable that the inorganic film is formed using both the downstream control unit and the upstream control unit.
Moreover, it is preferable that the control means for controlling the gas flow is a mask for regulating the gas flow.
In addition, it is preferable to form an inorganic film by the plurality of film forming means while conveying the long support in the longitudinal direction.
Further, it is preferable that the support is sent out from a support roll formed by winding the long support and transported, and the formed support is wound again in a roll shape.
And a cylindrical drum that conveys the long support by winding the long support around a circumferential surface of the long support, and the plurality of film forming means includes the drum. It is preferable to be disposed so as to face the peripheral surface.

  The functional film of the present invention having the above-described configuration is a functional film having an inorganic film on a plastic film. In the functional film, the inorganic film mainly forms an inorganic film in the thickness direction. And a low-density region A, and further has one or more stacked structures of region B-region A-region B, and preferably also has one or more stacked structures of region A-region B-region A.

Therefore, since the film stress of the entire inorganic film can be reduced / controlled by the buffering effect of the region A, even if the inorganic film is dense (dense), cracks or the like caused by the unbalance of the film stress The occurrence of peeling can be greatly prevented. In addition, even if cracks, separation, defects, and the like occur in the region being formed, the initial state can be once restored when the region changes, so that cracks, defects, and the like can be prevented from growing greatly.
Therefore, according to the present invention, a high-quality functional film having high adhesion between the inorganic film and the support, high density and low film stress, and greatly reducing cracks, peeling, defects, etc. Can be obtained. Furthermore, damage to the support due to the formation of the inorganic film can be greatly reduced. Therefore, for example, by using the present invention for a gas barrier film, a gas barrier film having excellent gas barrier performance can be obtained.

  Further, in the manufacturing method of the present invention, a plurality of plasma CVD forming means arranged in the support transport direction are used while transporting the support, and the control means controls the upstream and downstream ends of the formation region by the plasma CVD. By adjusting the gas flow flowing to the outside, a functional film having such excellent performance can be suitably produced.

It is a figure which shows notionally an example of the functional film of this invention. It is a figure which shows notionally an example of the plasma CVD apparatus which enforces an example of the manufacturing method of the functional film of this invention. It is a figure which expands and shows the film-forming means of the plasma CVD apparatus shown in FIG.

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

FIG. 1 conceptually shows an example of the functional film of the present invention.
The functional film 10 of the present invention has a support Z and an inorganic film 12 formed on the support Z.

  Here, the functional film 10 of the present invention is not limited to the one having only the support Z and the inorganic film 12, as long as it has the support Z and the inorganic film 12 formed thereon. Various layer configurations are available.

As an example, an organic film as an underlayer for forming the high-quality inorganic film 12 may be provided under the inorganic film 12. That is, the functional film 10 of the present invention may be used as the support Z in which a plastic film or the like is used as a base material and an organic film as a base layer is formed thereon.
Alternatively, various functions such as a protective layer, an adhesive layer, a light reflection layer, a light-shielding layer, a planarization layer, a buffer layer, and a stress relaxation layer can be used instead of the organic film or in the lower layer and / or upper layer of the organic film. A substrate on which a layer (film) for obtaining is formed may be used as the support Z.

Further, the functional film of the present invention may be one in which an organic film as a protective layer is formed on the inorganic film 12.
Further, a plurality of laminated structures of the organic film and the inorganic film 12 formed on the surface of the organic film may be repeatedly provided, or an organic film as a protective layer may be formed on the uppermost layer. .
In the case of having a plurality of inorganic films 12, each inorganic film 12 may be the same or different. Similarly, in the case of having a plurality of organic films, the organic films may be the same or different. In addition, when it has the some inorganic film 12, it is preferable that all the inorganic films 12 have the layer structure mentioned later, but this invention is not limited to this.

The functional film 10 of the present invention has an organic film as a base layer of the inorganic film 12 on the surface, like the support Z in which an organic film is formed on a substrate such as a plastic film. Is preferred.
Moreover, it is preferable that the functional film 10 of this invention has an organic film as a protective layer in the uppermost layer.

In the present invention, the material for forming the organic film is not particularly 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 organic silicon compound film is preferably exemplified.
Among them, an organic film composed of a radical polymerizable compound and / or a polymer of a cationic polymerizable compound having an ether group as a functional group is preferable in terms of excellent strength and the like. In addition, an acrylic resin or methacrylic resin empty organic film mainly composed of a polymer of an acrylate and / or methacrylate monomer or oligomer is preferable because it has a low refractive index and excellent optical properties.

In the functional film 10 of the present invention, the support (base material / substrate) Z is not particularly limited, and any of various sheet materials that can form the inorganic film 12 by plasma CVD can be used. .
Specifically, plastic films made of organic substances such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, polyacrylate, polymethacrylate ( Resin film) can be suitably used as the support Z.
As described above, as the support Z, a material in which an organic film or the like serving as a base layer of the inorganic film 12 is formed on the surface of such a plastic film is also preferably used.

As described above, the functional film 10 of the present invention is obtained by forming the inorganic film 12 on the support Z.
In the functional film 10 of the present invention, the inorganic film 12 is a film made of an inorganic compound. Here, the inorganic film 12 is a film made of the same inorganic compound in the entire thickness direction, but has a laminated structure of two types of regions (two types of layers) having different densities (denseness).

In the functional film 10 shown in FIG. 1, the inorganic film 12 is a film composed of seven layers (seven regions) of layers 12a to 12g, and the layers 12a, 12c, 12e and 12g are layers 12b, Thinner and lower density than 12d and 12f.
In this example, although referred to as a “layer” for convenience, each layer forming the inorganic film 12 is not a single independent film having an interface except that the density of adjacent layers is different. It is formed integrally. That is, the inorganic film 12 is a single film having seven regions.
Moreover, the area | region A may have an area | region where a density changes continuously (inclination) in the thickness direction inside. Alternatively, the density of the region A may change continuously throughout the thickness direction. Here, when the region A has a region where the density continuously changes, normally, the density of this region tends to gradually increase toward one of the adjacent regions B.

That is, in the functional film 10 in the illustrated example, the layers 12b, 12d, and 12f are the region B in the present invention, and mainly constitute the inorganic film 12.
In addition, the layers 12a, 12c, 12e, and 12g are the region A in the present invention in which the density is lower than the region B and the thickness is smaller.
The layers 12a, 12c, 12e, and 12g have basically the same density, and similarly, the layers 12b, 12d, and 12f have basically the same density.

Therefore, the functional film 10 in the illustrated example has a layered structure of region B-region A-region B in the present invention, a layered structure of layer 12b-layer 12c-layer 12d, and a layered structure of layer 12d-layer 12e-layer 12f. Has two, with structure.
In addition, as a stacked structure of region A-region B-region A in the present invention, a stacked structure of layer 12a-layer 12b-layer 12c, a stacked structure of layer 12c-layer 12d-layer 12e, and layer 12e-layer 12f- The layer 12g has a three-layer structure.

The functional film of the present invention has at least one laminated structure of region B-region A-region B composed of regions (layers) having different densities and thicknesses, preferably, region A-region B. -By having one or more laminated structures of the region A, the film stress of the entire inorganic film can be reduced / controlled mainly by the buffering effect of the region A between the regions B constituting the inorganic film 12. Therefore, even in the case of the high-density (dense) inorganic film 12, it is possible to greatly prevent the occurrence of cracks and peeling due to the unbalance of the film stress.
The inorganic film 12 is basically formed (deposited) by plasma CVD. Even if cracks, delamination, defects, etc. occur in the region being formed, once the region changes, the initial film formation is performed. Since it returns to this state (can be reset), cracks, defects and the like can be largely prevented from growing.
Furthermore, preferably, since the low-density region A is formed prior to the formation of the region B on the surface of the support Z by having a laminated structure of region A-region B-region A, the inorganic film is mainly used. It is possible to prevent the support Z from being damaged by plasma or the like for forming the region B constituting the region 12, and to improve the adhesion between the support Z and the inorganic film 12.

That is, according to the present invention, the damage to the support Z is small, the adhesiveness between the inorganic film 12 and the support Z is high, the inorganic film 12 has a high density and low film stress, and cracks and delamination It is possible to obtain a high-quality functional film with greatly reduced defects and the like.
Accordingly, for example, by using the present invention for a gas barrier film, a gas barrier film having high strength and excellent gas barrier performance can be obtained.

  In addition, in the functional film 10 of this invention, the structure of the inorganic film | membrane 12 is not limited to the example of illustration, It has the area | region A and the area | region B by turns in thickness direction, and area | region B-area | region A- Various configurations can be used as long as they have at least one layered structure of region B, and preferably at least one layered structure of region A-region B-region A.

For example, the inorganic film 12 of the illustrated functional film 10 may be an inorganic film that does not have at least one of the lowermost layer 12a and the uppermost layer 12g.
However, in view of preventing damage to the support Z and adhesion between the support Z and the inorganic film 12, it is preferable to form the region A on the lowermost layer 12a, that is, on the surface of the support Z. Therefore, also in this respect, the functional film 10 of the present invention preferably has one or more laminated structures of region A, region B, and region A.

Moreover, in the functional film 10 of the example of illustration, an inorganic film may be comprised from 4 layers (4 area | region) of the layer 12a-layer 12d, or what is comprised from 5 layers of the layer 12a-layer 12e. But you can. Alternatively, the inorganic film 12 may be composed of only three layers of the layer 12b to the layer 12d having only one region B-region A-region B.
Furthermore, the inorganic film | membrane which has the area | region A and the area | region B alternately and a total of 8 layers or more may be sufficient.

In the functional film 10 of the present invention, the density of the region A and the region B is not particularly limited, and may be appropriately set according to the use of the functional film 10 and the inorganic compound forming the inorganic film 12. .
Here, in the present invention, when the density of the region A is a and the density of the region B is b, the inorganic film 12 preferably satisfies “0.6 <a / b <1”.
When the inorganic film 12 satisfies “0.6 <a / b <1”, in terms of stress balance, adhesion with the support Z, durability (film quality aging under high temperature and high humidity, etc.), etc. Favorable results can be obtained.

Further, the thickness of the inorganic film 12 is not particularly limited, and the use of the functional film 10, the performance required for the functional film 10 (inorganic film 12), and the inorganic compound that forms the inorganic film 12 are required. What is necessary is just to set suitably according to productivity etc.
Here, in the functional film 10 of this invention, it is preferable that the thickness of area | region A-area | region B-area | region A is 5-100 nm. Moreover, it is preferable that the thickness of area | region B-area | region A-area | region B is 10-200 nm.
By having such a configuration, favorable results can be obtained in terms of stress balance, durability (such as changes in film quality over time under high temperature and high humidity), and productivity (such as device configuration).
The regions A and the regions B may have the same or different thickness.
The thickness ratio between the region A and the region B is not particularly limited, but for the same reason as described above, the thickness of the region A is 3 to 30% of the thickness of the adjacent region B. Is preferred.

Here, as described above, in the inorganic film 12 of the functional film 10 of the present invention, the region A and the region B are integrated only with different densities, and the boundary does not appear clearly.
Therefore, as an example, the thickness of the laminated structure is set by setting a region where a constant density assumed as the inorganic film 12 is continuous in the thickness direction as a region B and a region other than this as the region A.

In the present invention, the inorganic compound that forms the inorganic film 12 (the inorganic compound that is the main component of the inorganic film 12) is not particularly limited, and an inorganic material that exhibits a required function depending on the application of the functional film 10. Various compounds are available.
Examples include metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metal carbides such as aluminum carbide; silicon oxide, oxynitride Silicon oxides such as silicon, silicon oxycarbide and silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; mixtures of two or more of these; and these The film | membrane which consists of inorganic compounds, such as these hydrogen containing materials, is illustrated suitably.

Here, the functional film 10 of the present invention has an inorganic film 12 with extremely few cracks, peeling, defects and the like. Therefore, it is suitably used for applications where performance deterioration due to these is large, and particularly, it is suitably used for gas barrier films.
Therefore, the inorganic film 12 is preferably a film having gas barrier properties, and the inorganic compound that forms the inorganic film 12 is an inorganic compound that exhibits gas barrier properties such as silicon nitride, silicon oxide, silicon oxynitride, and aluminum oxide. Are preferably used. Among these, inorganic compounds containing silicon and nitrogen such as silicon nitride and silicon oxynitride are particularly suitable.

In FIG. 2, an example of the manufacturing method of the functional film of this invention is implemented, and an example of the plasma CVD apparatus which manufactures the functional film 10 of this invention is shown notionally.
A plasma CVD apparatus 14 (hereinafter, referred to as a CVD apparatus 14) shown in FIG. 2 conveys a long support Z (web-shaped film original fabric) in the longitudinal direction, and has a capacity on the surface of the support Z. The inorganic film 12 is formed (deposited) by coupled plasma CVD (CCP (Capacitively Coupled Plasma) -CVD) to produce the functional film 10 of the present invention such as a gas barrier film or various optical films.

  In the manufacturing method of the present invention, the formation of the inorganic film 12 is not limited to being performed by CCP-CVD, and various types of plasma CVD such as ICP-CVD (inductively coupled plasma CVD) can be used. is there.

The CVD apparatus 14 shown in FIG. 2 continuously feeds the support Z from a support roll Zr formed by winding a long support Z into a roll shape, and continuously conveys the support Z in the longitudinal direction. 12 is formed, and the support Z on which the inorganic film 12 is formed is wound around the take-up shaft 16 again in a roll shape, so that a so-called roll-to-roll (hereinafter referred to as RtoR) is used to make inorganic An apparatus for forming a film.
In addition, the manufacturing method of this invention is not limited to what utilizes RtoR using the elongate support body Z. FIG. That is, the present invention is a cut sheet-like support Z as long as the inorganic film 12 is formed by a plurality of plasma CVD means arranged in the transport direction while transporting the support Z forming the inorganic film 12. Alternatively, the inorganic film 12 may be formed. However, in consideration of productivity, it is preferable to form the inorganic film 12 by RtoR as shown in the illustrated example.

The CVD apparatus 14 includes a supply chamber 18, a film formation chamber 20, and a winding chamber 24.
In addition to the illustrated members, the CVD apparatus 14 includes various sensors, a pair of transport rollers, and a guide member that regulates the position of the support Z in the width direction. Various members of an apparatus for performing plasma CVD with RtoR may be provided on a long support Z such as the above member (conveying means).

The supply chamber 18 includes a rotating shaft 28, a guide roller 30, and a vacuum exhaust unit 32.
The support roll Zr around which the support Z is wound is mounted on the rotating shaft 28 of the supply chamber 18.
When the support roll Zr is mounted on the rotating shaft 28, the support Z is pulled out from the support roll Zr, and passes from the supply chamber 18 through the film forming chamber 20 to the winding shaft 14 of the winding chamber 24. The paper is passed through the transport path (through a predetermined transport path).
In the CVD apparatus 14, the feeding of the support Z from the support roll Zr and the winding of the support Z on the take-up shaft 14 of the take-up chamber 24 are performed in synchronization with each other to obtain a long support Z. In the film forming chamber 20, the inorganic film 12 is continuously formed on the support Z by CCP-CVD while being transported in the longitudinal direction along a predetermined transport path.

  The supply chamber 18 rotates the rotary shaft 28 counterclockwise in the figure by a drive source (not shown), feeds the support Z from the support roll Zr, guides a predetermined path by the guide roller 30, and supports the support Z. From the slit 34 a provided in the partition wall 34 to the film forming chamber 20.

In the illustrated CVD apparatus 14, as a preferred embodiment, a vacuum exhaust means 32 is provided in the supply chamber 18, and a vacuum exhaust means 70 is provided in the winding chamber 24. In the CVD apparatus 14, during formation, the pressure in the supply chamber 18 and the winding chamber 24 is maintained at a predetermined pressure corresponding to the pressure (formation pressure) in the film formation chamber 20 described later by the respective vacuum exhaust means. . This prevents the pressure in the adjacent chamber from affecting the pressure in the film forming chamber 20 (that is, formation in the film forming chamber 20).
The vacuum evacuation means 32 is not particularly limited, and includes a vacuum pump such as a turbo pump, a mechanical booster pump, a dry pump, and a rotary pump, an auxiliary means such as a cryocoil, a means for adjusting the ultimate vacuum level and the exhaust amount, and the like. Various known (vacuum) evacuation means used in the vacuum forming apparatus can be used. In this regard, the same applies to the other vacuum exhaust means 60 and 70 described later.

As described above, the support Z is guided by the guide roller 30 and is conveyed from the slit 34 a of the partition wall 34 to the film forming chamber 20.
The film forming chamber 20 is for forming (depositing) the inorganic film 12 formed in the region A and the region B on the surface of the support Z by CCP-CVD. As described above, the region B mainly constitutes the inorganic film 12, and the region A is thinner than the region B and has a lower density.
In the illustrated example, the film forming chamber 20 includes a drum 38, guide rollers 42, 46, 48 and 50, three film forming means 52 a, 52 b and 52 c for forming the inorganic film 12, and a vacuum exhaust means 60. .

  Although the CVD apparatus 14 in the illustrated example has three film forming units arranged in the transport direction of the support Z, the present invention is not limited to this, and there are two film forming units. Or you may have four or more film-forming means.

The drum 38 of the film forming chamber 20 is a hollow cylindrical member, and rotates in the direction of the arrow (clockwise) in the drawing around a rotation axis that coincides with the cylinder at the center line.
The drum 38 is rotated by a driving source (not shown) by wrapping the support Z guided by the guide rollers 42 and 46 in a predetermined path around a predetermined area on the surface (by a predetermined wrapping angle). Thus, the support Z is conveyed in the longitudinal direction while being positioned at a predetermined position.

In the production method of the present invention, the drum 38 that is wound around the support Z and acts also as a counter electrode in CCP-CVD. That is, an electrode pair for performing film formation by CCP-CVD is formed by the drum 38 and a shower electrode 40 (film formation electrode) of each film formation means described later.
Therefore, the drum 38 may be connected to a bias power source for supplying bias power, or may be grounded. Alternatively, the connection with the bias power source and the ground may be switched.
Further, the drum 38 may have a temperature adjusting means for adjusting the temperature of the peripheral surface that supports the support Z in order to cool and heat the support Z.

The film forming means 52a, 52b, and 52c all form the inorganic film 12 by CCP-CVD on the support Z that is wound around the drum 38 and conveyed.
The film forming means 52a, 52b, and 52c basically have the same configuration, and include the shower electrode 40, the high frequency power supply 54, and the gas supply means 58.
In addition, each film forming means includes an inlet mask 58a between the vicinity of the upstream end of the shower electrode 40 (the upstream side in the support conveyance direction and the same below) and the drum 38, and the vicinity of the downstream end of the shower electrode 40. And an exit mask 58a between the drum 38 and the drum 38 (see FIG. 3).

The shower electrode 40 is a known shower electrode (shower plate) that is used for film formation by CCP-CVD, in which a raw material gas is injected from the opposite surface of the support Z. In the film forming chamber 20, the shower electrode 40 and the drum 38 constitute an electrode pair for performing CCP-CVD as described above.
In the illustrated example, the shower electrode 40 has, for example, a substantially rectangular parallelepiped shape in which one surface is disposed facing the drum 38 (that is, the support Z) and a space (gas supply space) is formed therein. In addition, a large number of gas supply holes communicating with the internal space are formed on the surface of the shower electrode 40 facing the drum 38.
Further, in the illustrated example, the surface of the shower electrode 40 facing (facing) the drum 38 is parallel to the surface of the drum 38 (that is, the distance between the drum 38 and the shower electrode is uniform over the entire surface). Ii) a concave curved surface.

In the film forming chamber 20, the shower electrodes 40 of the respective film forming means are arranged in the conveying direction of the support Z, that is, the rotating direction of the drum 38.
That is, the CVD apparatus 14 in the illustrated example forms one inorganic film 12 by three film forming means by plasma CVD, and the support Z is wound around the drum 38 and conveyed, so that the CCP -The same inorganic film is formed three times at maximum by CVD, and the inorganic film 12 is formed on the surface.

The gas supply means 56 is a known gas supply means used in a vacuum forming apparatus such as a plasma CVD apparatus.
The gas supply means 56 supplies a source gas to the internal space of the shower electrode 40. As described above, a large number of gas supply holes communicating with the internal space are formed on the surface of the shower electrode 40 facing the drum 38. Therefore, the source gas supplied to the shower electrode 40 is supplied between the shower electrode 40 and the drum 38 through the gas supply hole.
The source gas (process gas / material gas) supplied by the gas supply means 56 may be a known gas corresponding to the inorganic film 12 to be formed. For example, when forming a silicon nitride film, the gas supply means 56 supplies silane gas, ammonia gas, and nitrogen gas (or hydrogen gas) as an example.

The high frequency power source 54 is a power source that supplies plasma excitation power to the shower electrode 40. The high-frequency power source 54 is also a known high-frequency power source that is used in various plasma CVD apparatuses such as a power source that supplies high-frequency power of 13.56 MHz.
The vacuum evacuation means 60 is for exhausting the inside of the forming chamber to maintain a predetermined pressure for film formation by plasma CVD. As described above, the known vacuum evacuation means used in the vacuum forming apparatus. It is.

In the manufacturing method of the present invention, there are no particular limitations on the film forming conditions of the inorganic film 12 such as the conveyance speed of the support Z, the forming pressure, the supply amount of the source gas, and the strength of the plasma excitation power. That is, the film formation conditions may be appropriately set according to the type and thickness of the inorganic film 12 to be formed, the type of the support Z, and the like, as in the case of film formation by normal plasma CVD.
When forming the inorganic film 12, the film forming means 52a, 52b and 52c basically perform film formation under the same film formation conditions. However, the present invention is not limited to this, and when forming the inorganic film 12, if necessary, one or more of the film forming units 52a, 52b, and 52c can be used to set other film forming units and film forming conditions. You may change it.

  As described above, the film forming means 52a, 52b, and 52c all include the inlet mask 58a between the vicinity of the upstream end of the shower electrode 40 and the drum 38, and the vicinity of the downstream end of the shower electrode 40 and the drum. 38, each having an exit mask 58a.

The inlet mask 58a is upstream control means for controlling the source gas flow that flows from the upstream side of the film formation region to the outside of the film formation region. Specifically, as schematically shown in FIG. 3 by taking the film forming means 52a as an example, the entrance mask 58a extends from the film forming region (the facing region between the shower electrode 40 and the support Z) to the shower electrode 40 (the formation electrode). The raw material gas flow flowing upstream of the membrane region is regulated. The inlet mask 58a of the most upstream film forming unit 52a is a control unit that controls the flow of the source gas flowing from the film forming region of the most upstream film forming unit to the upstream side of the shower electrode 40.
On the other hand, the outlet mask 58b is a downstream control unit that controls the flow of the source gas flowing from the downstream side of the film forming unit to the outside of the film forming region. Specifically, similarly, as schematically shown in FIG. 3, the outlet mask 58 b regulates the source gas flow that flows from the film formation region to the downstream side of the shower electrode 40.

  The film forming chamber 20 in the illustrated example has three film forming means 52a, 52b and 52c, and each film forming means has such an inlet mask 58a and an outlet mask 58b. Inorganic, mainly having the regions B in which the inorganic film 12 is formed and the regions A that are thinner and lower in density than the region B, and have one or more stacked structures of region B-region A-region B A film 12 is formed.

Since plasma CVD is a film formation that uses a raw material gas, a gas flow of a raw material gas (a raw material gas or an active radical serving as a film formation species) inevitably occurs from the film formation region to the outside of the film formation region.
Here, as schematically shown in FIG. 3 as an example of the film forming means 52a, the flow of the source gas flowing from the upstream side of the film forming region is regulated between the upstream and downstream ends of the shower electrode 40 and the drum 38. Provided with an inlet mask 58a and an outlet mask 58b that regulates the raw material gas flow flowing from the downstream side. The amount of gas flowing from the film formation region to the upstream and downstream of the film formation region is very small.

Therefore, in the film forming means 52a, the support Z is first formed with an inorganic film by the source gas leaked from the inlet mask 58a immediately upstream of the film forming region (inlet mask 58a). Here, the source gas leaking from the inlet mask 58a is a small amount. Further, outside the film formation region (upstream of the entrance mask 58a = outside the mask), no electric field is applied and no plasma is formed, so there are few active radicals (film formation species), and the density of the formed film is Lower. As a result, an extremely thin and very low density inorganic film, that is, region A is formed immediately upstream of the film formation region (entrance mask 58a).
Next, the support Z enters the film formation region, and an inorganic film is formed in the same manner as film formation by normal CCP-CVD. That is, in the film forming region of the film forming means 52a, a region B that mainly forms an inorganic film is formed.
Further, the support Z is unloaded from the film forming region of the film forming means 52a, and an inorganic film is formed by the source gas leaked from the outlet mask 58b immediately downstream of the film forming region (that is, the outlet mask 58a). . As before, the amount of the raw material gas leaking from the exit mask 58a is small, and the density of the film formed outside the film formation region is low. Therefore, the support Z is again extremely thin and has a very low density. The inorganic film, that is, the region A is formed.
The above operation is the same in the film forming means 52b and 52c.

As described above, the illustrated film forming chamber 20 includes three three film forming units 52a, 52b, and 52c. Further, the shower electrode 40 of each film forming means is arranged in the conveying direction of the support Z (the rotating direction of the drum 38) facing the drum 38.
Accordingly, in the support Z, first, the layer 12a as the region A is formed by the source gas leaked from the inlet mask 58a immediately upstream of the film formation region of the film formation unit 52a, and then the film formation of the film formation unit 52a. In the region, the layer 12b which is the region B is formed.
Here, since the layer 12a which is the region A is formed by the source gas leaked from the film formation region, the formation of the layer 12a does not damage the surface of the support Z due to plasma or the like. In addition, when the layer 12b, which is the region B mainly constituting the inorganic film 12, is formed, the layer 12a functions as a protective film. Therefore, a high-quality functional film in which damage to the support Z due to plasma for forming the layer 12b is suppressed can be manufactured.

Next, the support Z is formed with the layer 12c as the region A by the raw material gas leaked from the outlet mask 58b and the inlet mask 58a immediately downstream of the film forming means 52a and immediately upstream of the film forming region 52b. A layer 12d as the region B is formed in the film formation region of the film means 52b.
Next, in the support Z, the layer 12d as the region A is formed by the raw material gas leaked immediately downstream of the film forming unit 52b and immediately upstream of the film forming region 52c, and then the film forming region of the film forming unit 52c. The layer 12f which is the region B is formed.
Further, on the support Z, the layer 12g which is the region A is formed by the raw material gas leaked from the outlet mask 58b immediately downstream of the film forming unit 52c.
Thereby, the inorganic film 12 including the seven regions of the layers 12a to 12g in which the regions A and the regions B are alternately stacked as shown in FIG. 1 is formed.

As described above, film formation is performed while transporting the support Z as in the case of film formation by RtoR, and a plurality of film forming means are arranged in the transport direction of the support, and the entrance mask 58a and the exit mask 58b Thus, by providing a gas flow control means for controlling the raw material gas flow that flows from the film formation region to the outside of the film formation region on the upstream and downstream sides of the film formation region, the region A and the region B are alternately stacked, and The functional film of the present invention having at least one layered structure of region B-region A-region B, and preferably having at least one layered structure of region A-region B-region A can be preferably produced. it can.
Further, in this example, the amount of the source gas flow flowing from the film formation region to the outside of the film formation region, such as adjustment of the gap between the inlet mask 58a and / or the outlet mask 58b and the drum 38, is used. Further, the density, thickness, etc. of the region A can be adjusted by adjusting by controlling exhaust or the like. For example, the density of the region A can be increased and the thickness can be increased by increasing the amount of the source gas flow flowing from the film formation region to the outside of the film formation region.
Further, by adjusting the structure of the film forming chamber 20, the density and thickness of the region A can be adjusted in the same manner.

  The support Z on which the inorganic film 12 is formed, that is, the functional film 10 is guided by the guide rollers 48 and 50 and conveyed from the slit 64 a of the partition wall 64 to the winding chamber 24.

In the illustrated example, the winding chamber 24 includes a guide roller 68, a winding shaft 14, and a vacuum exhaust unit 70.
The support Z transported to the winding chamber 24 is guided by the guide roller 68 and transported to the winding shaft 14. The support Z is wound into a roll shape by the winding shaft 14 and winds a functional film such as a gas barrier film. The resulting roll is subjected to the next step.
Similarly to the previous supply chamber 18, the evacuation means 70 is also arranged in the winding chamber 24. During the formation, the winding chamber 24 is also decompressed to a degree of vacuum corresponding to the forming pressure in the film forming chamber 20. .

Hereinafter, the operation of the CVD apparatus 14 will be described.
When the support roll Zr is mounted on the rotary shaft 28, the support Z is pulled out from the support roll Zr. The support drawn from the support roll Zr is guided by the guide roller 30 to the film forming chamber 20, and is guided by the guide rollers 42 and 46 in the film forming chamber 20 to reach a predetermined region on the surface of the drum 38. Then, the paper is guided by guide rollers 48 and 50 to reach the take-up chamber 24. In the take-up chamber 24, the paper is passed through a predetermined conveyance path that is guided by the guide roller 68 and reaches the take-up shaft 14. The

When the feeding of the support Z is completed, the supply chamber 18, the film forming chamber 20, and the winding chamber 24 are closed (sealed). Next, the vacuum evacuation means 32, 60, and 70 are driven, and the supply chamber 18, the film forming chamber 20, and the winding chamber 24 are depressurized to a predetermined pressure. When the pressure in each chamber is stabilized, in the film forming chamber 20, the source gas is supplied from the gas supply means 56 to the shower electrode 40 in the film forming means 52a, 52b and 52c.
When the inside of the film forming chamber 20 is stabilized at a predetermined pressure corresponding to the formation, the conveyance of the support Z from the supply chamber 18 toward the winding chamber 24 is started, and the high-frequency power source is formed in the film forming units 52a, 52b and 52c. Supply of plasma excitation power from 54 to the shower electrode 40 is started.

  The support Z transported from the supply chamber 18 to the film forming chamber 20 is guided by the guide rollers 42 and 46 and transported while being wound around the drum 38, while being deposited in the transport direction. As described above, the layers 12a to 12g are sequentially formed by the layers 52b and 52c to form the inorganic film 12.

The support Z on which the inorganic film 12 is formed, that is, the functional film 10 is guided by the guide rollers 48 and 50 and conveyed to the winding chamber 24.
The support Z conveyed to the winding chamber 24 is guided to a predetermined path by the guide roller 68 and is wound in a roll shape by the winding shaft 14.

In the CVD apparatus 14 shown in FIGS. 2 and 3, all of the film forming means 52a, 52b and 52c have the entrance mask 58a and the exit mask 58b, but the present invention is not limited to this.
For example, it does not have either the outlet mask 58b of the film forming unit 52a or the inlet mask 58a of the film forming unit 52b, and further, either of the outlet mask 58b of the film forming unit 52b or the inlet mask 58a of the film forming unit 52c. Even if it is a structure which does not have, the inorganic film 12 which consists of seven layers of the layer 12a-layer 12b shown in FIG. 1 can be formed.

Further, when the inlet mask 58a of the most upstream film forming means 52a is not provided, the inorganic film 12 shown in FIG. 1 is composed of six layers 12b to 12g having no lowermost layer 12a. An inorganic film can be formed. However, as described above, it is preferable to form the region A on the surface of the support Z.
Further, when the outlet mask 58b of the most downstream film forming means 52c is not provided, the inorganic film 12 shown in FIG. 1 includes the six layers 12a to 12f that do not have the uppermost layer 12g. An inorganic film can be formed.

Further, the CVD apparatus 14 is not limited to driving all of the film forming units 52a, 52b and 52c, and may drive two or more.
That is, by not driving any one (by eliminating), an inorganic film composed of five layers of the layers 12a to 12e can be formed in the inorganic film 12 shown in FIG.

In the manufacturing method of the present invention, the control means for controlling the flow of the source gas flowing from the film formation region to the outside is not limited to the mask for regulating the flow of the source gas as shown in the illustrated example.
For example, by adjusting the supply direction of the source gas and the exhaust direction, the source gas flow flowing from the deposition region to the outside is controlled, and the region A is deposited immediately upstream and / or immediately downstream of the deposition region. You may make it do. Further, the adjustment of the electric field on the upstream side and the downstream side of the film formation electrode is regarded as a control means for controlling the source gas flow flowing from the film formation region to the outside, and the region A is set upstream and / or downstream of the film formation region. A film may be formed.

  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.

[Example 1]
A gas barrier film was manufactured by forming a silicon nitride film on the surface of the support Z using a CVD apparatus 14 as shown in FIG.

The drum 38 was made of stainless steel and had a diameter of 1500 mm. The drum 38 has a built-in temperature adjusting means, and the surface temperature of the drum 38 was adjusted to 10 ° C. during film formation.
As the support Z, a PET film having a width of 100 cm and a thickness of 70 μm was used.
Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), hydrogen gas (H ₂ ), and nitrogen gas (N ₂ ) were used as source gases. The film forming pressure was 100 Pa.
The shower electrode 40 was supplied with 3 kW of plasma excitation power from a high frequency power source 54 at a frequency of 13.5 MHz.

  Under the above conditions, the film forming means 52a and 52b were driven to form a silicon nitride film having a thickness of about 100 nm on the surface of the support Z, thereby producing a gas barrier film.

When measured by observing the cross-sectional structure with TEM, the silicon nitride film was composed of five layers of layers 12a to 12e in the inorganic film 12 shown in FIG. That is, this silicon nitride film has one laminated structure of region B-region A-region B and two laminated structures of region A-region B-region A.
In addition, the thickness of the layers 12a and 12e as the region A was about 5 nm, the thickness of the layer 12c was about 10 nm, and the thickness of the layers 12b and 12d as the region B was about 40 nm.

[Example 2]
All of the film forming means 52a, 52b and 52c were driven to form a silicon nitride film having a thickness of about 100 nm in the same manner as in Example 1 to produce a gas barrier film. The film thickness was adjusted by the conveyance speed of the support Z.
When measured in the same manner as in Example 1, the silicon nitride film was composed of seven layers 12a to 12g similar to the inorganic film 12 shown in FIG. That is, this silicon nitride film has two laminated structures of region B-region A-region B and three laminated structures of region A-region B-region A.
Further, the thickness of the layers 12a and 12g as the region A was about 5 nm, the thickness of the layers 12c and 12e was about 10 nm, and the thickness of the layers 12b, 12d and 12f as the region B was about 23 nm. .

[Comparative Example 1]
Only the film forming means 52a was driven to form a silicon nitride film having a thickness of about 100 nm in the same manner as in Example 1 to produce a gas barrier film. The film thickness was adjusted by the conveyance speed of the support Z as in the previous example.
When measured in the same manner as in Example 1, the silicon nitride film was composed of three layers 12a to 12c in the inorganic film 12 shown in FIG. Further, the thickness of the layers 12a and 12c in the region A was about 5 nm, and the thickness of the layer 12b in the region B was about 90 nm.

[Comparative Example 2]
Only the film forming means 52a was driven to form a silicon nitride film having a thickness of about 100 nm in the same manner as in Example 1 to produce a gas barrier film. In this example, the outlet mask 58b of the film forming means 52a is removed. The film thickness was adjusted by the conveyance speed of the support Z as in the previous example.
When measured in the same manner as in Example 1, the silicon nitride film was composed of two layers, layers 12a and 12b, in the inorganic film 12 shown in FIG. Further, the thickness of the layer 12a as the region A was about 5 nm, and the thickness of the layer 12b as the region B was about 95 nm.

[Comparative Example 3]
Two of the film forming means 52a and 52b were driven to form a silicon nitride film having a thickness of about 100 nm in the same manner as in Example 1 to produce a gas barrier film. In this example, the inlet mask 58a and the outlet mask 58b of the film forming means 52a and 52b are removed.
When measured in the same manner as in Example 1, the silicon nitride film was formed only in the region B.

The gas barrier properties and adhesion of the produced five types of gas barrier films were measured.
The gas barrier property was measured by measuring the water vapor transmission rate [g / (m ² · day)] by the Mocon method. In addition, the water vapor | steam permeability | transmittance was measured by the calcium corrosion method (method described in Unexamined-Japanese-Patent No. 2005-283561) as the example which exceeded the measurement limit of the mocon method.

The adhesion was measured by peeling the inorganic film by a tape peeling test.
Rank A in which the inorganic film did not peel at all by the tape peeling test;
Rank B where a part of the inorganic film was peeled off by the tape peeling test;
By the tape peeling test, the inorganic film peeled off was evaluated as Rank C;
The results are shown in the table below.

As shown in the above table, Example 1 and the implementation relating to the functional film of the present invention having one or more layered structures of region B-region A-region B and region A-region B-region A All of the gas barrier films of Example 2 have excellent gas barrier properties, and further have high adhesion of inorganic films.
On the other hand, the gas barrier films of Comparative Example 1 and Comparative Example 2 that have the laminated structure of the region A and the region B but do not have the laminated structure of the region B, the region A, and the region B have a gas barrier property and an inorganic film. The adhesiveness of both is insufficient. Furthermore, the gas barrier film of Comparative Example 3 that does not have a laminated structure of the region A and the region B has both low gas barrier properties and inorganic film adhesion.
From the above results, the effects of the present invention are clear.

  It can use suitably for manufacture of various functional films and functional films, such as a gas barrier film and an antireflection film.

DESCRIPTION OF SYMBOLS 10 Functional film 12 Inorganic film 14 (Plasma) CVD apparatus 16 Winding shaft 18 Supply chamber 20 Formation chamber 24 Winding chamber 28 Rotating shaft 30, 42, 46, 48, 50, 68 Guide roller 32, 60, 70 Vacuum exhaust Means 34, 64 Partition 38 Drum 40 Shower electrodes 52a, 52b, 52c Film forming means 54 High frequency power source 56 Gas supply means 58a Inlet mask 58b Outlet mask

Claims (12)

A functional film having a support and an inorganic film formed on the support,
The inorganic film, region B, and has a low density and thin region A than the region B, and one or more of the laminated structure of the laminated in the thickness direction region B- region A- region B, the thickness Having one or more stacked structures of region A-region B-region A stacked in the vertical direction;
The region A gradually increases in density toward the adjacent region B,
Furthermore, it has the said area | region A on the surface of the said support body, The functional film characterized by the above-mentioned . The functional film according to claim 1 , wherein a density of the region A is a and a density of the region B is b, which satisfies “0.6 <a / b <1”. The functional film according to claim 1 , wherein the inorganic film contains silicon and nitrogen. The functional film according to claim 1 , wherein the thickness of the laminated structure of the region B, the region A, and the region B is 10 to 200 nm. The functional film according to claim 1 , wherein a thickness of the laminated structure of the region A, the region B, and the region A is 5 to 100 nm. The functional film according to claim 1 , wherein the inorganic film has gas barrier properties. While transporting the support, the same inorganic film is formed by a plurality of film forming means by plasma CVD arranged in the transport direction of the support,
In the film forming means continuous in the transport direction of the support, the downstream control means for controlling the gas flow from the downstream side of the film forming area of the upstream film forming means to the outside of the film forming area, and the downstream forming means. At least one of the upstream control means for controlling the gas flow from the upstream side of the film formation area of the film means to the outside of the film formation area; and
A method for producing a functional film , wherein the inorganic film is formed using a control unit that controls a gas flow from the upstream side of the film formation region to the outside of the film formation region of the most upstream film formation unit. . The method for producing a functional film according to claim 7, wherein the inorganic film is formed using both the downstream control unit and the upstream control unit. The method for producing a functional film according to claim 7 or 8 , wherein the control means for controlling the gas flow is a mask for regulating the gas flow. The method for producing a functional film according to any one of claims 7 to 9 , wherein an inorganic film is formed by the plurality of film forming means while conveying the long support in the longitudinal direction. The method for producing a functional film according to claim 10 , wherein the support is fed out from a support roll formed by winding the long support, and the formed support is wound into a roll again. . A cylindrical drum that conveys the long support by winding the long support around a circumferential surface of the long support is rotated on the circumferential surface, and the plurality of film forming units are arranged around the periphery of the drum. The manufacturing method of the functional film of Claim 10 or 11 arrange | positioned facing a surface.

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