WO2013035682A1 - Functional film and method of producing functional film - Google Patents
Functional film and method of producing functional film Download PDFInfo
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- WO2013035682A1 WO2013035682A1 PCT/JP2012/072431 JP2012072431W WO2013035682A1 WO 2013035682 A1 WO2013035682 A1 WO 2013035682A1 JP 2012072431 W JP2012072431 W JP 2012072431W WO 2013035682 A1 WO2013035682 A1 WO 2013035682A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
- C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
Definitions
- 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 are used in parts and parts that require moisture-proof properties in optical devices, display devices such as liquid crystal displays and organic EL displays, various semiconductor devices, and various devices such as solar cells. Gas barrier films are also used for packaging materials for packaging food, electronic parts, and the like.
- 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.
- PET polyethylene terephthalate
- inorganic films films made of inorganic compounds
- 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.
- 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.
- 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.
- the density of the inorganic film (silicon oxynitride film) near the interface on the support side is A
- the density of the region excluding the vicinity of the interface is B
- the inorganic film is 0.905.
- 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.
- the inorganic film described in Patent Literature 1 has a density distribution as described above, so that the structure inside the inorganic film is not simple but complicated.
- the structure inside the inorganic film is complicated by the presence of portions having different densities inside the inorganic film.
- 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.
- 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.
- 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.
- the functional film of the present invention is a functional film having a support and an inorganic film formed on the support, and the inorganic film includes the region B and this film.
- 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.
- the thickness of the layered structure of region B-region A-region B is preferably 10 to 200 nm.
- the thickness of the layered structure of region A-region B-region A is preferably 5 to 100 nm.
- the inorganic film preferably has a gas barrier property.
- the method for producing a functional film of the present invention forms the same inorganic film by a plurality of film forming means by plasma CVD arranged in the transport direction of the support while transporting 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 film forming area of the downstream film forming means
- An inorganic film is formed using at least one of upstream control means for controlling the gas flow from the upstream side to the outside of the film formation region.
- the inorganic film is formed using a control means for controlling the gas flow from the upstream side of the film formation area of the uppermost film formation means to the outside of the film formation area. Preferably it is done. In addition, it is preferable to form the inorganic film using both the downstream control means and the upstream control means. Moreover, it is preferable that the control means for controlling the gas flow is a mask for regulating the gas flow. Further, it is preferable to use a long support as the support, and form the inorganic film by a plurality of film forming means while transporting the long support in the longitudinal direction.
- the support is sent out from a support roll formed by winding a long support and transported, and the formed support is wound again in a roll shape.
- a cylindrical drum that conveys the long support by winding the long support around the circumferential surface of the long support is rotated on the circumferential surface. It is preferable that they are arranged to face each other.
- the functional film of the present invention having the above-described configuration is a functional film having an inorganic film on a plastic film.
- the inorganic film mainly forms an inorganic film in the thickness direction.
- the functional film of the present invention preferably also has one or more laminated structures of region A, region B, and region A.
- the film stress of the entire inorganic film can be reduced / controlled by the buffering effect of the region A. For this reason, even with a high-density (dense) inorganic film, it is possible to greatly prevent the occurrence of cracks and peeling due to an unbalance of film stress. 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 functional film of the present invention for a gas barrier film, a gas barrier film having excellent gas barrier performance can be obtained.
- 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.
- the control means controls the upstream and downstream ends of the formation region by the plasma CVD.
- 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.
- the functional film 10 of the present invention is not limited to the one having only the support Z and the inorganic film 12. That is, as long as the functional film 10 of the present invention has the support Z and the inorganic film 12 formed thereon, various layer configurations can be used.
- 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.
- a layer (film) for obtaining various functions such as a protective layer, an adhesive layer, a light reflecting layer, a light shielding layer, a planarizing layer, a buffer layer, and a stress relaxation layer is formed instead of the organic film.
- An object may be used as the support Z. Or you may use the thing in which the layer for obtaining these various functions is formed in the lower layer and / or upper layer of an organic film as the support body Z.
- 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.
- a plurality of laminated structures of an organic film as a base layer and the inorganic film 12 formed on the surface of the organic film may be repeatedly provided.
- a plurality of laminated structures of the base organic film and the inorganic film 12 may be repeatedly provided, and an organic film as a protective layer may be formed on the uppermost layer.
- each inorganic film 12 may be the same or different.
- the organic films may be the same or different.
- 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.
- 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, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, or polysiloxane, etc.
- polyester acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide,
- An organic silicon compound film is preferably exemplified.
- 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 from the viewpoint of excellent strength and the like.
- an organic film containing an acrylic resin or a methacrylic resin which is mainly composed of a polymer of an acrylate and / or methacrylate monomer or oligomer, in addition to the aforementioned strength, in that it has a low refractive index and excellent optical properties.
- 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.
- 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.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- polyethylene polypropylene
- polystyrene polyamide
- polyvinyl chloride polycarbonate
- polyacrylonitrile polyacrylonitrile
- polyimide polyacrylate
- polymethacrylate Resin film
- the functional film 10 of the present invention is obtained by forming the inorganic film 12 on the support Z.
- the inorganic film 12 is a film made of an inorganic compound.
- 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).
- the inorganic film 12 is a film composed of seven layers (seven regions) of the layers 12a to 12g.
- the layers 12a, 12c, 12e and 12g are thinner and have a lower density than the layers 12b, 12d and 12f.
- 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.
- the layers 12b, 12d, and 12f are the region B in the present invention, and mainly constitute the inorganic film 12.
- 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 region A may have a region in which the density changes continuously (gradually) in the thickness direction.
- the density of the region A may change continuously throughout the thickness direction.
- the layers 12a, 12c, 12e, and 12g have basically the same density
- the layers 12b, 12d, and 12f have basically the same density.
- the functional film of the present invention has at least one layered structure of region B-region A-region B composed of regions (layers) having different densities and thicknesses, preferably region A-region B. -Having at least one layered structure of region A;
- the functional film of the present invention can reduce / control the film stress of the entire inorganic film mainly by the buffering effect of the area A between the areas 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.
- the low-density region A is formed prior to the formation of the region B on the surface of the support Z. Therefore, it is possible to prevent the support Z from being damaged mainly by plasma or the like for forming the region B constituting the inorganic film 12, and to improve the adhesion between the support Z and the inorganic film 12.
- the configuration of the inorganic film 12 is not limited to the illustrated example. That is, it has regions A and B alternately in the thickness direction, and has one or more layered structures of region B-region A-region B, preferably a stack of region A-region B-region A Various configurations can be used as long as they have one or more structures.
- 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.
- the functional film 10 of the present invention preferably has one or more laminated structures of region A, region B and region A.
- the inorganic film may be composed of four layers (four regions) of layers 12a to 12d.
- the inorganic film may be composed of five layers 12a to 12e.
- 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.
- membrane which has the area
- the density of the region A and the region B is not particularly limited.
- the density of the region A and the region B may be appropriately set according to the use of the functional film 10 and the inorganic compound forming the inorganic film 12.
- the inorganic film 12 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”.
- 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.
- the thickness of the inorganic film 12 is not particularly limited.
- the thickness of the inorganic film 12 is appropriately determined according to the use of the functional film 10, the performance required for the functional film 10 (inorganic film 12), the inorganic compound forming the inorganic film 12, the required productivity, and the like. , You can set.
- the thickness of the region A-region B-region A is preferably 5 to 100 nm.
- the thickness of the region B-region A-region B is preferably 10 to 200 nm.
- the regions A may have the same or different thickness.
- 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. 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.
- 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.
- 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 carbide such as silicon carbide; hydrides thereof; a mixture of two or more of these; and these
- membrane which consists of inorganic compounds, such as these hydrogen containing materials, is illustrated suitably.
- 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.
- 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.
- CCP Capacitively Coupled Plasma
- 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.
- RtoR roll-to-roll
- the manufacturing method of this invention is not limited to what utilizes RtoR using the elongate support body Z.
- the present invention provides 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 that forms the inorganic film 12.
- the inorganic film 12 may be formed.
- the CVD apparatus 14 includes a supply chamber 18, a film formation chamber 20, and a winding chamber 24.
- 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.
- the support Z is pulled out from the support roll Zr, passes through the film forming chamber 20 from the supply chamber 18, and reaches the winding shaft 16 of the winding chamber 24.
- the paper is passed through the transport path (through a predetermined transport path).
- the feeding of the support Z from the support roll Zr and the winding of the support Z on the winding shaft 16 of the winding chamber 24 are performed in synchronization, so that the long support Z is formed.
- the inorganic film 12 is continuously formed on the support Z by CCP-CVD in the film forming chamber 20 while being transported in the longitudinal direction along a predetermined transport path.
- 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.
- 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.
- 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.
- 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.
- the region B mainly constitutes the inorganic film 12, and the region A is thinner than the region B and has a lower density.
- 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. .
- the CVD apparatus 14 in the illustrated example is arranged in the transport direction of the support Z and has three film forming means.
- the production method of the present invention is not limited to this, and the number of film forming means may be two, or four or more film forming means may be provided.
- 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) after the support Z guided by the guide rollers 42 and 46 is hung on a predetermined area on the surface (around a predetermined winding angle).
- the drum 38 conveys the support Z in the longitudinal direction while being positioned at a predetermined position.
- the drum 38 that is wound around and supported by the support Z also functions 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.
- Each of the film forming means 52a, 52b and 52c forms the inorganic film 12 by CCP-CVD on the support Z which 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.
- 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 58b between the drum 38 and the drum 38 (see FIG. 3).
- the shower electrode 40 is a known shower electrode (shower plate) used for film formation by CCP-CVD, in which a raw material gas is injected from the opposing surface of the support Z.
- the shower electrode 40 and the drum 38 constitute an electrode pair for performing CCP-CVD as described above.
- 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.
- 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.
- the surface of the shower electrode 40 facing (facing) the drum 38 is a concave curved surface so as to be parallel to the surface of the drum 38. That is, the surface of the shower electrode 40 facing the drum 38 is a concave curved surface so that the distance between the drum 38 and the shower electrode is uniform over the entire surface.
- 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 illustrated CVD apparatus 14 forms one inorganic film 12 by three film forming means by plasma CVD. Accordingly, the support Z is wound around the drum 38 and conveyed, so that the same inorganic film is formed three times at maximum by CCP-CVD, and the inorganic film 12 is formed on the surface.
- 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.
- 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.
- the film forming means 52a, 52b and 52c basically perform film formation under the same film formation conditions.
- 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.
- the film forming means 52a, 52b, and 52c all include the entrance 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 58b.
- 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.
- 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.
- 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 thus has three film forming means, film forming means 52a, 52b and 52c, and each film forming means has such an inlet mask 58a and an outlet mask 58b.
- the film forming chamber 20 has alternately the regions B in which the inorganic film 12 is mainly formed and the regions A that are thinner and less dense than the regions B, and the regions B ⁇ An inorganic film 12 having at least one layered structure of region A and region B is formed.
- 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.
- 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. If the inlet mask 58a and the outlet mask 58b for restricting the raw material gas flow flowing from the downstream side are provided, the amount of gas flowing from the film formation region to the upstream and downstream of the film formation region becomes very small.
- 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).
- the source gas leaking from the inlet mask 58a is a small amount.
- 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.
- 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).
- 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 unit 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 58b). . Similarly to the above, since the source gas leaking from the exit mask 58b is small, and the density of the film formed outside the film formation region is low, the support Z is again very 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.
- 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.
- 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.
- the layer 12b which is the region B mainly constituting the inorganic film 12
- 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.
- 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.
- the support Z is formed with the layer 12d 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 52b and immediately upstream of the film forming region 52c.
- the layer 12f which is the region B is formed.
- 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
- 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.
- the amount of the source gas flow flowing from the film formation region to the outside of the film formation region is used.
- 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 64a of the partition wall 64 to the winding chamber 24.
- the winding chamber 24 includes a guide roller 68, a winding shaft 16, 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 16, wound around the winding shaft 16 in a roll shape, and wound with a functional film such as a gas barrier film.
- the resulting roll is subjected to the next step.
- the evacuation means 70 is also arranged in the winding chamber 24.
- the winding chamber 24 is also decompressed to a degree of vacuum corresponding to the forming pressure in the film forming chamber 20. .
- the supply chamber 18, the film forming chamber 20, and the winding chamber 24 are closed (sealed).
- 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.
- 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.
- the support Z transported from the supply chamber 18 to the film forming chamber 20 is guided by guide rollers 42 and 46, and transported while being wound around the drum 38, while being deposited in the transport direction, the film forming means 52a, By the layers 52b and 52c, the layers 12a to 12g are sequentially formed as described above 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 16.
- 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.
- 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.
- the inorganic film 12 including the seven layers 12a to 12b shown in FIG. 1 can be formed.
- the inorganic film 12 shown in FIG. 1 includes the six layers 12b to 12g that do not have the lowest 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 is composed of six layers 12a to 12f having no uppermost layer 12g. An inorganic film can be formed.
- 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 of them, it is possible to form an inorganic film composed of five layers 12a to 12e in the inorganic film 12 shown in FIG.
- 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.
- 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.
- 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 raw material gas flow flowing from the film formation region to the outside, and the region A is formed upstream and / or downstream of the film formation region.
- a film may be formed.
- 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 ⁇ m 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.
- two of 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.
- the silicon nitride 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.
- 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
- 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.
- 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.
- 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
- the thickness of the layers 12b, 12d and 12f as the region B was about 23 nm. .
- 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.
- 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.
- 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.
- the outlet mask 58b of the film forming means 52a is removed.
- the film thickness was adjusted with the conveyance speed of the support body Z like the previous example.
- 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.
- 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.
- the water vapor transmission rate was measured by a calcium corrosion method (a method described in JP-A-2005-283561).
- 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.
- Example 1 and Example relating to the functional film of the present invention having one or more layer B-region A-region B laminate structures and region A-region B-region A laminate structures
- All of the gas barrier films of Example 2 have excellent gas barrier properties, and further have high adhesion of inorganic films.
- 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.
- 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.
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Abstract
A functional film which comprises a support body and an inorganic membrane and which has less damage to the support body, has good adhesiveness of the inorganic membrane, and also suppresses occurrence of cracks and peeling due to compressive stress of the compact inorganic membrane, and a method of producing said functional film are provided. The inorganic membrane of the functional film comprises B regions and A regions thinner and less dense than the B regions, and has one or more (B region)-(A region)-(B region) laminate structures, wherein the inorganic membrane is formed while controlling the flow of gas from a membrane formation region to the outside by means of multiple plasma CVDs.
Description
本発明は、ガスバリアフィルム等の機能性フィルム、および、この機能性フィルムの製造方法に関する。
The present invention relates to a functional film such as a gas barrier film and a method for producing the functional film.
光学素子、液晶ディスプレイや有機ELディスプレイなどの表示装置、各種の半導体装置、太陽電池等の各種装置において防湿性が必要な部位や部品に、ガスバリアフィルムが利用されている。また、食品や電子部品等を包装する包装材料などにも、ガスバリアフィルムが利用されている。
ガスバリアフィルムは、一般的に、ポリエチレンテレフタレート(PET)フィルム等のプラスチックフィルムを支持体(基板)として、その上に、ガスバリア性を発現する膜(ガスバリア膜)を形成してなる構成を有する。 Gas barrier films are used in parts and parts that require moisture-proof properties in optical devices, display devices such as liquid crystal displays and organic EL displays, various semiconductor devices, and various devices such as solar cells. Gas barrier films are also used for packaging materials for packaging food, electronic parts, and the like.
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.
ガスバリアフィルムは、一般的に、ポリエチレンテレフタレート(PET)フィルム等のプラスチックフィルムを支持体(基板)として、その上に、ガスバリア性を発現する膜(ガスバリア膜)を形成してなる構成を有する。 Gas barrier films are used in parts and parts that require moisture-proof properties in optical devices, display devices such as liquid crystal displays and organic EL displays, various semiconductor devices, and various devices such as solar cells. Gas barrier films are also used for packaging materials for packaging food, electronic parts, and the like.
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.
また、ガスバリア性を発現する膜としては、各種の無機膜(無機化合物からなる膜)が知られている。
具体的には、窒化珪素、酸化珪素、酸化窒化珪素、酸化アルミニウム等の無機膜が、ガスバリアフィルムに利用されている。 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.
具体的には、窒化珪素、酸化珪素、酸化窒化珪素、酸化アルミニウム等の無機膜が、ガスバリアフィルムに利用されている。 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.
ここで、ガスバリアフィルムに利用される無機膜には、支持体(下層)との密着性等にも優れることが要求される。
また、無機膜にクラックや剥離等の欠陥部が有ると、ガスバリア性が大きく低下してしまう。そのため、高いガスバリア性能を得るためには、ガスバリアフィルムに形成される無機膜は、クラック、剥離、欠陥部等が無い(少ない)ことが要求される。
このような要求を満たすために、ガスバリア性を有する無機膜を形成してなるガスバリアフィルムにおいて、各種の提案が成されている。 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.
また、無機膜にクラックや剥離等の欠陥部が有ると、ガスバリア性が大きく低下してしまう。そのため、高いガスバリア性能を得るためには、ガスバリアフィルムに形成される無機膜は、クラック、剥離、欠陥部等が無い(少ない)ことが要求される。
このような要求を満たすために、ガスバリア性を有する無機膜を形成してなるガスバリアフィルムにおいて、各種の提案が成されている。 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.
例えば、特許文献1には、支持体(合成樹脂シート)の上に、ガスバリア性を有する無機膜として酸化窒化珪素を形成してなるガスバリアフィルムにおいて、無機膜の密度分布を調整したガスバリアフィルムが記載されている。
具体的には、特許文献1には、無機膜(酸化窒化珪素膜)の支持体側の界面付近の密度をA、この界面付近を除いた領域の密度をBとして、無機膜が、0.905≦A/B<1.000の関係を有する、膜厚方向で連続した1層の蒸着層であるガスバリアフィルムが記載されている。 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.
具体的には、特許文献1には、無機膜(酸化窒化珪素膜)の支持体側の界面付近の密度をA、この界面付近を除いた領域の密度をBとして、無機膜が、0.905≦A/B<1.000の関係を有する、膜厚方向で連続した1層の蒸着層であるガスバリアフィルムが記載されている。 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.
特許文献1に記載されるガスバリアフィルムでは、無機膜が上述のような密度分布を有することにより、無機膜内部の構造を単純なものでは無く、複雑化している。言い換えれば、特許文献1に記載されるガスバリアフィルムでは、無機膜内部に密度が異なる部分が存在することにより、無機膜内部の構造を複雑化している。
特許文献1に記載されるガスバリアフィルムは、この無機膜の内部構造の複雑化によって、水蒸気の透過を妨げる機能を発現し、高いガスバリア性を発現している。 In the gas barrier film described in Patent Literature 1, the inorganic film has a density distribution as described above, so that the structure inside the inorganic film is not simple but complicated. In other words, in the gas barrier film described in Patent Document 1, the structure inside the inorganic film is complicated by the presence of portions having different densities inside the inorganic film.
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.
特許文献1に記載されるガスバリアフィルムは、この無機膜の内部構造の複雑化によって、水蒸気の透過を妨げる機能を発現し、高いガスバリア性を発現している。 In the gas barrier film described in Patent Literature 1, the inorganic film has a density distribution as described above, so that the structure inside the inorganic film is not simple but complicated. In other words, in the gas barrier film described in Patent Document 1, the structure inside the inorganic film is complicated by the presence of portions having different densities inside the inorganic film.
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.
しかしながら、このような低密度な領域を形成した後に、高密度な領域を形成してなる無機膜では、膜厚や無機膜の組成によっては、必要な膜厚を形成する際に、全体の膜応力のバランスが崩れ易く、膜のクラックや剥離が生じ易い。
この傾向は、高いガスバリア性が得られる緻密な無機膜ほど、高くなる。 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.
この傾向は、高いガスバリア性が得られる緻密な無機膜ほど、高くなる。 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.
また、無機膜の形成途中で膜内でクラックや欠陥部が生じてしまった場合は、クラックや欠陥が、そのまま成長してしまうことが多い。
この場合には、形成された無機膜に、大きなクラックや欠陥が残存する結果となり、ガスバリア性能が、大幅に低下してしまう。 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.
この場合には、形成された無機膜に、大きなクラックや欠陥が残存する結果となり、ガスバリア性能が、大幅に低下してしまう。 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.
本発明の目的は、前記従来技術の問題点を解決することにあり、プラスチックフィルム等の支持体の上に無機膜を形成してなる、ガスバリアフィルムなどの機能性フィルムにおいて、支持体と無機膜との密着性に優れ、かつ、無機膜のクラック、剥離および欠陥部等を大幅に低減し、さらに、無機膜を形成する際の支持体のダメージも、大幅に低減することが可能な機能性フィルム、および、このような高性能な機能性フィルムを好適に製造できる製造方法を提供することにある。
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.
前記目的を達成するために、本発明の機能性フィルムは、支持体と、支持体の上に形成された無機膜とを有する機能性フィルムであって、無機膜は、領域B、および、この領域Bよりも低密度かつ薄い領域Aを有し、さらに、厚さ方向に積層された領域B-領域A-領域Bの積層構造を、1以上有することを特徴とする機能性フィルムを提供する。
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, and the inorganic film includes the region B and this film. Provided is a functional film having a region A having a density lower than that of 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. .
このような本発明の機能性フィルムにおいて、無機膜が、さらに、厚さ方向に積層された領域A-領域B-領域Aの積層構造を、1以上有するのが好ましい。
また、領域Aの密度をa、領域Bの密度をbとした際に、『0.6<a/b<1』を満たすのが好ましい。
また、無機膜が、珪素と窒素とを含むのが好ましい。
また、領域B-領域A-領域Bの積層構造の厚さが10~200nmであるのが好ましい。
また、領域A-領域B-領域Aの積層構造の厚さが5~100nmであるのが好ましい。
さらに、無機膜がガスバリア性を有するのが好ましい。 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.
The thickness of the layered structure of region B-region A-region B is preferably 10 to 200 nm.
The thickness of the layered structure of region A-region B-region A is preferably 5 to 100 nm.
Furthermore, the inorganic film preferably has a gas barrier property.
また、領域Aの密度をa、領域Bの密度をbとした際に、『0.6<a/b<1』を満たすのが好ましい。
また、無機膜が、珪素と窒素とを含むのが好ましい。
また、領域B-領域A-領域Bの積層構造の厚さが10~200nmであるのが好ましい。
また、領域A-領域B-領域Aの積層構造の厚さが5~100nmであるのが好ましい。
さらに、無機膜がガスバリア性を有するのが好ましい。 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.
The thickness of the layered structure of region B-region A-region B is preferably 10 to 200 nm.
The thickness of the layered structure of region A-region B-region A is preferably 5 to 100 nm.
Furthermore, the inorganic film preferably has a gas barrier property.
また、本発明の機能性フィルムの製造方法は、支持体を搬送しつつ、支持体の搬送方向に配列された複数のプラズマCVDによる成膜手段によって同じ無機膜を成膜すると共に、支持体の搬送方向に連続する成膜手段において、上流の成膜手段の成膜領域の下流側から成膜領域外に向かうガス流を制御する下流側制御手段、および、下流の成膜手段の成膜領域の上流側から成膜領域外へのガス流を制御する上流側制御手段の、少なくとも一方を用いて、無機膜の形成を行うことを特徴とする機能性フィルムの製造方法を提供する。
In addition, the method for producing a functional film of the present invention forms the same inorganic film by a plurality of film forming means by plasma CVD arranged in the transport direction of the support while transporting the support. In the film forming means continuous in the 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 film forming area of the downstream film forming means An inorganic film is formed using at least one of upstream control means for controlling the gas flow from the upstream side to the outside of the film formation region.
このような本発明の機能性フィルムの製造方法において、無機膜の形成を、最上流の成膜手段の成膜領域の上流側から成膜領域外へのガス流を制御する制御手段を用いて行うのが好ましい。
また、無機膜の形成を、下流側制御手段および上流側制御手段の両方を用いて行うのが好ましい。
また、ガス流を制御する制御手段が、ガス流を規制するマスクであるのが好ましい。
また、支持体として、長尺な支持体を用い、この長尺な支持体を長手方向に搬送しつつ、複数の成膜手段によって無機膜の形成を行うのが好ましい。
また、長尺な支持体を巻回してなる支持体ロールから支持体を送り出して搬送し、形成済の支持体を、再度、ロール状に巻回するのが好ましい。
さらに、長尺な支持体の搬送経路に、長尺な支持体を周面に巻き掛けて回転することによって搬送する円筒状のドラムを有し、複数の成膜手段は、ドラムの周面に対向して配置されるのが好ましい。 In such a method for producing a functional film of the present invention, the inorganic film is formed using a control means for controlling the gas flow from the upstream side of the film formation area of the uppermost film formation means to the outside of the film formation area. Preferably it is done.
In addition, it is preferable to form the inorganic film using both the downstream control means and the upstream control means.
Moreover, it is preferable that the control means for controlling the gas flow is a mask for regulating the gas flow.
Further, it is preferable to use a long support as the support, and form the inorganic film by a plurality of film forming means while transporting the long support in the longitudinal direction.
In addition, it is preferable that the support is sent out from a support roll formed by winding a long support and transported, and the formed support is wound again in a roll shape.
In addition, a cylindrical drum that conveys the long support by winding the long support around the circumferential surface of the long support is rotated on the circumferential surface. It is preferable that they are arranged to face each other.
また、無機膜の形成を、下流側制御手段および上流側制御手段の両方を用いて行うのが好ましい。
また、ガス流を制御する制御手段が、ガス流を規制するマスクであるのが好ましい。
また、支持体として、長尺な支持体を用い、この長尺な支持体を長手方向に搬送しつつ、複数の成膜手段によって無機膜の形成を行うのが好ましい。
また、長尺な支持体を巻回してなる支持体ロールから支持体を送り出して搬送し、形成済の支持体を、再度、ロール状に巻回するのが好ましい。
さらに、長尺な支持体の搬送経路に、長尺な支持体を周面に巻き掛けて回転することによって搬送する円筒状のドラムを有し、複数の成膜手段は、ドラムの周面に対向して配置されるのが好ましい。 In such a method for producing a functional film of the present invention, the inorganic film is formed using a control means for controlling the gas flow from the upstream side of the film formation area of the uppermost film formation means to the outside of the film formation area. Preferably it is done.
In addition, it is preferable to form the inorganic film using both the downstream control means and the upstream control means.
Moreover, it is preferable that the control means for controlling the gas flow is a mask for regulating the gas flow.
Further, it is preferable to use a long support as the support, and form the inorganic film by a plurality of film forming means while transporting the long support in the longitudinal direction.
In addition, it is preferable that the support is sent out from a support roll formed by winding a long support and transported, and the formed support is wound again in a roll shape.
In addition, a cylindrical drum that conveys the long support by winding the long support around the circumferential surface of the long support is rotated on the circumferential surface. It is preferable that they are arranged to face each other.
上記構成を有する本発明の機能性フィルムは、プラスチックフィルムの上に無機膜を有する機能性フィルムにおいて、無機膜が、厚さ方向に、主に無機膜を形成する領域Bと、この領域Bより薄く低密度な領域Aとを有し、さらに、領域B-領域A-領域Bの積層構造を1以上有する。また、本発明の機能性フィルムは、好ましくは、領域A-領域B-領域Aの積層構造も、1以上有する。
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. A low-density region A, and one or more stacked structures of region B-region A-region B. The functional film of the present invention preferably also has one or more laminated structures of region A, region B, and region A.
そのため、領域Aの緩衝効果によって、無機膜全体の膜応力を低減/制御することができる。そのため、高密度(緻密)な無機膜であっても、膜応力のバランスの崩れ等に起因するクラックや剥離の発生を大幅に防止できる。また、形成中の領域でクラック、剥離、欠陥等が生じても、領域が変わる際に、一度、初期の状態に戻せるため、クラックや欠陥等が大きく成長することを防止できる。
そのため、本発明によれば、無機膜と支持体との密着力が高く、かつ、高密度で膜応力も低く、しかも、クラック、剥離、欠陥等を大幅に低減した、高品質な機能性フィルムを得ることができる。さらに、無機膜の形成に起因する支持体のダメージも、大幅に低減できる。従って、例えば、本発明の機能性フィルムをガスバリアフィルムに利用することにより、優れたガスバリア性能を有するガスバリアフィルムを得ることができる。 Therefore, the film stress of the entire inorganic film can be reduced / controlled by the buffering effect of the region A. For this reason, even with a high-density (dense) inorganic film, it is possible to greatly prevent the occurrence of cracks and peeling due to an unbalance of film stress. 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 functional film of the present invention for a gas barrier film, a gas barrier film having excellent gas barrier performance can be obtained.
そのため、本発明によれば、無機膜と支持体との密着力が高く、かつ、高密度で膜応力も低く、しかも、クラック、剥離、欠陥等を大幅に低減した、高品質な機能性フィルムを得ることができる。さらに、無機膜の形成に起因する支持体のダメージも、大幅に低減できる。従って、例えば、本発明の機能性フィルムをガスバリアフィルムに利用することにより、優れたガスバリア性能を有するガスバリアフィルムを得ることができる。 Therefore, the film stress of the entire inorganic film can be reduced / controlled by the buffering effect of the region A. For this reason, even with a high-density (dense) inorganic film, it is possible to greatly prevent the occurrence of cracks and peeling due to an unbalance of film stress. 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 functional film of the present invention for a gas barrier film, a gas barrier film having excellent gas barrier performance can be obtained.
また、本発明の製造方法では、支持体を搬送しつつ、支持体搬送方向に配列された複数のプラズマCVDによる形成手段を用い、かつ、制御手段によって、プラズマCVDによる形成領域の上下流端から外部に流れるガス流を調整することにより、このような優れた性能を有する機能性フィルムを、好適に製造することができる。
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.
以下、本発明の機能性フィルムおよび機能性フィルムの製造方法について、添付の図面に示される好適例を基に、詳細に説明する。
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.
図1に、本発明の機能性フィルムの一例を概念的に示す。
本発明の機能性フィルム10は、支持体Zと、この支持体Zの上に形成された、無機膜12とを有するものである。 FIG. 1 conceptually shows an example of the functional film of the present invention.
Thefunctional film 10 of the present invention has a support Z and an inorganic film 12 formed on the support Z.
本発明の機能性フィルム10は、支持体Zと、この支持体Zの上に形成された、無機膜12とを有するものである。 FIG. 1 conceptually shows an example of the functional film of the present invention.
The
ここで、本発明の機能性フィルム10は、支持体Zと無機膜12のみを有するものに限定はされない。すなわち、本発明の機能性フィルム10は、支持体Zと、その上に形成された無機膜12とを有するものであれば、各種の層構成が利用可能である。
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. That is, as long as the functional film 10 of the present invention has the support Z and the inorganic film 12 formed thereon, various layer configurations can be used.
一例として、無機膜12の下に、高品質な無機膜12を形成するための下地層としての有機膜を有してもよい。すなわち、本発明の機能性フィルム10は、プラスチックフィルム等を基材として、その上に、下地層としての有機膜を形成したものを、支持体Zとして用いてもよい。
あるいは、有機膜に変えて、保護層、接着層、光反射層、遮光層、平坦化層、緩衝層、応力緩和層等の、各種の機能を得るための層(膜)が形成されている物を、支持体Zとして用いてもよい。もしくは、有機膜の下層および/または上層に、これらの各種の機能を得るための層が形成されている物を、支持体Zとして用いてもよい。 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, thefunctional 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, a layer (film) for obtaining various functions such as a protective layer, an adhesive layer, a light reflecting layer, a light shielding layer, a planarizing layer, a buffer layer, and a stress relaxation layer is formed instead of the organic film. An object may be used as the support Z. Or you may use the thing in which the layer for obtaining these various functions is formed in the lower layer and / or upper layer of an organic film as the support body Z.
あるいは、有機膜に変えて、保護層、接着層、光反射層、遮光層、平坦化層、緩衝層、応力緩和層等の、各種の機能を得るための層(膜)が形成されている物を、支持体Zとして用いてもよい。もしくは、有機膜の下層および/または上層に、これらの各種の機能を得るための層が形成されている物を、支持体Zとして用いてもよい。 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
Alternatively, a layer (film) for obtaining various functions such as a protective layer, an adhesive layer, a light reflecting layer, a light shielding layer, a planarizing layer, a buffer layer, and a stress relaxation layer is formed instead of the organic film. An object may be used as the support Z. Or you may use the thing in which the layer for obtaining these various functions is formed in the lower layer and / or upper layer of an organic film as the support body Z.
また、本発明の機能性フィルムは、無機膜12の上に、保護層としての有機膜が形成されたものであってもよい。
さらに、下地層としての有機膜と、この有機膜表面に形成された無機膜12との積層構造を、複数、繰り返し有するものでもよい。あるいは、下地有機膜と無機膜12との積層構造を、複数、繰り返し有し、さらに、最上層に保護層としての有機膜が形成されたものでもよい。
複数の無機膜12を有する場合には、各無機膜12は、同じ物でも、互いに異なる物でもよい。同様に、複数の有機膜を有する場合も、有機膜は、同じ物でも互いに異なる物でもよい。なお、複数の無機膜12を有する場合には、全ての無機膜12が、後述する層構成を有するのが好ましいが、本発明は、これに限定はされない。 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 an organic film as a base layer and the inorganic film 12 formed on the surface of the organic film may be repeatedly provided. Alternatively, a plurality of laminated structures of the base organic film and the inorganic film 12 may be repeatedly provided, and 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.
さらに、下地層としての有機膜と、この有機膜表面に形成された無機膜12との積層構造を、複数、繰り返し有するものでもよい。あるいは、下地有機膜と無機膜12との積層構造を、複数、繰り返し有し、さらに、最上層に保護層としての有機膜が形成されたものでもよい。
複数の無機膜12を有する場合には、各無機膜12は、同じ物でも、互いに異なる物でもよい。同様に、複数の有機膜を有する場合も、有機膜は、同じ物でも互いに異なる物でもよい。なお、複数の無機膜12を有する場合には、全ての無機膜12が、後述する層構成を有するのが好ましいが、本発明は、これに限定はされない。 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 an organic film as a base layer and the inorganic film 12 formed on the surface of the organic film may be repeatedly provided. Alternatively, a plurality of laminated structures of the base organic film and the inorganic film 12 may be repeatedly provided, and 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.
本発明の機能性フィルム10は、プラスチックフィルム等の基材の上に有機膜を形成した支持体Zのように、支持体Zは、表面に無機膜12の下地層となる有機膜を有するのが好ましい。
また、本発明の機能性フィルム10は、最上層に、保護層としての有機膜を有するのが好ましい。 Thefunctional 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 thefunctional film 10 of this invention has an organic film as a protective layer in the uppermost layer.
また、本発明の機能性フィルム10は、最上層に、保護層としての有機膜を有するのが好ましい。 The
Moreover, it is preferable that the
本発明において、有機膜の形成材料には、特に限定は無く、公知の有機化合物(樹脂/高分子化合物)が、各種、利用可能である。
具体的には、ポリエステル、アクリル樹脂、メタクリル樹脂、メタクリル酸?マレイン酸共重合体、ポリスチレン、透明フッ素樹脂、ポリイミド、フッ素化ポリイミド、ポリアミド、ポリアミドイミド、ポリエーテルイミド、セルロースアシレート、ポリウレタン、ポリエーテルエーテルケトン、ポリカーボネート、脂環式ポリオレフィン、ポリアリレート、ポリエーテルスルホン、ポリスルホン、フルオレン環変性ポリカーボネート、脂環変性ポリカーボネート、フルオレン環変性ポリエステル、アクリロイル化合物、などの熱可塑性樹脂、あるいはポリシロキサン、その他の有機珪素化合物の膜が好適に例示される。
中でも、強度等に優れる等の点で、ラジカル重合性化合物および/またはエーテル基を官能基に有するカチオン重合性化合物の重合物から構成された有機膜は、好適である。その、中でも特に、前記強度に加え、屈折率が低い、光学特性に優れる等の点で、アクリレートおよび/またはメタクリレートのモノマーやオリゴマーの重合体を主成分とするアクリル樹脂やメタクリル樹脂空なる有機膜は、好適に例示される。 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, polyethersulfone, 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.
Of these, 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 from the viewpoint of excellent strength and the like. Among them, in particular, an organic film containing an acrylic resin or a methacrylic resin which is mainly composed of a polymer of an acrylate and / or methacrylate monomer or oligomer, in addition to the aforementioned strength, in that it has a low refractive index and excellent optical properties. Is preferably exemplified.
具体的には、ポリエステル、アクリル樹脂、メタクリル樹脂、メタクリル酸?マレイン酸共重合体、ポリスチレン、透明フッ素樹脂、ポリイミド、フッ素化ポリイミド、ポリアミド、ポリアミドイミド、ポリエーテルイミド、セルロースアシレート、ポリウレタン、ポリエーテルエーテルケトン、ポリカーボネート、脂環式ポリオレフィン、ポリアリレート、ポリエーテルスルホン、ポリスルホン、フルオレン環変性ポリカーボネート、脂環変性ポリカーボネート、フルオレン環変性ポリエステル、アクリロイル化合物、などの熱可塑性樹脂、あるいはポリシロキサン、その他の有機珪素化合物の膜が好適に例示される。
中でも、強度等に優れる等の点で、ラジカル重合性化合物および/またはエーテル基を官能基に有するカチオン重合性化合物の重合物から構成された有機膜は、好適である。その、中でも特に、前記強度に加え、屈折率が低い、光学特性に優れる等の点で、アクリレートおよび/またはメタクリレートのモノマーやオリゴマーの重合体を主成分とするアクリル樹脂やメタクリル樹脂空なる有機膜は、好適に例示される。 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, polyethersulfone, 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.
Of these, 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 from the viewpoint of excellent strength and the like. Among them, in particular, an organic film containing an acrylic resin or a methacrylic resin which is mainly composed of a polymer of an acrylate and / or methacrylate monomer or oligomer, in addition to the aforementioned strength, in that it has a low refractive index and excellent optical properties. Is preferably exemplified.
本発明の機能性フィルム10において、支持体(基材/基体)Zには、特に限定はなく、プラズマCVDによる無機膜12の形成が可能な、各種のシート状物が、全て利用可能である。
具体的には、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリエチレン、ポリプロピレン、ポリスチレン、ポリアミド、ポリ塩化ビニル、ポリカーボネート、ポリアクリロニトリル、ポリイミド、ポリアクリレート、ポリメタクリレートなどの有機物からなるプラスチックフィルム(樹脂フィルム)が、支持体Zとして、好適に利用可能である。
なお、支持体Zは、このようなプラスチックフィルムの表面に、無機膜12の下地層となる有機膜などを形成した物も好適に利用されるのは、前述の通りである。 In thefunctional 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.
具体的には、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリエチレン、ポリプロピレン、ポリスチレン、ポリアミド、ポリ塩化ビニル、ポリカーボネート、ポリアクリロニトリル、ポリイミド、ポリアクリレート、ポリメタクリレートなどの有機物からなるプラスチックフィルム(樹脂フィルム)が、支持体Zとして、好適に利用可能である。
なお、支持体Zは、このようなプラスチックフィルムの表面に、無機膜12の下地層となる有機膜などを形成した物も好適に利用されるのは、前述の通りである。 In the
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.
前述のように、本発明の機能性フィルム10は、支持体Zの上に、無機膜12を形成してなるものである。
本発明の機能性フィルム10において、無機膜12は、無機化合物からなる膜である。ここで、無機膜12は、厚さ方向の全域が同じ無機化合物からなる膜であるが、密度(緻密さ)の異なる2種類の領域(2種類の層)の積層構造となっている。 As described above, thefunctional film 10 of the present invention is obtained by forming the inorganic film 12 on the support Z.
In thefunctional 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).
本発明の機能性フィルム10において、無機膜12は、無機化合物からなる膜である。ここで、無機膜12は、厚さ方向の全域が同じ無機化合物からなる膜であるが、密度(緻密さ)の異なる2種類の領域(2種類の層)の積層構造となっている。 As described above, the
In the
図1に示される機能性フィルム10において、無機膜12は、層12a~12gの7つの層(7つの領域)で構成される膜である。この無機膜12において、層12a、12c、12eおよび12gは、層12b、12dおよび12fよりも、薄く、かつ、低密度である。
なお、本例では、便宜的に『層』と称してはいるが、無機膜12を形成する各層は、隣接した層の密度が異なるだけで、界面を有する1枚の独立した膜というわけではなく、一体的に形成されている。すなわち、無機膜12は、7つの領域を有する1枚の膜である。 In thefunctional film 10 shown in FIG. 1, the inorganic film 12 is a film composed of seven layers (seven regions) of the layers 12a to 12g. In this inorganic film 12, the layers 12a, 12c, 12e and 12g are thinner and have a lower density than the layers 12b, 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.
なお、本例では、便宜的に『層』と称してはいるが、無機膜12を形成する各層は、隣接した層の密度が異なるだけで、界面を有する1枚の独立した膜というわけではなく、一体的に形成されている。すなわち、無機膜12は、7つの領域を有する1枚の膜である。 In the
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.
すなわち、図示例の機能性フィルム10においては、層12b、12dおよび12fが、本発明における領域Bであって、主に無機膜12を構成するものである。
また、層12a、12c、12eおよび12gが、領域Bよりも低密度で、かつ、厚さが薄い、本発明における領域Aである。
なお、領域Aは、内部に、厚さ方向に連続的(傾斜的)に密度が変化する領域を有してもよい。あるいは、領域Aは、全域が、厚さ方向に向けて連続的に密度が変化していてもよい。ここで、領域Aが、密度が連続的に変化する領域を有する場合には、通常、この領域の密度は、隣接する領域Bの一方に向かって、漸次、高くなる傾向を有する。
また、層12a、12c、12eおよび12gは、基本的に同じ密度であり、同様に、層12b、12dおよび12fも、基本的に同じ密度である。 That is, in thefunctional 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.
Note that the region A may have a region in which the density changes continuously (gradually) in the thickness direction. 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.
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.
また、層12a、12c、12eおよび12gが、領域Bよりも低密度で、かつ、厚さが薄い、本発明における領域Aである。
なお、領域Aは、内部に、厚さ方向に連続的(傾斜的)に密度が変化する領域を有してもよい。あるいは、領域Aは、全域が、厚さ方向に向けて連続的に密度が変化していてもよい。ここで、領域Aが、密度が連続的に変化する領域を有する場合には、通常、この領域の密度は、隣接する領域Bの一方に向かって、漸次、高くなる傾向を有する。
また、層12a、12c、12eおよび12gは、基本的に同じ密度であり、同様に、層12b、12dおよび12fも、基本的に同じ密度である。 That is, in the
In addition, the
Note that the region A may have a region in which the density changes continuously (gradually) in the thickness direction. 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.
The
従って、図示例の機能性フィルム10は、本発明における領域B-領域A-領域Bの積層構造として、層12b-層12c-層12dの積層構造と、層12d-層12e-層12fの積層構造との、2つを有する。
また、本発明における領域A-領域B-領域Aの積層構造として、層12a-層12b-層12cの積層構造と、層12c-層12d-層12eの積層構造と、層12e-層12f-層12gの積層構造との、3つを有する。 Therefore, thefunctional film 10 in the illustrated example has a layered structure of region B-region A-region B in the present invention, and a layered structure of layer 12b-layer 12c-layer 12d and layered layer 12d-layer 12e-layer 12f. Has two, with structure.
In the present invention, the layered structure of region A-region B-region A includes a layered structure oflayer 12a-layer 12b-layer 12c, a layered structure of layer 12c-layer 12d-layer 12e, and layer 12e-layer 12f- The layer 12g has a three-layer structure.
また、本発明における領域A-領域B-領域Aの積層構造として、層12a-層12b-層12cの積層構造と、層12c-層12d-層12eの積層構造と、層12e-層12f-層12gの積層構造との、3つを有する。 Therefore, the
In the present invention, the layered structure of region A-region B-region A includes a layered structure of
本発明の機能性フィルムは、このような密度と厚さの異なる領域(層)からなる領域B-領域A-領域Bの積層構造を1以上有し、好ましくは、さらに、領域A-領域B-領域Aの積層構造を1以上有する。本発明の機能性フィルムは、この構成を有することにより、主に無機膜12を構成する領域Bの間の領域Aの緩衝効果によって、無機膜全体の膜応力を低減/制御することができる。そのため、高密度(緻密)な無機膜12であっても、膜応力のバランスの崩れ等に起因するクラックや剥離の発生を大幅に防止できる。
また、無機膜12は、基本的にプラズマCVDによって形成(成膜)されるが、形成中の領域内でクラック、剥離、欠陥等が生じても、領域が変わる際に、一度、成膜初期の状態に戻るため(リセットできる)、クラックや欠陥等が大きく成長するのを防止できる。
さらに、好ましくは、領域A-領域B-領域Aの積層構造を有することにより、支持体Zの表面への領域Bの形成に先立ち、低密度な領域Aが形成される。そのため、主に無機膜12を構成する領域Bの形成するためのプラズマ等による支持体Zの損傷を防止でき、しかも、支持体Zと無機膜12との密着性も向上することができる。 The functional film of the present invention has at least one layered structure of region B-region A-region B composed of regions (layers) having different densities and thicknesses, preferably region A-region B. -Having at least one layered structure of region A; By having this structure, the functional film of the present invention can reduce / control the film stress of the entire inorganic film mainly by the buffering effect of the area A between the areas 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), it can be prevented that cracks, defects and the like grow greatly.
Further, preferably, by having a laminated structure of region A-region B-region A, the low-density region A is formed prior to the formation of the region B on the surface of the support Z. Therefore, it is possible to prevent the support Z from being damaged mainly by plasma or the like for forming the region B constituting the inorganic film 12, and to improve the adhesion between the support Z and the inorganic film 12.
また、無機膜12は、基本的にプラズマCVDによって形成(成膜)されるが、形成中の領域内でクラック、剥離、欠陥等が生じても、領域が変わる際に、一度、成膜初期の状態に戻るため(リセットできる)、クラックや欠陥等が大きく成長するのを防止できる。
さらに、好ましくは、領域A-領域B-領域Aの積層構造を有することにより、支持体Zの表面への領域Bの形成に先立ち、低密度な領域Aが形成される。そのため、主に無機膜12を構成する領域Bの形成するためのプラズマ等による支持体Zの損傷を防止でき、しかも、支持体Zと無機膜12との密着性も向上することができる。 The functional film of the present invention has at least one layered structure of region B-region A-region B composed of regions (layers) having different densities and thicknesses, preferably region A-region B. -Having at least one layered structure of region A; By having this structure, the functional film of the present invention can reduce / control the film stress of the entire inorganic film mainly by the buffering effect of the area A between the areas 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), it can be prevented that cracks, defects and the like grow greatly.
Further, preferably, by having a laminated structure of region A-region B-region A, the low-density region A is formed prior to the formation of the region B on the surface of the support Z. Therefore, it is possible to prevent the support Z from being damaged mainly by plasma or the like for forming the region B constituting the inorganic film 12, and to improve the adhesion between the support Z and the inorganic film 12.
すなわち、本発明によれば、支持体Zのダメージが少なく、無機膜12と支持体Zとの密着性が高く、しかも、無機膜12が、高密度で膜応力も低く、かつ、クラック、剥離、欠陥等を大幅に低減した、高品質な機能性フィルムを得ることができる。
従って、例えば、本発明をガスバリアフィルムに利用することにより、強度が高く、しかも、優れたガスバリア性能を有するガスバリアフィルムを得ることができる。 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.
従って、例えば、本発明をガスバリアフィルムに利用することにより、強度が高く、しかも、優れたガスバリア性能を有するガスバリアフィルムを得ることができる。 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.
なお、本発明の機能性フィルム10において、無機膜12の構成は、図示例に限定はされない。すなわち、領域Aと領域Bとを厚さ方向に交互に有し、かつ、領域B-領域A-領域Bの積層構造を1以上有し、好ましくは、領域A-領域B-領域Aの積層構造を1以上有するものであれば、各種の構成が利用可能である。
In the functional film 10 of the present invention, the configuration of the inorganic film 12 is not limited to the illustrated example. That is, it has regions A and B alternately in the thickness direction, and has one or more layered structures of region B-region A-region B, preferably a stack of region A-region B-region A Various configurations can be used as long as they have one or more structures.
例えば、図示例の機能性フィルム10の無機膜12において、最下層の層12aおよび最上層の層12gの少なくとも一方を有さない無機膜であってもよい。
ただし、支持体Zの損傷防止、支持体Zと無機膜12との密着性等の点で、最下層の層12a、すなわち、支持体Zの表面には、領域Aを形成するのが好ましい。従って、この点でも、本発明の機能性フィルム10は、領域A-領域B-領域Aの積層構造を1以上有するのが好ましい。 For example, the inorganic film 12 of the illustratedfunctional 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 thelowermost 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.
ただし、支持体Zの損傷防止、支持体Zと無機膜12との密着性等の点で、最下層の層12a、すなわち、支持体Zの表面には、領域Aを形成するのが好ましい。従って、この点でも、本発明の機能性フィルム10は、領域A-領域B-領域Aの積層構造を1以上有するのが好ましい。 For example, the inorganic film 12 of the illustrated
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
また、図示例の機能性フィルム10において、無機膜が、層12a~層12dの4層(4領域)から構成されるものでもよい。あるいは、無機膜が、層12a~層12eの5層から構成されるものでもよい。また、領域B-領域A-領域Bを1つのみ有する、層12b~層12dの3層のみで構成される無機膜12であってもよい。
さらに、領域Aと領域Bとを、交互に、合計で8層以上、有する無機膜でもよい。 In the illustratedfunctional film 10, the inorganic film may be composed of four layers (four regions) of layers 12a to 12d. Alternatively, the inorganic film may be composed of five layers 12a to 12e. 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.
さらに、領域Aと領域Bとを、交互に、合計で8層以上、有する無機膜でもよい。 In the illustrated
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.
本発明の機能性フィルム10において、領域Aおよび領域Bの密度には、特に限定はない。領域Aおよび領域Bの密度は、機能性フィルム10の用途や無機膜12を形成する無機化合物等に応じて、適宜、設定すればよい。
ここで、本発明においては、領域Aの密度をa、領域Bの密度をbとした際に、無機膜12が、『0.6<a/b<1』を満たすのが好ましい。
無機膜12が『0.6<a/b<1』を満たすことにより、応力バランス、支持体Zとの密着力、耐久性(高温高湿下での膜質経時変化など)等の点で、好ましい結果を得ることができる。 In thefunctional film 10 of the present invention, the density of the region A and the region B is not particularly limited. The density of the region A and the region B 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.
ここで、本発明においては、領域Aの密度をa、領域Bの密度をbとした際に、無機膜12が、『0.6<a/b<1』を満たすのが好ましい。
無機膜12が『0.6<a/b<1』を満たすことにより、応力バランス、支持体Zとの密着力、耐久性(高温高湿下での膜質経時変化など)等の点で、好ましい結果を得ることができる。 In the
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.
また、無機膜12の厚さにも、特に限定はない。無機膜12の厚さは、機能性フィルム10の用途、機能性フィルム10(無機膜12)に要求される性能、無機膜12を形成する無機化合物、要求される生産性等に応じて、適宜、設定すればよい。
ここで、本発明の機能性フィルム10においては、領域A-領域B-領域Aの厚さが、5~100nmであるのが好ましい。また、領域B-領域A-領域Bの厚さが、10~200nmであるのが好ましい。
このような構成を有することにより、応力バランス、耐久性(高温高湿下での膜質経時変化など)、生産性(装置構成など)等の点で好ましい結果を得ることができる。
なお、領域A同士は、互いに厚さが同じでも異なってもよい。領域B同士も、互いに厚さが同じでも異なってもよい。
また、領域Aと領域Bとの厚さの比にも特に限定はないが、先と同様の理由で、領域Aの厚さが、隣接する領域Bの厚さの3~30%であるのが好ましい。 Further, the thickness of the inorganic film 12 is not particularly limited. The thickness of the inorganic film 12 is appropriately determined according to the use of thefunctional film 10, the performance required for the functional film 10 (inorganic film 12), the inorganic compound forming the inorganic film 12, the required productivity, and the like. , You can set.
Here, in thefunctional film 10 of the present invention, the thickness of the region A-region B-region A is preferably 5 to 100 nm. The thickness of the region B-region A-region B is preferably 10 to 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 may have the same or different thickness. 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. 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.
ここで、本発明の機能性フィルム10においては、領域A-領域B-領域Aの厚さが、5~100nmであるのが好ましい。また、領域B-領域A-領域Bの厚さが、10~200nmであるのが好ましい。
このような構成を有することにより、応力バランス、耐久性(高温高湿下での膜質経時変化など)、生産性(装置構成など)等の点で好ましい結果を得ることができる。
なお、領域A同士は、互いに厚さが同じでも異なってもよい。領域B同士も、互いに厚さが同じでも異なってもよい。
また、領域Aと領域Bとの厚さの比にも特に限定はないが、先と同様の理由で、領域Aの厚さが、隣接する領域Bの厚さの3~30%であるのが好ましい。 Further, the thickness of the inorganic film 12 is not particularly limited. The thickness of the inorganic film 12 is appropriately determined according to the use of the
Here, in the
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 may have the same or different thickness. 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. 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.
ここで、前述のように、本発明の機能性フィルム10の無機膜12では、領域Aと領域Bとは密度が異なるだけで、一体的になっており、境界が明確に現れるわけではない。
従って、一例として、無機膜12として想定した一定の密度が厚さ方向に連続する領域を領域Bとし、これ以外の領域を領域Aとして、前記積層構造の厚さを設定する。 Here, as described above, in the inorganic film 12 of thefunctional 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.
従って、一例として、無機膜12として想定した一定の密度が厚さ方向に連続する領域を領域Bとし、これ以外の領域を領域Aとして、前記積層構造の厚さを設定する。 Here, as described above, in the inorganic film 12 of the
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.
本発明において、無機膜12を形成する無機化合物(無機膜12の主成分となる無機化合物)には、特に限定はない。無機膜12を形成する無機化合物は、機能性フィルム10の用途に応じて、要求される機能を発現する無機化合物が、各種、利用可能である。
一例として、酸化アルミニウム、酸化マグネシウム、酸化タンタル、酸化ジルコニウム、酸化チタン、酸化インジウムスズ(ITO)などの金属酸化物; 窒化アルミニウムなどの金属窒化物; 炭化アルミニウムなどの金属炭化物; 酸化珪素、酸化窒化珪素、酸炭化珪素、酸化窒化炭化珪素などの珪素酸化物; 窒化珪素、窒化炭化珪素などの珪素窒化物; 炭化珪素等の珪素炭化物; これらの水素化物; これら2種以上の混合物; および、これらの水素含有物等の、無機化合物からなる膜が、好適に例示される。 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. As the inorganic compound that forms the inorganic film 12, various inorganic compounds that exhibit a required function can be used depending on the application of thefunctional film 10.
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 carbide such as silicon carbide; hydrides thereof; a mixture 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.
一例として、酸化アルミニウム、酸化マグネシウム、酸化タンタル、酸化ジルコニウム、酸化チタン、酸化インジウムスズ(ITO)などの金属酸化物; 窒化アルミニウムなどの金属窒化物; 炭化アルミニウムなどの金属炭化物; 酸化珪素、酸化窒化珪素、酸炭化珪素、酸化窒化炭化珪素などの珪素酸化物; 窒化珪素、窒化炭化珪素などの珪素窒化物; 炭化珪素等の珪素炭化物; これらの水素化物; これら2種以上の混合物; および、これらの水素含有物等の、無機化合物からなる膜が、好適に例示される。 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. As the inorganic compound that forms the inorganic film 12, various inorganic compounds that exhibit a required function can be used depending on the application of the
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 carbide such as silicon carbide; hydrides thereof; a mixture 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.
ここで、本発明の機能性フィルム10は、クラック、剥離、欠陥等の極めて少ない無機膜12を有する。そのため、これらに起因する性能劣化が大きな用途には、好適に利用され、中でも特に、ガスバリアフィルムには、好適に利用される。
従って、無機膜12は、ガスバリア性を有する膜であるのが好ましく、無機膜12を形成する無機化合物は、窒化珪素、酸化珪素、酸化窒化珪素、酸化アルミニウム等のガスバリア性を発現する無機化合物が、好適に利用される。中でも、窒化珪素や酸化窒化珪素などの珪素と窒素とを含有する無機化合物は、特に好適である。 Here, thefunctional 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.
従って、無機膜12は、ガスバリア性を有する膜であるのが好ましく、無機膜12を形成する無機化合物は、窒化珪素、酸化珪素、酸化窒化珪素、酸化アルミニウム等のガスバリア性を発現する無機化合物が、好適に利用される。中でも、窒化珪素や酸化窒化珪素などの珪素と窒素とを含有する無機化合物は、特に好適である。 Here, the
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.
図2に、本発明の機能性フィルムの製造方法の一例を実施して、本発明の機能性フィルム10を製造する、プラズマCVD装置の一例を概念的に示す。
図2に示すプラズマCVD装置14(以下、CVD装置14とする)は、長尺な支持体Z(ウエブ状のフィルム原反)を長手方向に搬送しつつ、この支持体Zの表面に、容量結合型プラズマCVD(CCP(Capacitively Coupled Plasma)-CVD)によって無機膜12を形成(成膜)して、ガスバリアフィルムや各種の光学フィルムなどの本発明の機能性フィルム10を製造するものである。 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 thefunctional 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 thefunctional film 10 of the present invention such as a gas barrier film or various optical films.
図2に示すプラズマCVD装置14(以下、CVD装置14とする)は、長尺な支持体Z(ウエブ状のフィルム原反)を長手方向に搬送しつつ、この支持体Zの表面に、容量結合型プラズマCVD(CCP(Capacitively Coupled Plasma)-CVD)によって無機膜12を形成(成膜)して、ガスバリアフィルムや各種の光学フィルムなどの本発明の機能性フィルム10を製造するものである。 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
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
なお、本発明の製造方法においては、無機膜12の形成は、CCP-CVDによって行うのに限定はされず、ICP-CVD(誘導結合型プラズマCVD)等、各種のプラズマCVDが、利用可能である。
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.
図2に示すCVD装置14は、長尺な支持体Zをロール状に巻回してなる支持体ロールZrから支持体Zを送り出し、支持体Zを長手方向に搬送しつつ、連続的に無機膜12を形成し、無機膜12を形成した支持体Zを巻取り軸16に、再度、ロール状に巻き取る、いわゆるロール・トゥ・ロール(Roll to Roll 以下、RtoRともいう)を利用して無機膜を形成する装置である。
なお、本発明の製造方法は、長尺な支持体Zを用いるRtoRを利用するものに限定はされない。すなわち、本発明は、無機膜12を形成する支持体Zを搬送しつつ、搬送方向に配列された複数のプラズマCVD手段によって無機膜12を形成するものであれば、カットシート状の支持体Zに、無機膜12を形成するものでもよい。しかしながら、生産性を考慮すれば、図示例のようなRtoRによって無機膜12を形成するのが好ましい。 TheCVD 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 provides 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 that forms 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.
なお、本発明の製造方法は、長尺な支持体Zを用いるRtoRを利用するものに限定はされない。すなわち、本発明は、無機膜12を形成する支持体Zを搬送しつつ、搬送方向に配列された複数のプラズマCVD手段によって無機膜12を形成するものであれば、カットシート状の支持体Zに、無機膜12を形成するものでもよい。しかしながら、生産性を考慮すれば、図示例のようなRtoRによって無機膜12を形成するのが好ましい。 The
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 provides 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 that forms 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.
このCVD装置14は、供給室18と、成膜室20と、巻取り室24とを有している。
なお、CVD装置14は、図示した部材以外にも、各種のセンサ、搬送ローラ対や支持体Zの幅方向の位置を規制するガイド部材など、支持体Zを所定の経路で搬送するための各種の部材(搬送手段)等、長尺な支持体Zに、RtoRによって、プラズマCVDで形成を行なう装置が有する各種の部材を有してもよい。 TheCVD apparatus 14 includes a supply chamber 18, a film formation chamber 20, and a winding chamber 24.
In addition to the illustrated members, theCVD 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).
なお、CVD装置14は、図示した部材以外にも、各種のセンサ、搬送ローラ対や支持体Zの幅方向の位置を規制するガイド部材など、支持体Zを所定の経路で搬送するための各種の部材(搬送手段)等、長尺な支持体Zに、RtoRによって、プラズマCVDで形成を行なう装置が有する各種の部材を有してもよい。 The
In addition to the illustrated members, the
供給室18は、回転軸28と、ガイドローラ30と、真空排気手段32とを有する。
支持体Zを巻回した支持体ロールZrは、供給室18の回転軸28に装着される。
回転軸28に支持体ロールZrが装着されると、支持体Zが支持体ロールZrから引き出され、供給室18から、成膜室20を通り、巻取り室24の巻取り軸16に至る所定の搬送経路を通紙される(所定の搬送経路を通される)。
CVD装置14においては、支持体ロールZrからの支持体Zの送り出しと、巻取り室24の巻取り軸16における支持体Zの巻き取りとを同期して行なって、長尺な支持体Zを所定の搬送経路で長手方向に搬送しつつ、成膜室20において、支持体Zに、CCP-CVDによる無機膜12の形成を連続的に行なう。 Thesupply 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 therotating shaft 28 of the supply chamber 18.
When the support roll Zr is mounted on therotating shaft 28, the support Z is pulled out from the support roll Zr, passes through the film forming chamber 20 from the supply chamber 18, and reaches the winding shaft 16 of the winding chamber 24. The paper is passed through the transport path (through a predetermined transport path).
In theCVD apparatus 14, the feeding of the support Z from the support roll Zr and the winding of the support Z on the winding shaft 16 of the winding chamber 24 are performed in synchronization, so that the long support Z is formed. The inorganic film 12 is continuously formed on the support Z by CCP-CVD in the film forming chamber 20 while being transported in the longitudinal direction along a predetermined transport path.
支持体Zを巻回した支持体ロールZrは、供給室18の回転軸28に装着される。
回転軸28に支持体ロールZrが装着されると、支持体Zが支持体ロールZrから引き出され、供給室18から、成膜室20を通り、巻取り室24の巻取り軸16に至る所定の搬送経路を通紙される(所定の搬送経路を通される)。
CVD装置14においては、支持体ロールZrからの支持体Zの送り出しと、巻取り室24の巻取り軸16における支持体Zの巻き取りとを同期して行なって、長尺な支持体Zを所定の搬送経路で長手方向に搬送しつつ、成膜室20において、支持体Zに、CCP-CVDによる無機膜12の形成を連続的に行なう。 The
The support roll Zr around which the support Z is wound is mounted on the
When the support roll Zr is mounted on the
In the
供給室18は、図示しない駆動源によって回転軸28を図中反時計方向に回転して、支持体ロールZrから支持体Zを送り出し、ガイドローラ30によって所定の経路を案内して、支持体Zを、隔壁34に設けられたスリット34aから、成膜室20に送る。
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.
図示例のCVD装置14においては、好ましい態様として、供給室18に真空排気手段32を、巻取り室24に真空排気手段70を、それぞれ設けている。CVD装置14においては、形成中は、それぞれの真空排気手段によって、供給室18および巻取り室24の圧力を、後述する成膜室20の圧力(形成圧力)に応じた、所定の圧力に保つ。これにより、隣接する室の圧力が、成膜室20の圧力(すなわち、成膜室20での形成)に影響を与えることを防止している。
真空排気手段32には、特に限定はなく、ターボポンプ、メカニカルブースターポンプ、ドライポンプ、ロータリーポンプなどの真空ポンプ、さらには、クライオコイル等の補助手段、到達真空度や排気量の調整手段等を利用する、真空形成装置に用いられている公知の(真空)排気手段が、各種、利用可能である。この点に関しては、後述する他の真空排気手段60および70も同様である。 In theillustrated 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.
真空排気手段32には、特に限定はなく、ターボポンプ、メカニカルブースターポンプ、ドライポンプ、ロータリーポンプなどの真空ポンプ、さらには、クライオコイル等の補助手段、到達真空度や排気量の調整手段等を利用する、真空形成装置に用いられている公知の(真空)排気手段が、各種、利用可能である。この点に関しては、後述する他の真空排気手段60および70も同様である。 In the
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.
前述のように、支持体Zは、ガイドローラ30によって案内されて、隔壁34のスリット34aから成膜室20に搬送される。
成膜室20は、支持体Zの表面に、CCP-CVDによって領域Aおよび領域Bで形成される無機膜12を形成(成膜)するものである。前述のように、領域Bは、無機膜12を主に構成するものであり、領域Aは、領域Bよりも薄く、かつ、低密度である。
図示例において、成膜室20は、ドラム38と、ガイドローラ42、46、48および50と、無機膜12を形成する3つの成膜手段52a、52bおよび52cと、真空排気手段60とを有する。 As described above, the support Z is guided by theguide roller 30 and is conveyed from the slit 34 a of the partition wall 34 to the film forming chamber 20.
Thefilm 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, thefilm 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. .
成膜室20は、支持体Zの表面に、CCP-CVDによって領域Aおよび領域Bで形成される無機膜12を形成(成膜)するものである。前述のように、領域Bは、無機膜12を主に構成するものであり、領域Aは、領域Bよりも薄く、かつ、低密度である。
図示例において、成膜室20は、ドラム38と、ガイドローラ42、46、48および50と、無機膜12を形成する3つの成膜手段52a、52bおよび52cと、真空排気手段60とを有する。 As described above, the support Z is guided by the
The
In the illustrated example, the
なお、図示例のCVD装置14は、支持体Zの搬送方向に配列されて、3つの成膜手段を有する。しかしながら、本発明の製造方法は、これに限定はされず、成膜手段は2つであってもよく、あるいは、4つ以上の成膜手段を有してもよい。
The CVD apparatus 14 in the illustrated example is arranged in the transport direction of the support Z and has three film forming means. However, the production method of the present invention is not limited to this, and the number of film forming means may be two, or four or more film forming means may be provided.
成膜室20のドラム38は、中空の円筒状の部材で、中心線を前記円筒と一致する回転軸を中心に、図中矢印方向(時計方向)に回転する。
ドラム38は、ガイドローラ42および46によって所定の経路に案内された支持体Zを、表面の所定領域に掛け回して(所定の巻き掛け角で掛け回して)、図示しない駆動源によって回転する。ドラム38は、これにより、支持体Zを所定位置に位置しつつ、長手方向に搬送する。 Thedrum 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.
Thedrum 38 is rotated by a driving source (not shown) after the support Z guided by the guide rollers 42 and 46 is hung on a predetermined area on the surface (around a predetermined winding angle). Thus, the drum 38 conveys the support Z in the longitudinal direction while being positioned at a predetermined position.
ドラム38は、ガイドローラ42および46によって所定の経路に案内された支持体Zを、表面の所定領域に掛け回して(所定の巻き掛け角で掛け回して)、図示しない駆動源によって回転する。ドラム38は、これにより、支持体Zを所定位置に位置しつつ、長手方向に搬送する。 The
The
本発明の製造方法において、支持体Zを掛け回して搬送するドラム38は、CCP-CVDにおける対向電極としても作用する。すなわち、ドラム38と、後述する各成膜手段のシャワー電極40(成膜電極)とで、CCP-CVDによる成膜を行なうための電極対を形成する。
そのため、ドラム38には、バイアス電力を供給するためのバイアス電源を接続してもよく、あるいは、接地してもよい。あるいは、バイアス電源との接続と接地とが、切り換え可能であってもよい。
また、ドラム38は、支持体Zの冷却や加熱を行うため、支持体Zを支持する周面の温度を調整する、温度調整手段を有してもよい。 In the manufacturing method of the present invention, thedrum 38 that is wound around and supported by the support Z also functions 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, thedrum 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, thedrum 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.
そのため、ドラム38には、バイアス電力を供給するためのバイアス電源を接続してもよく、あるいは、接地してもよい。あるいは、バイアス電源との接続と接地とが、切り換え可能であってもよい。
また、ドラム38は、支持体Zの冷却や加熱を行うため、支持体Zを支持する周面の温度を調整する、温度調整手段を有してもよい。 In the manufacturing method of the present invention, the
Therefore, the
Further, the
成膜手段52a、52bおよび52cは、いずれも、ドラム38に巻き掛けられて搬送される支持体Zに、CCP-CVDによって無機膜12を形成するものである。
成膜手段52a、52bおよび52cは、基本的に、同じ構成を有するものであって、シャワー電極40と、高周波電源54と、ガス供給手段58とを有して構成される。
また、各成膜手段は、シャワー電極40の上流側(支持体搬送方向の上流側 以下、同様)端部近傍とドラム38との間に入口マスク58aを、シャワー電極40の下流側端部近傍とドラム38との間に出口マスク58bを、それぞれ有する(図3参照)。 Each of the film forming means 52a, 52b and 52c forms the inorganic film 12 by CCP-CVD on the support Z which 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 aninlet 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 58b between the drum 38 and the drum 38 (see FIG. 3).
成膜手段52a、52bおよび52cは、基本的に、同じ構成を有するものであって、シャワー電極40と、高周波電源54と、ガス供給手段58とを有して構成される。
また、各成膜手段は、シャワー電極40の上流側(支持体搬送方向の上流側 以下、同様)端部近傍とドラム38との間に入口マスク58aを、シャワー電極40の下流側端部近傍とドラム38との間に出口マスク58bを、それぞれ有する(図3参照)。 Each of the
The
In addition, each film forming means includes an
シャワー電極40は、支持体Zの対向面から原料ガスを噴射する、CCP-CVDによる成膜に利用される、公知のシャワー電極(シャワープレート)である。成膜室20では、シャワー電極40とドラム38とによって、CCP-CVDを行うための電極対を構成するのは、前述のとおりである。
図示例において、シャワー電極40は、一例として、一面がドラム38(すなわち支持体Z)に対面して配置される、内部に空間(ガス供給空間)が形成された、略直方体形状を有する。また、シャワー電極40のドラム38との対向面には、この内部空間に連通するガス供給孔が、多数、形成されている。
また、図示例において、シャワー電極40のドラム38と対向(対面)する面は、ドラム38と表面と平行になるように、凹状の曲面となっている。すなわち、シャワー電極40のドラム38と対向する面は、ドラム38とシャワー電極との間隔が全面的に均一になるように、凹状の曲面となっている。 Theshower electrode 40 is a known shower electrode (shower plate) used for film formation by CCP-CVD, in which a raw material gas is injected from the opposing 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, theshower 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.
In the illustrated example, the surface of theshower electrode 40 facing (facing) the drum 38 is a concave curved surface so as to be parallel to the surface of the drum 38. That is, the surface of the shower electrode 40 facing the drum 38 is a concave curved surface so that the distance between the drum 38 and the shower electrode is uniform over the entire surface.
図示例において、シャワー電極40は、一例として、一面がドラム38(すなわち支持体Z)に対面して配置される、内部に空間(ガス供給空間)が形成された、略直方体形状を有する。また、シャワー電極40のドラム38との対向面には、この内部空間に連通するガス供給孔が、多数、形成されている。
また、図示例において、シャワー電極40のドラム38と対向(対面)する面は、ドラム38と表面と平行になるように、凹状の曲面となっている。すなわち、シャワー電極40のドラム38と対向する面は、ドラム38とシャワー電極との間隔が全面的に均一になるように、凹状の曲面となっている。 The
In the illustrated example, the
In the illustrated example, the surface of the
成膜室20においては、各成膜手段のシャワー電極40が、支持体Zの搬送方向すなわちドラム38の回転方向に配列して、配置される。
すなわち、図示例のCVD装置14は、プラズマCVDによる3つの成膜手段によって、1つの無機膜12を形成するものである。従って、支持体Zは、ドラム38に巻き掛けられ搬送されることで、CCP-CVDによる同じ無機膜の成膜を最大で3回行われて、表面に無機膜12が形成される。 In thefilm 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, theillustrated CVD apparatus 14 forms one inorganic film 12 by three film forming means by plasma CVD. Accordingly, the support Z is wound around the drum 38 and conveyed, so that the same inorganic film is formed three times at maximum by CCP-CVD, and the inorganic film 12 is formed on the surface.
すなわち、図示例のCVD装置14は、プラズマCVDによる3つの成膜手段によって、1つの無機膜12を形成するものである。従って、支持体Zは、ドラム38に巻き掛けられ搬送されることで、CCP-CVDによる同じ無機膜の成膜を最大で3回行われて、表面に無機膜12が形成される。 In the
That is, the
ガス供給手段56は、プラズマCVD装置等の真空形成装置に用いられる、公知のガス供給手段である。
このガス供給手段56は、シャワー電極40の内部空間に原料ガスを供給する。また、前述のように、シャワー電極40のドラム38との対向面には、内部空間に連通する多数のガス供給孔が形成されている。従って、シャワー電極40に供給された原料ガスは、このガス供給孔から、シャワー電極40とドラム38との間に供給される。
なお、ガス供給手段56が供給する原料ガス(プロセスガス/材料ガス)は、形成する無機膜12に応じた公知のものでよい。例えば、窒化珪素膜を形成する場合には、ガス供給手段56は、一例として、シランガス、アンモニアガスおよび窒素ガス(あるいはさらに水素ガス)を供給する。 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 theshower 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.
このガス供給手段56は、シャワー電極40の内部空間に原料ガスを供給する。また、前述のように、シャワー電極40のドラム38との対向面には、内部空間に連通する多数のガス供給孔が形成されている。従って、シャワー電極40に供給された原料ガスは、このガス供給孔から、シャワー電極40とドラム38との間に供給される。
なお、ガス供給手段56が供給する原料ガス(プロセスガス/材料ガス)は、形成する無機膜12に応じた公知のものでよい。例えば、窒化珪素膜を形成する場合には、ガス供給手段56は、一例として、シランガス、アンモニアガスおよび窒素ガス(あるいはさらに水素ガス)を供給する。 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
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.
高周波電源54は、シャワー電極40に、プラズマ励起電力を供給する電源である。高周波電源54も、13.56MHzの高周波電力を供給する電源等、各種のプラズマCVD装置で利用されている、公知の高周波電源である。
真空排気手段60は、プラズマCVDによる成膜のために、形成室内を排気して、所定の圧力に保つものであり、前述のように、真空形成装置に利用されている、公知の真空排気手段である。 The highfrequency 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.
真空排気手段60は、プラズマCVDによる成膜のために、形成室内を排気して、所定の圧力に保つものであり、前述のように、真空形成装置に利用されている、公知の真空排気手段である。 The high
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.
なお、本発明の製造方法において、支持体Zの搬送速度、形成圧力、原料ガスの供給量、プラズマ励起電力の強さなど、無機膜12の成膜条件には、特に限定はない。すなわち、成膜条件は、通常のプラズマCVDによる成膜と同様に、形成する無機膜12の種類や膜厚、支持体Zの種類等に応じて、適宜、設定すればよい。
なお、無機膜12を形成する際には、成膜手段52a、52bおよび52cは、基本的に、同じ成膜条件で成膜を行う。しかしながら、本発明は、これに限定はされず、必要に応じて、無機膜12を形成する際に、成膜手段52a、52bおよび52cの1以上で、他の成膜手段と成膜条件を変えてもよい。 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.
なお、無機膜12を形成する際には、成膜手段52a、52bおよび52cは、基本的に、同じ成膜条件で成膜を行う。しかしながら、本発明は、これに限定はされず、必要に応じて、無機膜12を形成する際に、成膜手段52a、52bおよび52cの1以上で、他の成膜手段と成膜条件を変えてもよい。 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
前述のように、成膜手段52a、52bおよび52cは、いずれも、シャワー電極40の上流側端部近傍とドラム38との間に入口マスク58aを、シャワー電極40の下流側端部近傍とドラム38との間に出口マスク58bを、それぞれ、有する。
As described above, the film forming means 52a, 52b, and 52c all include the entrance 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 58b.
この入口マスク58aは、成膜領域の上流側から成膜領域外に流れる原料ガス流を制御する、上流側制御手段である。具体的には、図3に成膜手段52aを例に模式的に示すように、入口マスク58aは、成膜領域(シャワー電極40と支持体Zとの対面領域)から、シャワー電極40(成膜領域)の上流側に流れる原料ガス流を規制する。なお、最上流の成膜手段52aの入口マスク58aは、最上流の成膜手段の成膜領域から、シャワー電極40の上流側に流れる原料ガス流を制御する制御手段である。
他方、出口マスク58bは、成膜手段の下流側から成膜領域外に流れる原料ガス流を制御する、下流側制御手段である。具体的には、同じく、図3に模式的に示すように、出口マスク58bは、成膜領域から、シャワー電極40の下流側に流れる原料ガス流を規制する。 Theinlet 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, theoutlet 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.
他方、出口マスク58bは、成膜手段の下流側から成膜領域外に流れる原料ガス流を制御する、下流側制御手段である。具体的には、同じく、図3に模式的に示すように、出口マスク58bは、成膜領域から、シャワー電極40の下流側に流れる原料ガス流を規制する。 The
On the other hand, the
図示例の成膜室20は、このように、成膜手段52a、52bおよび52cの3つの成膜手段を有し、かつ、各成膜手段が、このような入口マスク58aおよび出口マスク58bを有する。成膜室20は、このような構成を有することにより、主に無機膜12を形成する領域Bと、領域Bよりも薄く低密度である領域Aとを交互に有し、かつ、領域B-領域A-領域Bの積層構造を1以上有する、無機膜12を形成している。
The film forming chamber 20 in the illustrated example thus has three film forming means, film forming means 52a, 52b and 52c, and each film forming means has such an inlet mask 58a and an outlet mask 58b. Have. By having such a configuration, the film forming chamber 20 has alternately the regions B in which the inorganic film 12 is mainly formed and the regions A that are thinner and less dense than the regions B, and the regions B− An inorganic film 12 having at least one layered structure of region A and region B is formed.
プラズマCVDは、原料ガスを利用する成膜であるので、必然的に、成膜領域から、成膜領域外に向かう原料ガス(原料ガスや成膜種となる活性ラジカル)のガス流が生じる。
ここで、図3に、成膜手段52aを例に模式的に示すように、シャワー電極40の上下流端とドラム38との間に、成膜領域の上流側から流れる原料ガス流を規制する入口マスク58aおよび同下流側から流れる原料ガス流を規制する出口マスク58bを設けると、成膜領域から、成膜領域の上下流に流れるガス量は、非常に少なくなる。 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 thefilm 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. If the inlet mask 58a and the outlet mask 58b for restricting the raw material gas flow flowing from the downstream side are provided, the amount of gas flowing from the film formation region to the upstream and downstream of the film formation region becomes very small.
ここで、図3に、成膜手段52aを例に模式的に示すように、シャワー電極40の上下流端とドラム38との間に、成膜領域の上流側から流れる原料ガス流を規制する入口マスク58aおよび同下流側から流れる原料ガス流を規制する出口マスク58bを設けると、成膜領域から、成膜領域の上下流に流れるガス量は、非常に少なくなる。 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
そのため、成膜手段52aにおいては、支持体Zは、まず、成膜領域(入口マスク58a)の直上流において、入口マスク58aから漏れた原料ガスによって、無機膜が形成される。ここで、入口マスク58aから漏れる原料ガスは、少量である。また、成膜領域外(入口マスク58aの上流側=マスクの外)は、電界が掛からずにプラズマが形成されていないので、活性ラジカル(成膜種)が少なく、形成される膜の密度は低くなる。その結果、成膜領域(入口マスク58a)の直上流では、極薄く、かつ、非常に低密度の無機膜すなわち領域Aが形成される。
次いで、支持体Zは、成膜領域に侵入して、通常のCCP-CVDによる成膜と同様に無機膜を形成される。すなわち、成膜手段52aの成膜領域において、主に無機膜を構成する領域Bが形成される。
さらに、支持体Zは、成膜手段52aの成膜領域から搬出され、成膜領域(すなわち、出口マスク58b)の直下流において、出口マスク58bから漏れた原料ガスによって、無機膜が形成される。先と同様、出口マスク58bから漏れる原料ガスは少量で、しかも、成膜領域外で形成される膜の密度は低くなるので、支持体Zには、再度、極薄く、かつ、非常に低密度の無機膜すなわち領域Aが形成される。
以上の作用は、成膜手段52bおよび52cでも同様である。 Therefore, in thefilm 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 thefilm 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 thefilm forming unit 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 58b). . Similarly to the above, since the source gas leaking from the exit mask 58b is small, and the density of the film formed outside the film formation region is low, the support Z is again very 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.
次いで、支持体Zは、成膜領域に侵入して、通常のCCP-CVDによる成膜と同様に無機膜を形成される。すなわち、成膜手段52aの成膜領域において、主に無機膜を構成する領域Bが形成される。
さらに、支持体Zは、成膜手段52aの成膜領域から搬出され、成膜領域(すなわち、出口マスク58b)の直下流において、出口マスク58bから漏れた原料ガスによって、無機膜が形成される。先と同様、出口マスク58bから漏れる原料ガスは少量で、しかも、成膜領域外で形成される膜の密度は低くなるので、支持体Zには、再度、極薄く、かつ、非常に低密度の無機膜すなわち領域Aが形成される。
以上の作用は、成膜手段52bおよび52cでも同様である。 Therefore, in the
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
Further, the support Z is unloaded from the film forming region of the
The above operation is the same in the film forming means 52b and 52c.
前述のように、図示例の成膜室20は、3つの3つの成膜手段52a、52bおよび52cを有する。また、各成膜手段のシャワー電極40は、ドラム38に対面して支持体Zの搬送方向(ドラム38の回転方向)に配列されている。
従って、支持体Zは、まず、成膜手段52aの成膜領域の直上流において、入口マスク58aから漏れた原料ガスによって領域Aである層12aを形成され、次いで、成膜手段52aの成膜領域において領域Bである層12bを形成される。
ここで、領域Aである層12aは、成膜領域から漏れた原料ガスによる成膜であるので、層12aの形成によって、支持体Zの表面にプラズマ等によるダメージを与えることはない。しかも、無機膜12を主に構成する領域Bである層12bを成膜する際には、層12aが保護膜として作用する。そのため、層12bを形成するためのプラズマによる支持体Zの損傷を抑制した高品質な機能性フィルムを製造できる。 As described above, the illustratedfilm 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, thelayer 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 thelayer 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.
従って、支持体Zは、まず、成膜手段52aの成膜領域の直上流において、入口マスク58aから漏れた原料ガスによって領域Aである層12aを形成され、次いで、成膜手段52aの成膜領域において領域Bである層12bを形成される。
ここで、領域Aである層12aは、成膜領域から漏れた原料ガスによる成膜であるので、層12aの形成によって、支持体Zの表面にプラズマ等によるダメージを与えることはない。しかも、無機膜12を主に構成する領域Bである層12bを成膜する際には、層12aが保護膜として作用する。そのため、層12bを形成するためのプラズマによる支持体Zの損傷を抑制した高品質な機能性フィルムを製造できる。 As described above, the illustrated
Accordingly, in the support Z, first, the
Here, since the
次いで、支持体Zは、成膜手段52aの直下流および成膜領域52bの直上流において、出口マスク58bおよび入口マスク58aから漏れた原料ガスによって領域Aである層12cを形成され、次いで、成膜手段52bの成膜領域において領域Bである層12dを形成される。
次いで、支持体Zは、成膜手段52bの直下流および成膜領域52cの直上流において、出口マスク58bおよび入口マスク58aから漏れた原料ガスによって領域Aである層12dを形成され、次いで、成膜手段52cの成膜領域において領域Bである層12fを形成される。
さらに、支持体Zは、成膜手段52cの直下流において、出口マスク58bから漏れた原料ガスによって領域Aである層12gを形成される。
これにより、図1に示す、領域Aおよび領域Bが交互に積層された、層12a~層12gの7つ領域のからなる無機膜12が形成される。 Next, the support Z is formed with thelayer 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, the support Z is formed with thelayer 12d 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 52b and immediately upstream of the film forming region 52c. In the film formation region of the film means 52c, the layer 12f which is the region B is formed.
Further, on the support Z, thelayer 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 composed of the seven regions of thelayers 12a to 12g in which the regions A and the regions B are alternately stacked as shown in FIG. 1 is formed.
次いで、支持体Zは、成膜手段52bの直下流および成膜領域52cの直上流において、出口マスク58bおよび入口マスク58aから漏れた原料ガスによって領域Aである層12dを形成され、次いで、成膜手段52cの成膜領域において領域Bである層12fを形成される。
さらに、支持体Zは、成膜手段52cの直下流において、出口マスク58bから漏れた原料ガスによって領域Aである層12gを形成される。
これにより、図1に示す、領域Aおよび領域Bが交互に積層された、層12a~層12gの7つ領域のからなる無機膜12が形成される。 Next, the support Z is formed with the
Next, the support Z is formed with the
Further, on the support Z, the
Thereby, the inorganic film 12 composed of the seven regions of the
以上のように、RtoRによる成膜のように支持体Zを搬送しつつ成膜を行うと共に、複数の成膜手段を支持体の搬送方向に配列し、さらに、入口マスク58aおよび出口マスク58bのように、成膜領域から、成膜領域の上下流側の成膜領域外に流れる原料ガス流を制御するガス流の制御手段を設けることにより、領域Aおよび領域Bが交互に積層され、かつ、領域B-領域A-領域Bの積層構造を1以上有し、好ましくは領域A-領域B-領域Aの積層構造も1以上有する、本発明の機能性フィルムを、好適に製造することができる。
また、本例においては、入口マスク58aおよび/または出口マスク58bと、ドラム38との間隙の調整等、成膜領域から成膜領域外に流れる原料ガス流の量などを、原料ガスの導入方法や排気の制御などで調整することにより、領域Aの密度や厚さ等を調整することができる。例えば、成膜領域から成膜領域外に流れる原料ガス流の量を多くすることで、領域Aの密度を高くし、かつ、厚さも厚くできる。
さらに、成膜室20の構造の調整によっても、同様に、領域Aの密度や厚さ等を調整することができる。 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 theentrance 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 theinlet 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 thefilm forming chamber 20, the density and thickness of the region A can be adjusted in the same manner.
また、本例においては、入口マスク58aおよび/または出口マスク58bと、ドラム38との間隙の調整等、成膜領域から成膜領域外に流れる原料ガス流の量などを、原料ガスの導入方法や排気の制御などで調整することにより、領域Aの密度や厚さ等を調整することができる。例えば、成膜領域から成膜領域外に流れる原料ガス流の量を多くすることで、領域Aの密度を高くし、かつ、厚さも厚くできる。
さらに、成膜室20の構造の調整によっても、同様に、領域Aの密度や厚さ等を調整することができる。 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
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
Further, by adjusting the structure of the
無機膜12が形成された支持体Zすなわち機能性フィルム10は、ガイドローラ48および50に案内されて、隔壁64のスリット64aから、巻取り室24に搬送される。
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 64a of the partition wall 64 to the winding chamber 24.
図示例において、巻取り室24は、ガイドローラ68と、巻取り軸16と、真空排気手段70とを有する。
巻取り室24に搬送された支持体Zは、ガイドローラ68に案内されて巻取り軸16に搬送され、巻取り軸16によってロール状に巻回されガスバリアフィルムなどの機能性フィルムを巻回してなるロールとして、次の工程に供される。
また、先の供給室18と同様、巻取り室24にも真空排気手段70が配置され、形成中は、巻取り室24も、成膜室20における形成圧力に応じた真空度に減圧される。 In the illustrated example, the windingchamber 24 includes a guide roller 68, a winding shaft 16, and a vacuum exhaust unit 70.
The support Z transported to the windingchamber 24 is guided by the guide roller 68 and transported to the winding shaft 16, wound around the winding shaft 16 in a roll shape, and wound with a functional film such as a gas barrier film. The resulting roll is subjected to the next step.
Similarly to theprevious 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. .
巻取り室24に搬送された支持体Zは、ガイドローラ68に案内されて巻取り軸16に搬送され、巻取り軸16によってロール状に巻回されガスバリアフィルムなどの機能性フィルムを巻回してなるロールとして、次の工程に供される。
また、先の供給室18と同様、巻取り室24にも真空排気手段70が配置され、形成中は、巻取り室24も、成膜室20における形成圧力に応じた真空度に減圧される。 In the illustrated example, the winding
The support Z transported to the winding
Similarly to the
以下、CVD装置14の作用を説明する。
回転軸28に支持体ロールZrが装着されると、支持体Zは、支持体ロールZrから引き出される。支持体ロールZrから引き出された支持体は、ガイドローラ30によって案内されて成膜室20に至り、成膜室20において、ガイドローラ42および46に案内されて、ドラム38の表面の所定領域に掛け回され、次いで、ガイドローラ48および50によって案内されて巻取り室24に至り、巻取り室24において、ガイドローラ68に案内されて巻取り軸16に至る、所定の搬送経路を通紙される。 Hereinafter, the operation of theCVD apparatus 14 will be described.
When the support roll Zr is mounted on therotary 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 16. The
回転軸28に支持体ロールZrが装着されると、支持体Zは、支持体ロールZrから引き出される。支持体ロールZrから引き出された支持体は、ガイドローラ30によって案内されて成膜室20に至り、成膜室20において、ガイドローラ42および46に案内されて、ドラム38の表面の所定領域に掛け回され、次いで、ガイドローラ48および50によって案内されて巻取り室24に至り、巻取り室24において、ガイドローラ68に案内されて巻取り軸16に至る、所定の搬送経路を通紙される。 Hereinafter, the operation of the
When the support roll Zr is mounted on the
支持体Zの通紙が終了すると、供給室18、成膜室20および巻取り室24が閉塞される(密閉される)。次いで、真空排気手段32、60、および70が駆動され、供給室18、成膜室20および巻取り室24が、所定の圧力まで減圧される。各室の圧力が安定したら、成膜室20では、成膜手段52a、52bおよび52cにおいて、ガス供給手段56からシャワー電極40に、原料ガスが供給される。
成膜室20内が形成に対応する所定圧力で安定したら、供給室18から巻取り室24に向かう支持体Zの搬送が、開始され、また、成膜手段52a、52bおよび52cにおいて、高周波電源54からシャワー電極40へのプラズマ励起電力の供給を開始する。 When the feeding of the support Z is completed, thesupply 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 thefilm 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.
成膜室20内が形成に対応する所定圧力で安定したら、供給室18から巻取り室24に向かう支持体Zの搬送が、開始され、また、成膜手段52a、52bおよび52cにおいて、高周波電源54からシャワー電極40へのプラズマ励起電力の供給を開始する。 When the feeding of the support Z is completed, the
When the inside of the
供給室18から成膜室20に搬送された支持体Zは、ガイドローラ42および46によって案内され、ドラム38に巻き掛けられた状態で搬送されつつ、搬送方向に配列された成膜手段52a、52bおよび52cによって、前述のように層12a~層12gが、順次、形成されて無機膜12が形成される。
The support Z transported from the supply chamber 18 to the film forming chamber 20 is guided by guide rollers 42 and 46, and transported while being wound around the drum 38, while being deposited in the transport direction, the film forming means 52a, By the layers 52b and 52c, the layers 12a to 12g are sequentially formed as described above to form the inorganic film 12.
無機膜12が形成された支持体Zすなわち機能性フィルム10は、ガイドローラ48および50によって案内されて、巻取り室24に搬送される。
巻取り室24に搬送された支持体Zは、ガイドローラ68によって所定の経路に案内され、巻取り軸16によってロール状に巻回される。 The support Z on which the inorganic film 12 is formed, that is, thefunctional film 10 is guided by the guide rollers 48 and 50 and conveyed to the winding chamber 24.
The support Z conveyed to the windingchamber 24 is guided to a predetermined path by the guide roller 68 and is wound in a roll shape by the winding shaft 16.
巻取り室24に搬送された支持体Zは、ガイドローラ68によって所定の経路に案内され、巻取り軸16によってロール状に巻回される。 The support Z on which the inorganic film 12 is formed, that is, the
The support Z conveyed to the winding
図2および図3に示すCVD装置14は、成膜手段52a、52bおよび52cの全てが入口マスク58aおよび出口マスク58bを有しているが、本発明は、これに限定はされない。
例えば、成膜手段52aの出口マスク58bおよび成膜手段52bの入口マスク58aのいずれかを有さず、さらに、成膜手段52bの出口マスク58bおよび成膜手段52cの入口マスク58aのいずれかを有さない構成であっても、図1に示す層12a~層12bの7つの層からなる無機膜12を形成できる。 In theCVD 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 theoutlet 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 without the configuration, the inorganic film 12 including the seven layers 12a to 12b shown in FIG. 1 can be formed.
例えば、成膜手段52aの出口マスク58bおよび成膜手段52bの入口マスク58aのいずれかを有さず、さらに、成膜手段52bの出口マスク58bおよび成膜手段52cの入口マスク58aのいずれかを有さない構成であっても、図1に示す層12a~層12bの7つの層からなる無機膜12を形成できる。 In the
For example, it does not have either the
また、最上流の成膜手段52aの入口マスク58aを有さない場合には、図1に示す無機膜12において、最も下の層12aを有さない層12b~層12gの6つの層からなる無機膜を形成できる。しかしながら、支持体Zの表面には、領域Aを成膜するのが好ましいのは、前述のとおりである。
さらに、最下流の成膜手段52cの出口マスク58bを有さない場合には、図1に示す無機膜12において、最も上の層12gを有さない層12a~層12fの6つの層からなる無機膜を形成できる。 Further, when theinlet mask 58a of the most upstream film forming means 52a is not provided, the inorganic film 12 shown in FIG. 1 includes the six layers 12b to 12g that do not have the lowest 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 theoutlet mask 58b of the most downstream film forming means 52c is not provided, the inorganic film 12 shown in FIG. 1 is composed of six layers 12a to 12f having no uppermost layer 12g. An inorganic film can be formed.
さらに、最下流の成膜手段52cの出口マスク58bを有さない場合には、図1に示す無機膜12において、最も上の層12gを有さない層12a~層12fの6つの層からなる無機膜を形成できる。 Further, when the
Further, when the
また、CVD装置14では、成膜手段52a、52bおよび52cの全てを駆動するのに限定もされず、2以上を駆動すればよい。
すなわち、何れかを駆動しないことにより(無くすことにより)、図1に示す無機膜12において、層12a~層12eの5つの層からなる無機膜を形成できる。 Further, theCVD 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 of them, it is possible to form an inorganic film composed of fivelayers 12a to 12e in the inorganic film 12 shown in FIG.
すなわち、何れかを駆動しないことにより(無くすことにより)、図1に示す無機膜12において、層12a~層12eの5つの層からなる無機膜を形成できる。 Further, the
That is, by not driving any of them, it is possible to form an inorganic film composed of five
本発明の製造方法において、成膜領域から外部に流れる原料ガス流を制御する制御手段は、図示例のような原料ガスの流れを規制するマスクに限定はされない。
例えば、原料ガスの供給方向と排気方向とを調整することにより、成膜領域から外部に流れる原料ガス流を制御して、成膜領域の直上流および/または直下流において、領域Aを成膜するようにしてもよい。また、成膜電極の上流側と下流側の電界の調整を、成膜領域から外部に流れる原料ガス流を制御する制御手段と見なして、成膜領域の上流および/または下流において、領域Aを成膜するようにしてもよい。 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 raw material gas flow flowing from the film formation region to the outside, and the region A is formed upstream and / or downstream of the film formation region. A film may be formed.
例えば、原料ガスの供給方向と排気方向とを調整することにより、成膜領域から外部に流れる原料ガス流を制御して、成膜領域の直上流および/または直下流において、領域Aを成膜するようにしてもよい。また、成膜電極の上流側と下流側の電界の調整を、成膜領域から外部に流れる原料ガス流を制御する制御手段と見なして、成膜領域の上流および/または下流において、領域Aを成膜するようにしてもよい。 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 raw material gas flow flowing from the film formation region to the outside, and the region A is formed upstream and / or downstream of the film formation region. A film may be formed.
以上、本発明の機能性フィルムおよび機能性フィルムの製造方法について詳細に説明したが、本発明は、上記実施例に限定はされず、本発明の要旨を逸脱しない範囲において、各種の改良や変更を行なってもよいのは、もちろんである。
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.
[実施例1]
図1に示すようなCVD装置14を用いて、支持体Zの表面に、窒化珪素膜を形成して、ガスバリアフィルムを製造した。 [Example 1]
A gas barrier film was manufactured by forming a silicon nitride film on the surface of the support Z using aCVD apparatus 14 as shown in FIG.
図1に示すようなCVD装置14を用いて、支持体Zの表面に、窒化珪素膜を形成して、ガスバリアフィルムを製造した。 [Example 1]
A gas barrier film was manufactured by forming a silicon nitride film on the surface of the support Z using a
ドラム38は、ステンレス製で、直径1500mmの物を用いた。また、このドラム38は、温度調節手段を内蔵しており、成膜中は、ドラム38の表面温度を10℃に調節した。
支持体Zは、幅100cm、厚さ70μmのPETフィルムを用いた。
原料ガスは、シランガス(SiH4)、アンモニアガス(NH3)、水素ガス(H2)および窒素ガス(N2)を用いた。成膜圧力は100Paとした。
シャワー電極40には、高周波電源54から、周波数13.5MHzで、3kWのプラズマ励起電力を供給した。 Thedrum 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.
Theshower 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.
支持体Zは、幅100cm、厚さ70μmのPETフィルムを用いた。
原料ガスは、シランガス(SiH4)、アンモニアガス(NH3)、水素ガス(H2)および窒素ガス(N2)を用いた。成膜圧力は100Paとした。
シャワー電極40には、高周波電源54から、周波数13.5MHzで、3kWのプラズマ励起電力を供給した。 The
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
以上の条件において、成膜手段52aおよび52bの2つを駆動して、支持体Zの表面に、厚さ約100nmの窒化珪素膜を形成し、ガスバリアフィルムを作製した。
Under the above conditions, two of 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.
TEMによる断面構造の観測によって測定した所、窒化珪素膜は、図1に示す無機膜12における層12a~層12eの5つの層からなるものであった。すなわち、この窒化珪素膜は、領域B-領域A-領域Bの積層構造を1つ、領域A-領域B-領域Aの積層構造を2つ、有するものである。
また、領域Aである層12aおよび12eの厚さは約5nmで層12cの厚さは約10nmであり、領域Bである層12bおよび12dの厚さは約40nmであった。 When measured by observing the cross-sectional structure with TEM, the silicon nitride film was composed of five layers oflayers 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.
また、領域Aである層12aおよび12eの厚さは約5nmで層12cの厚さは約10nmであり、領域Bである層12bおよび12dの厚さは約40nmであった。 When measured by observing the cross-sectional structure with TEM, the silicon nitride film was composed of five layers of
In addition, the thickness of the
[実施例2]
成膜手段52a、52bおよび52cの全てを駆動して、実施例1と同様にして、厚さ約100nmの窒化珪素膜を形成して、ガスバリアフィルムを作製した。なお、膜厚は、支持体Zの搬送速度で調整した。
実施例1と同様に測定したところ、窒化珪素膜は、図1に示す無機膜12と同様の層12a~層12gの7つの層からなるものであった。すなわち、この窒化珪素膜は、領域B-領域A-領域Bの積層構造を2つ、領域A-領域B-領域Aの積層構造を3つ、有するものである。
また、領域Aである層12aおよび12gの厚さは約5nmで、層12cおよび12eの厚さは約10nmであり、領域Bである層12b、12dおよび12fの厚さは約23nmであった。 [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 sevenlayers 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. .
成膜手段52a、52bおよび52cの全てを駆動して、実施例1と同様にして、厚さ約100nmの窒化珪素膜を形成して、ガスバリアフィルムを作製した。なお、膜厚は、支持体Zの搬送速度で調整した。
実施例1と同様に測定したところ、窒化珪素膜は、図1に示す無機膜12と同様の層12a~層12gの7つの層からなるものであった。すなわち、この窒化珪素膜は、領域B-領域A-領域Bの積層構造を2つ、領域A-領域B-領域Aの積層構造を3つ、有するものである。
また、領域Aである層12aおよび12gの厚さは約5nmで、層12cおよび12eの厚さは約10nmであり、領域Bである層12b、12dおよび12fの厚さは約23nmであった。 [Example 2]
All of the
When measured in the same manner as in Example 1, the silicon nitride film was composed of seven
Further, the thickness of the
[比較例1]
成膜手段52aのみを駆動して、実施例1と同様にして、厚さ約100nmの窒化珪素膜を形成して、ガスバリアフィルムを作製した。なお、膜厚は、先の例と同様に、支持体Zの搬送速度で調整した。
実施例1と同様に測定したところ、窒化珪素膜は、図1に示す無機膜12における層12a~12cの3つの層からなるものであった。また、領域Aである層12aおよび12cの厚さは約5nm、領域Bである層12bの厚さは、約90nmであった。 [Comparative Example 1]
Only thefilm 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 threelayers 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.
成膜手段52aのみを駆動して、実施例1と同様にして、厚さ約100nmの窒化珪素膜を形成して、ガスバリアフィルムを作製した。なお、膜厚は、先の例と同様に、支持体Zの搬送速度で調整した。
実施例1と同様に測定したところ、窒化珪素膜は、図1に示す無機膜12における層12a~12cの3つの層からなるものであった。また、領域Aである層12aおよび12cの厚さは約5nm、領域Bである層12bの厚さは、約90nmであった。 [Comparative Example 1]
Only the
When measured in the same manner as in Example 1, the silicon nitride film was composed of three
[比較例2]
成膜手段52aのみを駆動して、実施例1と同様にして、厚さ約100nmの窒化珪素膜を形成して、ガスバリアフィルムを作製した。なお、本例においては、成膜手段52aの出口マスク58bを取り外した。また、膜厚は、先の例と同様に、支持体Zの搬送速度で調整した。
実施例1と同様に測定したところ、窒化珪素膜は、図1に示す無機膜12における層12aおよび12bの2つの層からなるものであった。また、領域Aである層12a厚さは約5nm、領域Bである層12bの厚さは、約95nmであった。 [Comparative Example 2]
Only thefilm 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. Moreover, the film thickness was adjusted with the conveyance speed of the support body Z like 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 thelayer 12a as the region A was about 5 nm, and the thickness of the layer 12b as the region B was about 95 nm.
成膜手段52aのみを駆動して、実施例1と同様にして、厚さ約100nmの窒化珪素膜を形成して、ガスバリアフィルムを作製した。なお、本例においては、成膜手段52aの出口マスク58bを取り外した。また、膜厚は、先の例と同様に、支持体Zの搬送速度で調整した。
実施例1と同様に測定したところ、窒化珪素膜は、図1に示す無機膜12における層12aおよび12bの2つの層からなるものであった。また、領域Aである層12a厚さは約5nm、領域Bである層12bの厚さは、約95nmであった。 [Comparative Example 2]
Only the
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
[比較例3]
成膜手段52aおよび52bの2つを駆動して、実施例1と同様にして、厚さ約100nmの窒化珪素膜を形成し、ガスバリアフィルムを作製した。なお、本例においては、成膜手段52aおよび52bの入口マスク58aおよび出口マスク58bを取り外した。
実施例1と同様に測定したところ、窒化珪素膜は、領域Bのみで形成されていた。 [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, theinlet 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.
成膜手段52aおよび52bの2つを駆動して、実施例1と同様にして、厚さ約100nmの窒化珪素膜を形成し、ガスバリアフィルムを作製した。なお、本例においては、成膜手段52aおよび52bの入口マスク58aおよび出口マスク58bを取り外した。
実施例1と同様に測定したところ、窒化珪素膜は、領域Bのみで形成されていた。 [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
When measured in the same manner as in Example 1, the silicon nitride film was formed only in the region B.
作製した5種のガスバリアフィルムについて、ガスバリア性および密着性を測定した。
ガスバリア性は、モコン法によって水蒸気透過率[g/(m2・day)]を測定することで、測定した。なお、モコン法の測定限界を超えた例は、カルシウム腐食法(特開2005-283561号公報に記載される方法)によって、水蒸気透過率を測定した。 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, in an example exceeding the measurement limit of the Mocon method, the water vapor transmission rate was measured by a calcium corrosion method (a method described in JP-A-2005-283561).
ガスバリア性は、モコン法によって水蒸気透過率[g/(m2・day)]を測定することで、測定した。なお、モコン法の測定限界を超えた例は、カルシウム腐食法(特開2005-283561号公報に記載される方法)によって、水蒸気透過率を測定した。 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, in an example exceeding the measurement limit of the Mocon method, the water vapor transmission rate was measured by a calcium corrosion method (a method described in JP-A-2005-283561).
密着性は、テープ剥離試験によって無機膜を剥離することで測定した。
テープ剥離試験によって、無機膜が全く剥離しなかったものをランクA;
テープ剥離試験によって、無機膜の一部が剥離したものをランクB;
テープ剥離試験によって、無機膜が全面剥離しものをランクC; と評価した。
結果を下記表に示す。 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.
テープ剥離試験によって、無機膜が全く剥離しなかったものをランクA;
テープ剥離試験によって、無機膜の一部が剥離したものをランクB;
テープ剥離試験によって、無機膜が全面剥離しものをランクC; と評価した。
結果を下記表に示す。 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.
上記表に示されるように、領域B-領域A-領域Bの積層構造、および、領域A-領域B-領域Aの積層構造を1以上有する本発明の機能性フィルムにかかる実施例1および実施例2のガスバリアフィルムは、いずれも、優れたガスバリア性を有し、さらに、無機膜の密着性も高い。
これに対し、領域Aと領域Bとの積層構造であっても、領域B-領域A-領域Bの積層構造を有さない比較例1および比較例2のガスバリアフィルムは、ガスバリア性および無機膜の密着性が、共に、不十分である。さらに、領域Aと領域Bとの積層構造を有さない比較例3のガスバリアフィルムは、ガスバリア性および無機膜の密着性が、共に、低い。
以上の結果より、本発明の効果は明らかである。 As shown in the above table, Example 1 and Example relating to the functional film of the present invention having one or more layer B-region A-region B laminate structures and region A-region B-region A laminate structures 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.
これに対し、領域Aと領域Bとの積層構造であっても、領域B-領域A-領域Bの積層構造を有さない比較例1および比較例2のガスバリアフィルムは、ガスバリア性および無機膜の密着性が、共に、不十分である。さらに、領域Aと領域Bとの積層構造を有さない比較例3のガスバリアフィルムは、ガスバリア性および無機膜の密着性が、共に、低い。
以上の結果より、本発明の効果は明らかである。 As shown in the above table, Example 1 and Example relating to the functional film of the present invention having one or more layer B-region A-region B laminate structures and region A-region B-region A laminate structures 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.
ガスバリアフィルムや反射防止フィルムなど、各種の機能性フィルムおよび機能性フィルムの製造に、好適に利用可能である。
It can be suitably used for the production of various functional films and functional films such as gas barrier films and antireflection films.
10 機能性フィルム
12 無機膜
14 (プラズマ)CVD装置
16 巻取り軸
18 供給室
20 形成室
24 巻取り室
28 回転軸
30,42,46,48,50,68 ガイドローラ
32,60,70 真空排気手段
34,64 隔壁
38 ドラム
40 シャワー電極
52a,52b,52c 成膜手段
54 高周波電源
56 ガス供給手段
58a 入口マスク
58b 出口マスク DESCRIPTION OFSYMBOLS 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
12 無機膜
14 (プラズマ)CVD装置
16 巻取り軸
18 供給室
20 形成室
24 巻取り室
28 回転軸
30,42,46,48,50,68 ガイドローラ
32,60,70 真空排気手段
34,64 隔壁
38 ドラム
40 シャワー電極
52a,52b,52c 成膜手段
54 高周波電源
56 ガス供給手段
58a 入口マスク
58b 出口マスク DESCRIPTION OF
Claims (14)
- 支持体と、前記支持体の上に形成された無機膜とを有する機能性フィルムであって、
前記無機膜は、領域B、および、この領域Bよりも低密度かつ薄い領域Aを有し、さらに、厚さ方向に積層された領域B-領域A-領域Bの積層構造を、1以上有することを特徴とする機能性フィルム。 A functional film having a support and an inorganic film formed on the support,
The inorganic film has a region B and a region A that is lower in density and thinner than the region B, and further has one or more stacked structures of a region B, a region A, and a region B stacked in the thickness direction. A functional film characterized by that. - 前記無機膜が、さらに、厚さ方向に積層された領域A-領域B-領域Aの積層構造を、1以上有する請求項1に記載の機能性フィルム。 2. The functional film according to claim 1, wherein 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.
- 前記領域Aの密度をa、前記領域Bの密度をbとした際に、『0.6<a/b<1』を満たす請求項1または2に記載の機能性フィルム。 The functional film according to claim 1 or 2, wherein “0.6 <a / b <1” is satisfied when the density of the region A is a and the density of the region B is b.
- 前記無機膜が、珪素と窒素とを含む請求項1~3のいずれかに記載の機能性フィルム。 The functional film according to any one of claims 1 to 3, wherein the inorganic film contains silicon and nitrogen.
- 前記領域B-領域A-領域Bの積層構造の厚さが10~200nmである請求項1~4のいずれかに記載の機能性フィルム。 The functional film according to any one of claims 1 to 4, wherein a thickness of the laminated structure of the region B, the region A, and the region B is 10 to 200 nm.
- 前記領域A-領域B-領域Aの積層構造の厚さが5~100nmである請求項2~5のいずれかに記載の機能性フィルム。 6. The functional film according to claim 2, wherein the thickness of the laminated structure of the region A, the region B, and the region A is 5 to 100 nm.
- 前記無機膜がガスバリア性を有する請求項1~6のいずれかに記載の機能性フィルム。 The functional film according to any one of claims 1 to 6, wherein the inorganic film has gas barrier properties.
- 支持体を搬送しつつ、前記支持体の搬送方向に配列された複数のプラズマCVDによる成膜手段によって同じ無機膜を成膜すると共に、
前記支持体の搬送方向に連続する成膜手段において、上流の前記成膜手段の成膜領域の下流側から成膜領域外に向かうガス流を制御する下流側制御手段、および、下流の前記成膜手段の成膜領域の上流側から成膜領域外へのガス流を制御する上流側制御手段の、少なくとも一方を用いて、前記無機膜の形成を行うことを特徴とする機能性フィルムの製造方法。 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. Production of the functional film, wherein the inorganic film is formed using at least one of the upstream control means for controlling the gas flow from the upstream side of the film forming area to the outside of the film forming area. Method. - 前記無機膜の形成を、最上流の成膜手段の成膜領域の上流側から成膜領域外へのガス流を制御する制御手段を用いて行う請求項8に記載の機能性フィルムの製造方法。 The method for producing a functional film according to claim 8, wherein the inorganic film is formed by using a control unit that controls a gas flow from the upstream side of the film formation region of the uppermost film formation unit to the outside of the film formation region. .
- 前記無機膜の形成を、前記下流側制御手段および上流側制御手段の両方を用いて行う請求項8または9に記載の機能性フィルムの製造方法。 The method for producing a functional film according to claim 8 or 9, wherein the inorganic film is formed by using both the downstream control means and the upstream control means.
- 前記ガス流を制御する制御手段が、ガス流を規制するマスクである請求項8~10のいずれかに記載の機能性フィルムの製造方法。 11. The method for producing a functional film according to claim 8, wherein the control means for controlling the gas flow is a mask for regulating the gas flow.
- 前記支持体として、長尺な支持体を用い、この長尺な支持体を長手方向に搬送しつつ、前記複数の成膜手段によって無機膜の形成を行う請求項8~11のいずれかに記載の機能性フィルムの製造方法。 The inorganic film is formed by the plurality of film forming means while using a long support as the support, and transporting the long support in the longitudinal direction. A method for producing a functional film.
- 前記長尺な支持体を巻回してなる支持体ロールから支持体を送り出して搬送し、形成済の支持体を、再度、ロール状に巻回する請求項12に記載の機能性フィルムの製造方法。 The method for producing a functional film according to claim 12, 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. .
- 前記長尺な支持体の搬送経路に、前記長尺な支持体を周面に巻き掛けて回転することによって搬送する円筒状のドラムを有し、前記複数の成膜手段は、前記ドラムの周面に対向して配置される請求項12または13に記載の機能性フィルムの製造方法。 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 12 or 13 arrange | positioned facing a surface.
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