WO2016117223A1 - Gas barrier film manufacturing apparatus and manufacturing method - Google Patents

Abstract

[Problem] To provide a manufacturing apparatus and manufacturing method for a gas barrier film with good barrier properties and adhesiveness. [Solution] A manufacturing apparatus 100 for manufacturing a gas barrier film 10 using a roll-to-roll-type plasma CVD method comprises: an electric discharge space for converting a starting material gas and a reaction gas for forming a barrier layer 20 of the gas barrier film into a plasma; conveyance mechanisms 120, 125, 130, 132 for continuously conveying the substrate 30 of the gas barrier film through the electric discharge space; and a cryocoil 170 capable of condensing and trapping precursors generated by the conversion of the starting material gas and reaction gas to plasma. The cryocoil 170 is set at a position, which is on the upstream side of the electric discharge space in the conveyance direction of the substrate 30 and at which adhesion of precursors to the substrate 30 to be conveyed into the electric discharge space is limited by condensing and trapping precursors that have leaked from the electric discharge space.

Description

Gas barrier film manufacturing apparatus and manufacturing method

The present invention relates to a gas barrier film manufacturing apparatus and manufacturing method.

A gas barrier film that prevents permeation of water vapor, oxygen, and the like has a barrier layer having a barrier property and a base material portion that supports the barrier layer, and is manufactured by a plasma CVD (PECVD: plasma-enhanced chemical vapor deposition) method. . The barrier layer is formed by continuously transporting the base portion of the gas barrier film via a discharge space for converting the source gas and the reaction gas into plasma (see, for example, Patent Documents 1 and 2).

JP 2013-28163 A JP 2014-61679 A

However, there is a problem that the precursor generated by the plasma of the raw material gas and the reaction gas leaks from the discharge space and adheres to the base portion of the gas barrier film before being carried into the discharge space. For example, the layer formed by the adhesion of the precursor is very brittle and easily damaged, and deteriorates the smoothness of the base material portion. Therefore, the barrier property and adhesion of the barrier layer formed thereon are deteriorated. .

On the other hand, in order to reduce the precursor leaking from the discharge space, when narrowing the transport path of the base part of the gas barrier film that becomes the leak path of the precursor, the base part of the gas barrier film is inadvertently in contact with the transport path. There is a risk of damage. Therefore, it is difficult to suppress the leakage of the precursor from the conveyance path.

The present invention has been made to solve the problems associated with the above-described conventional technology, and an object thereof is to provide a gas barrier film manufacturing apparatus and manufacturing method having good barrier properties and adhesion.

The above object of the present invention is achieved by the following means.

(1) A manufacturing apparatus for manufacturing a gas barrier film having a barrier layer having a barrier property and a base material portion supporting the barrier layer by a roll-to-roll type plasma CVD method,
A discharge space for converting the source gas and the reaction gas to form the barrier layer into plasma;
A transport mechanism for continuously transporting the base portion of the gas barrier film via the discharge space;
A low-temperature condensing member having a temperature capable of condensing and trapping the precursor generated by plasmification of the source gas and the reaction gas,
The low temperature condensing member is
The gas barrier film upstream of the discharge space in the transport direction of the base material portion of the gas barrier film, before the precursor leaking from the discharge space is condensed and trapped, and is carried into the discharge space The manufacturing apparatus installed in the position which suppresses that the said precursor adheres to the said base material part.

(2) a film forming roll around which the base portion of the gas barrier film is wound;
A shower electrode disposed relative to the film forming roll and constituting an electrode pair together with the film forming roll;
The said discharge space is a manufacturing apparatus as described in said (1) comprised by the space between the said shower electrode and the said film-forming roll.

(3) The discharge space and the shower electrode are disposed, and a film forming chamber in which a portion around which the base material portion of the gas barrier film in the film forming roll is wound is further provided,
The manufacturing apparatus according to (2), wherein the low-temperature condensing member is disposed in the film forming chamber.

(4) The manufacturing apparatus according to (3), wherein the position where the low-temperature condensing member is installed is in the vicinity of the outer periphery of the film forming roll.

(5) The manufacturing apparatus according to (4), wherein the position where the low-temperature condensing member is installed is adjacent to the shower electrode.

(6) a first film forming roll;
It is located on the downstream side in the transport direction of the base material portion of the gas barrier film from the first film forming roll, and is disposed relative to the first film forming roll, and an electrode pair together with the first film forming roll. And further comprising a second film forming roll,
The said discharge space is a manufacturing apparatus as described in said (1) comprised by the space between a said 1st film-forming roll and a said 2nd film-forming roll.

(7) The manufacturing apparatus according to (6), wherein the position where the low-temperature condensing member is installed is in the vicinity of the outer periphery of the first film forming roll.

(8) The manufacturing according to (7), wherein the position where the low-temperature condensing member is installed is in the vicinity of a position immediately before the base portion of the gas barrier film is wound around the first film forming roll. apparatus.

(9) A baffle plate further disposed between the low-temperature condensing member and the discharge space,
The manufacturing apparatus according to any one of (1 to (8), wherein the baffle plate suppresses leakage of the precursor from the discharge space.

(10) a second low-temperature condensing member having a temperature at which the precursor generated by plasmification of the source gas and the reaction gas can be condensed and trapped;
The transport mechanism reverses the transport direction of the base material portion of the gas barrier film after the formation of the barrier layer on the base material portion of the gas barrier film is completed, and passes through the discharge space, The base portion of the gas barrier film is configured to be continuously re-transportable,
The second low-temperature condensing member condenses and traps the precursor leaking from the discharge space on the upstream side in the re-transport direction of the base material portion of the gas barrier film from the discharge space. 10. The production according to any one of (1) to (9), wherein the production is installed at a position where the precursor is prevented from adhering to the barrier layer of the gas barrier film before being carried into the container. apparatus.

(11) A manufacturing method for manufacturing a gas barrier film having a barrier layer having a barrier property and a base material portion supporting the barrier layer by a roll-to-roll type plasma CVD method,
When continuously transporting the base material portion of the gas barrier film via a discharge space for converting the raw material gas and the reaction gas to plasma into the barrier layer,
The precursor leaked from the discharge space is condensed and trapped by the low-temperature condensing member installed on the upstream side in the transport direction of the base material part of the gas barrier film from the discharge space, and before being carried into the discharge space. The manufacturing method which suppresses that the said precursor adheres to the said base material part of the said gas barrier film.

(12) The manufacturing method according to (11), wherein leakage of the precursor from the discharge space is suppressed by a baffle plate arranged between the low-temperature condensing member and the discharge space.

(13) After the formation of the barrier layer on the base portion of the gas barrier film is completed, the transport direction of the base portion of the gas barrier film is reversed, and the gas barrier passes through the discharge space. When continuously re-feeding the base part of the film,
The precursor leaked from the discharge space is condensed and trapped by the second low-temperature condensing member installed on the upstream side in the re-conveying direction of the base material portion of the gas barrier film from the discharge space, and trapped in the discharge space. The manufacturing method according to (11) or (12), wherein the precursor is prevented from adhering to the barrier layer of the gas barrier film before being carried in.

(14) The manufacturing method according to any one of (11) to (13), wherein the source gas is an organosilicon compound.

According to the gas barrier film manufacturing apparatus and the manufacturing method of the present invention, the precursor of the gas barrier film before being brought into the discharge space by condensing and trapping the precursor leaked from the discharge space by the low-temperature condensing member. It is suppressed that a precursor adheres to a part. Therefore, since a precursor-derived layer is not interposed between the base material portion and the barrier layer, the barrier layer has good barrier properties and adhesion. That is, it is possible to provide a gas barrier film manufacturing apparatus and manufacturing method having good barrier properties and adhesion.

Further objects, features, and characteristics of the present invention will become apparent by referring to the preferred embodiments illustrated in the following description and the accompanying drawings.

It is sectional drawing for demonstrating the gas barrier film which concerns on Embodiment 1. FIG. It is the schematic for demonstrating the manufacturing apparatus of the gas barrier film which concerns on Embodiment 1. FIG. FIG. 3 is an enlarged view of a main part of FIG. 2. 3 is a flowchart for explaining a method for producing a gas barrier film according to Embodiment 1. 3 is a table showing performance evaluation results of gas barrier films according to Examples 1 to 4 and Comparative Examples 1 to 4 according to Embodiment 1. FIG. It is the schematic for demonstrating the installation position of the cryocoil in the comparative examples 3 and 4. FIG. FIG. 6 is a schematic diagram for explaining a first modification according to the first embodiment. FIG. 10 is a schematic diagram for explaining a second modification according to the first embodiment. It is the schematic for demonstrating the gas barrier film manufacturing apparatus which concerns on Embodiment 2. FIG. 5 is a flowchart for explaining a method for producing a gas barrier film according to Embodiment 2. 6 is a table showing results of performance evaluation of gas barrier films according to Examples 1 and 2 and Comparative Example 1 according to Embodiment 2. FIG. 9 is a schematic diagram for explaining a first modification according to the second embodiment. FIG. 10 is a schematic diagram for explaining a second modification according to the second embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, the dimension ratio of drawing is exaggerated on account of description, and may differ from an actual ratio.

FIG. 1 is a cross-sectional view for explaining a gas barrier film according to Embodiment 1. FIG.

As shown in FIG. 1, the gas barrier film 10 according to Embodiment 1 includes a barrier layer 20 and a base material portion 30 and is applied to packaging, electronic devices, and the like. The electronic device is, for example, a solar cell element, an organic electro-luminescence (OEL) element, or a liquid crystal display (LCD) element.

The barrier layer 20 is a thin film having a barrier property manufactured by a roll-to-roll type plasma CVD method, and is disposed on one surface of the base material portion 30. The barrier layer 20 has a composition according to conditions such as a raw material gas and a reaction gas contained in the film forming gas, and a decomposition temperature. For example, the barrier layer 20 produced using a silicon compound and oxygen as a source gas and a reaction gas contains a silicon oxide.

The base material portion 30 includes a base material 32, a clear hard coat layer 34, and a bleed-out prevention layer 36. The base material 32 is a support for the barrier layer 20 and is made of, for example, a colorless and transparent resin film.

The clear hard coat layer 34 is located between the barrier layer 20 and the base material 32. The clear hard coat layer 34 has a function of improving adhesion between the barrier layer 20 and the base material 32, a function of relaxing internal stress resulting from a difference between expansion and contraction of the barrier layer 20 and the base material 32, and the barrier layer 20 Has a function of flattening the surface on which the low molecular weight component is disposed, and a function of preventing low molecular weight components such as monomers and oligomers from the substrate 32 from bleeding out.

The bleed-out prevention layer 36 is disposed on the other surface of the base material portion 30 (the surface of the base material 32 on which the barrier layer 20 and the clear hard coat layer 34 are not disposed). The bleed-out prevention layer 36 has a function of preventing bleed-out of low molecular weight components such as monomers and oligomers from the base material 32.

Next, materials of the barrier layer 20, the base material 32, the clear hard coat layer 34, and the bleed-out prevention layer 36 will be described.

The barrier layer 20 contains silicon oxide (SiO ₂ ), silicon nitride, silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon carbide, aluminum oxide, titanium oxide, aluminum silicate, a composite thereof, and the like. Is possible.

For example, when the barrier layer 20 contains silicon, oxygen, and carbon, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms determines the performance variation over time and the gas barrier properties. From the viewpoint, it is preferably 20 at% or more, more preferably 25% or more. From the viewpoint of moisture resistance, flexibility and flexibility, it is preferably 40% or less, more preferably 45 at% or less. The atomic ratio of the oxygen atom content is preferably 30 at% or more from the viewpoint of transparency and durability, and preferably 70 at% or less from the viewpoint of suppression of performance fluctuation over time and durability due to temperature change. is there. The atomic ratio of the carbon atom content is preferably 0.5 at% or more from the viewpoint of flexibility and durability due to temperature change, and preferably 40 at% or less from the viewpoint of transparency and suppression of film defects. .

The thickness of the barrier layer 20 is preferably 10 nm or more from the viewpoint of film thickness uniformity and gas barrier properties, and preferably 500 nm or less from the viewpoint of crack suppression.

The base material 32 is, for example, a polyester resin, a polyolefin resin, a polyamide resin, a polycarbonate resin, a polystyrene resin, a polyvinyl alcohol resin, a saponified ethylene-vinyl acetate copolymer, a polyacrylonitrile resin, or an acetal resin. It is comprised from resin, a polyimide-type resin, etc. The polyester resin is, for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). The polyolefin resin is, for example, polyethylene (PE), polypropylene (PP), or cyclic polyolefin. From the viewpoint of heat resistance, linear expansion coefficient, and production cost, polyester resins and polyolefin resins are preferable, and PET and PEN are particularly preferable. Two or more kinds of resins for the base material 32 can be used in combination.

The thickness of the base material 32 is appropriately set in consideration of the stability and mechanical strength when producing the gas barrier film 10, and is preferably in the range of 5 to 500 μm, for example, in the range of 50 to 200 μm. More preferably, it is in the range of 50 to 100 μm.

From the viewpoint of adhesion to the barrier layer 20, it is preferable to clean the surface of the substrate 32 by subjecting it to a surface activation treatment. The surface activation treatment is, for example, corona treatment, plasma treatment, or flame treatment.

The clear hard coat layer 34 can be formed, for example, by applying a photosensitive resin composition on one surface of the substrate 32 and curing it. The photosensitive resin composition contains a photosensitive resin, a photopolymerization initiator, a solvent, and the like. The photosensitive resin is, for example, a resin containing an acrylate compound having a radical reactive unsaturated bond, a resin containing an acrylate compound and a mercapto compound having a thiol group, or a resin containing a polyfunctional acrylate monomer. Resins containing a polyfunctional acrylate monomer are epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, glycerol methacrylate, and the like.

Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propane, α-acyloxime ester, thioxanthones. The photosensitive resin and the polymerization initiator can be used in combination of two or more.

The thickness of the clear hard coat layer is 1 μm or more, more preferably 2 μm or more from the viewpoint of heat resistance of the gas barrier film 10, and more preferably 10 μm or less from the viewpoint of optical characteristics and curl suppression of the gas barrier film 10. Is 7 μm.

The bleed-out prevention layer 36 can be formed, for example, by applying a photosensitive resin composition on the other surface of the substrate 32 and curing it. As the photosensitive resin and the polymerization initiator constituting the photosensitive resin composition, those described above can be applied.

The thickness of the bleed-out prevention layer is 1 μm or more, more preferably 2 μm or more from the viewpoint of heat resistance of the gas barrier film 10, similarly to the clear hard coat layer. From the viewpoint, it is 10 μm or less, more preferably 7 μm.

The gas barrier film 10 is not limited to the above-described form, and the clear hard coat layer 34 is disposed on both surfaces of the base material 32, or another functionalized layer is used instead of the clear hard coat layer 34 and / or the bleed out preventing layer 36. It is also possible to arrange another functional layer, or to omit the clear hard coat layer 34 and / or the bleed-out preventing layer 36. Another functionalized layer is, for example, a smooth layer, an anchor coat layer, a hygroscopic layer, an antistatic layer, or a protective layer. The protective layer is, for example, a layer containing an organic compound, and is disposed above the barrier layer 20 and has a function of preventing damage to the barrier layer 20. The organic compound is an organic resin such as an organic monomer, oligomer, or polymer, or an organic-inorganic composite resin using a siloxane or silsesquioxane monomer, oligomer, polymer, or the like having an organic group.

Next, an apparatus for manufacturing the gas barrier film 10 will be described.

FIG. 2 is a schematic view for explaining the gas barrier film manufacturing apparatus according to Embodiment 1, and FIG. 3 is an enlarged view of a main part of FIG.

A manufacturing apparatus 100 shown in FIG. 2 is used to manufacture the gas barrier film 10 by a roll-to-roll type plasma CVD method, and includes a vacuum chamber 110, a first vacuum pump 180, a second vacuum pump 182, and a plasma generating device. A power source 185, a bias power source 187, and a film forming gas supply unit 190 are included. The roll-to-roll type plasma CVD method is preferable from the viewpoint of high material utilization efficiency and high-speed film formation.

The vacuum chamber 110 has an unwinding chamber 115, a film forming chamber 140, a film forming roll 150, and partition walls 160 and 162.

The unwinding chamber 115 is located above the film forming chamber 140 through the partition walls 160 and 162 and is connected to the first vacuum pump 180. The unwinding roll 120, the winding roll 125, and the guide rollers 130 and 132 are connected to the unwinding chamber 115. Have The first vacuum pump 180 is used to depressurize the inside of the unwinding chamber 115 to a predetermined degree of vacuum so as not to affect the film forming chamber 140.

The delivery roll 120 is configured by winding the base material portion 30 of the gas barrier film 10 and is disposed so as to be rotatable around a shaft 122. The take-up roll 125 is disposed so as to be rotatable about a shaft 127 and is used to take up the base material portion 30 (gas barrier film 10) on which the barrier layer 20 is formed. The take-up roll 125 and the delivery roll 120 are driven in synchronization.

The guide roller 130 is located between the feed roll 120 and the film forming roll 150, guides the base material part 30 fed out from the feed roll 120, and carries (wraps) the film on the film forming roll 150 positioned below in the drawing. Used for. The guide roller 132 is positioned between the film forming roll 150 and the take-up roll 125, and guides the base material unit 30 carried out (separated) from the film forming roll 150 to cause the take-up roll 125 to take up the guide roller 132. Used for. In addition, the barrier layer 20 is formed on the base material part 30 carried out (separated) from the film forming roll 150.

As described above, the base material portion 30 of the gas barrier film 10 is unwound from the feed roll 120 and taken up by the take-up roll 125 via the guide roller 130, the film forming roll 150 and the guide roller 132. That is, the delivery roll 120, the guide rollers 130 and 132, the film forming roll 150, and the take-up roll 125 constitute a transport mechanism that continuously transports the base material portion 30 of the gas barrier film 10.

The film forming roll 150 is connected to a bias power source 187, is positioned between the unwinding chamber 115 and the film forming chamber 140, and is disposed so as to be rotatable about a shaft 152. The film forming roll 150 has a gap 164 between the partition walls 160 and 162. The gap 164 constitutes a conveyance path for carrying the base material portion 30 of the gas barrier film 10 from the unwind chamber 115 to the film formation chamber 140. The bias power source 187 includes, for example, a high-frequency power source, and is used to apply a bias electric field (apply a bias potential) to the base member 30 wound around the outer periphery of the film forming roll 150. The film forming roll 150 preferably has a temperature adjustment mechanism that adjusts the temperature of the base material portion 30. The temperature adjustment mechanism can use a refrigerant or a Peltier element, for example. The bias power source 187 is not limited to a high frequency power source.

The film forming chamber 140 is located below the unwinding chamber 115 in the drawing through the partition walls 160 and 162 and connected to the second vacuum pump 182, and has a shower electrode 142 and a cryocoil 170. The second vacuum pump 182 is used to depressurize the inside of the film forming chamber 140 to a degree of vacuum suitable for plasma CVD. For example, a turbo pump, a mechanical booster pump, a rotary pump, or a dry pump can be applied to the first vacuum pump 180 and the second vacuum pump 182.

The shower electrode 142 is made of, for example, aluminum, has a hollow portion 144 and a gas supply hole 146, is connected to the plasma generation power source 185, and is disposed relative to the film forming roll 150. The surface of the shower electrode 142 facing the film forming roll 150 has a curved surface shape corresponding to the shape of the outer peripheral surface of the film forming roll 150 and is separated by a predetermined interval. The shower electrode 142 constitutes an electrode pair together with the film forming roll 150 and functions as a counter electrode of the film forming roll 150. That is, the space between the shower electrode 142 and the film forming roll 150 constitutes a discharge space S (see FIG. 3) that generates plasma.

The hollow portion 144 is connected to the film forming gas supply unit 190. The deposition gas includes a source gas and a reactive gas, and the deposition gas supply unit 190 includes a source gas source 192 and a reactive gas source 194. The source gas and the reaction gas held in the source gas source 192 and the reaction gas source 194 are supplied to the hollow portion 144 in a mixed state via, for example, a vaporizer or a bubbler. The film-forming gas can contain a carrier gas and a discharge gas for generating plasma discharge as necessary. Carrier gas and discharge gas are rare gas, hydrogen, and nitrogen, for example. The rare gas is helium, argon, neon, xenon, or the like.

The gas supply hole 146 communicates with the hollow portion 144 and is disposed on the surface facing the film forming roll 150. The plasma generation power source 185 is a high frequency power source used to supply plasma excitation power to the shower electrode 142.

Therefore, the shower electrode 142 has a function as a high frequency electrode and a function of supplying the source gas and the reaction gas to the discharge space S. The surface facing the film forming roll 150 in the shower electrode 142 may be roughened by blasting or the like, or a sprayed film may be formed in order to prevent separation of deposits generated when the barrier layer 20 is formed. Is also preferable. Note that the shower electrode 142 is not limited to the above embodiment.

The degree of vacuum of the film forming chamber 140 is, for example, 1 to several hundred Pa. The applied power of the plasma generation power source 185 is, for example, 0.1 to 10 kW. The frequency of the plasma generation power source 185 is, for example, several tens to several hundreds kHz (HF), 13.56 MHz (RF), and 2.45 GHz (microwave). The conveyance speed of the base material portion 30 of the gas barrier film 10 is 0.1 to 100 m / min.

The source gas contained in the film forming gas is, for example, an organic silicon compound containing carbon and silicon, or an organic compound gas containing carbon, and is appropriately selected according to the use or type of the barrier layer 20.

Organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, Trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetra Such as siloxane. HMSO and HMDS are preferable from the viewpoints of handleability and gas barrier properties. The organosilicon compounds can be used in combination of two or more.

The organic compound gas containing carbon is methane, ethane, ethylene, acetylene, tetraisopropyl titanate, titanium tetraethoxide, titanium tetrabutoxide, cyclopentadinier titanium triisopropoxide, tetrakisdimethylaminotitanium, tetrakisdiethylaminotitanium, tetra Methoxy aluminum, tetraethoxy aluminum, tetraisopropoxy aluminum, tetra n butoxy aluminum, aluminum sec-butyrate, and the like.

The reaction gas contained in the deposition gas is a gas that reacts with the raw material gas to generate an inorganic compound such as an oxide or a nitride, and contains at least an oxygen gas.

The reactive gas that generates an oxide by reacting with the raw material gas is, for example, oxygen gas or ozone gas. Examples of the reactive gas that reacts with the raw material gas to generate nitride are nitrogen gas and ammonia gas. The reaction gas can be used by combining two or more kinds. For example, an oxynitride is formed by using a reaction gas for forming an oxide and a reaction gas for forming a nitride in combination.

From the viewpoint of barrier properties and bending resistance of the barrier layer 20 to be formed, the ratio of the reaction gas to the source gas is higher than the ratio of the reaction gas that is theoretically necessary to completely react the source gas and the reaction gas. It is preferable not to make it excessively large. When the source gas is an organosilicon compound and the reaction gas is oxygen, the oxygen amount is preferably equal to or less than the theoretically required oxygen amount to completely oxidize the entire organosilicon compound.

Next, the cryocoil 170 will be described.

The cryocoil 170 is a low-temperature condensing member having a temperature at which, for example, a refrigerant of −120 to −130 ° C. circulates, and a precursor that is generated by converting the raw material gas and the reaction gas into plasma can be condensed and trapped. The cryocoil 170 is upstream of the discharge space S in the transport direction of the base material portion 30 of the gas barrier film 10, condenses and traps the precursor leaking from the discharge space S, and before being carried into the discharge space S. It is installed in the position which suppresses that a precursor adheres to the base-material part 30 of this gas barrier film 10. FIG.

The layer formed by the precursor is very brittle and easily damaged, and deteriorates the smoothness of the substrate. However, when the cryocoil 170 is installed, the precursor adheres to the base material portion 30 before being carried into the discharge space S (a precursor-derived layer is formed between the base material portion 30 and the barrier layer 20). ) Is suppressed. That is, since the precursor-derived layer is not interposed between the base material portion 30 and the barrier layer 20, the barrier layer 20 has good barrier properties and adhesion.

The installation position of the cryocoil 170 is not particularly limited as long as it is possible to suppress the adhesion of the precursor to the base material portion 30 before being carried into the discharge space S. For example, the installation positions of the cryocoil 170 are three locations P ₁ , P ₂ and P ₃ inside the film forming chamber 140. The installation position P ₁ is a position near the outer periphery of the film forming roll 150 upstream of the discharge space S and adjacent to the shower electrode 142. The installation position P < _b > ₂ is a substantially central position in the film formation chamber 140 region located upstream from the discharge space S. The installation position P ₃ is a position near the outer periphery of the film forming roll 150 upstream of the discharge space S and adjacent to the gap 164. In this embodiment, cryogenic coil 170 is installed at a position P _1.

The precursor includes a raw material gas and a reaction gas contained in the film forming gas, and a substance generated by decomposition of the film forming gas. For example, when the source gas is HMDSO, Si (CH ₃ ) ₃ generated by decomposition of HMDSO, OSi (CH ₃ ) ₃ , and Si (CH ₃ ) ₃ reacts with OH to generate Si (CH ₃ ) ₃ (OH), H ₂ O and CO ₂ produced by reaction of MDSO and O ₂ .

The low-temperature condensing member is not particularly limited to the form of the cryocoil 170 as long as the precursor can be condensed and trapped.

Next, a method for manufacturing the gas barrier film according to Embodiment 1 will be described.

FIG. 4 is a flowchart for explaining the method for manufacturing the gas barrier film according to the first embodiment.

The present manufacturing method includes an attaching process, a feeding process, a carrying-in process, a barrier layer forming process, a carrying-out process, a winding process, and a removing process, as shown in FIG.

In the attaching step, the feed roll 120 configured by winding the base material portion 30 of the gas barrier film 10 is attached to be rotatable about the shaft 122. Then, the first vacuum pump 180 and the second vacuum pump 182 are operated, and the inside of the unwinding chamber 115 and the film forming chamber 140 is depressurized to a degree of vacuum suitable for plasma CVD.

In the feeding process, the base material portion 30 of the gas barrier film 10 is fed from the feeding roll 120 toward the guide roller 130.

In the carrying-in process, the base material portion 30 of the gas barrier film 10 is guided by the guide roller 130 and carried (wrapped) onto the film forming roll 150.

At this time, the cryocoil 170 installed at the position P ₁ upstream of the discharge space S that is the space between the shower electrode 142 and the film forming roll 150 and adjacent to the shower electrode 142 is upstream of the discharge space S. Condensate the precursor leaking into the trap. Therefore, the precursor is prevented from adhering to the base material part 30 before being carried into the discharge space S (the precursor-derived layer is formed between the base material part 30 and the barrier layer 20).

In the barrier layer forming step, the base material portion 30 of the gas barrier film 10 passes through the discharge space S in a state of being wound (adhered to) the film forming roll 150. The shower electrode 142 is connected to a plasma generation power source 185 and also connected to a film forming gas supply unit 190. A bias power source 187 is connected to the film forming roll 150. Therefore, the shower electrode 142 and the film-forming roll 150 constitute an electrode pair, and the film-forming gas (raw material gas and reaction gas) from the film-forming gas supply unit 190 of the shower electrode 142 is converted into plasma, so that the gas barrier film 10 The barrier layer 20 is formed on the base material portion 30.

The base material portion 30 of the gas barrier film 10 is suppressed from forming a precursor-derived layer by the action of the cryocoil 170 in the carrying-in process immediately before the barrier layer forming process. Therefore, since the precursor-derived layer is not interposed between the base material portion 30 and the barrier layer 20, the barrier layer 20 having good barrier properties and adhesiveness is formed.

In the unloading step, the gas barrier film 10 in which the barrier layer 20 is formed on the base member 30 is unloaded (separated) from the film forming roll 150 toward the guide roller 132.

In the winding process, the gas barrier film 10 in which the barrier layer 20 is formed on the base member 30 is guided to the winding roll 125 by the guide roller 132 and is wound on the winding roll 125.

In the removal process, when the operation of the first vacuum pump 180 and the second vacuum pump 182 is stopped and the inside of the unwinding chamber 115 and the film forming chamber 140 is returned to the atmospheric pressure, a barrier layer is formed on the base material portion 30. A take-up roll 125 on which the gas barrier film 10 having 20 formed thereon is taken up. Removed.

Next, the performance evaluation results of the gas barrier film will be described.

FIG. 5 is a table showing the performance evaluation results of the gas barrier films according to Examples 1 to 4 and Comparative Examples 1 to 4 according to Embodiment 1, and FIG. 6 is the installation of the cryocoil in Comparative Examples 3 and 4. It is the schematic for demonstrating a position.

First, the production conditions of the gas barrier films according to Examples 1 to 4 and Comparative Examples 1 to 4 will be described.

The base material portion of the gas barrier film according to Example 1 has a base material, a clear hard coat layer, and a bleed out prevention layer.

The base material is a 125 μm-thick polyester film (manufactured by Teijin DuPont Films Ltd., extremely low heat yield PET Q83) with easy adhesion on both sides.

The clear hard coat layer had a thickness of 4 μm, and was formed by applying the photosensitive resin composition to the substrate, drying it, and curing it with a high-pressure mercury lamp in an air atmosphere. The photosensitive resin composition is a UV curable organic / inorganic hybrid hard coat material (OPSTAR Z7501) manufactured by JSR Corporation. A die coater was used for application of the photosensitive resin composition. Drying conditions are 80 ° C. and 3 minutes. The curing condition of the high pressure mercury lamp is 1.0 J / cm ² .

The bleed-out prevention layer was formed in the same manner as the clear hard coat layer except for the photosensitive resin composition. The photosensitive resin composition is a UV curable organic / inorganic hybrid hard coat material (OPSTAR Z7535) manufactured by JSR Corporation.

Barrier layer in the gas barrier film manufacturing apparatus 100 has established a cryocoil 170 to the position P _2, and between the film-forming roll 150 and the shower head electrode 142 is passed through once, to form. Incidentally, the installation position P ₂ is a substantially central position of the film forming chamber 140 region located upstream of the discharge space S (see FIG. 2).

The source gas is SiH ₄ , and the supply amount thereof is 100 sccm (Standard Cubic Centimeter per Minute). The reaction gases are NH ₄ and H ₂ , the supply amount of NH ₄ is 200 sccm, and the supply amount of H ₂ is 1500 sccm. The degree of vacuum in the vacuum chamber 110 is 100 Pa. The applied power of the plasma generation power source 185 is 1.2 kW, and the frequency is 13.56 MHz. The conveyance speed of a gas barrier film base material part is 1 m / min. The temperature of the film forming roll 150 is −10 ° C.

Gas barrier film according to the second embodiment, except that established the cryocoil 170 to the position P ₃ were prepared in the same manner as the gas barrier film according to the first embodiment. Incidentally, the installation position P ₃ is a near and a position adjacent to the gap 164 of the outer periphery of the upstream side of the film-forming roll 150 from the discharge space S (see FIG. 2).

Gas barrier film according to Example 3, except that was installed cryocoil 170 in position P ₁ was prepared in the same manner as the gas barrier film according to the first embodiment. Incidentally, the installation position P ₁ is a position adjacent to the near and the shower electrode 142 of the outer periphery of the upstream side of the film-forming roll 150 from the discharge space S (see FIG. 2).

The gas barrier film according to Example 4 was produced in the same manner as the gas barrier film according to Example 1 except for the raw material gas, the reaction gas, and the degree of vacuum. Specifically, the source gas is HMDSO, the reaction gas is O ₂ , the supply amount is 500 sccm, and the degree of vacuum is 50 Pa.

The gas barrier film according to Comparative Example 1 was manufactured in the same manner as the gas barrier film according to Example 1 with no cryocoil 170 installed in the gas barrier film manufacturing apparatus 100.

The gas barrier film according to Comparative Example 2 was manufactured in the same manner as the gas barrier film according to Example 4 with no cryocoil 170 installed in the gas barrier film manufacturing apparatus 100.

Gas barrier film according to Comparative Example 3, except that was installed cryocoil 170 to the position P ₄ were prepared in the same manner as the gas barrier film according to the fourth embodiment. Position P _4, as shown in FIG. 6, a position adjacent to the partition wall 162 on the downstream side and the film forming chamber 140 from the discharge space S.

Gas barrier film according to Comparative Example 4, except that established the cryocoil 170 to the position P ₅ was prepared in the same manner as the gas barrier film according to the fourth embodiment. As shown in FIG. 6, the position P <b> ₅ is a position downstream from the discharge space S and spaced from the partition wall 162 in the unwind chamber 115.

Next, the barrier property evaluation method and evaluation criteria will be described.

Evaluation of barrier properties was carried out using an evaluation cell. The evaluation cell was prepared as follows by sealing both sides of the gas barrier film on the barrier layer side and the bleed-out prevention layer side.

First, the surface of the barrier layer of the gas barrier film was masked except for 9 areas, and then calcium, which is a metal that reacts with water and corrodes, was deposited in a vacuum state. The size of the nine areas is 12 mm × 12 mm. Thereafter, in a state where the vacuum state was maintained, the mask was removed, aluminum was deposited, and then the vacuum state was released. Thereby, the barrier layer side of the gas barrier film was sealed with aluminum. For vapor deposition of calcium and aluminum, a vacuum deposition apparatus (manufactured by JEOL Ltd., vacuum deposition apparatus JEE-400) was used.

Then, after the gas barrier film is quickly transferred to the dry nitrogen gas atmosphere, quartz glass is disposed on the surface of the bleed-out prevention layer of the gas barrier film via an ultraviolet curable resin, and irradiated with ultraviolet rays. The UV curable resin was cured. Thereby, the bleed-out prevention layer side of the gas barrier film was sealed with quartz glass.

The produced evaluation cell was stored under high temperature and high humidity of 85 ° C. and 85% RH, and based on the calcium corrosion method (Ca method), the amount of moisture permeated into the cell from the corrosion amount of metallic calcium (permeated moisture amount) ) Was calculated and classified into four evaluation criteria AD. Evaluation criterion A means that the amount of permeated water is less than 5 × 10 ⁻⁴ g / m ² / day. Evaluation criterion B means that the amount of permeated water is 1 × 10 ⁻⁴ g / m ² / day or more and less than 1 × 10 ⁻³ g / m ² / day. Evaluation criterion C means that the amount of permeated water is 1 × 10 ⁻³ g / m ² / day or more and less than 1 × 10 ⁻² g / m ² / day. Evaluation criteria D means that the amount of permeated water is 1 × 10 ⁻² g / m ² / day or more. The calcium corrosion method is described in, for example, Japanese Patent Application Laid-Open No. 2005-283561.

In addition, a comparative sample in which a quartz glass plate having a thickness of 0.2 mm was substituted for the gas barrier film was prepared. When the comparative sample was stored under high temperature and high humidity of 85 ° C. and 85% RH, it was confirmed that no calcium corrosion occurred even after 1000 hours.

Next, the adhesion evaluation method and evaluation criteria will be described.

The adhesion was classified into four evaluation criteria A to D according to the results of a cross cut test according to JIS-K5400. Specifically, 100 1 mm square grids are formed on the barrier layer surface of the gas barrier film so as to intersect 11 cuts in the vertical and horizontal directions, and A cellophane tape was stuck on the surface, and it was quickly peeled off at an angle of 90 °. The portion of the barrier layer that adhered to the cellophane tape and peeled off was visually evaluated. Evaluation criterion A means that it is not peeled off at all. Evaluation criteria B means that although a slight float is observed in some grids, the quality is good. Evaluation criteria C means that the quality is acceptable for practical use, although peeling is observed at one or two grids. Evaluation criteria D means that the quality is a problem that is practically problematic because peeling is observed at three or more grids.

Next, an evaluation method and evaluation criteria for bending resistance (flexibility) will be described.

Bending resistance (flexibility) is based on four evaluation criteria A based on the change in the water vapor transmission coefficient of the gas barrier film before and after the bending test (ratio of the water vapor transmission coefficient after the bending test to the water vapor transmission coefficient before the bending test). Classified into ~ D. Specifically, a gas barrier film whose water vapor transmission coefficient has been measured in advance is wound around a metal rod, bent, and allowed to stand for 1 minute, and then the gas barrier film is returned flat and the water vapor transmission coefficient is measured again. did. Note that the radius of curvature of the gas barrier film is set to 8 mm, which corresponds to ½ of the diameter of the metal rod. However, when the number of turns of the gas barrier film increased, 1/2 of the diameter when the gas barrier film was wound was taken as the radius of curvature.

Evaluation criteria A means that the ratio is 0.95 or more. Evaluation criterion B means that the ratio is 0.85 or more and less than 0.95. Evaluation criterion C means that the ratio is 0.70 or more and less than 0.85. Evaluation criteria D means that the ratio is less than 0.70.

Next, referring to FIG. 5, the barrier properties, adhesion, and bending resistance (flexibility) of the gas barrier films according to Examples 1 to 4 and Comparative Examples 1 to 4 according to Embodiment 1 will be sequentially described.

Regarding the barrier properties, the gas barrier films according to Examples 1 to 4 have an evaluation criterion B or higher, and the gas barrier films according to Comparative Examples 1 to 4 have an evaluation criterion C or lower. Therefore, the gas barrier films according to Examples 1 to 4 show better results than the gas barrier films according to Comparative Examples 1 to 4. In particular, the gas barrier film according to the third embodiment cryocoil 170 was installed at a position P ₁ was evaluated criteria A.

Regarding the adhesiveness, the gas barrier films according to Examples 1 to 4 are equal to or higher than the evaluation standard B, and the gas barrier films according to Comparative Examples 1 to 4 are equal to or lower than the evaluation standard C, as in the barrier property. Therefore, the gas barrier films according to Examples 1 to 4 show better results than the gas barrier films according to Comparative Examples 1 to 4. In particular, the gas barrier film according to Example 2 and Example 3 cryocoil 170 was installed at a position P ₃ and the position P _1, was a measure A.

Regarding the bending resistance (flexibility), as with the barrier property, the gas barrier films according to Examples 1 to 4 are evaluation criteria B or higher, and the gas barrier films according to Comparative Examples 1 to 4 are evaluation criteria C or lower. It is. Therefore, the gas barrier films according to Examples 1 to 4 show better results than the gas barrier films according to Comparative Examples 1 to 4. In particular, the gas barrier film according to the third embodiment cryocoil 170 was installed at a position P ₁ was evaluated criteria A.

As described above, the gas barrier films according to Examples 1 to 4 showed better results with respect to the barrier properties, adhesion, and bending resistance (flexibility) than the gas barrier films according to Comparative Examples 1 to 4. Yes. In addition, the gas barrier film according to Example 3 in which the cryocoil 170 was installed at the position P ₁ was Evaluation Criteria A in all of barrier properties, adhesion properties, and bending resistance (flexibility), and Examples 1-4 Among them, particularly excellent results are shown.

The gas barrier films according to Comparative Examples 2 to 4 in which the source gas is HMDSO are evaluation criteria D regarding the barrier properties and adhesion, and are compared with the gas barrier film according to Comparative Example 1 in which the source gas is SiH _4. It was inferior. This indicates that the precursor produced when the source gas is HMDSO contains silicon containing organic matter, and the strength of the formed film is weaker than when SiH ₄ is used as the starting material. . Therefore, the improvement effect by the action of the cryocoil 170 is remarkable when the source gas is an organosilicon compound.

Next, Modification 1 and Modification 2 according to Embodiment 1 will be sequentially described.

FIG. 7 is a schematic diagram for explaining a first modification according to the first embodiment.

Cryocoil is limited to a mode of installing only the upstream side of the discharge space S Zarezu, for example, it is also to place the second cryocoil 172 to the position P ₆ adjacent to the downstream side and the shower head electrode 142 from the discharge space S Is possible. In this case, the transport mechanism is configured so that the transport direction can be reversed (re-transportable), and after the formation of the barrier layer 20 on the base material portion 30 of the gas barrier film 10 is completed, the transport direction is reversed (reversed). The cryocoil 172 is positioned upstream of the discharge space S in the re-conveying direction when the barrier layer 20 is increased in thickness by being re-conveyed continuously and re-introduced into the discharge space S. For this reason, the precursor is prevented from adhering to the barrier layer 20 before being re-loaded into the discharge space S (the formation of a precursor-derived layer on the surface of the barrier layer 20 is suppressed. Intervening layers from the precursor are avoided.

Second cryocoil 172, the discharge space is not limited to the form is placed in a position P ₆ located on the opposite side of the position P ₁ through S, for example, through the discharge space S position P ₂ and the position P It is also possible to install it at a position located on the opposite side of ₃ .

FIG. 8 is a schematic diagram for explaining a second modification according to the first embodiment.

It is also possible to arrange a baffle plate 175 between the cryocoil 170 and the discharge space S. In order to suppress the leakage of the precursor, the baffle plate 175 further suppresses the precursor from adhering to the base material portion 30 before being carried into the discharge space S (a precursor-derived layer is formed).

As described above, in the first embodiment, the precursor leaked from the discharge space is condensed and trapped by the low-temperature condensing member, and the precursor is placed on the base of the gas barrier film before being carried into the discharge space. Adhesion is suppressed. Therefore, since a precursor-derived layer is not interposed between the base material portion and the barrier layer, the barrier layer has good barrier properties and adhesion. That is, it is possible to provide a gas barrier film manufacturing apparatus and manufacturing method having good barrier properties and adhesion.

Next, the second embodiment will be described. In addition, about the member which has the function similar to Embodiment 1, the same code | symbol is used and in order to avoid duplication, the description is abbreviate | omitted suitably.

FIG. 9 is a schematic diagram for explaining the gas barrier film manufacturing apparatus according to the second embodiment.

The gas barrier film manufacturing apparatus 200 shown in FIG. 2 is generally different from the gas barrier film manufacturing apparatus 100 according to Embodiment 1 in that it has opposed film forming rolls and does not use a dedicated electrode (shower electrode). . The gas barrier film manufacturing apparatus 200 is preferable in that it has good high-speed film forming properties and does not cause contamination through a dedicated electrode (shower electrode). Specifically, the gas barrier film manufacturing apparatus 200 includes a vacuum chamber 210, a vacuum pump 280, a plasma generation power source 285, and a film forming gas supply unit 290.

The vacuum chamber 210 includes a feed roll 220, a take-up roll 225, guide rollers 230, 232, 234, 236, a first film forming roll 240, a second film forming roll 245, a film forming gas supply port 250, and a cryocoil 270. And a vacuum pump 280 is connected.

The delivery roll 220 is configured by winding the base material portion 30 of the gas barrier film 10, and is arranged so as to be rotatable around a shaft 222. The take-up roll 225 is disposed so as to be rotatable about a shaft 227 and is used to take up the base material portion 30 (the gas barrier film 10) on which the barrier layer 20 is formed.

The guide roller 230 is located between the delivery roll 220 and the first film formation roll 240, guides the base material part 30 fed out from the delivery roll 220, and carries (winds) the first film formation roll 240. used. The guide roller 232 is located between the first film forming roll 240 and the guide roller 234, guides the base material unit 30 carried out (separated) from the first film forming roll 240, and transfers it to the guide roller 234. Used for.

The guide roller 234 is located between the guide roller 232 and the second film forming roll 245, and carries the base material part 30 on which the barrier layer 20 transferred from the guide roller 232 is formed into the second film forming roll 245. Used to do (wrap). The guide roller 236 is located between the second film-forming roll 245 and the take-up roll 225, guides the base material part 30 carried out (separated) from the second film-forming roll 245, and guides it to the take-up roll 225. Used to wind up. In addition, the barrier layer 20 is formed on the base material part 30 carried out (separated) from the first film-forming roll 240, and the thickness of the barrier layer increases in the second film-forming roll 245.

As described above, the base material portion 30 of the gas barrier film 10 is fed from the feed roll 220, and the guide roller 230, the first film forming roll 240, the guide rollers 232 and 234, the second film forming roll 245, and the guide roller 236. Through the winding roll 225. That is, the delivery roll 220, the guide rollers 230, 232, 234, 236, the first film forming roll 240, the second film forming roll 245, and the take-up roll 225 continuously convey the base material portion 30 of the gas barrier film 10. A transport mechanism is configured.

The first film-forming roll 240 is connected to a plasma generation power source 285, and has a first magnetic field generation device 244, and is disposed so as to be rotatable about an axis 242. The second film forming roll 245 is connected to the plasma generating power source 285 and has a second magnetic field generating device 249 and is arranged to be rotatable about the shaft 247. The first film forming roll 240 and the second film forming roll 245 are positioned so as to face each other. In order to efficiently form the barrier layer 20, the first film-forming roll 240 and the second film-forming roll 245 are positioned so that their central axes are substantially parallel to each other on the same plane, and have the same diameter. It is preferable that

The power source 285 for generating plasma is used to supply power to the first film forming roll 240 and the second film forming roll 245 and to use it as a counter electrode for discharging. Therefore, the space between the first film forming roll 240 and the second film forming roll 245 constitutes the discharge space S, and the supplied film forming gas (source gas and reaction gas) can be converted into plasma. is there. The plasma generating power source 285 is configured by an AC power source capable of alternately inverting the polarities of the first film forming roll 240 and the second film forming roll 245. The plasma generating power source 285 is not limited to an AC power source.

The first magnetic field generator 244 is fixedly arranged inside the first film forming roll 240 so as not to follow the rotation of the first film forming roll 240. The second magnetic field generator 249 is fixedly disposed inside the second film forming roll 245 so as not to follow the rotation of the second film forming roll 245.

The first magnetic field generator 244 and the second magnetic field generator 249 preferably have magnetic poles arranged so that the magnetic lines of force do not cross each other and form a substantially closed magnetic circuit. For example, the magnetic pole of the first magnetic field generator 244 has a racetrack shape that is long in the axial direction of the first film forming roll 240, and the magnetic pole of the second magnetic field generator 249 is a long race in the axial direction of the second film forming roll 245. It is configured in a track shape and has the same polarity as the magnetic poles of the first magnetic field generator 244 facing each other. In this case, since the formation of a magnetic field in which the magnetic lines of force swell is promoted near the opposing surface in the first film forming roll 240 and the second film forming roll 245, the plasma is easily converged on the magnetic field, and the barrier layer 20 Formation efficiency is improved.

The film formation gas supply port 250 is connected to a film formation gas supply unit 290 having a source gas source 192 and a reaction gas source 194, and is disposed adjacent to the discharge space S in the upper part of the figure. Therefore, the mixed source gas and reaction gas can be supplied to the discharge space S from the film forming gas supply port 250. The supply of the deposition gas is not limited to the above form, and the source gas and the reaction gas can be individually supplied through independent paths.

The vacuum pump 280 is used to depressurize the inside of the vacuum chamber 210 to a degree of vacuum suitable for plasma CVD, and for example, a turbo pump, a mechanical booster pump, a rotary pump, or a dry pump can be applied. The vacuum pump 280 is preferably disposed to face the film forming gas supply port 250 with the discharge space S interposed therebetween. In this case, since the film forming gas (the raw material gas and the reactive gas) is efficiently supplied to the discharge space S, the formation efficiency of the barrier layer 20 is improved.

The cryocoil 270 is upstream of the discharge space S in the transport direction of the base material portion 30, condenses and traps the precursor leaked from the discharge space S, and before the base material portion 30 is carried into the discharge space S. In addition, it is installed at a position that suppresses the adhesion of the precursor. In the present embodiment, the cryocoil 270 is installed in the vicinity of the outer periphery of the first film forming roll 240 and in the vicinity of the position P ₁ immediately before the base member 30 is wound around the first film forming roll 240. . Note that the cryocoil 270 is not limited to the form of being installed at the position P _1, and can be installed at another position in the vicinity of the outer periphery of the first film forming roll 240, for example.

Next, a method for manufacturing a gas barrier film according to Embodiment 2 will be described.

FIG. 10 is a flowchart for explaining a method for manufacturing a gas barrier film according to the second embodiment.

As shown in FIG. 10, this manufacturing method includes an attaching process, a feeding process, a carrying-in process, a barrier layer forming process, a transferring process, a barrier layer film increasing process, a carrying-out process, a winding process, and a removing process.

In the attachment process, a feed roll 220 configured by winding the base material portion 30 of the gas barrier film 10 is attached to be rotatable about a shaft 222. Then, the vacuum pump 280 is operated, and the inside of the vacuum chamber 210 is depressurized to a degree of vacuum suitable for plasma CVD.

In the feeding process, the base material part 30 of the gas barrier film 10 is fed from the feeding roll 220 toward the guide roller 230.

In the carrying-in process, the base material portion 30 of the gas barrier film 10 is guided by the guide roller 230 and carried (wrapped) onto the first film forming roll 240.

At this time, it is located on the upstream side of the discharge space S, in the vicinity of the outer periphery of the first film forming roll 240 and in the vicinity of the position P ₁ immediately before the base member 30 is wound around the first film forming roll 240. The cryocoil 270 condenses and traps the precursor leaking from the discharge space S to the upstream side. Therefore, the precursor is prevented from adhering to the base material part 30 before being carried into the discharge space S (the precursor-derived layer is formed between the base material part 30 and the barrier layer 20).

In the barrier layer forming step, the base material portion 30 of the gas barrier film 10 passes through the discharge space S while being in close contact with the first film forming roll 240.

The first film-forming roll 240 and the second film-forming roll 245 facing the first film-forming roll 240 are connected to the plasma generating power source 285 and function as counter electrodes for discharging. That is, the space between the first film-forming roll 240 and the second film-forming roll 245 constitutes the discharge space S, and is adjacent to the discharge space S from the film-forming gas supply port 250 disposed in the upper part in the drawing. The film-forming gas (source gas and reaction gas) is turned into plasma to form the barrier layer 20 on the base material portion 30 of the gas barrier film 10.

The base material portion 30 of the gas barrier film 10 is suppressed from forming a precursor-derived layer by the action of the cryocoil 270 in the carry-in process immediately before the barrier layer forming process. Therefore, since the precursor-derived layer is not interposed between the base material portion 30 and the barrier layer 20, the barrier layer 20 has good barrier properties and adhesion.

In the transfer step, the gas barrier film 10 in which the barrier layer 20 is formed on the base material portion 30 is separated from the first film forming roll 240, guided by the guide rollers 232 and 234, and moved to the second film forming roll 245. It is transferred (wound around the second film forming roll 245 via the guide rollers 232 and 234).

In the barrier layer thickening step, the base material portion 30 of the gas barrier film 10 passes through the discharge space S in a state of being wound (adhered to) the second film forming roll 245. Thereby, the thickness of the barrier layer 20 on the base material part 30 of the gas barrier film 10 increases.

In the unloading step, the gas barrier film 10 in which the thickness of the barrier layer 20 on the base member 30 is increased is unloaded (separated) from the second film forming roll 245 toward the guide roller 236.

In the winding process, the gas barrier film 10 in which the thickness of the barrier layer 20 on the base member 30 is increased is guided to the winding roll 225 by the guide roller 236 and wound on the winding roll 225.

In the removal process, when the operation of the vacuum pump 280 is stopped and the inside of the vacuum chamber 210 is returned to the atmospheric pressure, the gas barrier film 10 in which the thickness of the barrier layer 20 on the substrate 30 is increased is wound up. The take-up roll 225 is removed.

Next, the performance evaluation results of the gas barrier film will be described.

FIG. 11 is a table showing the performance evaluation results of the gas barrier films according to Examples 1 and 2 and Comparative Example 1 according to the second embodiment.

First, manufacturing conditions for the gas barrier films according to Examples 1 and 2 and Comparative Example 1 will be described. The configuration of the base portion of the gas barrier film is the same as that of the gas barrier films according to Examples 1 to 4 and Comparative Examples 1 to 4 according to Embodiment 1, and therefore the description thereof is omitted. Only the layer structure will be described.

In the gas barrier film manufacturing apparatus 200, the barrier layer of the gas barrier film according to Example 1 has the cryocoil 270 installed at the position P ₁ and passes the first film forming roll 240 and the second film forming roll 245 once. Formed. The installation position P ₁ is upstream of the discharge space S, in the vicinity of the outer periphery of the first film forming roll 240 and in the vicinity of the position immediately before the base member 30 is wound around the first film forming roll 240 (see FIG. 9).

The source gas is HMDSO, and the supply amount is 100 sccm. The reaction gas is O ₂ and its supply amount is 500 sccm. The degree of vacuum in the vacuum chamber 210 is 1.5 Pa. The applied power of the plasma generation power source 185 is 1.2 kW, and the frequency is 80 kHz. The conveyance speed of a gas barrier film base material part is 1 m / min. The temperature of the film forming roll 150 is 30 ° C.

The barrier layer of the gas barrier film according to Example 2 was manufactured in the same manner as the gas barrier film according to Example 1 except that the source gas was HMDS.

The gas barrier film according to Comparative Example 1 was manufactured in the same manner as the gas barrier film according to Example 1 except that the cryocoil 270 was not installed in the gas barrier film manufacturing apparatus 200.

Evaluation methods and evaluation criteria for barrier properties, evaluation methods and evaluation criteria for adhesion, and evaluation methods and evaluation criteria for bending resistance (flexibility) are the same as in Examples 1 to 4 and Comparative Examples 1 to 4 according to Embodiment 1. Since it is the same as that of the gas barrier film which concerns, the description is abbreviate | omitted.

Next, referring to FIG. 11, the barrier properties, adhesion, and bending resistance (flexibility) of the gas barrier films according to Examples 1 and 2 and Comparative Example 1 will be sequentially described.

Regarding the barrier properties, the gas barrier films according to Examples 1 and 2 are evaluation criteria A, and the gas barrier film according to Comparative Example 1 is evaluation criteria C. Therefore, the gas barrier films according to Examples 1 and 2 show better results than the gas barrier film according to Comparative Example 1.

Regarding the adhesion, the gas barrier film according to Examples 1 and 2 is the evaluation standard A, and the gas barrier film according to Comparative Example 1 is the evaluation standard C, as in the barrier property. Therefore, the gas barrier films according to Examples 1 and 2 show better results than the gas barrier film according to Comparative Example 1.

Regarding the bending resistance (flexibility), the gas barrier film according to Examples 1 and 2 is the evaluation standard A, and the gas barrier film according to Comparative Example 1 is the evaluation standard C, similarly to the barrier property. Therefore, the gas barrier films according to Examples 1 and 2 show better results than the gas barrier film according to Comparative Example 1.

As described above, the gas barrier films according to Examples 1 and 2 are evaluation criteria A in all of the barrier properties, adhesion and bending resistance (flexibility), and are better than the gas barrier films according to Comparative Example 1. Results.

Next, Modification 1 and Modification 2 according to Embodiment 2 will be sequentially described.

FIG. 12 is a schematic diagram for explaining the first modification according to the second embodiment.

The cryocoil is not limited to the form installed only on the upstream side of the discharge space S. For example, the cryocoil is positioned downstream of the discharge space S and adjacent to the discharge space S (the gas barrier film 10 is separated from the second film forming roll 245). It is also possible to install the second cryocoil 272 at a position immediately after the operation. In this case, the transport mechanism is configured so that the transport direction can be reversed (re-transportable), and after the formation of the barrier layer 20 on the base material portion 30 of the gas barrier film 10 is completed, the transport direction is reversed (reversed). The cryocoil 272 is positioned upstream of the discharge space S in the re-transport direction when the barrier layer 20 is increased in thickness by being re-transported continuously and re-loaded into the discharge space S. For this reason, the precursor-derived layer is suppressed from being formed on the surface of the barrier layer 20 before being carried into the discharge space S again. Accordingly, it is possible to avoid a precursor-derived layer intervening in the barrier layer 20.

FIG. 13 is a schematic diagram for explaining a second modification according to the second embodiment.

It is also possible to arrange a baffle plate 275 between the cryocoil 270 and the discharge space S. In order to suppress the leakage of the precursor, the baffle plate 275 further suppresses the precursor from adhering to the base material part 30 before being carried into the discharge space S (a layer derived from the precursor is formed).

As described above, also in the second embodiment related to the roll-to-roll type plasma CVD method having the facing film-forming rolls, the implementation related to the roll-to-roll type plasma CVD method having a dedicated electrode (shower electrode) is performed. As in the case of Form 1, the barrier layer has good barrier properties and adhesion.

The present invention is not limited to the above-described embodiment, and various modifications can be made within the scope of the claims. For example, the low-temperature condensing members (cryocoils 170 and 270) and the second low-temperature condensing members (cryocoils 172 and 272) can be installed at a plurality of locations as necessary. The barrier layer 20 can also be configured to have a multilayer structure by disposing the second barrier layer 20 above the intermediate layer via an intermediate layer. For example, the intermediate layer is composed of, for example, a polysiloxane modified layer.

This application is based on Japanese Patent Application No. 2015-10658 filed on January 22, 2015, the disclosure content of which is referenced and incorporated as a whole.

10 Gas barrier film,
20 barrier layer,
30 substrate part,
32 base material,
34 Clear hard coat layer,
36 Bleed-out prevention layer,
100 gas barrier film manufacturing equipment,
110 vacuum chamber,
115 unwinding chamber,
120 feed roll,
125 take-up roll,
122,127 axes,
130, 132 guide rollers,
140 Deposition chamber,
142 shower electrodes,
144 hollow part,
146 gas supply holes,
150 film forming roll,
152 axes,
160, 162 Bulkhead,
164 gap,
170 cryocoil (low temperature condensing member),
172 cryocoil (second low-temperature condensing member),
175 baffle,
180 first vacuum pump,
182 second vacuum pump,
185 Power supply for plasma generation,
187 bias power supply,
190 Deposition gas supply unit,
192 Source gas source,
194 reaction gas source,
200 Gas barrier film manufacturing equipment,
210 vacuum chamber,
220 feed roll,
225 take-up roll,
222, 227 axes,
230, 232, 234, 236 guide rollers,
240 first film forming roll,
244 first magnetic field generator,
245 Second film forming roll,
249 Second magnetic field generator,
242 and 247 axes,
250 Deposition gas supply port,
270 cryocoil (low temperature condensing member),
272 cryocoil (second low-temperature condensing member),
275 baffle,
280 vacuum pump,
285 power supply for plasma generation,
290 Deposition gas supply unit,
P ₁ , P ₂ , P ₃ , P ₄ , P ₅ . P ₆ installation position,
S Discharge space.

Claims (14)

1. A manufacturing apparatus for manufacturing a gas barrier film having a barrier layer having a barrier property and a base material portion supporting the barrier layer by a roll-to-roll type plasma CVD method,
   A discharge space for converting the source gas and the reaction gas to form the barrier layer into plasma;
   A transport mechanism for continuously transporting the base portion of the gas barrier film via the discharge space;
   A low-temperature condensing member having a temperature capable of condensing and trapping the precursor generated by plasmification of the source gas and the reaction gas,
   The low temperature condensing member is
   The gas barrier film upstream of the discharge space in the transport direction of the base material portion of the gas barrier film, before the precursor leaking from the discharge space is condensed and trapped, and is carried into the discharge space The manufacturing apparatus installed in the position which suppresses that the said precursor adheres to the said base material part.
2. A film forming roll on which the base material portion of the gas barrier film is wound;
   A shower electrode disposed relative to the film forming roll and constituting an electrode pair together with the film forming roll;
   The manufacturing apparatus according to claim 1, wherein the discharge space is configured by a space between the shower electrode and the film forming roll.
3. A film forming chamber in which the discharge space and the shower electrode are arranged, and a portion around which the base portion of the gas barrier film in the film forming roll is wound is located,
   The manufacturing apparatus according to claim 2, wherein the low temperature condensing member is disposed in the film forming chamber.
4. The manufacturing apparatus according to claim 3, wherein the position where the low-temperature condensing member is installed is in the vicinity of the outer periphery of the film forming roll.
5. The manufacturing apparatus according to claim 4, wherein the position where the low-temperature condensing member is installed is adjacent to the shower electrode.
6. A first film forming roll;
   It is located on the downstream side in the transport direction of the base material portion of the gas barrier film from the first film forming roll, and is disposed relative to the first film forming roll, and an electrode pair together with the first film forming roll. And further comprising a second film forming roll,
   The manufacturing apparatus according to claim 1, wherein the discharge space is configured by a space between the first film forming roll and the second film forming roll.
7. The manufacturing apparatus according to claim 6, wherein the position where the low-temperature condensing member is installed is in the vicinity of the outer periphery of the first film forming roll.
8. The manufacturing apparatus according to claim 7, wherein the position where the low-temperature condensing member is installed is near a position immediately before the base portion of the gas barrier film is wound around the first film forming roll.
9. A baffle plate disposed between the low-temperature condensing member and the discharge space,
   The manufacturing apparatus according to any one of claims 1 to 8, wherein the baffle plate suppresses leakage of the precursor from the discharge space.
10. A second low-temperature condensing member having a temperature capable of condensing and trapping the precursor generated by plasmification of the source gas and the reaction gas;
    The transport mechanism reverses the transport direction of the base material portion of the gas barrier film after the formation of the barrier layer on the base material portion of the gas barrier film is completed, and passes through the discharge space, The base portion of the gas barrier film is configured to be continuously re-transportable,
    The second low-temperature condensing member condenses and traps the precursor leaking from the discharge space on the upstream side in the re-transport direction of the base material portion of the gas barrier film from the discharge space. The manufacturing apparatus according to any one of claims 1 to 9, wherein the manufacturing apparatus is installed at a position where the precursor is prevented from adhering to the barrier layer of the gas barrier film before being carried into the container.
11. A gas barrier film having a barrier layer having a barrier property and a base material portion supporting the barrier layer, a manufacturing method for manufacturing by a roll-to-roll type plasma CVD method,
    When continuously transporting the base material portion of the gas barrier film via a discharge space for converting the raw material gas and the reaction gas to plasma into the barrier layer,
    The precursor leaked from the discharge space is condensed and trapped by the low-temperature condensing member installed on the upstream side in the transport direction of the base material part of the gas barrier film from the discharge space, and before being carried into the discharge space. The manufacturing method which suppresses that the said precursor adheres to the said base material part of the said gas barrier film.
12. The manufacturing method according to claim 11, wherein leakage of the precursor from the discharge space is suppressed by a baffle plate disposed between the low-temperature condensing member and the discharge space.
13. After the formation of the barrier layer with respect to the base portion of the gas barrier film is completed, the transport direction of the base portion of the gas barrier film is reversed, and through the discharge space, the gas barrier film When re-feeding the base material continuously,
    The precursor leaked from the discharge space is condensed and trapped by the second low-temperature condensing member installed on the upstream side in the re-conveying direction of the base material portion of the gas barrier film from the discharge space, and trapped in the discharge space. The manufacturing method of Claim 11 or Claim 12 which suppresses that the said precursor adheres to the said barrier layer of the said gas barrier film before carrying in.
14. The method according to any one of claims 11 to 13, wherein the source gas is an organosilicon compound.

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