WO2021106636A1

WO2021106636A1 - Laminated film production method

Info

Publication number: WO2021106636A1
Application number: PCT/JP2020/042464
Authority: WO
Inventors: 美保大関; 山下　恭弘; 花岡　秀典
Original assignee: 住友化学株式会社
Priority date: 2019-11-25
Filing date: 2020-11-13
Publication date: 2021-06-03
Also published as: JP2021084233A

Abstract

An embodiment of the present invention provides a laminated film with which it is possible to suppress winding displacement and defects caused by foreign matter.　This method uses plasma-enhanced chemical vapor deposition to produce a laminated film including a substrate, and at least one inorganic thin-film layer formed on at least one surface of the substrate. Said method comprises: a step (I) in which a rolled substrate is advanced so as to unwind from a roller; a step (II) in which a reaction gas and a feedstock gas are supplied to between a pair of film-forming rollers, and an inorganic thin-film layer is formed on at least one side of the transported substrate as a result of plasma discharge generated between the rollers so as to obtain a laminated film; and a step (III) in which the laminated film is wound up by a winding roller. In step (I), the absolute value of the electric charge amount of the substrate surface during said unwinding is 2.0 kV or more when measured in the atmosphere. In steps (II) and (III), after formation of the inorganic thin-film layer and until said film is wound up, the absolute value of the electric charge amount of the inorganic thin-film layer surface is 1.5 kV or less when measured in a vacuum.

Description

Laminated film manufacturing method

One embodiment of the present invention relates to a method for producing a laminated film by a plasma chemical vapor deposition method (plasma CVD method).

The laminated film imparted with gas barrier properties can be suitably used as a packaging container suitable for filling and packaging articles such as foods and drinks, cosmetics, and detergents. In recent years, a laminated film has been proposed in which a plastic film or the like is used as a base material and a thin film layer such as silicon oxide, silicon nitride, silicon oxynitride, or aluminum oxide is laminated on one surface of the base material. For example, Patent Document 1 is characterized in that a gas barrier film (thin film layer) is formed by a plasma CVD method using a raw material gas of an organosilicon compound and a reaction gas such as nitrogen gas as raw materials. The manufacturing method of is disclosed.

Japanese Unexamined Patent Publication No. 2010-222690

However, according to the study of the present inventor, it has been found that, in the conventional method, the laminated film wound in a roll shape may have a winding deviation or a foreign matter defect may occur.

Therefore, an object of one embodiment of the present invention is to provide a method for producing a laminated film capable of suppressing the occurrence of unwinding and foreign matter defects.

As a result of diligent studies to solve the above problems, the present inventor measured the absolute value of the amount of charge on the surface of the substrate at the time of unwinding in the atmosphere in the method for producing a laminated film in the plasma chemical vapor deposition method. It was found that the above purpose can be achieved by adjusting the absolute value of the amount of charge on the surface of the inorganic thin film layer from the formation of the inorganic thin film layer to 1.5 kV or less, sometimes by adjusting the value to 2.0 kV or more. , The present invention has been completed. That is, one embodiment of the present invention includes the following aspects.

[1] A method for producing a laminated film containing a base material and one or more inorganic thin film layers formed on at least one surface of the base material by using a plasma chemical vapor deposition method. The method is a step (I) of unwinding a roll-shaped base material from a feeding roll, supplying a reaction gas and a raw material gas between a pair of film forming rolls, and a group conveyed by plasma discharge generated between the rolls. It includes a step (II) of forming an inorganic thin film layer on at least one side of the material to obtain a laminated film, and a step (III) of winding the laminated film with a take-up roll.
In the step (I), the absolute value of the charge amount on the surface of the base material at the time of unwinding is 2.0 kV or more when measured in the atmosphere, and in the steps (II) and (III) after the formation of the inorganic thin film layer. The method, wherein the absolute value of the amount of charge on the surface of the inorganic thin film layer up to the time of winding is 1.5 kV or less when measured under vacuum.
[2] The method according to [1], wherein the inorganic thin film layer contains at least silicon atoms, oxygen atoms and carbon atoms.
[3] The atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changes continuously in a region of 90% or more in the film thickness direction of the inorganic thin film layer. , [1] or [2].
[4] The method according to any one of [1] to [3], wherein the substrate comprises a flexible film and an organic layer formed on at least one side of the flexible film.
[5] The method according to any one of [1] to [4], wherein the laminated film is a gas barrier film.

According to the manufacturing method of one embodiment of the present invention, it is possible to suppress the unwinding of the obtained laminated film and the occurrence of foreign matter defects.

It is the schematic which shows an example of the manufacturing apparatus used in one Embodiment of this invention. It is the schematic which shows an example of the layer structure of the laminated film obtained by the manufacturing method of one Embodiment of this invention.

One embodiment of the present invention is a method of producing a laminated film containing a base material and one or more inorganic thin film layers formed on at least one surface of the base material by using a plasma chemical vapor deposition method. Is. In the method, the reaction gas and the raw material gas are supplied between the pair of film forming rolls in the step (I) of unwinding the roll-shaped base material from the feeding rolls, and the roll-shaped base material is conveyed by plasma discharge generated between the rolls. This includes a step (II) of forming an inorganic thin film layer on at least one side of the base material to obtain a laminated film, and a step (III) of winding the laminated film with a take-up roll.

In one embodiment of the present invention, in step (I), the absolute value of the amount of charge on the surface of the base material at the time of unwinding is 2.0 kV or more when measured in the atmosphere, and step (II). In (III), the absolute value of the amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer until the time of winding is 1.5 kV or less when measured under vacuum.

According to the present inventor, in step (I), when the absolute value of the amount of charge on the surface of the base material when the roll-shaped base material is unwound is 2.0 kV or more when measured in the atmosphere, the roll-shaped base material has a roll-like base material. It has been found that since the surface is unwound while having high adhesion to each other, unwinding is unlikely to occur at the time of unwinding, and as a result, the occurrence of unwinding of the laminated film wound by the winding roll can be suppressed. .. Here, since the film formation is performed under vacuum, it is usual to measure the amount of charge under vacuum. However, although the reason is not clear, there was no correlation between the amount of charge at the time of unwinding under vacuum and the unwinding due to the occurrence of large variations and the like. Surprisingly, the present inventor measured and examined the amount of charge at the time of unwinding in an atmosphere that is not normally performed, and found that there is a correlation with unwinding. Furthermore, the present inventor in the steps (II) and (III), the absolute value of the amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer until the time of winding is 1.5 kV or less when measured under vacuum. It was also found that, in that case, foreign matter is hard to adhere and the occurrence of foreign matter defects can be suppressed.

[Step (I)]
Step (I) is a step of unwinding the roll-shaped base material fixed to the delivery roll from the delivery roll. In one embodiment of the present invention, as described above, the absolute value of the amount of charge on the surface of the base material when the roll-shaped base material is unwound is 2.0 kV or more when measured in the atmosphere, so that unwinding occurs. Can be suppressed.

The absolute value of the amount of charge at the time of unwinding is preferably 3.0 kV or more, more preferably 4.0 kV or more, still more preferably 5.0 kV or more, still more preferably 6.0 kV or more when measured in the atmosphere. , Especially preferably 7.0 kV or more. When the absolute value of the amount of charge is at least the above lower limit, it is easier to suppress the occurrence of unwinding. The upper limit of the absolute value of the charge amount at the time of unwinding is preferably 20 kV or less, more preferably 15 kV or less, and further preferably 10 kV or less. The amount of charge (under the atmosphere) at the time of unwinding can be measured using an electrostatic potential monitoring device, for example, by the method described in Examples. Further, the charge amount at the time of unwinding indicates the charge amount immediately after unwinding by the unwinding roll (also referred to as immediately after the unwinding roll), and within 5 seconds after unwinding or after unwinding using the above device. It is obtained by measuring at a place within a transport distance of 10 cm. Further, since the film formation by the plasma CVD method is usually performed under vacuum, the inorganic thin film layer can be formed after measuring the amount of charge at the time of unwinding under the atmosphere.

The amount of charge at the time of unwinding is the take-up tension at the time of making the unwinding base material (roll-shaped base material), the transport speed (or unwinding speed) at the time of unwinding the base material; the material or type of the base material; the roll shape. It can be adjusted by appropriately changing the area where the base materials are in contact with each other on the surface of the base material (hereinafter, also referred to as the contact area). For example, by increasing the take-up tension when creating the unwinding base material, increasing the transport speed (or unwinding speed) and contact area, and configuring both sides of the base material with different materials, the charge amount can be increased. Absolute values tend to increase. Since the roll-shaped base material is in contact with one surface of the base material and the other surface, the contact area is the material, type, or surface of the layer arranged on one surface and the other surface of the base material. It may be adjusted appropriately depending on the roughness and the like.

[Base material]
The base material is a base material capable of holding an inorganic thin film layer.
<Flexible film>
The substrate preferably contains at least a flexible film. The flexible film is a resin film containing at least one kind of resin as a resin component, and is preferably a transparent flexible film.

Examples of the resin used for the flexible film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP) and cyclic polyolefins; polyamide resins; Polycarbonate resin; polystyrene resin; polyvinyl alcohol resin; saponified product of ethylene-vinyl acetate copolymer; polyacrylonitrile resin; acetal resin; polyimide resin; polyether sulfide (PES) can be mentioned. As the flexible film, one of the above resins may be used, or two or more kinds of resins may be used in combination. Among these, a polyester resin or a polyolefin resin is preferable, a polyester resin PET or PEN is more preferable, and a PEN is further preferable, from the viewpoint of heat resistance, transparency, and dimensional stability.

The flexible film may be an unstretched resin film, or the unstretched resin film may be uniaxially stretched, tenter-type sequential biaxially stretched, tenter-type simultaneous biaxially stretched, tubular-type simultaneous biaxially stretched, or the like. A stretched resin film may be stretched by a known method in the flow direction of the resin film (MD direction) and / or in the direction perpendicular to the flow direction of the resin film (TD direction). The flexible film may be a laminate in which two or more layers of the above-mentioned resin films are laminated.

The thickness of the flexible film may be appropriately set in consideration of stability during manufacturing of the laminated film, but is 5 μm or more from the viewpoint of easy unwinding and easy adjustment of the charge amount at the time of unwinding. , More preferably 10 μm or more, still more preferably 15 μm or more, preferably 500 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less.
The thickness of the flexible film can be measured with a film thickness meter, for example, by the method described in Examples.

<Primer layer>
The substrate may include a primer layer. From the viewpoint that the absolute value of the charge amount at the time of unwinding can be easily adjusted to 2.0 kV or more and the unwinding can be easily suppressed, the primer layer is preferably formed on at least one surface of the flexible film, and particularly the substrate. It is more preferable to have a primer layer on one outermost layer and another layer, for example, an organic layer described later, on the other outermost layer of the base material. This is because the primer layer often functions as an adhesive layer and often has a large surface roughness, so that the contact area between the surface of the primer layer and the surface of the organic layer (preferably the flattening layer) can be increased. Further, when the base material is laminated in the order of the flexible film, the primer layer and the organic layer, the primer layer can improve the adhesion between the flexible film and the organic layer. Further, when a primer layer is formed on the surface of the flexible film opposite to the side on which the inorganic thin film layer is formed and the primer layer is the outermost layer, the primer layer functions as a protective layer of the laminated film. It also has the function of improving slipperiness during manufacturing and preventing blocking.

The primer layer preferably contains at least one selected from urethane resin, acrylic resin, polyester resin, epoxy resin, melamine resin and amino resin.
Among these, the primer layer preferably contains a polyester resin as a main component from the viewpoint of easily adjusting the heat resistance and the amount of charge of the laminated film.

The primer layer can contain additives in addition to the above resin. As the additive, a known additive can be used for forming the primer layer, for example, silica particles, alumina particles, calcium carbonate particles, magnesium carbonate particles, barium sulfate particles, aluminum hydroxide particles, titanium dioxide particles. , Zirconium oxide particles, clay, talc and other inorganic particles. Among these, silica particles are preferable from the viewpoint of easily adjusting the heat resistance and the amount of charge of the laminated film.

The average primary particle size of the silica particles that can be contained in the primer layer is preferably 5 nm or more, more preferably 10 nm or more, further preferably 15 nm or more, particularly preferably 20 nm or more, preferably 100 nm or less, and more preferably 80 nm or less. It is more preferably 60 nm or less, and particularly preferably 40 nm or less. When the average primary particle size of the silica particles is in the above range, the aggregation of the silica particles can be suppressed, and the transparency and heat resistance of the laminated film can be improved. In addition, it is easy to adjust the amount of charge and suppress winding misalignment. Further, when the outermost layer is a primer layer, the slipperiness of the laminated film during production can be further improved and blocking can be effectively prevented. The average primary particle size of the silica particles can be measured by the BET method or TEM observation of the particle cross section.

The content of the silica particles is preferably 1 to 50% by mass, more preferably 1.5, based on the mass of the primer layer, from the viewpoint of heat resistance and transparency of the laminated film and from the viewpoint of easily adjusting the charge amount. It is ~ 40% by mass, more preferably 2 to 30% by mass.

The thickness of the primer layer is preferably 1 μm or less, more preferably 500 nm or less, still more preferably 500 nm or less, from the viewpoint of easily improving the heat resistance of the laminated film, the adhesion between the primer layer and the organic layer, and easily adjusting the amount of charge. It is 200 nm or less, preferably 10 nm or more, more preferably 20 nm or more, and further preferably 30 nm or more. The thickness of the primer layer can be measured with a film thickness meter. When the laminated film contains two or more primer layers, the thickness of each primer layer may be the same or different.

The primer layer can be obtained by applying a resin composition containing a resin, a solvent and, if necessary, an additive to a flexible film or the like, and drying the coating film to form a film. The order in which the primer layers are formed is not particularly limited.

The solvent is not particularly limited as long as it can dissolve the resin, and is, for example, an alcohol solvent such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol; diethyl ether, diisopropyl ether, tetrahydrofuran, 1 , 4-Dioxane, propylene glycol monomethyl ether and other ether solvents; acetone, 2-butanone, methyl isobutyl ketone and other ketone solvents; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- Aprotonic polar solvents such as pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate; nitrile solvents such as acetonitrile and benzonitrile; n-pentane, Hydrocarbon solvents such as n-hexane, n-heptane, octane, cyclohexane, methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylen; methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, Examples thereof include halogenated hydrocarbon solvents such as monochlorobenzene and dichlorobenzene. The solvent can be used alone or in combination of two or more.

As a method of applying the primer layer to a flexible film or the like, various conventionally used application methods such as spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, etc. Methods such as reverse roll coating, gravure coating, and extraction coating can be mentioned.

Examples of the method for drying the coating film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method, and heat drying can be preferably used. The drying temperature is usually about 50 to 350 ° C., and the drying time is usually about 30 to 300 seconds, although it depends on the type of resin and solvent.

As described above, for example, a primer layer may be formed on at least one surface of the flexible film, but a commercially available film having primer layers on both sides of the flexible film, for example, "Theonex" manufactured by Teijin Film Solutions Co., Ltd. (Registered trademark) ”etc. may be used.

The primer layer may be a single layer or a multilayer of two or more layers. When two or more primer layers are included, each primer layer may be a layer having the same composition or a layer having a different composition.

The surface roughness of the primer layer is preferably 1 nm or more, more preferably 1.5 nm or more, and further preferably 2 nm or more. When the surface roughness of the primer layer is equal to or higher than the above lower limit, for example, a primer layer is provided on one outermost layer of the base material, and another layer, for example, an organic layer described later (preferably a flattening layer) is provided on the other outermost layer. The contact area can be increased when the above is provided. Therefore, it is easy to adjust the absolute value of the charge amount at the time of unwinding to 2.0 kV or more, and it is easy to suppress unwinding. The upper limit of the surface roughness of the primer layer is preferably 5 nm or less. The surface roughness can be measured by observing the primer layer with a white interference microscope and forming interference fringes according to the unevenness of the sample surface.

<Organic layer>
The base material may include an organic layer. From the viewpoint that the absolute value of the charge amount at the time of unwinding can be easily adjusted to 2.0 kV or more and the unwinding can be easily suppressed, the base material is formed on the flexible film and at least one side of the flexible film. It is preferable to include the above-mentioned organic layer, and it is more preferable to have a primer layer on one outermost layer of the base material and an organic layer on the other outermost layer of the base material. Further, from the viewpoint of ensuring the adhesion between the primer layer and the organic layer in addition to adjusting the charge amount at the time of unwinding, the primer layers are provided on both sides of the base material, and the organic layer is provided on one of the primer layers. Is preferable.

The organic layer may be a layer having a function as a flattening layer, a layer having a function as an anti-blocking layer, or a layer having both of these functions. Further, from the viewpoint of ensuring slipperiness during film transport and easily adjusting the amount of charge, the organic layer is preferably an anti-blocking layer, and the gas barrier property is stabilized by homogenizing the inorganic thin film layer, and during film transport. The organic layer is preferably a flattened layer from the viewpoint of ensuring the slipperiness of the film and easily adjusting the amount of charge. When forming organic layers on both sides of a flexible film, both organic layers may be anti-blocking layers or flattening layers, one organic layer being an anti-blocking layer and the other organic layer. It may be a flattening layer. Further, the organic layer may be a single layer or a multilayer of two or more layers, and when two or more organic layers are formed, even if the plurality of organic layers have the same composition, they have different compositions. Layer may be.

When one outermost layer of the base material has an organic layer, the organic layer is appropriately made into a flattening layer or an anti-blocking layer, or an organic layer, depending on the material and surface roughness of the other outermost layer. Compounds and additives that form the above can be selected.

The thickness of the organic layer may be appropriately adjusted according to the intended use, but is preferably 0.1 μm or more from the viewpoint of easily improving the surface hardness and bending resistance of the laminated film and easily adjusting the amount of charge. It is preferably 0.5 μm or more, more preferably 0.7 μm or more, preferably 10 μm or less, more preferably 9 μm or less, still more preferably 8 μm or less. When the laminated film has two or more organic layers, it is preferable that each organic layer has a thickness in the above range, and the thickness of each organic layer may be the same or different. The thickness of the organic layer can be measured by a film thickness meter, for example, by the method described in Examples.

The organic layer can be formed, for example, by applying a composition containing a photocurable compound having a polymerizable functional group to the surface of a flexible film, a primer layer, or the like and curing the composition. Examples of the photocurable compound contained in the composition for forming the organic layer include an ultraviolet or electron beam curable compound, and such a compound has one or more polymerizable functional groups in the molecule. Examples of the compound include compounds having a polymerizable functional group such as a (meth) acryloyl group, a vinyl group, a styryl group and an allyl group. The composition for forming the organic layer (hereinafter, may be referred to as the composition for forming the organic layer) may contain one kind of photocurable compound, or may contain two or more kinds of photocurable compounds. You may. By curing the photocurable compound having a polymerizable functional group contained in the composition for forming an organic layer, the photocurable compound is polymerized to form an organic layer containing a polymer of the photocurable compound.

The reaction rate of the polymerizable functional group of the photocurable compound having the polymerizable functional group in the organic layer is preferably 70% or more, more preferably 75% or more, still more preferably 80% from the viewpoint of easily improving the appearance quality. That is all. The upper limit of the reaction rate is not particularly limited, but is preferably 95% or less, more preferably 90% or less, from the viewpoint of easily improving the appearance quality. When the reaction rate is equal to or higher than the above lower limit, it tends to be colorless and transparent. Further, when the reaction rate is not more than the above upper limit, it is easy to improve the bending resistance. Since the reaction rate increases as the polymerization reaction of the photocurable compound having a polymerizable functional group proceeds, for example, when the photocurable compound is an ultraviolet curable compound, the intensity of the ultraviolet rays to be irradiated may be increased. It can be increased by lengthening the irradiation time. By adjusting the curing conditions as described above, the reaction rate can be kept within the above range.

The reaction rate is a coating film before curing obtained by applying the composition for forming an organic layer to the surface of a flexible film or a primer layer and drying it if necessary, and a coating film after curing. The infrared absorption spectrum of the film can be measured from the surface of the coating film using a total reflection type FT-IR, and can be measured from the amount of change in the intensity of the peak derived from the polymerizable functional group. For example, when the polymerizable functional group is a (meth) acryloyl group, the C = C double bond moiety in the (meth) acryloyl group is a group involved in the polymerization, and C = C as the reaction rate of the polymerization increases. The intensity of the peak derived from the double bond decreases. On the other hand, the C = O double bond portion in the (meth) acryloyl group does not participate in the polymerization, and the intensity of the peak derived from the C = O double bond does not change before and after the polymerization. Therefore, the peak derived from the C = C double bond with respect to _{the intensity (ICO1} ) of the peak derived from the C = O double bond in the (meth) acryloyl group in the infrared absorption spectrum measured for the coating film before curing. Percentage of intensity ( _ICC1 _{) (ICC1} / _ICO1 ) and intensity of peak derived from C = O double bond in (meth) acryloyl group in infrared absorption spectrum measured for cured coating (I) _The reaction rate can be calculated by comparing the ratio of _{the peak intensity (ICC2} ) derived from the C = C double bond to _CO2 _{) (ICC2} / I CO2). In this case, the reaction rate is calculated by the formula (1) :.
Reaction rate [%] = [1- (I _CC2 / I _CO2 ) / (I _CC1 / I _CO1 )] x 100 (1)
Is calculated by. Incidentally, C = infrared absorption peak derived from C double bonds in the range of usually 1350 ~ 1450 cm ^-1, are observed in the vicinity of example 1400 cm ^-1, infrared absorption peak is usually 1700 derived from the C = O double bond It is observed in the range of ~ 1800 cm ^-1 , for example, ^{around 1700 cm -1.}

When the 1000 to intensity of the infrared absorption peak in the range of 1100 cm ^-1 in the infrared absorption spectrum of the organic layer and _{I c,} the intensity of the infrared absorption peak in the range of 1700 - 1800 cm ^-1 and _{I d,} _{I c} and I _d is the equation (2):
0.05 ≤ I _d / I _c ≤ 1.0 (2)
It is preferable to satisfy. Here, the infrared absorption peak in the range of 1000 to 1100 cm ^-1 is present in the compound and the polymer contained in the organic layer (for example, the photocurable compound having a polymerizable functional group and / or the polymer thereof). Infrared absorption peaks derived from Si—O—Si bonds derived from siloxane, and infrared absorption peaks in ^{the range of 1700 to 1800 cm -1} are compounds and polymers contained in the organic layer (for example, polymerizable functional groups). It is considered that the infrared absorption peak is derived from the C = O double bond present in the photocurable compound and / or its polymer).
The ratio of the intensities of these peaks ( _Id / I _c ) is considered to represent the relative ratio of the C = O double bond to the siloxane-derived Si—O—Si bond in the organic layer. If the ratio of the intensity of peak _(I d _/ I _c) is within the above predetermined range, the easily enhance the uniformity of the organic layer, adhesion between the layers, made especially easily improving the adhesion under high humidity environment. The peak intensity ratio ( _Id / I _c ) is preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.20 or more. When the peak intensity ratio ( _Id / I _c ) is equal to or greater than the above lower limit, the uniformity of the organic layer is likely to be improved. This is not limited to the mechanism described later in the present invention, but if the amount of siloxane-derived Si—O—Si bonds present in the compound and polymer contained in the organic layer becomes too large, aggregates are generated in the organic layer. It is considered that this is because the layer may be embrittled and the formation of such agglomerates can be easily reduced. The peak intensity ratio ( _Id / I _c ) is preferably 1.0 or less, more preferably 0.8 or less, still more preferably 0.5 or less. When the ratio of peak intensities ( _Id / I _c ) is not more than the above upper limit, it is easy to improve the adhesion of the organic layer. This is not limited to the mechanism described later in the present invention, but the hardness of the organic layer is increased by the presence of a certain amount or more of siloxane-derived Si—O—Si bonds in the compounds and polymers contained in the organic layer. It is considered that this is because it is moderately reduced. The infrared absorption spectrum of the organic layer can be measured by a Fourier transform infrared spectrophotometer (FT / IR-460Plus manufactured by JASCO Corporation) equipped with an ATR attachment (PIKE MIRacle).

The photocurable compound contained in the composition for forming an organic layer is a compound that starts polymerization by ultraviolet rays or the like and progresses to cure to become a resin which is a polymer. The photocurable compound is preferably a compound having a (meth) acryloyl group from the viewpoint of curing efficiency. The compound having a (meth) acryloyl group may be a monofunctional monomer or oligomer, or may be a polyfunctional monomer or oligomer. In the present specification, "(meth) acryloyl" means acryloyl and / or methacryloyl, and "(meth) acrylic" means acrylic and / or methacrylic.

Examples of the compound having a (meth) acryloyl group include (meth) acrylic compounds, and specifically, alkyl (meth) acrylate, urethane (meth) acrylate, ester (meth) acrylate, epoxy (meth) acrylate, and the like. In addition, the polymer and copolymer thereof and the like can be mentioned. Specifically, methyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth). ) Acrylate, neopentyl glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and pentaerythritol tri (meth) acrylate, and their polymers. And copolymers and the like.

The photocurable compound contained in the composition for forming an organic layer may be, for example, in place of the compound having a (meth) acryloyl group or in addition to the compound having a (meth) acryloyl group, for example, metetramethoxysilane. Tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltri It preferably contains ethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, trimethylethoxysilane, triphenylethoxysilane and the like. Alkoxysilanes other than these may be used.

Examples of the photocurable compound other than the photocurable compound having a polymerizable functional group described above include polyester resin, isocyanate resin, ethylene vinyl alcohol resin, vinyl-modified resin, epoxy resin, phenol resin, urea melamine resin, etc. by polymerization. Examples thereof include monomers or oligomers that serve as styrene resins and resins such as alkyl titanates.

The composition for forming an organic layer may contain the inorganic particles described in the <Primer layer> section, preferably silica particles. The average primary particle size of the silica particles contained in the composition for forming an organic layer is preferably 5 to 100 nm, more preferably 5 to 75 nm. When inorganic particles are contained, the heat resistance of the laminated film can be easily improved and the amount of charge can be easily adjusted.

The content of the inorganic particles, preferably the silica particles, is preferably 20 to 90%, more preferably 40 to 85%, based on the mass of the solid content of the composition for forming the organic layer. When the content of the inorganic particles is in the above range, the heat resistance of the laminated film can be easily improved and the charge amount can be easily adjusted. The solid content of the composition for forming an organic layer means a component excluding volatile components such as a solvent contained in the composition for forming an organic layer.

The composition for forming an organic layer may contain a photopolymerization initiator from the viewpoint of curability of the organic layer.
The content of the photopolymerization initiator is preferably 2 to 15%, more preferably 3 to 11%, based on the mass of the solid content of the composition for forming the organic layer, from the viewpoint of enhancing the curability of the organic layer. Is.

The composition for forming an organic layer may contain a solvent from the viewpoint of coatability. As the solvent, a solvent capable of dissolving the compound can be appropriately selected depending on the type of the photocurable compound having a polymerizable functional group, and examples thereof include the solvent described in the <Primer layer> section. The solvent may be used alone or in combination of two or more.

In addition to the photocurable compound having a polymerizable functional group, the inorganic particles, the photopolymerization initiator and the solvent, if necessary, a thermal polymerization initiator, an antioxidant, an ultraviolet absorber, a plasticizer, and leveling. Additives such as agents and curl inhibitors may be included.

As described above, for the organic layer, for example, a composition for forming an organic layer (photocurable composition) containing a photocurable compound is applied to the surface of a flexible film, a primer layer, or the like, and after drying if necessary. , The photocurable compound can be cured and formed by irradiating with ultraviolet rays or electron beams.

Examples of the coating method include the same method as the method of coating the primer layer.

When the organic layer has a function as a flattening layer, the organic layer is a (meth) acrylate resin, a polyester resin, an isocyanate resin, an ethylene vinyl alcohol resin, a vinyl-modified resin, an epoxy resin, a phenol resin, a urea melamine resin, or a styrene resin. , And alkyl titanates and the like may be contained. The organic layer may contain one kind or a combination of two or more kinds of these resins.

When the organic layer has a function as a flattening layer, the flattening layer is subjected to a rigid pendulum type physical property tester (for example, RPT-3000W manufactured by A & D Co., Ltd.) to determine the temperature of the elastic modulus of the surface of the flattening layer. When the change is evaluated, it is preferable that the temperature at which the elastic modulus of the surface of the flattening layer decreases by 50% or more is 150 ° C. or higher.

When the organic layer has a function as a flattening layer, the surface roughness of the organic layer is preferably 3 nm or less, more preferably 2 nm or less, and further preferably 1 nm or less. When the surface roughness of the flattening layer is not more than the above upper limit, the defects of the inorganic thin film layer are reduced, and the gas barrier property is further enhanced. Further, for example, when an organic layer as a flattening layer is provided on one outermost layer of the base material and a primer layer is provided on the other side, the contact area can be increased, whereby the absolute value of the charge amount at the time of unwinding can be increased. Is easy to adjust to 2.0 kV or more. The lower limit of the surface roughness of the organic layer is preferably 0.01 nm or more, more preferably 0.1 nm or more. When the surface roughness of the flattening layer is at least the above lower limit, the adhesion to the inorganic thin film layer is improved, and there is an effect of preventing problems such as peeling between the inorganic thin film layer and the organic layer. The surface roughness is measured by observing the flattening layer with a white interference microscope and forming interference fringes according to the unevenness of the sample surface.

When the organic layer has a function as an anti-blocking layer, it is particularly preferable that the organic layer contains the above-mentioned inorganic particles.

The thickness of the base material may be appropriately set in consideration of stability in manufacturing the laminated film, etc., but from the viewpoint of facilitating the transfer of the base material in vacuum and the ease of unwinding, the charge amount is adjusted. From the viewpoint of easy easiness, it is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, preferably 550 μm or less, more preferably 250 μm or less, still more preferably 200 μm or less. The thickness of the base material can be measured with a film thickness meter, for example, by the method described in Examples.

The base material is preferably a long base material, and the length thereof is not particularly limited, but is preferably 100 m or more, more preferably 150 m or more, still more preferably 200 m or more, and particularly preferably 300 m or more. Is 5000 m or less, more preferably 4000 m or less, still more preferably 3000 m or less, and particularly preferably 2500 m or less. In one embodiment of the present invention, the absolute value of the charge amount at the time of unwinding and the absolute value of the charge amount at the time of winding after the formation of the inorganic thin film layer are adjusted within a predetermined range, and therefore, the above lower limit or more. Even with a long base material, it is possible to effectively suppress the occurrence of unwinding and foreign matter defects. The width of the base material is not particularly limited, and is preferably 50 mm or more, more preferably 100 mm or more, further preferably 150 mm or more, preferably 5000 mm or less, more preferably 4000 mm or less, still more preferably 3000 mm or less. .. The length of the long base material indicates the size in the longitudinal direction, and the width of the long base material indicates the size in the lateral direction (direction orthogonal to the longitudinal direction).

In step (I), the take-up tension at the time of preparing the unwinding base material is preferably 20 N / m or more, more preferably 35 N / m or more, still more preferably 50 N / m or more, and preferably 500 N / m or less. , More preferably 400 N / m or less, still more preferably 250 N / m or less. When the winding tension is at least the above lower limit, it is easy to adjust the absolute value of the measured value of the amount of charge at the time of unwinding in the atmosphere to 2.0 kV or more, and it is easy to suppress winding misalignment. Further, when the winding tension is not more than the above upper limit, the unwinding base material can be produced without damaging the film at the time of winding. The take-up tension (N / m) indicates the tension (unit: N) applied in the longitudinal direction with respect to the base material width (unit: m), and the base material width indicates the length of the base material in the lateral direction. .. The tension applied in the longitudinal direction is measured by, for example, a tension meter and can be controlled by using a tension controller.

In the step (I), the unwinding speed of the base material may be preferably 0.1 to 100 m / min, more preferably 0.3 to 20 m / min, and the unwinding speed of the base material is particularly preferable. Is 1.2 m / min or more, more preferably 1.5 m / min or more, still more preferably 2.0 m / min or more, still more preferably 2.5 m / min or more, when unwinding in the atmosphere. It is easy to adjust the absolute value of the measured value of the charge amount to 2.0 kV or more, and it is easy to suppress winding misalignment.

In step (I), the unwound base material is transported to a pair of film forming rolls by a transport roll or the like.

[Process (II)]
In step (II), a reaction gas and a raw material gas are supplied between the pair of film forming rolls, and an inorganic thin film layer is formed on at least one side of the conveyed base material by plasma discharge generated between the rolls. This is the process of obtaining a laminated film.

As described above, the base material preferably contains a flexible film, and in addition to the flexible film, a primer layer and / or an organic layer can be optionally contained. Therefore, the inorganic thin film layer is formed on the flexible film when the base material contains only the flexible film; preferably on the primer layer when the base material contains the primer layer; the base material. When contains an organic layer, it is preferably formed on the organic layer.

The film forming roll has a function of generating a discharge plasma of a film forming gas between a pair of film forming rolls. Such a pair of film forming rolls may be connected to a plasma generation power source so as to supply power between the film forming rolls and function as a pair of counter powers for plasma discharge. The plasma generation power source makes it possible to generate discharge plasma between the film forming rolls, and more specifically, in the space between the film forming rolls. As the power source for plasma generation, a known power source can be used as appropriate, and plasma CVD can be performed more efficiently. Therefore, an AC power source or the like capable of alternately reversing the polarities of a pair of film forming rolls. It is preferable to use. A medium frequency, for example 50 Hz to 500 kHz, preferably 1 kHz to 300 kHz, more preferably 1 kHz to 200 kHz, can be supplied between the pair of film forming rolls. When the medium frequency is in the above range, damage to the film forming roll due to the generation of an excessive amount of heat can be suppressed. The applied power can be 100 W to 10 kW, preferably 100 W to 5 kW. When the applied power is not less than the above lower limit, the generation of particles can be suppressed, and when it is not more than the above upper limit, damage to the film forming roll due to the generation of an excessive amount of heat can be suppressed.

It is preferable to provide a fixed magnetic field forming device inside the pair of film forming rolls so that the film forming rolls do not rotate even if they rotate. With the magnetic field forming device, a magnetic field can be applied to a pair of film forming rolls, and an inorganic thin film layer can be formed at the same time on the surface of the base material arranged on each film forming roll, so that the film forming rate can be doubled. .. As the magnetic field forming device, a known one may be used as appropriate.

The pressure for generating the discharge plasma between the pair of film forming rolls can be appropriately selected depending on the type of the raw material gas and the like, and is preferably 0.1 to 50 Pa, more preferably 0.1 to 30 Pa. In the case of the low pressure CVD method, the pressure in the space is preferably 0.1 to 10 Pa, more preferably 0.1 Pa to 8.0 Pa.

A known roll can be appropriately used as the film-forming roll, but from the viewpoint of forming the inorganic thin film layer more efficiently, it is preferable that the pair of film-forming rolls have the same diameter, and the diameter of the film-forming roll is discharged. From the viewpoint of conditions and the like, it is preferably 5 to 30 cm. It is preferable that the pair of film forming rolls are arranged so that their central axes are substantially parallel, particularly parallel, on the same plane.
By arranging in this way, the inorganic thin film layer can be formed at the same time on the surface of the base material arranged on each film forming roll, so that the film forming rate can be doubled and the inorganic thin film layer having the same structure can be formed. Is. Further, since it is possible to deposit an inorganic thin film layer on the surface of the base material on one film forming roll and further deposit an inorganic thin film layer on the other film forming roll, the inorganic thin film layer can be efficiently formed. You can also do it.

The transport speed of the base material transported by the film forming roll or the like is usually the same as the unwinding speed. When the transport speed is at least the above lower limit, the generation of wrinkles due to heat on the base material can be suppressed, and when it is at least the above upper limit, the thickness of the inorganic thin film layer can be suppressed from becoming too thin. ..

Examples of the raw material gas include an organosilicon compound containing a silicon atom and a carbon atom. Specific examples of organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and the like. Propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, (methoxymethyl) trimethylsilane, (ethoxymethyl) ) Trimethylsilane, (methoxyethyl) trimethylsilane and the like. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of the handleability of the compound and the gas barrier property of the obtained laminated film. As the raw material gas, one kind of these organosilicon compounds may be used alone, or two or more kinds may be used in combination.

The reaction gas contains oxygen. Oxygen can react with the raw material gas to form an inorganic compound such as an oxide. The reaction gas may contain other gases capable of forming oxides or nitrides. Examples of other gases for forming oxides include ozone and the like. Moreover, as another gas for forming a nitride, for example, nitrogen, ammonia and the like can be mentioned. These gases can be used alone or in combination of two or more. For example, in the case of forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride are used in combination. be able to. The flow rate ratio of the raw material gas and the reaction gas can be appropriately adjusted according to the atomic number ratio (also referred to as atomic ratio) of the inorganic material to be formed.

In addition to the raw material gas and the reaction gas, the film-forming gas may contain a carrier gas, if necessary, in order to supply these gases between the pair of film-forming rolls. Further, the film-forming gas may contain a discharge gas, if necessary, in order to generate a plasma discharge. As the carrier gas and the discharge gas, known ones can be used as appropriate, and for example, rare gases such as helium, argon, neon, and xenon, and hydrogen can be used. In this specification, the raw material gas, the reaction gas, the carrier gas, and the discharge gas are collectively referred to as a film-forming gas.

The flow rate of the raw material gas is preferably 10 to 1000 sccm, more preferably 20 to 500 sccm, and further preferably 30 to 300 sccm based on 0 ° C. and 1 atm. The flow rate of the reaction gas is preferably 10 to 10000 sccm, more preferably 100 to 5000 sccm, and more preferably 200 to 1000 sccm based on 0 ° C. and 1 atm.

The inorganic thin film layer formed by the production method of one embodiment of the present invention can easily improve gas barrier properties (particularly water vapor barrier properties) and bending resistance, and can easily reduce the amount of charge after forming the inorganic thin film layer. , Silicon atom (Si), oxygen atom (O), and carbon atom (C) are preferably contained at least.

In this case, the inorganic thin film layer may be mainly composed of a compound whose _{general formula is represented by SiO x} _Cy. In the formula, X and Y each independently represent a positive number less than 2. Here, "the main component" means that the content of the component is 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more with respect to the mass of all the components of the material. Say. Inorganic thin layer may contain one kind of compound represented by the general formula SiO _x C _y, may contain a general formula SiO _x C _y 2 or more compounds represented by. X and / or Y in the general formula may be a constant value or may change in the film thickness direction of the inorganic thin film layer.

Further, the inorganic thin film layer contains elements other than silicon atom, oxygen atom and carbon atom, for example, one or more atoms of hydrogen atom, nitrogen atom, boron atom, aluminum atom, phosphorus atom, sulfur atom, fluorine atom and chlorine atom. It may be contained.

In one embodiment of the present invention, the inorganic thin film layer has high density when the average atomic number ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is represented by C / Si. From the viewpoint of reducing defects such as fine voids and cracks, the range of C / Si preferably satisfies the formula (3).
0.02 <C / Si <0.50 (3)
From the same viewpoint, C / Si is more preferably in the range of 0.03 <C / Si <0.45, further preferably in the range of 0.04 <C / Si <0.40, and 0. It is particularly preferable that the range is 05 <C / Si <0.35.

Further, the inorganic thin film layer has high density when the average number of atoms ratio of oxygen atom (O) to silicon atom (Si) in the inorganic thin film layer is represented by O / Si, and fine voids, cracks, etc. From the viewpoint of reducing the number of defects, the range of 1.50 <O / Si <1.98 is preferable, the range of 1.55 <O / Si <1.97 is more preferable, and 1.60 <O. It is more preferably in the range of / Si <1.96, and particularly preferably in the range of 1.65 <O / Si <1.95.

The average atomic number ratios C / Si and O / Si were measured in XPS depth profile under the following conditions, and from the obtained distribution curves of silicon atoms, oxygen atoms, and carbon atoms, the averages in the thickness direction of each atom were obtained. After determining the atomic concentration, it can be calculated from the average atomic concentration, for example, by the method described in Examples.
<XPS depth profile measurement>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film equivalent): 0.027 nm / sec
Spatter time: 0.5 min
Using X-ray photoelectron spectrometer Irradiation X-ray: Single crystal spectroscopy AlKα (1486.6 eV)
X-ray spot and its size: 100 μm
Detector: Pass Energy 69eV, Step size 0.125eV
Charge correction: Neutralizing electron gun (1eV), low-speed Ar ion gun (10V)

When performing infrared spectroscopy with respect to the surface of the inorganic thin film layer (ATR method), a peak exists in the 950 ~ 1050 cm ^-1 strength _{(I 3),} the peak intensity existing in the 1240 ~ 1290cm ^-1 _{(I 4} ) And the absorption intensity ratio (I ₄ / I ₃ ) preferably satisfy the formula (4).
0.01 ≤ I ₄ / I ₃ <0.05 (4)

In one embodiment of the present invention, the peak intensity ratio I ₂ / I ₁ calculated from infrared spectroscopy (ATR method) is the relative ratio _{of Si—CH 3} to Si—O—Si in the inorganic thin film layer. It is thought to represent. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (4) has high density and easily reduces defects such as fine voids and cracks, and thus easily enhances gas barrier properties and impact resistance. The peak intensity ratio I ₄ / I ₃ is more preferably in the range of _{0.02 ≦ I 4} / I ₃ <0.04 from the viewpoint of easily maintaining the high density of the inorganic thin film layer.

When the inorganic thin film layer _{satisfies the range of the peak intensity ratio I 4} / I ₃ , the laminated film produced by one embodiment of the present invention becomes moderately slippery and blocking is easily reduced. If the peak intensity ratio I ₄ / I ₃ is too large, it means that there is too much SiC, and in this case, the flexibility tends to be poor and slipperiness tends to occur. Further, if the peak intensity ratio I ₄ / I ₃ is too small, the flexibility tends to decrease due to the amount of Si—C being too small.

The infrared spectroscopic measurement of the surface of the inorganic thin film layer can be measured by a Fourier transform infrared spectrophotometer equipped with an ATR attachment using a germanium crystal on the prism.

When performing infrared spectroscopy with respect to the surface of the inorganic thin film layer (ATR method), a peak exists in the 950 ~ 1050 cm ^-1 intensity _{(I 3),} the peak intensity existing in the 770 ~ 830cm ^-1 _{(I 5} ) And the intensity ratio (I ₅ / I ₃ ) preferably satisfy the formula (5).
0.25 ≤ I ₅ / I ₃ ≤ 0.50 (5)

_{The peak intensity ratio I 5} / I ₃ calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—C, Si—O, etc. to Si—O—Si in the inorganic thin film layer. .. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (5) is likely to have high bending resistance and impact resistance because carbon is introduced while maintaining high density. The peak intensity ratio I ₅ / I ₃ _{is preferably in the range of 0.25 ≤ I 5} / I ₃ ≤ 0.50, preferably 0.30 ≤ I, from the viewpoint of maintaining a balance between the compactness and the bending resistance of the inorganic thin film layer. _{The range of 3} / I ₁ ≤ 0.45 is more preferable.

The inorganic thin film layer, when subjected infrared spectrometry the inorganic thin film layer surface (ATR method), a peak exists in the 770 ~ 830 cm ^-1 intensity _{(I 5),} present in the 870 ~ 910 cm ^-1 It is preferable that the intensity ratio with the peak intensity (I _{6) satisfies the formula (6).}
0.70 ≤ I ₆ / I ₅ <1.00 (6)

_{The peak intensity ratio I 6} / I ₅ calculated from infrared spectroscopic measurement (ATR method) is considered to represent the ratio of peaks related to Si—C in the inorganic thin film layer. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (6) is likely to have high bending resistance and impact resistance because carbon is introduced while maintaining high density. Regarding the range of the peak intensity ratio I ₆ / I ₅ _{, the range of 0.70 ≦ I 6} / I ₅ <1.00 is preferable, and 0.80 from the viewpoint of maintaining the balance between the compactness and the bending resistance of the inorganic thin film layer. The range of ≦ I ₆ / I ₅ <0.95 is more preferable.

The inorganic thin film layer may be a single layer or a multilayer of two or more layers. Further, an inorganic thin film layer may be provided on both surfaces of the base material. When two or more or a plurality of inorganic thin film layers are formed, each layer may be a layer having the same composition or a layer having a different composition, but from the viewpoint of easily improving the gas barrier property and heat resistance of the laminated film. Therefore, it is preferable that the layers have the same composition. Further, when two or more or a plurality of inorganic thin film layers are formed, the example may be carried out by a plurality of passes described later.

The thickness of the inorganic thin film layer is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 50 nm, from the viewpoint of easily improving gas barrier properties and bending resistance and easily reducing the amount of charge after forming the inorganic thin film layer. As described above, it is particularly preferably 100 nm or more, preferably 3000 nm or less, more preferably 2000 nm or less, and further preferably 1000 nm or less. When there are two or more or a plurality of inorganic thin film layers, the thickness of each layer may be the same or different.

The inorganic thin film layer can preferably have a high average density of ^{1.8 g / cm 3 or more.} Here, the "average density" of the inorganic thin film layer is the number of silicon atoms, the number of carbon atoms, the number of oxygen atoms obtained by the Rutherford Backscattering Spectrometry (RBS), and the hydrogen forward scattering method (Hydrogen Forward). The weight of the inorganic thin film layer in the measurement range is calculated from the number of hydrogen atoms obtained by scattering Spectrometry (HFS), and divided by the volume of the inorganic thin film layer in the measurement range (the product of the ion beam irradiation area and the film thickness). It is required by doing. When the average density of the inorganic thin film layer is at least the above lower limit, the density is high and the structure is preferable because defects such as fine voids and cracks can be easily reduced. In a preferred embodiment of the present invention in which the inorganic thin film layer is composed of silicon atoms, oxygen atoms, carbon atoms and hydrogen atoms, the average density of the inorganic thin film layers is preferably less than ^{2.22 g / cm 3.}

In a preferred embodiment of the present invention in which the inorganic thin film layer contains at least silicon atoms (Si), oxygen atoms (O), and carbon atoms (C), from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer. The curve showing the relationship between the distances and the atomic number ratio of silicon atoms at each distance is called a silicon distribution curve. Here, the surface of the inorganic thin film layer refers to a surface that becomes the surface of the laminated film produced by one embodiment of the present invention. Similarly, a curve showing the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic number ratio of oxygen atoms at each distance is called an oxygen distribution curve. Further, a curve showing the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic number ratio of carbon atoms at each distance is called a carbon distribution curve. The atomic number ratio of silicon atom, the atomic number ratio of oxygen atom, and the atomic number ratio of carbon atom mean the ratio of the number of atoms to the total number of silicon atom, oxygen atom, and carbon atom contained in the inorganic thin film layer. ..

The ratio of the number of carbon atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the inorganic thin film layer from the viewpoint of suppressing the decrease in gas barrier property due to bending and easily reducing the amount of charge after forming the inorganic thin film layer. However, it is preferable that the inorganic thin film layer continuously changes in a region of 90% or more in the film thickness direction. Here, the fact that the atomic number ratio of the carbon atoms changes continuously in the film thickness direction of the inorganic thin film layer means that, for example, in the carbon distribution curve described above, the atomic number ratio of carbon changes discontinuously as described later. It means that it does not include a part.

It is preferable that the carbon distribution curve of the inorganic thin film layer has eight or more extreme values from the viewpoint of bending resistance and gas barrier property of the laminated film.

It is preferable that the silicon distribution curve, oxygen distribution curve and carbon distribution curve of the inorganic thin film layer satisfy the following conditions (i) and (ii) from the viewpoint of bending resistance and gas barrier property of the laminated film.
(I) The condition represented by the following formula (7) is satisfied in a region where the atomic number ratio of silicon, the atomic number ratio of oxygen, and the atomic number ratio of carbon are 90% or more in the film thickness direction of the inorganic thin film layer. ,as well as,
(Atomic number ratio of oxygen)> (Atomic number ratio of silicon)> (Atomic number ratio of carbon) (7) (ii) The carbon distribution curve preferably has at least one, more preferably eight or more extreme values. Have.

The carbon distribution curve of the inorganic thin film layer is preferably substantially continuous. The fact that the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic number ratio of carbon changes discontinuously. Specifically, it is preferable that the formula (8) is satisfied when the distance from the surface of the inorganic thin film layer in the film thickness direction is x [nm] and the atomic number ratio of carbon is C.
| DC / dx | ≤0.01 (8)

Further, the carbon distribution curve of the inorganic thin film layer preferably has at least one extreme value, and more preferably has eight or more extreme values. The extreme value here is the maximum value or the minimum value of the atomic number ratio of each element with respect to the distance from the surface of the inorganic thin film layer in the film thickness direction. The extreme value is at the point where the atomic number ratio of the element changes from increase to decrease or the atomic number ratio of the element changes from decrease to increase when the distance from the surface of the inorganic thin film layer in the film thickness direction is changed. It is the value of the atomic number ratio. The extreme value can be obtained, for example, based on the atomic number ratio measured at a plurality of measurement positions in the film thickness direction. At the measurement position of the atomic number ratio, the interval in the film thickness direction is set to, for example, 20 nm or less. For the positions showing extreme values in the film thickness direction, for discrete data groups including the measurement results at each measurement position, for example, the measurement results at three or more different measurement positions are compared, and the measurement results increase or decrease. It can be obtained by finding the position where it turns to or the position where it turns from decrease to increase. The position showing the extremum can also be obtained, for example, by differentiating the approximate curve obtained from the discrete data group. When the section where the atomic number ratio monotonically increases or decreases monotonically from the position showing the extreme value is, for example, 20 nm or more, the atomic number ratio at the position moved by 20 nm in the film thickness direction from the position showing the extreme value and the pole. The absolute value of the difference from the value is, for example, 0.03 or more.

As described above, the inorganic thin film layer formed so as to satisfy the condition that the carbon distribution curve preferably has at least one, more preferably eight or more extreme values has gas permeation after bending with respect to the gas permeability before bending. The amount of increase in the rate is smaller than that in the case where the above conditions are not satisfied. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier property due to bending can be obtained. When the inorganic thin film layer is formed so that the number of extreme values of the carbon distribution curve is two or more, the amount of increase is smaller than that of the case where the number of extreme values of the carbon distribution curve is one. .. Further, when the inorganic thin film layer is formed so that the number of extreme values of the carbon distribution curve is three or more, the amount of increase is larger than that of the case where the number of extreme values of the carbon distribution curve is two. Less. When the carbon distribution curve has two or more extrema, the distance from the surface of the inorganic thin film layer in the film thickness direction at the position showing the first extremum and the second extremum adjacent to the first extremum. The absolute value of the difference from the distance from the surface of the inorganic thin film layer in the film thickness direction of the position showing the value is preferably in the range of 1 nm to 200 nm, and more preferably in the range of 1 nm to 100 nm.

Further, it is preferable that the absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of carbon in the carbon distribution curve of the inorganic thin film layer is larger than 0.01. In the inorganic thin film layer formed so as to satisfy the above conditions, the amount of increase in the gas permeability after bending with respect to the gas permeability before bending is smaller than that in the case where the above conditions are not satisfied. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier property due to bending can be obtained. When the absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of carbon is 0.02 or more, the above effect is high, and when it is 0.03 or more, the above effect is further high.

The lower the absolute value of the difference between the maximum and minimum values of the atomic number ratio of silicon in the silicon distribution curve, the better the gas barrier property of the inorganic thin film layer tends to be. From this point of view, the absolute value is preferably less than 0.05 (less than 5 at%), more preferably less than 0.04 (less than 4 at%), and less than 0.03 (3 at%). Less than) is particularly preferable.

In addition, in the oxygen carbon distribution curve, when the total of the atomic number ratio of oxygen atoms and the atomic number ratio of carbon atoms at each distance is defined as the "total atomic number ratio", the difference between the maximum value and the minimum value of the total atomic number ratio. The lower the absolute value of, the better the gas barrier property of the inorganic thin film layer tends to be. From this point of view, the total atomic number ratio is preferably less than 0.05 (less than 5 at%), more preferably less than 0.04 (less than 4 at%), and less than 0.03 (less than 0.03). It is particularly preferable that it is less than 3 at%).

When the inorganic thin film layer has a substantially uniform composition in the surface direction of the inorganic thin film layer, the gas barrier property of the inorganic thin film layer can be improved. The substantially uniform composition means the number of extreme values existing in the film thickness direction at any two points on the surface of the inorganic thin film layer in the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve. Is the same, and the absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of carbon in each carbon distribution curve is the same as each other or the difference is within 0.05.

The inorganic thin film layer formed so as to satisfy the above conditions can exhibit the gas barrier property required for a flexible electronic device using, for example, an organic electro-luminescence element.

For the composition, film thickness, shape of each distribution curve, etc. of the above-mentioned inorganic thin film layer, the type of film-forming gas, the flow rate ratio of these gases (for example, the flow rate ratio of the reaction gas and the film-forming gas), the film forming conditions, etc. The choices include, for example, the film-forming gas exemplified above; the flow rate range of the reaction gas and the source gas; and the pressure range, applied power range, frequency range and film transfer when generating the discharge plasma described above. It can be adjusted by appropriately selecting from the speed range and the like.

Here, in one embodiment in which the obtained inorganic thin film layer contains at least silicon atoms, oxygen atoms, and carbon atoms, a preferable method for adjusting the raw material gas and the reaction gas will be described below.
_{In such an embodiment, SiO 2} and SiO _x _Cy (0 <x <2, 0 <y <2) are produced by the decomposition reaction of the raw material gas containing the organosilicon compound containing silicon atoms and carbon atoms with the reaction gas. It may be generated to form an inorganic thin film layer. The ratio of the raw material gas and the reaction gas supplied to the space between the pair of film forming rolls is a reaction theoretically required to completely react the raw material gas and the reaction gas (completely oxidize the raw material gas). It is preferable not to exceed the gas ratio. This is because when the organosilicon compound contained in the raw material gas is completely oxidized, a SiO ₂ layer is formed and the SiO _x _Cy layer is not formed, that is, the unoxidized carbon atom in the organosilicon compound is formed. This is because it is not incorporated into the inorganic thin film layer, which is disadvantageous from the viewpoint of gas barrier property. On the other hand, if the ratio of the reaction gas is too small, unoxidized carbon atoms may be excessively incorporated into the inorganic thin film layer, and the transparency of the inorganic thin film layer may decrease. Therefore, the flow rate ratio of the volume flow V ₁ of the volume flow V ₂ and the raw material gas in the reaction gas to be supplied between the pair of deposition rolls (V 2 _{/ V} ₁₎ is the organosilicon compound contained in the raw material gas When the minimum flow rate ratio (V ₀₂ / V ₀₁ ) of _{the volumetric flow rate V 02} _{of the reaction gas and the volume flow rate V 01} of the raw material gas, which is necessary for complete oxidation of the _{gas, is P 0} , it is preferably 0.98 P ₀ to It is 0.20P ₀ , more preferably 0.95P ₀ to 0.25P ₀ , and even more preferably 0.90P ₀ to 0.30P ₀ .
When the flow rate ratio V ₂ / V ₁ is not more than the above upper limit, the decrease in transparency due to the excess carbon atom derived from the organic silane compound can be effectively suppressed in the inorganic thin film layer, and the flow rate ratio V ₂ / V _{1 can be effectively suppressed.} When is greater than or equal to the above lower limit, it is possible to effectively suppress a decrease in gas barrier property due to a small amount of carbon atoms derived from the organic silane compound in the inorganic thin film layer.

The minimum flow rate ratio P ₀ (V ₀₂ / V ₀₁ ) is obtained as follows. For example, when hexamethyldisiloxane (HMDSO) [(CH ₃ ) ₃ Si—O—Si (CH ₃ ) ₃ ] is used as the raw material gas and oxygen is used as the reaction gas, the reaction between the raw material gas and the reaction gas causes the reaction. The reaction according to the following reaction formula (I): (CH ₃ ) ₃ Si—O—Si (CH ₃ ) ₃ + 12O ₂ → 6CO ₂ + 9H ₂ O + _{2SiO 2} (I) occurs, and SiO ₂ is produced. In such a reaction, the amount of oxygen for complete oxidation of 1 mol of HMDSO is 12 mol.
Therefore, the minimum flow rate ratio P ₀ is V ₀₂ / V ₀₁ = 12.

A known gas supply pipe or the like may be used to supply the film-forming gas to the space between the pair of rolls. In order to plasma discharge the film-forming gas under the above pressure, it is preferable to arrange at least the film-forming roll and the gas supply pipe in a vacuum chamber or the like.

The laminated film obtained by forming the inorganic thin film layer in step (II) is conveyed to the take-up roll by a conveying roll or the like.

[Step (III)]
The step (III) is a step of winding the laminated film obtained in the step (II) with a take-up roll.

In the production method of one embodiment of the present invention, when the absolute value of the amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer and the time of winding is measured under vacuum in steps (II) and (III). In addition, it is 1.5 kV or less. Therefore, foreign matter is unlikely to adhere during transportation or after being wound up, so that the occurrence of foreign matter defects in the obtained laminated film can be suppressed. In addition, in this specification, under vacuum means a pressure of 10 Pa or less.

The absolute value of the amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer until winding is preferably 1.4 kV or less, more preferably 1.2 kV or less, still more preferably 1 when measured under vacuum. It is 0.0 kV or less. When the absolute value of the amount of charge is not more than the above upper limit, it is easier to suppress the occurrence of foreign matter defects. The amount of charge (under vacuum) after the formation of the inorganic thin film layer until the time of winding can be measured using an electrostatic potential monitoring device and a vacuum-compatible electrostatic potential sensor, and can be measured, for example, by the method described in Examples.

The amount of charge from the formation of the inorganic thin film layer to the time of winding is from immediately after the formation of the inorganic thin film layer (immediately after the second film forming roll of the pair of film forming rolls) to immediately before winding with the winding roll (immediately after the winding film forming roll). Indicates the amount of charge (also referred to as immediately before the take-up roll), and within 5 seconds after passing through the second film-forming roll or within 10 cm of the transport distance after passing through the second film-forming roll using the above apparatus. It was obtained by measuring at least the amount of charge between the above-mentioned part and the part within 5 seconds before the start of winding with the take-up roll or within the transport distance of 10 cm until the start of winding. Further, depending on the distance between the film forming roll and the take-up roll and the like, further measurement points may be appropriately provided between these measurement points.

The high amount of charge at the time of unwinding is due to the transfer by the conductive transfer roll and the film forming roll; the passage through the plasma space where many positive charges or negative charges exist; the formation of an inorganic thin film layer on the substrate, etc. Movement and the like occur and are reduced. Therefore, the amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer until the time of winding can be adjusted to 1.5 kV or less, preferably by appropriately changing the production conditions within the range shown above.

The manufacturing method according to one embodiment of the present invention may be carried out in one pass or in a plurality of passes. Here, 1 pass means a series of operations from unwinding a base material having a certain length, forming an inorganic thin film layer, and winding the laminated film having a certain length. In other words, it means an operation from the start to the stop of plasma generation. Therefore, the plurality of passes means that the laminated film is manufactured in two or more passes. In the manufacturing method in which a plurality of passes are performed, since the inorganic thin film layer is further formed by the discharge plasma on the surface of the inorganic thin film layer formed on the base material, two or more inorganic thin film layers are formed on at least one surface of the base material. To.

In the production method of one embodiment of the present invention, the step (I) of unwinding the base material, that is, the predetermined charge amount at the time of unwinding may be satisfied in the first pass. In particular, unwinding is likely to occur when unwinding a base material on which an inorganic thin film layer is not formed, and if the amount of charge at unwinding in step (I) satisfies a predetermined range, unwinding will occur even after the second pass. Can be suppressed. Further, after the formation of the inorganic thin film layer in the steps (II) and (III) and until the time of winding, the predetermined charge amount may be satisfied at least in the first pass, but from the viewpoint of more easily suppressing the occurrence of foreign matter defects. It is preferable that the predetermined charge amount is satisfied even after the second pass. When unwinding the laminated film after the second pass, the absolute value of the amount of charge (in the atmosphere) at the time of unwinding may be 2.0 kV or more.

In a preferred embodiment of the present invention, in step (I), the absolute value of the amount of charge on the surface of the base material at the time of unwinding is controlled to 2.0 kV or more when measured in the atmosphere, and step (II) and In (III), the absolute value of the amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer until the time of winding is controlled to 1.5 kV or less when measured under vacuum. Further, in a preferred embodiment of the present invention, in the production method of the present invention, in the step (I), the amount of charge on the surface of the base material at the time of unwinding is measured in the atmosphere, and the absolute value of the amount of charge is 2. It is controlled (or adjusted) so that it becomes 0 kV or more, and in steps (II) and (III), the amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer and before winding is measured under vacuum. The absolute value of the charge amount is controlled (or adjusted) so as to be 1.5 kV or less.

[One Embodiment of the present invention]
Hereinafter, the production method according to one embodiment of the present invention will be described with reference to FIG. 1, but the present invention is not limited to the embodiment according to FIG.

FIG. 1 is a schematic view showing an example of a manufacturing apparatus used in one embodiment of the present invention, and is a schematic diagram of an apparatus for forming an inorganic thin film layer by a plasma chemical vapor deposition method. In FIG. 1, the dimensions and ratios of each component are appropriately adjusted in order to make the drawings easier to see. Therefore, the dimensions, ratio, and the like can be changed as appropriate.

The manufacturing apparatus 10 shown in FIG. 1 includes a feeding roll 11, a winding roll 12, a transport roll 13 to 18, a first film forming roll 25, a second film forming roll 26, a gas supply pipe 19, a plasma generation power supply 20, and an electrode. It has 21, an electrode 22, a magnetic field forming device 23 installed inside the first film forming roll 25, and a magnetic field forming device 24 installed inside the second film forming roll 26.

Of the components of the manufacturing apparatus 10, at least the first film forming roll 25, the second film forming roll 26, the gas supply pipe 19, the magnetic field forming device 23, and the magnetic field forming device 24 are not shown when manufacturing the laminated film. Is placed in the vacuum chamber of. This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

By using this device, by controlling the plasma generation power supply 20, the film-forming gas supplied from the gas supply pipe 19 into the space 27 between the first film-forming roll 25 and the second film-forming roll 26. Discharge plasma can be generated, and plasma CVD film formation can be performed by a continuous film formation process using the generated discharge plasma.

The feeding roll 11 is arranged with the base material 29 before film formation wound up, that is, in the state of a roll-shaped base material. In step (I), the roll-shaped base material 29 is unwound from the delivery roll 11 in the longitudinal direction. The unwinding speed is preferably 1.2 m / min or more from the viewpoint of making it easy to adjust the absolute value of the charge amount at the time of unwinding to 2.0 kV or more. The amount of charge at the time of unwinding can be measured at the measurement position 101 immediately after the feeding roll by an electrostatic potential monitoring device (not shown). The measurement position 101 is a position within 5 seconds after unwinding, or a position within a transport distance of 10 cm after unwinding. Since it is necessary to measure the amount of charge at the time of unwinding in the atmosphere, the measurement is performed when the base material 29 is unwound from the delivery roll 11 in the atmosphere. Next, after the inside of the manufacturing apparatus 10 is evacuated, the base material 29 is transferred to the first film forming roll 25 by the transfer rolls 13 and 14. In one embodiment of the present invention, the absolute value of the amount of charge at the time of unwinding is 2.0 kV or more when measured in the atmosphere, and the occurrence of unwinding of the obtained laminated film can be suppressed.

In step (II), the reaction gas and the raw material gas are supplied between the pair of

film forming rolls

25 and 26, and the plasma discharge generated between the rolls causes the inorganic material to be transferred to at least one side of the base material 29. A thin film layer is formed to obtain a laminated film. Details of step (II) are shown below.

The first film-forming roll 25 and the second film-forming roll 26 are made of a conductive material, and each of them conveys the base material 29 while rotating. The first film forming roll 25 and the second film forming roll 26 extend in parallel and are arranged to face each other. The first film forming roll 25 and the second film forming roll 26 preferably have the same diameter, and have a diameter of 5 cm to 30 cm. Further, the first film forming roll 25 and the second film forming roll 26 are insulated from each other and connected to a common plasma generation power source 20. When an AC voltage is applied from the plasma generation power source 20, an electric field is formed in the space 27 between the first film forming roll 25 and the second film forming roll 26. The applied power of the plasma generation power supply 20 is preferably 100 W to 10 kW, and the AC frequency is preferably 50 Hz to 500 kHz.

The magnetic field forming device 23 and the magnetic field forming device 24 are members that form a magnetic field in the space 27, and are housed inside the first film forming roll 25 and the second film forming roll 26. The magnetic field forming device 23 and the magnetic field forming device 24 are fixed so as not to rotate together with the first film forming roll 25 and the second forming film roll 26 (that is, the posture relative to the vacuum chamber does not change). ..

The magnetic field forming device 23 and the magnetic field forming device 24 are formed around the central magnets 23a and 24a extending in the same direction as the extending direction of the first film forming roll 25 and the second film forming roll 26 and around the central magnets 23a and 24a. While surrounding, it has an annular

outer magnets

23b and 24b that are arranged so as to extend in the same direction as the extending direction of the first film forming roll 25 and the second film forming roll 26. In the magnetic field forming device 23, the magnetic field lines (magnetic fields) connecting the central magnet 23a and the external magnet 23b form an endless tunnel. Similarly, in the magnetic field forming device 24, the magnetic field lines connecting the central magnet 24a and the external magnet 24b form an endless tunnel.

The discharge plasma of the film-forming gas is generated by the magnetron discharge in which the magnetic field lines and the electric field formed between the first film-forming roll 25 and the second film-forming roll 26 intersect. That is, as will be described in detail later, the space 27 is used as a film forming space for performing plasma CVD film formation, and the surface of the base material 29 that does not come into contact with the first film forming roll 25 and the second film forming roll 26 (film formation). On the surface), an inorganic thin film layer in which the film-forming gas is deposited via the plasma state is formed.

In the vicinity of the space 27, a gas supply pipe 19 for supplying a film-forming gas 28 containing a plasma CVD raw material gas and a reaction gas is provided in the space 27. The gas supply pipe 19 has a tubular shape extending in the same direction as the extending direction of the first film forming roll 25 and the second film forming roll 26, and the space 27 is provided through openings provided at a plurality of locations. 28 is supplied with the film-forming gas 28. In FIG. 1, an arrow indicates how the film-forming gas 28 is supplied from the gas supply pipe 19 toward the space 27.

As the raw material gas and reaction gas, the above-exemplified raw material gas and reaction gas are used, and the flow rate and ratio thereof can also be selected from the above-exemplified range. The film-forming gas may include the carrier gas and the discharge gas. The pressure in the vacuum chamber (degree of vacuum), that is, the pressure in the space 27 is preferably 0.1 to 50 Pa. The electric power of the electrode drum of the plasma generator is preferably 100 W to 10 kW. The transport speed (line speed) of the base material 29 is usually the same as the unwinding speed, and is preferably 1.2 m / min or more.

In the manufacturing apparatus 10, the film is formed on the base material 29 as follows. That is, an inorganic thin film layer is formed on the surface of the base material 29. First, before film formation, it is advisable to perform a pretreatment so that the outgas generated from the base material 29 is sufficiently reduced.

Examples of the method for reducing the amount of outgas generated from the base material 29 include vacuum drying, heat drying, drying by a combination thereof, and drying by natural drying. Regardless of the drying method, in order to accelerate the drying of the inside of the base material 29 wound in a roll shape, the roll is repeatedly rewound (unwinding and winding) during drying, and the entire base material 29 is taken up. Is preferably exposed to a dry environment.

Vacuum drying is performed by placing the base material 29 in a pressure-resistant vacuum container and evacuating the inside of the vacuum container using a decompressor such as a vacuum pump to create a vacuum. The pressure in the vacuum vessel during vacuum drying is preferably 1000 Pa or less, more preferably 100 Pa or less, and even more preferably 10 Pa or less. Exhaust in the vacuum vessel may be performed continuously by continuously operating the decompressor, or intermittently by operating the decompressor intermittently while controlling the internal pressure so as not to exceed a certain level. It may be done in. The drying time is preferably at least 8 hours or more, more preferably 1 week or more, and further preferably 1 month or more.

Heat drying is performed by exposing the base material 29 to an environment of room temperature or higher. The heating temperature is preferably room temperature or higher and 200 ° C. or lower, and more preferably room temperature or higher and 150 ° C. or lower. At a temperature exceeding 200 ° C., the base material 29 may be deformed, or defects may occur due to elution of, for example, an oligomer component from the base material 29 and precipitation on the surface. The drying time can be appropriately selected depending on the heating temperature and the heating means used.

The heating means may be any as long as it can heat the base material 29 to room temperature or higher and 200 ° C. or lower under normal pressure. Among the commonly known devices, an infrared heating device, a microwave heating device, and a heating drum are preferably used. The infrared heating device is a device that heats an object by radiating infrared rays from an infrared generating means. The microwave heating device is a device that heats an object by irradiating a microwave from a microwave generating means. The heating drum is a device that heats the surface of the drum and brings the object into contact with the surface of the drum to heat the drum surface by heat conduction from the contact portion.

Natural drying is performed by arranging the base material 29 in a low humidity atmosphere and allowing dry gas (dry air, dry nitrogen) to pass through to maintain a low humidity atmosphere. When performing natural drying, it is preferable to place a desiccant such as silica gel together in a low humidity environment in which the base material 29 is placed. The drying time is preferably 8 hours or more, more preferably 1 week or more, and further preferably 1 month or more. These dryings may be performed separately before mounting the base material 29 on the manufacturing apparatus, or may be performed in the manufacturing apparatus after mounting the base material 29 on the manufacturing apparatus. As a method of mounting the base material 29 on the manufacturing apparatus and then drying it, it is possible to reduce the pressure in the chamber while feeding and transporting the base material 29 from the delivery roll 11. Further, the roll to be passed may be provided with a heater, and the roll may be heated by using the roll as the above-mentioned heating drum.

Another method of reducing the outgas from the base material 29 is to form an inorganic film on the surface of the base material 29 in advance. Examples of the method for forming an inorganic film include a physical film forming method such as vacuum vapor deposition (heat vapor deposition), electron beam (EB) vapor deposition, sputtering, and ion plating. The inorganic film may be formed by a chemical deposition method such as thermal CVD, plasma CVD, or atmospheric pressure CVD. The influence of outgas may be further reduced by subjecting the base material 29 having an inorganic film formed on the surface to a drying treatment by the above-mentioned drying method.

Next, a vacuum chamber (not shown) is used as a reduced pressure environment, and an electric field is generated in the space 27 by applying it to the first film forming roll 25 and the second film forming roll 26. At this time, since the magnetic field forming device 23 and the magnetic field forming device 24 form the above-mentioned non-terminal tunnel-shaped magnetic field, the magnetic field and the electrons emitted into the space 27 are generated by introducing the film-forming gas. , A discharge plasma of a donut-shaped film-forming gas is formed along the tunnel. Since this discharge plasma can be generated at a low pressure of around several Pa, the temperature inside the vacuum chamber can be set to around room temperature.

On the other hand, since the temperature of the electrons captured at high density in the magnetic field formed by the magnetic field forming device 23 and the magnetic field forming device 24 is high, discharge plasma generated by the collision between the electrons and the film-forming gas is generated. That is, electrons are confined in the space 27 by the magnetic field and the electric field formed in the space 27, so that a high-density discharge plasma is formed in the space 27. More specifically, a high-density (high-intensity) discharge plasma is formed in a space that overlaps with an unterminated tunnel-shaped magnetic field, and a low-density (low) in a space that does not overlap with an unterminated tunnel-shaped magnetic field. (Intensity) discharge plasma is formed. The intensity of these discharge plasmas changes continuously.

When discharge plasma is generated, a large amount of radicals and ions are generated and the plasma reaction proceeds, and the reaction between the raw material gas contained in the film-forming gas and the reaction gas occurs. Here, in the space where the high-intensity discharge plasma is formed, the reaction easily proceeds because the energy given to the oxidation reaction is large, and the complete oxidation reaction of the organosilicon compound can be mainly caused. On the other hand, in the space where the low-intensity discharge plasma is formed, the energy given to the oxidation reaction is small, so that the reaction is difficult to proceed, and the incomplete oxidation reaction of the organosilicon compound can be mainly caused.

In the present specification, the "complete oxidation reaction of an organosilicon compound containing a silicon atom and a carbon atom" means that the reaction between the organosilicon compound and oxygen proceeds, and the organosilicon compound has the above-mentioned reaction formula ( It means that it is oxidatively decomposed into _{SiO 2} , water and carbon dioxide as shown in I).

Further, in the present specification, "incomplete oxidation reaction of an organosilicon compound containing a silicon atom and a carbon atom" means SiOxCy in which the organosilicon compound does not undergo a complete oxidation reaction and contains carbon in the structure instead of _{SiO 2.} It means that the reaction is such that (0 <x <2, 0 <y <2) occurs.

As described above, in the manufacturing apparatus 10, since the discharge plasma is formed in a donut shape on the surfaces of the first film forming roll 25 and the second film forming roll 26, the first film forming roll 25 and the second film forming roll 26 The base material 29 transported on the surface alternately passes through the space in which the high-intensity discharge plasma is formed and the space in which the low-intensity discharge plasma is formed. Therefore, on the surface of the base material 29 that passes through the surfaces of the first film forming roll 25 and the second film forming roll 26, a layer containing a large amount of _{SiO 2} _{generated by the complete oxidation reaction (referred to as Ha1} layer or _Ha2 layer). A layer containing a large amount of SiOxCy (referred to as an H _b1 layer or an H _b2 layer) generated by an incomplete oxidation reaction is sandwiched and formed therein. For example, a laminate composed of a base material 29 / HA layer ( _Ha1 layer / _Hb1 layer / _Ha1 layer) / HB layer ( _Ha2 layer / _Hb2 layer / _Ha2 layer) in the order of being laminated, or the like. Is formed.

In addition to these, high-temperature secondary electrons are prevented from flowing into the base material 29 due to the action of the magnetic field, so that high power can be applied while keeping the temperature of the base material 29 low, and high-speed film formation is achieved. Will be done. The film deposition mainly occurs only on the film-forming surface of the base material 29, and the film-forming roll is covered with the base material 29 to prevent stains, so that stable film formation can be performed for a long time.

In one embodiment of the present invention, the laminated film produced has at least an HA layer and an HB layer. First, it is preferable to form the HB layer after forming the HA layer on the base material side. When forming the HB layer, it is preferable to form the HA layer at a temperature higher than the temperature of the film surface at the time of formation. As a method of controlling the temperature of the film surface, 1. 2. Reduce the pressure during film formation in the vacuum chamber. 2. Increase the applied power from the plasma generation power supply. 3. Reduce the flow rate of the raw material gas (and the flow rate of the reaction gas). 4. Reduce the transport speed of the base material. Raise the temperature of the film forming roll itself, 6. For example, lowering the frequency of the power source for plasma generation at the time of film formation. One of these conditions 1 to 6 may be selected, the other conditions may be fixed, and the selected conditions may be optimized so that the temperature becomes appropriate at the time of film formation. Two or three or more of these conditions may be changed to optimize the film formation so that the temperature becomes appropriate at the time of film formation. It is preferable to optimize conditions 1 to 4 and 6 within the above range. Regarding the above condition 5, the surface temperature of the first film forming roll 25 and the second film forming roll 26 is preferably −10 to 80 ° C.

In the step (III), the laminated film in which the inorganic thin film layer is formed on the surface of the base material 29 is conveyed by the conveying rolls 17 and 18, and is wound into a roll by the winding roll 12.

In step (II) and step (III), the absolute value of the amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer until the time of winding is 1.5 kV or less when measured under vacuum. It is possible to prevent foreign matter from adhering to the surface of the laminated film and effectively suppress the occurrence of foreign matter defects. The amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer until the time of winding is measured at the measurement position 102 immediately after the second film forming roll by the electrostatic potential monitoring device and the vacuum-compatible electrostatic potential sensor (not shown). It can be measured at the measurement position 103 immediately before the take-up roll. The measurement position 102 is a position within 5 seconds after passing through the second film forming roll 26 or within a transport distance of 10 cm after passing through the second film forming roll 26. The measurement position 103 is a position within 5 seconds before the start of winding with the take-up roll 12 or within a transport distance of 10 cm until the start of winding.

In the manufacturing method of one embodiment of the present invention, in the step (A), the operation from the start to the stop of plasma generation is performed once or more, that is, in one pass or more. In the manufacturing apparatus of FIG. 1, when manufacturing a laminated film of a certain length, a base material 29 of a certain length is unwound, and an inorganic thin film layer is formed when passing through a pair of

film forming rolls

25 and 26. The operation of filming and winding with the take-up roll 12 is one pass. Further, usually, in the second pass, the film is sent out from the winding roll 12 in which the film having the inorganic thin film layer formed on the base material 29 is wound in the first pass, and the film is conveyed by the conveying rolls 18 to 16. Next, when passing through the second film forming roll 26 and the first film forming roll 25, an inorganic thin film layer is further formed on the inorganic thin film layer formed in the first pass, and then the transport rolls 15 to 13 are formed. Finally, the film is wound up by the delivery roll 11. Therefore, the inorganic thin film layer can be made into multiple layers by performing the film formation in a plurality of passes. In such a case, even when the inorganic thin film layer having the same thickness is formed, the transport speed can be increased, so that thermal damage to the base material can be suppressed. As described above, the predetermined charge amount may be satisfied in the step (I) of unwinding the base material, that is, in the first pass. Further, after the formation of the inorganic thin film layer in the steps (II) and (III) and until the time of winding, the predetermined charge amount may be satisfied at least in the first pass, but from the viewpoint of more easily suppressing the occurrence of foreign matter defects. It is preferable that the predetermined charge amount is satisfied even after the second pass. Here, when the number of passes is a plurality of times, the amount of charge from the formation of the inorganic thin film layer in the steps (II) and (III) to the time of winding is the measurement position on one side, that is, based on the film forming roll. , The measurement may be performed at the measurement position 102 and the measurement position 103, and the measurement can be performed on both sides by providing the corresponding measurement positions on the other side.

In one embodiment of the present invention according to FIG. 1, the base material 29 is the same as the base material described in the above [base material] section, and the inorganic thin film layer is described in the section [step (II)]. It is similar to the inorganic thin film layer of.

[Laminated film]
The laminated film obtained by the production method of one embodiment of the present invention includes the base material and one or more layers of the inorganic thin film formed on at least one surface of the base material. The substrate may include the primer layer and / or the organic layer in addition to the flexible film. The laminated film obtained by the production method of one embodiment of the present invention has an absolute value of the amount of charge on the surface of the base material at the time of unwinding of 2.0 kV or more when measured in the atmosphere in step (I). Moreover, in steps (II) and (III), the absolute value of the amount of charge on the surface of the inorganic thin film layer after the formation of the inorganic thin film layer until winding is 1.5 kV or less when measured under vacuum, so that the winding shift occurs. And foreign matter defects are suppressed. Therefore, the laminated film obtained by the production method of one embodiment of the present invention can be suitably used for electronic device applications such as organic EL elements and organic thin-film solar cells.
FIG. 2 shows an example of the layer structure of the laminated film obtained by the production method of one embodiment of the present invention, but the present invention is not limited to this aspect. The laminated film 1 can be manufactured by, for example, the manufacturing apparatus shown in FIG. 1, and the inorganic thin film layer 2 is formed (or laminated) on the base material 6 having the flexible film 5, the primer layer 4, and the organic layer 3 in this order. ) Is a film. In FIG. 1, the dimensions and ratios of each component are appropriately adjusted in order to make the drawings easier to see. Therefore, the dimensions, ratio, and the like can be changed as appropriate.

The laminated film obtained by one embodiment of the present invention is preferably a gas barrier film.
Since the gas barrier film is excellent in gas barrier property, particularly water vapor barrier property, the water vapor permeability is small. The water vapor permeability of the gas barrier film is preferably 5 × 10 ^-2 g / m ² / day or less, more preferably 1 × 10 ^-2 g / m ² / day or less, and further preferably 5 × 10 ^-3 g. It is less than / m ^{2 / day.} When the water vapor permeability of the gas barrier film is not more than the above upper limit, the gas barrier property can be improved. The lower limit of the water vapor permeability of the gas barrier film is usually 0 g / m ² / day or more. The water vapor permeability can be measured by a Ca corrosion test method based on ISO / WD 15106-7 (Annex C), for example, by the method described in Examples.

The laminated film may have other layers between each layer or between the outermost layers, if necessary. Other layers include, for example, an easy-slip layer, a hard coat layer, a transparent conductive film layer, a color filter layer, an easy-adhesion layer, a curl adjustment layer, a stress relaxation layer, a heat-resistant layer, an abrasion-resistant layer, a pressing-resistant layer, a protective layer, and the like. Can be mentioned.

The thickness of the laminated film is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, preferably 600 μm or less, from the viewpoint of gas barrier property, bending resistance, durability, surface hardness, etc. of the laminated film. It is more preferably 300 μm or less, still more preferably 250 μm or less. The thickness (film thickness) of the laminated film can be measured with a film thickness meter.

The laminated film is preferably a long film, and the length and width thereof can be selected from the same range as the length and width of the base material, respectively. In one embodiment of the present invention, the absolute value of the charge amount at the time of unwinding and the absolute value of the charge amount at the time of winding after the formation of the inorganic thin film layer are adjusted within a predetermined range, and thus are equal to or higher than the above lower limit. Even with a long base material, it is possible to effectively suppress the occurrence of unwinding and foreign matter defects.

[Film thickness]
For the film thickness of each of the flexible film, the organic layer and the inorganic thin film layer of the laminated film obtained in Examples and Comparative Examples, a film thickness meter (manufactured by Kosaka Laboratory Co., Ltd., "Surfcoder ET200") was used. Then, the step between the non-deposited portion and the film-deposited portion was measured.

[X-ray photoelectron spectroscopy measurement of the surface of the inorganic thin film layer]
The atomic number ratio of the surface of the inorganic thin film layer of the laminated film obtained in the examples was measured by X-ray photoelectron spectroscopy (“QuantaraSXM” manufactured by ULVAC-PHI Co., Ltd.) according to the following XPS depth profile. An AlKα ray (1486.6 eV, X-ray spot 100 μm) was used as the X-ray source, and a neutralizing electron gun (1 eV) and a low-speed Ar ion gun (10 V) were used for charge correction at the time of measurement. For post-measurement analysis, spectrum analysis was performed using MultiPak V6.1A (ULVAC-PHI, Inc.), and Si 2p, O 1s, N 1s, and C 1s obtained from the measured wide scan spectrum. The surface atomic number ratios of C (C / Si) to Si and O (O / Si) to Si were calculated using the peaks corresponding to the respective binding energies. As the surface atomic number ratio, the average value of the values measured five times was adopted. From this result, a distribution curve of silicon atom, oxygen atom and carbon atom is created, the average atomic concentration in the thickness direction of each atom is obtained, and then the average atomic number ratios C / Si and O / Si are obtained from the average atomic concentration. Calculated.
<XPS depth profile measurement>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film equivalent): 0.027 nm / sec
Spatter time: 0.5 min
X-ray photoelectron spectrometer: ULVAC-PHI, model name "Quantara SXM"
Irradiated X-ray: Single crystal spectroscopy AlKα (1486.6 eV)
X-ray spot and its size: 100 μm
Detector: Pass Energy 69eV, Step size 0.125eV
Charge correction: Neutralizing electron gun (1eV), low-speed Ar ion gun (10V)

[Infrared spectroscopic measurement of the surface of the inorganic thin film layer (ATR method)]
The infrared spectroscopic measurement of the surface of the inorganic thin film layer of the laminated film obtained in the examples was performed by a Fourier transform infrared spectrophotometer equipped with an ATR attachment (PIKE MIRacle) using a germanium crystal for the prism (JASCO Corporation). Manufactured by FT / IR-460Plus).

[Water vapor permeability of laminated film]
The water vapor permeability of the laminated film obtained in the examples was measured by a Ca corrosion test method in accordance with ISO / WD 15106-7 (Annex C) under the conditions of a temperature of 23 ° C. and a humidity of 50% RH.

[Manufacturing method of inorganic thin film layer]
In Examples and Comparative Examples, an inorganic thin film layer was laminated on the surface of the base material on the organic layer side using the manufacturing apparatus shown in FIG. Specifically, as shown in FIG. 1, after the base material 29 is attached to the delivery roll 10 and the inside of the vacuum chamber is reduced to 1 × 10 ^-3 Pa or less, the pressure around the exhaust port in the vacuum chamber is increased. A film-forming gas 28 containing hexamethyldisiloxane (HMDSO) as a raw material gas and an oxygen gas (which also functions as a discharge gas) as a reaction gas is supplied to the film-forming space 27 so as to be 1 Pa. The exhaust volume was adjusted. After that, AC power was supplied to the first film forming roll 25 and the second film forming roll 26, respectively, and plasma was generated by electric discharge between the pair of

film forming rolls

25 and 26. At that time, the displacement was finely adjusted again so that the pressure around the exhaust port in the vacuum chamber became 1 Pa. Next, the raw material gas and the reaction gas are decomposed and reacted using the generated plasma to form a thin film by the plasma CVD method under the following film forming conditions, and the surface of the base material 29 on the organic layer side is densely formed. An inorganic thin film layer was laminated. Further, the laminated film was wound by the winding roll 12 via the transport roll. The pair of

film forming rolls

25 and 26 are electrodes connected to the plasma generation power supply 20, and the transfer was performed while the base material was brought into close contact with the surface of the electrodes. Further, in the pair of film forming rolls 25 and 26 (electrodes), magnetic

field forming devices

23 and 24 are arranged inside the electrodes so that the magnetic flux density is high on the electrodes and the surface of the base material, and the magnetic fields cause the plasma when plasma is generated. The plasma was densely constrained on the electrodes and substrate.
<Film formation condition 1>
Supply amount of raw material gas: 50 sccm (Standard Cubic Centimeter per Minute, 0 ° C, 1 atm standard)
Oxygen gas supply: 500 sccm
Vacuum degree in vacuum chamber: 1Pa
Power applied from the plasma generation power supply: 0.4 kW
Frequency of power supply for plasma generation: 70kHz
Film transport speed; 3.0 m / min
Number of passes: 28 times

[Evaluation of charge amount of laminated film]
As described above, after mounting the base material 29 on the manufacturing apparatus shown in FIG. 1, an electrostatic potential monitoring apparatus (SP-WATCH KSD-0110, manufactured by Kasuga Electric Co., Ltd.) under the conditions of a temperature of 23 ° C. and a humidity of 50% RH. The amount of charge on the surface of the base material 29 was measured at the measurement position 101 immediately after the delivery roll 11. Next, after the inside of the manufacturing apparatus was evacuated, the amount of charge on the surface of the base material 29 was measured at the measurement position 101 immediately after the delivery roll 11 under the condition that the base material 29 was conveyed and plasma was generated. The amount of charge on the surface of the formed inorganic thin film layer was measured at the measurement position 102 immediately after the film roll 26 and the measurement position 103 immediately before the take-up roll.

[Evaluation of unwinding of laminated film]
In the laminated films of Examples and Comparative Examples wound on the take-up roll 12, the case where the unwinding at both ends of the roll was less than 5 mm was evaluated as ◯, and the case where the unwinding was 5 mm or more was evaluated as x.
The winding deviation indicates the degree of deviation from the end face of the roll-shaped laminated film.

[Evaluation of appearance of laminated film>
A rectangular area of 210 mm × 297 mm was cut out from the laminated films obtained in Examples and Comparative Examples taken out from the manufacturing apparatus, and the entire surface was visually confirmed with a surface inspection lamp (FY series, manufactured by Funatec), and a microscope (trade name). Full-scale observation was performed with a "digital microscope", manufactured by Hirox, and an objective lens of 35 times. In each observation, if there was no foreign matter defect of 20 μm or more, it was evaluated as ◯, and when a foreign matter defect of 20 μm or more was confirmed, it was judged as x.

[Example 1]
Flexible film with primer layers on both sides (manufactured by Teijin Film Solution Co., Ltd., trade name "Theonex (registered trademark)", biaxially stretched polyethylene naphthalate film, Q65HWA, thickness 100 μm, length 500 m, width 350 mm, both sides An organic layer forming composition (Nippon Kako Paint Co., Ltd., "TOMAX FA-3292") is applied to one side of the (easy-adhesive treatment) by a gravure coating method, dried at 100 ° C. for 1 minute, and then high-pressure mercury. Using a lamp, ultraviolet rays are irradiated under the condition of an integrated light amount of 500 mJ / cm ² , and an organic layer having a thickness of 2.5 μm is laminated to obtain a base material in which a flexible film, a primer layer and an organic layer are laminated in this order. It was. Here, the composition for forming an organic layer contains 8.1% by mass of ethyl acetate as a solvent, 52.1% by mass of propylene glycol monomethyl ether, 10 to 20% by mass of UV-curable oligomer as a solid content, and silica particles (average). It is a composition containing 20 to 30% by mass of a primary particle size (20 nm) and 2 to 3% by mass of a photopolymerization initiator as an additive. The UV curable oligomer is a photocurable compound having a (meth) acryloyl group as a polymerizable functional group. Further, the winding base material was prepared with the tension (unit: N) applied in the longitudinal direction with respect to the base material width (unit: m), that is, the winding tension (N / m) being 90 N / m. The tension applied in the longitudinal direction was measured with a tension meter. An inorganic thin film layer was laminated on the surface of the base material thus obtained on the organic layer side according to the method for producing an inorganic thin film layer to obtain a laminated film A. The thickness of the inorganic thin film layer of the obtained laminated film A was 700 nm, and the length of the laminated film A was 500 m and the width was 350 mm. The water vapor permeability under the conditions of a temperature of 40 ° C. and a humidity of 90% RH was 5.0 × ^10-5 g / (m ² · day).

When the XPS depth profile was measured under the above conditions, in the laminated film A, the ratio of the number of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer was the thickness of the inorganic thin film layer. It changed continuously in the region of 90% or more in the direction, and in that region, the order of oxygen, silicon, and carbon was from the one with the largest atomic number ratio. The average atomic number ratio C / Si was 0.30, and the average atomic number ratio O / Si was 1.73.

The inorganic thin film layer of the laminated film A was subjected to infrared spectroscopic measurement under the above conditions. From infrared absorption spectra, determined the peak present in the 950 ~ 1050 cm ^-1 intensity _{(I 3),} the peak intensity existing in the 1240 ~ 1290cm ^-1 _{(I 4)} and absorption intensity ratio of the _{_(I} 4 / I ₃₎ And I ₄ / I ₃ = 0.03. Further, a peak exists in the 950 ~ 1050 cm ^-1 intensity _{(I 3),} when determining the peak exists in the 770 ~ 830 cm ^-1 intensity _{(I 5)} and the absorption intensity ratio _{_{(I 5 / I 3),}} I 5 / I ₃ = 0.36. Further, a peak exists in the 770 ~ 830 cm ^-1 intensity _{(I 5),} when determining the peak intensity existing in the 870 ~ 910cm ^-1 _{(I 6)} and the absorption intensity ratio _{_{(I 6 / I 5),}} I 6 / I ₅ = 0.84.

[Comparative Example 1]
Flexible film with primer layers on both sides (manufactured by Teijin Film Solution Co., Ltd., trade name "Theonex (registered trademark)", biaxially stretched polyethylene naphthalate film, Q65HWA, thickness 100 μm, length 500 m, width 350 mm, both sides Easy-adhesion processing) is used to create a take-up base material with the tension (unit: N) applied in the longitudinal direction with respect to the base material width (unit: m), that is, the take-up tension (N / m) being 90 N / m. did. Next, the inorganic thin film layer was laminated on the base material according to the method for producing the inorganic thin film layer to obtain a laminated film B.

During the production of the laminated films of Example 1 and Comparative Example 1, the charge amount of the laminated films was measured according to the above method. The results obtained are shown in Table 1. Further, with respect to the laminated films obtained in Example 1 and Comparative Example 1, the unwinding of the laminated film and the appearance were evaluated according to the above method. The results obtained are shown in Table 1.

As shown in Tables 1 and 2, in Example 1, the absolute value of the amount of charge on the surface of the base material at the time of unwinding is 2.0 kV or more when measured in the atmosphere, and an inorganic thin film layer is formed. After that, the absolute value of the amount of charge on the surface of the inorganic thin film layer until winding is adjusted to 1.5 kV or less when measured under vacuum, so that the resulting laminated film is prevented from unwinding and foreign matter defects. It was confirmed that it would be done. On the other hand, in Comparative Example 1, since the absolute value of the amount of charge on the surface of the base material at the time of unwinding was less than 2.0 kV when measured in the atmosphere, it was confirmed that unwinding occurred.

1 ... Laminated film, 2 ... Inorganic thin film layer, 3 ... Organic layer, 4 ... Primer layer, 5 ... Flexible film, 6 ... Base material, 10 ... Manufacturing equipment, 11 ... Feeding roll, 12 ... Winding roll, 13 ~ 18 ... Transfer roll, 19 ... Gas supply pipe, 20 ... Plasma generation power supply, 21,22 ... Electrode, 23, 24 ... Magnetic field forming device, 25 ... First film forming roll, 26 ... Second film forming roll, 27 ... Space (deposition space), 28 ... film formation gas, 29 ... base material, 101, 102, 103 ... measurement position

Claims

A method for producing a laminated film containing a base material and one or more inorganic thin film layers formed on at least one surface of the base material by using a plasma chemical vapor deposition method. In the step (I) of unwinding the roll-shaped base material from the delivery roll, at least the base material conveyed by the plasma discharge generated between the rolls by supplying the reaction gas and the raw material gas between the pair of film forming rolls It includes a step (II) of forming an inorganic thin film layer on one side to obtain a laminated film and a step (III) of winding the laminated film with a take-up roll.
In the step (I), the absolute value of the charge amount on the surface of the base material at the time of unwinding is 2.0 kV or more when measured in the atmosphere, and in the steps (II) and (III) after the formation of the inorganic thin film layer. The method, wherein the absolute value of the amount of charge on the surface of the inorganic thin film layer up to the time of winding is 1.5 kV or less when measured under vacuum.
The method according to claim 1, wherein the inorganic thin film layer contains at least silicon atoms, oxygen atoms, and carbon atoms.
The claim that the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changes continuously in a region of 90% or more in the film thickness direction of the inorganic thin film layer. The method according to 1 or 2.
The method according to any one of claims 1 to 3, wherein the base material comprises a flexible film and an organic layer formed on at least one side of the flexible film.
The method according to any one of claims 1 to 4, wherein the laminated film is a gas barrier film.