JPWO2017086035A1 - Gas barrier film - Google Patents

Abstract

An object of the present invention is to provide a gas barrier film having excellent gas barrier properties and high bending resistance even under high temperature and high humidity.
The gas barrier film of the present invention is a gas barrier film comprising a gas barrier layer on a base film, wherein the gas barrier layer contains Si atoms, O atoms and C atoms, and the gas barrier layer includes the gas barrier layer. Based on C1s waveform analysis measured by X-ray photoelectron spectroscopy at a position of 0 to 100% in the layer thickness direction from the surface opposite to the base film to the surface on the base film side, C-C, C- The C—C bond distribution curve representing the ratio of C—C bonds to the total of SiO, C—O, C═O and C═OO bonds is at least one maximum at a position in the layer thickness direction of 75 to 100%. It has a value.

Description

  The present invention relates to a gas barrier film, and more particularly, to a gas barrier film having excellent gas barrier properties and high bending resistance even under high temperature and high humidity.

  Conventionally, lightweight and highly flexible gas barrier films have been used for sealing electronic devices such as organic EL (Electro Luminescence) elements, liquid crystal display elements, and solar cells. The gas barrier film generally has a gas barrier layer formed on a resin base film, and can prevent intrusion of gases such as water and oxygen in the atmosphere.

Gas barrier films used in electronic devices are required to have excellent gas barrier properties, but high flex resistance is also required so that excellent gas barrier properties can be maintained even when used for flexible substrates.
In order to improve the bending resistance of gas barrier films, a method is known in which hexamethyldisiloxane (HMDSO) is used as a raw material and the distribution of carbon atoms in the thickness direction of the gas barrier layer is adjusted to satisfy certain conditions. (For example, refer to Patent Document 1).

  In order to extend the life, high bending resistance is desired even under high temperature and high humidity. Since the base film swells under high temperature and high humidity, a difference in film stress between the base film and the gas barrier layer occurs, and the adhesion between the two tends to decrease. When the adhesiveness is lowered, when the deformation of the base film due to bending propagates to the gas barrier layer, the gas barrier layer is likely to be damaged, such as cracks, and the gas barrier property is lowered.

JP 2012-96531 A

  This invention is made | formed in view of the said problem and the situation, and the solution subject is providing the gas barrier property film which is excellent in gas barrier property, and has high bending resistance also under high temperature, high humidity.

  In order to solve the above-mentioned problems, the present inventor, in the process of examining the cause of the above-mentioned problems, the gas barrier layer containing Si atoms, O atoms and C atoms is excellent in gas barrier properties, and the base in the gas barrier layer It has been found that when the ratio of C—C bonds on the film side is high, high bending resistance can be obtained even under high temperature and high humidity, leading to the present invention.

That is, the subject concerning this invention is solved by the following means.
1. A gas barrier film comprising a gas barrier layer on a base film,
The gas barrier layer contains Si atoms, O atoms and C atoms;
Based on the waveform analysis of C1s measured by X-ray photoelectron spectroscopy at a position of 0 to 100% in the layer thickness direction from the surface opposite to the base film of the gas barrier layer to the surface on the base film side, The C—C bond distribution curve representing the ratio of C—C bonds to the sum of C—C, C—SiO, C—O, C═O and C═OO bonds is 75-100% in the layer thickness direction. A gas barrier film having at least one local maximum at a position.

  2. 2. The average value of the ratio of C—C bonds at a position in the layer thickness direction of 90 to 100% in the CC bond distribution curve is in the range of 20 to 90%. Gas barrier film.

  3. The gas barrier film according to claim 1 or 2, wherein the maximum value of one or a plurality of maximum values of the CC bond distribution curve is in a range of 20 to 90%.

  By the above means of the present invention, a gas barrier film having excellent gas barrier properties and high bending resistance even under high temperature and high humidity can be provided.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
A gas barrier layer containing at least Si atoms, O atoms, and C atoms forms a dense network of Si—O—Si, Si—C—Si, and the like, and has a dense structure. It is presumed that barrier properties can be obtained.
Further, when the ratio of C—C bonds on the base film side in the layer thickness direction of the gas barrier layer is high, the C—C bonds relax the membrane stress of the base film swollen under high temperature and high humidity, and the base film and It is presumed that a decrease in the adhesion of the gas barrier layer can be suppressed and the resistance to a load during bending can be increased. Furthermore, the deformation of the base film at the time of bending can also be reduced because the CC bond is relaxed and the deformation propagated into the gas barrier layer can be reduced, so that high bending resistance can be obtained even under high temperature and high humidity. Is done.

Sectional drawing which shows schematic structure of the gas barrier film of this Embodiment The graph which shows the CC bond distribution curve of the gas barrier layer in an Example The graph which shows a CC bond distribution curve for the gas barrier layer in an Example The graph which shows the CC bond distribution curve of the gas barrier layer in a comparative example The front view which shows schematic structure of the manufacturing apparatus of a gas barrier film

  The gas barrier film of the present invention is a gas barrier film comprising a gas barrier layer on a base film, wherein the gas barrier layer contains Si atoms, O atoms and C atoms, and the gas barrier layer includes the gas barrier layer. Based on C1s waveform analysis measured by X-ray photoelectron spectroscopy at a position of 0 to 100% in the layer thickness direction from the surface opposite to the base film to the surface on the base film side, C-C, C- The C—C bond distribution curve representing the ratio of C—C bonds to the total of SiO, C—O, C═O and C═OO bonds is at least one maximum at a position in the layer thickness direction of 75 to 100%. It has a value. This feature is a technical feature common to the claimed invention.

  As an embodiment of the present invention, from the viewpoint of obtaining higher bending resistance, in the CC bond distribution curve, the average value of the ratio of CC bonds at the position in the layer thickness direction of 90 to 100% is 20%. It is preferable to be in the range of ˜90%.

  From the same viewpoint, it is preferable that the maximum value of one or a plurality of maximum values that the CC bond distribution curve has is in a range of 20 to 90%.

Hereinafter, the present invention, its components, and modes for carrying out the present invention will be described in detail.
In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

[Gas barrier film]
FIG. 1 is a cross-sectional view showing a schematic configuration of a gas barrier film F according to an embodiment of the present invention.
As shown in FIG. 1, the gas barrier film F includes a base film 1 and a gas barrier layer 2 formed on the base film 1.

(Gas barrier layer)
The gas barrier layer 2 has gas barrier properties.
In the present invention, the gas barrier property means that the water vapor permeability measured at a temperature of 38 ° C. and a humidity of 90% RH by a MOCON water vapor permeability measuring apparatus Aquatran (manufactured by MOCON) is 0.1 [g / ( m ² · 24h)]. From the viewpoint of obtaining higher gas barrier properties, the water vapor permeability is preferably less than 0.01 [g / (m ² · 24 h)].

The gas barrier layer 2 contains at least Si atoms, O atoms, and C atoms.
Such a gas barrier layer 2 can be obtained, for example, by reacting an organosilicon compound having a Si—C skeleton with oxygen to form a silicon oxide carbide (SiOC) film. Note that the gas barrier layer 2 further containing N atoms may be formed by supplying a gas such as nitrogen or ammonia during the film formation and nitriding.

As the organosilicon compound that can be used, those having a small number of Si—C bonds in one molecule are preferable. For example, tetramethylcyclohexane having 2 or less Si—C bonds per Si atom in one molecule. Examples thereof include cyclic siloxanes such as tetrasiloxane (TMCTS) and octamethylcyclotetrasiloxane (OMCTS), and alkoxysilanes such as methyltrimethoxysilane (MTMS) and tetramethoxysilane (TMOS). These organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
Among them, from the viewpoint of increasing the bending resistance by increasing the ratio of C—C bonds in the gas barrier layer 2 and increasing the transparency by reducing the ratio of C═C bonds and C═OO bonds, one More preferably, the number of Si—C bonds in the Si atom is 1 or 0.

The structures of TMCTS, OMCTS and MTMS are shown below.

  The gas barrier layer 2 is formed by physical vapor deposition (PVD: Physical Vapor Deposition) such as vapor deposition or sputtering, CVD such as Plasma Enhanced Chemical Vapor Deposition (PECVD), or atomic layer deposition ( From the viewpoint of facilitating adjustment of the atomic composition of the gas barrier layer 2, the PECVD method is preferable. Among them, the counter-roller type PECVD method, in which plasma is generated between two opposing rollers and a gas barrier layer is formed in parallel on the base film transported by each roller, continues the atomic composition in the layer thickness direction. This is preferable because it can be changed.

  As shown in FIG. 1, the gas barrier layer 2 is formed at a position of 0 to 100% in the layer thickness direction from the surface Sa on the opposite side of the base film 1 of the gas barrier layer 2 to the surface Sb on the base film 1 side. C for the total of each bond of C—C, C—SiO, C—O, C═O, and C═OO based on the waveform analysis of C1s measured by X-ray photoelectron spectroscopy (XPS). A C—C bond distribution curve representing a ratio of —C bonds has at least one maximum value at a position in the layer thickness direction of 75 to 100%.

The maximum value is an inflection point at which the ratio of CC bond changes from increase to decrease in the CC bond distribution curve, and is 2 to 20 nm from the inflection point than the ratio at the inflection point. The point where the ratio in the position in the layer thickness direction is 5% or more lower.
The minimum value is an inflection point at which the ratio of C—C bonds changes from decrease to increase in the C—C bond distribution curve.
These maximum values and minimum values are called extreme values.

  As described above, the gas barrier layer 2 having a high C—C bond ratio on the base film 1 side whose position in the layer thickness direction is in the range of 75 to 100% has many C—C bonds distributed on the base film 1 side. However, the film stress of the base film 1 swollen under high temperature and high humidity and the load on the gas barrier layer 2 that is propagated by deformation of the base film when bent are alleviated. Even under high temperature and high humidity, the adhesion between the base film 1 and the gas barrier layer 2 is improved, the resistance to a load at the time of bending is increased, and the deterioration of the gas barrier property can be suppressed. A barrier layer 2 is obtained.

From the viewpoint of obtaining higher bending resistance, in the CC bond distribution curve, the average value of the ratio of CC bonds at 90-100% in the layer thickness direction is within the range of 20-90%. Preferably there is.
Since such a gas barrier layer 2 has a particularly high C—C bond ratio in the vicinity of the interface with the base film 1, higher bending resistance can be obtained.

It is preferable that the maximum value of one or a plurality of maximum values that the CC bond distribution curve has is in the range of 20 to 90%.
Since such a gas barrier layer 2 has abundant C—C bonds that relieve the film stress and deformation of the base film 1, higher bending resistance can be obtained.

The CC bond distribution curve can be created by combining the XPS method and rare gas ion sputtering. The XPS method measures the kinetic energy of photoelectrons emitted from the sample surface irradiated with X-rays and analyzes the composition and chemical bonding state of atoms constituting the sample surface. ESCA (Electron Spectroscopy for Chemical Analysis) It is also called.
Specifically, by analyzing the atomic composition and chemical bonding state of the sample surface exposed by etching the sample by rare gas ion sputtering using the XPS method, changes in the atomic composition and chemical bonding state in the layer thickness direction of the sample are analyzed. I can grasp it.

An example of measurement conditions combining the XPS method and rare gas ion sputtering is shown.
(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 2.5 nm
X-ray photoelectron spectrometer: Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

The ratio of C—C bonds in the gas barrier layer 2 is determined by analyzing the waveform of the C1s peak in the spectrum obtained by measuring the binding energy of C atoms by the XPS method. Specifically, a peak derived from the C—C bond is separated from the C1s peak, and the ratio (Q2 / Q1 × 100) of the peak area (Q2) of the C—C bond to the peak area (Q1) of the C1s peak is expressed as gas. It is determined as the ratio of C—C bonds in the barrier layer 2. That is, the ratio of the C—C bond is the ratio of the C—C bond to the total (total number of bonds) of C—C, C—SiO, C—O, C═O, and C═OO that form the C1s peak. Equal to the ratio of numbers. Commercially available analysis software such as PeakFIT (manufactured by Sysstat) can be used for waveform analysis (peak separation, peak area calculation, peak position specification, etc.) necessary for calculating the ratio.
Each time the gas barrier layer 2 is etched at the above-described etching interval by rare gas ion sputtering, the ratio of C—C bonds at the position in the layer thickness direction is obtained, and an approximate curve of the ratio at the position in each layer thickness direction is expressed as 0-100. It is obtained as a C—C bond distribution curve representing the percentage of C—C bonds at the position in the layer thickness direction of%.

As shown in FIG. 1, the position of the gas barrier layer 2 in the layer thickness direction is 0% of the position of the surface Sa on the opposite side of the base film 1 of the gas barrier layer 2 and 100% of the position of the surface Sb on the base film 1 side. % Is expressed in a ratio of 0 to 100%.
That is, the position in the layer thickness direction of the gas barrier layer 2 is represented by the ratio of the sputtering depth from the surface Sa to the distance from the surface Sa to the surface Sb of the gas barrier layer 2 (layer thickness of the gas barrier layer 2). Can do.
The layer thickness of the gas barrier layer 2 is determined by observing the cross section of the gas barrier film F with a transmission electron microscope (TEM). Specifically, the cross section of the gas barrier film F is observed, and the distance from the surface Sa to the surface Sb of the gas barrier layer 2 is measured. The interface between the gas barrier layer 2 and the base film 1 is determined from the contrast difference between the two. This distance is measured at 10 points at different positions on the film surface, and the average value of the measured values is determined as the layer thickness of the gas barrier layer 2.

The following apparatus can be used as a focused ion beam (FIB) apparatus for preparing a TEM and a sample for TEM.
(TEM)
Apparatus: JEM2000FX (manufactured by JEOL Ltd.)
Accelerating voltage: 200kV
(FIB equipment)
Apparatus: SMI2050 (manufactured by SII)
Processed ion: Ga (30 kV)
Sample thickness: 100-200 nm

2 and 3 show CC bond distribution curves obtained by analyzing the gas barrier layer of the gas barrier film which is an example of the present invention.
2 shows a C—C bond distribution curve of a gas barrier layer formed by PECVD using methyltrimethoxysilane (MTMS) and oxygen as raw materials, and FIG. 3 shows PECVD using tetramethylcyclotetrasiloxane (TMCTS) as raw materials. The CC bond distribution curve of the gas barrier layer formed by the method is shown.

  FIG. 4 shows a C—C bond distribution curve obtained by analyzing a gas barrier layer of a gas barrier film as a comparative example. The CC bond distribution curve shown in FIG. 4 is a CC bond distribution curve of a gas barrier layer formed by PECVD using hexamethyldisiloxane (HMDSO) and oxygen as raw materials.

As shown in FIGS. 2 and 3, the CC bond distribution curves in the examples all have one maximum value at a position in the layer thickness direction of 75 to 100%. Each maximum value is at a position in the layer thickness direction of about 83% and about 85%, and the ratio of C—C bonds on the base film side is high, so that the gas barrier layer has high bending resistance as described above.
On the other hand, as shown in FIG. 4, the CC bond distribution curve in the comparative example has one maximum value at a position in the layer thickness direction of less than 75%, but at a position in the layer thickness direction of 75 to 100%. There is no local maximum. Since the distribution of CC bonds on the base film side is small, the film stress of the base film under high temperature and high humidity and the deformation of the base film at the time of bending cannot be alleviated, and the gas barrier layer such as cracks may be damaged. There is.

The average value of the C—C bond ratio within the range of 90-100% in the layer thickness direction is about 35% in the C—C bond distribution curve shown in FIG. 2, and the C—C bond shown in FIG. The distribution curve is about 69%, both in the range of 20-90%. Moreover, the CC bond distribution curve in FIG.2 and FIG.3 has several local maximum values, and the maximum value exists in the range of 20 to 90%, respectively. Since the ratio of C—C bonds in the vicinity of the interface with the base film is high and the C—C bonds are abundant, high bending resistance can be obtained.
On the other hand, in the CC bond distribution curve shown in FIG. 4, although the maximum maximum value is in the range of 20 to 90%, the average of the CC bond ratios at the positions in the layer thickness direction of 90 to 100%. The value is as low as less than 20%, and high bending resistance similar to that in the examples cannot be expected.

2 to 4, the ratio of each bond of C—Si bond, C—O bond, C═O bond, and C═OO bond at a position in the layer thickness direction of 0 to 100% of the gas barrier layer 2. A bond distribution curve representing is also shown. Similarly to the C—C bond, the peak derived from each bond is separated from the C1s peak, and the ratio of the peak area of the peak derived from each bond to the peak area of the C1s peak is obtained as the ratio of each bond.
When FIG. 2 and FIG. 3 are compared with FIG. 4, the ratio of the C = O bond and the C = OO bond is lower in the example than in the comparative example. A gas barrier layer having few C═O bonds and C═OO bonds, which are chromophores, is preferable because it has less yellowing and is highly useful for sealing electronic devices that require high transparency.

  The ratio of the C—C bond in the layer thickness direction of the gas barrier layer 2 is one or a plurality of kinds used depending on the ratio of C atom, H atom and O atom in the molecule from those exemplified as usable organosilicon compounds. This can be adjusted by selecting an organosilicon compound.

The ratio of C—C bonds in the layer thickness direction can be adjusted not only by selecting the raw materials but also by adjusting the film forming conditions.
For example, in the case of forming the gas barrier layer 2 by supplying oxygen gas supplied as a raw material gas together with an organosilicon compound by PECVD method, by adjusting the supply amount of oxygen gas, C— in the gas barrier layer 2 The ratio of C bond can be adjusted.

  In addition, an inert gas such as nitrogen, argon or helium is supplied during film formation, and by adjusting the supply amount of this inert gas, the plasma is stabilized and the oxidation reaction and deposition of oxygen gas and organosilicon compound are performed. It is also possible to adjust the ratio of the target C—C bonds in the thickness direction of the gas barrier layer 2 by controlling the gas barrier layer 2.

Further, the C—C bond ratio in the layer thickness direction can be adjusted to a target ratio by continuously changing the distance between the electrodes that generate plasma.
When the film is formed by the counter-roller type PECVD method, if the distance between the electrodes built in each roller is changed, the density of the plasma generated on the surface of the base film 1 in contact with the roller continuously changes. The composition of layer 2 can also be changed continuously.

The layer thickness of the gas barrier layer 2 is preferably in the range of 50 to 500 nm, and preferably in the range of 50 to 300 nm.
If the layer thickness is 50 nm or more, sufficient gas barrier properties can be obtained, and if the layer thickness is 500 nm or less, a thin gas barrier film F can be obtained.

(Base film)
As the base film 1, a resin, glass, metal, or the like formed into a film shape can be used. Especially, resin is preferable and it is preferable that it is resin with high transparency. If the transparency of the resin is high and the transparency of the base film 1 is high, a highly transparent gas barrier film F can be obtained and can be preferably used for an electronic device such as an organic EL element.

Examples of the resin that can be used as the base film 1 include methacrylate ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, and polyether ether. Ketone, polysulfone, polyethersulfone, polyimide (PI), polyetherimide and the like can be mentioned. Of these, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferable from the viewpoint of cost and availability.
The base film 1 may be a laminated film in which two or more of the above resins are laminated.

The resin base film 1 can be manufactured by a conventionally known general manufacturing method. For example, an unstretched resin base material that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, by dissolving the resin used as a material in a solvent, casting (casting) it onto an endless metal resin support, drying, and peeling, an unstretched film that is substantially amorphous and not oriented is used as a base. It can be obtained as film 1.
The unstretched film may be stretched in the film transport (MD) direction or the width (TD) direction orthogonal to the transport direction, and the resulting stretched film may be used as the base film 1.

  The base film 1 preferably has a thickness in the range of 5 to 500 μm, and more preferably in the range of 25 to 250 μm.

  The gas barrier film F can include other layers such as an anchor layer, a smoothing layer, and a bleed-out prevention layer depending on the purpose. As an anchor layer, a smoothing layer, and a bleed-out prevention layer, those described in JP2013-52561A can be used.

(Anchor layer)
The gas barrier film F can include an anchor layer between the base film 1 and the gas barrier layer 2 from the viewpoint of improving the adhesion between the base film 1 and the gas barrier layer 2.
For the anchor layer, for example, a coating solution containing polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, alkyl titanate, etc. is applied and dried. Can be formed.

(Smoothing layer)
The gas barrier film F can also include a smoothing layer as a lower layer of the gas barrier layer 2. By the smoothing layer, the gas barrier layer 2 can be formed on a flat surface, and generation of pinholes due to unevenness can be prevented, and the gas barrier layer 2 having high gas barrier properties can be obtained.
The smoothing layer can be formed, for example, by applying a coating liquid containing a photosensitive resin and performing a curing process. Examples of the photosensitive resin include a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, poly Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as ether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved.

(Bleed-out prevention layer)
The gas barrier film F can be provided with a bleed-out prevention layer from the viewpoint of suppressing a bleed-out phenomenon in which unreacted oligomers or the like migrate from the base film 1 to the surface and contaminate the contacting surface. The bleed-out prevention layer is provided on the surface of the base film 1 opposite to the smooth layer. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has a function of suppressing bleed-out.

[Light permeability of gas barrier film]
When the gas barrier film F has high transparency, the utility as a sealing material for electronic devices is increased, which is preferable.
Specifically, the light transmittance measured in accordance with JIS K 7105: 1981 is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. .

[Production equipment for gas barrier film]
FIG. 5 shows a schematic configuration of a manufacturing apparatus 100 capable of manufacturing the gas barrier film F.
As shown in FIG. 5, the gas barrier film manufacturing apparatus 100 transports the base film 1 by a plurality of rollers 11 to 18 in the vacuum chamber 10 and applies a voltage between a pair of rollers 13 and 16 facing each other. Apply and supply source gas. Thereby, the manufacturing apparatus 100 causes a plasma reaction of the source gas, forms a gas barrier layer on the base film 1, and manufactures the gas barrier film F.

As shown in FIG. 5, the vacuum chamber 10 is provided with an exhaust port 41, and a vacuum pump 42 is provided at the end of the exhaust port 41.
Moreover, as shown in FIG. 5, the roller 11 unwinds the base film 1, and the roller 18 winds up the gas barrier film F obtained by forming the gas barrier layer.
The rollers 12 to 17 convey the base film 1 until it is unwound by the roller 11 and wound by the roller 18.

The pair of rollers 13 and 16 are disposed so as to face each other, and a gas supply unit 21 that supplies a raw material gas between the rollers 13 and 16 is provided adjacent to the rollers 13 and 16.
The pair of rollers 13 and 16 are each connected to a power source 22 and incorporate a magnetic field generator 23. By supplying a source gas by the gas supply unit 21 and applying a voltage between the rollers 13 and 16 by the power source 22, plasma is generated in the discharge space between the rollers 13 and 16, and the plasma reaction of the source gas proceeds. Thus, gas barrier layers are formed on the base film 1 conveyed by the rollers 13 and 16, respectively. At this time, since a racetrack-like magnetic field is formed around the rollers 13 and 16 by the magnetic field generator 23, plasma is generated along the magnetic field lines of the magnetic field. Electrons are confined in the film formation space by the electric and magnetic fields in the discharge space, and high-density plasma is generated, so that the film formation efficiency is improved.

  The gas supply unit 21 illustrated in FIG. 5 is provided on the center line of the roller 13 and the roller 16, but the gas supply unit 21 may be offset from the center line toward one of the rollers 13 and 16. Thereby, the supply amount of the source gas to the rollers 13 and 16 can be made different, and the atomic composition of the film formed on the roller 13 and the film formed on the roller 16 can be made different. Similarly, in order to make the atomic composition of the film different, the position of the gas supply unit 21 can be shifted on the center line so that the distance to the rollers 13 and 16 is increased or decreased.

When the deposition conditions such as the amount of source gas supplied during deposition are changed, films with different atomic compositions are stacked each time the deposition conditions are changed, and the atomic composition in the layer thickness direction changes continuously. .
Specifically, when the base film 1 passes through the point A of the roller 13 and the point B of the roller 16, the ratio of the number of C atoms in the layer thickness direction in the gas barrier layer 2 changes from decrease to increase, and O atoms The ratio of the number changes from increasing to decreasing.
On the other hand, when the base film 1 passes the points C1 and C2 of the roller 13 and the points C3 and C4 of the roller 16, the ratio of C atoms in the layer thickness direction in the gas barrier layer 2 changes from increase to decrease. , The ratio of O atoms changes from decreasing to increasing.
Thus, the existence of an extremum that shifts from decrease to increase or from increase to decrease indicates that the abundance ratio of C atoms and O atoms in the gas barrier layer 2 is not uniform, and the density of C atoms is partially small. The presence of such a low part makes the gas barrier layer 2 a flexible structure and improves the bending resistance.

  The rollers 13 and 16 are preferably arranged so that the rotation axes thereof are parallel to each other on the same plane, and the surfaces on which the gas barrier layers of the base film 1 conveyed by the rollers 13 and 16 face each other. With such a configuration, after the gas barrier layer is formed on the base film 1 by the roller 13 upstream in the transport direction, the gas barrier layer can be further laminated by the roller 16 downstream in the transport direction, thereby further improving the film formation efficiency. Can be made.

The rollers 13 and 16 preferably have the same diameter from the viewpoint of increasing the film formation efficiency.
The diameters of the rollers 13 and 16 are preferably in the range of 100 to 1000 mm, and in the range of 100 to 700 mm, from the viewpoints of optimization of discharge conditions, space reduction in the vacuum chamber 10 and the like. More preferably.
When the diameter φ is 100 mm or more, a sufficiently large discharge space can be formed, and a reduction in productivity can be prevented. In addition, a sufficient layer thickness can be obtained by short-time discharge, the amount of heat applied to the base film 1 during discharge can be suppressed, and residual stress can be suppressed. If the diameter φ is 1000 mm or less, the uniformity of the discharge space can be maintained, which is practical in device design.

  The gas supply unit 21 supplies the source gas of the gas barrier layer to the discharge space formed between the pair of rollers 13 and 16. For example, when an organic silicon compound is oxidized to form a gas barrier layer containing silicon oxide carbide, the gas supply unit 21 supplies an organic silicon compound gas and a gas such as oxygen or ozone as a source gas. In the case of nitriding, a source gas such as nitrogen or ammonia may be supplied.

  The gas supply unit 21 can use a carrier gas to supply the raw material gas as needed, and can also supply a plasma generation gas to promote the generation of plasma. Examples of the carrier gas include rare gases such as helium, argon, neon, xenon, and krypton, nitrogen gas, and examples of the plasma generating gas include hydrogen.

As the power source 22, a known power source for generating plasma can be used. However, an AC power source that can alternately reverse the polarities of the rollers 13 and 16 can improve the film formation efficiency, and is preferable.
The amount of power supplied by the power source 22 can be in the range of 0.1 to 10.0 kW. If it is 0.1 kW or more, the generation of foreign matters called particles can be suppressed. Moreover, if it is 10.0 kW or less, the emitted heat amount can be suppressed and generation | occurrence | production of the wrinkle of the base film 1 by a temperature rise can be suppressed. Moreover, when setting it as alternating current power supply, it is preferable that the frequency of alternating current exists in the range of 50 Hz-500 kHz.

The pressure in the vacuum chamber 10, that is, the degree of vacuum, can be adjusted by the vacuum pump 42 according to the type of the source gas, but is preferably in the range of 0.5 to 100.0 Pa.
Moreover, although the conveyance speed (line speed) of the base film 1 can be determined according to the kind of raw material gas, a vacuum degree, etc., it is preferable that it exists in the range of 0.25-100.00 m / min, More preferably, it is in the range of 0.5 to 20.0 m / min. Within this range, generation of wrinkles in the base film 1 can be suppressed and a gas barrier layer having a sufficient thickness can be formed.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless there is particular notice, it represents "mass part" or "mass%".

[Gas barrier film 1]
A KB film (registered trademark) G1SBF (produced by Kimoto Co., Ltd.) having a thickness of 125 nm was prepared as a base film.
A gas barrier layer was formed on the KB film G1SBF using hexamethyldisiloxane (HMDSO) and oxygen as raw materials.
The gas barrier layer was formed under the following film formation conditions using a manufacturing apparatus having the same configuration as that shown in FIG.

(Deposition conditions)
Source gas 1: HMDSO
Source gas 2: Oxygen Source gas 1 supply: 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of raw material gas 2: 650 sccm
Degree of vacuum: 2Pa
Power supplied by power source for plasma generation: 0.8kW
Frequency of power source for plasma generation: 80 kHz
Film transport speed: 2 m / min

[Gas barrier film 2-7]
In the production of the gas barrier film 1, except that the type of the source gas 1 and the supply amounts of the source gases 1 and 2 were changed as shown in Table 1 below, Gas barrier films 2 to 7 were produced.

[CC bond distribution curve]
In each manufactured gas barrier film 1-7, the CC bond distribution curve in the layer thickness direction of a gas barrier layer was calculated | required as follows.

TEM samples of the respective gas barrier films 1 to 7 were produced using the following FIB apparatus. This sample was set in the following TEM, the cross section of each gas barrier film 1-7 was observed, and the distance from the surface of the gas barrier layer opposite to the base film to the surface on the base film side was measured. The interface between the gas barrier layer and the base film was determined from the contrast difference between the two. This measurement was performed at 10 points at different positions on the film surface, and the average value of each measurement value was determined as the layer thickness (nm) of the gas barrier layer.
(TEM)
Apparatus: JEM2000FX (manufactured by JEOL Ltd.)
Accelerating voltage: 200kV
(FIB equipment)
Apparatus: SMI2050 (manufactured by SII)
Processed ion: Ga (30 kV)
Sample thickness: 100-200 nm

Moreover, in each gas barrier film 1-7, from the surface on the opposite side to the base film of the gas barrier layer to the surface on the base film side is etched by rare gas ion sputtering, and the bonding of C atoms on the surface exposed by the XPS method is performed. An energy spectrum was obtained. The measurement conditions for the XPS method and rare gas ion sputtering are as follows.
(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 2.5 nm
X-ray photoelectron spectrometer: Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

The peak due to C—C bond is separated from the C1s peak in the spectrum obtained by the XPS method, and the ratio of the peak area (Q2) of the C—C bond to the peak area (Q1) of the C1s peak (Q2 / Q1 × 100) was determined as the ratio of C—C bonds in the gas barrier layer 2.
A depth profile was created by plotting the obtained ratio of C—C bonds against the position in the layer thickness direction etched from the surface opposite to the base film of the gas barrier layer. In this depth profile, an approximate curve of the plotted ratio was obtained as a CC bond distribution curve. In the depth profile, the position in the layer thickness direction from the surface opposite to the base film of the gas barrier layer is 0% in the layer thickness direction on the surface opposite to the base film, and the layer thickness direction on the surface on the base film side The position of is represented as 100%, and is represented by the ratio of the etched depth distance (nm) to the thickness (nm) of the gas barrier layer determined by the TEM.

In the depth profiles of the respective gas barrier films 1 to 7, the position (%) in the layer thickness direction of the maximum value of the CC bond distribution curve at the position in the layer thickness direction of 65 to 100% was obtained. In each CC bond distribution curve, the maximum value at a position in the layer thickness direction of 65 to 100% was one.
Further, the ratio of the CC bond at the position (%) in the layer thickness direction of the maximum value and the position in the layer thickness direction of 90 to 100% among one or a plurality of maximum values that the CC bond distribution curve has. The average value (%) was obtained. The results are shown in Table 1 below.

[Evaluation]
(Gas barrier properties)
Using a MOCON water vapor permeability measuring device Aquatran (manufactured by MOCON), the water vapor permeability [g / (m ² · 2) at a temperature of 38 ° C. and a humidity of 90% RH of the gas barrier films 1 to 7
4h)] was measured.
From the measured water vapor transmission rate, the gas barrier property was ranked according to the following evaluation criteria. As the water vapor permeability is smaller, the gas barrier property is higher, and rank 3 or higher is a practical gas barrier property.
5: Water vapor permeability is less than 0.005 4: Water vapor permeability is 0.005 or more and less than 0.010 3: Water vapor permeability is 0.010 or more and less than 0.100 2: Water vapor permeability is 0. 100 or more and less than 0.500 1: Water vapor permeability is 0.500 or more

(Flexibility)
The water vapor permeability (g / m ² · 24 h) of the gas barrier films 1 to 7 at a temperature of 38 ° C. and a humidity of 90% RH was measured using a MOCON water vapor permeability measuring apparatus Aquatran (manufactured by MOCON).
After the measurement, each gas barrier film 1 to 7 was subjected to a bending test. In the bending test, first, each of the gas barrier films 1 to 7 was stored for 100 hours at a high temperature and high humidity of a temperature of 60 ° C. and a humidity of 90% RH. Each gas barrier film 1-7 taken out from high temperature and high humidity is cut into a size of 3 cm × 10 cm and wound around the circumference of a metal rod (diameter 6 mm) 100 times so that the gas barrier layer is outside 100 times Repeated. The water vapor permeability of each of the gas barrier films 1 to 7 after the bending test was measured in the same manner as before the bending test.

From the water vapor permeability measured before and after the bending test, the change rate of the water vapor permeability was calculated by the following formula.
Change rate of water vapor permeability (%)
= (Water vapor permeability after bending test) / (Water vapor permeability before bending test)

From the calculated rate of change in water vapor permeability, the bending resistance was evaluated as follows. The smaller the value of the change rate, the better the bending resistance, and the rank 3 or higher is the practical bending resistance.
5: Change rate of water vapor permeability is 1.0 or more and less than 2.0 4: Change rate of water vapor permeability is 2.0 or more and less than 4.5 3: Change rate of water vapor permeability is 4.5 or more Less than 7.0 2: Change rate of water vapor permeability is 7.0 or more and less than 10.0 1: Change rate of water vapor permeability is 10.0 or more

Table 1 below shows the evaluation results.
In Table 1 below, HMDSO, TMCTS, and MTMS are abbreviations for hexamethyldisiloxane, tetramethylcyclotetrasiloxane, and methyltrimethoxysilane, respectively.

  As shown in Table 1 above, the gas barrier films 2 to 7 having at least one maximum value in the layer thickness direction position where the C—C bond distribution curve is 75 to 100% not only have excellent gas barrier properties. It can be seen that the gas barrier property hardly decreases even after being subjected to high temperature and high humidity, and the bending resistance is also high.

  The gas barrier film of the present invention can be used for long-term use under high temperature and high humidity.

F Gas barrier film 1 Base film 2 Gas barrier layer Sa Surface of the gas barrier layer opposite to the base film Sb Surface of the gas barrier layer on the base film side 100 Gas barrier film manufacturing apparatus 11 to 18 Roller 22 Power supply

Claims (3)

A gas barrier film comprising a gas barrier layer on a base film,
The gas barrier layer contains Si atoms, O atoms and C atoms;
Based on the waveform analysis of C1s measured by X-ray photoelectron spectroscopy at a position of 0 to 100% in the layer thickness direction from the surface opposite to the base film of the gas barrier layer to the surface on the base film side, The C—C bond distribution curve representing the ratio of C—C bonds to the sum of C—C, C—SiO, C—O, C═O and C═OO bonds is 75-100% in the layer thickness direction. A gas barrier film having at least one local maximum at a position.   2. The average value of the ratio of C—C bonds at a position in the layer thickness direction of 90 to 100% in the CC bond distribution curve is in the range of 20 to 90%. Gas barrier film.   The gas barrier film according to claim 1 or 2, wherein the maximum value of one or a plurality of maximum values of the CC bond distribution curve is in a range of 20 to 90%.

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