CN108349210A - Gas barrier film - Google Patents

Abstract

An object of the present invention is to provide a gas barrier film having good gas barrier properties, a small decrease in gas barrier properties due to front-to-back contact during roll winding, and suppressed occurrence of cracks during cutting. This gas barrier film is characterized in that, in the spectrum obtained by X-ray photoelectron spectroscopy, the ratio of the composition ratio converted from the ratio of the peak intensities derived from silicon atoms, oxygen atoms, and carbon atoms in the layer thickness direction of the gas barrier layer is When the total amount is set to 100%, the ratio X (%) of the composition ratio converted from the ratio of the peak intensities derived from C-C, C=C, and C-H bonds based on the waveform analysis of C1s related to carbon atoms Satisfy the maximum value (% ) is in the range of 5 to 41 (%).

Description

gas barrier film

technical field

The present invention relates to gas barrier films. More specifically, the present invention relates to a gas barrier film having good gas barrier properties, a small decrease in gas barrier properties due to front-to-back contact during roll winding, and suppressed occurrence of cracks at cut surfaces during cutting.

Background technique

Conventionally, a gas barrier film in which a thin film (gas barrier layer) of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide is formed on the surface of a plastic substrate or film has been used for packaging articles in the fields of food and medical supplies. use. By using the gas barrier film, it is possible to prevent deterioration of articles caused by gases such as water vapor and oxygen.

In recent years, such a gas barrier film that prevents the permeation of water vapor, oxygen, etc., has been eagerly expected to be developed into electronic devices such as organic electroluminescence (EL) elements and liquid crystal display (Liquid Crystal Display: LCD) elements. A lot of research has been done. In these electronic devices, high gas barrier properties, such as gas barrier properties comparable to those of glass substrates, are required.

As a method of producing a gas barrier film that is more flexible than a glass substrate, for example, a CVD method (Chemical Vapor Deposition: chemical vapor deposition method, chemical vapor deposition method) is used.

For example, Patent Document 1 discloses that a silicon carbide (SiOC) film formed by a plasma chemical vapor deposition method has improved gas barrier properties, flexibility, and impact resistance.

However, the gas barrier film described in Patent Document 1 has a problem of insufficient gas barrier properties. In addition, especially when sealing electronic devices, when the size is cut into the desired width and shape, starting from the generation of tiny cracks on the cut surface, the cracks propagate to the entire film due to external forces such as bending, and it is easy to cause significant damage. There is a problem that the effective area having gas barrier properties decreases due to the generation of cracks.

In addition, Patent Document 2 describes a gas barrier that improves durability against cracks while obtaining a dense structure by making carbon atoms, silicon atoms, and oxygen atoms fall within a specific ratio range in the layer thickness direction. membrane.

However, since such a gas barrier film has relatively uniform density and strength in the layer thickness direction, there is a problem that sufficient strength cannot be obtained against stresses received from the surface and side surfaces during roll winding and cutting.

prior art literature

patent documents

Patent Document 1: Japanese Unexamined Patent Publication No. 2011-73430

Patent Document 2: Japanese Unexamined Patent Publication No. 2014-00782

Contents of the invention

The problem to be solved by the invention

The present invention was made in view of the above-mentioned problems and situations, and the problem to be solved is to provide a product with good gas barrier properties, a small decrease in the gas barrier properties caused by the front-to-back contact during roll winding, and a reduction in the occurrence of cracks in the cut surface during cutting. Inhibited gas barrier film.

means to solve the problem

In order to solve the above-mentioned problems, the inventors of the present invention found that in a gas barrier film having a gas barrier layer containing at least silicon atoms, oxygen atoms, and carbon atoms on a substrate, the gas barrier The proportion of carbon atoms derived from C-C, C=C, and C-H bonds in a predetermined region near the outermost surface of the layer is within a predetermined range, thereby providing a good gas barrier property and a smooth surface caused by contact between the front and the back during roll winding. The present invention has been accomplished with a gas barrier film in which the decrease in gas barrier properties is small and the occurrence of cracks in the cut surface during cutting is suppressed.

That is, the above-mentioned problems related to the present invention are solved by the following means.

1. The gas barrier film is characterized in that, on the substrate, there is a gas barrier layer containing at least silicon atoms (Si), oxygen atoms (O) and carbon atoms (C), in the spectrum obtained by X-ray photoelectron spectroscopy When the total amount of the composition ratio converted from the ratio of peak intensities derived from silicon atoms (Si), oxygen atoms (O) and carbon atoms (C) in the layer thickness direction of the gas barrier layer is 100%, based on the The ratio X (%) of the composition ratio converted from the ratio of peak intensities derived from C-C, C=C, and C-H bonds in the waveform analysis of C1s related to carbon atoms satisfies the following (1).

(1): With regard to the layer thickness direction of the gas barrier layer, when the layer thickness of the outermost surface of the gas barrier layer is 0%, and the layer thickness of the interface with the substrate is 100%, the layer thickness is 5 to 10%. The maximum value (%) of the ratio X in the 30% region is within the range of 5 to 41 (%).

2. The gas barrier film according to item 1, wherein the average value (%) of the ratio X in the region of 5 to 30% of the layer thickness is in the range of 2 to 20%.

3. The gas barrier film according to item 1 or 2, wherein the minimum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is in the range of 1 to 10%.

4. The gas barrier film according to any one of items 1 to 3, wherein the maximum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is 30 to 95% higher than the layer thickness. The maximum value (%) of the above ratio X in the % region is larger.

5. The gas barrier film according to any one of items 1 to 4, wherein the average value (%) of the ratio X in the region of 5 to 30% of the layer thickness is 30 to 95% higher than the layer thickness. The average value (%) of the above ratio X in the % region is larger.

6. The gas barrier film according to any one of items 1 to 5, wherein the minimum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is 30 to 95% higher than the layer thickness. The minimum value (%) of the above ratio X in the % area is larger.

The effect of the invention

According to the above means of the present invention, it is possible to provide a gas barrier film having good gas barrier properties, a small decrease in gas barrier properties due to front-to-back contact during roll winding, and suppressed occurrence of cracks at cut surfaces during cutting.

The mechanism of expression and action of the effect of the present invention is not yet clear, but it is presumed as follows.

In the gas barrier film of the present invention, carbon atoms derived from C-C, C=C, and C-H bonds exist in a predetermined ratio in a region near the outermost surface of the gas barrier film layer, and the amount of carbon atoms present is different from that of conventional gas barrier films. Compared to increase. As a result, the region near the outermost surface of the gas barrier layer of the present invention can be made dense and moderately flexible, so it is considered that the gas barrier property is good, and it is possible to suppress friction caused by front-to-back contact during roll winding. damage. Furthermore, since the region near the outermost surface of the gas barrier layer can be made into a region with few fine voids, it is considered that when cutting from the outermost surface side, the occurrence of cracks on the cut surface is suppressed, and it becomes difficult to generate cracks caused by cutting. Cracks caused by shear force.

Description of drawings

FIG. 1 is a cross-sectional view showing an example of the gas barrier film of the present invention.

Fig. 2 is a graph showing an example of the distribution of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer according to the present invention.

FIG. 3 is a schematic diagram showing an example of a production apparatus used for forming a gas barrier layer according to the present invention.

4 is a graph showing an example of the distribution of silicon atoms, oxygen atoms, and carbon atoms in a gas barrier layer according to a comparative example.

Detailed ways

The gas barrier film of the present invention is characterized in that it has a gas barrier layer containing at least silicon atoms (Si), oxygen atoms (O) and carbon atoms (C) on the substrate, and the spectrum obtained by X-ray photoelectron spectroscopy In the above, when the total amount of the composition ratio converted from the ratio of peak intensities derived from silicon atoms (Si), oxygen atoms (O) and carbon atoms (C) in the layer thickness direction of the gas barrier layer is 100%, then The ratio X (%) of the composition ratio converted from the ratio of peak intensities derived from C-C, C=C, and C-H bonds based on the waveform analysis of C1s related to carbon atoms satisfies the following (1). This feature is a common technical feature of the inventions covered by the claims.

(1): Regarding the layer thickness direction of the gas barrier layer, when the layer thickness of the outermost surface of the gas barrier layer is 0%, and the layer thickness at the interface with the base material is 100%, the layer thickness is 5 The maximum value (%) of the ratio X in the range of -30% is within the range of 5 to 41 (%).

As an embodiment of the present invention, it is preferable that the average value (%) of the ratio X in the layer thickness range of 5 to 30% is in the range of 2 to 20% from the viewpoint of more effectively expressing the effect of the present invention.

As an embodiment of the present invention, it is preferable that the minimum value (%) of the ratio X in the layer thickness region of 5 to 30% is within the range of 1 to 10% from the viewpoint of more effectively expressing the effects of the present invention.

As an embodiment of the present invention, from the viewpoint of expressing the effect of the present invention more effectively, it is preferable that the maximum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is higher than that in the region of 30 to 95% of the layer thickness. The maximum value (%) of the above ratio X is larger.

As an embodiment of the present invention, from the viewpoint of expressing the effects of the present invention more effectively, it is preferable that the average value (%) of the ratio X in the region of 5 to 30% of the layer thickness is higher than that in the region of 30 to 95% of the layer thickness. The average value (%) of the above ratio X is larger.

As an embodiment of the present invention, from the viewpoint of expressing the effects of the present invention more effectively, it is preferable that the minimum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is higher than that in the region of 30 to 95% of the layer thickness. The minimum value (%) of the above ratio X is larger.

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

[Gas barrier film]

As shown in FIG. 1 , a gas barrier film 1 of the present invention is formed by laminating a gas barrier layer 3 on a substrate 2 .

The gas barrier layer 3 contains silicon carbide oxide (SiOC) while its composition and bonding state vary in the layer thickness direction.

"Gas barrier layer"

The gas barrier layer according to the present invention is characterized in that it contains at least silicon atoms (Si), oxygen atoms (O) and carbon atoms (C), and in the spectrum obtained by X-ray photoelectron spectroscopy, the layer of the gas barrier layer When the total amount of the composition ratio converted from the ratio of the peak intensities derived from silicon atoms (Si), oxygen atoms (O) and carbon atoms (C) in the thickness direction is set to 100%, based on C1s related to carbon atoms The ratio X (%) of the composition ratio converted from the ratio of the peak intensities derived from the C-C, C=C, and C-H bonds in the waveform analysis satisfies the following (1). (1): Regarding the layer thickness direction of the gas barrier layer, when the layer thickness of the outermost surface of the gas barrier layer is 0%, and the layer thickness at the interface with the base material is 100%, the layer thickness is 5 The maximum value (%) of the ratio X in the range of -30% is within the range of 5 to 41 (%).

As a result, the gas barrier layer can be made highly dense, moderately flexible, and has few fine voids, so that the gas barrier properties are good and the gas barrier properties are reduced due to front-to-back contact during roll winding. Small, and the occurrence of cracks on the cut surface during cutting is suppressed.

Here, the "interface with the substrate" in the present invention refers to "the interface in the layer thickness direction of the gas barrier layer when the composition ratio of oxygen atoms (O) as a part of the composition of the gas barrier layer is 30% or less." The position of the depth from the most surface side". It should be noted that the composition ratio of oxygen atoms (O) can be calculated by X-ray photoelectron spectroscopy described later.

In addition, the gas barrier film of the present invention preferably has an average value (%) of the ratio X in the region of 5 to 30% of the layer thickness in the range of 2 to 20%, and preferably the minimum value (%) of the ratio X is 1 to 10%. %In the range. Thereby, the durability inside the gas barrier layer due to the distribution of a certain amount or more of carbon bonds from C-C, C=C, and C-H can be improved in the region of 5 to 30% of the layer thickness of the gas barrier layer, and the gas barrier layer can be used more effectively. The effects of the present invention appear.

In addition, in the gas barrier film of the present invention, the maximum value (%), average value (%) and minimum value (%) of the above ratio X in the region of 5 to 30% of the layer thickness are preferably higher than those in the region of 30 to 95% of the layer thickness. The maximum value (%), the average value (%) and the minimum value (%) of the above ratio X are large. As a result, the amount of carbon bonds derived from C-C, C=C, and C-H can be more distributed in absolute terms near the outermost surface of the gas barrier layer where stress is concentrated during cutting and roll winding of the gas barrier film. That is, in the region of 5 to 30% of the layer thickness, the effect of the present invention can be more effectively exhibited.

＜X-ray Photoelectron Spectroscopy＞

It is possible to perform the so-called XPS depth distribution measurement by combining X-ray Photoelectron Spectroscopy (XPS) measurement with rare gas ion sputtering such as argon to sequentially perform surface composition analysis while exposing the inside of the sample. A carbon distribution curve (expressing the distance (L) from the outermost surface of the gas barrier layer in the layer thickness direction of the gas barrier layer and the number of carbon atoms relative to the total number of atoms (100at%) of carbon atoms, silicon atoms, and oxygen atoms was prepared. The curve of the relationship between the ratio (carbon atom ratio)), the silicon distribution curve (expressing the ratio of the distance L to the number of silicon atoms relative to the total number of atoms (100at%) of carbon atoms, silicon atoms and oxygen atoms (silicon atom ratio) The curve of the relationship) and the oxygen distribution curve (the curve showing the relationship between the distance L and the ratio of the number of oxygen atoms (oxygen atom ratio) to the total number of atoms (100at%) of carbon atoms, silicon atoms and oxygen atoms).

(Determination of element distribution curve)

The XPS depth profile can be measured, for example, under the following conditions to obtain a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve with respect to the distance from the surface of the thin film layer in the layer thickness direction.

Etching ion species: argon (Ar ⁺ )

Etching rate (SiO ₂ thermal oxide film conversion value): 0.05nm/sec

Etching interval (SiO ₂ conversion value): 2nm

X-ray photoelectron spectroscopy device: manufactured by Thermo Fisher Scientific, model name "VG ThetaProbe"

Irradiation of X-rays: single crystal spectroscopic AlKα

X-ray spot (spot) and its size: 800μm×400μm oval

A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis representing the atomic ratio (at%) of each element and the horizontal axis representing the etching time (sputtering time).

In addition, the atomic ratio (at%) in each area|region is made into the value which averaged the value which etched in the depth direction by XPS depth profile measurement, for example, measured at 2 nm interval.

By performing wide-scan spectroscopic analysis measuring the entire region of the gas barrier layer as described above, a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve can be obtained.

＜Analysis of the bonding state of carbon atoms＞

Regarding the carbon atom, the bonding state of carbon was analyzed by C1s high-resolution spectrum (narrow scan analysis). Specifically, in the present invention, for example, regarding the carbon bond (C), waveform analysis based on C1s such as (1) C-C, C=C and C-H, (2) C-SiO, (3) C-O, (4) C=O and (5) O-C-O were divided into five bonding groups, and the ratio of carbon atoms derived from (1) to (5) was calculated from the intensity ratio of each peak. Then, the total amount (100%) of the composition ratio converted from the ratio of the peak intensities of the respective spectra of the silicon atom, the oxygen atom, and the carbon atom was calculated from each bonding group (1) to (5). Proportion (%) of carbon atoms. In addition, analysis of peak intensity can be performed using data analysis software PeakFit (manufactured by SYSTAT Software Inc.), for example.

In addition, the analysis results for the gas barrier film of the present invention are shown in FIG. 2 . In the graph of FIG. 2 , the horizontal axis represents the depth in the layer thickness direction of the gas barrier layer (the depth (%) when the outermost surface is 0% and the interface with the base material is 100%), and the vertical axis represents the gas barrier layer obtained by The ratio (%) of each atom when the total amount of the composition ratio converted from the ratio of peak intensities derived from silicon atoms, oxygen atoms, and carbon atoms determined by X-ray photoelectron spectroscopy is 100%. In addition, the carbon atom is represented by the ratio divided into the above-mentioned 5 bonding groups. (1)～(5) in Fig. 2 correspond to from (1) C-C, C=C and C-H, (2) C-SiO, (3) C-O, (4) C=O, (5) O-C-O Carbon atoms, (6) correspond to oxygen atoms, and (7) correspond to silicon atoms.

It should be noted that, in the above description, for carbon atoms, waveform analysis based on C1s, such as (1) C-C, C=C and C-H, (2) C-SiO, (3) C-O, (4) C=O, ( 5) O-C-O is divided into 5 bonding groups, and according to the composition of the gas barrier layer, the peaks related to all carbon bonds in the waveform analysis of C1s are analyzed, and the respective ratios are calculated.

<Measuring method of layer thickness of gas barrier layer>

The layer thickness of the gas barrier layer can be obtained by measuring the depth from the outermost surface to the interface with the substrate in the stacking direction of the gas barrier layer through cross-sectional observation using a transmission electron microscope (Transmission Electron Microscope: TEM). In cross-sectional observation using a transmission electron microscope, the layer thickness was measured at 10 locations arbitrarily, and the average value was taken as the layer thickness of the gas barrier layer.

(TEM image of cross-section in layer thickness direction)

For the TEM observation of the cross-section, the TEM observation was carried out after thin sections were fabricated using the following focused ion beam (Focused Ion Beam: FIB) processing apparatus for the observation sample. Here, if the sample is continuously irradiated with electron beams, a contrast difference will appear between a portion damaged by the electron beams and a portion not damaged, and thus the layer thickness of the gas barrier layer can be measured using the contrast difference.

(FIB processing)

Device: SMI2050 made by SII

Processing ion: Ga (30kV)

Sample thickness: 100~200nm

(TEM observation)

Device: JEM2000FX manufactured by JEOL (accelerating voltage: 200kV)

<Layer thickness of gas barrier layer>

The layer thickness of the gas barrier layer according to the present invention is preferably within a range of 10 to 500 nm, and more preferably within a range of 20 to 300 nm, from the viewpoint of achieving both thin film reduction and gas barrier properties.

＜Water Vapor Permeability of Gas Barrier Layer＞

The gas barrier layer preferably has gas barrier properties. Here, "having gas barrier properties" means that only the gas barrier layer is laminated on the substrate, and the water vapor transmission rate (38°C, relative humidity 90% RH) is less than 0.1 g/(m ² ·day), preferably less than 0.01 g/(m ² ·day).

"Substrate"

As the base material of the gas barrier film of the present invention, a plastic film is used. The plastic film to be used is not particularly limited in terms of material, thickness, etc., as long as it can hold the gas barrier layer, and can be appropriately selected according to the purpose of use.

Specific examples of plastic films include polyester resins, methacrylic resins, methacrylic acid-maleic acid copolymers, polystyrene resins, transparent fluororesins, polyimides, and fluorinated polyimides. Resins, polyamide resins, polyamideimide resins, polyetherimide resins, cellulose acylate resins, polyurethane resins, polyether ether ketone resins, polycarbonate resins, alicyclic polyolefin resins, polyarylates Resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring-modified polycarbonate resin, fluorene ring-modified polyester resin, acryl compound and other thermoplastic resins.

When the gas barrier film is used as a substrate of an electronic device such as an organic EL element, it is preferable that the base material is made of a material having heat resistance. Specifically, a resin base material having a linear expansion coefficient in the range of 15×10 ^-6 to 100×10 ^-6 (/K) and a glass transition temperature Tg in the range of 100 to 300° C. is used. This base material satisfies the requirements as a multilayer film for electronic component applications and displays.

That is, when a gas barrier film is used for these applications, there may be a step of exposing the gas barrier film to 150° C. or higher. In this case, when the coefficient of linear expansion of the base material in the gas barrier film is in the range of 15×10 ^-6 to 100×10 ^-6 (/K), it becomes a base material with high heat resistance and good flexibility. . The linear expansion coefficient and Tg of the base material can be adjusted by additives and the like.

As a more preferable specific example of the thermoplastic resin which can be used as a base material, polyethylene terephthalate (PET: 70 degreeC), polyethylene naphthalate (PEN: 120 degreeC) is mentioned, for example. , polycarbonate (PC: 140°C), alicyclic polyolefin (such as ZEONOR (registered trademark) 1600: 160°C manufactured by Zeon Co., Ltd.), polyarylate (PAr: 210°C), polyethersulfone ( PES: 220°C), polysulfone (PSF: 190°C), cycloolefin copolymer (COC: compound described in JP-A-2001-150584: 162°C), polyimide (e.g. Mitsubishi Gas Chemical Co., Ltd. Manufactured, Neoprim (registered trademark): 260°C), fluorene ring-modified polycarbonate (BCF-PC: compound described in Japanese Patent Laid-Open No. 2000-227603: 225°C), alicyclic-modified polycarbonate (IP - PC: Compounds described in JP-A-2000-227603: 205°C), acryloyl compounds (compounds described in JP-A-2002-80616: 300°C or higher), etc. Values represent Tg). Especially when transparency is required, alicyclic polyolefin and the like are preferably used.

As for the gas barrier film, it is preferable that the plastic film is transparent from the viewpoint of utilization as an electronic device such as an organic EL element. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.

For the light transmittance, the method described in JIS K 7105:1981 can be used, that is, the total light transmittance and the amount of scattered light are measured using an integrating sphere type light transmittance measuring device, and the diffuse transmittance is obtained by subtracting the diffuse transmittance from the total light transmittance. figured out.

However, even when the gas barrier film is used for a display, transparency is not necessarily required when it is not installed on the viewing side. In such cases, therefore, opaque materials can also be used as the plastic film. Examples of opaque materials include polyimide, polyacrylonitrile, and known liquid crystal polymers.

The thickness of the plastic film used for the gas barrier film is appropriately selected depending on the application, and therefore is not particularly limited. Typically, it is within the range of 1 to 800 μm, preferably within the range of 10 to 200 μm. These plastic films may have functional layers such as known transparent conductive layers and smoothing layers already used in conventional gas barrier films. As the functional layer, in addition to the functional layers described above, functional layers described in paragraphs 0036 to 0038 of JP-A-2006-289627 can be preferably employed.

In addition, the substrate using the resins listed above may be an unstretched film or a stretched film.

The substrate can be produced by a conventionally known general method. For example, a substantially amorphous and non-oriented unstretched base material can be produced by melting a resin to be a material with an extruder, extruding through a ring die or a T-die, and quenching. In addition, the unstretched base material is stretched on the base material by a known method such as uniaxial stretching, tenter type sequential biaxial stretching, tenter type simultaneous biaxial stretching, tubular type simultaneous biaxial stretching, etc. The stretched substrate can be produced by stretching in the direction of the flow (longitudinal axis) or at right angles to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin used as the raw material of the base material, and is preferably in the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

On both sides of the substrate, at least the side on which the gas barrier layer is provided, various known treatments for improving adhesion, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, smoothing, etc., can be combined as needed. layer stacking etc.

"Anchor Coating"

On the surface of the substrate according to the present invention, an anchor coat layer may be formed as an easily bonding layer in order to improve adhesiveness (adhesiveness). The materials, methods, and the like disclosed in paragraphs 0229 to 0232 of JP-A-2013-52561 are suitably used for the constituent materials, formation methods, and the like of the anchor coat layer.

"Smooth Layer"

The gas barrier film of the present invention may have a smooth layer on the surface of the substrate having the gas barrier layer. The smoothing layer is provided to flatten the rough surface of the base material with protrusions or the like, or to fill and flatten unevenness and pinholes generated in the gas barrier layer due to the protrusions present on the resin base material. For the constituent material, formation method, surface roughness, layer thickness, and the like of the smooth layer, materials, methods, and the like disclosed in paragraphs 0233 to 0248 of JP-A-2013-52561 are suitably used.

"Anti-seepage layer"

The gas barrier film of the present invention can further have an anti-bleed layer. The anti-bleeding layer is provided on the opposite side of the substrate having the smooth layer in order to suppress the phenomenon that when the film having the smooth layer is heated, unreacted oligomers, etc. migrate from the resin substrate to the surface, and the Contamination of contact surfaces. As long as the seepage prevention layer has this function, basically the same configuration as that of the smooth layer can be employed. As the constituent material, formation method, layer thickness, etc. of the anti-bleeding layer, the materials, methods, etc. disclosed in paragraphs 0249 to 0262 of JP-A-2013-52561 are suitably used.

"Electronic Devices"

The gas barrier film of the present invention described above has excellent gas barrier properties, transparency, and flexibility. Therefore, the gas barrier film of the present invention can be used in packages of electronic devices, etc., gas barrier films used in electronic devices such as photoelectric conversion elements (solar cell elements), organic EL elements, and liquid crystal display elements, and electronic devices using the same. used in various purposes.

[Manufacturing method of gas barrier film]

The gas barrier layer according to the present invention can be formed by plasma chemical vapor deposition (plasma CVD, PECVD (plasma-enhanced chemical vapor deposition), hereinafter also referred to as "plasma CVD method").

The plasma CVD method is not particularly limited, and examples include the plasma CVD method described in International Publication No. 2006/033233 at or near atmospheric pressure, and plasma using a plasma CVD apparatus having an opposing roll electrode. CVD method. The plasma CVD method may be a Penning discharge plasma plasma CVD method.

Among them, it is preferable to form by a discharge plasma chemical vapor deposition method (roll-to-roll method) with a discharge space between rolls to which a magnetic field is applied, using a source gas containing an organosilicon compound and oxygen gas. By using the discharge plasma chemical vapor deposition method as described above, a gas barrier layer having an extreme value and controlling the carbon atom ratio in each region within a certain range can be easily produced, and a gas barrier layer with an appropriate stress balance in the layer can be produced. barrier film. Furthermore, by using the discharge plasma chemical vapor deposition method, the gas barrier layer can be densified and the gas barrier properties can be improved.

A method of forming the gas barrier layer according to the present invention is described below by a discharge plasma chemical vapor deposition method using a source gas containing an organosilicon compound and oxygen gas with a discharge space between rolls to which a magnetic field is applied.

When plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in the space between a plurality of film-forming rolls, and it is more preferable to use a pair of film-forming rolls on which substrates ( The base material mentioned here also includes the form which processed the base material), and discharge is performed between a pair of film-forming rolls, and plasma is generated.

By using a pair of film-forming rollers in this way, disposing the substrate on the pair of film-forming rollers, and performing discharge between the pair of film-forming rollers, it is possible to reduce the temperature of the substrate existing on one film-forming roller during film formation. The film is formed on the surface part, and at the same time, the film is formed on the surface part of the substrate existing on another film forming roll, so that a thin film can be produced efficiently. In addition, the film formation rate can be doubled compared with the usual plasma CVD method that does not use a roller.

Moreover, when discharging between a pair of film-forming rolls like this, it is preferable to alternately reverse the polarity of a pair of film-forming rolls. Furthermore, the film-forming gas used in such a plasma CVD method preferably contains an organosilicon compound and oxygen, and the composition is preferably adjusted according to the theoretical amount of oxygen required to completely oxidize the entire amount of the organosilicon compound in the film-forming gas. Oxygen content in the membrane gas.

The method for forming the gas barrier layer according to the present invention will be described in more detail below with reference to FIG. 3 . In addition, FIG. 3 is a schematic diagram which shows an example of the manufacturing apparatus which can be used preferably for manufacturing the gas barrier layer which concerns on this invention. In addition, in the following description and drawings, the same reference numerals are assigned to the same or corresponding elements, and overlapping descriptions are omitted.

The manufacturing apparatus 10 shown in FIG. 3 is equipped with a delivery roller 12, conveying rollers 13-18, film forming rollers 19 and 20, a gas supply pipe 21, and a power supply 22 for plasma generation, which are respectively provided inside the film forming rollers 19 and 20. The magnetic field generating devices 23 and 24, and the take-up roller 25. In addition, in such manufacturing apparatus 10 , at least film forming rollers 19 and 20 , gas supply pipe 21 , plasma generating power source 22 , and magnetic field generating devices 23 and 24 are arranged in film forming (vacuum) chamber 28 . Furthermore, in such a manufacturing apparatus 10 , the film formation chamber 28 is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber 28 can be appropriately adjusted by the vacuum pump.

The feeding roller 12 and the conveying roller 13 are arranged in the conveying system chamber 27 , and the take-up roller 25 and the conveying roller 18 are arranged in the conveying system chamber 29 . The transport system chambers 27 and 29 are connected to the film formation chamber 28 via connecting portions 30 and 31 , respectively. For example, vacuum gate valves may be provided at the connection portions 30 and 31 to physically isolate the film formation chamber 28 from the transport system chambers 27 and 29 . By using the vacuum gate valve, for example, only the inside of the film forming chamber 28 can be made into a vacuum system, and the inside of the conveyance system chambers 27 and 29 can be made under the atmosphere. In addition, by physically separating the film formation chamber 28 from the transport system chambers 27 and 29 , contamination of the transport system chambers 27 and 29 with particles generated in the film formation chamber 28 can be suppressed.

In such a manufacturing apparatus, each film forming roller 19 and 20 is connected to a plasma generating power source 22 so that a pair of film forming rollers (film forming rollers 19 and 20) can function as a pair of opposing electrodes. connect. Therefore, in such a manufacturing apparatus 10, by supplying electric power from the power supply 22 for plasma generation, discharge can be performed in the space between the film forming roller 19 and the film forming roller 20, whereby the film forming roller 19 and the film forming roller 20 can be discharged. Plasma is generated in the space between the deposition rollers 20 . It should be noted that, when the deposition roller 19 and the deposition roller 20 are also used as electrodes in this way, their materials and designs can be appropriately changed so that they can also be used as electrodes.

In addition, in such a manufacturing apparatus 10 , it is preferable to arrange a pair of deposition rollers (deposition rollers 19 and 20 ) so that their central axes are substantially parallel on the same plane. By arranging a pair of film-forming rollers (film-forming rollers 19 and 20 ) in this way, it is possible to double the film-forming rate compared to the usual plasma CVD method that does not use rollers.

According to such a manufacturing apparatus 10, the gas barrier layer 3 can be formed on the surface of the base material 2 (the base material referred to here also includes the form in which the base material has been processed) by the CVD method, and can also be formed on the film forming roller 19. Since the gas barrier layer components are deposited on the surface of the substrate 2 and the gas barrier layer components are also deposited on the surface of the substrate 2 on the film forming roller 20, it is possible to efficiently deposit the gas barrier layer components on the surface of the substrate 2. Form a gas barrier layer.

Inside the deposition rollers 19 and 20 , magnetic field generators 23 and 24 that are fixed so as not to rotate even if the deposition rollers 19 and 20 rotate are provided, respectively.

With regard to the magnetic field generators 23 and 24 provided respectively at the deposition rollers 19 and 20, it is preferable to generate the magnetic field with the magnetic field generation device 23 arranged on one deposition roller 19 and the magnetic field generation device 20 arranged on the other deposition roller 20. The magnetic poles are arranged such that the lines of magnetic force do not cross between the devices 24 and the magnetic field generating devices 23 and 24 each form a substantially closed magnetic circuit. By arranging such magnetic field generators 23 and 24, the formation of a magnetic field in which magnetic lines of force bulge near the opposite side surfaces of each film forming roller 19 and 20 can be promoted, and the plasma can be easily converged on the bulge, so the improvement can be improved. Film formation efficiency is excellent in this point.

In addition, the magnetic field generators 23 and 24 respectively provided on the deposition rollers 19 and 20 each have racetrack-shaped magnetic poles elongated in the roll axis direction, and the magnetic field generator 23 on one side and the magnetic field generator 24 on the other side are In other words, it is preferable to arrange the magnetic poles so that the opposing magnetic poles have the same polarity. By arranging such magnetic field generating devices 23 and 24, for each magnetic field generating device 23 and 24, the magnetic field line will not cross the magnetic field generating device on the opposite roller side, and can be in the opposite space (discharge) along the longitudinal direction of the roller axis. region) near the surface of the roller facing the surface of the racetrack can easily form a magnetic field, and plasma can be converged in this magnetic field, so it is possible to efficiently form a vapor-deposited film using a wide substrate 2 wound in the width direction of the roller. The gas barrier layer 3 is excellent in this point.

The tensions to the base material 2 in the film forming rollers 19 and 20 may be all the same, or only the film forming roller 19 or the film forming roller 20 may have a high tension to form a film. By increasing the tension to the substrate 2 in the film-forming rollers 19 and 20, there are advantages as follows: the adhesion between the substrate 2 and the film-forming rollers 19 and 20 is improved, heat exchange is carried out efficiently, and the uniformity of the film is improved. In addition, heat wrinkles are also suppressed.

Well-known rolls can be used suitably as film formation rolls 19 and 20 . As such film forming rollers 19 and 20 , it is preferable to use rollers having the same diameter from the viewpoint of more efficiently forming a thin film. In addition, the diameter of such deposition rollers 19 and 20 is preferably in the range of 300 to 1000 mmφ, particularly preferably in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions and chamber space. If the diameter of the film-forming roller is more than 300mmφ, because the plasma discharge space will not become small, there will be no deterioration in productivity, and it will be possible to avoid applying all the heat of the plasma discharge to the substrate 2 in a short time. It is preferable to reduce damage to the base material 2 . On the other hand, if the diameter of the deposition roller is 1000 mmφ or less, it is preferable since the uniformity of the plasma discharge space and the like can be maintained in terms of device design. Each film forming roll 19 and 20 may have a nip roll, and the adhesiveness of the base material 2 to the film forming roll 19 and 20 improves by having a nip roll. Thereby, there are advantages in that heat exchange is efficiently performed between the base material 2 and the deposition rollers 19 and 20, the uniformity of the film is improved, and thermal wrinkles are also suppressed.

In such a manufacturing apparatus 10 , the base material 2 is arranged on a pair of deposition rolls (deposition rolls 19 and 20 ) such that the surfaces of the base material 2 face each other. By arranging the base material 2 in this way, when the plasma is generated by discharging in the facing space between the film-forming roller 19 and the film-forming roller 20, it is possible to simultaneously discharge the plasma between a pair of film-forming rollers (film-forming rollers 19 and 20). Films are formed on the respective surfaces of the existing substrates 2 . That is, according to such a manufacturing apparatus 10, the gas barrier layer components can be deposited on the surface of the substrate 2 on the film forming roll 19 by the plasma CVD method, and the gas barrier layer components can be further deposited on the film forming roll 20. Therefore, A gas barrier layer can be efficiently formed on the surface of the substrate 2 .

Well-known rolls can be used suitably as the delivery roll 12 and conveyance rolls 13-18 used in the manufacturing apparatus 10. The take-up roll 25 is not particularly limited as long as the gas barrier film 1 having the gas barrier layer 3 formed on the substrate 2 can be taken up, and known rolls can be used as appropriate. In addition, the delivery roller 12 and the take-up roller 25 may be of a turntable type. The turntable may be multi-axis with two or more axes, or may have a structure in which only some of the axes can be opened to the atmosphere.

In addition, as the gas supply pipe 21 and the vacuum pump, a gas supply pipe and a vacuum pump capable of supplying or discharging a source gas or the like at a predetermined speed can be suitably used.

In addition, the gas supply pipe 21 as a gas supply means is preferably arranged on one side of the facing space (discharge region, film formation region) between the film forming roller 19 and the film forming roller 20, and a vacuum pump (not shown) as a vacuum exhausting means Shown) is preferably arranged on the other side of the facing space. By arranging the gas supply pipe 21 as the gas supply means and the vacuum pump as the vacuum exhaust means in this way, the film formation gas can be efficiently supplied to the facing space between the film formation roller 19 and the film formation roller 20, and the Film formation efficiency is excellent in this point.

To illustrate, in FIG. 3 , the gas supply pipe 21 is arranged on the center line between the film forming roller 19 and the film forming roller 20, but it is not limited thereto. The centerline between them is offset to either side (can be offset from the centerline in the left and right directions). By making the gas supply pipe 21 deviate from the center line between the film-forming roll 19 and the film-forming roll 20, thereby approaching one film-forming roll and away from the other film-forming roll, the supply of the raw material gas is carried out on the film-forming roll 19. The composition of the formed film is different from that of the film formed on the deposition roller 20 , and the position of the gas supply pipe 21 can be shifted as appropriate when the film quality is to be changed. In addition, the gas supply pipe 21 may be moved away from or close to the film forming roller on the center line as appropriate (the arrangement position may be moved on the center line in the vertical direction). By making the gas supply pipe 21 far away from the central axis of the film-forming roller, the gas supply pipe 21 is separated from the discharge space, thereby having the advantages of being able to suppress particles from adhering to the gas supply pipe 21. The central axis is close to the discharge space, which has the advantages of being able to increase the film forming rate.

In FIG. 3 , there is one gas supply pipe 21 , but there may be a plurality of gas supply pipes 21 , and different supply gases may be emitted from each nozzle.

Furthermore, as the power source 22 for plasma generation, the power source of a well-known plasma generation apparatus can be used suitably. Such a plasma generation power supply 22 supplies electric power to the deposition roller 19 and the deposition roller 20 connected thereto, and these can be used as counter electrodes for discharging. As such a plasma generating power source 22 , it is preferable to use a power source (AC power source, etc.) capable of alternately reversing the polarity of a pair of deposition rollers, since plasma CVD can be performed more efficiently.

In addition, as such a plasma generating power supply 22, since plasma CVD can be performed more efficiently, the applied power is preferably within a range of 100W to 20kW, more preferably within a range of 100W to 10kW, and preferably The frequency of alternating current is within the range of 50 Hz to 13.56 MHz, more preferably within the range of 50 Hz to 500 kHz.

In addition, from the viewpoint of stabilizing the plasma process, a high-frequency power supply in which both the high-frequency current wave and the voltage wave are sine waves can be used.

In Fig. 3, a power supply 22 for plasma generation is used to supply power to both film forming rollers 19 and 20 (two film forming rollers are powered), but it is not limited to such a form, and it can be to supply power to one film forming roller (Single-side film-forming roller is powered), and the other film-forming roller is grounded.

In addition, as a method of feeding electricity to the film-forming roller, it may be single-ended roller feeding from only one end of the roller, or may be double-roller feeding from both ends of the roller. In the case of supplying a high-frequency band, it is possible to supply electricity to both ends of the roller in order to allow uniform supply.

In addition, as the power feeding method, dual-frequency power feeding with different frequencies may be applied, and different dual-frequency power may be applied to one film-forming roll, or may be applied between one film-forming roll and another film-forming roll. different frequency forms. By such dual-frequency power feeding, the plasma density is increased, and the film formation rate can be increased.

In addition, although not shown in FIG. 3 , a feedback circuit may be provided which monitors the plasma luminous intensity in the discharge space from the outside, and adjusts the distance between magnetic fields (distance between opposing rollers) and The strength of the magnetic field, the applied power of the power supply, the frequency of the power supply, the amount of gas supplied, etc. are used to achieve the desired plasma luminous intensity. By having such a feedback circuit, film formation and production can be stabilized.

In addition, as the magnetic field generating devices 23 and 24 , known magnetic field generating devices can be appropriately used. Furthermore, as the base material 2 , other than the base material used in the present invention, a base material on which the gas barrier layer 3 is formed in advance can be used. By using, as the base material 2 , a base material on which the gas barrier layer 3 has been formed in advance, the layer thickness of the gas barrier layer 3 can also be increased.

Using such a manufacturing apparatus 10 shown in FIG. 3 , for example, a gas barrier layer containing carbon atoms, silicon atoms, and oxygen atoms can be formed. At this time, the method of controlling the atomic ratio of the carbon atom content in the gas barrier layer is not particularly limited, and the atomic ratio of the carbon atom content can be controlled by controlling the ratio of raw materials used, electric power, pressure, and the like.

The pressure (vacuum degree) in the vacuum chamber can be appropriately adjusted depending on the type of source gas, etc., but is preferably about 0.5 to 50 Pa, more preferably within a range of 0.5 to 10 Pa.

In addition, in such a plasma CVD method, in order to discharge between the deposition roller 19 and the deposition roller 20, the electrode drum connected to the power source 22 for generating plasma (in this embodiment, provided on the deposition roller 19 and 20) The electric power to be applied can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but it cannot be generalized, but it is preferably specified within the range of 0.1 to 10 kW. If the applied power is 0.1kW (100W) or more, the generation of particles can be sufficiently suppressed. On the other hand, if it is 10kW or less, the heat generated during film formation can be suppressed, and the temperature rise of the substrate surface during film formation can be suppressed. . Therefore, the base material does not fail to withstand heat, and is excellent in that wrinkles can be prevented during film formation.

The conveying speed (linear speed) of the substrate 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., and is preferably within the range of 0.25 to 100 m/min, more preferably within the range of 0.5 to 100 m/min. .

The adjustment of the respective composition ratios of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer, and further, the ratio of the types of carbon bonds can be controlled within the scope of the present invention by employing, for example, the following methods (1) to (4). .

(1) Control of raw material gas for plasma CVD

Control can be achieved by appropriately using raw materials for plasma CVD with different ratios of carbon, hydrogen, oxygen, and silicon in the molecule.

Specifically, as a raw material for plasma CVD, an organosilicon compound having a low ratio of intramolecular Si—C bonds is preferably used. The number of Si-C bonds in one molecule of these organosilicon compounds is preferably two or less, more preferably one or zero, relative to one Si atom in one molecule.

Specifically, compared with disiloxanes such as hexamethyldisiloxane and tetramethyldisiloxane, it is preferable to use cyclic compounds such as octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane. An alkoxysilane containing one Si in 1 molecule, such as siloxane, tetramethoxysilane, and methyltrimethoxysilane. These compounds can be used individually by 1 type or in combination of 2 or more types.

(2) Adopting the control of the supply amount of oxygen as a reaction gas

Control can be performed by increasing or decreasing the supply amount of oxygen, which is a reaction gas supplied during CVD film formation.

Specifically, when the above-mentioned preferred raw materials are oxidized to form a gas barrier film mainly composed of silicon atoms, oxygen atoms, and carbon atoms, the supply amount of oxygen is controlled to such an extent that it is not completely oxidized. The degree to which excess carbon does not remain in the gas barrier layer is controlled by supplying a certain amount of oxygen to the source gas.

(3) Control of the amount of inert gas added

Inert gas such as nitrogen, argon, and helium is supplied during film formation, and by adjusting the supply amount of the inert gas, the plasma is stabilized when forming the gas barrier layer, and the oxidation reaction can be controlled by adjusting the oxidation reaction.

(4) Control of the distance between electrodes in plasma discharge

It can also be controlled by continuously changing the distance between electrodes for generating plasma discharge.

In the case of using the above-mentioned device with a pair of roller electrodes facing each other, the space of the plasma generated on the surface of the substrate in contact with the electrodes changes continuously, so the change of the film formation conditions caused by the continuous change of the distance between the electrodes , the composition in the gas barrier layer can be continuously changed.

Next, the film-forming gas used for forming the gas barrier layer will be described.

As the film-forming gas, a reaction gas can be used in addition to the source gas. As such a reactive gas, a gas that reacts with a source gas to become an inorganic compound such as an oxide can be appropriately selected and used. Since the gas barrier layer 3 of the present embodiment contains oxygen, oxygen and ozone can be used as the reaction gas, for example, but oxygen is preferably used from the viewpoint of simplicity. In addition, in addition to this, a reaction gas for forming a nitride can be used, for example, nitrogen and ammonia can be used. These reaction gases can be used alone or in combination of two or more. For example, in the case of forming oxynitrides, a reaction gas for forming an oxide and a reaction gas for forming a nitride can be used in combination.

As the film-forming gas, a carrier gas may be used as necessary in order to supply the source gas into the film-forming chamber 28 . Furthermore, as the film-forming gas, in order to generate plasma discharge, a discharge gas may be used as necessary. As such carrier gas and discharge gas, known gases can be used appropriately, for example, rare gases such as helium, argon, neon, and xenon, hydrogen, and nitrogen can be used.

In this way, when the film-forming gas contains the source gas and the reaction gas, the ratio of the source gas to the reaction gas is the ratio of the amount of the reaction gas theoretically required to completely oxidize the source gas and the reaction gas 100%, preferably adjusted to 50% or more, 300% or more. By adjusting the ratio of the reaction gas within this range, the carbon atoms inside the formed gas barrier layer can be adjusted to a preferred composition distribution, and excellent gas barrier properties and bending resistance can be obtained.

When the ratio is lower than the above ratio, the ratio of carbon atoms in the gas barrier layer increases, making it difficult to maintain sufficient gas barrier properties. The carbon-related linkages of the present invention are formed within the barrier layer.

By using the manufacturing apparatus 10 shown in FIG. 3 , a film-forming gas (raw material gas, etc.) is supplied into the film-forming chamber 28, and a discharge is generated between a pair of film-forming rollers (film-forming rollers 19 and 20), thereby The film-forming gas (raw material gas, etc.) is decomposed by plasma, and the surface of the substrate 2 on the film-forming roller 19 and the surface of the substrate 2 on the film-forming roller 20 are formed by the plasma CVD method for the first time. film layer. At this time, a racetrack-shaped magnetic field is formed near the roller surface facing the opposing space (discharge region) along the longitudinal direction of the roller axis of the deposition rollers 19 and 20, and the plasma is converged in the magnetic field. By repeating this process for the second film-forming layer and the third film-forming layer in which one or more of the above-mentioned conditions are changed, the composition of each constituent atom is continuously changed in the layer thickness direction.

Specifically, in the carbon distribution curve, the silicon distribution curve and the oxygen distribution curve, when the substrate 2 passes through the point A of the film-forming roller 19 and the point B of the film-forming roller 20, the maximum value of the carbon distribution curve and the oxygen distribution curve are formed minimum value of . And when the substrate 2 passes through the points C1 and C2 of the film-forming roller 19 and the points C3 and C4 of the film-forming roller 20, the minimum value of the carbon distribution curve and the maximum value of the oxygen distribution curve are formed.

The existence of such an extreme value indicates that it is a layer in which the ratio of carbon atoms and oxygen atoms in the film is not uniform. By the presence of a part with a low density and a small number of carbon atoms locally, the entire layer becomes a flexible structure, and the bending durability sexual enhancement.

As described above, as a more preferable form of this embodiment, it is characterized in that the plasma CVD method using the plasma CVD apparatus (roll-to-roll method) shown in FIG. The invention relates to the formation of a gas barrier layer. This is because, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having opposing roll electrodes, it is possible to efficiently manufacture a product with excellent flexibility (bendability) and high gas barrier properties under high temperature and high humidity. , A gas barrier layer having few defects in which mechanical strength, especially durability during roll-to-roll conveyance, and gas barrier properties are reduced. Such a manufacturing apparatus is also excellent in that it can easily mass-produce gas barrier films used in solar cells, electronic components, and the like, which require durability against temperature changes, at low cost.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

"Manufacturing of Gas Barrier Films 1-12"

(Preparation of resin substrate)

As the sheet-shaped resin base material, a polyethylene terephthalate film with a thickness of 100 μm (manufactured by Toyobo Co., Ltd., Cosmosine A4300) was used as a thermoplastic resin support, and both sides were processed for easy adhesion. ).

(formation of anchor coating)

On the easy-adhesive side of one of the above-mentioned resin substrates, a UV-curable organic/inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 manufactured by JSR Corporation was used, and a wire was used so that the layer thickness after drying became 3 μm. After bar coating, drying was performed at 80° C. for 3 minutes as drying conditions. Next, curing was performed under the curing condition: 1.0 J/cm ² using a high-pressure mercury lamp in an air atmosphere to form an anchor coating.

(formation of anti-seepage layer)

UV-curable organic/inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 manufactured by JSR Co., Ltd. was coated with a wire bar on the other easy-adhesive side of the resin substrate so that the layer thickness after drying became 3 μm. Finally, after drying at 80° C. for 3 minutes, it was cured under the curing condition: 1.0 J/cm ² using a high-pressure mercury lamp in an air atmosphere to form an anti-seepage layer. After forming the anti-bleeding layer, it was used as a resin base material that was stored under a reduced pressure of 5 Pa and at a temperature of 35° C. for 96 hours to adjust the humidity.

(Formation of gas barrier layer: roll CVD method)

Using the inter-roll discharge plasma CVD apparatus (hereinafter referred to as the roll CVD method) to which a magnetic field is applied as described in FIG. The substrate was installed in the device, and the following film-forming conditions (plasma CVD conditions) were changed within the ranges described below in terms of the raw material gas, oxygen, the degree of vacuum in the vacuum chamber, and the applied power from the power supply for plasma generation. The ratio of carbon atoms is different, and by combining multiple times, a film is formed on the anchor coating layer so that the final layer thickness becomes 140nm according to the measurement method of the layer thickness of the gas barrier layer described later, and this is used as the gas barrier layer.

In addition, in the gas barrier layer of the present invention, in order to increase the carbon atom ratio, it is mainly adjusted by increasing the supply amount of the raw material gas in the total supply gas or reducing the supply amount of oxygen. For the adjustment of the layer thickness, the vacuum The vacuum in the chamber has been increased or decreased. In addition, the supply amount of raw material gas and oxygen was adjusted so that it might become the value described in Table 1, and it supplied.

In addition, in Table 1, TMCTS and MTMS are the abbreviations of tetramethylcyclotetrasiloxane and methyltrimethoxysilane, respectively.

<Plasma CVD conditions>

Supply amount of raw material gas (recorded in Table 1): 50 or 100 sccm (Standard Cubic Centimeterper Minute)

Supply amount of oxygen (O ₂ ): 50～1000sccm

Vacuum degree in vacuum chamber: 1.0～3.5Pa

Applied power from the power supply for plasma generation: 1.0 to 3.0kW

Frequency of power supply for plasma generation: 70kHz

Conveying speed of resin substrate: 3～6m/min

In addition, the gas barrier films 1 to 9 were formed in one pass at a conveying speed of 3 m/min. In addition, for the gas barrier films 10 to 12, the films were formed twice at a conveying speed of 6 m/min, and the oxygen supply rates of the first (lower layer side) and second (upper layer side) are shown in Table The supply amount (sccm) described in 1 was used to form a film.

<Measuring method of layer thickness of gas barrier layer>

Regarding the layer thickness of the gas barrier layer, the depth from the outermost surface to the interface with the base material in the stacking direction of the gas barrier layer was measured by cross-sectional observation with a transmission electron microscope (Transmission Electron Microscope: TEM). In the present invention, the layer thickness is measured at 10 locations arbitrarily, and the average value is taken as the layer thickness of the gas barrier layer.

(TEM image of cross-section in layer thickness direction)

As the TEM observation of the cross-section, TEM observation was performed on the observation sample after producing thin slices using the following focused ion beam (Focused Ion Beam: FIB) processing apparatus. Here, when the sample was continuously irradiated with electron beams, there was a difference in contrast between the portion damaged by the electron beam and the portion not damaged, so the layer thickness of the gas barrier layer was measured using the difference in contrast.

(FIB processing)

Device: SMI2050 made by SII

Processing ion: Ga (30kV)

Sample thickness: 100~200nm

(TEM observation)

Device: JEM2000FX manufactured by JEOL (accelerating voltage: 200kV)

"Analysis of Gas Barrier Layers"

(Determination of element distribution curve)

The gas barrier layer formed above was subjected to XPS depth distribution measurement under the following conditions to obtain carbon distribution curves, silicon distribution curves and oxygen distribution curves with respect to the distance from the surface of the thin film layer in the layer thickness direction.

Etching ion species: argon (Ar ⁺ )

Etching rate (SiO ₂ thermal oxide film conversion value): 0.05nm/sec

Etching interval (SiO ₂ conversion value): 2nm

X-ray photoelectron spectroscopy device: manufactured by Thermo Fisher Scientific, model name "VG ThetaProbe"

Irradiation of X-rays: single crystal spectroscopic AlKα

X-ray spot and its size: 800μm×400μm oval

Carbon distribution curves, silicon distribution curves and oxygen distribution curves were obtained by performing wide-scan spectroscopic analysis measuring the entire layer region of the gas barrier layer as described above. Here, the depth from the outermost side in the layer thickness direction of the gas barrier layer when the composition ratio of oxygen atoms (O), which is a part of the entire composition forming the gas barrier layer, is 30% or less was calculated and used as the position of the interface. In addition, regarding the layer thickness direction of the gas barrier layer, the outermost surface of the gas barrier layer was set to 0%, and the interface with the base material was set to 100%, and the silicon atoms, oxygen atoms, and carbon atoms of the gas barrier layer were processed as follows. Analysis of atoms.

(Analysis of silicon atoms, oxygen atoms and carbon atoms of the gas barrier layer)

For the depth in the layer thickness direction of the gas barrier layer, the total amount of the composition ratio converted from the ratio of the peak intensities derived from silicon atoms, oxygen atoms, and carbon atoms obtained by X-ray photoelectron spectroscopy was calculated as 100%. The ratio (%) of each atom at the time. In addition, regarding carbon atoms, the bonding state of carbon was analyzed by C1s high-resolution spectroscopy (narrow scan analysis). Specifically, it is divided into 5 bonding groups of (1) C-C, C=C and C-H, (2) C-SiO, (3) C-O, (4) C=O, (5) O-C-O, according to each spectrum The ratio of carbon atoms derived from each group was calculated from the composition ratio converted from the ratio of the peak intensities.

Here, when the total amount of the composition ratio converted from the ratio of peak intensities derived from silicon atoms, oxygen atoms, and carbon atoms in the layer thickness direction of the gas barrier layer is 100%, the waveform analysis based on C1s related to carbon atoms The proportion of the composition ratio converted from the ratio of the peak intensities derived from the C-C, C=C, and C-H bonds (the above (1)) was defined as the ratio X (%).

Table 1 shows the area of 5 to 30% of the layer thickness and the layer thickness when the outermost surface of the gas barrier layer is 0% and the interface with the base material is 100% with respect to the layer thickness direction of the gas barrier layer. The maximum value (%), the average value (%), and the minimum value (%) of the ratio X in the range of 30 to 95%.

In addition, a graph showing the analysis results of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier film 5 of the present invention is shown in FIG. 2 . In addition, as a reference example, a graph of analysis results of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier film 1 of the comparative example is shown in FIG. 4 .

It should be noted that the graphs in Fig. 2 and Fig. 4 represent the depth (% when the outermost surface is 0% and the interface with the substrate is 100% when the horizontal axis is defined as the depth in the layer thickness direction of the gas barrier layer. )), the vertical axis is the ratio of each atom when the total amount of the composition ratio converted from the ratio of the peak intensities derived from silicon atoms, oxygen atoms, and carbon atoms obtained by X-ray photoelectron spectroscopy is 100% (%). Here, carbon atoms are represented by the ratio of the above-mentioned 5 bonding groups. In addition, (1)-(5) in Fig. 2 and Fig. 4 respectively correspond to from (1) C-C, C=C and C-H, (2) C-SiO, (3) C-O, (4) C=O, (5) A carbon atom of O-C-O, (6) corresponds to an oxygen atom, and (7) corresponds to a silicon atom.

"Evaluation of Gas Barrier Films"

＜Evaluation of Gas Barrier Property＞

(1) Determination of Water Vapor Transmission Rate (WVTR)

For each of the produced gas barrier films, the water vapor transmission rate [g/(m ² ·day)] at 38° C. and 90% RH was measured using the MOCON water vapor transmission rate measurement device Aquatran manufactured by MOCON Corporation, as follows The gas barrier properties were evaluated on the evaluation scale.

The evaluation results are shown in Table 1. In the present invention, the cases where the water vapor permeability is less than 0.100 g/(m ² ·day) (ranks 3 to 5) are regarded as acceptable.

5: The water vapor permeability is less than 0.005g/(m ² ·day)

4: The water vapor permeability is 0.005g/(m ² ·day) or more and less than 0.010g/(m ² ·day)

3: The water vapor permeability is 0.010g/(m ² ·day) or more and less than 0.100g/(m ² ·day)

2: The water vapor permeability is 0.100g/(m ² ·day) or more and less than 0.500g/(m ² ·day)

1: The water vapor permeability is above 0.500g/(m ² ·day)

<Evaluation of reduction in gas barrier properties due to front-to-back contact during roll winding: evaluation of scratch resistance>

Each produced gas barrier film was wound into a roll with a length of 10 m at a radius of 3.8 cm and a tension of 20 N/m. For the re-rolled gas barrier film, the number of corrosion sites obtained by the calcium test was compared with that without winding. The number of corroded sites of the rolled gas barrier film was compared, and the evaluation was performed based on the increase rate of corroded sites.

The calcium test will be described below. On the gas barrier layer (the outermost surface), use a vacuum deposition device (manufactured by JEOL Ltd., vacuum deposition device JEE-400) to place the part of the barrier film sample where gas is to be deposited (a square with a side of 5 cm square) Outside the mask, metallic calcium was vapor-deposited. Then, the mask was removed while maintaining the vacuum state, and aluminum was vapor-deposited on the calcium vapor-deposition surface from another metal vapor-deposition source. After the aluminum was sealed, the vacuum state was released, and in a dry nitrogen atmosphere, the quartz glass with a thickness of 0.2mm was placed opposite to the aluminum sealing side through the ultraviolet curable resin for sealing (manufactured by Nagase Chemtex), and ultraviolet rays were irradiated to prepare the evaluation unit. .

After storing the obtained sample (unit for evaluation) sealed on both sides at 60° C. and 90% RH for 360 hours at high temperature and high humidity, the corrosion spots newly grown from the initial state of the Ca vapor-deposited layer were observed using an optical microscope. The following evaluation scales were evaluated. In the present invention, the case where the increase rate of the number of corrosion sites was less than 50% (ranks 3 to 5) was defined as acceptable. The evaluation results are shown in Table 1.

In addition, in order to confirm that there is no permeation of water vapor from other than the surface of the gas barrier film, as a comparison sample, a quartz glass plate with a thickness of 0.2 mm was used instead of the sample of the gas barrier film and metal calcium was vapor-deposited. It was stored under the same high temperature and high humidity of 60° C. and 90% RH, and it was confirmed that there were no corrosion spots growing with a diameter exceeding 100 μm even after 1000 hours.

5: No change in the number of corrosion sites was observed at all

4: The increase rate of the number of corrosion parts is less than 10%.

3: The increase rate of the number of corrosion sites is 10% or more and less than 50%

2: The increase rate of the number of corrosion sites is 50% or more and less than 100%

1: The increase rate of the number of corrosion sites exceeds 100%.

<Evaluation of the number of cracks on the cut surface during cutting: Evaluation of crack resistance>

Each gas barrier film was cut into a size of 10 cm square from the outermost side of the gas barrier layer toward the layer thickness direction of the gas barrier layer using DISK CUTTER DC-230 (CADL Co.), and each cut end was observed with a magnifying glass. The total number of occurrences of cracks on the four sides was checked, and the cutting suitability was evaluated according to the following criteria. In the present invention, when the number of cracks generated is 5 or less (ranks 3 to 5), it is defined as a pass. The evaluation results are shown in Table 1.

5: No cracks were found at all

4: The number of cracks generated is 1 or more and 2 or less

3: The number of cracks generated is 3 or more and 5 or less

2: The number of cracks generated is 6 or more and 10 or less

1: The number of cracks generated is 11 or more

From the above results, it can be seen that the gas barrier film of the present invention has good gas barrier properties, a small decrease in the gas barrier properties due to the front-to-back contact during roll winding, and suppressed the occurrence of cracks at the cut surface during cutting. barrier film. On the other hand, the gas barrier film of the comparative example was inferior in any item.

Industrial availability

The gas barrier film of the present invention has good gas barrier properties, the reduction in gas barrier properties due to front-to-back contact during roll winding is small, and the occurrence of cracks during cutting is suppressed. Such a gas barrier film can be suitably used in electronic devices requiring high gas barrier properties, such as organic electroluminescence elements and liquid crystal display elements.

Explanation of reference signs

1 Gas barrier film

2 Substrate

3 gas barrier layer

10 manufacturing device

12 Delivery roller

13～18 Conveyor rollers

19, 20 film forming roller

21 Gas supply tube

22 Power supply for plasma generation

23, 24 Magnetic field generating device

25 take-up roll

27, 29 conveying system chamber

28 film forming room

30, 31 connection part

Claims (6)

1. a kind of gas barrier film, which is characterized in that its on base material have at least contain silicon atom (Si), oxygen atom (O) and The gas-barrier layer of carbon atom (C),

In by the obtained spectrum of x-ray photoelectron optical spectroscopy, by the thickness direction of gas-barrier layer by coming from silicon original When the total amount for the ratio of components that the ratio of the peak intensity of sub (Si), oxygen atom (O) and carbon atom (C) is converted is set as 100%, base It is converted in the ratio of the peak intensity by coming from C-C, C=C and c h bond of the wave analysis of C1s related with carbon atom The ratio X (%) of ratio of components meets following (1),

(1)：For the thickness direction of above-mentioned gas barrier layer, the thickness of the most surface of above-mentioned gas barrier layer is set as 0%, with When the thickness at the interface of above-mentioned base material is set as 100%, the maximum value (%) of the aforementioned proportion X in 5~30% region of thickness is 5~ In the range of 41 (%).

2. gas barrier film according to claim 1, which is characterized in that the above-mentioned ratio in 5~30% region of above-mentioned thickness In the range of the average value (%) of example X is 2~20%.

3. gas barrier film according to claim 1 or 2, which is characterized in that above-mentioned in 5~30% region of above-mentioned thickness In the range of the minimum value (%) of ratio X is 1~10%.

4. gas barrier film according to any one of claim 1-3, which is characterized in that 5~30% region of above-mentioned thickness In aforementioned proportion X maximum value (%) of the maximum value (%) than the aforementioned proportion X in 30~95% region of thickness it is big.

5. according to the gas barrier film described in any one of claim 1-4, which is characterized in that 5~30% region of above-mentioned thickness In aforementioned proportion X average value (%) of the average value (%) than the aforementioned proportion X in 30~95% region of thickness it is big.

6. gas barrier film according to any one of claims 1-5, which is characterized in that 5~30% region of above-mentioned thickness In aforementioned proportion X minimum value (%) of the minimum value (%) than the aforementioned proportion X in 30~95% region of thickness it is big.