WO2017086035A1 - ガスバリアー性フィルム - Google Patents

ガスバリアー性フィルム Download PDF

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Publication number
WO2017086035A1
WO2017086035A1 PCT/JP2016/079232 JP2016079232W WO2017086035A1 WO 2017086035 A1 WO2017086035 A1 WO 2017086035A1 JP 2016079232 W JP2016079232 W JP 2016079232W WO 2017086035 A1 WO2017086035 A1 WO 2017086035A1
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Prior art keywords
gas barrier
gas
barrier layer
film
base film
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PCT/JP2016/079232
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English (en)
French (fr)
Japanese (ja)
Inventor
千明 門馬
鈴木　一生
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コニカミノルタ株式会社
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Priority to JP2017551761A priority Critical patent/JP6720980B2/ja
Priority to CN201680067287.7A priority patent/CN108290376B/zh
Publication of WO2017086035A1 publication Critical patent/WO2017086035A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00

Definitions

  • the present invention relates to a gas barrier film, and in particular, to a gas barrier film having excellent gas barrier properties and high bending resistance even under high temperature and high humidity.
  • gas barrier films that are lightweight and highly flexible 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.
  • HMDSO hexamethyldisiloxane
  • 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).
  • the present invention has been made in view of the above problems and circumstances, and a solution to that problem is to provide a gas barrier film that has excellent gas barrier properties and high bending resistance even under high temperature and high humidity.
  • 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, and the present invention has been achieved.
  • 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;
  • a 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.
  • a gas barrier film having excellent gas barrier properties and high bending resistance even under high temperature and high humidity can be provided.
  • a gas barrier layer containing at least Si atoms, O atoms and C atoms forms a high-density bond network such as Si—O—Si and Si—C—Si, and has a dense structure. It is presumed that barrier properties can be obtained. Further, when the ratio of CC bond on the base film side in the layer thickness direction of the gas barrier layer is high, the CC bond relaxes the film 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 is also presumed that the CC bond is relaxed and the deformation propagating 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 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.
  • the gas barrier layer contains Si atoms, O atoms and C atoms
  • the gas barrier layer includes the gas barrier layer.
  • the average value of the ratio of C—C bonds at the position in the layer thickness direction of 90 to 100% in the CC bond distribution curve is 20%. It is preferably in the range of ⁇ 90%.
  • 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%.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • 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.
  • the gas barrier film F includes a base film 1 and a gas barrier layer 2 formed on the base film 1.
  • the gas barrier layer 2 has gas barrier properties.
  • 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.
  • 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.
  • 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.
  • organosilicon compound those having a small number of Si—C bonds in one molecule are preferable.
  • 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).
  • TCTS tetrasiloxane
  • OCTS octamethylcyclotetrasiloxane
  • MTMS methyltrimethoxysilane
  • TMOS tetramethoxysilane
  • the number of Si—C bonds in the Si atom is 1 or 0.
  • TMCTS TMCTS
  • OMCTS OMCTS
  • MTMS MTMS
  • the gas barrier layer 2 is formed by a chemical vapor deposition (PVD: Physical Vapor Deposition) method such as vapor deposition or sputtering, or a CVD method such as Plasma Chemical Vapor Deposition (PECVD) or atomic layer deposition (PDE).
  • PVD Physical Vapor Deposition
  • CVD plasma Chemical Vapor Deposition
  • PDE atomic layer deposition
  • the PECVD method is preferable.
  • 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.
  • the gas barrier layer 2 has an X 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 with respect to the sum of each bond of C—C, C—SiO, C—O, C ⁇ O and C ⁇ OO, based on the waveform analysis of C1s measured by the X-ray photoelectron spectroscopy (XPS) method
  • the C—C bond distribution curve representing the —C bond ratio has at least one local maximum at a position in the layer thickness direction of 75 to 100%.
  • the maximum value is an inflection point where 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 CC bonds changes from decrease to increase in the CC bond distribution curve.
  • 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 CC bonds distributed on the base film 1 side.
  • 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.
  • 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.
  • the average value of the ratio of CC bonds at the position in the layer thickness direction of 90 to 100% is within the range of 20 to 90%.
  • the 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.
  • 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 CC 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 Electrode 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.
  • 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 bond energy of C atoms by the XPS method. Specifically, the peak derived from the C—C bond is separated from the C 1 s peak, and the ratio of the peak area (Q 2) of the C—C bond to the peak area (Q 1) of the C 1 s peak (Q2 / Q1 ⁇ 100) It is determined as the ratio of C—C bonds in the barrier layer 2. In other words, 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.
  • 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.
  • 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).
  • 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.
  • FIB focused ion beam
  • TEM Apparatus: JEM2000FX (manufactured by JEOL Ltd.) Accelerating voltage: 200kV (FIB equipment)
  • SMI2050 manufactured by SII
  • Processed ion Ga (30 kV) Sample thickness: 100-200 nm
  • FIG. 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.
  • FIG. 2 shows a CC bond distribution curve of a gas barrier layer formed by PECVD using methyltrimethoxysilane (MTMS) and oxygen as raw materials
  • FIG. 3 shows PECVD using tetramethylcyclotetrasiloxane (TMCTS) as raw materials.
  • MTMS methyltrimethoxysilane
  • TCTS tetramethylcyclotetrasiloxane
  • FIG. 4 shows a CC bond distribution curve obtained by analyzing the gas barrier layer of the 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.
  • HMDSO hexamethyldisiloxane
  • each of the CC bond distribution curves in the example has 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 since the ratio of CC bond on the base film side is high, the gas barrier layer has high bending resistance as described above.
  • 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 during bending cannot be alleviated, and the gas barrier layer such as cracks may be damaged. There is.
  • the average value of the CC bond ratio within the range of 90-100% in the layer thickness direction is about 35% in the CC bond distribution curve shown in FIG. 2, and the CC bond shown in FIG. The distribution curve is about 69%, both in the range of 20-90%.
  • the CC bond distribution curves in FIGS. 2 and 3 have a plurality of maximum values, and the maximum values are 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.
  • 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.
  • 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 CC bonds in the layer thickness direction can be adjusted not only by selecting the raw materials but also by adjusting the film forming conditions.
  • the gas barrier layer 2 is formed by supplying oxygen gas supplied as a raw material gas together with the organosilicon compound by PECVD, by adjusting the supply amount of oxygen gas, the C— in the gas barrier layer 2 is adjusted.
  • the ratio of C bond can be adjusted.
  • 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. And the target CC bond ratio in the thickness direction of the gas barrier layer 2 can be adjusted.
  • the C—C bond ratio in the layer thickness direction can be adjusted to a desired ratio by continuously changing the distance between electrodes for generating plasma.
  • 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.
  • the resin that can be used as the base film 1 examples 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.
  • 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.
  • 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 ⁇ m, more preferably in the range of 25 to 250 ⁇ m.
  • 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.
  • an anchor layer such as a anchor layer, a smoothing layer, and a bleed-out prevention layer depending on the purpose.
  • the smoothing layer, and the bleed-out prevention layer those described in JP2013-52561A can be used.
  • 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.
  • an 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.
  • the gas barrier film F can also include a smoothing layer as a lower layer of the gas barrier layer 2.
  • a smoothing layer 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.
  • the photosensitive resin examples 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.
  • a polyfunctional acrylate monomer such as ether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved.
  • 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.
  • the gas barrier film F has high transparency, the utility as a sealing material for electronic devices is increased, which is preferable.
  • 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. .
  • FIG. 5 shows a schematic configuration of a manufacturing apparatus 100 capable of manufacturing the gas barrier film F.
  • the gas barrier film manufacturing apparatus 100 transports the base film 1 by a plurality of rollers 11 to 18 in a vacuum chamber 10 and applies a voltage between a pair of rollers 13 and 16 facing each other. Apply and supply source gas.
  • 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.
  • 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.
  • 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.
  • 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.
  • gas barrier layers are formed on the base film 1 conveyed by the rollers 13 and 16, respectively.
  • the gas supply unit 21 shown in FIG. 5 is provided on the center line of the roller 13 and the roller 16, 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.
  • the ratio of O atoms changes from decreasing to increasing.
  • 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 to be conveyed 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 diameter of each of the rollers 13 and 16 is preferably in the range of 100 to 1000 mm, and in the range of 100 to 700 mm, from the viewpoint of optimizing the discharge conditions and reducing the space in the vacuum chamber 10. More preferably.
  • the diameter ⁇ is 100 mm or more, a sufficiently large discharge space can be formed, and a reduction in productivity can be prevented.
  • 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 ⁇ 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 material gas of the gas barrier layer to the discharge space formed between the pair of rollers 13 and 16.
  • the gas supply unit 21 supplies an organic silicon compound gas and a gas such as oxygen or ozone as a source gas.
  • a source gas such as nitrogen or ammonia may be supplied.
  • the gas supply unit 21 can use a carrier gas for supplying the raw material gas as needed, and can also supply a plasma generating gas in order to promote plasma generation.
  • 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.
  • the power source 22 a known power source for generating plasma can be used.
  • 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
  • the AC frequency is preferably in the range of 50 Hz to 500 kHz.
  • the pressure in the vacuum chamber 10, that is, the degree of vacuum can be adjusted by the vacuum pump 42 in accordance with the type of the raw material gas, but is preferably in the range of 0.5 to 100.0 Pa.
  • the transport speed (line speed) of the base film 1 can be determined according to the type of raw material gas, the degree of vacuum, etc., but is preferably in the range of 0.25 to 100.00 m / min. More preferably, it is within 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.
  • 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 this 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.
  • HMDSO hexamethyldisiloxane
  • 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
  • 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 For each of the produced gas barrier films 1 to 7, a CC bond distribution curve in the thickness direction of the gas barrier layer was determined as follows.
  • TEM samples of the respective gas barrier films 1 to 7 were prepared using the following FIB apparatus. This sample was set in the following TEM, the cross sections of the gas barrier films 1 to 7 were observed, and the distance from the surface of the gas barrier layer opposite to the base film to the surface of 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
  • etching is performed by rare gas ion sputtering from the surface opposite to the base film of the gas barrier layer to the surface on the base film side, and 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.
  • 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 AlK ⁇ X-ray spot and size: 800 ⁇ 400 ⁇ m oval.
  • the peak due to CC bond is separated from the C1s peak in the spectrum obtained by XPS method, and the ratio of the peak area (Q2) of CC bond to the peak area (Q1) of 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 CC 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.
  • 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.
  • the maximum value (%) in the layer thickness direction of the CC bond distribution curve at the position in the layer thickness direction of 65 to 100% was obtained.
  • the maximum value at a position in the layer thickness direction of 65 to 100% was one.
  • 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.
  • 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
  • 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 of the gas barrier films 1 to 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.
  • Table 1 below shows the evaluation results.
  • HMDSO, TMCTS, and MTMS are abbreviations for hexamethyldisiloxane, tetramethylcyclotetrasiloxane, and methyltrimethoxysilane, respectively.
  • the gas barrier films 2 to 7 having at least one maximum value in the layer thickness direction position where the CC 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.

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PCT/JP2016/079232 2015-11-18 2016-10-03 ガスバリアー性フィルム WO2017086035A1 (ja)

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Cited By (2)

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WO2018092657A1 (ja) * 2016-11-18 2018-05-24 コニカミノルタ株式会社 光学フィルム、偏光板保護フィルム、およびこれらを含む偏光板、ならびにこれらを含む表示装置
US20200259118A1 (en) * 2017-08-25 2020-08-13 Sumitomo Chemical Company, Limited Laminated film

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WO2006043464A1 (ja) * 2004-10-19 2006-04-27 Toray Industries, Inc. フィルムの製造方法、および、フィルム
JP2008023898A (ja) * 2006-07-24 2008-02-07 Toppan Printing Co Ltd 蒸着フィルム
JP2012096531A (ja) * 2010-10-08 2012-05-24 Sumitomo Chemical Co Ltd 積層フィルム
WO2014092085A1 (ja) * 2012-12-14 2014-06-19 コニカミノルタ株式会社 ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス
JP2014136805A (ja) * 2013-01-15 2014-07-28 Konica Minolta Inc ガスバリアーフィルム及びガスバリアーフィルムの製造方法

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WO2013146964A1 (ja) * 2012-03-27 2013-10-03 住友化学株式会社 積層フィルム、有機エレクトロルミネッセンス装置、光電変換装置および液晶ディスプレイ
JP6156388B2 (ja) * 2012-10-19 2017-07-05 コニカミノルタ株式会社 ガスバリアー性フィルムの製造方法、ガスバリアー性フィルム及び電子デバイス
KR102381102B1 (ko) * 2013-12-26 2022-03-30 스미또모 가가꾸 가부시끼가이샤 적층 필름, 유기 일렉트로 루미네선스 장치, 광전 변환 장치 및 액정 디스플레이

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JP2005103870A (ja) * 2003-09-30 2005-04-21 Dainippon Printing Co Ltd 積層材およびそれを使用した液体充填包装用小袋
WO2006043464A1 (ja) * 2004-10-19 2006-04-27 Toray Industries, Inc. フィルムの製造方法、および、フィルム
JP2008023898A (ja) * 2006-07-24 2008-02-07 Toppan Printing Co Ltd 蒸着フィルム
JP2012096531A (ja) * 2010-10-08 2012-05-24 Sumitomo Chemical Co Ltd 積層フィルム
WO2014092085A1 (ja) * 2012-12-14 2014-06-19 コニカミノルタ株式会社 ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス
JP2014136805A (ja) * 2013-01-15 2014-07-28 Konica Minolta Inc ガスバリアーフィルム及びガスバリアーフィルムの製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018092657A1 (ja) * 2016-11-18 2018-05-24 コニカミノルタ株式会社 光学フィルム、偏光板保護フィルム、およびこれらを含む偏光板、ならびにこれらを含む表示装置
US20200259118A1 (en) * 2017-08-25 2020-08-13 Sumitomo Chemical Company, Limited Laminated film

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JP6720980B2 (ja) 2020-07-08
CN108290376B (zh) 2020-04-07
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CN108290376A (zh) 2018-07-17

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