WO2014123201A1 - Film barrière au gaz et son procédé de fabrication - Google Patents

Film barrière au gaz et son procédé de fabrication Download PDF

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Publication number
WO2014123201A1
WO2014123201A1 PCT/JP2014/052800 JP2014052800W WO2014123201A1 WO 2014123201 A1 WO2014123201 A1 WO 2014123201A1 JP 2014052800 W JP2014052800 W JP 2014052800W WO 2014123201 A1 WO2014123201 A1 WO 2014123201A1
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layer
film
gas
oxygen
carbon
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PCT/JP2014/052800
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English (en)
Japanese (ja)
Inventor
廣瀬　達也
河村　朋紀
千明 門馬
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コニカミノルタ株式会社
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Priority to JP2014560806A priority Critical patent/JPWO2014123201A1/ja
Publication of WO2014123201A1 publication Critical patent/WO2014123201A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays

Definitions

  • the present invention relates to a gas barrier film and a method for producing the same.
  • a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles in the fields of food, medicine, etc. It is used for.
  • a gas barrier film By using the gas barrier film, it is possible to prevent alteration of the article due to gas such as water vapor or oxygen.
  • Japanese Patent Application Laid-Open No. 2011-73430 for example, in a carbon distribution curve that includes silicon, oxygen, and carbon with a specific composition, the carbon amount changes in the film thickness direction, and indicates the ratio of the carbon atom weight to the film thickness direction, A gas barrier film having a thin film layer having one or more values is disclosed. According to the gas barrier film having such a configuration, it is said that a decrease in gas barrier characteristics when the film is bent is suppressed.
  • Japanese Patent Application Laid-Open No. 2011-73430 discloses a method of forming a pair of base materials as described in Japanese Patent No. 4268195 (corresponding to US Patent Application Publication No. 2010/313810). An apparatus is used that is disposed on a roll and generates plasma by discharging between a pair of film forming rolls.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide sufficient gas barrier performance under high-temperature and high-humidity conditions even in a film having a composition in which the carbon / oxygen composition ratio changes in the film. It is to provide the gas barrier film shown.
  • Another object of the present invention is to provide a method for producing a gas barrier film having high productivity and exhibiting sufficient gas barrier performance even when the produced film is subjected to high temperature and high humidity conditions.
  • the gas barrier film of the present invention includes a base material, a first layer containing silicon, oxygen, and carbon, and a second layer in this order, and the first layer includes the following conditions (i) and ( ii): (i) The distance (L) from the surface of the first layer in the thickness direction of the first layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms ( Silicon distribution curve showing the relationship between the atomic ratio of silicon and the oxygen distribution curve showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of oxygen) , And a carbon distribution curve showing the relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (carbon atomic ratio), 80% of the film thickness of the first layer In the above region, the formula (A) (carbon atom ) ⁇ (Atomic ratio of
  • the manufacturing method of the gas barrier film of this invention forms a 1st layer containing a silicon
  • a method for producing a gas barrier film comprising: a step; and a step of forming a second layer containing an inorganic oxide by an atomic layer deposition method.
  • FIG. 5 is a schematic diagram illustrating an example of a coating head for ALD film formation used in the apparatus illustrated in FIGS. 3 and 4. It is an example of the organic electroluminescent panel which is an electronic device using the gas-barrier film which concerns on this invention as a sealing film.
  • the ratio of the total amount of oxygen atoms and carbon atoms to the distance (L) from the surface of the barrier layer in the film thickness direction of the first layer in the gas barrier film 2 and the total amount of silicon atoms, oxygen atoms, and carbon atoms It is a figure which shows the distribution curve which shows the relationship with (atomic ratio of oxygen and carbon), a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve.
  • 2 is a graph showing a carbon / oxygen distribution curve of a first layer in a gas barrier film 2.
  • One embodiment of the present invention includes a base material, a first layer containing silicon, oxygen, and carbon, and a second layer in this order, and the first layer includes the following conditions (i) to ( ii): (i) The distance (L) from the surface of the first layer in the thickness direction of the first layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms ( Silicon distribution curve showing the relationship between the atomic ratio of silicon and the oxygen distribution curve showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of oxygen) , And a carbon distribution curve showing the relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (carbon atomic ratio), 80% of the film thickness of the first layer
  • the present invention includes a layer having a specific gas barrier performance that satisfies the above conditions (i) and (ii) (hereinafter also simply referred to as a gas barrier layer) and an inorganic oxide layer (second layer) formed by an atomic layer deposition method. ) In combination. If the gas barrier layer is subjected to a severe condition in which the temperature and humidity greatly change, a decrease in the gas barrier property is induced (see the following comparative example, gas barrier film 5). On the other hand, when the second layer is combined with the gas barrier layer, the gas barrier performance is maintained even under severe conditions in which the temperature and humidity change greatly.
  • a gas barrier film that satisfies the above condition (i) has improved gas barrier performance.
  • Condition (ii) also indicates that the carbon and oxygen atomic ratio varies periodically, meaning that the carbon / oxygen distribution curve has at least two peaks / valleys. That is, the film satisfying the condition (ii) means that there are a portion where the carbon abundance ratio in the film thickness direction is high and a portion where the carbon abundance ratio is low. This corresponds to the condition “(ii) the carbon distribution curve has at least one extreme value” described in JP2011-73430A.
  • Such a film has moderately high carbon abundance in the film compared to a film made of silicon oxide, so that a flexible part is formed in the film and cracks even when the film is bent. Is suppressed.
  • the present inventors have found that the gas barrier performance (particularly bending resistance) of a film in which the carbon / oxygen atomic ratio changes in the film thickness direction is not maintained when the film is placed under high temperature and high humidity conditions. It was. As a cause of this, the present inventors may apply an external force to the gas barrier layer under high temperature and high humidity conditions due to changes in the shape (shrinkage / expansion) of the base material due to changes in temperature and humidity. When microdefects exist in the layer, it was thought that the gas barrier performance could not be maintained because cracks due to external forces further spread starting from such microdefects.
  • the change in the carbon abundance ratio with respect to the film thickness direction changes, for example, in a plasma CVD apparatus having a counter roll electrode as shown in FIG.
  • a plasma CVD apparatus having a counter roll electrode as shown in FIG.
  • the change in the carbon abundance ratio with respect to the film thickness direction will increase. Therefore, when the inventors try to increase the conveyance speed of the base material in order to increase productivity, the change in the carbon abundance ratio in the film thickness direction increases, the change in the carbon composition in the film increases, and the film It was thought that the number of minute defects inside increased.
  • a micro defect may increase when passing a roller etc. at the time of conveyance.
  • the present invention relates to a gas barrier film having a first layer that satisfies the conditions (i) and (ii), and further an inorganic oxide formed by an atomic layer deposition method (hereinafter also referred to simply as an ALD method).
  • a physical layer (second layer) is laminated. If the second layer of the inorganic oxide formed by the ALD method is provided, even if the carbon / oxygen abundance ratio in the film thickness direction changes periodically, the gas barrier performance under high temperature and high humidity conditions is improved. The decrease is suppressed and sufficient gas barrier properties are secured.
  • the inorganic oxide formed by the ALD method has a relatively small molecular weight, can fill in the minute defects present in the first layer, and can repair the minute defects.
  • the said mechanism is estimation and the effect of this invention is not bound to these mechanisms.
  • the gas barrier film of the present invention has excellent gas barrier properties and exhibits sufficient gas barrier performance even under high temperature and high humidity conditions.
  • the method for producing a gas barrier film of the present invention has high productivity, and the produced film exhibits sufficient gas barrier performance even under high temperature and high humidity conditions.
  • a preferred embodiment is that the base material, the first layer, and the second layer formed (directly) on the first layer are arranged in this order. It is a form to have.
  • the gas barrier unit having the first layer and the second layer may be formed on one surface of the base material, or may be formed on both surfaces of the base material.
  • the gas barrier unit may include a layer that does not necessarily have a gas barrier property.
  • the gas barrier film of the present invention preferably has a permeated water amount measured by the method described in Examples below of less than 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h), and is 1 ⁇ 10 ⁇ . More preferably, it is less than 4 g / (m 2 ⁇ 24 h).
  • X to Y indicating the range means “X or more and Y or less”, “weight” and “mass”, “weight%” and “mass%”, “part by weight” and “weight part”. “Part by mass” is treated as a synonym. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
  • the thickness of the first layer is not particularly limited, but is usually in the range of 20 to 1000 nm, preferably 50 to 300 nm in order to improve the gas barrier performance while making it difficult to cause defects.
  • the thickness of the first layer employs a film thickness measurement method by observation with a transmission microscope (TEM) described later.
  • the first layer may have a stacked structure including a plurality of sublayers. In this case, the number of sublayers is preferably 2 to 30. Moreover, each sublayer may have the same composition or a different composition.
  • the first layer contains silicon, oxygen and carbon.
  • the first layer according to the present invention contains carbon atoms in addition to silicon atoms and oxygen atoms.
  • the presence of silicon atoms and oxygen atoms can impart gas barrier properties
  • the presence of carbon atoms can impart flexibility to the barrier layer.
  • the permeated water amount measured by the method described in Examples described later is 0. is preferably 1g / (m 2 ⁇ 24h) or less, and more preferably 0.01g / (m 2 ⁇ 24h) or less.
  • the film thickness of the first layer in the “region of 80% or more of the film thickness of the first layer” in the condition (i) is calculated from a distribution curve obtained by “XPS depth profile measurement” described below. It refers to the “film thickness of the first layer”.
  • the “film thickness of the first layer calculated from the distribution curve obtained by XPS depth profile measurement” is the depth from the surface of the first layer in the silicon distribution curve (at%) and the carbon distribution curve (at%).
  • a point P where the silicon atomic ratio changes by ⁇ 0.5 at% / nm or more and the carbon atomic ratio changes by +1.0 at% or more is defined as the first layer. It is defined as the interface with the lower layer, and the distance from the surface to the interface is defined as “the film thickness of the first layer calculated from the distribution curve obtained by XPS depth profile measurement”.
  • the etching time generally correlates with the distance (L) from the surface of the first layer in the film thickness direction of the first layer.
  • the silicon distribution curve, oxygen distribution curve, carbon distribution curve and carbon / oxygen distribution curve were prepared under the following measurement conditions.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): SiO 2 equivalent film thickness of the barrier film ⁇ 20 nm
  • X-ray photoelectron spectrometer Model “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 plot position is defined by the number of counter rolls that pass (etching interval below).
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value) (data plot interval): SiO 2 equivalent film thickness of the barrier film ⁇ 10 ⁇ TR number (number of opposing rolls) (nm)
  • X-ray photoelectron spectrometer Model “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 film having the first layer having a small interval between adjacent extreme values that is, a rapid change in the composition of the film, has a remarkable decrease in gas barrier performance under high temperature and high humidity conditions.
  • a film comprising a first layer (the second layer is a layer having an extreme interval larger than the extreme interval in the first layer of the film of the present invention) Gas barrier performance at high temperature and high humidity is good.
  • the interval between at least one set of adjacent extreme values is a value proportional to the conveyance speed of the base material when the apparatus shown in FIG. Specifically, when the conveyance speed of the base material is increased, the interval between adjacent extreme values tends to be shortened. In consideration of a realistic conveyance speed, the interval between at least one set of adjacent extreme values is 1 nm or more.
  • the maximum value in the carbon / oxygen distribution curve is a point where the value of the atomic ratio of carbon atoms to oxygen atoms (C / O) changes from increasing to decreasing when the distance from the surface of the first layer is changed. That means. Further, the minimum value in the carbon / oxygen distribution curve is that the value of the atomic ratio (C / O) of the carbon to oxygen element changes from decreasing to increasing when the distance from the surface of the first layer is changed. I mean.
  • the film thickness (nm) measured by the film thickness measurement method by observation with a transmission electron microscope (TEM) described in the examples described later is divided by the number of extreme values of the carbon / oxygen distribution curve.
  • the measured value (hereinafter referred to as “film thickness (nm) by TEM / number of extreme values”) is preferably 20 (nm / number) or less. This value indicates the relationship between the film thickness and the extreme value. For example, when the film thickness is the same and the number of extreme values on one side is larger, the first layer having the larger number of extreme values is more The extreme value interval is smaller than that of the other first layer.
  • TEM transmission electron microscope
  • film thickness (nm) by TEM / number of extreme values A value obtained by dividing the film thickness (nm) measured by the film thickness measurement method by observation by the number of extreme values of the carbon / oxygen distribution curve (hereinafter referred to as “film thickness (nm) by TEM / number of extreme values”), This is a form having a requirement of 20 (nm / number) or less.
  • the carbon distribution curve preferably has at least two extreme values, preferably has at least three extreme values, and more preferably has at least five extreme values.
  • the carbon distribution curve has at least two extreme values, the carbon atom ratio continuously changes with a concentration gradient, and the gas barrier performance during bending is enhanced.
  • the “extreme value” in the carbon distribution curve means the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the maximum or minimum value of carbon atoms in the carbon distribution curve. That means.
  • the maximum value in the carbon distribution curve means that when the distance from the surface of the first layer is changed, the value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms decreases from an increase.
  • the minimum value in the carbon distribution curve means that when the distance from the surface of the first layer is changed, the value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms increases from a decrease. It refers to a changing point.
  • the oxygen distribution curve of the first layer preferably has at least one extreme value, more preferably at least two extreme values, more preferably at least three extreme values, and at least five extreme values. It is particularly preferred to have When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved.
  • the upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the thickness of the barrier layer, and it cannot be defined unconditionally.
  • the “extreme value” in the oxygen distribution curve is the distance (L) from the surface of the first layer in the film thickness direction of the first layer, and the maximum or minimum value of oxygen atoms in the oxygen distribution curve. That means.
  • the maximum value in the oxygen distribution curve means that when the distance from the surface of the first layer is changed, the value of the oxygen atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms decreases from an increase. A point that changes.
  • the minimum value in the oxygen distribution curve means that when the distance from the surface of the first layer is changed, the value of the oxygen atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms increases from a decrease. A point that changes.
  • the total amount of carbon and oxygen atoms in the film thickness direction of the first layer is substantially constant.
  • the 1st layer exhibits moderate flexibility, and the crack generation at the time of bending of a gas barrier film can be controlled and prevented more effectively.
  • the absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the distribution curve (hereinafter simply referred to as “OC max ⁇ OC”). preferably also referred min difference ”) is less than 5at%, more preferably less than 4at%, more preferably less than 3at%.
  • the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is further improved.
  • the lower limit of the OC max -OC min difference since preferably as OC max -OC min difference is small, but is 0 atomic%, it is sufficient if more than 0.1 at%.
  • the first layer is substantially uniform in the film surface direction (direction parallel to the surface of the first layer). It is preferable that the fact that the first layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon distribution curve are measured at any two measurement points on the film surface of the first layer by XPS depth profile measurement.
  • the oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the maximum value of the atomic ratio of carbon in each carbon distribution curve And the absolute value of the difference between the minimum values is the same as each other or within 5 at%.
  • the carbon distribution curve is substantially continuous.
  • the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously.
  • the carbon distribution curve is calculated from the etching rate and the etching time. Satisfying the condition expressed by the following formula (1) in the relationship between the distance from the surface in the film thickness direction (x, unit: nm) and the atomic ratio of carbon (C, unit: at%). Say.
  • the plasma CVD method is not particularly limited, but the plasma CVD method at or near atmospheric pressure described in International Publication No. 2006/033233 (corresponding to US Patent Application Publication No. 2008/085418), counter roll electrode And a plasma CVD method using a plasma CVD apparatus having In particular, since the productivity is high, it is preferable to form the first layer by a plasma CVD method using a plasma CVD apparatus having a counter roll electrode.
  • the plasma CVD method may be a Penning discharge plasma type plasma CVD method.
  • plasma discharge is generated in a space between a plurality of film forming rollers.
  • a pair of film forming rollers is used, and each of the pair of film forming rollers has a base material (herein, the base material is treated with the base material, or an intermediate layer is formed on the base material). It is more preferable that a plasma is generated by disposing between the pair of film forming rollers.
  • the gas barrier film according to the present invention forms the first layer on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity.
  • an apparatus that can be used when manufacturing the barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair of film forming processes. It is preferable that the apparatus has a configuration capable of discharging between rollers. For example, when the manufacturing apparatus shown in FIG. 1 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible.
  • FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the first layer according to the present invention.
  • the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.
  • the manufacturing apparatus 13 shown in FIG. 1 includes a delivery roller 14, transport rollers 15, 16, 17, 18, film formation rollers 19, 20, a gas supply pipe 21, a plasma generation power source 22, and a film formation roller 19. And 20 are provided with magnetic field generators 23 and 24 and winding rollers 25. Further, in such a manufacturing apparatus, at least the film forming rollers 19 and 20, the gas supply pipe 21, the plasma generating power source 22, and the magnetic field generating apparatuses 23 and 24 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 13, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.
  • each film-forming roller has a power source for generating plasma so that the pair of film-forming rollers (film-forming roller 19 and film-forming roller 20) can function as a pair of counter electrodes. 22 is connected. Therefore, in such a manufacturing apparatus 13, it is possible to discharge to the space between the film forming roller 19 and the film forming roller 20 by supplying electric power from the plasma generating power source 22, thereby Plasma can be generated in the space between the film roller 19 and the film formation roller 20.
  • the material and design may be changed as appropriate so that the film-forming roller 19 and the film-forming roller 20 can also be used as electrodes.
  • the pair of film forming rollers (film forming rollers 19 and 20) be arranged so that their central axes are substantially parallel on the same plane.
  • the film forming rate can be doubled as compared with a normal plasma CVD method that does not use a roller, and the structure is the same. Since the film can be formed, the extreme value in the carbon distribution curve can be at least doubled.
  • the base material 12 on the surface of the base material 12 (here, the base material includes a form in which the base material is processed or has an intermediate layer on the base material) by the CVD method.
  • the first layer 26 can be formed on the film forming roller 19 while the first layer component is deposited on the surface of the base material 12 on the film forming roller 19 and also on the film forming roller 20. Since the first layer component can also be deposited on the surface, the barrier layer can be efficiently formed on the surface of the substrate 12.
  • magnetic field generators 23 and 24 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.
  • the magnetic field generators 23 and 24 provided on the film forming roller 19 and the film forming roller 20 respectively are a magnetic field generator 23 provided on one film forming roller 19 and a magnetic field generator provided on the other film forming roller 20. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between the magnetic field generators 24 and the magnetic field generators 23 and 24 form a substantially closed magnetic circuit.
  • the magnetic field generators 23 and 24 provided on the film forming roller 19 and the film forming roller 20 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generating device 23 and the other magnetic field generating device. It is preferable to arrange the magnetic poles so that the magnetic poles facing 24 have the same polarity.
  • the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 23 and 24 are opposed.
  • a racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained.
  • the material 12 is excellent in that the first layer 26 which is a vapor deposition film can be efficiently formed.
  • the film forming roller 19 and the film forming roller 20 known rollers can be appropriately used. As such film forming rollers 19 and 20, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently.
  • the diameters of the film forming rollers 19 and 20 are preferably in the range of 300 to 1000 mm ⁇ , particularly in the range of 300 to 700 mm ⁇ , from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mm ⁇ or more, the plasma discharge space will not be reduced, so that the productivity is not deteriorated, and it is possible to avoid applying the total amount of plasma discharge to the substrate 12 in a short time. It is preferable because damage to the material 12 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mm ⁇ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.
  • the base material 12 is disposed on a pair of film forming rollers (the film forming roller 19 and the film forming roller 20) so that the surfaces of the base material 12 face each other.
  • the base material 12 By disposing the base material 12 in this way, when the plasma is generated by performing discharge in the facing space between the film forming roller 19 and the film forming roller 20, the base existing between the pair of film forming rollers is present.
  • Each surface of the material 12 can be formed simultaneously. That is, according to such a manufacturing apparatus, the barrier layer component is deposited on the surface of the substrate 12 on the film forming roller 19 by the plasma CVD method, and the barrier layer component is further deposited on the film forming roller 20. Therefore, the barrier layer can be efficiently formed on the surface of the substrate 12.
  • the feed roller 14 and the transport rollers 15, 16, 17, 18 used in such a manufacturing apparatus known rollers can be used as appropriate.
  • the winding roller 25 is not particularly limited as long as the gas barrier film 11 having the first layer 26 formed on the substrate 12 can be wound, and a known roller is appropriately used. be able to.
  • gas supply pipe 21 and the vacuum pump those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used.
  • the gas supply pipe 21 serving as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 19 and the film formation roller 20 and is a vacuum serving as a vacuum exhaust means.
  • a pump (not shown) is preferably provided on the other side of the facing space. In this way, by providing the gas supply pipe 21 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 19 and the film formation roller 20. It is excellent in that the film formation efficiency can be improved.
  • the magnetic field generators 23 and 24 known magnetic field generators can be used as appropriate.
  • the base material 12 in addition to the base material used in the present invention, a material in which the first layer 26 is formed in advance can be used. As described above, by using the substrate 12 in which the first layer 26 is formed in advance, the thickness of the first layer 26 can be increased.
  • the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the conveyance of the film (base material) By appropriately adjusting the speed, the first layer according to the present invention can be produced. That is, using the manufacturing apparatus 13 shown in FIG. 1, discharge is generated between a pair of film forming rollers (film forming rollers 19 and 20) while supplying a film forming gas (raw material gas or the like) into the vacuum chamber.
  • the distance between the extreme values of the first layer (the surface of the first barrier layer in the film thickness direction of the first layer at one extreme value of the carbon / oxygen distribution curve and the extreme value adjacent to the extreme value) (The absolute value of the difference in distance (L) from) can be adjusted by the rotation speed of the film forming rollers 19 and 20 (the conveyance speed of the substrate).
  • the substrate 12 is transported by the delivery roller 14 and the film formation roller 19, respectively, so that the surface of the substrate 12 is formed by a roll-to-roll continuous film formation process.
  • First layer 26 is formed.
  • a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more.
  • the source gas in the film forming gas used for forming the first layer 26 can be appropriately selected and used according to the material of the first layer 26 to be formed.
  • a source gas for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used.
  • organosilicon compounds examples include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane.
  • HMDSO hexamethyldisiloxane
  • HMDS hexamethyldisilane
  • 1,1,3,3-tetramethyldisiloxane vinyltrimethylsilane
  • methyltrimethylsilane hexamethyldisilane.
  • Methylsilane dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • phenyltrimethoxysilane methyltriethoxy
  • Examples include silane and octamethylcyclotetrasiloxane.
  • hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting barrier layer.
  • organosilicon compounds can be used alone or in combination of two or more.
  • organic compound gas containing carbon examples include methane, ethane, ethylene, and acetylene.
  • an appropriate source gas is selected according to the type of the first layer 26.
  • a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • carrier gas and discharge gas known ones can be used as appropriate, for example, rare gases such as helium, argon, neon and xenon; hydrogen; nitrogen can be used.
  • the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not making the ratio of the reaction gas excessive, it is excellent in that excellent barrier properties and bending resistance can be obtained by the first layer 26 to be formed. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.
  • hexamethyldisiloxane organosilicon compound, HMDSO, (CH 3 ) 6 Si 2 O
  • oxygen (O 2 ) oxygen
  • the preferred ratio of the raw material gas to the reactive gas in the film forming gas will be described in more detail.
  • a film-forming gas containing hexamethyldisiloxane (HMDSO, (CH 3 ) 6 Si 2 O) as a source gas and oxygen (O 2 ) as a reactive gas is reacted by plasma CVD to form a silicon-oxygen-based system
  • HMDSO, (CH 3 ) 6 Si 2 O hexamethyldisiloxane
  • O 2 oxygen
  • the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, a uniform silicon dioxide film is formed when oxygen is contained in the film forming gas in an amount of 12 moles or more per mole of hexamethyldisiloxane and a uniform silicon dioxide film is formed (a carbon distribution curve exists). Therefore, the first layer that satisfies the above conditions (i) and (ii) cannot be formed. Therefore, in the present invention, when the first layer is formed, the amount of oxygen is set to the stoichiometric amount with respect to 1 mol of hexamethyldisiloxane so that the reaction of the reaction formula (1) does not proceed completely.
  • the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced.
  • the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material.
  • the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. .
  • the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.
  • the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.
  • an electrode drum in this embodiment, the film forming roller 19 connected to the plasma generating power source 22 for discharging between the film forming roller 19 and the film forming roller 20.
  • the power to be applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed, and if it is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the substrate during film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.
  • the conveyance speed (line speed) of the substrate 12 can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 5 to 100 m / min.
  • a preferable manufacturing method of the present invention includes a step of forming a first layer containing silicon, oxygen, and carbon by conveying a substrate to a plasma CVD apparatus having a counter roll electrode at a conveyance speed of 1 m / min or more. And a step of forming a second layer containing an inorganic oxide by an atomic layer deposition method.
  • the first layer is formed by plasma CVD using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is characterized by.
  • This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode.
  • Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.
  • an atmospheric pressure plasma discharge treatment apparatus of a method of treating a substrate between opposed electrodes described in FIG. 4 of International Publication No. 2006/033233 (corresponding to US Patent Application Publication No. 2008/085418). It can.
  • Other examples of the atmospheric pressure plasma discharge treatment apparatus include Japanese Patent Application Laid-Open No. 2004-68143, Japanese Patent Application Laid-Open No. 2003-49272, and International Application Publication No. 02/48428 (corresponding to US Patent Application Publication No. 2003/082412). .
  • FIG. 2 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus that treats a substrate between counter electrodes that is useful when forming the first layer of the present invention.
  • a method of changing the gap between the electrodes by tilting the fixed electrode group with respect to the roll rotating electrode, or The first layer can be obtained by appropriately selecting the type and supply amount of the film forming raw material to be supplied or the output conditions at the time of plasma discharge.
  • a first filter 43 is installed between the roll rotation electrode (first electrode) 35 and the first power supply 41, and the first filter 43 easily passes a current from the first power supply 41 to the first electrode.
  • the current from the second power supply 42 is grounded so that the current from the second power supply 42 to the first power supply is difficult to pass.
  • a second filter 44 is provided between the square tube type fixed electrode group (second electrode) 36 and the second power source 42, and the second filter 44 is connected to the second electrode from the second power source 42. It is designed so that the current from the first power supply 41 is grounded and the current from the first power supply 41 to the second power supply is difficult to pass.
  • the roll rotation electrode 35 may be the second electrode, and the rectangular tube-shaped fixed electrode group 36 may be the first electrode.
  • the first power source is connected to the first electrode, and the second power source is connected to the second electrode.
  • the first power supply preferably applies a higher high-frequency electric field strength (V 1 > V 2 ) than the second power supply. Further, the frequency has the ability to satisfy ⁇ 1 ⁇ 2 .
  • the current is preferably I 1 ⁇ I 2 .
  • the current I 1 of the first high-frequency electric field is preferably 0.3 mA / cm 2 to 20 mA / cm 2 , more preferably 1.0 mA / cm 2 to 20 mA / cm 2 .
  • the current I 2 of the second high-frequency electric field is preferably 10 mA / cm 2 to 100 mA / cm 2 , more preferably 20 mA / cm 2 to 100 mA / cm 2 .
  • the gas G generated by the gas generator 51 of the gas supply means 50 is introduced into the plasma discharge treatment vessel 31 from the air supply port while controlling the flow rate.
  • a medium whose temperature is adjusted by the electrode temperature adjusting means 60 is used as a liquid feed pump. P is sent to both electrodes through the pipe 61, and the temperature is adjusted from the inside of the electrode.
  • Reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.
  • source gas As the film forming gas (source gas etc.) supplied from the gas generator 51 to the counter electrode (discharge space) 32, source gas, reaction gas, carrier gas, discharge gas are used alone or in combination of two or more. Can be used.
  • the source gas, reaction gas, carrier gas, or discharge gas used in this case is described in the column of (1) Method for forming the first layer by plasma CVD using a plasma CVD apparatus having a counter roll electrode. The gas used can be used as appropriate.
  • Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500 A2 Shinko Electric Co., Ltd. 5kHz SPG5-4500 A3 Kasuga Electric 15kHz AGI-023 A4 Shinko Electric 50kHz SPG50-4500 A5 HEIDEN Laboratory 100kHz * PHF-6k A6 Pearl Industry 200kHz CF-2000-200k A7 Pearl Industry 400kHz CF-2000-400k And the like, and any of them can be used.
  • * indicates a HEIDEN Laboratory impulse high-frequency power source (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave. It is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.
  • the power applied between the electrodes facing each other supplies power (power density) of 1 W / cm 2 or more to the second electrode (second high-frequency electric field), excites the discharge gas to generate plasma, and the energy is thinned.
  • a thin film is formed by applying the forming gas.
  • the upper limit value of the power supplied to the second electrode is preferably 50 W / cm 2 , more preferably 20 W / cm 2 .
  • the lower limit is preferably 1.2 W / cm 2 .
  • discharge area (cm ⁇ 2 >) points out the area of the range which discharge occurs in an electrode.
  • the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved.
  • it is 5 W / cm 2 or more.
  • the upper limit value of the power supplied to the first electrode is preferably 50 W / cm 2 .
  • the waveform of the high-frequency electric field is not particularly limited.
  • a continuous sine wave continuous oscillation mode called a continuous mode
  • an intermittent oscillation mode called ON / OFF intermittently called a pulse mode
  • the second electrode side second
  • the high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.
  • controlling the film quality it can be achieved by controlling the electric power on the second power source side.
  • An electrode used for such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance.
  • Such an electrode is preferably a metal base material coated with a dielectric.
  • the first layer can also be formed by a vacuum plasma apparatus as described in US Pat. No. 7,015,640.
  • the second layer contains an inorganic oxide and is formed by an atomic layer deposition method (ALD method).
  • the ALD method is a method of depositing atomic layers layer by layer by alternately introducing two or more kinds of gases (first gas and second gas) onto a substrate. More specifically, first, a first gas (raw material gas) is introduced onto a substrate to form a gas molecular layer (monoatomic layer). Next, the first gas is purged (removed) by introducing an inert gas (purge gas). Note that the gas molecule layer of the formed first gas is not purged even when an inert gas is introduced by chemical adsorption. Next, an inorganic film is formed by oxidizing the gas molecule layer formed by introducing a second gas (for example, an oxidizing gas).
  • a second gas for example, an oxidizing gas
  • the second gas is purged by introducing an inert gas, and one cycle of the ALD method is completed.
  • the atomic layers are deposited one by one, and the first gas barrier layer having a predetermined film thickness can be formed.
  • the ALD method can form an inorganic film including a shaded portion regardless of unevenness on the surface of the substrate.
  • Film formation temperature requires activation of the substrate surface for adsorption of gas molecules to the substrate.
  • the film forming temperature is preferably high to some extent, and may be appropriately adjusted within a range not exceeding the glass transition temperature or decomposition start temperature of the plastic substrate as the base material.
  • the temperature in the reactor is usually about 50 to 200 ° C.
  • the deposition rate for one cycle is usually 0.01 to 0.3 nm, and a desired film thickness is obtained by repeating the film forming cycle.
  • the aluminum compound is not particularly limited as long as it contains aluminum and can be vaporized.
  • Specific examples of the aluminum compound include trimethylaluminum (TMA), triethylaluminum (TEA), and trichloroaluminum.
  • the source gas may be appropriately selected depending on the inorganic oxide film to be formed.
  • Ritala Appl. Surf. Sci. 112, 223 (1997) can be used.
  • the first gas is a gas obtained by vaporizing a silicon compound. Examples of such silicon compounds include monochlorosilane (SiH 3 Cl, MCS), hexachlorodisilane (Si 2 Cl 6 , HCD), tetrachlorosilane (SiCl 4 , STC), and trichlorosilane (SiHCl 3 , TCS).
  • Inorganic raw materials such as chlorosilane, trisilane (Si 3 H 8 , TS), disilane (Si 2 H 6 , DS), monosilane (SiH 4 , MS), and aminosilane tetrakisdimethylaminosilane (Si [N (CH 3 ) 2] 4,4DMAS), tris (dimethylamino) silane (Si [N (CH 3) 2] 3 H, 3DMASi), bis diethylamino silane (Si [N (C 2 H 5) 2] 2 H 2, 2DEAS), Bicester tert-butylamino silane (SiH 2 [NH (C 4 H 9)] 2, B BAS) and the like.
  • chlorosilane such as chlorosilane, trisilane (Si 3 H 8 , TS), disilane (Si 2 H 6 , DS), monosilane (SiH 4 , MS), and aminosilane tetraki
  • the first gas is a gas obtained by vaporizing a titanium compound.
  • titanium compounds include titanium tetrachloride (TiCl 4) , titanium (IV) isopropoxide (Ti [(OCH) (CH 3 ) 2 ] 4 ), tetrakisdimethylamino titanium ([(CH 3 ) 2 N ] 4 Ti, TDMATi), tetrakis (diethylamino) titanium (Ti [N (CH 2 CH 3) 2] 4, TDEATi) and the like.
  • the first gas is a gas obtained by vaporizing a zirconium compound.
  • zirconium compounds include tetrakisdimethylaminozirconium (IV); [(CH 3 ) 2 N] 4 Zr and the like.
  • the oxidizing gas is not particularly limited as long as it can oxidize a gas molecular layer.
  • ozone (O 3 ), water (H 2 O), hydrogen peroxide (H 2 O 2 ), methanol (CH 3 OH), and ethanol (C 2 H 5 OH) and the like can be used.
  • oxygen radicals it is possible to generate high-density oxygen radicals by exciting the gas using a high-frequency power source (for example, a power source having a frequency of 13.56 MHz), which further promotes oxidation and nitridation reactions. be able to.
  • ICP Inductively Coupled Plasma
  • a preferred embodiment according to the manufacturing method of the present invention is a method of forming the second layer by an atomic layer deposition method using water or ozone as an oxidizing agent at least from the surface of the first layer to the stacking direction of 5 nm. .
  • nitrogen radicals can be used when nitrides and nitride oxides are desired. Nitrogen radicals can be generated in the same manner as the oxygen radical generation described above.
  • the inert gas a rare gas (helium, neon, argon, krypton, xenon), nitrogen gas or the like can be used.
  • the introduction time of the first gas is 0.05 to It is preferably 10 seconds, more preferably 0.1 to 3 seconds, and further preferably 0.5 to 2 seconds. It is preferable for the introduction time of the first gas to be 0.05 seconds or longer because sufficient time for forming the gas molecular layer can be secured. On the other hand, when the introduction time of the first gas is 10 seconds or less, it is preferable because the time required for one cycle can be reduced.
  • the introduction time of the inert gas for purging the first gas is preferably 0.05 to 10 seconds, more preferably 0.5 to 6 seconds, and 1 to 4 seconds. More preferably. It is preferable that the introduction time of the inert gas is 0.05 seconds or longer because the first gas can be sufficiently purged. On the other hand, when the introduction time of the inert gas is 10 seconds or less, it is preferable because the time required for one cycle can be reduced and the influence on the formed gas molecular layer is reduced. Further, the introduction time of the second gas is preferably 0.05 to 10 seconds, and more preferably 0.1 to 3 seconds. It is preferable for the introduction time of the second gas to be 0.05 seconds or longer because sufficient time for oxidizing the gas molecular layer can be secured.
  • the introduction time of the second gas is 10 seconds or less, the time required for one cycle can be reduced, and side reactions can be prevented.
  • the introduction time of the inert gas for purging the second gas is preferably 0.05 to 10 seconds. It is preferable that the introduction time of the inert gas is 0.05 seconds or longer because the second gas can be sufficiently purged. On the other hand, an inert gas introduction time of 10 seconds or less is preferable because the time required for one cycle can be reduced and the influence on the formed atomic layer is small.
  • the second layer may be formed using a roll-to-roll film forming apparatus.
  • the film can be continuously produced by the roll-to-roll method. Therefore, when the second layer is formed using a roll-to-roll film forming apparatus, productivity is improved. Improved and preferred.
  • apparatuses described in US Patent Application Publication No. 2007/0224348 and US Patent Application Publication No. 2008/0026162 can be used.
  • the formation of the second layer by the roll-to-roll method as described in JP 2010-541242 (US Patent Application Publication No. 2009/081886) and the like, as shown in FIG. 3 and FIG.
  • An apparatus can also be used.
  • the substrate 82 on which the first layer and other layers are laminated if necessary
  • the take-up roller 81 It is done.
  • the second layer is formed by the gas supplied from the coating head.
  • the base material 84 (with the first layer and other layers laminated if necessary) is unwound from the feed roller 83, and the base material is guided by the guide roll 85. Then, it is supplied onto the MR (main roll) 86. A coating head 87 is disposed on the MR, and the substrate 84 is exposed to a gas supplied from the coating head. The temperature of the substrate 84 is appropriately adjusted by the temperature adjusting means 90 before being supplied to the coating head. Next, the base material 84 on which the second layer is formed passes through the guide roll 88 and is taken up by the take-up roller-89.
  • a stepped roll as disclosed in JP-A-2009-256709 may be used so as to be in contact with the film formation surface (barrier surface) and the water vapor transmission rate is not deteriorated.
  • an adhesive protective film is attached to the film-forming surface before winding with a winding roller or a protective layer is provided, damage during winding will occur. Is more preferable (“protective film winding” shown in FIGS. 3 and 4).
  • by providing an adhesive protective film it helps to protect the gas barrier film surface from damage, and is easy to install on an object to which the gas barrier film is applied.
  • the adhesive protective film is not particularly limited as long as it can be applied to a gas barrier film, and conventionally known ones can be used.
  • acrylic resin, urethane resin, epoxy resin, polyester resin, melamine resin, phenol resin, polyamide, Those formed of a ketone resin, a vinyl resin, a hydrocarbon resin or the like can be used.
  • FIG. 5 is a schematic diagram showing an example of a coating head for ALD film formation used in the apparatus shown in FIGS.
  • the coating head 70 includes a source gas supply device 71 that supplies a source gas, an inert gas supply device 72 that supplies an inert gas, a second gas supply device that supplies a second gas, and a gas.
  • An introduction pipe 74 and an exhaust pipe 75 are provided.
  • the substrate 76 (laminated with the first layer and other layers if necessary) is conveyed in the A to B directions.
  • the source gas is supplied from the first gas (source gas) supply device 71 through the gas introduction pipe 74 to the base material.
  • the supplied gas is then exhausted through the exhaust pipe 75.
  • an inert gas is introduced into the base material 76 from the inert gas supply device 72 and the source gas is purged (removed).
  • the second gas is introduced from the second gas (for example, oxidizing gas) supply device 73 through the gas introduction pipe 74 to form an inorganic film.
  • the inert gas is introduced from the inert gas supply device 72 to purge the second gas, and one cycle of the ALD method is completed.
  • the inert gas and the second gas are exhausted through the exhaust pipe before the gas supply in the next step.
  • the source gas and the second gas may be supplied after being mixed with an inert gas (carrier gas) (see FIGS. 3 and 4).
  • an inert gas carrier gas
  • an ALD film can be formed with high productivity.
  • the thickness of the second layer is preferably 1 to 100 nm, and more preferably 10 to 50 nm.
  • the film thickness of the second layer is 1 nm or more, the effect of the ALD layer such as repair of fine defects is appropriately obtained, and in view of the ALD film forming speed, it is preferably 100 nm or less from the viewpoint of productivity.
  • the gas barrier performance of the second layer alone may not be high because the gas barrier performance of the first layer is high. Therefore, the gas barrier performance of the second layer is such that the amount of permeated moisture measured by the method described in Examples below in the laminate in which the second layer is formed on the substrate is 0.5 g / (m 2 ⁇ 24 h) or less, and more preferably 0.1 g / (m 2 ⁇ 24 h) or less.
  • the gas barrier film of the present invention usually uses a plastic film as a substrate.
  • the plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold the barrier laminate, and can be appropriately selected depending on the purpose of use and the like.
  • Specific examples of the plastic film include polyester resins such as polyethylene terephthalate, methacrylic resins, methacrylic acid-maleic acid copolymers, polystyrene resins, transparent fluororesins, polyimides, fluorinated polyimide resins, polyamide resins, and polyamideimide resins.
  • thermoplastic resins such as resins, alicyclic modified polycarbonate resins, fluorene ring modified polyester resins, and acryloyl compounds.
  • the base material is preferably made of a heat-resistant material. Specifically, a resin base material having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and Tg of 100 ° C. or more and 300 ° C. or less is used.
  • the plastic film of the present invention can be used as a device such as an organic EL element
  • the plastic film is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
  • the thickness of the plastic film used for the gas barrier film of the present invention is not particularly limited because it is appropriately selected depending on the use, but is typically 1 to 800 ⁇ m, preferably 10 to 200 ⁇ m.
  • These plastic films may have functional layers such as a transparent conductive layer and a smooth layer.
  • As the functional layer in addition to those described above, those described in JP-A 2006-289627, paragraphs 0036 to 0038 (US Patent Application Publication No. 2006/251905, paragraphs 0075 to 0079) are preferably employed. it can.
  • the substrate preferably has a high surface smoothness.
  • the surface smoothness those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.
  • the base material using the above-described resins or the like may be an unstretched film or a stretched film.
  • An intermediate layer may be separately provided on the substrate, the first layer, and the second interlayer or the surface as long as the effects of the present invention are not impaired.
  • the intermediate layer may be inorganic, organic, or a hybrid structure thereof, and an intermediate layer can be provided for the purpose of improving the gas barrier property or the like for improving the adhesion between the first layer and the second layer.
  • the gas barrier film may have a curable resin layer formed by curing a curable resin on a substrate.
  • the curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material with an active energy ray such as ultraviolet ray to be cured is heated.
  • the thermosetting resin etc. which are obtained by curing by the above method.
  • Such a curable resin layer is at least one of (1) smoothing the surface of the substrate, (2) relieving the stress of the upper layer to be laminated, and (3) improving the adhesion between the substrate and the upper layer. Has one function. For this reason, the curable resin layer may also be used as a smooth layer and an anchor coat layer (easy adhesion layer) described later.
  • the active energy ray-curable material examples include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene
  • examples thereof include compositions containing polyfunctional acrylate monomers such as glycol acrylate and glycerol methacrylate.
  • OPSTAR registered trademark
  • JSR Corporation JSR Corporation. It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no particular limitation.
  • thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nittobo Co., Ltd.
  • thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydrin Butter, and the like can be mentioned.
  • the method of forming the curable resin layer is not particularly limited, but a coating liquid containing a curable material is applied to a spin coating method, a spray method, a blade coating method, a dipping method, a gravure printing method or other wet coating method, or a vapor deposition method.
  • a coating film is formed, and then the coating is performed by irradiation with active energy rays such as visible light, infrared rays, ultraviolet rays, X rays, ⁇ rays, ⁇ rays, ⁇ rays, electron rays and / or heating.
  • active energy rays such as visible light, infrared rays, ultraviolet rays, X rays, ⁇ rays, ⁇ rays, ⁇ rays, electron rays and / or heating.
  • a method of forming the film by curing is preferred.
  • an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm.
  • a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator can be used.
  • Solvents used when forming a curable resin layer using a coating solution in which a curable material is dissolved or dispersed in a solvent include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, and the like.
  • the curable resin layer can contain additives such as a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a plasticizer as necessary in addition to the above-described materials.
  • additives such as a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a plasticizer as necessary in addition to the above-described materials.
  • an appropriate resin or additive may be used for improving the film formability and preventing the occurrence of pinholes in the film.
  • the thickness of the curable resin layer is not particularly limited, but is preferably in the range of 0.1 to 10 ⁇ m.
  • the gas barrier film may have a primer layer (smooth layer) on the surface of the substrate having the barrier layer.
  • the primer layer is provided for flattening the rough surface of the substrate on which protrusions and the like exist.
  • Such a primer layer is basically formed by curing an active energy ray-curable material or a thermosetting material.
  • the primer layer may basically have the same configuration as the curable resin layer as long as it has the above-described function.
  • the examples of the active energy ray-curable material and the thermosetting material, and the method for forming the primer layer are the same as those described in the column of the curable resin layer, and thus the description thereof is omitted here.
  • the smooth layer may be used as the following anchor coat layer.
  • an anchor coat layer may be formed as an easy-adhesion layer for the purpose of improving adhesion (adhesion) with the barrier layer.
  • the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One or two or more can be used in combination.
  • a commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” 3% isopropyl alcohol solution) can be used.
  • the above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do.
  • the application amount of the anchor coating agent is preferably about 0.1 to 5 g / m 2 (dry state).
  • a commercially available base material with an easy-adhesion layer may be used.
  • the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition.
  • a vapor phase method such as physical vapor deposition or chemical vapor deposition.
  • an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.
  • the thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 ⁇ m.
  • a bleed-out prevention layer In the gas barrier film of the present invention, a bleed-out prevention layer can be provided.
  • the purpose of the bleed-out prevention layer is to suppress the phenomenon in which unreacted oligomers migrate from the film base material to the surface when the film having the curable resin layer / smooth layer is heated and contaminate the contact surface. And provided on the opposite surface of the substrate having the curable resin layer / smooth layer.
  • the bleed-out prevention layer may basically have the same configuration as the curable resin layer / smooth layer as long as it has this function.
  • the hard coat agent that can be included in the bleed-out prevention layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated in the molecule. Examples thereof include monounsaturated organic compounds having a group.
  • Matting agents may be added as other additives.
  • the matting agent inorganic particles having an average particle diameter of about 0.1 to 5 ⁇ m are preferable.
  • inorganic particles one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .
  • the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.
  • the bleed-out prevention layer as described above is prepared as a coating solution by blending a hard coat agent and other components as necessary, and appropriately using a diluting solvent as necessary.
  • After coating by a conventionally known coating method it can be formed by irradiating with ionizing radiation and curing.
  • ionizing radiation ultraviolet rays emitted from an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, etc. are preferably irradiated in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm.
  • the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.
  • the thickness of the bleed-out preventing layer in the present invention is 1 to 10 ⁇ m, preferably 2 to 7 ⁇ m. By making it 1 ⁇ m or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 ⁇ m or less, it becomes easy to adjust the balance of optical properties of the smooth film, and the curable resin layer / smooth layer is transparent. When it is provided on one surface of the polymer film, curling of the gas barrier film can be easily suppressed.
  • the substrate is transferred to a plasma CVD apparatus having a counter roll electrode at a transfer speed of 1 m / min or more and contains silicon, oxygen and carbon.
  • a method for producing a gas barrier film comprising: forming a layer; and forming a second layer containing an inorganic oxide by an atomic layer deposition method.
  • the atomic deposition method it is more preferable to use at least water or ozone as the oxidizing agent. Since water or ozone rarely has a physical influence on the first layer, micro defects or the like are rarely generated in the lower layer.
  • a preferred embodiment according to the manufacturing method of the present invention is an atomic layer deposition method using water or ozone as an oxidizing agent at least from the surface of the first layer to the stacking direction of 5 nm in the step of forming the second layer. This is a method of forming two layers. Details of each step are as described above for each layer.
  • the gas barrier film of the present invention as described above has excellent gas barrier properties, transparency, and flexibility. Therefore, the gas barrier film of the present invention is a gas barrier film used for electronic devices such as packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various purposes such as an electronic device using the same.
  • packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various purposes such as an electronic device using the same.
  • the electronic element main body is the main body of the electronic device, and is disposed on the gas barrier film side according to the present invention.
  • a known electronic device body to which sealing with a gas barrier film can be applied can be used.
  • an organic EL element, a solar cell (PV), a liquid crystal display element (LCD), electronic paper, a thin film transistor, a touch panel, and the like can be given.
  • the electronic device body is preferably an organic electroluminescence (EL) device or a solar cell.
  • EL organic electroluminescence
  • Organic EL device (Organic EL device) The organic EL element 5 sealed with the gas barrier film 10 in the organic EL panel 9 will be described.
  • FIG. 6 shows an example of an organic EL panel 9 which is an electronic device using the gas barrier film 10 according to the present invention as a sealing film.
  • the organic EL panel 9 is formed on the gas barrier film 10 through the gas barrier film 10, the transparent electrode 4 such as ITO formed on the gas barrier film 10, and the transparent electrode 4.
  • the organic EL element 5 and a counter film 7 disposed via an adhesive layer 6 so as to cover the organic EL element 5 are provided. It can be said that the transparent electrode 4 forms part of the organic EL element 5.
  • the transparent electrode 4 and the organic EL element 5 are formed on the surface of the gas barrier film 10 on which the gas barrier layer is formed.
  • the counter film 7 may be a gas barrier film according to the present invention in addition to a metal film such as an aluminum foil. When a gas barrier film is used as the counter film 7, the surface on which the gas barrier layer is formed may be attached to the organic EL element 5 with the adhesive layer 6.
  • an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • the film thickness of the anode depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • a material having a low work function (4 eV or less) metal referred to as an electron injecting metal
  • an alloy referred to as an electrically conductive compound
  • a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are suitable as the cathode.
  • the film thickness of the cathode is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the light emission luminance is improved, which is convenient.
  • the injection layer includes an electron injection layer and a hole injection layer, and an electron injection layer and a hole injection layer are provided as necessary, between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport. Exist between the layers.
  • An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.
  • Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
  • anode buffer layer hole injection layer
  • JP-A-9-45479 US Pat. No. 5,719,467)
  • JP-A-9-260062 JP-A-8-288069 and the like.
  • a phthalocyanine buffer layer typified by copper phthalocyanine
  • an oxide buffer layer typified by vanadium oxide
  • an amorphous carbon buffer layer a conductive polymer such as polyaniline (emeraldine) or polythiophene was used.
  • Examples include a polymer buffer layer.
  • the cathode buffer layer (electron injection layer) is disclosed in JP-A-6-325871, JP-A-9-17574 (US Pat. No. 5,739,635), JP-A-10-74586 (US Pat. No. 5,776,622). ), Etc., specifically, a metal buffer layer typified by strontium and aluminum, an alkali metal compound buffer layer typified by lithium fluoride, and an alkali typified by magnesium fluoride. Examples thereof include an earth metal compound buffer layer and an oxide buffer layer typified by aluminum oxide.
  • the buffer layer (injection layer) is preferably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 ⁇ m.
  • the light emitting layer in the organic EL element 5 is a layer that emits light by recombination of electrons and holes injected from an electrode (cathode, anode) or an electron transport layer or a hole transport layer, and the light emitting portion is a light emitting layer.
  • the interface between the light emitting layer and the adjacent layer may be used.
  • the light emitting layer of the organic EL element 5 contains a known dopant compound (light emitting dopant) and a host compound (light emitting host). Thereby, the luminous efficiency can be further increased.
  • the light emitting layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.
  • the thickness of the light emitting layer is not particularly limited, but is usually selected in the range of 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the light emitting layer may have a single layer structure in which the dopant compound and the host compound are one kind or two or more kinds, or may have a laminated structure having a plurality of layers having the same composition or different compositions.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
  • the hole transport layer can be provided as a single layer or a plurality of layers.
  • organic EL element 5 a method for producing an organic EL element composed of an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.
  • a desired electrode material for example, a thin film made of an anode material is formed on the gas barrier film 10 so as to have a thickness of 1 ⁇ m or less, preferably 10 to 200 nm, for example, by a method such as vapor deposition, sputtering, or plasma CVD. Then, an anode is produced.
  • an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which are organic EL element materials, is formed thereon.
  • a method for forming this organic compound thin film there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method), etc., but a homogeneous film is easily obtained and pinholes are not easily generated. From the point of view, the vacuum deposition method, the spin coating method, the ink jet method, and the printing method are particularly preferable. Further, different film forming methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁇ 6 to 10 ⁇ 2 Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within a range of 50 nm / second, a substrate temperature of ⁇ 50 to 300 ° C., and a film thickness of 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm, and a cathode is provided.
  • a desired organic EL element can be obtained.
  • the organic EL element 5 is preferably produced from the anode and the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere. In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.
  • the voltage is about 2 to 40 V with the anode as the positive and the cathode as the negative polarity. Luminescence can be observed by applying.
  • An alternating voltage may be applied.
  • the alternating current waveform to be applied may be arbitrary.
  • Example 1 Production of gas barrier film (Production of gas barrier film 1) ⁇ Preparation of sample> (Base material) A 125 ⁇ m thick polyester film (manufactured by Teijin DuPont Films Ltd., extremely low heat yield PET Q83), which is a thermoplastic resin and is easily bonded on both sides, was used as a base material.
  • Base material A 125 ⁇ m thick polyester film (manufactured by Teijin DuPont Films Ltd., extremely low heat yield PET Q83), which is a thermoplastic resin and is easily bonded on both sides, was used as a base material.
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied to one side of the substrate, and after applying with a die coater so that the film thickness after drying was 4 ⁇ m, drying conditions: 80 ° C., After drying for 3 minutes, curing was performed in air using a high-pressure mercury lamp, curing conditions: 1.0 J / cm 2 to form a bleed-out prevention layer.
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the surface opposite to the surface on which the bleed-out prevention layer of the base material is formed, and a die coater so that the film thickness after drying is 4 ⁇ m.
  • a first layer was formed on the curable resin layer using the vacuum plasma CVD apparatus shown in FIG.
  • FIG. 7A shows the relationship between the distance (L) from the surface of the barrier layer in the film thickness direction of the first layer in the gas barrier film 1 and the total amount of silicon atoms, oxygen atoms, and carbon atoms. It is a figure which shows the distribution curve which shows the relationship with the ratio (total atomic ratio of oxygen and carbon), a carbon distribution curve, and an oxygen distribution curve.
  • FIG. 7B is a diagram showing a carbon / oxygen distribution curve of the first layer in the gas barrier film 1.
  • the horizontal axis represents the SiO 2 equivalent film thickness
  • the vertical axis represents the composition (at%) of each atom.
  • the horizontal axis represents the SiO 2 equivalent film thickness
  • the vertical axis represents oxygen atoms / carbon atoms (C / O ratio).
  • the film thickness of the first layer at this time was 250 nm (TEM observation film thickness).
  • the first layer had an order of magnitude relationship represented by the formula (A) in an area of 80% or more of the film thickness.
  • the base material on which the first layer was formed was set in the ALD film forming apparatus of FIG. 4, a coating head for 150 cycles was prepared, and vacuuming was performed to 100 Pa or less. Then, the gas described in the following film formation conditions was allowed to flow through the coating head, an Al 2 O 3 film was formed, and an adhesive protective film was attached and wound up. At this time, the thickness of the second layer was 15 nm.
  • the first layer had an order of magnitude relationship represented by the formula (A) in an area of 80% or more of the film thickness.
  • a set of a roll electrode covered with a dielectric and a plurality of rectangular tube electrodes was produced as follows.
  • the roll electrode serving as the first electrode is coated with a high-density, high-adhesion alumina sprayed film by an atmospheric plasma method on a jacket roll metallic base material made of titanium alloy T64 having cooling means by cooling water, and roll diameter It was set to 1000 mm ⁇ .
  • the square electrode of the second electrode is a hollow rectangular tube-shaped titanium alloy T64 covered with 1 mm of the same dielectric material with the same thickness under the same conditions, and the opposing rectangular tube-shaped fixed electrode group and did.
  • the second electrode square tube type fixed electrode group
  • the first electrode roll rotating electrode
  • a pair of second electrodes square tube type fixed electrodes
  • the first electrode (roll rotating electrode) and the second electrode (square tube fixed electrode group) were adjusted and kept at 80 ° C., and the roll rotating electrode was rotated by a drive to form a thin film.
  • the 24 rectangular tube-shaped fixed electrodes four from the upstream side are used for forming the following first layer, the next two are used for forming the second layer below, and the next two are used for forming the following third layer The following two are used for forming the fourth layer, the next two are used for forming the fifth layer, and the next two are used for forming the sixth layer.
  • next two are for film formation of the following seventh layer
  • the next two are for film formation of the following eighth layer
  • the next two are for film formation of the following ninth layer
  • the remaining four was used for forming the tenth layer, and the first to tenth layers were laminated in one pass by setting each condition. This condition was further repeated twice to produce a gas barrier film 4.
  • HMDSO Hexamethyldisiloxane
  • the film thickness composition of this first layer was as shown in FIGS.
  • the first layer has three extreme values in the carbon / oxygen distribution curve.
  • the gas barrier film 1 was produced in the same manner as the gas barrier film 1 except that the second layer was not formed.
  • the film thickness composition (carbon / oxygen distribution curve) of the first layer was the same as that of the gas barrier film 1.
  • the gas barrier film 3 was prepared in the same manner as the gas barrier film 3 except that the second layer was not formed.
  • the film thickness composition (carbon / oxygen distribution curve) of the first layer was the same as that of the gas barrier film 3.
  • the gas barrier film 4 was produced in the same manner as the gas barrier film 4 except that the second layer was not formed.
  • the film thickness composition (carbon / oxygen distribution curve) of the first layer was the same as that of the gas barrier film 4.
  • metal aluminum ( ⁇ 3 to 5 mm, granular), which is a water vapor impermeable metal, was deposited on the entire surface of one side of the sheet from another metal deposition source.
  • metal aluminum ⁇ 3 to 5 mm, granular
  • the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere
  • the cell for evaluation was produced by irradiating with ultraviolet rays.
  • the amount of moisture permeated into the cell was calculated from the corrosion amount of metallic calcium.
  • a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample was stored under high temperature and high humidity at 60 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.
  • the permeated water amount (g / m 2 ⁇ day; “WVTR” in the table) of each gas barrier film measured as described above was evaluated by the Ca method.
  • Table 1 below shows the composition of each gas barrier film, and Table 2 below shows the evaluation results.
  • the gas barrier films 1 to 4 as examples were excellent in bending resistance, and the gas barrier performance was maintained even when the gas barrier film was stored under high temperature and high humidity conditions. Further, it can be said that the gas barrier films 2 and 3 are excellent in productivity because they maintain the bending resistance and the performance under the high temperature and high humidity conditions even if the transport speed during production is high.
  • the gas barrier films 5 and 8 as comparative examples have a relatively low transport speed, the gas barrier performance does not deteriorate during bending, but the barrier performance deteriorates under high temperature and high humidity conditions.
  • the gas barrier films 6 to 7 and 9 comparativative examples in which the substrate transport speed is high, a significant decrease in gas barrier performance was observed under high temperature and high humidity conditions as well as a decrease in gas barrier performance during bending.
  • Example 2 Production of Organic EL Element A transparent conductive film was produced on the gas barrier layers of the produced gas barrier films 1 to 9 by the following method.
  • an electrode having a parallel plate type was used as the plasma discharge apparatus.
  • the gas barrier film of each sample was placed between the electrodes, and a mixed gas was introduced to form a thin film.
  • a ground (ground) electrode a 200 mm ⁇ 200 mm ⁇ 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed film, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried.
  • An electrode was used which was cured by ultraviolet irradiation and sealed, and the dielectric surface thus coated was polished, smoothed and processed to have an Rmax of 5 ⁇ m.
  • an electrode obtained by coating a dielectric on a hollow square pure titanium pipe under the same conditions as the ground electrode was used.
  • a plurality of application electrodes were prepared and provided to face the ground electrode to form a discharge space.
  • a power source used for plasma generation a high frequency power source CF-5000-13M manufactured by Pearl Industry Co., Ltd. was used, and 5 W / cm 2 of power was supplied at a frequency of 13.56 MHz.
  • a mixed gas having the following composition is caused to flow between the electrodes to form a plasma state, the gas barrier film is subjected to atmospheric pressure plasma treatment, and a tin-doped indium oxide (ITO) film having a thickness of 100 nm is formed on the gas barrier layer (ceramic film).
  • ITO indium oxide
  • Discharge gas Helium 98.5% by volume Reactive gas 1: 0.25% by volume of oxygen
  • Reactive gas 2 Indium acetylacetonate 1.2% by volume
  • Reactive gas 3 Dibutyltin diacetate 0.05% by volume -Fabrication of organic EL element 100 mm x 100 mm of the obtained samples 1 to 9 with a transparent conductive film was used as a substrate, and after patterning, the gas barrier film substrate provided with the ITO transparent electrode was ultrasonicated with isopropyl alcohol. Washed and dried with dry nitrogen gas.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of ⁇ -NPD (the following formula (2)) is put in a molybdenum resistance heating boat, and the host compound is put in another molybdenum resistance heating boat.
  • 200 mg of CBP (the following formula (3)) is added, 200 mg of bathocuproine (BCP (the following formula (4))) is put in another molybdenum resistance heating boat, and Ir-1 ( 100 mg of the following formula (5) was put, and 200 mg of Alq 3 (the following formula (6)) was put in another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.
  • the pressure in the vacuum chamber is reduced to 4 ⁇ 10 ⁇ 4 Pa, and the heating boat containing ⁇ -NPD is energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second to transport holes.
  • a layer was provided.
  • the heating boat containing CBP and Ir-1 was energized and heated, and a light emitting layer was provided by co-evaporation on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • Table 3 shows the above evaluation results (5-level evaluation).
  • Organic EL element sample No. 1-4 showed good results in dark spot evaluation for high temperature and high humidity environment and bending resistance.
  • the organic EL element sample No. In Nos. 5 to 9 remarkable dark spots were observed in a high-temperature and high-humidity environment and bending resistance.

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Abstract

L'invention concerne un film barrière au gaz comprenant, dans l'ordre suivant : un substrat ; une première couche contenant du silicium, de l'oxygène, et du carbone ; et une seconde couche. La première couche satisfait les conditions suivantes (i) et (ii). (i) La zone à 80 % ou plus de l'épaisseur du film de la première couche présente des rapports atomiques possédant une relation d'amplitude dans l'ordre hiérarchique représenté par l'équation « (rapport atomique moyen du carbone) < (rapport atomique moyen du silicium) < (rapport atomique moyen de l'oxygène) » ou « (rapport atomique moyen de l'oxygène) < (rapport atomique moyen du silicium) < (rapport atomique moyen du carbone). » (ii) Il existe au moins deux valeurs extrêmes par rapport à une courbe de distribution de carbone/d'oxygène exprimant la relation entre le rapport du nombre d'atomes de carbone par rapport au nombre d'atomes d'oxygène et la distance (L) par rapport à la surface de la première couche dans la direction de l'épaisseur du film de la première couche. La seconde couche comprend un oxyde inorganique et est formée par un procédé de dépôt de couche atomique.
PCT/JP2014/052800 2013-02-08 2014-02-06 Film barrière au gaz et son procédé de fabrication WO2014123201A1 (fr)

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WO2015053189A1 (fr) * 2013-10-09 2015-04-16 コニカミノルタ株式会社 Film barrière contre les gaz et son procédé de fabrication
WO2015115510A1 (fr) * 2014-01-31 2015-08-06 コニカミノルタ株式会社 Film de barrière contre les gaz et procédé pour sa fabrication
JP2016056390A (ja) * 2014-09-05 2016-04-21 積水化学工業株式会社 フィルム表面処理方法及び装置
WO2016132901A1 (fr) * 2015-02-19 2016-08-25 コニカミノルタ株式会社 Film barrière au gaz et son procédé de fabrication
WO2016159206A1 (fr) * 2015-04-03 2016-10-06 コニカミノルタ株式会社 Film barrière au gaz et son procédé de fabrication
WO2018074524A1 (fr) * 2016-10-19 2018-04-26 凸版印刷株式会社 Film optique barrière contre les gaz et dispositif d'affichage électroluminescent organique
WO2018101027A1 (fr) * 2016-11-30 2018-06-07 コニカミノルタ株式会社 Film barrière aux gaz et procédé de moulage de film barrière aux gaz
JPWO2017073037A1 (ja) * 2015-10-27 2018-08-09 凸版印刷株式会社 積層体及びガスバリアフィルム
WO2019057273A1 (fr) * 2017-09-20 2019-03-28 Applied Materials, Inc. Procédé de formation d'alumine pour une cellule électrochimique à l'aide d'un procédé d'ionisation par plasma
CN111032338A (zh) * 2017-08-25 2020-04-17 住友化学株式会社 层叠膜
US10899108B2 (en) 2015-04-16 2021-01-26 Toppan Printing Co., Ltd. Laminates and gas barrier films
US10961622B2 (en) 2015-02-26 2021-03-30 Toppan Printing Co., Ltd. Gas barrier film and method of manufacturing the same
EP3674078A4 (fr) * 2017-08-25 2021-05-05 Sumitomo Chemical Company Limited Film stratifié

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JP2012076292A (ja) * 2010-09-30 2012-04-19 Dainippon Printing Co Ltd ガスバリア性フィルム積層体
JP2012096531A (ja) * 2010-10-08 2012-05-24 Sumitomo Chemical Co Ltd 積層フィルム
JP2012116151A (ja) * 2010-12-03 2012-06-21 Sony Corp バリアフィルム及びその製造方法

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JP2011241421A (ja) * 2010-05-17 2011-12-01 Toppan Printing Co Ltd ガスバリア性積層体の製造方法およびガスバリア性積層体
JP2012076292A (ja) * 2010-09-30 2012-04-19 Dainippon Printing Co Ltd ガスバリア性フィルム積層体
JP2012096531A (ja) * 2010-10-08 2012-05-24 Sumitomo Chemical Co Ltd 積層フィルム
JP2012116151A (ja) * 2010-12-03 2012-06-21 Sony Corp バリアフィルム及びその製造方法

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015053189A1 (fr) * 2013-10-09 2015-04-16 コニカミノルタ株式会社 Film barrière contre les gaz et son procédé de fabrication
WO2015115510A1 (fr) * 2014-01-31 2015-08-06 コニカミノルタ株式会社 Film de barrière contre les gaz et procédé pour sa fabrication
JP2016056390A (ja) * 2014-09-05 2016-04-21 積水化学工業株式会社 フィルム表面処理方法及び装置
WO2016132901A1 (fr) * 2015-02-19 2016-08-25 コニカミノルタ株式会社 Film barrière au gaz et son procédé de fabrication
JPWO2016132901A1 (ja) * 2015-02-19 2017-11-30 コニカミノルタ株式会社 ガスバリアーフィルム及びその製造方法
US10961622B2 (en) 2015-02-26 2021-03-30 Toppan Printing Co., Ltd. Gas barrier film and method of manufacturing the same
WO2016159206A1 (fr) * 2015-04-03 2016-10-06 コニカミノルタ株式会社 Film barrière au gaz et son procédé de fabrication
JPWO2016159206A1 (ja) * 2015-04-03 2018-02-01 コニカミノルタ株式会社 ガスバリアーフィルム及びその製造方法
US10899108B2 (en) 2015-04-16 2021-01-26 Toppan Printing Co., Ltd. Laminates and gas barrier films
JPWO2017073037A1 (ja) * 2015-10-27 2018-08-09 凸版印刷株式会社 積層体及びガスバリアフィルム
WO2018074524A1 (fr) * 2016-10-19 2018-04-26 凸版印刷株式会社 Film optique barrière contre les gaz et dispositif d'affichage électroluminescent organique
WO2018101027A1 (fr) * 2016-11-30 2018-06-07 コニカミノルタ株式会社 Film barrière aux gaz et procédé de moulage de film barrière aux gaz
CN111032338A (zh) * 2017-08-25 2020-04-17 住友化学株式会社 层叠膜
EP3674078A4 (fr) * 2017-08-25 2021-05-05 Sumitomo Chemical Company Limited Film stratifié
EP3674079A4 (fr) * 2017-08-25 2021-05-05 Sumitomo Chemical Company Limited Film stratifié
CN111032338B (zh) * 2017-08-25 2022-06-17 住友化学株式会社 层叠膜
WO2019057273A1 (fr) * 2017-09-20 2019-03-28 Applied Materials, Inc. Procédé de formation d'alumine pour une cellule électrochimique à l'aide d'un procédé d'ionisation par plasma

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