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WO2016159206A1 - 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
WO2016159206A1
WO2016159206A1 PCT/JP2016/060602 JP2016060602W WO2016159206A1 WO 2016159206 A1 WO2016159206 A1 WO 2016159206A1 JP 2016060602 W JP2016060602 W JP 2016060602W WO 2016159206 A1 WO2016159206 A1 WO 2016159206A1
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WIPO (PCT)
Prior art keywords
gas barrier
film
barrier layer
carbon
barrier film
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Ceased
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PCT/JP2016/060602
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English (en)
Japanese (ja)
Inventor
廣瀬　達也
和喜 田地
千明 門馬
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2017510168A priority Critical patent/JPWO2016159206A1/ja
Publication of WO2016159206A1 publication Critical patent/WO2016159206A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C23C16/42—Silicides
    • 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
    • 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
    • C23C16/54—Apparatus specially adapted for continuous coating

Definitions

  • the present invention relates to a gas barrier film and a method for producing the same, and more particularly to a gas barrier film excellent in gas barrier performance, bending resistance and adhesion 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 prevents deterioration due to various gases such as water vapor and oxygen. Therefore, it is used in applications for packaging articles that require shutoff of various gases.
  • 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 prevents deterioration due to various gases such as water vapor and oxygen. Therefore, it is used in applications for packaging articles that require shutoff of various gases.
  • it is used for sealing electronic devices such as solar cells, liquid crystal display elements, organic electroluminescence elements (hereinafter also referred to as organic EL elements). Has also been used.
  • a film having a gas barrier layer formed on a substrate such as a film by a plasma chemical vapor deposition method (hereinafter also referred to as a plasma CVD method (CVD: Chemical Vapor Deposition)),
  • a plasma CVD method Chemical Vapor Deposition
  • a gas barrier performance and bending resistance are formed by forming a composition film in which the ratio of carbon amount to oxygen amount (C / O) continuously changes in the thickness direction of the gas barrier layer. It is known that a gas barrier layer that can satisfy both of these requirements can be formed (see, for example, Patent Document 4).
  • Such a barrier film can form a dense film by converging plasma with a magnetic field, and can continuously change the carbon / oxygen content in the gas barrier layer. In this case, a decrease in gas barrier properties is suppressed.
  • adhesion and bending resistance after holding in a high temperature and high humidity environment are not sufficient.
  • JP 2009-255040 A Japanese Patent No. 3511325 JP 2012-106421 A JP 2012-96531 A
  • the present invention has been made in view of the above problems and situations, and a solution to that problem is to provide a gas barrier film excellent in gas barrier performance, bending resistance and adhesion, and a method for producing the same.
  • the present inventor in the process of examining the cause of the above problems, the carbon / oxygen distribution curve in which the ratio between the carbon amount and the oxygen amount in the gas barrier layer is plotted in the thickness direction is thick.
  • the carbon / oxygen distribution curve in which the ratio between the carbon amount and the oxygen amount in the gas barrier layer is plotted in the thickness direction is thick.
  • it has many maximum values, and by shortening the interval between adjacent maximum values, gas barrier performance, bending resistance and adhesion are improved.
  • the inventors have found that an excellent gas barrier film can be obtained, and have reached the present invention.
  • a gas barrier film having a gas barrier layer on a flexible substrate The gas barrier film satisfies the following requirements (1) and (2).
  • the gas barrier layer contains at least silicon, oxygen, and carbon as constituent elements.
  • a carbon / oxygen distribution curve in which the value of the ratio of the carbon amount to the oxygen amount in the gas barrier layer is plotted in the thickness direction has a maximum value, and the number (n) of the maximum values and the gas barrier layer The ratio (n / d) to the thickness (d) is 0.10 / nm or more.
  • the gas barrier film is produced by a plasma chemical vapor deposition method using plasma generated by applying a voltage between opposed roller electrodes having a magnetic field generating member that generates at least a magnetic field. Manufacturing method.
  • the flexible substrate is transported while being brought into contact with each of the pair of film forming rollers, the film forming gas is supplied between the pair of film forming rollers in the film forming chamber, and Performing a plasma discharge while removing moisture and forming a gas barrier layer on the substrate;
  • the apparatus used for the plasma enhanced chemical vapor deposition method can converge the plasma near the counter roller electrode by using a magnetic field, and as a result, a dense gas barrier layer can be formed.
  • the apparatus Since the apparatus has a structure having a magnetic field generating member having an N pole and an S pole in each of a pair of opposed roller electrodes, a region having a strong and weak plasma discharge intensity exists between the pair of opposed roller electrodes due to the magnetic field. And the composition of the gas barrier layer can be continuously changed depending on the region.
  • the carbon / oxygen distribution curve in which the value of the ratio of the carbon amount to the oxygen amount in the gas barrier layer is plotted in the thickness direction has a maximum value, and the number (n) of the maximum values and the gas barrier layer
  • the thickness of each region (oxygen-rich layer) containing a large amount of oxygen that is considered to be weak against stress can be reduced.
  • the oxygen-rich layer is sandwiched between regions containing a large amount of carbon (carbon-rich layer) when the oxygen-rich layer is thin, it is considered that cracks are less likely to occur due to stress. In addition, it is considered that the resistance to the stress generated by the thermal deformation of the substrate when stored in a high temperature and high humidity environment is similarly increased and the durability is improved.
  • Example of configuration of gas barrier film of the present invention Another example of the structure of the gas barrier film of the present invention An example of the distribution curve of carbon, nitrogen, oxygen and silicon atoms in the thickness direction according to the XPS depth profile of the gas barrier layer according to the present invention An example of the carbon / oxygen distribution curve in the thickness direction according to the XPS depth profile of the gas barrier layer according to the present invention Schematic showing an example of gas barrier film manufacturing equipment Enlarged view of film formation space of gas barrier film manufacturing equipment
  • the gas barrier film of the present invention is a gas barrier film having a gas barrier layer on a flexible substrate, and the gas barrier layer satisfies the requirements (1) and (2).
  • This feature is a technical feature common to the inventions according to claims 1 to 9.
  • 80% or more of the interval between adjacent maximum values is preferably in the range of 2 to 15 nm from the viewpoint of the effect of the present invention.
  • all the intervals between adjacent maximum values are in the range of 2 to 15 nm.
  • the manufacturing method is an embodiment in which the plasma is generated by plasma chemical vapor deposition using plasma generated in this manner.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the gas barrier film of the present invention is a gas barrier film having a gas barrier layer on a flexible substrate,
  • the gas barrier layer satisfies the following requirements (1) and (2).
  • the gas barrier layer contains at least silicon, oxygen, and carbon as constituent elements.
  • a carbon / oxygen distribution curve in which the value of the ratio of the carbon amount to the oxygen amount in the gas barrier layer is plotted in the thickness direction has a maximum value, and the number (n) of the maximum values and the gas barrier layer
  • the ratio (n / d) to the thickness (d) is 0.10 / nm or more.
  • Plastruction chemical vapor deposition method using plasma generated by applying a voltage between opposed roller electrodes having a magnetic field generating member for generating a magnetic field is simply referred to as “plasma CVD method between roller electrodes” in the present application. Or, more simply, “plasma CVD method”.
  • the ratio of the carbon amount to the total amount of silicon, oxygen, and carbon which is measured by the XPS depth profile described later, is expressed as “carbon atom ratio (at%)”, the ratio of the oxygen amount to the total amount of silicon, oxygen, and carbon. Is referred to as “oxygen atomic ratio (at%)”, and the ratio of the amount of silicon to the total amount of silicon, oxygen and carbon is referred to as “silicon atomic ratio (at%)”. In any case, the total amount of silicon, oxygen and carbon is 100 at%.
  • the value of the ratio of the carbon amount to the oxygen amount in the gas barrier layer is specifically profiled by a carbon / oxygen distribution curve.
  • the carbon / oxygen distribution curve refers to a continuous distribution curve in which the distance (L) from the surface of the gas barrier layer according to the present invention is plotted on the horizontal axis and the ratio of the carbon amount to the oxygen content is plotted on the vertical axis.
  • Measurement of the silicon content, oxygen content, and carbon content with respect to the distance (L) from the gas barrier layer surface is performed by the element distribution measurement in the depth direction (hereinafter also referred to as XPS depth profile) by the following X-ray photoelectron spectroscopy. Can do.
  • XPS depth profile The amount of silicon, the amount of oxygen, and the amount of carbon of the gas barrier layer according to the present invention can be measured by combining X-ray photoelectron spectroscopy (XPS) measurement with rare gas ion sputtering such as argon. It can be obtained by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while being exposed.
  • XPS depth profile measurement in which surface composition analysis is sequentially performed while being exposed.
  • the vertical axis is the atomic ratio (at%) of each element, or the ratio of the carbon amount to the oxygen amount, and the horizontal axis Can be created as the etching time (sputtering time).
  • the etching time is generally correlated with the distance (L) in the layer thickness direction from the surface of the gas barrier layer according to the present invention.
  • the layer thickness (nm) in terms of SiO 2 is used as the distance (L) in the layer thickness direction from the surface of the gas barrier layer.
  • the layer thickness (nm) in terms of SiO 2 is also referred to as the sputter depth (nm).
  • the distribution curve representing the atomic ratio (at%) of each element and the ratio of carbon amount to oxygen amount (C / O) are determined by measuring the silicon amount, oxygen amount, and carbon amount under the following measurement conditions. Created.
  • Etching ion species Argon (Ar + ) Etching rate (equivalent to SiO 2 thermal oxide film): 0.01 nm / sec
  • 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 ⁇ m ⁇ 400 ⁇ m oval.
  • the maximum value in the present invention can be obtained from a curve obtained by measuring the carbon / oxygen distribution curve in the layer thickness direction measured by the above-mentioned XPS depth profile and plotting the above-mentioned SiO 2 equivalent layer thickness every 1 nm. .
  • each maximum value is calculated from the SiO 2 equivalent layer thickness (sputter depth (nm)) from the surface of the gas barrier layer according to the present invention.
  • the interval between adjacent maximum values refers to the present invention in the thickness direction of the gas barrier layer according to the present invention between one maximum value of the carbon / oxygen distribution curve and the maximum value adjacent to the maximum value. It refers to the absolute value of the difference in distance (L) from the surface of the gas barrier layer (hereinafter also simply referred to as “interval between maximum values”).
  • the “maximum value” in the carbon / oxygen distribution curve refers to the maximum value of C / O (carbon content / oxygen content) in the carbon / oxygen distribution curve.
  • the maximum value in the carbon / oxygen distribution curve means that the value of the atomic ratio of the carbon amount to the oxygen amount changes from increasing to decreasing when the distance from the surface of the gas barrier layer according to the present invention is changed.
  • the carbon / oxygen distribution curve in the layer thickness direction measured by the above-described evaluation method is measured by sputtering at the above-described etching rate, and the composition is about 0.20 nm within 1 nm as the SiO 2 equivalent layer thickness. Is measured 5 times. It is obtained from a carbon / oxygen distribution curve in which the average value of the five times is plotted.
  • FIG. 1A shows an example.
  • the gas barrier film 10 a is a gas barrier film in which the gas barrier layer 3 is laminated on the substrate 1.
  • providing the smooth layer 2 as an organic layer between the base material 1 and the gas barrier layer 3 improves the adhesion between the base material and the gas barrier layer, or the unevenness of the base material interface is a thin layer. This is a preferred embodiment in order to make it difficult to affect a certain gas barrier layer.
  • the gas barrier film 10b of this invention which is another aspect is equipped with the smooth layer 2 on the resin base material 1, as shown to FIG. 1B, for example, and the gas barrier layer 3 is laminated
  • a second gas barrier layer 5 containing a metal oxide may be laminated on the gas barrier layer 3.
  • An overcoat layer 6 may be laminated on the second gas barrier layer 5.
  • the gas barrier layer according to the present invention is characterized in that the gas barrier layer satisfies the following requirements (1) and (2).
  • the gas barrier layer contains at least silicon, oxygen, and carbon as constituent elements.
  • a carbon / oxygen distribution curve in which the value of the ratio of the carbon amount to the oxygen amount in the gas barrier layer is plotted in the thickness direction has a maximum value, and the number (n) of the maximum values and the gas barrier layer
  • the ratio (n / d) to the thickness (d) is 0.10 / nm or more.
  • the thickness of the gas barrier layer according to the present invention is not particularly limited. In order to improve the gas barrier performance while making it difficult to cause defects, it can be in the range of 20 to 1000 nm. In the present invention, in order to increase the number of maximum values in the carbon / oxygen distribution curve in which the value of the ratio of the carbon amount to the oxygen amount in the gas barrier layer is plotted in the thickness direction, the gas barrier layer is formed once.
  • the hit layer thickness is preferably in the range of 10 to 100 nm, and more preferably in the range of 20 to 40 nm. Thus, by reducing the layer thickness per film formation process and performing the film formation process a plurality of times, the number of local maximum values per unit layer thickness in the thickness direction of the gas barrier layer can be increased.
  • per film forming process means that in the film forming apparatus that performs plasma CVD including the counter roller electrode, a flexible base material passes through each of the pair of counter roller electrodes to form a gas barrier layer. This process is referred to as “one film formation process”.
  • the gas barrier layer according to the present invention may have a laminated structure including a plurality of sublayers.
  • the number of sublayers is preferably 2 to 30.
  • each sublayer may have the same composition or a different composition.
  • the “gas barrier property” as used in the present invention is, for example, a water vapor transmission rate measured by a method according to JIS K 7129-1992, or an oxygen transmission rate measured by a method according to JIS K 7126-1987. Indicated. In general, if the water vapor transmission rate is 1 g / (m 2 ⁇ day) or less or the oxygen transmission rate is 1 mL / (m 2 ⁇ day ⁇ atm) or less, it is said to have gas barrier properties. Furthermore, if the water vapor transmission rate is less than 5 ⁇ 10 ⁇ 3 g / (m 2 ⁇ day), it is said to have high gas barrier properties, and can be used for electronic devices such as organic EL, electronic paper, solar cells, and LCDs. .
  • the gas barrier layer according to the present invention is characterized by containing silicon, oxygen, and carbon as constituent elements as the requirement (1).
  • carbon is present in addition to silicon and oxygen.
  • gas barrier properties can be imparted by the presence of silicon and oxygen, and bending resistance can be imparted to the gas barrier layer by the presence of carbon.
  • the gas barrier layer according to the present invention includes a silicon distribution curve indicating a relationship between a distance (L) from the surface of the gas barrier layer according to the present invention in the thickness direction of the gas barrier layer according to the present invention and a silicon atomic ratio, L
  • L silicon atomic ratio
  • the region has an order magnitude relationship represented by the following formula (A) or the following formula (B).
  • Formula (A) (carbon atom ratio) ⁇ (silicon atom ratio) ⁇ (oxygen atom ratio)
  • Formula (B) (oxygen atom ratio) ⁇ (silicon atom ratio) ⁇ (carbon atom ratio)
  • at least 80% or more of the thickness of the gas barrier layer according to the present invention does not have to be continuous in the gas barrier layer, and only needs to satisfy the above-described relationship at a portion of 80% or more. .
  • the relationship between the oxygen atom ratio, the silicon atom ratio, and the carbon atom ratio is more preferably satisfied in a region of at least 90% or more (upper limit: 100%) of the thickness of the gas barrier layer, and at least 93 More preferably, it is satisfied in an area of at least% (upper limit: 100%).
  • the atomic ratio satisfies C ⁇ Si ⁇ O, and the order magnitude relationship represented by the formula (A) is satisfied. Is preferred. By satisfying such conditions, the obtained gas barrier film has sufficient gas barrier properties and bending resistance.
  • the silicon atom ratio in the gas barrier layer is preferably in the range of 25 to 45 at%, and more preferably in the range of 30 to 40 at%.
  • the oxygen atom ratio in the gas barrier layer according to the present invention is preferably in the range of 20 to 67 at%, more preferably in the range of 25 to 67 at%.
  • the carbon atom ratio in the layer is preferably in the range of 3 to 50 at%, more preferably in the range of 3 to 40 at%.
  • the total amount of carbon and oxygen atoms with respect to the thickness direction of the gas barrier layer according to the present invention is preferably substantially constant.
  • the gas barrier layer according to the present invention exhibits moderate bending resistance, and the generation of cracks when the gas barrier film is bent can be more effectively suppressed / prevented.
  • the absolute value of the difference between the maximum and minimum total oxygen and carbon atomic ratios in the distribution curve (hereinafter also simply referred to as “OC max ⁇ OC min difference”) is less than 5 at%.
  • 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 gas barrier layer according to the present invention is in the direction of the film surface (on the surface of the gas barrier layer according to the present invention). It is preferably substantially uniform in the (parallel direction).
  • the gas barrier layer according to the present invention is substantially uniform in the film surface direction means that the oxygen distribution at any two measurement points on the film surface of the gas barrier layer according to the present invention by XPS depth profile measurement.
  • the number of local maximum values of the carbon distribution curve obtained at any two measurement locations is the same, and each carbon distribution curve
  • the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is the same as each other or within 5 at%.
  • the carbon distribution curve is substantially continuous.
  • substantially continuous carbon distribution curve 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. In the relationship between the distance from the surface in the thickness direction of the gas barrier layer (x, unit: nm) and the atomic ratio of carbon (C, unit: at%), the condition represented by the following formula (1) Satisfying.
  • the method for forming a gas barrier layer according to the present invention includes a plasma chemical vapor deposition method (plasma CVD method) using plasma generated by applying a voltage between opposed roller electrodes having a magnetic field generating member for generating a magnetic field. Preferably it is formed.
  • plasma CVD method plasma chemical vapor deposition method
  • the gas barrier layer As a material of the gas barrier layer according to the present invention, it is a material having a function of suppressing the ingress of gas such as water and oxygen causing deterioration of the performance of the electronic device in which the gas barrier film is used.
  • Inorganic silicon compounds such as silicon oxide, silicon oxynitride, silicon dioxide, and silicon nitride, organic silicon compounds, and the like can be used.
  • the gas barrier layer is preferably formed by oxidizing or nitriding a gas in which an organosilicon compound is vaporized.
  • a carbon / oxygen distribution curve obtained by plotting a value of the ratio of the carbon amount to the oxygen amount in the gas barrier layer in the thickness direction has a maximum value, and the maximum The ratio (n / d) between the number of values (n) and the thickness (d) of the gas barrier layer is 0.10 / nm or more.
  • the carbon / oxygen distribution curve in which the value of the ratio of the carbon amount to the oxygen amount in the gas barrier layer is plotted in the thickness direction has a maximum value, and the number (n) of the maximum values and the gas barrier layer
  • the maximum value is large, the thickness of each oxygen-rich layer that is considered to be weak against stress can be reduced.
  • the oxygen-rich layer is sandwiched between the carbon-rich layers while the oxygen-rich layer is thin, it is considered that cracks are unlikely to occur due to stress.
  • the resistance to the stress generated by the thermal deformation of the base material when stored in a high temperature and high humidity environment is similarly increased and the durability is improved.
  • the maximum value per unit layer thickness is large. Therefore, in the carbon / oxygen distribution curve, the interval between the maximum values is preferably narrow. That is, in the carbon / oxygen distribution curve, it is preferable that 80% or more of the interval between adjacent maximum values is in the range of 2 to 15 nm.
  • the interface side of the base material is a trace amount of water held by the base material (herein, the base material includes a form in which the base material is processed or has an organic layer on the base material).
  • the base material includes a form in which the base material is processed or has an organic layer on the base material.
  • it may be released into the plasma discharge space to promote the oxidation of the film, impair the continuous gradient of the composition of carbon and oxygen, and widen the interval between the maximum values in the carbon / oxygen distribution curve. It has been found that the bending resistance is deteriorated as the carbon amount is reduced. For this reason, in particular, in the carbon / oxygen distribution curve in the gas barrier film within a distance range from the interface of the substrate to 30 nm, all the intervals between the adjacent maximum values are in the range of 2 to 15 nm. Is preferred.
  • 80% or more of the interval between the adjacent maximum values is in the range of 2 to 5 nm, and more preferably, in the carbon / oxygen distribution curve, All of the intervals between adjacent maxima are in the range of 2-5 nm.
  • the layer thickness can be controlled by the following method.
  • the amount of raw material to be introduced For example, if the amount of an organosilicon compound described later is increased, the amount of raw material decomposed in the plasma space increases, and thus the layer thickness increases.
  • the maximum value in the carbon / oxygen distribution curve is usually (number of passes ⁇ 2), and the number of maximum values is dominated by the number of passes through two rollers regardless of the layer thickness. Therefore, the ratio (n / d) between the number of maximum values (n) in the barrier layer and the thickness (d) of the gas barrier layer can be controlled by appropriately controlling the above (i) to (iv). it can. Specifically, a gas barrier having many local maximum values in a carbon / oxygen distribution curve by reducing the thickness of a layer formed by a single film formation process and passing through the discharge space of the plasma CVD many times. A layer can be formed. Note that the number of maximum values can also be adjusted by changing conditions such as a reactive atmosphere in the deposition chamber.
  • the interval between the maximum values may be wide.
  • a region in which a certain amount of carbon is distributed in the thickness direction of the layer is necessary, but in order to form the gas barrier layer, film formation is performed at a higher substrate transport speed,
  • film formation is performed under conditions that increase productivity, such as increasing the temperature of the film formation roller, a region with a reduced carbon distribution is likely to be formed in a specific range on the side in contact with the substrate interface due to the influence of moisture described above. It is believed that there is. In particular, this phenomenon is likely to occur in the first film formation process in the formation of a multilayer film by plasma CVD.
  • the influence of such moisture is particularly large in the vicinity of the interface of the base material that greatly affects the adhesion between the base material and the gas barrier layer, and thus the gas barrier within a distance range from the base material interface to 30 nm. In the layer, it is effective and preferable to shorten the interval between the maximum values in the carbon / oxygen distribution curve.
  • the “substrate interface” as used in the present invention plots XPS depth profile data from the gas barrier layer surface in the depth direction in the silicon atomic ratio (at%) profile and the carbon atomic ratio (at%) profile. Then, 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 “substrate interface”.
  • the surface of the sample is irradiated with X-rays under vacuum, and the kinetic energy of photoelectrons emitted from the surface into the vacuum by the photoelectric effect is observed to obtain information on the elemental composition and chemical state of the surface.
  • X-rays reach not only the film but also the base material, and are affected by this, so that there is a compositionally mixed transition region. It is difficult to specify a clear position as an interface. Therefore, the “base material interface” as used in the present invention is a transition region in which both the gas barrier layer component and the base material component are detected, and the point P which is the above change point is the “base material interface”. Defined.
  • FIG. 2A and FIG. 2B are examples of the distribution curve and carbon / oxygen distribution curve of each element in the thickness direction according to the XPS depth profile of the gas barrier layer according to the present invention.
  • FIG. 2A shows XPS depth profiles of carbon, nitrogen, oxygen and silicon atoms.
  • FIG. 2B shows a carbon / oxygen distribution curve.
  • the ratio (atomic%) of the carbon amount to the oxygen amount on the vertical axis is simply expressed as a C / O ratio.
  • the horizontal axis represents the sputter depth (thickness) from the barrier layer surface.
  • the point P where the silicon atom ratio changes by ⁇ 0.5 at% / nm or more and the carbon atom ratio changes by +1.0 at% or more is the sputter depth of 115.6 nm.
  • To 30 nm corresponds to a range of sputter depth of 85.6 to 115.6 nm.
  • the carbon / oxygen distribution curve has many local maximum values, and the interval between the local maximum values in the gas barrier layer is narrow.
  • the carbon amount is distributed within a range of 10 to 30 at% as a carbon atom ratio within a distance range of 30 nm from the substrate interface.
  • ⁇ Method for producing gas barrier layer >>
  • the method for producing a gas barrier film of the present invention has high productivity, plasma chemical vapor deposition using plasma generated by applying a voltage between opposed roller electrodes having a magnetic field generating member that generates at least a magnetic field. It is preferable to manufacture by the method (plasma CVD method).
  • the plasma CVD method may be a Penning discharge plasma type plasma CVD method.
  • a pair of film forming rollers function as a pair of counter electrodes. Is preferred.
  • a pair of film-forming rollers is used, and a base material is used for each of the pair of film-forming rollers (herein, the base material includes a form in which the base material is processed or has an organic layer on the base material). It is more preferable that a plasma is generated by disposing and discharging between a pair of film forming rollers.
  • the film formation rate can be doubled compared to the normal plasma CVD method without using a roller, and a film with almost the same structure can be formed, so that the maximum value in the carbon distribution curve can be at least doubled. It becomes.
  • the film forming gas used in such a plasma CVD method preferably includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation.
  • the gas barrier layer according to the present invention is preferably a layer formed by a continuous film forming process.
  • the gas barrier film according to the present invention is preferably formed from the viewpoint of productivity by forming the gas barrier layer according to the present invention on the surface of the substrate by a roll-to-roll method.
  • An apparatus that can be used when forming a gas 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. It is preferable that the apparatus has a configuration capable of discharging between the film rollers. For example, when the manufacturing apparatus shown in FIG. 3 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible to do.
  • FIG. 3 is a schematic view showing an example of a manufacturing apparatus that can be suitably used for manufacturing the gas barrier layer according to the present invention.
  • the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.
  • the method for producing a gas barrier film for producing the gas barrier film of the present invention is as follows: A step of feeding the belt-shaped flexible base material from the feed roller and transporting it with the transport roller; The flexible substrate is transported while being brought into contact with each of the pair of film forming rollers, the film forming gas is supplied between the pair of film forming rollers in the film forming chamber, and Performing a plasma discharge while removing moisture and forming a gas barrier layer on the substrate; And a step of winding the gas barrier film having the gas barrier layer formed on the flexible substrate with a winding roller while transporting the gas barrier film with a transporting roller. preferable.
  • the conveyance speed of the flexible substrate is 20 m / min or more.
  • the plasma CVD manufacturing apparatus 30 shown in FIG. 3 sends out the base material 1, a delivery roller 31, delivery chambers 32 to 36, a chamber A having a feeding / conveying process, film formation rollers 40 and 41, and gas supply A chamber B having a film formation process (synthetic process) having a tube 44, a plasma generation power source 52, magnetic field generators 42 and 43 installed inside the film formation rollers 40 and 41, and transfer rollers 37, 38 and 39. It is also a film chamber, and is a plasma CVD apparatus comprising three chambers of a C chamber having a winding process, which includes transport rollers 45 and 46 and a winding roller 47. Each room is independent, and it is preferable to have a device (not shown) that can individually control the pressure and temperature. The temperature of each chamber is measured by a commercially available temperature monitor 49-51.
  • the film forming rollers 40 and 41, the gas supply pipe 44, the plasma generating power source 52, and the magnetic field generating apparatuses 42 and 43 are arranged in a vacuum chamber (not shown). Yes. Further, in such a manufacturing apparatus 30, the vacuum chamber is connected to a vacuum pump (not shown), and the atmospheric pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.
  • a coiled pipe 53 of a cryocoil through which a cooling medium circulates is installed at least in the B chamber (film formation chamber).
  • transport rollers 33 and 34 have a heating means, function as a heating roller, and have a temperature adjustment device 48 that performs temperature adjustment is also preferable.
  • cryocoil which is a preferred embodiment of the method for producing a gas barrier film of the present invention, will be described.
  • the cryocoil is a low-temperature exhaust means composed of a low-temperature condensing source, a cooler that cools the cooling medium circulating through the low-temperature condensing source, and a coiled pipe that circulates the cooling medium. It is a device that can exhaust.
  • a cooled refrigerant By circulating a cooled refrigerant through a coiled pipe installed in the vacuum layer, the gas in the vacuum layer can be discharged by freezing the surface of the pipe. For example, water vapor is frozen and trapped, the partial pressure of water in the vacuum layer can be greatly reduced, and the exhaust speed can be increased.
  • Fluorocarbon refrigerant or mixed refrigerant, liquid nitrogen or liquid helium can be used as the cooling medium.
  • the cryocoil can be installed in combination with other evacuation means such as a vacuum pump or as a switchable structure.
  • the installation location of the coiled piping of the cryocoil can be installed near the unwinding location of the roll when used in a roll-to-roll vacuum device. This is because the resin base material retains a large amount of moisture that has permeated in the air itself, and when it is unwound in a vacuum, it releases a large amount of water and greatly deteriorates the degree of vacuum in the vacuum layer. Also, when the moisture enters the film formation process space, it acts as a plasma impurity, changes the plasma, acts as an oxidant, oxidizes the film, and so the desired film cannot be obtained. You can also Preferably, it is installed in at least B room (film formation room), more preferably, both B room and A room, more preferably cryocoil is installed in A, B and C rooms. It is that you are.
  • the base material since moisture is released from the base material, it is preferable to install a coiled pipe in the vicinity of the base material being transported. Furthermore, in order to prevent frozen water and the like from peeling off from the coiled pipe and adhering to the base material, it is more preferable to install it below the passage portion of the base material. When the peeled water or the like is placed on the base material, a normal film is not formed there, and the barrier performance is deteriorated.
  • Stainless steel and copper are mainly used for coiled piping.
  • the water exhaust speed can be adjusted by extending the length of the coiled pipe.
  • As the cooler for example, an apparatus described in JP2011-62600A or JP2013-53848 can be used.
  • the transport rollers 33 and 34 have heating means and function as heating rollers.
  • the heat treatment is preferably performed at a temperature of 10 ° C. or higher than the temperature of the film forming roller, preferably 70 ° C. or higher, and 80 ° C. or higher, in order to obtain the desired effect of the treatment. It is more preferable to heat. Further, from the viewpoint of preventing deformation of the base material and the like, it is preferable to carry out at a temperature below the glass transition temperature of the base material.
  • the glass transition temperature (Tg) refers to a temperature measured at a heating rate of 10 ° C./min by a differential scanning calorimetry method based on JIS K7121, for example, a thermomechanical analyzer (TMA: Thermo Mechanical Analysis) or the like. It can be detected by measuring in the range of 30 to 290 ° C. with an apparatus.
  • TMA thermomechanical analyzer
  • the organic layer can be heated at a temperature higher than the lowest glass transition temperature of the substance constituting the organic layer. Therefore, it is preferable to heat the base material or the organic layer at a temperature lower than the lowest glass transition temperature.
  • the conditions for the heat treatment can be appropriately changed.
  • the heating temperature is preferably 70 ° C. to (the lowest glass transition temperature of the material constituting the base material or the organic layer) for 1 second.
  • the intended purpose can be achieved if it is performed within a range of about 10 minutes.
  • the heat treatment time may be a long time if the heating temperature is low, or a short time if the temperature is high.
  • the heat treatment method includes a hot plate, hot air treatment, infrared irradiation method, radiant heat method and the like, and is not particularly limited, but it is convenient and preferable to use the heating roller shown in FIG. Although a pair of heating rollers is illustrated as the heating rollers 33 and 34 in FIG. 3, a plurality of pairs of heating rollers may be used.
  • the heating rollers 33 and 34 are controlled by the temperature adjusting device 48 so as to keep the temperature in a predetermined temperature range.
  • the temperature adjusting device 48 is preferably a device capable of controlling the temperature in the range of 50 to 200 ° C.
  • each film-forming roller is for plasma generation so that a pair of film-forming rollers (film-forming roller 40 and film-forming roller 41) can function as a pair of counter electrodes.
  • a power source 52 is connected. Therefore, in such a manufacturing apparatus 30, it is possible to discharge to the space between the film formation roller 40 and the film formation roller 41 by supplying electric power from the plasma generation power source 52. Plasma can be generated in the space between the film roller 40 and the film formation roller 41. In this way, when the film forming roller 40 and the film forming roller 41 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes.
  • the film-forming rollers 40 and 41 it is preferable to arrange
  • the film forming rate can be doubled compared with a normal plasma CVD method that does not use a roller, and the structure is the same. Since a film can be formed, the maximum value in the carbon distribution curve can be at least doubled.
  • the surface of the base material 1 here, the base material includes a form in which the base material is processed or has an organic layer on the base material
  • the gas barrier layer 3 according to the present invention is formed on the film forming roller 41 while depositing the gas barrier layer component according to the present invention on the surface of the substrate 1 on the film forming roller 40. Since the gas barrier layer component according to the present invention can also be deposited on the surface of the substrate 1, the gas barrier layer can be efficiently formed on the surface of the substrate 1.
  • magnetic field generators 42 and 43 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.
  • the magnetic field generators 42 and 43 provided on the film forming roller 40 and the film forming roller 41, respectively, are a magnetic field generating device 42 provided on one film forming roller 40 and a magnetic field generating device provided on the other film forming roller 41. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between 43 and the magnetic field generators 42 and 43 form a substantially closed magnetic circuit.
  • By providing such magnetic field generators 42 and 43 it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surface of each of the film forming rollers 40 and 41, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.
  • the magnetic field generators 42 and 43 provided on the film forming roller 40 and the film forming roller 41 respectively have racetrack-like magnetic poles that are long in the roller axis direction, and one magnetic field generating device 42 and the other magnetic field generating device. It is preferable to arrange the magnetic poles so that the magnetic poles facing 43 have the same polarity.
  • 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 1 is excellent in that the gas barrier layer 3 according to the present invention, which is a vapor deposition film, can be efficiently formed.
  • the film forming roller 40 and the film forming roller 41 known rollers can be appropriately used. As such film forming rollers 40 and 41, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameters of the film forming rollers 40 and 41 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 1 in a short time. It is preferable because damage to the material 1 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 temperature of the film forming roller affects the formation rate of the gas barrier layer, but is preferably in the range of 40 to 60 ° C. from the viewpoint of preventing heat loss of the substrate and generation of wrinkles.
  • rollers As the feed roller 31 and the transport rollers 32, 35, 36, 37, 38, 39, 45, and 46 used in such a manufacturing apparatus, known rollers can be appropriately used. Further, the winding roller 47 is not particularly limited as long as it can wind the gas barrier film 10 in which the gas barrier layer 3 according to the present invention is formed on the substrate 1, and is appropriately known. A roller can be used.
  • gas supply pipe 44 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 44 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 40 and the film formation roller 41, and is a vacuum as a vacuum exhaust means.
  • a pump (not shown) is preferably provided on the other side of the facing space.
  • the gas supply pipe 44 as the gas supply means and the vacuum pump as the vacuum exhaust means are arranged to efficiently supply the film formation gas to the facing space between the film formation roller 40 and the film formation roller 41. It is excellent in that the film formation efficiency can be improved.
  • the plasma generating power source 52 a known power source of a plasma generating apparatus can be used as appropriate.
  • a plasma generating power supply 52 supplies power to the film forming roller 40 and the film forming roller 41 connected thereto, and makes it possible to use them as a counter electrode for discharging.
  • Such a plasma generating power source 52 can perform plasma CVD more efficiently, so that the polarity of the pair of film forming rollers can be alternately reversed (AC power source or the like). Is preferably used.
  • the plasma generating power source 52 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible to do this.
  • the magnetic field generators 42 and 43 known magnetic field generators can be used as appropriate.
  • the base material 1 in addition to the base material used in the present invention, a material in which the gas barrier layer 3 according to the present invention is formed in advance can be used. As described above, by using the substrate 1 in which the gas barrier layer 3 according to the present invention is formed in advance, the thickness of the gas barrier layer 3 according to the present invention 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 transport of the film (base material) can be produced by appropriately adjusting the speed.
  • FIG. 4 is an enlarged view of a film formation space for performing plasma CVD. That is, using the manufacturing apparatus 30 shown in FIG. 3, a discharge is generated between the pair of film forming rollers (film forming rollers 40 and 41) while supplying a film forming gas (such as a raw material gas) into the vacuum chamber.
  • a film forming gas such as a raw material gas
  • the film-forming gas is decomposed by plasma, and the gas barrier according to the present invention is formed on the surface of the substrate 1 on the film-forming roller 40 and on the surface of the substrate 1 on the film-forming roller 41.
  • Layer 3 is formed by plasma CVD.
  • a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axis of the film forming rollers 40 and 41, and the plasma is converged on the magnetic field.
  • the maximum value of the carbon / oxygen distribution curve is obtained in the gas barrier layer according to the present invention. It is formed.
  • the substrate 1 passes through the points C1 and C2 of the film forming roller 40 and the points C3 and C4 of the film forming roller 41 in FIG. A local minimum is formed. For this reason, two local maximum values are usually generated for the two film forming rollers.
  • 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 gas barrier layer 3 according to the present invention can be appropriately selected and used depending on the material of the gas barrier layer 3 according to the present invention 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 the handleability of the compound and the 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 gas barrier layer 3 according to the present invention.
  • a reactive gas may be used in addition to the raw material gas.
  • a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • a reactive gas for forming nitride nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.
  • 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.
  • a carrier gas and a discharge gas known ones can be used as appropriate, for example, a rare gas such as helium, argon, neon, xenon, hydrogen, or 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.
  • the gas barrier layer 3 according to the present invention to be formed is excellent in that excellent gas barrier properties and bending resistance can be obtained by not excessively increasing the ratio of the reaction gas.
  • 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.
  • 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 to 50 Pa.
  • an electrode drum connected to the plasma generating power source 52 (in this embodiment, the film forming roller 40).
  • the power 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. On the other hand, if the applied power is 10 kW or less, the amount of heat generated at the time of film formation can be suppressed. An increase in the interface 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 interval between the maximum values is narrowed by increasing the conveying speed of the base material for the purpose of improving productivity, and high gas barrier properties and bending. Resistance is maintained. For this reason, when the conveyance speed of a base material is quick, the effect of this invention becomes more remarkable. That is, the preferred production method of the present invention forms a gas barrier layer according to the present invention containing silicon, oxygen and carbon by conveying a substrate to a plasma CVD apparatus having a counter roller electrode at a conveyance speed of 5 m / min or more. It is preferable to do.
  • a more preferable embodiment includes a step of forming a gas barrier layer according to the present invention containing silicon, oxygen and carbon by conveying the substrate to a plasma CVD apparatus having a counter roller electrode at a conveyance speed of 20 m / min or more.
  • the upper limit of the line speed is not particularly limited, and is preferably faster from the viewpoint of productivity. However, if it is 100 m / min or less, it is excellent in that a sufficient thickness can be secured as a gas barrier layer. Yes.
  • the gas barrier layer according to the present invention is formed by the plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roller electrode shown in FIG. It is characterized by forming a film.
  • This is excellent in bending resistance and adhesion when mass-produced using a plasma CVD apparatus having a counter roller electrode (roll-to-roll method), and particularly in durability during conveyance by roll-to-roll and gas barrier properties. This is because it is possible to efficiently produce a gas barrier layer in which both are compatible.
  • Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce a gas barrier film that is required for durability against temperature changes used in solar cells, electronic parts, and the like.
  • the gas barrier film of the present invention usually uses a plastic film as a flexible substrate.
  • the term “flexibility” as used herein refers to a base material that does not crack even when wound around a ⁇ (diameter) 50 mm roll, and more preferably a base material that can be wound around a ⁇ 30 mm roll.
  • the plastic film used is not particularly limited as long as it is a film capable of holding a gas barrier laminate, and can be appropriately selected according to the purpose of use.
  • Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide.
  • Resin cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring
  • thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.
  • the base material is preferably made of a heat-resistant material.
  • Polyolefin for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.
  • polyarylate PAr: 210 ° C
  • polyethersulfone PES: 220 ° C
  • polysulfone PSF: 190 ° C
  • cycloolefin copolymer COC: Compound described in JP-A No. 2001-150584: 162 ° C.
  • polyimide for example, Neoprim (registered trademark): 260 ° C.
  • 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 paragraph numbers 0036 to 0038 of JP-A-2006-289627 can be preferably employed.
  • 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 gas 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.
  • the base material and gas barrier layer according to the present invention may be separately provided with an organic layer containing an organic compound as long as the effects of the present invention are not impaired.
  • an organic layer is provided in advance on at least one surface of the base material, and that the organic layer further contains inorganic particles, It is preferable from the viewpoint of improving the adhesion to the substrate.
  • the gas barrier layer of the present invention is formed on a substrate on which the organic layer is formed in advance, the gas barrier layer is formed after the moisture contained in the organic layer is vaporized and desorbed by heat treatment.
  • a manufacturing method for forming a film it is possible to form a gas barrier layer without the influence of moisture.
  • the organic layer as used in the present invention is synonymous with a functional layer containing an organic compound, and is preferably each functional layer listed below.
  • the gas barrier film of the present invention may have a curable resin layer (generally also referred to as a hard coat 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 interface of the substrate, (2) relaxing 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 restriction in particular.
  • composition containing the active energy ray-curable material contains a photopolymerization initiator.
  • 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 resistance epoxy resin), silicone resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nittobo Co., Ltd.
  • thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydride Down resins.
  • the method for forming the curable resin layer is not particularly limited, but a coating solution 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 solution 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.
  • active energy rays such as visible rays, infrared rays, ultraviolet rays, X-rays, ⁇ rays, ⁇ rays, ⁇ rays, electron rays and / or heating are performed.
  • 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.
  • 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 film from generating pinholes.
  • the curable resin layer contains inorganic particles that are matting agents.
  • the adhesion between the gas barrier layer and the substrate can be improved.
  • the OH groups and H 2 O are adsorbed in a hydrogen bond state, and the amount of water that can be held by the substrate itself is increased.
  • the vaporization and desorption of moisture due to heating is promoted, so that the influence of moisture can be reduced in the film forming process.
  • 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 matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 100 parts by mass of the solid content of the hard coating agent. It is preferable that they are mixed in a proportion of 18 parts by mass or less, more preferably 16 parts by mass or less.
  • the thickness of the curable resin layer is not particularly limited, but is preferably in the range of 0.1 to 10 ⁇ m.
  • a gas barrier film has a smooth layer in the surface which has a gas barrier layer of a base material.
  • the smooth layer is provided in order to flatten the rough surface of the substrate on which protrusions and the like exist.
  • Such a smooth layer is basically formed by curing an active energy ray curable material or a thermosetting material.
  • the smooth layer may basically have the same material and configuration as the curable resin layer as long as it has the above-described function.
  • Examples of the active energy ray-curable material and thermosetting material used in the smooth layer, examples of the matting agent, and the method of forming the smooth layer are the same as those described in the column of the curable resin layer above, so here Then, explanation is omitted.
  • the thickness of the smooth layer is not particularly limited, but is preferably in the range of 0.1 to 10 ⁇ m.
  • the smooth layer may be used as the following anchor coat layer.
  • An anchor coat layer may be formed on the substrate interface according to the present invention as an easy-adhesion layer for the purpose of improving adhesion (adhesion) with the gas barrier layer.
  • the anchor coat 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 silicone resin, and alkyl titanate. 1 or 2 or more types 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 also 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 ⁇ m.
  • 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.
  • 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 includes 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.
  • examples of the polyunsaturated organic compound include ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate.
  • examples of the monounsaturated organic compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like.
  • the matting agent described in the cured resin layer may be contained.
  • the matting agent inorganic particles having an average particle diameter of about 0.1 to 5 ⁇ m are preferable, which improves the slipperiness of the gas barrier film.
  • 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 matting agent.
  • the bleed-out prevention layer as described above is prepared as a coating solution by using a hard coat agent and other components as required, and appropriately preparing a coating solution by using a diluent solvent as necessary.
  • After coating by a conventionally known coating method it can be formed by irradiating with ionizing radiation and curing.
  • irradiating with 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.
  • a layer having gas barrier properties can be further provided as a second gas barrier layer on the gas barrier layer according to the present invention.
  • the second gas barrier layer may be a layer in which two or more first gas barrier layers are stacked, and is not limited. Among them, it is also preferable to provide a coating film of a polysilazane-containing liquid of a coating method and to provide a second gas barrier layer that is formed by irradiating vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less and performing a modification treatment. .
  • VUV light vacuum ultraviolet light
  • the coating film of the polysilazane-containing liquid in the coating method can take a conventionally known configuration. For example, paragraphs [0134] to [0183] of JP2013-180520A, JP2013-123895A This is the configuration described in paragraphs [0042] to [0065].
  • the thickness of the second gas barrier layer is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm.
  • An overcoat layer may be formed on the second gas barrier layer used in the present invention in order to further improve the bending resistance.
  • an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used. Can do.
  • These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed by coating from the organic resin composition coating solution to be cured.
  • the gas barrier film of the present invention has excellent gas barrier properties, bending resistance and adhesion.
  • 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.
  • Example 1 Production of gas barrier film 1> (Flexible substrate) As a flexible substrate, a 1 m wide hard coat film G1STB manufactured by Kimoto Co., Ltd. (PET film thickness 50 ⁇ m, no matting agent: described as PET with CHC in the table) was used.
  • the base material was set as it was on the delivery roller of the film forming apparatus of FIG. Then, after the degree of vacuum reached 5 ⁇ 10 ⁇ 3 Pa, the heating rollers 33 and 34 were set to 60 ° C. Then, the base material was conveyed at the conveyance speed of the following film-forming conditions, the base material was conveyed to the film-forming chamber (B room), and film-forming was implemented on the following plasma conditions. The time until the degree of vacuum reached 5 ⁇ 10 ⁇ 3 Pa was 3 hours, and the time until the heating roller reached a predetermined temperature was 0.5 hours.
  • ⁇ Film formation condition 2> -Supply amount of source gas (HMDSO): 200 sccm (Standard Cubic Centimeter per Minute) ⁇ Supply amount of oxygen gas (O 2 ): 500 sccm ⁇ Degree of vacuum in the vacuum chamber: 1.5 Pa ⁇ Applied power from the power source for plasma generation: 2.0 kW ⁇ Power supply frequency for plasma generation: 80 kHz -Film conveyance speed: 40 m / min-Film-forming roller diameter: 300 mm ⁇ -Number of times TR passes: 4 times-Heating roller temperature: 60 ° C ⁇ Film roller temperature: 60 °C ⁇ Example 4: Production of gas barrier film 4> In production of the gas barrier film 1, a gas barrier film 4 was produced in the same manner as the gas barrier film 1 except that the plasma film formation conditions were as follows.
  • the carbon / oxygen distribution curve in the layer thickness direction measured by the above-described evaluation method is measured by sputtering at the above-mentioned etching rate, and the composition is measured 5 times for every about 0.20 nm within 1 nm as the SiO 2 equivalent layer thickness. .
  • the average value of the five times was obtained from the plotted carbon / oxygen distribution curve, and the number of points at which the value of the atomic ratio of the carbon amount to the oxygen amount changed from increasing to decreasing was determined.
  • the thickness of the gas barrier layer was determined by observation with a transmission microscope (TEM).
  • ⁇ Gas barrier property evaluation method> The permeated water amount of each gas barrier film was measured according to the following measurement method, and the water vapor barrier property was evaluated according to the following criteria.
  • Vapor deposition device JEOL Ltd., vacuum vapor deposition device JEE-400 Constant temperature and humidity oven: Yamato Humidic Chamber IG47M Metal that reacts with water and corrodes: Calcium (granular) Water vapor impermeable metal: Aluminum ( ⁇ 3-5mm, granular) (Preparation of water vapor barrier property evaluation cell)
  • a vacuum vapor deposition device vacuum vapor deposition device JEE-400, manufactured by JEOL Ltd.
  • a portion (12 mm ⁇ 12 mm) to be vapor deposited on the gas barrier film sample Other than 9 places were masked to deposit metal calcium (granular) (deposition layer thickness 80 nm).
  • 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 water 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”) of each gas barrier film measured as described above was evaluated according to the following criteria. Three or more are good as a gas barrier film.
  • the gas barrier films 1 to 4 of the present invention are all excellent in bending resistance and adhesion as compared with the comparative gas barrier films 5 and 6.
  • the gas barrier film 2 in which the intervals between all extreme values are in the range of 2 to 15 nm, and the gas barrier film 4 in which the intervals of all the maximum values are all in the range of 2 to 5 nm are further resistant to bending. It turns out that it is excellent in adhesiveness.
  • the gas barrier film of the present invention is excellent in gas barrier performance, bending resistance and adhesion, and is used for 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 applications such as a gas barrier film used for electronic devices such as the above and an electronic device using the same.

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Abstract

La présente invention aborde le problème de fourniture : d'un film barrière au gaz possédant une exceptionnelle performance de barrière aux gaz, une exceptionnelle résistance à la flexion, et une exceptionnelle adhésivité; et un procédé de fabrication de celui-ci. Ce film barrière au gaz possède une couche de barrière au gaz sur un substrat souple, le film barrière au gaz étant caractérisé en ce que la couche de barrière au gaz satisfait les conditions (1) et (2) ci-dessous. (1) La couche de barrière au gaz contient au moins du silicium, de l'oxygène et du carbone en tant qu'éléments constitutifs. (2) La courbe de distribution de carbone/oxygène, dans laquelle la valeur de la proportion de la quantité de carbone dans la couche de barrière au gaz par rapport à la quantité d'oxygène dans la couche de barrière au gaz est tracée le long de la direction d'épaisseur, présente des valeurs maximales; et le rapport du nombre de valeurs maximales et de l'épaisseur de la couche de barrière au gaz est de 0,10/nm ou plus élevé.
PCT/JP2016/060602 2015-04-03 2016-03-31 Film barrière au gaz et son procédé de fabrication Ceased WO2016159206A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014123201A1 (fr) * 2013-02-08 2014-08-14 コニカミノルタ株式会社 Film barrière au gaz et son procédé de fabrication
WO2014203892A1 (fr) * 2013-06-20 2014-12-24 コニカミノルタ株式会社 Film de barrière aux gaz et procédé pour sa production
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
JP2016097500A (ja) * 2014-11-18 2016-05-30 コニカミノルタ株式会社 ガスバリアーフィルム、その製造方法及びプラズマ化学気相蒸着法用基材

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014123201A1 (fr) * 2013-02-08 2014-08-14 コニカミノルタ株式会社 Film barrière au gaz et son procédé de fabrication
WO2014203892A1 (fr) * 2013-06-20 2014-12-24 コニカミノルタ株式会社 Film de barrière aux gaz et procédé pour sa production
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
JP2016097500A (ja) * 2014-11-18 2016-05-30 コニカミノルタ株式会社 ガスバリアーフィルム、その製造方法及びプラズマ化学気相蒸着法用基材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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