WO2018101027A1 - Film barrière aux gaz et procédé de moulage de film barrière aux gaz - Google Patents

Film barrière aux gaz et procédé de moulage de film barrière aux gaz Download PDF

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Publication number
WO2018101027A1
WO2018101027A1 PCT/JP2017/040900 JP2017040900W WO2018101027A1 WO 2018101027 A1 WO2018101027 A1 WO 2018101027A1 JP 2017040900 W JP2017040900 W JP 2017040900W WO 2018101027 A1 WO2018101027 A1 WO 2018101027A1
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Prior art keywords
gas barrier
barrier film
barrier layer
film
region
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PCT/JP2017/040900
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English (en)
Japanese (ja)
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森　孝博
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コニカミノルタ株式会社
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Priority to JP2018553752A priority Critical patent/JPWO2018101027A1/ja
Publication of WO2018101027A1 publication Critical patent/WO2018101027A1/fr

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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

Definitions

  • the present invention relates to a gas barrier film having a gas barrier layer and a method for forming the gas barrier film.
  • a metal sealing As a sealing member of an organic electroluminescence (EL) element using a glass substrate, a metal sealing can having a curved surface having a flange shape formed on the outer four sides in a box shape with the side facing the substrate open. It is known (see Patent Document 1). Such a sealing can can be filled with a desiccant in the gap and can be easily designed to improve the durability of the element. On the other hand, since it is a metal, it has drawbacks such as being heavy, poor in flexibility, and being damaged when the metal surface comes into contact with the element when bent.
  • a gas barrier layer that can suppress the occurrence of cracks on a curved surface having a large curvature has been proposed (see Patent Document 2).
  • a plasma-deposited amorphous glass layer containing silicon, carbon, and hydrogen is formed on the film by a vapor deposition method.
  • the WVTR is as large as several g. For this reason, even if it can be molded into a shape having a curved surface, the barrier property is insufficient for application to sealing of electronic devices that require high barrier properties. Thus, a gas barrier film having a high barrier property and a curved surface is desired.
  • the present invention provides a gas barrier film having a high barrier property and a curved surface.
  • the gas barrier film of the present invention includes a base material and a gas barrier layer formed on the base material.
  • the gas barrier layer contains silicon, oxygen, and carbon, and when the composition of the gas barrier layer is expressed by SiOxCy, a region having a composition of y ⁇ 0.20 and a region having a composition of y> 1.40. Is less than 20 nm in the thickness direction.
  • the gas barrier film has a substantially flat region and a region having a cubic curved surface surrounded by the flat region, and a region having a cubic curved surface when the flat region is in contact with the flat plate. Are not in contact with the flat plate, and an average gap of 0.5 mm or more is formed between the region having the cubic curved surface and the flat plate.
  • a gas barrier film having a high barrier property and a curved surface can be provided.
  • FIG. 2 is a cross-sectional view taken along line AA of the gas barrier film shown in FIG. It is sectional drawing which shows the structure of a gas barrier film. It is a graph which shows the distribution curve of the silicon of a gas barrier layer, carbon, and oxygen. It is a graph which shows the distribution curve of C / Si ratio of a gas barrier layer, and O / Si ratio. It is a graph which shows the distribution curve of the silicon of a gas barrier layer, carbon, and oxygen. It is a graph which shows the distribution curve of C / Si ratio of a gas barrier layer, and O / Si ratio. It is an orthogonal coordinate showing the composition of SiOxCy which comprises a gas barrier layer.
  • FIG. 2 is a cross-sectional view taken along line AA of the gas barrier film shown in FIG.
  • WVTR water vapor permeability
  • FIG. 1 is a plan view of a gas barrier film.
  • FIG. 2 is a cross-sectional view taken along line AA of the gas barrier film 10 shown in FIG.
  • the gas barrier film 10 includes a base material 11 and a gas barrier layer 12 formed on one surface of the base material 11.
  • the gas barrier film 10 includes a substantially flat region (flat region) 13 and a region (curved region) 14 having a cubic curved surface surrounded by the flat region 13. Is provided. In the curved region, a concave portion is formed on one surface of the gas barrier film 10, and a convex portion is formed on the other surface.
  • the gas barrier layer 12 side is a surface having a concave portion
  • the base material 11 side is a surface having a convex portion.
  • FIG. 2 the position of the surface of the flat plate in contact with the gas barrier film 10 on the gas barrier layer 12 side (the surface side having the recesses) of the gas barrier film 10 is indicated by a broken line 20.
  • This flat plate is illustrated for explaining the shape of the gas barrier film 10 and is not included in the configuration of the gas barrier film 10.
  • the flat region 13 is provided on the peripheral side of the gas barrier film 10.
  • “substantially flat” means that, as shown in FIG. 2, the gas barrier film 10 is flat when the gas barrier layer 12 side (surface side having a recess) is in contact with a flat plate. It shows that the gap 15 between the region 13 and the surface of the flat plate (broken line 20) is 0.1 mm or less.
  • region 13 corresponds to the area
  • the curved surface region 14 is provided on the center side in the gas barrier film 10.
  • the gap 16 between the recess formed on one surface side and the surface of the flat plate (broken line 20) in contact with the gas barrier film 10 is 0.5 mm or more on average.
  • the gas barrier film 10 is defined by the shape of the surface side (gas barrier layer 12 side) where the concave portion is formed in the curved region 14. For this reason, it does not specifically limit about the shape by the side of the surface (base material 11 side) in which a convex part is formed. In general, the shape of the gas barrier layer 12 is also deformed following the deformation of the base material 11, so that the shape on the surface side (gas barrier layer 12 side) where the concave portion is formed in the curved region 14 and the convex portion are formed. The shape on the surface side (base material 11 side) to be applied substantially matches except for the deviation due to the thickness.
  • a method of forming into a shape having the curved region 14 can be considered.
  • the gas barrier layer 12 is directly formed on the base material 11 having the curved region 14
  • a gas barrier layer 12 is first formed on a flat substrate 11 to form a flat gas barrier film. 10 is produced. And the heat
  • the gas barrier layer 12 contains silicon, oxygen, and carbon. For this reason, it is possible to suppress the occurrence of defects in the gas barrier layer 12 even when the curved region 14 is molded into a shape having a cubic curved surface in which gaps of 0.5 mm or more are formed on average. For this reason, the gas barrier film 10 has a water vapor permeability (WVTR) of 0.1 (g / m 2 / day) measured under the conditions of 60 ° C., 90% RH and 2 hours even after the above-described molding process. The following can be achieved: Further, in the gas barrier film 10 after the molding process, a preferable water vapor permeability (WVTR) can be 1 ⁇ 10 ⁇ 2 (g / m 2 / day) or less.
  • WVTR water vapor permeability
  • the substrate 11 may be a laminate of a plurality of substrates.
  • the base material 11 may have a configuration in which the first base material 17 and the second base material 18 are bonded with an adhesive layer 19.
  • the gas barrier layer 12 is provided on one surface of the first base material 17, and the second base material 18 is provided on the other surface through the adhesive layer 19.
  • the structure of those other than this is the structure similar to the gas barrier film 10 of the above-mentioned FIG.1 and FIG.2.
  • the first base material 17 and the second base material 18 are preferably bonded so as to be peelable in the pressure-sensitive adhesive layer 19.
  • the adhesive layer 19 and the second substrate 18 are bonded so as to be peelable from the first substrate 17.
  • the second base material 18 functions as a protective film for the first base material 17.
  • the manufacturing process of the gas barrier film 10 or the manufacturing process of the electronic device to which the gas barrier film 10 is applied if the substrate disposed on the outermost surface is damaged such as scratches, the appearance of the electronic device is defective. Will occur. For this reason, it is preferable to provide a peelable protective film on the surface of the base material 11 in order to prevent the base material from being damaged during each manufacturing process.
  • the adhesive layer 19 and the second base material 18 are peeled from the first base material 17, thereby having the same configuration as the gas barrier film 10 shown in FIG. 1.
  • the first base material 17 shown in FIG. 3 corresponds to the base material 11 shown in FIG.
  • the thickness [X] of the first base material 17 and the second base material is 50 ⁇ m or more and 150 ⁇ m or less. Furthermore, [X] / [Y] is preferably 0.15 or more and 0.90 or less.
  • the thickness [X] of the first base material 17 and the thickness [Y] of the second base material 18 is 50 ⁇ m or more, the thickness becomes easy to handle in the formation of the gas barrier layer 12. Moreover, if the sum total of the thickness [X] of the 1st base material 17 and the thickness [Y] of the 2nd base material 18 is 150 micrometers or less, the base material 11 has sufficient softness
  • the thickness of the second base material 18 serving as the protective film is larger than the first base material 17 on which the gas barrier layer 12 is formed.
  • the first base material 17 when the first base material 17 is applied to an electronic device or the like, the first base material 17 remains as the gas barrier film 10, so that the degree of freedom in design is limited by the requirements of the electronic device or the like.
  • the second substrate 18 when the second substrate 18 is used as a protective film, the second substrate 18 is peeled off when the gas barrier film 10 is applied to an electronic device or the like. For this reason, the second base material 18 has a higher degree of design freedom than the first base material 17. Therefore, it is preferable that the mechanical strength required for the base material 11 when the gas barrier layer 12 is produced is secured on the second base material 18 side. Therefore, it is preferable that the thickness [Y] of the second base material 18 is larger than the thickness [Y] of the first base material 17 and the thickness [Y] of the second base material 18. / [Y] is preferably 0.15 or more and 0.90 or less.
  • the gas barrier layer 12 contains silicon, oxygen, and carbon. That is, the gas barrier layer 12 is represented by a composition of SiOxCy.
  • the value of x in SiOxCy is expressed as the oxygen content (O / Si) with respect to silicon, and the value of y is expressed as the carbon content (C / Si) with respect to silicon.
  • FIG. 4 shows a curve showing the distribution of the silicon atom content in the thickness direction of the gas barrier layer 12 (hereinafter referred to as a silicon distribution curve) and a curve showing the distribution of the carbon atom content in the thickness direction of the gas barrier layer 12
  • a graph of a carbon distribution curve) and a curve showing the distribution of the content of oxygen atoms in the thickness direction of the gas barrier layer 12 (hereinafter, oxygen distribution curve) are shown.
  • FIG. 5 shows a curve (hereinafter referred to as a C / Si ratio distribution curve) showing the distribution of the composition ratio (C / Si) of carbon to silicon in the thickness direction of the gas barrier layer 12, and the thickness direction of the gas barrier layer 12.
  • the graph of the curve (henceforth O / Si ratio distribution curve) which shows distribution of the composition ratio (O / Si) of oxygen with respect to silicon is shown.
  • the ratio of silicon is defined as 1 based on the composition formula of SiOxCy.
  • the content of each element in the thickness direction of the gas barrier layer 12 shown in FIG. 4 and the curve and maximum value indicating this content can be obtained by measurement of an XPS depth profile described later. Further, the composition ratio (C / Si) of carbon atoms to silicon atoms in the thickness direction of the gas barrier layer 12 shown in FIG. 5, the composition ratio of oxygen atoms (O / Si), and a curve or maximum representing this composition ratio The value can be calculated from the measured value of the XPS depth profile in FIG.
  • each distribution curve indicating the relationship between the distance (L) from the layer surface in the film thickness direction and the content of silicon atoms, carbon atoms, and oxygen atoms is , Continuously changing.
  • the C / Si ratio distribution curve showing the distance (L) from the layer surface in the film thickness direction and the ratio of carbon atoms to silicon atoms continuously changes.
  • the O / Si ratio distribution curve indicating the ratio of oxygen atoms to silicon atoms changes continuously.
  • the gas barrier film 10 has a maximum of four or more carbon distribution curves (requirement (1)). Furthermore, [film thickness / maximum value number] of the gas barrier layer 12 is 25 nm or less (requirement (2)). In the graph shown in FIG. 4, in the gas barrier layer having a thickness of about 55 nm, the carbon distribution curve has six maximum values indicated by arrows in the drawing. Therefore, [film thickness / maximum value number] is about 9 nm.
  • the number of maximum values and [film thickness / maximum number of values] can be arbitrarily adjusted by changing the film formation conditions of the gas-phase film-forming gas barrier layer using the vacuum plasma CVD method described later.
  • the distance between the adjacent maximum values can be reduced by increasing the conveyance speed of the base material in the vapor deposition gas barrier layer deposition.
  • the number of maximum values tends to increase in the gas barrier layer 12 having the same thickness.
  • the carbon distribution curve of the gas barrier layer 12 it can be considered as one region where the composition continuously changes between adjacent maximum values. For this reason, the gas barrier layer 12 has a region where the composition continuously changes in the thickness direction by the number of maximum values. Therefore, the configuration in which the carbon distribution curve has six or more maximum values has a plurality of regions with different composition ratios of silicon, oxygen, and carbon in the film thickness direction, and the plurality of regions are stacked in the film thickness direction. Indicates that Furthermore, in the carbon distribution curve of the gas barrier layer 12, as the number of local maximum values increases, there are more regions in the gas barrier layer 12 where the composition changes continuously.
  • a configuration in which the [film thickness / maximum value number] of the carbon distribution curve is 25 nm or less indicates the occurrence probability of the maximum value in the carbon distribution curve. For example, if [film thickness / number of local maximum values] is 25 nm, it indicates that there is one local maximum per 25 nm average in the thickness direction. By reducing the rate at which the maximum value occurs to 25 nm or less, the thickness of one region where the composition continuously changes can be reduced. That is, the gas barrier layer 12 can have the same configuration as a state in which thinner layers are stacked.
  • the average distance between adjacent maximum values is 25 nm or less, and there are six or more regions where the composition continuously changes in the thickness direction.
  • WVTR water vapor permeability
  • the gas barrier layer 12 By having the gas barrier layer 12 having a plurality of regions in which the composition continuously changes, it is possible to suppress the deterioration of the water vapor permeability (WVTR) of the gas barrier film 10 even after a molding process involving the formation of a cubic curved surface.
  • WVTR water vapor permeability
  • Etc. are not limited to the following description.
  • the gas barrier layer has a single layer structure
  • the crack when a crack occurs in one place in the gas barrier layer in the molding process of the gas barrier film, the crack propagates in the thickness direction, and the crack is in the thickness direction of the gas barrier layer. Easy to penetrate.
  • moisture and the like can easily pass through the crack, so that the water vapor permeability (WVTR) of the gas barrier film is deteriorated.
  • WVTR water vapor permeability
  • the gas barrier layer 12 has a plurality of regions where the composition changes continuously, a crack occurs in one place (one region) in the gas barrier layer 12, and the crack occurs in the thickness direction in the generated region. Even when the crack penetrates, the crack terminates in the other area, and the crack hardly propagates to the other area. Furthermore, since the gas barrier layer 12 has a plurality of regions laminated, the region where the crack has occurred is covered with another region. For this reason, the micro crack which generate
  • the gas barrier layer 12 has a plurality of regions in which the composition continuously changes in the thickness direction, thereby suppressing the deterioration of the water vapor permeability (WVTR) of the gas barrier film after forming processing accompanied by the formation of a cubic curved surface. can do.
  • WVTR water vapor permeability
  • the gas barrier layer 12 has a maximum value of four or more carbon distribution curves.
  • the number of layers in the region where the composition continuously changes is the number of maximum values of the carbon distribution curve plus one layer. Therefore, if the carbon distribution curve has four or more maximum values, the composition is continuous. 5 or more layers are provided. By providing five or more regions where the composition continuously changes, the effect of covering other regions with the region where the microcracks have occurred is easily exhibited, and the effect of preventing the penetration of cracks in the entire gas barrier layer 12 is achieved. It is easy to express.
  • the number of maximum values in the carbon distribution curve increases, the number of layers in the region where the composition continuously changes increases.
  • the number of maximum values in the carbon distribution curve is preferably as large as possible, and the number of maximum values in the carbon distribution curve is preferably 6 or more, more preferably 8 or more, and particularly preferably 12 or more.
  • FIGS. 6 and 7 show the distribution curves in the gas barrier layer when the maximum value of the carbon distribution curve is twelve.
  • the graphs shown in FIGS. 6 and 7 correspond to FIGS. 4 and 5 described above, and the details of the graphs are the same as those in FIGS. 4 and 5.
  • FIG. 6 is a graph showing a silicon distribution curve, a carbon distribution curve, and an oxygen distribution curve of the gas barrier layer 12.
  • FIG. 7 is a graph showing a C / Si ratio distribution curve and an O / Si ratio distribution curve of the gas barrier layer 12. In the graph shown in FIG. 7, the silicon ratio is defined as 1 based on the composition formula of SiOxCy.
  • the gas barrier film 10 of the example shown in FIGS. 6 and 7 has a carbon distribution curve having 12 maximum values indicated by arrows in the drawings in a gas barrier layer having a thickness of about 105 nm. For this reason, in the graph shown in FIG. 4, [film thickness / maximum value number] is about 9 nm. Accordingly, in the example shown in FIGS. 6 and 7 as well, the [film thickness / maximum value] of the gas barrier layer 12 required for the gas barrier film 10 is 25 nm or less, as in the examples shown in FIGS. Meet the provisions of
  • the thickness of the gas barrier layer 12 is constant, the smaller the thickness of the region where the composition changes continuously, the more regions are laminated. That is, the smaller the value [film thickness / maximum value] obtained by dividing the total thickness of the gas barrier layer 12 by the number of maximum values of the carbon distribution curve, the smaller the thickness of each region where the composition changes continuously. . Therefore, under the condition that the thickness of the gas barrier layer 12 is constant, the smaller the [film thickness / maximum value], the more regions can be stacked, and the region where the microcracks have occurred is replaced with other regions. It becomes easy to express the effect
  • the gas barrier layer 12 contains silicon, oxygen, and carbon, and is represented by a composition of SiOxCy.
  • the value of x in SiOxCy is expressed as the oxygen content (O / Si) with respect to silicon, and the value of y is expressed as the carbon content (C / Si) with respect to silicon.
  • the gas barrier layer 12 has a thickness of a region having a composition of y ⁇ 0.20 and a thickness of a region having a composition of y> 1.40 when the composition of the gas barrier layer 12 is expressed by SiOxCy. Is less than 20 nm.
  • the composition of y ⁇ 0.20 is a region with a low carbon ratio and a high oxygen ratio. That is, the gas barrier layer 12 has a composition close to SiO 2 . A region having a composition close to SiO 2 is easily cracked by elongation treatment. If a region having a composition of y ⁇ 0.20 exceeds 20 nm in the thickness direction, the crack generated in this region causes a crack. Difficult to propagate to other regions of different composition. For this reason, the barrier property of the gas barrier layer 12 tends to deteriorate.
  • the composition of y> 1.40 is a region where the oxygen ratio is small and the carbon ratio is large. That is, the gas barrier layer 12 becomes a composition close to SiC 2. Also in this composition, as in the region having a composition close to the above-mentioned SiO 2 , cracks are easily generated by the elongation treatment, and cracks are easily propagated to regions having different compositions, so that the barrier property of the gas barrier layer 12 is deteriorated. It's easy to do.
  • 8 to 11 show orthogonal coordinates in which the horizontal axis is x and the vertical axis is y in the composition of SiOxCy constituting the gas barrier layer 12.
  • 8 and 9 show (x, y) of the composition represented by SiOxCy for each thickness in the gas barrier layer 12 having the C / Si ratio distribution curve and the O / Si ratio distribution curve shown in FIG. ).
  • 10 and 11 show the composition (x) of SiOxCy for each thickness in the gas barrier layer 12 having the C / Si ratio distribution curve and the O / Si ratio distribution curve shown in FIG. , Y).
  • Each of (x, y) shown in FIGS. 8 to 11 is a thickness at a point indicated by a white triangle in the C / Si ratio distribution curve and the O / Si ratio distribution curve of FIGS. Represents the composition.
  • the gas barrier film 10 has a composition that falls within the range of 4 points of the following ABCD in the distribution of (x, y) for each thickness in the composition represented by SiOxCy. It is preferable to have 40 to 200 nm in the 12 thickness direction.
  • the gas barrier film 10 has a composition that falls within the range of 4 points of the following ABEF in the distribution of (x, y) for each thickness in the composition represented by SiOxCy, More preferably, the gas barrier layer 12 has a thickness of 40 nm or more and 200 nm or less in the thickness direction.
  • the gas barrier layer 12 preferably has a composition that falls within the range of 4 points of the ABCD, and particularly preferably has a composition that falls within the range of 4 points of the ABEF.
  • a narrow range surrounded by the four points ABCD in the vicinity of the SiC 2 —SiO 2 theoretical line is a preferable composition for the gas barrier layer 12 in terms of gas barrier properties, physical characteristics, and optical characteristics.
  • a narrower range surrounded by four points of ABEF is a particularly preferable composition for the gas barrier layer 12 in terms of gas barrier properties, physical characteristics, and optical characteristics.
  • the gas barrier layer 12 preferably has both a region where the C / Si has a composition of 0.95 or more and a region where the C / Si has a composition of 0.7 or less. Furthermore, the gas barrier layer 12 has both a region where the composition of C / Si is 0.95 or more and a region where the composition of C / Si is 0.7 or less, and 70% or more of the gas barrier layer 12. Is preferably included in any region where C / Si is 0.95 or more or C / Si is 0.7 or less, and all regions of the gas barrier layer 12 have a C / Si of 0. It is preferably included in any region of 95 or more or C / Si of 0.7 or less.
  • a region where the C / Si has a composition of 0.95 or more and a region where the C / Si has a composition of 0.7 or less are formed in the thickness direction. It is preferable that they are laminated. In particular, it is preferable that four or more regions each having a composition having a C / Si composition of 0.95 or more and a region having a composition having a C / Si composition of 0.7 or less are alternately stacked. As shown in the carbon distribution curve shown in FIG. 7, it is more preferable that six or more regions are alternately stacked.
  • the physical characteristics are different in regions having different compositions, and the conditions under which cracks are likely to occur in the regions are also different.
  • the composition of SiOxCy constituting the gas barrier layer 12 small atomic ratio of carbon, the atomic ratio of oxygen is increased, the composition of the gas barrier layer 12 approaches the composition of SiO 2, the physical properties of the gas barrier layer 12 Is brittle like glass and easily breaks.
  • the gas barrier layer 12 includes a composition having a large carbon atomic ratio and a C / Si ratio of 0.95 or more, it is possible to make it difficult for the gas barrier layer 12 to crack.
  • a region having a composition with a C / Si of 0.95 or more, a region with a composition with a small C / Si, and a region with a composition with a C / Si of 0.70 or less have different crack resistance.
  • a crack is likely to occur in either one of a region having a composition in which C / Si is 0.95 or more and a region having a composition in which C / Si is 0.70 or less.
  • cracks hardly occur in the other region. For this reason, when there are two or more regions having greatly different compositions in the gas barrier layer 12, regions having different crack resistances are stacked, and large cracks that penetrate the thickness direction of the gas barrier layer 12 at a time are formed.
  • the gas barrier layer 12 is preferably less contaminated with foreign matters such as particles.
  • foreign substances such as particles mixed during film formation are present inside the gas barrier layer 12
  • the gas barrier film 10 is molded to form a cubic curved surface and the gas barrier layer is stretched, stress is applied around the foreign substances. It is thought that this becomes the starting point for cracks to concentrate. Therefore, it is considered that the smaller the number of foreign matters per unit area of the gas barrier layer 12, the generation of cracks after the molding process accompanied by the formation of the cubic curved surface in the gas barrier film 10 is suppressed.
  • the number of protrusions with a height of 10 nm or more observed on the surface is preferably 100 pieces / mm 2 or less. If the number of protrusions is 100 / mm 2 or less, the crack resistance of the gas barrier layer 12 is not lowered, and the gas barrier property of the gas barrier film 10 is hardly lowered.
  • minute protrusions of about 10 nm are difficult to separate and detect due to the influence of the undulation component of the surface roughness (unevenness having a long wavelength). For this reason, the number of minute protrusions of 10 nm or more in the gas barrier layer 12 is defined by a value detected and counted by the following method.
  • the surface of the gas barrier layer 12 is measured using an optical interference type three-dimensional surface roughness measuring device (Veeco WYKO NT9300). And by this measurement, the three-dimensional surface roughness data of the gas barrier layer 12 are acquired.
  • the acquired three-dimensional surface roughness data is subjected to a process of removing a roughness waviness component by applying a high-pass filter having a wavelength of 10 ⁇ m.
  • protrusions having a height of 10 nm or more are counted when the maximum peak position when the data is displayed as a histogram is set to zero.
  • the counted number of protrusions is calculated as the number per mm 2 . More specifically, under the conditions of a measurement resolution of about 250 nm, it was measured and counted (0.114 mm 2 as the area) range 6 field of 159.2 ⁇ m ⁇ 119.3 ⁇ m, calculated as the number per 1 mm 2.
  • images 159.2 ⁇ m ⁇ 119.3 ⁇ m in which the three-dimensional surface roughness conversion data obtained by processing by the above method are displayed as histograms are shown in FIGS. 12 to 14, the color is displayed in white as the height increases from the reference position on the surface of the gas barrier layer 12.
  • FIG. 12 is an image of the surface obtained by the above processing for the gas barrier layer 12 having a number of protrusions of less than 10 / mm 2 .
  • FIG. 13 is an image of the surface obtained by the above-described treatment with respect to the gas barrier layer 12 having the number of protrusions of 50 pieces / mm 2 or more and less than 100 pieces / mm 2 .
  • FIG. 14 is an image of the surface obtained by the above processing for the gas barrier layer 12 having a number of protrusions of 200 pieces / mm 2 or more.
  • the number of protrusions is 50 / mm 2 or more and less than 100 / mm 2 and the number of protrusions is 200 / mm 2 or more, and the number of protrusions exceeding 10 nm in height increases. Every time, the number of white spots displayed in the image increases. Therefore, by detecting and counting with the above method, the number of minute protrusions of about 10 nm on the surface of the gas barrier layer 12 can be defined.
  • the gas barrier film of 2nd Embodiment is the structure similar to the gas barrier film of the above-mentioned 1st Embodiment except that the processing shape of a cubic curved surface differs. For this reason, in the following description, description is abbreviate
  • FIG. 15 and 16 show the configuration of the gas barrier film.
  • FIG. 15 is a plan view of the gas barrier film.
  • FIG. 16 is a cross-sectional view taken along line AA of the gas barrier film 70 shown in FIG.
  • the gas barrier film 70 includes a base material 11 and a gas barrier layer 12 formed on one surface of the base material 11 of the base material 11.
  • the gas barrier film 70 which consists of the base material 11 and the gas barrier layer 12 satisfy
  • the gas barrier film 70 includes a tertiary curved surface portion 76 on which a three-dimensional curved surface is formed, and a substantially flat surface disposed outside the tertiary curved surface portion 76. And a flat region 74 composed of a large region.
  • the gas barrier film 70 includes a flat region 74 disposed in the cubic curved surface portion 76, and the curved region is formed from the flat region 74 disposed in the cubic curved surface portion 76 and the cubic curved surface portion 76. 14 is formed.
  • the flat region 74 formed of a substantially flat region is a region that is in contact with the flat plate as a surface with substantially no gap.
  • the cubic curved surface portion 76 having a three-dimensional curved surface is a region in contact with the flat plate by a line or a point.
  • the gas barrier film 70 has a concave surface on one surface and a convex surface on the other surface.
  • the gas barrier layer 12 side is a surface having a concave portion
  • the base material 11 side is a surface having a convex portion.
  • the position of the surface of the flat plate in contact with the gas barrier film 70 on the gas barrier layer 12 side (the surface side having the recesses) of the gas barrier film 70 is indicated by a broken line 20. Further, in FIG. 16, the position of the surface of the flat plate in contact with the gas barrier film 70 on the base material 11 side (surface side having the convex portion) of the gas barrier film 70 is indicated by a broken line 21.
  • This flat plate is illustrated for explaining the shape of the gas barrier film 70 and is not included in the configuration of the gas barrier film 70.
  • the flat region 74 is provided in the gas barrier film 70 at the peripheral side and the central portion.
  • the flat portion around the frustoconical convex portion provided at the center of the gas barrier film 70 is a flat region 74 on the peripheral side.
  • the flat portion of the portion serving as the upper base of the truncated cone is a flat region 74 at the center of the gas barrier film 70.
  • substantially flat and substantially in contact with no gap means that, as shown in FIG. 16, the gas barrier layer 70 side (surface side having a recess) of the gas barrier film 70 is used.
  • the gap 15 between the flat plate surface (broken line 20) is 0.1 mm or less, and the base material 11 side (surface side having the convex portion) of the gas barrier film 70 is in contact with the flat plate.
  • the gap 22 between the surface of the flat plate (broken line 21) is 0.1 mm or less.
  • the flat region 74 on the peripheral side of the gas barrier film 70 corresponds to a region where a portion for taking out an electrode from the device region is formed when the gas barrier film 70 is applied to an electronic device or the like. For this reason, the configuration in which slight unevenness of 0.1 mm or less due to wiring or the like is formed also in the “substantially flat region”.
  • the flat region 74 provided on the center side of the cubic curved surface portion 76 is a recess formed on one surface side of the gas barrier film 70 and a flat plate in contact with the gas barrier film 70.
  • the gap 16 with the surface (broken line 20) is 0.5 mm or more on average.
  • the tertiary curved surface portion 76 is provided between the peripheral flat region 74 and the central flat region 74.
  • the part that becomes the hypotenuse of the side surface of the truncated cone is the tertiary curved surface portion 76 of the gas barrier film 70.
  • the tertiary curved surface portion 76 of the gas barrier film 70 is provided at 9% or more and 11% or less of the projected area of the entire region including the flat region 74 on the peripheral side, the tertiary curved surface portion 76, and the flat region 74 at the center. ing.
  • the projection area of the flat region 74 and the cubic curved surface portion 76 is not a projection area of the entire gas barrier film 70 but a specific area for measuring the gas barrier property in the gas barrier film 70.
  • the measurement area 73 is an area in a range that can be measured by the measurement apparatus, and is defined in accordance with the area obtained from the area ratio between the flat area 74 and the cubic curved surface portion 76. That is, the area of the measurement region 73 is defined so that the projected area of the cubic curved surface portion 76 is 9% or more and 11% or less of the projection area of the measurement region 73.
  • the gas barrier film 70 has a three-dimensional curved surface molded so that the measured area of the cubic curved surface portion 76 is 5% or more larger than the projected area of the cubic curved surface portion 76 described above.
  • the actual measurement area is an area assumed to be a state in which a processed surface having a curved surface is extended on a plane.
  • the flat region 74 and the tertiary curved surface portion 76 are either on the surface side where the concave portion is formed (gas barrier layer 12 side) or on the surface side where the convex portion is formed (base material 11 side). It is defined by the shape of In general, since the shape of the gas barrier layer 12 is also deformed following the deformation of the base material 11, the shape of the flat region 74 and the tertiary curved surface portion 76 is a surface on which a recess is formed except for deviation due to thickness. The shape on the side (gas barrier layer 12 side) and the shape on the surface side (base material 11 side) on which the convex portions are formed substantially coincide. For this reason, by defining the shape of one surface, the shape of the other surface is also defined.
  • a flat gas barrier film 70 is formed in order to suppress a decrease in gas barrier property, as in the first embodiment. After that, it is molded into a shape having a tertiary curved surface portion 76. In this method, film formation failure of the gas barrier layer 12 of the cubic curved surface portion 76 is unlikely to occur, so that even when the measured area of the cubic curved surface portion 76 is processed to a shape that is 5% or more larger than the projected area, The gas barrier film 70 in which the deterioration of the property is suppressed can be produced.
  • the gas barrier layer 12 contains silicon, oxygen, and carbon. For this reason, it is possible to suppress the occurrence of defects in the gas barrier layer 12 even when forming into a shape having a curved surface in which the measured area is 5% or more larger than the projected area.
  • the gas barrier film 70 includes both a flat gas barrier film [A] in a state before the curved surface processing is formed and a gas barrier film [B] in which the flat region 74 and the tertiary curved surface portion 76 are formed by molding.
  • WVTR water vapor transmission rate measured under the conditions of 38 ° C. and 100% RH for 2 hours is 0.1 (g / m 2 / day) or less.
  • the water vapor transmission rate (WVTR) in the measurement region 73 of the flat gas barrier film [A] in the state before forming the curved surface processing under the above conditions, and the gas barrier film [B after forming the cubic curved surface portion 76 into processing [B] ] In relation to the water vapor transmission rate (WVTR) in the measurement area 73 satisfies “(B water vapor transmission rate (WVTR) / [A] water vapor transmission rate (WVTR)) ⁇ 5”.
  • both the gas barrier film [A] before molding and the gas barrier film [B] after molding satisfy the water vapor transmission rate (WVTR) of 0.1 (g / m 2 / day) or less, the curved surface Both of the gas barrier films 70 have sufficient gas barrier properties before and after the forming process. For this reason, the gas barrier film 70 satisfying this condition has a sufficient gas barrier property.
  • WVTR water vapor transmission rate
  • the gas barrier film [B] after the molding process slightly deteriorates in water vapor permeability (WVTR) due to the elongation treatment of the gas barrier layer 12 accompanying the curved surface processing of the cubic curved surface portion 76.
  • WVTR water vapor permeability
  • WVTR water vapor permeability
  • each configuration of the gas barrier film 10 shown in FIGS. 1 to 3 and the gas barrier film 70 shown in FIGS. 15 to 16 will be described.
  • the following description is an example of a gas barrier film, and the structure of a gas barrier film is not limited to these.
  • the gas barrier film may have a configuration other than these.
  • the gas barrier films 10 and 70 have a base material 11 and a gas barrier layer 12, and the gas barrier layer contains silicon, oxygen, and carbon, and is surrounded by a substantially flat region and the flat region.
  • Other configurations are not limited as long as they have a region (curved surface region) having a cubic curved surface portion on which a three-dimensional curved surface is formed.
  • Examples of the base material 11 used for the gas barrier films 10 and 70 include a resin film.
  • the resin film is a film that can hold the gas barrier layer, the material, the thickness, and the like are not particularly limited, and can be appropriately selected according to the purpose of use.
  • As the resin film a conventionally known resin film can be used.
  • the base material 11 may be formed from a plurality of materials. Examples of the resin film include resin films described in paragraphs [0124] to [0136] of JP2013-226758A, paragraphs [0044] to [0047] of WO2013 / 002026, and the like. .
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • COP polycycloolefin
  • the base material 11 has little light absorption and small haze. For this reason, the base material 11 can be appropriately selected from resin films that are generally applied to optical films.
  • the base material 11 may be a resin film or a plurality of layers may be used alone or may be formed of a plurality of layers.
  • the first base material 17 and the second base material 18 may be bonded by an adhesive layer 19.
  • the resin film can be used.
  • the adhesive layer 19 the structure similar to the adhesive layer of the protective film mentioned later is applicable.
  • the substrate 11 is not limited to a single wafer shape and a roll shape, but a roll shape that can be handled by a roll-to-roll method is preferable from the viewpoint of productivity.
  • the thickness of the substrate 11 is not particularly limited, but is preferably about 5 to 500 ⁇ m.
  • the hard coat layer is preferably formed from a curable resin.
  • the curable resin include epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, vinyl benzyl resins and other thermosetting resins, ultraviolet curable urethane acrylate resins, and ultraviolet curable polyesters.
  • active energy ray curable resins such as acrylate resins, ultraviolet curable epoxy acrylate resins, ultraviolet curable polyol acrylate resins, and ultraviolet curable epoxy resins.
  • the hard coat layer has fine particles of inorganic compounds such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, or polymethyl methacrylate to adjust the scratch resistance, slipperiness and refractive index.
  • the hard coat layer may contain a silicone-based surfactant, a polyoxyether compound, and a fluorine-siloxane graft polymer.
  • Examples of the organic solvent contained in the coating solution for forming the hard coat layer include hydrocarbons (eg, toluene, xylene, etc.), alcohols (eg, methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.). , Ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (eg, methyl acetate, ethyl acetate, methyl lactate, etc.), glycol ethers, other organic solvents, or these Can be used as a mixture.
  • the content of the curable resin contained in the coating solution is, for example, 5 to 80% by mass.
  • the hard coat layer can be applied by a known wet coating method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method using the above coating solution.
  • the layer thickness of the coating solution is, for example, 0.1 to 30 ⁇ m.
  • surface treatment such as vacuum ultraviolet irradiation on the base material 11 in advance.
  • the coating film formed by applying the coating solution is irradiated with active energy rays such as ultraviolet rays to cure the resin.
  • active energy rays such as ultraviolet rays
  • a hard coat layer is formed.
  • the light source used for curing include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, and a xenon lamp.
  • the irradiation conditions are preferably in the range of 50 to 2000 mJ / cm 2 , for example.
  • the gas barrier layer 12 constituting the gas barrier films 10 and 70 is a layer having a barrier property and contains silicon, oxygen, and carbon, and four curves indicating the carbon content in the thickness direction of the gas barrier layer. It has the above maximum value, and satisfies the above-mentioned composition of the gas barrier layer and the carbon distribution curve.
  • the gas barrier layer 12 is preferably formed by vapor-phase film formation of an inorganic compound that can be applied by a roll-to-roll method, which will be described later.
  • the gas barrier layer 12 formed by vapor deposition of an inorganic compound includes an inorganic compound containing silicon, oxygen, and carbon.
  • the gas-phase film-forming gas barrier layer containing an inorganic compound may contain an element other than the inorganic compound as a secondary component.
  • the gas barrier property of the gas-phase film-forming gas barrier layer is preferably a water vapor transmission rate (WVTR) of 1 ⁇ 10 ⁇ 1 (g / m 2 / day) or less, preferably 1 ⁇ 10 ⁇ 2 (g / m 2 / day). day) or less.
  • the gas barrier film after the molding process preferably has a water vapor transmission rate (WVTR) of 1 ⁇ 10 ⁇ 2 (g / m 2 / day) or less.
  • the film thickness of the gas-phase film-forming gas barrier layer is not particularly limited, but is preferably 5 to 1000 nm. If it is such a range, it will be excellent in high gas barrier performance, bending tolerance, and cutting workability. Further, the vapor deposition gas barrier layer may be composed of two or more layers.
  • the vapor phase film forming method for forming the vapor phase film forming gas barrier layer is not particularly limited.
  • An existing thin film deposition technique can be used to form the vapor deposition gas barrier layer.
  • a conventionally known vapor deposition method such as a vapor deposition method, a reactive vapor deposition method, a sputtering method, a reactive sputtering method, or a chemical vapor deposition method can be used.
  • the gas barrier layer formed by these vapor deposition methods can be manufactured by applying known conditions.
  • a raw material gas containing a target thin film component is supplied onto a base material, and the film is deposited by a chemical reaction on the surface of the base material or in the gas phase.
  • CVD chemical Vapor Deposition
  • a method of generating plasma for the purpose of activating a chemical reaction such as a thermal CVD method, a catalytic chemical vapor deposition method, a photo CVD method, or a plasma CVD method (PECVD method) using plasma as an excitation source.
  • Known CVD methods such as a vacuum plasma CVD method and an atmospheric pressure plasma CVD method may be mentioned.
  • the PECVD method is a preferable method.
  • the vacuum plasma CVD method will be described in detail as a preferred method of the chemical vapor deposition method.
  • a gas-phase film-forming gas barrier layer obtained by a vacuum plasma CVD method can produce a target compound by selecting conditions such as a raw material metal compound, decomposition gas, decomposition temperature, input power, and the like.
  • the raw material compound it is preferable to use a compound containing silicon and a compound containing metal, such as a silicon compound, a titanium compound, and an aluminum compound. These raw material compounds may be used alone or in combination of two or more.
  • known compounds can be used as these silicon compounds, titanium compounds, and aluminum compounds.
  • known compounds include those described in paragraphs [0028] to [0031] of JP2013-063658A, paragraphs [0078] to [0081] of JP2013-047002A, and the like. it can.
  • silane, tetramethoxysilane, tetraethoxysilane, hexamethyldisiloxane, etc. are mentioned.
  • a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide
  • examples thereof include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, and water vapor.
  • the decomposition gas may be used by mixing with an inert gas such as argon gas or helium gas.
  • a desired vapor deposition gas barrier layer can be obtained by appropriately selecting a source gas containing a raw material compound and a decomposition gas.
  • FIG. 17 shows an example of a schematic diagram of an inter-roller discharge plasma CVD apparatus using a roll-to-roll method, which is applied to the vacuum plasma CVD method.
  • FIG. 17 is a schematic diagram showing an example of an inter-roller discharge plasma CVD apparatus to which a magnetic field that can be suitably used in the production of a gas phase deposition gas barrier layer is applied.
  • An inter-roller discharge plasma CVD apparatus (hereinafter also simply referred to as a plasma CVD apparatus) 50 to which a magnetic field shown in FIG. 17 is applied includes a feeding roller 51, a transport roller 52, a transport roller 54, a transport roller 55, and a transport roller 57.
  • Film roller 53 and film formation roller 56, film formation gas supply pipe 59, plasma generation power source 63, magnetic field generation device 61 and magnetic field generation device 62 installed inside film formation rollers 53 and 56, winding And a roller 58.
  • at least the film forming rollers 53 and 56, the film forming gas supply pipe 59, the plasma generating power source 63, and the magnetic field generating apparatuses 61 and 62 are not shown in the vacuum.
  • electrode drums connected to the plasma generating power source 63 are installed on the film forming rollers 53 and 56. Further, in such a plasma CVD manufacturing apparatus, a vacuum chamber (not shown) is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by this vacuum pump. Yes.
  • each film forming roller generates plasma so that a pair of film forming rollers (film forming roller 53 and film forming roller 56) can function as a pair of counter electrodes.
  • the power supply 63 is connected. By supplying electric power to the pair of film forming rollers from the plasma generating power source 63, it is possible to discharge into the space between the film forming roller 53 and the film forming roller 56 and generate plasma.
  • the pair of film forming rollers 53 and 56 are preferably arranged so that their central axes are substantially parallel on the same plane. By arranging the pair of film forming rollers 53 and 56 in this manner, the film forming rate can be doubled and a film having the same structure can be formed.
  • a magnetic field generator 61 and a magnetic field generator 62 which are fixed so as not to rotate even when the film forming roller rotates, are provided.
  • known rollers can be used as appropriate, and those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently.
  • the feed roller 51 and the transport rollers 52, 54, 55, 57 used in such a plasma CVD manufacturing apparatus known rollers can be appropriately selected and used.
  • the winding roller 58 is not particularly limited as long as it can wind the substrate 60 on which the vapor-phase film-forming gas barrier layer is formed, and a known roller can be appropriately used.
  • the film forming gas supply pipe 59 one capable of supplying or discharging the source gas and the oxygen gas at a predetermined rate can be appropriately used.
  • the plasma generating power source 63 a conventionally known power source of a plasma generating apparatus can be used.
  • a power source AC power source or the like
  • it is more preferable that such a plasma generating power source 63 is one that can apply electric power in a range of 100 W to 10 kW and an AC frequency in a range of 50 Hz to 500 kHz.
  • the magnetic field generators 61 and 62 known magnetic field generators can be used as appropriate.
  • a desired gas barrier layer can be produced by appropriately adjusting the conveying speed of the resin substrate.
  • a film forming gas (raw material gas or the like) is supplied into the vacuum chamber, and plasma discharge is performed while a magnetic field is generated between the pair of film forming rollers 53 and 56.
  • a gas-phase film-forming gas barrier layer is formed on the surface of the base material 60 held by the film-forming roller 53 and on the surface of the base material 60 held by the film-forming roller 56 when the film gas (source gas or the like) is decomposed by plasma. Is formed.
  • the substrate 60 is conveyed by the feed roller 51, the conveyance rollers 52, 54, 55, 57, the take-up roller 58, the film formation rollers 53, 56, etc.
  • the gas-phase film-forming gas barrier layer can be formed by a continuous roll-type film forming process.
  • Deposition gas As a film forming gas used in the plasma chemical vapor deposition method, a source gas containing an organosilicon compound and an oxygen gas are used, and the content of the oxygen gas in the film forming gas is the same as that of the organosilicon compound in the film forming gas. It is preferable that the amount is less than the theoretical oxygen amount necessary for complete oxidation of the whole amount.
  • organosilicon compound containing at least silicon is preferable to use as the source gas constituting the film forming gas used for the production of the vapor phase film forming gas barrier layer.
  • organosilicon compound applicable to the production of the gas-phase film-forming gas barrier layer include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane Etc.
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of handling in film formation and gas barrier properties of the obtained gas-phase film formation gas barrier layer. preferable.
  • these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • the film forming gas can contain oxygen gas as a reaction gas in addition to the source gas.
  • Oxygen gas is a gas that reacts with a raw material gas to become an inorganic compound such as an oxide.
  • 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, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.
  • a film forming gas contains a source gas containing an organosilicon compound containing silicon and an oxygen gas
  • the ratio of the source gas to the oxygen gas is such that the source gas and the oxygen gas are completely reacted. It is preferable that the oxygen gas ratio is not excessively larger than the theoretically required oxygen gas ratio.
  • 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 100 Pa.
  • the electric power applied to the electrode drum connected to the plasma generating power source 63 to discharge between the film forming rollers 53 and 56 is the raw material gas. It can be appropriately adjusted according to the type, the pressure in the vacuum chamber, and the like.
  • the power applied to the electrode drum is preferably in the range of 0.1 to 10 kW, for example. If the applied power is in such a range, no particles (illegal particles) are generated, and the amount of heat generated during film formation is within the control range. Thermal deformation of the material, performance deterioration due to heat, and generation of wrinkles during film formation can be suppressed.
  • the conveyance speed (line speed) of the substrate 60 can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., but is within the range of 0.25 to 100 m / min. Preferably, it is more preferably in the range of 0.5 to 20 m / min. If the line speed is within the range, wrinkles due to the heat of the resin base material are not easily generated, and the thickness of the gas-phase film-forming gas barrier layer to be formed can be sufficiently controlled.
  • the average value of the carbon atom content ratio in the gas barrier layer can be determined by the following XPS depth profile measurement.
  • the silicon distribution curve, oxygen distribution curve, silicon distribution curve, etc. in the thickness direction of the gas barrier layer use both X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon.
  • XPS X-ray photoelectron spectroscopy
  • rare gas ion sputtering such as argon.
  • XPS depth profile measurement in which the composition of the surface is sequentially analyzed while exposing the inside of the sample.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
  • the etching time is generally correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer.
  • the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement is referred to as “distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer”.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 3 nm or less
  • X-ray photoelectron spectrometer Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific Irradiation
  • X-ray Single crystal spectroscopy AlK ⁇ X-ray spot and size: 800 ⁇ 400 ⁇ m oval
  • the carbon distribution curve is preferably substantially continuous.
  • the carbon distribution curve is substantially continuous, specifically, the distance from the surface of the gas barrier layer in the film thickness direction of at least one of the gas barrier layers calculated from the etching rate and the etching time ( x, unit: nm) and the atomic ratio of carbon (C, unit: at%) satisfy the condition represented by [(dC / dx) ⁇ 0.5].
  • the gas barrier layer contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements of the gas barrier layer.
  • the composition continuously changes in the layer thickness direction, and the carbon distribution curve among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy satisfies the requirement (1).
  • the gas barrier layer preferably has a configuration in which the carbon atom ratio continuously changes with a concentration gradient in a specific region.
  • the carbon distribution curve in the layer has a plurality of extreme values.
  • the carbon distribution curve has a plurality of extreme values, sufficient gas barrier properties can be obtained even when the gas barrier layer is bent.
  • the extreme value of the above distribution curve is the maximum or minimum value of the atomic ratio of the element to the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer.
  • the maximum value is an inflection point at which the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed, and 2 in the thickness direction from the position of the inflection point. It means that the atomic ratio value of the element at a position changed by ⁇ 20 nm decreases by 1 at% or more.
  • the minimum value is an inflection point at which the atomic ratio value of the element changes from decrease to increase when the distance from the surface of the gas barrier layer is changed, and the thickness direction from the position of the inflection point
  • the atomic ratio of the element at the position changed by 2 to 20 nm is increased by 1 at% or more. That is, the maximum value and the minimum value are points where the atomic ratio value of the element decreases or increases by 1 at% or more in any range when the position in the thickness direction is changed in the range of 2 to 20 nm.
  • the gas barrier layer is characterized by containing carbon atoms, silicon atoms, and oxygen atoms as constituent elements. Preferred embodiments of the ratio of each atom and the maximum and minimum values will be described below.
  • the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio in the carbon distribution curve is preferably 3 at% or more, and more preferably 5 at% or more. .
  • the difference between the maximum value and the minimum value of the carbon atom ratio is set to 3 at% or more, sufficient gas barrier properties can be obtained when the manufactured gas barrier layer is bent.
  • the difference between the maximum value and the minimum value is 5 at% or more, sufficient gas barrier properties can be obtained even when the gas barrier layer is bent.
  • the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) in the oxygen distribution curve is preferably 3 at% or more, and more preferably 5 at% or more.
  • the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) in the silicon distribution curve is preferably less than 10 at%, and more preferably less than 5 at%. . If the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) is less than 10 at%, the gas barrier properties and mechanical strength of the gas barrier layer can be obtained.
  • the gas barrier layer is substantially uniform in the film surface direction (direction parallel to the surface of the gas barrier layer).
  • the gas barrier layer is substantially uniform in the film surface direction.
  • the XPS depth profile measurement indicates that the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon total distribution at any two measurement points on the film surface of the gas barrier layer.
  • the thickness of the gas barrier layer is preferably in the range of 5 to 1000 nm, more preferably in the range of 20 to 500 nm, and particularly preferably in the range of 40 to 300 nm. If the thickness of the gas barrier layer is within the range, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are excellent, and good gas barrier properties can be obtained even in a bent state. Further, when the total thickness of the gas barrier layers is within the range, desired flatness can be realized in addition to the above effects.
  • a method for forming a gas barrier layer that simultaneously satisfies the requirements (1) and (2) is not particularly limited, and a known method can be used. From the viewpoint of forming a gas barrier layer whose element distribution is precisely controlled, discharge plasma chemistry having a discharge space between rollers to which a magnetic field is applied using the inter-roller discharge plasma CVD apparatus shown in FIG. It is preferable to use a vapor deposition method. For example, the method described in paragraphs [0049] to [0069] of International Publication No. 2012/046767 can be referred to.
  • an inter-roller discharge plasma processing apparatus to which a magnetic field is applied is used, the substrate is wound around a pair of film forming rollers, and the film is formed between the pair of film forming rollers. It is preferable to form the gas barrier layer by a plasma chemical vapor deposition method in which plasma discharge is performed while supplying a film gas. Further, when discharging while applying a magnetic field between the pair of film forming rollers, it is preferable to reverse the polarity between the pair of film forming rollers alternately.
  • the surface portion of the substrate existing on one film forming roller can be formed, and the surface portion of the substrate existing on the other film forming roller can be formed simultaneously. It becomes possible. That is, since the film formation efficiency can be doubled and a film having the same structure is formed, the extreme value of the carbon distribution curve can be doubled, and the above requirements (1) and (2) can be efficiently performed simultaneously. It is possible to form a gas barrier layer that fills.
  • the base material 11 for preparing the gas barrier films 10 and 70 having a flat shape is prepared.
  • a commercially available resin film capable of satisfying the above regulations is prepared.
  • the 2nd base material 18 is bonded together to the 1st base material 17 using the adhesive layer 19, and the base material 11 of a laminated structure is produced.
  • the base material 11 the first base material 17, the second base material 18, and the pressure-sensitive adhesive layer 19, the above-described materials and conventionally known materials can be applied.
  • the second base material 18 is prepared, and then the second base material 18 is prepared.
  • the pressure-sensitive adhesive layer 19 is formed on one surface of the film.
  • the 2nd base material 18 is bonded to the back surface side of the 1st base material 17 through the adhesive layer 19. As shown in FIG.
  • the bonding method of the 2nd base material 18 to the 1st base material 17 is not specifically limited, A conventionally well-known method is applicable.
  • an on-line method in which the gas barrier layer 12 described later is formed continuously with the bonding of the second base material 18. Moreover, the 2nd base material 18 is bonded to the 1st base material 17, and the base material 11 of the laminated structure which consists of the 1st base material 17, the adhesive layer 19, and the 2nd base material 18 is wound up with a winding shaft. After that, an off-line method in which the base material 11 having a laminated structure is unwound in a separate process and the gas barrier layer 12 is formed on the surface side of the first base material 17 may be used.
  • the gas barrier layer 12 is produced on the base material 11.
  • the gas barrier layer 12 may be produced as long as a film satisfying the above-described composition can be formed, and the above-described conventionally known method can be applied as a method for forming the gas barrier layer 12.
  • the gas barrier layer 12 is produced using an inter-roller discharge plasma CVD apparatus to which a magnetic field having a configuration shown in FIG. 17 is applied.
  • a substrate (mold) having a predetermined surface shape to be used for molding the gas barrier film 10 is prepared.
  • FIG. 18 the perspective view which shows schematic structure of a board
  • a substrate 30 shown in FIG. 18 includes a substantially flat portion (flat portion) 31 provided on the peripheral side and a convex portion 32 provided on the center side surrounded by the flat portion 31.
  • the portion where the flat portion 31 of the substrate 30 abuts becomes the flat region 13 of the gas barrier film 10.
  • the portion with which the convex portion 32 abuts becomes the curved region 14 of the gas barrier film 10.
  • substrate 30 needs to have the convex part 32 corresponding to the curved-surface area
  • the convex portion 32 has a quadrangular frustum shape provided with a predetermined height from the flat portion 31.
  • the height of the convex portion 32 becomes a gap 16 with the flat plate surface (broken line 20) in the curved region 14 of the gas barrier film 10.
  • the height of the convex part 32 in the substrate 30 is 0.5 mm or more higher than the flat part 31 on average.
  • the convex portion 32 has an inclined surface forming a side surface of the quadrangular pyramid with an angle of 15 ° to 45 ° with respect to the flat portion 31, and preferably 15 ° to 30 °. It is more preferable. Moreover, it is preferable that the corner
  • the curved region 14 of the gas barrier film 10 is formed into a shape having a cubic curved surface by the side surfaces of the quadrangular pyramid and the corners around the upper surface.
  • the gas barrier It is possible to suppress a decrease in gas barrier properties of the cubic curved surface portion due to the forming process of the conductive film 10.
  • the gas barrier layer 12 side of the gas barrier film 10 is disposed so as to face the substrate 30, and a buffer layer is interposed between the gas barrier layer 12 and the substrate 30.
  • the buffer layer is preferably a protective film, a pressure-sensitive adhesive layer, an adhesive layer, or the like.
  • Examples of the method for pressing the gas barrier film 10 having a flat shape against the substrate 30 include vacuum forming using a vacuum laminating apparatus and pressure forming using a mold having a recess corresponding to the shape of the substrate 30. It is done.
  • the application of heat to the gas barrier film 10 is preferably not less than the softening temperature of the substrate 11 and preferably less than the melting point of the substrate 11. By setting the heating temperature to be equal to or higher than the softening temperature, the gas barrier film 10 can be molded quickly.
  • the molding processing time of the gas barrier film 10 is not particularly limited, and can be arbitrarily set between several seconds to 60 minutes.
  • the gas barrier film 10 can be molded.
  • what is necessary is just to select suitably according to the shape etc. which are requested
  • the molding process conditions of the gas barrier film 10 can be arbitrarily adjusted according to the configuration of the gas barrier film 10.
  • the gas barrier film 70 has a curved surface area 14 composed of a cubic curved surface portion 76 and a flat region 74 disposed in the cubic curved surface portion 76, and a flat surface disposed outside the cubic curved surface portion 76.
  • a molding method for forming the region 74 will be described.
  • a substrate (mold) having a predetermined surface shape to be used for molding the gas barrier film 70 is prepared.
  • FIG. 19 the perspective view which shows schematic structure of a board
  • a substrate 80 shown in FIG. 19 includes a substantially flat portion (flat portion) 81 provided around the frustoconical convex portion disposed in the center of the substrate 80 and on the upper bottom portion of the truncated cone.
  • a curved surface processing part 82 is provided between the peripheral flat part 81 and the central flat part 81, which is provided on the hypotenuse of the truncated cone.
  • the portion where the flat portion 81 of the substrate 80 abuts becomes the flat region 74 of the gas barrier film 70.
  • the portion with which the curved surface processed portion 82 abuts becomes the tertiary curved surface portion 76 of the gas barrier film 70.
  • the curved surface processing portion 82 of the substrate 80 needs to have a shape corresponding to the tertiary curved surface portion 76 of the gas barrier film 70.
  • the curved surface processing portion 82 is a side surface of a truncated cone provided with a predetermined height from the flat portion 81 on the peripheral side, and the height of the truncated cone (curved surface processing portion 82) is the same.
  • the height of the frustoconical convex portion on the substrate 80 is preferably 0.5 mm or more higher than the flat portion 81 on the average.
  • the width of the truncated cone (curved surface processing portion 82) is the width of the cubic curved surface portion 76.
  • the width of the oblique side of the truncated cone shape on the substrate 80 is arbitrarily set according to the area of the cubic curved surface portion 76.
  • the curved surface processing portion 82 preferably has an angle of a slope forming the side surface of the truncated cone of 15 ° or more and 45 ° or less with respect to the flat portion 81 around the convex portion of the truncated cone shape. More preferably, the angle is 15 ° or more and 30 ° or less. Moreover, it is preferable that the corner
  • the cubic curved surface portion 76 of the gas barrier film 70 is formed into a shape having a curved surface by the corners of the upper base periphery and the side surface bottom portion of the truncated cone. For this reason, even if the cubic curved surface portion 76 having a curved surface is formed by setting the corners of the upper base periphery and side surface bottom portions of the truncated cone to the shapes within the above definition, the gas barrier film 70 is molded. It is possible to suppress a decrease in gas barrier properties of the tertiary curved surface portion.
  • the gas barrier layer 12 side of the gas barrier film 70 is disposed so as to face the substrate 80, and a buffer layer is interposed between the gas barrier layer 12 and the substrate 80.
  • the buffer layer is preferably a protective film, a pressure-sensitive adhesive layer, an adhesive layer, or the like.
  • Examples of the method for pressing the gas barrier film 70 having a flat shape against the substrate 80 include vacuum forming using a vacuum laminating apparatus and pressure forming using a mold having a recess corresponding to the shape of the substrate 80. It is done.
  • the application of heat to the gas barrier film 70 is preferably not less than the softening temperature of the substrate 11 and preferably less than the melting point of the substrate 11. By setting the heating temperature to be equal to or higher than the softening temperature, the gas barrier film 70 can be quickly formed.
  • the molding processing time of the gas barrier film 70 is not particularly limited, and can be arbitrarily set between several seconds to 60 minutes.
  • the gas barrier film 70 can be molded.
  • what is necessary is just to select suitably about the shape etc. of a board
  • the molding process conditions of the gas barrier film 70 can be arbitrarily adjusted according to the configuration of the gas barrier film 70.
  • the protective film includes a protective substrate and a pressure-sensitive adhesive layer for bonding the protective substrate onto the gas barrier layer 12 of the gas barrier films 10 and 70.
  • materials used for the protective substrate and the pressure-sensitive adhesive layer are not particularly limited.
  • the protective film may be provided not only on the gas barrier layer 12 of the gas barrier films 10 and 70 but also on the substrate 11 side of the gas barrier films 10 and 70.
  • the surface of the base material 11 can be protected by providing a protective film on the base material 11 side of the gas barrier films 10 and 70.
  • a self-adhesive coextrusion stretched multilayer film can be used as the protective film.
  • self-adhesive coextrusion stretched multilayer films include self-adhesive OPP films FSA-010M, FSA-020M, FSA-050M, FSA-100M, FSA-150M, and FSA-300M manufactured by Futamura Chemical Co., Ltd. FSA-010B or the like can be used.
  • the same resin film as the base material 11 of the gas barrier films 10 and 70 described above can be used. From the viewpoint of heat resistance and optical properties, it is preferable to use polypropylene (PP), polyethylene terephthalate (PET), or polyethylene naphthalate (PEN) as the protective substrate.
  • PP polypropylene
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the protective substrate may be a single resin film or a plurality of resin films, or may be formed of a plurality of layers.
  • the protective substrate is not limited to a single wafer shape and a roll shape, but a roll shape that can be handled by a roll-to-roll method is preferable from the viewpoint of productivity.
  • the thickness of the protective substrate is not particularly limited, but is preferably about 5 to 500 ⁇ m, and more preferably 25 to 150 ⁇ m. If the thickness of the protective substrate is 5 ⁇ m or more, the thickness becomes a sufficient thickness that is easy to handle. Moreover, if the thickness of a protective base material is 500 micrometers or less, it has sufficient softness
  • An adhesive layer is comprised including an adhesive.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is not particularly limited as long as the pressure-sensitive adhesive force required for the protective film can be obtained, and conventionally known materials can be used.
  • As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer a pressure-sensitive pressure-sensitive adhesive is preferable.
  • the pressure sensitive adhesive has cohesive strength and elasticity, and can maintain stable adhesiveness for a long time. Moreover, when forming an adhesive layer, requirements, such as a heat
  • the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer a material having excellent transparency is preferable.
  • the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer include pressure-sensitive adhesives including epoxy resins, acrylic resins, rubber resins, urethane resins, vinyl ether resins, and silicon resins.
  • a solvent type, an emulsion type, and a hot melt type can be used as the form of the pressure-sensitive adhesive.
  • an acrylic pressure-sensitive adhesive is preferable from the viewpoints of durability, transparency, and ease of adjustment of pressure-sensitive adhesive properties.
  • the acrylic pressure-sensitive adhesive is obtained by adding an acrylic polymer having an acrylic acid alkyl ester as a main component and copolymerizing a polar monomer component thereto.
  • the alkyl acrylate ester is an alkyl ester of acrylic acid or methacrylic acid and is not particularly limited.
  • ethyl acrylate isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, (meth ) Pentyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like.
  • Toyo Ink BPS5978 can be used.
  • an isocyanate-based, epoxy-based, or alidiline-based curing agent can be used as the curing agent for the acrylic pressure-sensitive adhesive.
  • an isocyanate curing agent it is preferable to use an aromatic system such as toluylene diisocyanate (TDI) in order to obtain a stable adhesive force even after long-term storage and to form a harder adhesive layer.
  • TDI toluylene diisocyanate
  • Toyo Ink BXX5134 can be used.
  • the addition amount of the curing agent is preferably 3% by mass to 9% by mass and more preferably 5% by mass to 7% by mass with respect to the pressure-sensitive adhesive.
  • the pressure-sensitive adhesive component can be sufficiently cured, sufficient adhesive force can be secured, and after the protective film is peeled off from the gas barrier film 10, 70, the gas barrier film 10, The pressure-sensitive adhesive layer hardly remains on the 70 side.
  • the weight average molecular weight of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is preferably 400,000 or more and 1.4 million or less. If the weight average molecular weight is a value within this range, the adhesive force is rarely excessive, and the adhesive force can be obtained within a necessary range. Furthermore, if it is the range of said weight average molecular weight, the residual of the adhesive layer to the gas barrier films 10 and 70 side after peeling can be prevented.
  • various additives can be used from the viewpoint of improving the physical properties of the pressure-sensitive adhesive layer.
  • natural resins such as rosin, modified rosin, rosin and modified rosin derivatives, polyterpene resins, terpene modified products, aliphatic hydrocarbon resins, cyclopentadiene resins, aromatic petroleum resins, phenolic resins, alkyl- Tackifiers such as phenol-acetylene resins, coumarone-indene resins, vinyltoluene- ⁇ -methylstyrene copolymers, anti-aging agents, stabilizers, and softeners can be used as necessary. . Two or more of these may be used as necessary.
  • organic ultraviolet absorbers such as a benzophenone series and a benzotriazole series, can also be added to an adhesive.
  • the thickness of the pressure-sensitive adhesive layer is preferably 10 ⁇ m or more and 50 ⁇ m or less for easy handling of the protective film. If it is such a range, sufficient contact
  • the method for forming (coating) the pressure-sensitive adhesive layer on the surface of the protective substrate is not particularly limited.
  • the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive on a protective substrate using a screen method, a gravure method, a mesh method, a bar coating method, or the like, and drying or curing.
  • An adhesive bond layer is a layer for protecting the surface of the gas barrier layer 12 of the gas barrier films 10 and 70 similarly to the above-mentioned protective film and adhesive layer.
  • the adhesive used as the adhesive layer is preferably one that can be adhesively cured from room temperature to 80 ° C.
  • the adhesive may be applied using a commercially available dispenser or screen printing.
  • the adhesive layer examples include photocurable or thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, moisture curable adhesives such as 2-cyanoacrylates, and epoxy.
  • Thermosetting or chemical curable (two-component mixed) adhesives such as hot-melt adhesives, hot-melt type polyamide-based, polyester-based, polyolefin-based adhesives, cationic-curing type UV-curable epoxy resin adhesives, etc. .
  • the base material 1 having a hard coat layer formed on both sides of the support was produced by the following method.
  • a hard coat coating solution HC1 in which the following materials were mixed was prepared.
  • Polymerizable binder SR368 manufactured by Sartomer 12.0 parts by mass
  • Polymerized binder Beam set 575 manufactured by Arakawa Chemical Co., Ltd. 22.0 parts by mass
  • Polymerization initiator Irgacure 651 manufactured by BASF Co.
  • Solvent Propylene glycol monomethyl ether 65 .0 parts by mass
  • HC1 was applied to one side of a support (PET film) so that the dry film thickness was 4 ⁇ m, dried, and then irradiated with ultraviolet rays under the condition of 500 mJ / cm 2. Cured and wound up.
  • a hard coat layer having a thickness of 4 ⁇ m is formed on the opposite surface of the support (PET film) in the same manner as described above, and further, a PET film (second substrate) having a thickness [Y] of 50 ⁇ m is formed.
  • the protective film provided with the slightly adhesive layer was bonded inline on the hard coat layer on the opposite side, and then wound up.
  • Substrate 2 As a support, prepared by Teijin DuPont Films Co., Ltd., a 23 ⁇ m-thick PET film having an easy-adhesion layer on both sides, KFL12W # 23 was prepared, and HC2 was used as a hard coat coating solution.
  • the base material 2 was produced by the method.
  • a base material 3 was prepared in the same manner as the base material 1 except that a 100 ⁇ m-thick PET film having an easy-adhesion layer on both sides and Lumirror U34 were prepared as a support.
  • the film forming conditions in the first film forming unit and the second film forming unit were set to any of the conditions C1 to C14 shown in Table 1 below. And in each film-forming part, the gas barrier layer was produced by applying one of the conditions of C1-C14. As common conditions for C1 to C14, the film formation effective width was converted to 1000 mm, the power supply frequency was 80 kHz, and the film formation roll temperature was 10 ° C.
  • the gas barrier layer in forming the gas barrier layer, an apparatus having two film forming units (a first film forming unit and a second film forming unit) is used, so that two layers each time the substrate is passed through the film forming apparatus.
  • the gas barrier layer is formed.
  • the first film formation transports the substrate from the first film formation unit to the second film formation unit (forward direction), and the second film formation starts from the second film formation unit.
  • the substrate was transported toward the first film forming unit (reverse direction).
  • the substrate in the odd-numbered film formation, the substrate is transported from the first film-forming unit to the second film-forming unit (forward direction), and in the even-numbered film formation, the first film-forming unit starts from the second film-forming unit.
  • the base material was conveyed toward the film part (reverse direction).
  • the base materials 1 to 3, the film formation conditions C1 to C14 and the number of film formations are selected from the combinations shown in Table 2 below to produce gas barrier films of samples 101 to 122, and further molded by the following method. processed.
  • SiO 2 was produced as a gas barrier layer by a conventional method using a roll-to-roll type sputtering film forming apparatus.
  • sputtering film formation a polycrystalline Si target was used as a target, and oxygen was introduced to adjust the composition to SiO 2 .
  • the film thickness was adjusted by adjusting the sputtering rate and the conveyance speed.
  • a metal substrate 30 having a flat portion 31 and a quadrangular pyramid-shaped convex portion 32 provided at the center of the flat portion 31 shown in FIG. 18 was prepared.
  • the upper surface of the convex portion 32 of the quadrangular pyramid is approximately 24 ⁇ 24 mm, and the angle of each hypotenuse of the quadrangular pyramid with respect to the flat portion 31 is 20 degrees.
  • the convex part 32 of the quadrangular pyramid is rounded around the upper surface with a radius of 0.5 mm.
  • five types of substrates 30 having different heights of the convex portions 32 of 0.2 mm, 0.6 mm, 0.8 mm, 1.0 mm, or 1.2 mm were prepared.
  • both sides of the gas barrier film were bonded using FSA-020M manufactured by Phutamura Chemical Co., Ltd. as a protective film to prepare a gas barrier film laminate.
  • the gas barrier film laminate is opposed to the substrate so that the gas barrier layer of the gas barrier film is on the substrate 30 side, the substrate 30 is heated to 100 ° C. using a vacuum laminating apparatus, and the molding processing time is 10 minutes. As described above, a gas barrier film was molded.
  • the XPS analysis was measured at 2.8 nm intervals in the thickness direction. Further, in determining the composition of SiOxCy constituting the gas barrier layer, the measurement points on the surface layer of the gas barrier layer were excluded because of the influence of the surface adsorbate. In addition, in the gas barrier layer, the thickness within the range of ABCD and ABEF described above is such that the composition immediately below the surface layer and the composition at the second measurement point from the surface layer are close because the film is continuously formed. The thickness was measured on the assumption that the composition of the second measurement point from the surface layer was continuously formed up to the surface position.
  • the surface of the gas barrier layer was measured using an optical interference type three-dimensional surface roughness measuring apparatus (WYKO NT9300 manufactured by Veeco) to obtain three-dimensional surface roughness data.
  • WYKO NT9300 manufactured by Veeco
  • the maximum when the data is displayed as a histogram When the peak height position was 0, protrusions having a height of 10 nm or more were counted and calculated as the number per mm 2 .
  • the number of protrusions of the obtained gas barrier layer was evaluated according to the following criteria (rank). Less than 5:10 pieces / mm 2 4:10 pieces / mm 2 or more, 50 / mm 2 less than 3:50 pieces / mm 2 or more, 100 / mm 2 less than 2: 100 pieces / mm 2 or more, 200 / Less than mm 2 1: 200 / mm 2 or more
  • the water vapor transmission rate (WVTR) was determined using the following Ca method evaluation. In the evaluation of each sample, when Ca was completely corroded at the time of storage for 2 hours, the water vapor transmission rate (WVTR) was set to 1.5 (g / m 2 / d) or more.
  • the shape of the quadrangular frustum-shaped convex portion 42 is the same as the shape of the substrate used for the molding process of the gas barrier film described above. That is, five types of glass substrates 40 each having a height of the convex portion 42 of 0.2 mm, 0.6 mm, 0.8 mm, 1.0 mm, or 1.2 mm were prepared.
  • calcium (Ca: corrosive metal) is vapor-deposited in the center of the convex portion 42 of the glass substrate 40 with an area of 20 mm ⁇ 20 mm using a vacuum evaporation apparatus JEE-400 manufactured by JEOL Ltd., and the thickness is 80 nm.
  • the Ca layer 43 was prepared.
  • the surface of the gas barrier layer was cleaned under a condition of 6 J / cm 2 using a UV cleaning device. Further, the gas barrier film was dried in a glove box.
  • a gas barrier film was bonded and sealed on the glass substrate 40 on which the Ca layer 43 was formed using an adhesive (manufactured by ThreeBond 1655) to prepare a Ca method evaluation sample.
  • the gas barrier film to which the adhesive was bonded was left in a glove box (GB) for one day and night in order to remove the moisture of the adhesive and the adsorbed water on the surface of the gas barrier film.
  • TB3124 (20 ⁇ m gap agent included) manufactured by ThreeBond Co., Ltd. as a sealing adhesive was applied to the flat portion 41 of the glass substrate 40 using a dispenser.
  • the sealing adhesive application position and application amount do not run on the Ca deposition part when the flat part around the molded gas barrier film is adhered and pressed to increase the adhesive thickness to 20 ⁇ m. And it adjusted so that it might not protrude from the circumference.
  • the Ca method evaluation sample was stored in an environment of 40 ° C. and 90% RH, and images of Ca corrosion state were taken under transmission conditions at regular intervals.
  • the amount of Ca corrosion was calculated from the concentration change of the Ca vapor deposition part, and WVTR was calculated under the condition that the evaluation area was 20 mm ⁇ 20 mm.
  • the gas barrier layer contains silicon, oxygen, and carbon, and y ⁇ 0.20 or y> 1.40 when represented by SiOxCy.
  • the sum of the thickness of the region having the composition is less than 20 nm. For this reason, even if it is molded into a shape having a gap of 0.5 mm or more in the bent region, the water vapor transmission rate (WVTR) is sufficiently low.
  • the water vapor permeability (WVTR) is 1 ⁇ 10 ⁇ 2 (g / m 2 / day) or less, and the gas barrier property is particularly good. This is because when the number of maximum values in the carbon distribution curve is large, the number of layers in the gas barrier layer where the composition continuously changes increases. This is probably because the fine cracks that were easily covered with other regions became difficult to penetrate the gas barrier layer.
  • the gas barrier films of Samples 101 to 113 have a composition that falls within the range of the above four points of ABCD in the distribution of (x, y) for each thickness in the composition represented by SiOxCy, in the thickness direction of the gas barrier layer. 40 nm to 200 nm.
  • the thickness of the composition within the range of the four points of ABEF described above was the same as the thickness of the composition within the range of the four points of ABCD.
  • the total thickness of regions having a composition of y ⁇ 0.20 or y> 1.40 in the composition of SiOxCy is more than 20 nm and 110 nm or more.
  • the thickness of the region having an extremely large oxygen ratio or carbon ratio is large, cracks are likely to occur, and cracks are likely to propagate to the entire gas barrier layer. it is conceivable that.
  • the gas barrier films of Samples 118 to 122 having a gas barrier layer of SiO 2 composition formed by sputtering film formation have a water vapor transmission rate (WVTR) of 1 ⁇ 10 ⁇ 1 (g / m 2 / day) or more. .
  • WVTR water vapor transmission rate
  • the gas barrier films of the sample 118 having a small gap of 0.2 mm in the bent region the water vapor permeability (WVTR) is 0.15 (g / m 2 / day), and the gas barrier properties of the samples 101 to 113 are as follows. Water vapor transmission rate (WVTR) is worse than film.
  • the gas barrier layer contains silicon, oxygen, and carbon, and y ⁇ 0.20 or y> 1.40 when represented by SiOxCy.
  • the sum of the thickness of the region having the composition is less than 20 nm.
  • the gas barrier films of Samples 201 to 206 have a composition that falls within the range of the four points of ABCD described above in the distribution of (x, y) for each thickness in the composition expressed by SiOxCy. 40 nm to 200 nm.
  • the thickness of the composition within the range of 4 points of the above-described ABEF was also the same as the thickness of the composition within the range of 4 points of ABCD. For this reason, even if it is molded into a shape having a gap of 0.5 mm or more in the bent region, the water vapor transmission rate (WVTR) is sufficiently low.
  • the gas barrier films of the sample 207 and the sample 208 have a SiOxCy composition in which the total thickness of regions having a composition of y ⁇ 0.20 or y> 1.40 exceeds 20 nm and is 122 nm or more. is there.
  • the thickness of the region having an extremely large oxygen ratio or carbon ratio is large, cracks are likely to occur, and cracks are likely to propagate to the entire gas barrier layer. it is conceivable that.
  • the gas barrier films of Samples 209 to 211 having a gas barrier layer of SiO 2 composition formed by sputtering film formation have a water vapor transmission rate (WVTR) of 1 ⁇ 10 ⁇ 1 (g / m 2 / day) or more. .
  • WVTR water vapor transmission rate
  • the gas barrier films of the sample 209 having a small gap of 0.2 mm in the bent region the water vapor permeability (WVTR) is 0.14 (g / m 2 / day), and the gas barrier properties of the samples 201 to 206 are as follows. Water vapor transmission rate (WVTR) is worse than film.
  • the base material 1 and the base material 2 were produced by the same method as in Example 1 described above. Further, in the same manner as in Example 1 described above, in the inter-roller discharge plasma CVD apparatus using the roll-to-roll method shown in FIG. The conditions of C14 were set.
  • a metal substrate 80 having a truncated cone-shaped convex portion formed at the center was prepared.
  • the convex shape of the truncated cone has a lower bottom radius of 56 mm and an upper bottom radius of 50 mm.
  • the height of the truncated cone is 1 mm
  • the width of the hypotenuse that becomes the side surface of the truncated cone is 3 mm.
  • the corner between the flat portion 81 and the curved surface processing portion 82 is rounded with a curvature radius of 0.5 mm.
  • the side surface of the truncated cone has a projected area of 499.5 mm 2 in a state where the corners are not rounded. This corresponds to about 10% of 5000 mm 2 which is a measurement area of Aquatran MODEL1 (manufactured by Mocon) used for water vapor permeability (WVTR) evaluation described later.
  • the side surface of this truncated cone has a ratio of projected area / measured area of 1.054. Even if the corners are rounded, these numbers are almost the same. Accordingly, when molding is performed using the substrate 80, the measured area of the curved surface area becomes 5% or more larger than the projected area.
  • both sides of the gas barrier film were bonded using FSA-020M manufactured by Phutamura Chemical Co., Ltd. as a protective film to prepare a gas barrier film laminate.
  • the gas barrier film laminate is made to face the substrate so that the gas barrier layer of the gas barrier film is on the substrate 80 side, the substrate 80 is heated to 100 ° C. using a vacuum laminating apparatus, and the molding processing time is 10 minutes. As described above, a gas barrier film was molded.
  • the surface protective film and the back surface protective film were peeled off from the gas barrier film.
  • Each gas barrier film was set in a measurement chamber of a water vapor transmission rate measuring device (trade name: Aquatran Model 1 manufactured by Mocon) so that the surface on which the gas barrier layer was formed was on the detection side of the device.
  • the gas barrier film was set so that the portion subjected to the cubic curved surface processing was approximately the center of the measurement chamber.
  • the water vapor permeability (WVTR) of the gas barrier film was measured in an atmosphere of 38 ° C. and 100% RH.
  • WVTR water vapor permeability
  • the gas barrier layer contains silicon, oxygen, and carbon, and the number of protrusions on the surface of the gas barrier layer is 100 pieces / mm 2 or less. For this reason, in the region of 10% of the projected area of the gas barrier film, the water vapor transmission rate (WVTR) is sufficient even after the molding process is performed to form a curved region where the measured area is 5% or more larger than the projected area. Very low.
  • the gas barrier films of Samples 301 to 309 have a composition that falls within the range of the above four points of ABCD in the distribution of (x, y) for each thickness in the composition represented by SiOxCy, in the thickness direction of the gas barrier layer. 40 nm to 200 nm.
  • the thickness of the composition within the range of the four points of ABEF described above was the same as the thickness of the composition within the range of the four points of ABCD.
  • the gas barrier film of the sample 308 has a sufficient gas barrier property with a water vapor transmission rate (WVTR) of 0.1 (g / m 2 / day) or less, but compared with the sample 301, the sample 302, and the like.
  • the gas barrier property with respect to the thickness is low. This is because the gas barrier film such as the sample 301 or the sample 302 has a C / Si ratio of 0.95 or more or 0.7 or less because the region having a composition of 90% or more is C / Si 0.95 or more or This is presumably because the gas barrier property is easier to improve than the sample 308 in which the region having a composition of 0.7 or less is less than 80%.
  • the gas barrier films of Samples 310 to 313 having a low evaluation of the number of surface protrusions of the gas barrier layer, and the gas barrier films of Samples 314 to 316 having a gas barrier layer having a SiO 2 composition formed by sputtering deposition are [B].
  • WVTR water vapor transmission rate
  • [B] water vapor permeability / [A] water vapor permeability is 5 or more.
  • the gas barrier films of Samples 301 to 309 have a total thickness of less than 20 nm with a region having a composition of y ⁇ 0.20 or y> 1.40 when expressed in SiOxCy.
  • the total thickness of regions having a composition of y ⁇ 0.20 or y> 1.40 exceeds 110 nm and is 110 nm or more in the composition of SiOxCy. .
  • the thickness of the region having an extremely large oxygen ratio or carbon ratio is large, cracks are likely to occur, and cracks are likely to propagate to the entire gas barrier layer. it is conceivable that.
  • the gas barrier layer contains silicon, oxygen, and carbon, and the number of protrusions on the surface is small, so that the measured area is 5% or more larger than the projected area in the area of 9 to 11% of the projected area. Even when this is performed, a gas barrier film with little deterioration of water vapor permeability can be realized. Furthermore, when the gas barrier layer is represented by SiOxCy, the total thickness of the regions having a composition of y ⁇ 0.20 or y> 1.40 is less than 20 nm, so that the gas barrier film is less deteriorated in water vapor permeability. Can be realized.

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Abstract

Selon la présente invention, lorsque la composition d'une couche barrière aux gaz est représentée par SiOxCy, le total de la région présentant une composition y<0,20 et de la région présentant une composition y>1,40 d'un film barrière aux gaz est inférieur à 20 nm dans le sens de l'épaisseur. De plus, le film barrière aux gaz a une région qui est sensiblement plate et une région ayant une surface incurvée en trois dimensions entourée par la région plate, et un espace moyen supérieur ou égal à 0,5 mm est formé entre la région présentant la surface incurvée en trois dimensions et une plaque plate.
PCT/JP2017/040900 2016-11-30 2017-11-14 Film barrière aux gaz et procédé de moulage de film barrière aux gaz WO2018101027A1 (fr)

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