WO2018101026A1 - ガスバリア性フィルム - Google Patents

ガスバリア性フィルム Download PDF

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Publication number
WO2018101026A1
WO2018101026A1 PCT/JP2017/040899 JP2017040899W WO2018101026A1 WO 2018101026 A1 WO2018101026 A1 WO 2018101026A1 JP 2017040899 W JP2017040899 W JP 2017040899W WO 2018101026 A1 WO2018101026 A1 WO 2018101026A1
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Prior art keywords
gas barrier
barrier layer
film
composition
gas
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PCT/JP2017/040899
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English (en)
French (fr)
Japanese (ja)
Inventor
美帆 宮▲崎▼
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コニカミノルタ株式会社
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Priority to JP2018553751A priority Critical patent/JPWO2018101026A1/ja
Priority to CN201780073940.5A priority patent/CN110214080B/zh
Publication of WO2018101026A1 publication Critical patent/WO2018101026A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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 provided with a gas barrier layer.
  • a gas barrier film in which a gas barrier layer is formed of an inorganic material layer using a roll-to-roll method on a long resin substrate, and a barrier film roll in which the gas barrier film is wound are known.
  • the barrier film roll and the gas barrier film may be transported in a state in which tension and heat are applied when processing such as sealing of an electronic device is performed.
  • the elastic modulus of the resin base material used for the gas barrier film is lowered by heating, the gas barrier film is stretched by 1 to 2% in a process in which tension and heat are applied.
  • the gas barrier layer is likely to crack at the elongation of 1 to 2%. Even when cracks are not detected by observation with an optical microscope, they are generated in a very fine region and affect the gas barrier properties. For this reason, in the barrier property evaluation using Ca corrosion, which will be described later, the average value of deterioration of the water vapor transmission rate (Water Vapor Transmission Rate; WVTR) over the entire film surface and the local VWTR abruptly caused by fine cracks. The difference with the bad deterioration becomes large.
  • WVTR Water Vapor Transmission Rate
  • Patent Document 1 a method of forming a plasma-deposited amorphous glass layer as a gas barrier layer (see Patent Document 1) or an organic material having a specific internal stress
  • Patent Document 2 A configuration of a gas barrier layer in which a material layer is formed as a base layer of an inorganic material layer (see Patent Document 2) has been proposed.
  • the WVTR is very large, about several grams, and it is suitable for application to sealing of electronic devices. Insufficient barrier properties.
  • the configuration in which an organic material layer having a specific internal stress is formed as an underlayer the generation of fine cracks that cannot be detected by optical microscope observation is suppressed, although the generation of cracks that can be detected by optical microscope observation can be suppressed. Not done. For this reason, there is a need for a gas barrier film that can suppress a decrease in gas barrier properties even when stretched.
  • the present invention provides a gas barrier film capable of suppressing a decrease in gas barrier properties.
  • 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 the curve indicating the carbon content in the thickness direction of the gas barrier layer has four or more maximum values (requirement (1)), and the gas barrier layer When the [film thickness / maximum value] of the curve indicating the carbon content in the thickness direction is 25 nm or less (requirement (2)) and the composition of the gas barrier layer is expressed by SiOxCy, y ⁇ 0 The total of the region having a composition of 20 and the region having a composition of y> 1.40 is less than 20 nm in the thickness direction.
  • the gas barrier film [A] that has not been subjected to the stretching treatment and the gas barrier film [B] that has been subjected to the stretching treatment of 2% satisfy all the following provisions (1) to (3).
  • the average value of the water vapor permeability (WVTR) of [A] and the average value of the water vapor permeability (WVTR) of [B] are 0.2 (g / m 2 / day) or less.
  • the standard deviation ( ⁇ ) of the water vapor transmission rate (WVTR) of [A] and the standard deviation ( ⁇ ) of the water vapor transmission rate (WVTR) of [B] satisfy [ ⁇ ⁇ 0.30].
  • Embodiment 2 of gas barrier film 2. Components of the gas barrier film laminate Method for producing gas barrier film laminate
  • FIG. 1 the structure of the gas barrier film laminated body by which the protective film was bonded to both main surfaces of a gas barrier film and a gas barrier film is shown.
  • the gas barrier film laminate shown in FIG. 1 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.
  • a gas barrier film laminated body has the gas barrier film 10 which satisfy
  • the substrate 11 includes a support 13 and hard coat layers 14 and 15 provided on both surfaces of the support 13. Hard coat layers 14 and 15 are provided on both surfaces of the support 13.
  • a hard coat layer 14 is provided on the surface on which the gas barrier layer 12 is formed, and a hard coat layer 15 is provided on the surface opposite to the surface on which the gas barrier layer 12 is formed. ing.
  • the first protective film 20 and the second protective film 25 are provided on both main surfaces of the gas barrier film 10. If damage such as scratches occurs in the base material 11 or the gas barrier layer 12 during 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, the gas barrier property is lowered, the electronic device, etc. Defects in appearance will occur. For this reason, in each said manufacturing process, in order to prevent damage to the base material 11, the gas barrier layer 12, etc., the 1st protective film 20 and the 2nd protective film 25 which can peel are provided in both the main surfaces of the gas barrier film 10. It is preferable.
  • the first protective film 20 includes a first protective substrate 21 and a first pressure-sensitive adhesive layer 22.
  • the first pressure-sensitive adhesive layer 22 is provided so as to cover the gas barrier layer 12, and the first protective base material 21 is bonded to the gas barrier film 10 via the first pressure-sensitive adhesive layer 22.
  • the 1st protective film 20 is bonded so that the 1st protective film 20 can peel from the gas barrier film 10, or the 1st protective base material 21 can peel from the 1st adhesive layer 22. Has been.
  • the second protective film 25 includes a second protective substrate 26 and a second pressure-sensitive adhesive layer 27. And the 2nd adhesive layer 27 is provided so that the back surface side (hard-coat layer 14 side) of the base material 11 may be covered, and the 2nd protective base material 26 is the gas barrier film 10 through this 2nd adhesive layer 27. Is pasted. Moreover, the 2nd protective film 25 is bonded so that the 2nd protective film 25 can peel from the gas barrier film 10.
  • the gas barrier film laminate having the configuration shown in FIG. 1 includes the first protective film 20 and the gas barrier between the gas barrier layer 12 of the gas barrier film 10 and the first pressure-sensitive adhesive layer 22 of the first protective film 20. Can be peeled off from the conductive film 10.
  • the first protective substrate 21 and the gas barrier film 10 can be peeled between the first protective substrate 21 of the first protective film 20 and the first adhesive layer 22 of the first protective film 20. is there.
  • the second protective film 25 and the gas barrier film 10 can be peeled between the base material 11 and the second pressure-sensitive adhesive layer 27 of the second protective film 25.
  • 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. 2 shows a curve indicating the content of silicon atoms in the thickness direction of the gas barrier layer 12 (hereinafter referred to as silicon distribution curve) and a curve indicating the content of carbon atoms in the thickness direction of the gas barrier layer 12 (hereinafter referred to as carbon distribution).
  • a curve) and a curve indicating the content of oxygen atoms in the thickness direction of the gas barrier layer 12 (hereinafter, oxygen distribution curve).
  • FIG. 3 shows a curve (hereinafter referred to as C / Si ratio distribution curve) showing a composition ratio (C / Si) of carbon to silicon in the thickness direction of the gas barrier layer 12 and silicon in the thickness direction of the gas barrier layer 12.
  • C / Si ratio distribution curve shows a curve showing a composition ratio (C / Si) of carbon to silicon in the thickness direction of the gas barrier layer 12 and silicon in the thickness direction of the gas barrier layer 12.
  • 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. 2 and the curve and maximum value indicating this content can be obtained by measuring the XPS depth profile described later. 3, the composition ratio (C / Si) of carbon atoms to silicon atoms in the thickness direction of the gas barrier layer 12, 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 distance (L) from the layer surface in the film thickness direction and the C / Si ratio distribution curve indicating the ratio of carbon atoms to silicon atoms change continuously.
  • the O / Si ratio distribution curve indicating the ratio of oxygen atoms to silicon atoms changes continuously.
  • the gas barrier film 10 has a carbon distribution curve having four or more maximum values (requirement (1)) and [film thickness / maximum number] is 25 nm or less (requirement (2)).
  • 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 four 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 interval between adjacent maximum values is 25 nm or less, and there are four or more regions where the composition continuously changes in the thickness direction.
  • the deterioration of the water vapor transmission rate (WVTR) of the gas barrier film 10 can be suppressed against elongation.
  • the reason why the gas barrier layer 12 can suppress deterioration of the water vapor transmission rate (WVTR) of the gas barrier film 10 after stretching by having a plurality of regions whose compositions continuously change is considered as follows. It is done. In addition, the following description is one of the guesses with respect to the mechanism for suppressing the deterioration of water vapor permeability (WVTR), which is derived from the configuration and effect of the gas barrier layer 12, and the mechanism for suppressing the deterioration of water vapor permeability (WVTR). Etc. are not limited to the following description.
  • the gas barrier layer has a single-layer structure
  • the crack when a crack occurs in the gas barrier layer when the gas barrier film is stretched, the crack propagates in the thickness direction, and the crack penetrates in the thickness direction of the gas barrier layer. It's easy to do.
  • 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 continuously changes, a crack occurs in one place (one region) in the gas barrier layer 12, and the inside of the region where the crack occurs is in the thickness direction. Even if the crack penetrates, the crack terminates between other areas, and the crack is difficult to propagate to the other areas. 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 minute crack does not grow so as to penetrate the entire gas barrier layer 12, and the crack may be caused by another region. 12 is contained. Therefore, when the gas barrier layer 12 has a plurality of regions in which the composition changes continuously in the thickness direction, deterioration of the water vapor permeability (WVTR) of the stretched gas barrier film can be suppressed.
  • WVTR water vapor permeability
  • the gas barrier layer 12 preferably has a maximum value of 6 or more in the carbon distribution curve.
  • 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 six or more maximum values, the composition is continuous. 7 or more layers are provided. By providing seven or more regions where the composition changes continuously, it is easy to express the effect that other regions cover the region where minute cracks have occurred, and the effect of preventing 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 gas barrier layer 12 in a state in which more regions are laminated is more likely to exhibit an effect that other regions cover the region where the crack is generated.
  • 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 8 or more, and more preferably 12 or more.
  • FIGS. 4 and 5 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. 4 and 5 correspond to FIGS. 2 and 3 described above, and the details of the graphs are the same as those in FIGS. 2 and 3.
  • FIG. 4 is a graph showing a silicon distribution curve, a carbon distribution curve, and an oxygen distribution curve of the gas barrier layer 12.
  • FIG. 5 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. 5, the ratio of silicon is defined as 1 based on the composition formula of SiOxCy.
  • the gas barrier film 10 of the example shown in FIGS. 4 and 5 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. Therefore, in the example shown in FIGS. 4 and 5 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 film 10 is composed of the gas barrier film 10 consisting of only the base material 11 and the gas barrier layer 12 before and after the 2% elongation treatment, and the elongation treatment with the gas barrier film [A] before the elongation treatment.
  • the applied gas barrier film [B] satisfies all the following provisions (1) to (3).
  • the average value of the water vapor permeability (WVTR) of [A] and the average value of the water vapor permeability (WVTR) of [B] are 0.2 (g / m 2 / day) or less.
  • (3) ( ⁇ ) of the water vapor transmission rate (WVTR) of [A] and the standard deviation ( ⁇ ) of the water vapor transmission rate (WVTR) of [B] satisfy [ ⁇ ⁇ 0.30].
  • the water vapor permeability (WVTR) of the gas barrier film 10 is a measured value at 60 ° C., 90% RH, 2 hours.
  • the water vapor permeability of the gas barrier film 10 is measured by the following methods a to e.
  • a water vapor permeability evaluation cell is produced by laminating a corrosive metal layer that reacts with moisture and corrodes on a moisture impermeable substrate, and a gas barrier film to be evaluated in this order.
  • Both the gas barrier film [A] before the stretching treatment and the gas barrier film [B] subjected to the stretching treatment satisfy the average value of water vapor permeability (WVTR) of 0.2 (g / m 2 / day) or less. Accordingly, the gas barrier film has sufficient gas barrier properties before and after stretching. For this reason, the gas barrier film 10 satisfying this condition has a sufficient gas barrier property.
  • WVTR water vapor permeability
  • the gas barrier film [B] subjected to the elongation treatment has a slight deterioration in water vapor transmission rate (WVTR) due to the elongation treatment.
  • WVTR water vapor transmission rate
  • the gas barrier film [B] is sufficient. It has a good gas barrier property. Therefore, the gas barrier film 10 was stretched by satisfying [(average value of water vapor permeability (WVTR) of [B] / average value of water vapor permeability (WVTR) of [A]) ⁇ 2]. Even after this, it has a sufficient gas barrier property.
  • the water vapor transmission rate (WVTR) if there is a defect in the gas barrier layer 12 in each region divided by a certain unit area, the water vapor transmission rate (WVTR) deteriorates in the region where the defect exists. For example, if a crack in the gas barrier layer 12 generated by the extension of the gas barrier film 10 penetrates the gas barrier layer 12, the water vapor permeability (WVTR) in the region where the crack is generated deteriorates.
  • the standard deviation ( ⁇ ) of the water vapor transmission rate (WVTR) of each divided region is calculated, when there is no region where the water vapor transmission rate (WVTR) deteriorates, the standard deviation ( ⁇ ) is 0. Less than 30. That is, even if a minute crack is generated in the gas barrier layer 12, the minute crack does not grow so as to penetrate the entire gas barrier layer 12, and all the generated cracks are enclosed in the gas barrier layer 12. The gas barrier property of the gas barrier layer 12 does not deteriorate in all the regions divided by a certain unit area, and the standard deviation ( ⁇ ) of the water vapor permeability (WVTR) remains small.
  • 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, 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 with a low oxygen ratio and a high carbon ratio. That is, the gas barrier layer 12, 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.
  • 6 to 9 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.
  • 6 and 7 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. ).
  • 8 and 9 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. 6 to 9 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 following four points of 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.
  • the composition of SiOxCy constituting the gas barrier layer 12 tends to be distributed along the SiC 2 —SiO 2 theoretical line shown in FIGS. As a whole, it tends to be distributed in a region having a higher carbon atomic ratio than the SiC 2 —SiO 2 theoretical line.
  • 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. In particular, it is preferable that all the regions of the gas barrier layer 12 are included in any region where C / Si is 0.95 or more or C / Si is 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 alternately. In particular, it is preferable that four or more regions in which C / Si has a composition of 0.95 or more and a region in which C / Si has a composition of 0.7 or less are alternately stacked. As shown in FIG. 5, it is more preferable that six or more regions are 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 atomic ratio of carbon having C / Si of 0.95 or more, it is possible to prevent cracks from being generated in the gas barrier layer 12.
  • regions having different crack resistance are stacked. It becomes the composition which was done.
  • the other region Are less likely to crack.
  • a region having different crack resistance is laminated, and a large crack that penetrates the thickness direction of the gas barrier layer 12 at a time. Can be suppressed. Therefore, in the gas barrier layer 12, the region where the above-described crack is generated is covered with another region, and the effect that the crack is shielded by the other region and is contained in the gas barrier layer 12 is more easily obtained.
  • 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, it is considered that if the gas barrier film 10 is subjected to stretching treatment, stress concentrates around the foreign substances and cracks are generated. It is done. Therefore, it is considered that the generation of cracks when the gas barrier film 10 is stretched is suppressed when the number of foreign matters per unit area of the gas barrier layer 12 is small.
  • the number of projections 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, in terms of measurement resolution 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
  • the color is displayed in white as the height increases from the reference position on the surface of the gas barrier layer 12.
  • FIG. 10 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. 11 is an image of the surface obtained by the above-described treatment with respect to the gas barrier layer 12 having a protrusion number of 50 / mm 2 or more and less than 100 / mm 2 .
  • FIG. 12 is an image of the surface obtained by the above process for the gas barrier layer 12 having a number of protrusions of 200 pieces / mm 2 or more.
  • the number of protrusions of less than 10 / mm 2 there are few protrusions exceeding a height of 10 nm displayed as white dots in the image. Then, as shown in FIGS. 11 and 12, less than the number of projections 50 / mm 2 or more 100 / mm 2, and a number of protrusions 200 / mm 2 or more, the number of projections is increased more than the height of 10nm As 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.
  • each structure of the gas barrier film laminate shown in FIG. 1 will be described.
  • the following description is an example of the gas barrier film laminated body by which the protective film was bonded by the gas barrier film, and the structure of a gas barrier film and a gas barrier film laminated body is not limited to these.
  • the gas barrier film and the gas barrier film laminate may have a configuration other than these.
  • the gas barrier film 10 includes a base material 11 and a gas barrier layer 12.
  • the gas barrier layer contains silicon, oxygen, and carbon, and the curve (carbon distribution curve) indicating the carbon content in the thickness direction of the gas barrier layer has a maximum value of 4 or more.
  • the [film thickness / maximum value number] of the curve (carbon distribution curve) showing the carbon content in the thickness direction of the gas barrier layer is 25 nm or less.
  • the gas barrier film [A] that has not been subjected to the stretching treatment and the gas barrier film [B] that has been subjected to the stretching treatment of 2% satisfy all of the above-mentioned regulations (1) to (3).
  • Other configurations of the gas barrier film 10 are not particularly limited as long as the above-described regulations are satisfied.
  • Examples of the substrate 11 used for the gas barrier film 10 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.
  • a structure in which a resin film is used as the support 13 and the hard coat layers 14 and 15 are provided on both surfaces of the support 13 may be used.
  • 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 layers 14 and 15 are 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 layers 14 and 15 include fine particles of inorganic compounds such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide in order to adjust the scratch resistance, slipperiness, and refractive index, and polymeta Methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester
  • An ultraviolet curable resin composition such as resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added.
  • the hard coat layers 14 and 15 may contain a silicone surfactant, a polyoxyether compound, and a fluorine-siloxane graft polymer.
  • Examples of the organic solvent contained in the coating liquid for forming the hard coat layers 14 and 15 include hydrocarbons (for example, toluene, xylene, etc.), alcohols (for example, methanol, ethanol, isopropanol, butanol, cyclohexane). Hexanol, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (eg, methyl acetate, ethyl acetate, methyl lactate, etc.), glycol ethers, and other organic solvents, Or these can be mixed and utilized.
  • the content of the curable resin contained in the coating solution is, for example, 5 to 80% by mass.
  • the hard coat layers 14 and 15 can be coated 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.
  • 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 to cure the resin.
  • the hard coat layers 14 and 15 are 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 film 10 is a layer having a barrier property, which contains the above-described silicon, oxygen, and carbon, and a curve indicating the carbon content in the thickness direction of the gas barrier layer. It has four or more maximum values 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 (hereinafter, also referred to as a vapor deposition gas barrier layer) 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 such that the water vapor transmission rate (WVTR) is preferably 0.2 (g / m 2 / day) or less, and 1 ⁇ 10 ⁇ 2 (g / m 2 / day). The following is more preferable.
  • 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 processability.
  • the vapor deposition gas barrier layer may be composed of two or more layers.
  • the vapor deposition method for forming the vapor deposition gas barrier layer is not particularly limited.
  • a vapor deposition method an existing thin film deposition technique can be used.
  • 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.
  • raw material compound it is preferable to use a silicon-containing compound or a metal-containing compound 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 the silicon compound, titanium compound, and aluminum compound.
  • 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. 13 shows an example of a schematic view of a roll-to-roll (roll to roll) inter-roller discharge plasma CVD apparatus applied to the vacuum plasma CVD method.
  • FIG. 13 is a schematic view 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. 13 is applied mainly includes a feeding roller 51, a transport roller 52, a transport roller 54, a transport roller 55, and a transport roller. 57, film formation 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 the film formation rollers 53 and 56. And a take-up roller 58.
  • a plasma CVD manufacturing apparatus In such a plasma CVD manufacturing apparatus, 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. Located in the chamber. In FIG. 13, 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 of the film forming rollers is plasma so that the pair of film forming rollers (the film forming roller 53 and the film forming roller 56) can function as a pair of counter electrodes.
  • the power supply 63 for generation is connected.
  • the pair of film forming rollers 53 and 56 are preferably arranged so that their central axes are substantially parallel on the same plane.
  • a magnetic field generator 61 and a magnetic field generator 62 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.
  • 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 by the film gas (raw material gas etc.) being 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 viewpoints of handling in film formation and gas barrier properties of the obtained gas-phase film-forming gas barrier layer. Moreover, 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 ratio of the oxygen gas is not excessively larger than the ratio of the amount of oxygen gas that is theoretically necessary to achieve this.
  • description, such as international publication 2012/046767, can be referred, for example.
  • 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 generation of particles (illegal particles) is observed, and the amount of heat generated during film formation is within the control range. There is no thermal deformation of the base material, performance deterioration due to heat, and no wrinkles during film formation.
  • 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 surface composition analysis is sequentially performed while the inside of the sample is exposed.
  • 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 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%) it means that the condition represented by [(dC / dx) ⁇ 0.5] is satisfied.
  • the gas barrier layer contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements of the gas barrier layer. And the composition changes continuously in the layer thickness direction, and among the distribution curves of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy, the carbon distribution curve has the above requirements (1) and ( 2) is satisfied.
  • the carbon atomic ratio has a configuration in which the carbon atom ratio continuously changes with a concentration gradient in a specific region of the gas barrier layer from the viewpoint of achieving both gas barrier properties and flexibility.
  • the carbon distribution curve in the layer has a plurality of extreme values.
  • the gas barrier property when the obtained film of the gas barrier layer is bent can be sufficiently exhibited.
  • 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.
  • the 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 is formed, and the surface portion of the resin substrate existing on the other film forming roller is formed simultaneously. Is 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 first protective film 20 includes a first protective substrate 21 and a first pressure-sensitive adhesive layer 22 for bonding the first protective substrate 21 on the gas barrier layer 12 of the gas barrier film 10.
  • the second protective film 25 includes a second protective substrate 26 and a second pressure-sensitive adhesive layer 27 for bonding the second protective substrate 26 onto the substrate 11 of the gas barrier film 10.
  • the protective film which comprises the 1st protective film 20 and the 2nd protective film 25 is the 1st protective base material 21 and the 2nd protective group by the adhesive layer which comprises the 1st adhesive layer 22 and the 2nd adhesive layer 27. If the protective base material which comprises the material 26 can peel from the gas barrier film 10, the material used for a protective base material and an adhesive layer will not be specifically limited.
  • 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 substrate 11 of the gas barrier film 10 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 type 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 strength can be secured, and the protective film is peeled off from the gas barrier film 10 and then adhered to the gas barrier film 10 side.
  • the agent layer is difficult to remain.
  • 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 film 10 side after peeling can be prevented. Furthermore, when the weight average molecular weight is in the above range, when the gas barrier layer 12 is formed using a method that requires heat and energy such as plasma CVD, transfer of the adhesive and peeling are less likely to occur, Peeling can be suppressed.
  • 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.
  • the gas barrier film laminate shown in FIG. 1 is formed by bonding the gas barrier film 10, the first protective film 20, and the second protective film 25 together.
  • the gas barrier film 10 includes a base material 11 and a gas barrier layer 12 formed on the first surface (front surface) side of the base material 11.
  • the first protective film 20 includes a first protective substrate 21 and a first pressure-sensitive adhesive layer 22 formed on the first surface (front surface) side of the first protective substrate 21.
  • the second protective film 25 includes a second protective substrate 26 and a second pressure-sensitive adhesive layer 27 formed on the first surface (front surface) side of the second protective substrate 26.
  • the 2nd adhesive layer 27 of the 2nd protective film 25 is bonded by the 2nd surface (back surface) side of the base material 11 of the gas barrier film 10, and the 1st surface (of the gas barrier layer 12 of the gas barrier film 10) ( It is the structure by which the 1st adhesive layer 22 of the 1st protective film 20 was bonded by the (surface) side.
  • the manufacturing method of a gas-barrier film laminated body forms the gas barrier layer 12 on the 1st surface of the base material 11, the process of bonding the 2nd protective film 25 which can peel on the 2nd surface side of the base material 11. And a step of bonding the first protective film 20 to the first surface side of the gas barrier layer 12. That is, the gas barrier film laminate forms the gas barrier layer 12 on the surface side of the substrate 11 of the substrate laminate after forming the substrate laminate in which the second protective film 25 is bonded to the substrate 11. Furthermore, it can produce by bonding the 1st protective film 20 on the gas barrier layer 12.
  • the step of forming the gas barrier layer 12 is a so-called transporting of the substrate laminate in which the second protective film 25 is bonded to the substrate 11 using a transport roller. It is preferable to apply a roll-to-roll manufacturing method.
  • the base material 11 for producing the gas barrier film 10 is prepared.
  • the base material 11 produces the resin film which can produce the gas barrier layer 12 with the manufacturing method of a roll to roll system.
  • the commercially available resin film which can produce the gas barrier layer 12 with the manufacturing method of a roll-to-roll system is prepared as the base material 11.
  • FIG. 1 The above-mentioned various resin films can be used as the resin film.
  • the production method of a conventionally well-known resin film is applicable to production of a resin film.
  • the first protective film 20 and the second protective film 25 are prepared by preparing a resin film to be the first protective base material 21 and the second protective base material 26 in the same manner as the base material 11.
  • the first pressure-sensitive adhesive layer 22 and the second pressure-sensitive adhesive layer 27 can be formed on the surface.
  • a commercially available resin film with an adhesive layer may be prepared as the first protective film 20 and the second protective film 25.
  • a conventionally known manufacturing method can be applied to the production of the first protective film 20 and the second protective film 25.
  • a clear hard coat layer or a layer having other functions is provided on the surfaces of the first protective substrate 21 and the second protective substrate 26. It may be formed. In the case of forming these layers, these layers are also included in the first protective substrate 21 and the second protective substrate 26 as part of the first protective substrate 21 and the second protective substrate 26. Also good.
  • the adhesive composition containing the adhesive for forming the 1st adhesive layer 22 and the 2nd adhesive layer 27 is prepared first.
  • the pressure-sensitive adhesive composition can be prepared, for example, by mixing a curing agent, a solvent, an additive, or the like with the above-described various resins serving as a pressure-sensitive adhesive as necessary.
  • a conventionally known method can be applied to the preparation of the adhesive composition.
  • the prepared adhesive composition is applied to one surface (front surface) side of the first protective substrate 21 and the second protective substrate 26.
  • the application of the adhesive composition is formed so that the thicknesses of the first adhesive layer 22 and the second adhesive layer 27 after curing satisfy the thickness specifications of the first protective film 20 and the second protective film 25.
  • the coating method of an adhesive composition is not specifically limited, A conventionally well-known method can be applied.
  • the pressure-sensitive adhesive composition is cured to form the first pressure-sensitive adhesive layer 22 and the second pressure-sensitive adhesive layer 27 by drying, heating, or irradiating active energy rays to the formed coating film.
  • Various methods for curing the pressure-sensitive adhesive composition and various conditions can be arbitrarily set according to the pressure-sensitive adhesive, solvent, additive, and the like to be used.
  • the 1st protective film 20 and the 2nd protective film 25 can be bonded to the gas barrier film 10, and the 1st protective film 20 and the 2nd protective film 25 can be peeled from the gas barrier film 10. If it can form, the formation method of the 1st adhesive layer 22 and the 2nd adhesive layer 27 will not be specifically limited.
  • the second protective film 25 is bonded to the base material 11.
  • the 2nd adhesive layer 27 of the 2nd protective film 25 is bonded with respect to the 2nd surface (back surface) of the base material 11, and a base material laminated body is produced.
  • the bonding method of the 2nd protective film 25 to the base material 11 is not specifically limited, A conventionally well-known method is applicable.
  • the gas barrier layer 12 is formed on the surface side of the substrate 11.
  • an arbitrary configuration may be selected from the various gas barrier layers 12 described above, and layers other than the various gas barrier layers 12 described above may be produced.
  • a roll-to-roll method in which the base material laminate in which the second protective film 25 is bonded to the base material 11 is unwound from the roller and the gas barrier layer 12 is formed on the film forming roller. It is preferable to use the manufacturing apparatus and the manufacturing method.
  • film formation method of the gas barrier layer 12 using a roll-to-roll manufacturing apparatus for example, film formation is performed using a plasma CVD film forming apparatus using the roll-to-roll method having the configuration shown in FIG. Is preferred.
  • the first protective film 20 is bonded to the gas barrier layer 12.
  • the first pressure-sensitive adhesive layer 22 of the first protective film 20 is bonded to the first surface (surface) of the gas barrier layer 12.
  • the method for bonding the first protective film 20 to the gas barrier layer 12 is not particularly limited, and a conventionally known method can be applied.
  • a gas barrier film laminate comprising the gas barrier film 10, the first protective film 20, and the second protective film 25 can be produced.
  • the bonding of the second protective film 25 to the base material 11 and the film formation of the gas barrier layer 12 are performed by bonding the second protective film 25 to the base material 11 and using the winding shaft with the base material 11. After winding up the base material laminate with the protective film 25, the base material laminate made up of the base material 11 and the second protective film 25 is unwound in a separate process to form the gas barrier layer 12 on the base material 11. An off-line method may be used. Further, the bonding of the second protective film 25 to the substrate 11 and the film formation of the gas barrier layer 12 are performed in an online manner in which the gas barrier layer 12 is formed continuously with the bonding of the second protective film 25. It is preferable.
  • 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 in the same manner as described above, and further, a protective film in which a slightly adhesive layer is provided on a 50 ⁇ m thick PET film is reversed. After bonding inline on the hard coat layer on the surface side, it was 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 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 standard deviation ( ⁇ ) of the water vapor transmission rate (WVTR) was evaluated according to the following criteria (rank). 5: Less than 0.01 4: 0.01 or more, less than 0.10 3: 0.10 or more, less than 0.30 2: 0.30 or more, less than 0.50 1: 0.50 or more
  • Tensilon (manufactured by A & D, RTC TENSILON RTC-1250A) is used as a chucking part for each 50 mm x 100 mm sample in the top and bottom direction, 80.8 mm (1% extension), 81.6 mm for the length of 80 mm.
  • the elongation treatment was performed under three conditions (2% elongation) and 82.4 mm (3% elongation).
  • the elongation rate was constant (0.5 mm / min), held for 1 minute, unloaded and returned to 80 mm, and the sample was removed from Tensilon.
  • the produced Ca method evaluation sample was stored at 60 ° C. and 90% RH environment for 2 hours. Then, light was incident on the Ca method evaluation sample after storage from the normal direction on the glass surface side, and photographed from the opposite surface side using an area type CCD camera, an evaluation image of the Ca layer was obtained.
  • the obtained evaluation image is divided into 100, the water permeation amount is calculated from the concentration change of the Ca vapor deposition part of each divided image, and the average value of the water vapor transmission rate (WVTR) from the slope of the water permeation amount with respect to time. (G / m 2 / day) was calculated. Further, the standard deviation ( ⁇ ) of the water vapor transmission rate (WVTR) was calculated from the value of the water vapor transmission rate (WVTR) for each of the 100 divided images.
  • the gas barrier layer contains silicon, oxygen, and carbon, and there are four or more curves indicating the carbon content in the thickness direction of the gas barrier layer.
  • the average value of water vapor permeability (WVTR) is 0.2 (g / g) for both the gas barrier film [A] that has not been subjected to stretching treatment and the gas barrier film [B] that has undergone 2% stretching treatment.
  • a high gas barrier layer of m 2 / day) or less is obtained. Further, the samples 101 to 110 satisfy (average value of water vapor transmission rate (WVTR) of [B] / average value of water vapor transmission rate (WVTR) of [A]) ⁇ 2, and [A] and [B The water vapor permeability (WVTR) standard deviation ( ⁇ ) satisfies [ ⁇ ⁇ 0.30].
  • the gas barrier films of Samples 101 to 110 have a composition in the range of 4 points of the above-mentioned 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 that falls within the range of the four points of ABEF described above was the same as the thickness of the composition that falls within the range of the four points of ABCD.
  • the gas barrier layer contains silicon, oxygen, and carbon
  • the carbon distribution curve in the thickness direction of the gas barrier layer has a maximum value of 4 or more
  • the [film thickness / maximum number] of the gas barrier layer is By being 25 nm or less, it is possible to realize a gas barrier film with little decrease in gas barrier properties even after the stretching treatment.
  • the gas barrier films of Samples 111 to 119 have a standard deviation ( ⁇ ) of the water vapor permeability (WVTR) of the water vapor permeability (WVTR) of the gas barrier film [B] subjected to the elongation treatment of 2%, [ ⁇ ⁇ 0.30] is not satisfied. That is, in the gas barrier films of Samples 111 to 119, the fine cracks generated by the stretching process penetrated the gas barrier layer, and a portion where the gas barrier property was locally reduced occurred in any of the divided areas. The standard deviation ( ⁇ ) of the internal distribution is thought to have increased.
  • the [film thickness / maximum value] of the gas barrier layer is more than 25 nm and 30 nm and 27.5 nm. As described above, when the average distance between adjacent maximum values is increased, it is considered that fine cracks generated by the stretching process easily penetrate the gas barrier layer, and the water vapor permeability is greatly decreased by the stretching process.
  • 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 Sample 115 and Sample 116 have two local maximum values in the carbon distribution curve. As described above, when the number of maximum values of the carbon distribution curve is small, the number of stacked layers in which the composition constituting the gas barrier layer continuously changes decreases, and fine cracks generated in one region due to the stretching process are reduced. It becomes difficult to be covered by the region. For this reason, it is thought that the fine crack which generate
  • the gas barrier films of Samples 117 to 119 have a gas barrier layer having a SiO 2 composition formed by sputtering film formation. For this reason, this gas barrier layer does not have the structure where the area
  • the gas barrier layer has a composition formula of SiOxCy, has a plurality of regions where the composition continuously changes in the thickness direction, and the thickness of one region where the composition continuously changes is sufficient. Since the small crack generated in one region by the stretching process is covered by another region, and the penetration of the gas barrier layer by this fine crack is suppressed, the water vapor permeability after the stretching process is reduced. A small gas barrier film can be realized.
  • SYMBOLS 10 Gas barrier film, 11, 60 ... Base material, 12 ... Gas barrier layer, 13 ... Support body, 14, 15 ... Hard-coat layer, 20 ... 1st protective film, 21 ... 1st protective base material, 22 ... 1st adhesive layer, 25 ... 2nd protective film, 26 ... 2nd protective base material, 27 ... 2nd adhesive layer, 50 ... Plasma CVD equipment, 51 ... Feeding rollers, 52, 54, 55, 57 ... Conveying rollers, 53,56 ... Film forming rollers, 58 ... Winding rollers, 59 ... Making Membrane gas supply pipe, 61, 62 ... Magnetic field generator, 63 ... Power source for plasma generation

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