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WO2019049618A1 - Film formant barrière aux gaz, pièce de test d'évaluation des propriétés de barrière à la vapeur d'eau, et procédé d'évaluation des propriétés de barrière à la vapeur d'un film formant barrière aux gaz - Google Patents

Film formant barrière aux gaz, pièce de test d'évaluation des propriétés de barrière à la vapeur d'eau, et procédé d'évaluation des propriétés de barrière à la vapeur d'un film formant barrière aux gaz Download PDF

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Publication number
WO2019049618A1
WO2019049618A1 PCT/JP2018/030332 JP2018030332W WO2019049618A1 WO 2019049618 A1 WO2019049618 A1 WO 2019049618A1 JP 2018030332 W JP2018030332 W JP 2018030332W WO 2019049618 A1 WO2019049618 A1 WO 2019049618A1
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WIPO (PCT)
Prior art keywords
layer
water vapor
gas barrier
reactive metal
metal layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/030332
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English (en)
Japanese (ja)
Inventor
森　孝博
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
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Konica Minolta Inc
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Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2019540853A priority Critical patent/JP7006694B2/ja
Priority to CN201880057076.4A priority patent/CN111065515B/zh
Priority to KR1020207005745A priority patent/KR102351115B1/ko
Publication of WO2019049618A1 publication Critical patent/WO2019049618A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier

Definitions

  • the present invention relates to a water vapor barrier film, a water vapor barrier property evaluation test piece, and a water vapor barrier property evaluation method of the gas barrier film.
  • the present invention particularly relates to a gas barrier film, a water vapor barrier property evaluation test piece, which makes it possible to detect with high precision the periodicity of fine streaks in the form of longitudinal streaks and changes in the gas barrier properties that appear in horizontal steps. And a method for evaluating the water vapor barrier properties of gas barrier films using them.
  • gas barrier films that block various gases such as water vapor and oxygen are used in various applications such as packaging materials such as food and medicine, and electronic devices such as solar cells and flat-screen TVs.
  • the said multilayer laminated structure is generally formed by conveying a manufacturing line multiple times, and laminating
  • a method of forming each constituent layer there are various methods such as a method of forming by vapor phase deposition in vacuum, a method of forming by solution coating in the atmosphere, and the like.
  • a long streak-like flaw in the transport direction can be mentioned as one of the defects of concern in the gas barrier film having a gas barrier layer having a multilayer laminated structure.
  • This longitudinal stripe-like flaw may take various forms by being stacked in a plurality of layers by different methods such as a film forming method and the like, and may be buried by being stacked, so that it may not be detected by an optical method. is there.
  • a failure derived from solution coating for example, a lateral step failure (longitudinal direction) in which a plurality of cycles are superimposed due to various effects during transportation
  • a lateral step failure longitudinal direction
  • the film thickness unevenness extending in the lateral direction which is periodically formed in the direction, may occur.
  • a gas barrier film roll having test sites provided with a 10 mm square Ca deposited layer at the center of the width of the gas barrier film roll manufactured by the roll to roll method at intervals of 4 m (see Patent Document 1).
  • Patent Document 1 a gas barrier film roll having test sites provided with a 10 mm square Ca deposited layer at the center of the width of the gas barrier film roll manufactured by the roll to roll method at intervals of 4 m.
  • the present invention has been made in view of the above problems and circumstances, and the problem to be solved is to detect with high precision the periodicity of gas barrier property changes which appear as fine streaks in the form of longitudinal stripes or lateral steps.
  • the present invention is to provide a gas barrier film, a water vapor barrier property evaluation test piece, and a water vapor barrier property evaluation method of the gas barrier film using them.
  • the present invention relates to a gas barrier film having a gas barrier layer on at least one surface of a long resin substrate as a result of examining the causes of the above problems and the like in order to solve the above problems according to the present invention.
  • the first and second water vapor barrier test regions are provided on the layer, and the first water vapor barrier test region is formed by sealing the first water reactive metal layer and the first water reactive metal layer.
  • a second water vapor barrier test region portion comprising a second water reactive metal layer and a second water vapor impermeable layer sealing the second water reactive metal layer.
  • the first moisture-reactive metal layer and the second moisture-reactive metal layer are partially overlapped with each other when viewed from at least one of the longitudinal direction and the width direction of the resin substrate
  • the longitudinal stripes are formed by Scratches and fine-found that the periodicity of the gas barrier property changes appearing beside stepped can be detected with high accuracy. That is, the subject concerning the present invention is solved by the following means.
  • a gas barrier film having a gas barrier layer on at least one surface of a long resin base material, A first water vapor barrier property test area and a second water vapor barrier property test area on the gas barrier layer;
  • the first water vapor barrier property test area portion includes a first water reactive metal layer and a first water vapor impermeable layer sealing the first water reactive metal layer in this order on the gas barrier layer.
  • Have The second water vapor barrier test region portion includes a second water reactive metal layer and a second water vapor impermeable layer sealing the second water reactive metal layer in this order on the gas barrier layer.
  • a gas-barrier film characterized in that it is arranged to be arranged as follows.
  • the first moisture-reactive metal layer and the second moisture-reactive metal layer are disposed such that there is a portion where they partially overlap with each other when viewed from the lateral direction.
  • the first moisture-reactive metal layer and the second moisture-reactive metal layer are disposed such that there is a portion overlapping each other when viewed from the longitudinal direction.
  • the first water vapor barrier test region portion further includes a first adhesive layer for fixing the first water vapor impermeable layer to the gas barrier layer,
  • the first vapor-impermeable layer is formed of a plate-like member selected from a metal, an opaque metal compound and a transparent metal compound.
  • the gas barrier film as described in.
  • the second water vapor barrier test area portion further includes a second adhesive layer for fixing the second water vapor impermeable layer to the gas barrier layer,
  • the second water-impermeable layer is formed of a plate-like member selected from a metal, an opaque metal compound and a transparent metal compound; The gas barrier film according to any one of the above.
  • first water vapor impermeable layer and the second water vapor impermeable layer are viewed from at least one of the longitudinal direction and the lateral direction, there is a portion in which the first water vapor impermeable layer and the second water vapor impermeable layer partially overlap with each other.
  • the length in the other of the hand direction is such that the first moisture-reactive metal layer and the second moisture-reactive metal layer are different from each other when viewed from either the longitudinal direction or the lateral direction 8.
  • the gas barrier film according to any one of items 1 to 7, characterized in that it is longer than the length in the other of the longitudinal direction and the lateral direction of the partially overlapping portion.
  • a gas barrier film capable of detecting with high precision the periodicity of fine streaks in the form of longitudinal streaks and changes in gas barrier properties appearing in the form of horizontal steps, a water vapor barrier property evaluation specimen, And the water vapor barrier property evaluation method of a gas barrier film using them can be provided.
  • the expression mechanism or action mechanism of the effects of the present invention is presumed as follows.
  • the first moisture reactive metal layer and the second moisture reactive metal layer are viewed from at least one of the longitudinal direction and the lateral direction of the resin substrate, Since the portions overlapping with each other are disposed, the water vapor barrier property can be evaluated without any gap in either the longitudinal direction or the width direction.
  • the periodicity of the gas barrier property change appearing in a horizontal step can be detected with high accuracy.
  • a schematic plan view showing an example of the gas barrier film of the present invention Arrow sectional view of a plane along line II-II in FIG. 1
  • a schematic plan view showing an example of the first water vapor barrier property test area and the second water vapor barrier property test area A schematic plan view showing another example of the first water vapor barrier property test area and the second water vapor barrier property test area
  • Schematic plan view showing another example of the gas barrier film of the present invention Schematic plan view showing another example of the gas barrier film of the present invention
  • the gas barrier film of the present invention is a gas barrier film having a gas barrier layer on at least one surface of a long resin base material, and the first water vapor barrier test region is formed on the gas barrier layer. Part and a second water vapor barrier property test area part, wherein the first water vapor barrier property test area part seals the first water reactive metal layer and the first water reactive metal layer on the gas barrier layer And a second water vapor reactive metal layer on the gas barrier layer, the second water vapor reactive metal layer, and the second water vapor reactive metal layer.
  • This feature is a technical feature that is common to or corresponds to each embodiment.
  • the first moisture-reactive metal layer and the second moisture-reactive metal layer are arranged such that there is a portion where they partially overlap with each other when viewed from the lateral direction. Is preferred.
  • the first moisture-reactive metal layer and the second moisture-reactive metal layer are disposed such that there is a portion where they partially overlap with each other when viewed from the longitudinal direction.
  • the first water vapor impermeable layer and the second water vapor impermeable layer is a vapor deposition layer.
  • the first or second water vapor impermeable layer can be disposed directly on the first or second water reactive metal layer without providing the adhesive layer, and the first or second water vapor barrier can be provided. It is possible to reduce the amount of water intruding from the end of the sex test area.
  • the first water vapor barrier property test area portion further includes a first adhesive layer for fixing the first water vapor impermeable layer to the gas barrier layer, and the first water vapor impermeable layer is It is preferable that the permeable layer is formed of a kind of plate-like member selected from metals, opaque metal compounds and transparent metal compounds.
  • the second water vapor barrier test region portion further includes a second adhesive layer for fixing the second water vapor impermeable layer to the gas barrier layer, and the second water vapor impermeable layer It is preferable that the permeable layer is formed of a kind of plate-like member selected from metals, opaque metal compounds and transparent metal compounds.
  • the first moisture-reactive metal layer and the second moisture-reactive metal layer partially overlap each other when viewed from either the longitudinal direction or the lateral direction.
  • the length in the other of the longitudinal direction and the lateral direction is preferably 1.0 mm or more.
  • the first or second moisture reactive metal layer is corroded from the periphery by the influence of the water vapor intruding from the end of the first or second water vapor barrier test area portion, and the overlapping portion disappears
  • the time of (4) is longer, and the water vapor barrier property of the gas barrier film in the overlapping portion can be evaluated in more detail.
  • the longitudinal direction or the lateral direction of the gas barrier film can be more reliably covered without gaps by the first and second water vapor barrier test regions.
  • the first water vapor impermeable layer and the second water vapor impermeable layer are partially mutually when viewed from at least one of the longitudinal direction and the lateral direction.
  • the first water vapor impermeable layer and the second water vapor impermeable layer are disposed such that there is an overlapping portion, and when viewed from either the longitudinal direction or the lateral direction
  • the first moisture-reactive metal layer and the second moisture-reactive metal layer have a length in the other of the longitudinal direction and the lateral direction of the partially overlapping portion in the longitudinal direction and the lateral direction. When viewed from any one of the above, it is preferable that the length in the longitudinal direction and the other in the lateral direction of the portion partially overlapping each other is longer than the other.
  • the first or second moisture reactive metal layer is corroded from the periphery by the influence of the water vapor intruding from the end of the first or second water vapor barrier test area portion, and the overlapping portion disappears This contributes to the fact that the time of (3) is longer, and more detailed evaluation can be performed on the water vapor barrier property of the gas barrier film in the overlapping portion.
  • the first water vapor impermeable layer and the second water vapor impermeable layer partially overlap each other when viewed from either the longitudinal direction or the lateral direction. It is preferable that the length in any one of the said longitudinal direction and the said width direction is 3.0 mm or more.
  • the first or second moisture reactive metal layer is corroded from the periphery by the influence of the water vapor intruding from the end of the first or second water vapor barrier test area portion, and the overlapping portion disappears This contributes to the fact that the time of (3) is longer, and more detailed evaluation can be performed on the water vapor barrier property of the gas barrier film in the overlapping portion.
  • the water vapor barrier property evaluation test piece of the present invention is a water vapor barrier which evaluates the water vapor barrier property of a section cut out from a gas barrier film having a gas barrier layer on at least one surface of a long resin base material.
  • a moisture-receptive metal layer provided on the gas barrier layer, and a water-vapor impermeable layer sealing the water-reactive metal layer, and the longitudinal direction of the gas barrier film It is characterized in that a marker indicating coordinates in at least one of the direction and the width direction is formed.
  • the water vapor barrier property evaluation method of the gas barrier property film of the present invention is characterized by using the above-mentioned gas barrier property film or the above-mentioned water vapor barrier property evaluation test piece. As a result, it is possible to detect with high precision the fine streaks of the longitudinal stripes of the gas barrier film and the periodicity of the change in the gas barrier properties that appears in the form of lateral steps.
  • the gas barrier film of the present invention is a gas barrier film having a gas barrier layer on at least one surface of a long resin base material, and the first water vapor barrier test region portion on the gas barrier layer And a second water vapor barrier property test area portion, the first water vapor barrier property test area portion sealing the first water reactive metal layer and the first water reactive metal layer on the gas barrier layer;
  • the second water vapor barrier test region portion has a second water reactive metal layer and a second water reactive metal layer sealed on the gas barrier layer.
  • first moisture-reactive metal layer and the second moisture-reactive metal layer are viewed from at least one of the longitudinal direction and the width direction of the resin substrate, having a water vapor impermeable layer in this order So that there are parts that overlap each other Characterized in that forming a structure which is arranged.
  • the gas barrier film of the present invention is preferably a resin substrate on which a gas barrier layer is formed by roll-to-roll, and is usually wound and stored as a master roll.
  • the transport direction of the roll-to-roll method is the longitudinal direction MD of the gas barrier film.
  • gas barrier property means, for example, the water vapor permeability measured by the method according to JIS K 7129-1992, or the oxygen transmission rate measured by the method according to JIS K 7126-1987. Indicated. Generally, when the water vapor transmission rate is 1 g / (m 2 ⁇ 24 hr) or less or the oxygen transmission rate is 1 mL / (m 2 ⁇ 24 hr ⁇ atm) or less, it is said to have gas barrier properties.
  • the water vapor transmission rate is 1 ⁇ 10 -2 g / (m 2 ⁇ 24 hr) or less, it is said to have high gas barrier properties, and it can be used for electronic devices such as organic EL, electronic paper, solar cells, and LCD it can.
  • FIG. 1 is a schematic plan view of a long gas barrier film 1 as viewed from the thickness direction.
  • FIG. 2 is an arrow sectional view of a plane along line II-II in FIG.
  • FIG. 3 is a schematic plan view of a part of the gas barrier film 1 as viewed in the thickness direction.
  • the gas barrier film 1 has a first water vapor barrier property test region 10 and a second film on a gas barrier layer 5 provided on one surface of a long resin base 4.
  • a plurality of water vapor barrier property test areas 20 are provided along the lateral direction TD.
  • the first water vapor barrier property test area portion 10 and the second water vapor barrier property test area portion 20 are alternately provided over the entire effective width (product effective width) of the gas barrier film 1 in the lateral direction TD. .
  • the first water vapor barrier test region portion 10 and the second water vapor barrier test region portion 20 partially overlap with each other.
  • the first water vapor barrier property test region portion 10 seals the first moisture reactive metal layer 12 and the first moisture reactive metal layer 12 on the gas barrier layer 5. It further has a first adhesive layer 13 having a water vapor impermeable layer 11 in this order and fixing the first water vapor impermeable layer 11 to the gas barrier layer 5.
  • the second water vapor barrier property test region portion 20 is similarly configured, and the second water vapor impermeability that seals the first moisture reactive metal layer 22 and the second moisture reactive metal layer 22 on the gas barrier layer 5 And a second adhesive layer (not shown) for fixing the first water vapor impermeable layer to the gas barrier layer 5 in this order.
  • first water vapor barrier property test areas 10 and four second water vapor barrier property test areas 20 are provided, but the present invention is not limited to this. One to three of each may be provided, or five or more may be provided. Further, the numbers of the first water vapor barrier property test area portion 10 and the second water vapor barrier property test area portion 20 on the gas barrier layer 5 may be different from each other.
  • the first moisture reactive metal layer 12 is formed on the first water vapor impermeable layer 11 so that the first moisture reactive metal layer 12 faces the gas barrier layer 5.
  • the first water vapor impermeable layer 11 is disposed and fixed by the adhesive layer 13, it is not limited thereto. That is, the first moisture reactive metal layer 12 may be formed on the gas barrier layer 5, and the first water vapor impermeable layer 11 may be fixed to the gas barrier layer 5 by the adhesive layer 13. .
  • the first water vapor impermeable layer 11 when the first water vapor impermeable layer 11 is a plate-like member, the first water vapor impermeable layer 11 has a certain degree of rigidity and flatness, so that the first moisture on the first water vapor impermeable layer 11 is
  • the reactive metal layer 12 can be formed in a large area by vapor deposition, and the film thickness unevenness can be reduced, so the embodiment shown in FIG. 2 is preferable.
  • the gas barrier film 1 is configured to include the resin base 4, the gas barrier layer 5, and the first and second water vapor barrier property test areas 10 and 20. However, it is not limited to this.
  • the gas barrier film 1 preferably further includes various functional layers such as, for example, a hard coat layer, a bleed out preventing layer, and a smooth layer. A conventionally known structure can be adopted for these various functional layers.
  • the first water vapor barrier property test area portion has a first water reactive metal layer and a first water vapor impermeable layer sealing the first water reactive metal layer in this order on the gas barrier layer.
  • the first water vapor barrier property test region portion further includes a first adhesive layer for fixing the first water vapor impermeable layer to the gas barrier layer.
  • the shortest distance to the part is, for example, preferably 1.0 mm or more, more preferably 2.0 mm or more, and still more preferably 3.0 mm or more.
  • the first water vapor barrier is performed before the evaluation of the water vapor barrier property of the portion where the first water reactive metal layer and the second water reactive metal layer to be described later partially overlap with each other is completed. It is possible to more reliably suppress the corrosion of the first moisture reactive metal from the surroundings and the disappearance of the overlapping portion due to the influence of water vapor intruding from the end of the sex test area.
  • each layer constituting the first water vapor barrier property test area may be different from each other in the first water vapor barrier property test area, but from the viewpoint of performing uniform water vapor barrier property evaluation in the plane of the gas barrier film, these are the same. Is preferred.
  • the first moisture-reactive metal layer according to the present invention is a layer containing a metal having reactivity with water, and is preferably a metal layer whose optical characteristics are changed by reaction with water.
  • Examples of the metal material used for the first moisture reactive metal layer include alkali metals, alkaline earth metals or alloys thereof, and alkali metals such as lithium and potassium, or alkaline earths such as calcium, magnesium and barium. Metal is preferred. Among them, calcium is more preferable because it is inexpensive and relatively easy to form a deposited film.
  • Calcium combines with water to form calcium hydroxide, which turns from silver to clear.
  • the degree of corrosion can be analyzed by measuring the change in light reflectance, light transmittance or luminance value of calcium, and the water vapor transmission rate can be measured.
  • the method for forming the first moisture reactive metal layer is not particularly limited, and may be a vapor deposition method or a coating method. It is preferable that it is a vapor deposition method from a viewpoint of workability
  • the metal material is deposited on the surface of the base member masked except for the portion to be deposited.
  • the sample can be sealed without being exposed to the atmosphere.
  • the underlying member may be a gas barrier layer or a first water vapor impermeable layer.
  • the base member is a gas barrier layer
  • a support substrate such as a glass plate
  • the layer thickness of the first moisture reactive metal layer is, for example, preferably in the range of 10 to 500 nm. If it is 10 nm or more, the first moisture reactive metal layer is uniformly formed on the surface of the base member. When sealing with the first water vapor impermeable layer at 500 nm or less, it is possible to reduce the level difference at the boundary between the portion where the first moisture reactive metal layer is formed and the portion where the first water reactive metal layer is not formed. This makes it difficult to cause peeling or sealing defects at the boundary.
  • the first moisture reactive metal layer is disposed on the gas barrier layer, it is preferably formed at a predetermined distance from the peripheral portion of the gas barrier layer from the viewpoint of accurately evaluating the water vapor barrier property. preferable.
  • the first water vapor impermeable layer is provided so as not to transmit moisture and covering the surface of the first water reactive metal layer (except the surface in contact with the gas barrier layer or the first adhesive layer).
  • a layer for sealing a moisture reactive metal layer That is, the first water vapor impermeable layer may be formed to be larger than the area of the first moisture reactive metal layer when viewed in the layer thickness direction.
  • the first water vapor impermeable layer is provided separately for each first moisture reactive metal layer and configured to seal them respectively. However, all the first moisture reactive metal layers may be sealed collectively by covering the entire surface of the gas barrier layer.
  • the first water vapor impermeable layer may be transparent (light transmissive) or opaque.
  • transparent means that the average light transmittance in the visible light region is 50% or more, and “opaque” means that the average light transmittance is less than 50%.
  • the transmitted light is used to observe the corrosion state of the first moisture reactive metal layer from the reaction with the water vapor from the resin base and the gas barrier layer side, and it is known
  • the water vapor barrier property can be evaluated by the method of When the first water vapor impermeable layer is opaque, the reflected light is used to observe the corroded state of the first moisture reactive metal layer from the reaction with the water vapor from the resin base and the gas barrier layer side, The water vapor barrier properties can be evaluated by known methods. It is preferable that the first water vapor impermeable layer is transparent because the evaluation using transmitted light can detect corrosion due to the influence of fine scratches and the like with high sensitivity.
  • the shortest distance from the peripheral portion of the first water vapor impermeable layer to the peripheral portion of the first moisture reactive metal layer is preferably 0.5 mm or more, more preferably 1.0 mm or more, More preferably, it is 2.0 mm or more. If the shortest distance is 0.5 mm or more, the first water vapor barrier is completed before the evaluation of the water vapor barrier property of the portion where the first water reactive metal layer and the second water reactive metal layer to be described later partially overlap with each other is completed. It is possible to more reliably suppress the corrosion of the first moisture reactive metal layer from the periphery and the disappearance of the overlapping portion due to the influence of water vapor intruding from the end of the sex test area portion.
  • the first water vapor impermeable layer may be formed of a plate-like member selected from metals, opaque metal compounds and transparent metal compounds, or may be a vapor deposition layer. If the first water vapor impermeable layer is a vapor deposition layer, the first water vapor impermeable layer can be disposed directly on the first water reactive metal layer without providing the first adhesive layer; (1) It is possible to further reduce the amount of water intruding from the end of the water vapor barrier test area.
  • the first water vapor impermeable layer is a plate-like member
  • the first water vapor impermeable layer is, for example, a glass substrate Is preferred.
  • the material of the glass substrate include soda lime glass, silicate glass and the like, preferably silicate glass, and more preferably silica glass or borosilicate glass.
  • the thickness of the glass substrate is, for example, in the range of 0.1 to 2 mm.
  • the first water vapor barrier test area portion may not have the first adhesive layer, and the first water vapor impermeable layer which is a vapor deposition layer Is provided in contact with the gas barrier layer and the first moisture reactive metal layer. Also, in this case, after the first moisture reactive metal layer is formed on the gas barrier layer, the first water vapor impermeable layer, which is a deposited layer, is formed to cover the first moisture reactive metal layer. Preferably it is formed.
  • the first water vapor impermeable layer known inorganic compounds generally used as a gas barrier layer can be preferably used.
  • the vapor deposition method generally known methods for forming a gas barrier layer can be used.
  • a resin base material and a gas barrier layer it is preferable to fix a resin base material and a gas barrier layer to support substrates, such as a glass plate, and to give flatness.
  • the first water vapor impermeable layer preferably has higher water vapor barrier properties than the water vapor barrier property of the combination of the resin base material and the gas barrier layer. Therefore, as the first water vapor impermeable layer, for example, a silicon nitride layer, a silicon oxynitride layer, a silicon oxide layer, a silicon oxide carbide layer or the like by PECVD is preferable, or a combination thereof.
  • a known organic layer or plasma polymerization layer may be provided as an intermediate layer.
  • the layer thickness of the first water vapor impermeable layer is not particularly limited, and may be any as long as it can exhibit a desired water vapor barrier property.
  • the adhesive used for the first adhesive layer is not particularly limited, and those generally used as adhesives and adhesives, such as acrylic adhesives, rubber adhesives, polyurethane adhesives, silicone adhesives, etc.
  • Photocurable or thermosetting adhesives having a reactive vinyl group of acrylic acid type oligomers or methacrylic acid type oligomers, thermosetting or chemically curable (two-component mixture) adhesives such as epoxy type, hot melt
  • polyamide, polyester, polyolefin, UV curable epoxy resin adhesive of cationic curing type, or the like are preferred.
  • the first adhesive layer it is preferable to use an adhesive processed into a sheet shape.
  • the sheet-like adhesive is preferably one which exhibits non-flowability at normal temperature (about 25 ° C.) and exhibits fluidity within the range of 50 to 120 ° C. when heated.
  • a layer thickness of a 1st contact bonding layer there is no restriction
  • the lower limit of the layer thickness of the first adhesive layer is not particularly limited as long as the required adhesiveness can be obtained, but is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more.
  • the water vapor transmission rate in the first adhesive layer having a layer thickness of 50 ⁇ m is, for example, preferably 25 g / (m 2 ⁇ 24 hr) or less, more preferably 10 g / (m 2 ⁇ 24 hr) under an atmosphere of 40 ° C. and 90% RH. Or less, more preferably 8 g / (m 2 ⁇ 24 hr) or less. When it is 25 g / (m 2 ⁇ 24 hr) or less, water infiltration from the end can be more reliably prevented.
  • the light transmittance of the first adhesive layer is, for example, preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more in total light transmittance.
  • the total light transmittance can be measured in accordance with JIS K 7375: 2008 "Plastics-Determination of total light transmittance and total light reflectance".
  • the method of forming the first water vapor barrier property test region is not particularly limited as long as it has the above-described configuration.
  • the first water vapor impermeable layer is a plate-like member
  • the first moisture reactive metal layer is formed with a smaller area. It is preferable that the first moisture reactive metal layer is formed so that an unformed region exists in the vicinity of the peripheral portion of the first water vapor impermeable layer.
  • a first adhesive layer is formed on the gas barrier layer.
  • a sheet-like adhesive is preferably bonded to the gas barrier layer.
  • the first water vapor impermeable layer is bonded to the gas barrier layer such that the first moisture reactive metal layer faces the first adhesive layer.
  • a vacuum laminating apparatus can be used.
  • a curing treatment of the first adhesive layer is performed.
  • the curing treatment for example, heating, UV irradiation, a combination of both, or the like is used.
  • the second water vapor barrier test area has a second moisture reactive metal layer and a second water vapor impermeable layer, and the second water vapor impermeable layer When it is a plate-like member, it further has a second adhesive layer.
  • the second moisture reactive metal layer, the second water vapor impermeable layer and the second adhesive layer are substantially similar to the first water reactive metal layer, the first water vapor impermeable layer and the first adhesive layer, respectively.
  • the layers (the material, the layer thickness, the forming method, etc.) of the layers constituting the first water vapor barrier test region and the layers constituting the second water vapor barrier test region may be different from each other. It is preferable that these are the same from the viewpoint of performing uniform water vapor barrier property evaluation in the surface of a gas barrier film.
  • each layer constituting the second water vapor barrier property test area material, layer The thickness, formation method, etc.
  • the configuration of each layer constituting the second water vapor barrier property test area may be different for each second water vapor barrier property test area, but from the viewpoint of performing uniform water vapor barrier property evaluation in the plane of the gas barrier film, these are the same. Is preferred.
  • the first moisture-reactive metal layer 12 and the second moisture-reactive metal layer 22 are arranged such that there is a portion L1 overlapping each other when viewed from the longitudinal direction MD. It is done. The presence of the overlapping portion L1 allows the first moisture reactive metal layer 12 and the second moisture reactive metal layer 22 to cover the gas barrier film in the lateral direction TD without a gap.
  • the first moisture-reactive metal layer 12 and the second moisture-reactive metal layer 22 are not completely overlapped with each other when viewed in the longitudinal direction MD, the first moisture-reactive metal layer 12 and the second moisture reactive metal layer 22 are not
  • the second moisture reactive metal layer 22 can cover a wider range of the gas barrier film in the lateral direction TD at low cost. Therefore, for example, when there is a fine streak defect which extends along the longitudinal direction MD of the gas barrier film and can not be detected optically, it is more reliably detected. Can.
  • the length in the lateral direction TD of the overlapping portion L1 is preferably, for example, 1.0 mm or more, more preferably 1.5 mm or more, and still more preferably 2.0 mm or more. . If it is 1.0 mm or more, the first or second moisture reactive metal layer corrodes from the periphery due to the influence of the water vapor intruding from the end of the first or second water vapor barrier test area, and the overlapping portion L1 becomes The time until disappearance is longer, and the water vapor barrier property of the gas barrier film in the overlapping portion L1 can be evaluated in more detail. When the thickness is 1.0 mm or more, the transverse direction TD of the gas barrier film can be more reliably covered without a gap.
  • the length of the first moisture reactive metal layer 12 and the second moisture reactive metal layer 22 in the lateral direction TD is the overlapping portion L1 from the viewpoint of covering a wider range of the gas barrier film at low cost. Is preferably twice or more, more preferably five times or more, and still more preferably ten times or more the length of the transverse direction TD.
  • the total area of the overlapping portions L1 of the first moisture reactive metal layer 12 and the second moisture reactive metal layer 22 is, for example, the whole of the first moisture reactive metal layer 12 and the second moisture reactive metal layer
  • the total area of 22 is preferably 1% or more, more preferably 2% or more, and still more preferably 3% or more. If it is 1% or more, the first or second moisture reactive metal layer is corroded from the periphery by the influence of the water vapor entering from the end of the first or second water vapor barrier test area, and the overlapping portion L1 becomes The time until disappearance is longer, and the water vapor barrier property of the gas barrier film in the overlapping portion L1 can be evaluated in more detail.
  • a configuration may be considered in which one water vapor barrier property test area portion is formed over the entire product effective width of the gas barrier film in the lateral direction TD.
  • the width of the gas barrier film has been widened to 1 m or more, and in order to cope with this, it is necessary to form a water vapor barrier test area having a length of 1 m or more.
  • the apparatus for exclusive use which forms a large sized water-vapor-barrier test area part is needed, and it becomes a cost increase very much.
  • the first water vapor impermeable layer 11 and the second water vapor impermeable layer 21 are arranged such that there is a portion L2 overlapping each other when viewed from the longitudinal direction MD.
  • the length in the lateral direction TD of the overlapping portion L2 is preferably longer than the length in the lateral direction TD of the overlapping portion L1, and more preferably 3.0 mm or more.
  • the first water vapor barrier property test area portion and the second water vapor barrier property test area portion are both in the rectangular shape extending in the same direction, but the arrangement is made such that the overlapping portion exists. If it is done, it is not limited to this.
  • the first water vapor barrier test area 10 has a rectangular shape extending in the lateral direction TD
  • the second water vapor barrier test area 20 extends in the longitudinal direction MD. It may be rectangular. Even in this case, there may be portions L1 partially overlapping one another when viewed from the longitudinal direction MD.
  • the first water vapor barrier property test area portion and the second water vapor barrier property test area portion are disposed along the lateral direction TD, but the first water reactive metal layer
  • the present invention is not limited to this, as long as the second water-reactive metal layer and the second water-reactive metal layer are disposed such that there is a portion overlapping each other when viewed from at least one of the longitudinal direction and the lateral direction.
  • the first water vapor barrier property test area portion 10 and the second water vapor barrier property test area portion 20 may be arranged along the longitudinal direction MD.
  • the first moisture-reactive metal layer 12 and the second moisture-reactive metal layer 22 are disposed such that there is a portion overlapping each other when viewed in the lateral direction TD, and the gas barrier It is possible to detect a lateral failure in which a plurality of cycles are superimposed in the sexing film. Further, since the cycle can be accurately detected, it is possible to identify the cause of occurrence of the horizontal stage failure and take measures to solve the same. Further, for example, as shown in FIG. 6, the first water vapor barrier property test area portion 10 and the second water vapor barrier property test area portion 20 may be disposed along the arrow direction a.
  • the first moisture-reactive metal layer 12 and the second moisture-reactive metal layer 22 are arranged such that there is a portion L1 overlapping each other when viewed from the longitudinal direction MD and the lateral direction TD.
  • the first moisture-reactive metal layer 12 and the second moisture-reactive metal layer 22 are arranged such that there is a portion L1 overlapping each other when viewed from the longitudinal direction MD and the lateral direction TD.
  • Resin base material As a resin base material, the bendable resin film which has flexibility is mentioned.
  • the term "flexibility" as used herein refers to a resin base material that is wound around a 50 mm diameter (diameter) roll and is not cracked or the like before and after winding with a constant tension. More preferably, a softer gas barrier film can be provided if it is a resin base material that can be wound around a ⁇ 30 mm roll.
  • the resin base is not particularly limited as long as it is a material capable of holding a gas barrier layer and other various functional layers.
  • resin materials applicable to the resin substrate include acrylic polymers, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylates, polyvinyl chloride (PVC), polyethylene Resin film composed of resin material such as (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, etc.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • PVC polyarylates
  • PVC polyethylene Resin film composed of resin material such as (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, etc.
  • a heat-resistant transparent film (product name: Silplus, manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) having a silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton, and a resin constituted by laminating two or more layers of the above-mentioned film materials Or the like can be used Irumu.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • a transparent polyimide film having both heat resistance and transparency for example, a transparent polyimide film (eg, type HM) manufactured by Toyobo Co., Ltd., Mitsubishi Gas Chemical Co., Ltd.
  • a transparent polyimide film (for example, Neoprim L-3430) manufactured by a company can be preferably used.
  • the thickness of the resin substrate applied to the present invention is preferably in the range of 5 to 500 ⁇ m, but is not particularly limited.
  • the resin base material using the above-mentioned resin material may be an unstretched film or a stretched film.
  • the gas barrier layer according to the present invention may be provided on at least one surface of the resin substrate, and may be provided on both surfaces.
  • the gas barrier layer according to the present invention is not particularly limited, and a layer formed by applying a coating solution containing polysilazane and then drying the layer, or a layer containing at least silicon, may be vacuum plasma It may be a gas barrier layer formed by chemical vapor deposition (Chemical Vapor Deposition) such as CVD or physical vapor deposition (Physical Vapor Deposition, PVD) such as sputtering.
  • chemical Vapor Deposition Chemical Vapor Deposition
  • PVD Physical Vapor Deposition
  • the gas barrier film of the present invention is a gas barrier from the viewpoint of achieving both flexibility (flexibility, bending resistance), mechanical strength, durability in roll-to-roll conveyance, and gas barrier performance.
  • the layer contains carbon, silicon and oxygen as constituent elements, and film formation is carried out by plasma enhanced chemical vapor deposition using plasma generated by applying a voltage between opposing roller electrodes having a magnetic field generating member generating at least a magnetic field. It is preferable that the gas barrier layer is treated by the method for producing a gas barrier film satisfying all of the following requirements (i) to (iii):
  • the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve are exposed to the inside of the sample by combining measurement of X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering such as argon. While performing surface composition analysis sequentially, so-called XPS depth profile measurement can create.
  • the 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 generally correlates with the distance (L) from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer.
  • L the distance from the surface of the gas barrier layer in the layer thickness direction of the 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 XPS depth profile measurement is adopted as it is can do.
  • a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve can be created on the following measurement conditions.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide film conversion value): 0.05 nm / sec Etching interval (SiO 2 conversion value): 10 nm
  • X-ray photoelectron spectrometer manufactured by Thermo Fisher Scientific, model name "VG Theta Probe” Irradiated X-ray: Single crystal spectroscopy AlK ⁇ X-ray spots and their sizes: 800 ⁇ m ⁇ 400 ⁇ m oval
  • the gas barrier layer preferably has (ii) a carbon distribution curve having at least two extreme values.
  • the carbon distribution curve more preferably has at least three extreme values, further preferably has at least four extreme values, and may have five or more. If the extreme value of the carbon distribution curve is less than or equal to one, the gas barrier properties may be insufficient when the resulting gas barrier film is bent.
  • the upper limit of the number of extreme values of the carbon distribution curve is not particularly limited, for example, it is preferably 30 or less, more preferably 25 or less, but the number of extreme values is also due to the layer thickness of the gas barrier layer In order to do so, it can not be specified in a general way.
  • the absolute value of the difference between L) (hereinafter also referred to simply as the "distance between extremes") is preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably 75 nm or less. preferable.
  • a region (maximum value) having a large carbon atom ratio is present in a suitable cycle in the gas barrier layer, so that the gas barrier layer is provided with appropriate flexibility, It is possible to more effectively suppress and prevent the occurrence of cracks at the time of bending of the elastic film, and to improve the deterioration of the gas barrier properties when the bending is repeated.
  • the "extreme value” refers to the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer.
  • the “maximum value” is a point at which the value of the atomic ratio of the element (oxygen, silicon or carbon) changes from an increase to a decrease when the distance from the surface of the gas barrier layer is changed.
  • the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer is further changed in the range of 4 to 20 nm from the value of the atomic ratio of the element at that point The point at which the value of decreases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the value of the atomic ratio of the elements may be reduced by 3 at% or more in any range.
  • minimal value means that the value of the atomic ratio of an element (oxygen, silicon or carbon) changes from a decrease to an increase when the distance from the surface of the gas barrier layer is changed.
  • the lower limit of the distance between the extreme values is because the smaller the distance between the extreme values is, the higher the improvement effect of crack generation suppression / prevention at the time of bending of the gas barrier film is
  • the thickness is preferably 10 nm or more, more preferably 30 nm or more, in consideration of the flexibility of the gas barrier layer, the crack suppression / prevention effect, the thermal expansion property, and the like, though not particularly limited.
  • the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the (iii) carbon distribution curve (hereinafter, also simply referred to as “C max -C min difference”) is 3 at% or more. Is preferred. If the absolute value is less than 3 at%, the gas barrier properties may be insufficient when the obtained gas barrier film is bent.
  • the C max -C min difference is preferably 5 at% or more, more preferably 7 at% or more, and particularly preferably 10 at% or more. By setting the C max -C min difference, the gas barrier property can be further improved.
  • the “maximum value” is the atomic ratio of each element which becomes the largest in the distribution curve of each element, and is the highest value among the maximum values.
  • the “minimum value” is an atomic ratio of each element which is minimum in the distribution curve of each element, and is the lowest value among the minimum values.
  • the upper limit of the C max -C min difference is not particularly limited, but is preferably 50 at% or less, in consideration of the improvement effect of crack generation suppression / prevention at the time of bending of the gas barrier film, etc., 40 at% It is more preferable that
  • the layer thickness (dry layer thickness) of the gas barrier layer formed by the above-mentioned plasma CVD method is not particularly limited as long as it satisfies the above (i) to (iii).
  • the layer thickness per one layer of the gas barrier layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 100 to 1000 nm. With such a layer thickness, the gas barrier film can exhibit excellent gas barrier properties and a crack generation suppression / prevention effect at the time of bending.
  • each gas barrier layer has the above-mentioned layer thickness.
  • the gas barrier layer substantially corresponds to one in the film surface direction (direction parallel to the surface of the gas barrier layer). And the variation is preferably small.
  • the number of extremums possessed by the carbon distribution curve obtained at any two measurement points is the same, and the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve The absolute values of the differences are equal to one another or within 5 at%.
  • the film forming apparatus for forming the gas barrier layer according to the present invention comprises a pair of opposed roller electrodes for opposingly arranging a resin base in a vacuum chamber, and forms a thin film layer on the resin base. It is preferable to have at least one set of the following means (1) to (5).
  • the method for producing a gas barrier layer according to the present invention is a film forming method in which a resin base material is disposed opposite to each other in a vacuum chamber, and a thin film layer is formed on the resin base material. It is preferable to have (1) to (5).
  • Step (1) A step of supplying a film forming gas to the facing space between the resin substrates to be placed facing each other
  • the concentration gradient of the carbon atomic component in the gas barrier layer is Because continuous change does not occur, it is difficult to achieve both gas barrier properties and bending resistance.
  • the concentration gradient of carbon atomic components is continuous It is possible to achieve both gas barrier properties and bending resistance by changing as appropriate.
  • FIG. 7 is a schematic configuration view showing an example of a film forming apparatus.
  • the film forming apparatus 100 includes a delivery roll 110, transport rolls 111 to 114, 112 ′, 113 ′, and first, second, third, and fourth film forming rolls 115, 116, 115 ′. , 116 ', a take-up roll 117, a gas supply pipe 118, 118', a plasma generation power supply 119, 119 ', a magnetic field generator 120, 121, 120', 121 ', a vacuum chamber 130, a vacuum It has pump 140, 140 ', and the control part 141.
  • the delivery roll 110, the transport rolls 111 to 114, 112 ′, 113 ′, the first, second, third, and fourth film forming rolls 115, 116, 115 ′, 116 ′, and the winding roll 117 are vacuum chambers 130. Housed in
  • the delivery roll 110 delivers the resin base material 1a installed in a previously wound state toward the transport roll 111.
  • the delivery roll 110 is a cylindrical roll extending in a direction perpendicular to the paper surface, and wound on the delivery roll 110 by rotating counterclockwise (see the arrow in FIG. 7) by a drive motor (not shown). The rotated resin base material 1a is fed toward the transport roll 111.
  • the transport rolls 111 to 114, 112 'and 113' are cylindrical rolls configured to be rotatable about a rotation axis substantially parallel to the delivery roll 110.
  • the transport roll 111 is a roll for transporting the resin base material 1 a from the delivery roll 110 to the first film forming roll 115 while applying an appropriate tension to the resin base material 1 a.
  • the transport rolls 112 and 113 apply appropriate tension to the resin base 1 b formed by the first film forming roll 115, and the resin base 1 b is transferred from the first film forming roll 115 to the second film forming roll 116. It is a roll for conveying.
  • the transfer rolls 112 ′ and 113 ′ apply a suitable tension to the resin base 1 e formed by the third film forming roll 115 ′ while forming the resin base 1 e from the third film forming roll 115 ′. It is a roll for conveying to film roll 116 '. Furthermore, while the transfer roll 114 applies an appropriate tension to the resin base 1c formed by the fourth film forming roll 116 ′, the resin base 1c is transferred from the fourth film forming roll 116 ′ to the winding roll 117. It is a roll for conveying.
  • the first film forming roll 115 and the second film forming roll 116 have a rotation axis substantially parallel to the delivery roll 110, and are a film forming roll pair disposed opposite to each other with a predetermined distance therebetween.
  • the third film forming roll 115 ′ and the fourth film forming roll 116 ′ have a rotation axis substantially parallel to the delivery roll 110, and are a film forming roll pair disposed opposite to each other with a predetermined distance therebetween. is there.
  • the second film forming roll 116 forms a film on the resin base 1 b and conveys the resin base 1 d to the third film forming roll 115 ′ while applying an appropriate tension to the formed resin base 1 d.
  • the fourth film forming roll 116 ′ transfers the resin base 1 c to the transfer roll 114 while forming a film on the resin base 1 e and applying an appropriate tension to the formed resin base 1 c.
  • the separation distance between the first film forming roll 115 and the second film forming roll 116 is a distance connecting the point A and the point B
  • the separation distance from the roll 116 ' is a distance connecting the point A' and the point B '.
  • the first to fourth film forming rolls 115, 116, 115 'and 116' are discharge electrodes formed of a conductive material
  • the 115 'and the fourth film forming roll 116' are mutually insulated.
  • the material and configuration of the first to fourth film forming rolls 115, 116, 115 'and 116' can be appropriately selected so as to achieve a desired function as an electrode.
  • the temperature may be adjusted independently of each of the first to fourth film forming rolls 115, 116, 115 'and 116'.
  • the temperatures of the first to fourth film forming rolls 115, 116, 115 'and 116' are not particularly limited, but are, for example, in the range of -30 to 100 ° C, but the glass transition of the resin substrate 1a If the temperature is set to an excessively high temperature, the resin base material may be deformed by heat.
  • Magnetic field generators 120, 121, 120 'and 121' are respectively installed inside the first to fourth film forming rolls 115, 116, 115 'and 116'.
  • the first film forming roll 115 and the second film forming roll 116 use plasma generating power supply 119
  • the third film forming roll 115 'and the fourth film forming roll 116' use plasma generating power supply 119 '
  • a high frequency voltage for generation is applied.
  • An electric field is formed in the discharge chamber, and a discharge plasma of the film forming gas supplied from the gas supply pipe 118 or 118 'is generated.
  • the voltage applied by the plasma generation power supply 119 and the voltage applied by the plasma generation power supply 119 ′ may be the same or different.
  • the power supply frequency of the plasma generation power supply 119 or 119 ' can be set arbitrarily, but the apparatus of this configuration is, for example, in the range of 60 to 100 kHz, and the applied power is 1 m for the effective film formation width. For example, it is in the range of 1 to 10 kW.
  • the take-up roll 117 has a rotation axis substantially parallel to the delivery roll 110, takes up the resin base 1c, and stores it in a roll shape.
  • the take-up roll 117 takes up the resin substrate 1c by rotating counterclockwise (see the arrow in FIG. 7) by a drive motor (not shown).
  • the resin substrate 1a delivered from the delivery roll 110 is transported between the delivery roll 110 and the take-up roll 117, with the transport rolls 111 to 114, 112 ', 113', and the first to fourth film forming rolls 115, 116, It is conveyed by rotation of each of these rolls while maintaining an appropriate tension by being wound around 115 'and 116'.
  • the conveyance direction of resin base material 1a, 1b, 1c, 1d, 1e is shown by the arrow.
  • the transfer speed (line speed) of the resin substrates 1a to 1e (for example, the transfer speed at point C or point C 'in FIG. 7) can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber 130, etc. .
  • the conveying speed is adjusted by controlling the rotational speed of the drive motor of the delivery roll 110 and the winding roll 117 by the control unit 141. As the transport speed is reduced, the thickness of the formed area is increased.
  • the transport direction of the resin substrates 1a to 1e is opposite to the direction (hereinafter referred to as the forward direction) indicated by the arrow in FIG. 7 (hereinafter referred to as the reverse direction). It is also possible to execute the film forming step of the gas barrier film by setting it to Specifically, in a state in which the resin base 1c is taken up by the take-up roll 117, the control unit 141 reverses the rotational direction of the drive motor of the delivery roll 110 and the take-up roll 117 to the above. Control to rotate.
  • the resin base material 1c delivered from the take-up roll 117 is transported between the delivery roll 110 and the take-up roll 117, as the transfer rolls 111 to 114, 112 ′, 113 ′, and the first to fourth By being wound around the film forming rolls 115, 116, 115 ', 116', they are conveyed in the opposite direction by the rotation of each of these rolls while maintaining an appropriate tension.
  • the resin base material 1a is transported in the forward and reverse directions to reciprocate the film forming unit S or the film forming unit S '.
  • the formation (film formation) step can also be repeated multiple times.
  • the gas supply pipes 118 and 118 ′ supply a film forming gas such as a source gas of plasma CVD into the vacuum chamber 130.
  • the gas supply pipe 118 has a tubular shape extending in the same direction as the rotation axis of the first film forming roll 115 and the second film forming roll 116 above the film forming unit S, and provided at a plurality of places A film forming gas is supplied to the film forming unit S from the opening.
  • the gas supply pipe 118 ' has a tubular shape extending in the same direction as the rotation axis of the third film forming roll 115' and the fourth film forming roll 116 'above the film forming unit S'.
  • the film forming gas is supplied to the film forming unit S ′ from the openings provided at a plurality of places.
  • the film forming gas supplied from the gas supply pipe 118 and the film forming gas supplied from the gas supply pipe 118 ′ may be the same or different. Furthermore, the supply gas pressures supplied from these gas supply pipes may be the same or different.
  • a silicon compound can be used as the source gas.
  • silicon compounds include hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, Examples thereof include propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane and the like.
  • HMDSO hexamethyldisiloxane
  • vinyltrimethylsilane vinyltriethoxysilane
  • vinyltrimethoxysilane vinyltrimethoxysilane
  • the compounds described in paragraph 0075 of JP 2008-056967 A can also be used.
  • HMDSO is preferably used in the formation of the gas barrier layer, from the viewpoint of the ease of handling the compound and the high gas barrier properties of the obtained gas barrier film.
  • two or more of these silicon compounds may be used in combination.
  • the source gas may contain monosilane.
  • a reactive gas may be used in addition to the source gas.
  • a gas that reacts with the source gas and becomes a silicon compound such as an oxide or a nitride is selected.
  • a reaction gas for forming an oxide as a thin film for example, oxygen gas or ozone gas can be used. These reaction gases may be used in combination of two or more.
  • a carrier gas may be further used to supply the source gas into the vacuum chamber 130.
  • a discharge gas may be further used as a deposition gas to generate plasma.
  • a carrier gas and the discharge gas for example, a rare gas such as argon, and hydrogen or nitrogen are used.
  • the magnetic field generating devices 120 and 121 are members that form a magnetic field in the film forming unit S between the first film forming roll 115 and the second film forming roll 116, and the magnetic field generating devices 120 ′ and 121 ′ are similarly It is a member which forms a magnetic field in film-forming part S 'between 3rd film-forming roll 115' and 4th film-forming roll 116 '.
  • the magnetic field generators 120, 120 ', 121, 121' are stored at predetermined positions without following the rotation of the first to fourth film forming rolls 115, 116, 115 ', 116'.
  • the delivery roll 110, the transport rolls 111 to 114, 112 ′, 113 ′, the first to fourth film forming rolls 115, 116, 115 ′, 116 ′ and the winding roll 117 are sealed and decompressed. Maintain the same condition.
  • the pressure (degree of vacuum) in the vacuum chamber 130 can be appropriately adjusted in accordance with the type of source gas and the like.
  • the pressure of the film forming unit S or S ′ is preferably in the range of 0.1 to 50 Pa.
  • the vacuum pumps 140 and 140 ′ are communicably connected to the control unit 141, and appropriately adjust the pressure in the vacuum chamber 130 according to a command from the control unit 141.
  • the control unit 141 controls each component of the film forming apparatus 100.
  • the control unit 141 is connected to drive motors of the delivery roll 110 and the winding roll 117, and adjusts the transport speed of the resin base 1a by controlling the number of rotations of these drive motors. Moreover, the conveyance direction of the resin base material 1a is changed by controlling the rotation direction of a drive motor.
  • the control unit 141 is communicably connected to a film forming gas supply mechanism (not shown) and controls the supply amounts of the respective component gases of the film forming gas.
  • the control unit 141 is communicably connected to the plasma generation power supplies 119 and 119 'and controls the output voltage and output frequency of the plasma generation power supplies 119 and 119'.
  • the control unit 141 is communicably connected to the vacuum pumps 140 and 140 ', and controls the vacuum pumps 140 and 140' so as to maintain the inside of the vacuum chamber 130 at a predetermined reduced pressure atmosphere.
  • the control unit 141 includes a central processing unit (CPU), a hard disk drive (HDD), a random access memory (RAM), and a read only memory (ROM).
  • the HDD stores a software program in which a procedure for realizing the formation of the gas barrier layer by controlling each component of the film forming apparatus 100 is stored. Then, when the power of the film forming apparatus 100 is turned on, the software program is loaded to the RAM and sequentially executed by the CPU. Further, various data and parameters used when the CPU executes the software program are stored in the ROM.
  • a coating film of a polysilazane-containing liquid is provided on a resin substrate by a coating method, and reformed by irradiating vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less. It is also preferable to form a gas barrier layer.
  • VUV light vacuum ultraviolet light
  • coating method on the gas barrier layer provided by the said plasma CVD method.
  • minute defects remaining in the underlying gas barrier layer can be filled with the gas barrier component of polysilazane, the overall gas barrier properties and flexibility can be further improved, and variations in the gas barrier properties can be reduced.
  • the thickness of the gas barrier layer formed by the coating method is, for example, preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm.
  • the layer thickness is 1 nm or more, sufficient gas barrier performance can be exhibited, and when the layer thickness is 500 nm or less, a crack does not easily occur in the dense silicon oxynitride film.
  • Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution.
  • examples of commercial products of the polysilazane solution include NN120-20, NAX120-20, NL120-20 and the like manufactured by AZ Electronic Materials Co., Ltd.
  • a metal alkoxide compound or a metal chelate compound, or a low molecular weight silazane / siloxane may be added to the polysilazane solution.
  • the water vapor barrier property evaluation test piece of the present invention is a water vapor barrier property evaluation for evaluating the water vapor barrier property of a section cut out from a gas barrier film having a gas barrier layer on at least one surface of a long resin substrate.
  • a test piece comprising a water-reactive metal layer provided on a gas barrier layer and a water-vapor impermeable layer sealing the water-reactive metal layer, wherein the longitudinal direction and the width direction of the gas barrier film
  • the marker which shows the coordinate in at least any one of 1 is formed.
  • the resin base material, the gas barrier layer, the moisture reactive metal layer and the water vapor impermeable layer constituting the test piece for evaluation of the water vapor barrier property of the present invention respectively have the resin base material constituting the gas barrier film of the present invention described above And substantially the same as the gas barrier layer, the first and second moisture reactive metal layers, and the first and second water vapor impermeable layers.
  • the coordinates in at least one of the longitudinal direction and the width direction of the gas barrier film can be determined so that the arrangement before being cut out from the base gas barrier film can be determined.
  • the markers shown are formed.
  • the marker is preferably formed in a region that does not overlap the water reactive metal layer.
  • the marker may be formed in any form as long as it does not affect the water vapor barrier property evaluation, and is printed on the back surface (surface opposite to the surface on which the gas barrier layer is formed) of the resin substrate with a predetermined ink It is good also as what is engraved on the back surface of the said resin base material. In the case of using an ink, it is preferable that generation of outgassing be small in the process of forming the moisture reactive metal layer.
  • a method of producing a water vapor barrier property evaluation test piece of the present invention a method of cutting out a region in which a first water vapor barrier property test area or a second water vapor barrier property test area is formed from the gas barrier film of the present invention described above Alternatively, a method of forming a water reactive metal layer and a water vapor impermeable layer on the gas barrier layer of the cut-out section by cutting out a predetermined region of the resin base on which the gas barrier layer is formed can be mentioned.
  • the water vapor barrier property evaluation method of the gas barrier property film of the present invention is characterized by using the above-mentioned gas barrier property film or the above-mentioned water vapor barrier property evaluation test piece.
  • a photomultiplier tube or a spectroscope can be used as a measuring means.
  • a spectroscope When a spectroscope is used, light is incident from one surface side of the gas barrier film or the water vapor barrier property evaluation test piece, and a change in the optical property of the water reactive metal layer is spotted by reflected light or transmitted light. It is preferable to measure while moving.
  • the specified range of the moisture reactive metal layer is photographed as an image
  • light is incident from one surface side of the gas barrier film or the water vapor barrier property evaluation test piece, and the reflected light or the transmitted light is Photographing can be performed using a type or line sensor type CCD or a CMOS camera, and among them, an area type CCD or a CMOS camera is preferably used.
  • the measurement is preferably performed every predetermined time after exposure to water vapor. This makes it possible to make data on how the corrosion of the water reactive metal layer proceeds with time.
  • the above "exposure to water vapor” means that the gas barrier film or the water vapor barrier property evaluation test piece is stored in, for example, a constant temperature and humidity chamber and brought into contact with the water vapor.
  • a constant temperature and humidity chamber for example, the temperature is preferably in the range of room temperature to 90 ° C., and the humidity is in the range of 40 to 90% RH. Is preferred.
  • the storage time in the constant temperature and humidity chamber is not particularly limited, it is preferably about 10 to 2000 hours, and the sample may be taken out and evaluated at appropriate intervals during storage time. good.
  • Example 1 Preparation of gas barrier film 1-1 >> (1) Preparation of Resin Base As a resin base, a 100 ⁇ m-thick PET film having an easy-adhesion layer on both sides, made by Toray Industries, Inc., Lumirror U403 was prepared.
  • the surface hard coat coating solution HC1 consisting of the following composition is coated on one side of the resin substrate to a dry film thickness of 4 ⁇ m and dried, and then ultraviolet light is applied.
  • Polymerizable binder SR2.0 12.0 parts by mass manufactured by Sartmar Polymerizable binder: Beam set 575 manufactured by Arakawa Chemical Co., Ltd. 22.0 parts by mass
  • Solvent propylene glycol monomethyl ether 65 .0 parts by mass
  • a conductive polymer organic solvent dispersion was prepared, and the following materials were mixed to prepare a hard coat coating solution HC2 for the back surface.
  • Conductive polymer organic solvent dispersion solid content 0.5 mass%) 53.5 parts by mass
  • Polymerizable binder SR 368 SR2.0 12.0 parts by mass
  • Polymerizable binder Arakawa Chemical Beam Set 575 22.0 mass Part
  • Polymerization initiator Irgacure 651 manufactured by BASF 1.0 parts by mass Silica dispersion: MA-ST-ZL manufactured by Nissan Chemical Co. 2.0 parts by mass Solvent: Diacetone alcohol 9.5 parts by mass
  • the above-described hard coat coating solution HC2 for the back surface is applied to the opposite surface of the resin substrate so as to have a dry film thickness of 4 ⁇ m and dried, and then cured by irradiation with ultraviolet light under the condition of 500 mJ / cm 2 I took it and wound it up.
  • the antistatic function and the anti block function were provided to the resin base material.
  • the said resin base material was slitted to 1200 mm width, it wound up, and the resin base material roll of 1200 mm width was obtained.
  • a gas barrier layer was formed as follows using the film forming apparatus 100 shown in FIG. As film forming conditions, effective film forming width: 1040 mm, conveying speed: 20.0 m / min, source gas (HMDSO) supply amount of the first film forming unit: 150 sccm, oxygen gas supply amount of the first film forming unit: 500 sccm Vacuum degree of the first film forming unit: 1.5 Pa, applied power of the first film forming unit of 4.5 kW, supply amount of the source gas (HMDSO) of the second film forming unit: 150 sccm, oxygen gas of the second film forming unit The supply amount was 1000 sccm, the degree of vacuum of the second film forming unit was 1.5 Pa, and the applied power of the second film forming unit was 4.5 kW.
  • the power supply frequency was 84 kHz
  • the temperature of the film forming roll was all 30 ° C.
  • the odd-numbered pass (first pass, third pass, fifth pass, ...) is the direction in which the resin base is unwound
  • the even-numbered pass (the second pass, the fourth pass, the sixth pass,...) Transports the resin base material in the rewinding direction, but it passes first even if the pass direction is different.
  • the first film forming unit is a film forming unit to be formed
  • the second film forming unit is a film forming unit to be passed next.
  • the number of times of film formation was 10 passes, and a gas barrier layer having a total layer thickness of 300 nm in which 20 layers were laminated on a resin substrate was formed.
  • the roll circumferential surface of the transport roll 112 shown in FIG. 7 that touches the film-forming surface side of the resin base is not wound, but the roll circumferential surface is exposed.
  • the needle-like metal member was pressed to the above portion at intervals of 100 mm in the axial direction of the transport roll 112.
  • fine metal powder is generated during film formation at 11 places of 100 to 1100 mm from one end in the width direction (hereinafter referred to as film edge) of the resin base material, and transferred to the film formation surface
  • a film formation abnormal portion was formed in a continuous streak in the longitudinal direction MD.
  • the needle-like metal member was removed before the second pass film formation, and normal film formation was performed after the second pass.
  • the resin base is formed.
  • streak-like defects extending in the longitudinal direction MD were formed.
  • the streak-like defect part could not be confirmed.
  • the water vapor barrier test region is formed on the back surface of the resin substrate (the surface opposite to the surface on which the gas barrier layer is formed). Positioning marking was performed at a position corresponding to the region where the end portions of the calcium layer described later partially overlap each other when viewed from the longitudinal direction MD. After marking, as shown in FIG. 8, the laminate of the resin base material and the gas barrier layer was cut respectively, and eight pieces to be a target for forming a water vapor barrier property test area were cut out. Since each section is marked, it can be determined from which position of the matrix resin base each section is cut out. In addition, each section was cut out so that there was a portion overlapping each other when viewed from the longitudinal direction MD.
  • a glass plate member (first and second water vapor impermeable layers) having an area of 40 mm (longitudinal direction MD) ⁇ 180 mm (lateral direction TD) using a vacuum evaporation apparatus JEE-400 manufactured by Nippon Denshi Co., Ltd.
  • a calcium layer (first and second moisture-reactive metal layers) was vapor-deposited in an area of 20 mm (longitudinal direction MD) ⁇ 152 mm (lateral direction TD) in the central portion of. Eight such glass plate members were produced.
  • adhesive layers (Sleebond 1655, first and second adhesive layers) having an area of 33 mm (longitudinal direction) ⁇ 165 mm (lateral direction TD) were provided. This was left in a glove box (GB) for one day to remove the moisture of the adhesive layer and the adsorbed water of the surface of the gas barrier layer. Then, the said glass plate-like member was bonded so that a calcium layer might oppose each of the adhesion layer of each section, and a total of eight 1st and 2nd water-vapor-barrier test area parts were formed on the gas barrier layer. .
  • gas barrier film 1-2 In the production of the gas barrier film 1-1, the area size of the calcium layer is 20 mm (longitudinal direction MD) ⁇ 215 mm (lateral direction TD), and the area size of the glass plate member and the adhesive layer is 40 mm (longitudinal direction MD)
  • a gas barrier film 1-2 was produced in the same manner except that the width was changed to 243 mm (in the lateral direction TD) and a total of five first and second water vapor barrier property test areas were formed.
  • the length in width direction TD of the part which the edge parts of a calcium layer mutually overlap mutually was 5.0 mm.
  • gas barrier film 1-3 In the production of the gas barrier film 1-1, the area size of the calcium layer is 20 mm (longitudinal direction MD) ⁇ 20 mm (lateral direction TD), and the area size of the glass plate member and the adhesive layer is 40 mm (longitudinal direction MD)
  • a gas barrier film 1-3 was produced in the same manner as in Example 1 except that the width was changed to 40 mm (in the width direction TD), and a total of four water vapor barrier test areas were formed. As shown in FIG. 8, the four water vapor barrier test regions were formed so that there was no overlapping portion of the calcium layers when viewed from the longitudinal direction MD.
  • gas barrier film 1-4 In the production of the gas barrier film 1-1, the area size of the calcium layer is 20 mm (longitudinal direction MD) ⁇ 146 mm (lateral direction TD), and the area size of the glass plate member and the adhesive layer is 40 mm (longitudinal direction MD)
  • a gas barrier film 1-4 was produced in the same manner except that the width was changed to 174 mm (in the width direction TD). As shown in FIG. 8, the eight water vapor barrier test regions were formed so that there was no overlapping portion of the calcium layers when viewed from the longitudinal direction MD.
  • gas barrier film 1-5 In the production of the gas barrier film 1-1, the area size of the calcium layer is 20 mm (longitudinal direction MD) ⁇ 150 mm (lateral direction TD), and the area size of the glass plate member and the adhesive layer is 40 mm (longitudinal direction MD) A gas barrier film 1-5 was produced in the same manner except that the width was changed to 178 mm (width direction TD). In the eight water vapor barrier test areas, as shown in FIG. 8, the glass plate member and the adhesive layer partially overlap each other when viewed from the longitudinal direction MD, but there is a portion where the calcium layers overlap each other. Not formed.
  • the gas barrier films 1-1 and 1-2 have all the eleven streak defects [1] to [11] detected, whereas the gas barrier film 1 In -3 to 1-5, a part of the streak defect portion is not detected. Therefore, it can be said that the gas barrier films 1-1 and 1-2 can detect fine streaks in the form of longitudinal stripes with high accuracy.
  • Example 2 Preparation of gas barrier film 2-1 >> (1) Preparation of resin substrate In the preparation of the resin substrate of the gas barrier film 1-1, a hard coat coating solution HC1 for the surface is applied and cured, and then a protective film (Futamura Chemical Co., Ltd.) is formed. A resin base was produced in the same manner except that FSA-020M was used.
  • the coating apparatus 200 conveys the resin base material unwound from the unwinding roll 201 by a plurality of conveyance rollers, and peels off the protective film 203 from the resin base material by the protective film winding roll 202. To recover.
  • the coating device 200 peels the protective film 203, applies the coating solution for forming a gas barrier layer by the coater 204, and makes the dryer 205 dry it, and then the coating film is irradiated with vacuum ultraviolet light by the vacuum ultraviolet irradiation device 206. Apply.
  • the coating device 200 brings the surface touch roll 207 into contact with the layer formation surface after vacuum ultraviolet ray irradiation, and bonds the protection film 209 to the layer formation surface by the protection film unwinding roll 208, and then takes up the roll.
  • the resin substrate is wound up by 210.
  • the protective film is peeled from the resin substrate by the protective film winding roll 202 while conveying the resin substrate at a conveying speed of 3.0 m / min using the coating apparatus 200, and the dry layer thickness of 110 nm is obtained by the coater 204.
  • drying was performed at a temperature of 80 ° C. for 3.3 minutes, and vacuum ultraviolet irradiation treatment was performed at 4.0 J / cm 2 .
  • the surface touch roll 207 (diameter: 120 mm ⁇ ) was brought into contact with the layer forming surface.
  • the surface touch roll 207 On the circumferential surface of the surface touch roll 207, one scratch is formed in the lateral direction TD (the axial direction of the surface touch roll 207) by bringing a needle-like metal member into contact in advance. Thereby, the surface touch roll 207 has fine projections due to the formation of the scratch, and contacts the layer formation surface on the resin base to form the layer surface in the lateral direction TD. A series of fine scratches are formed. Therefore, in the gas barrier layer formed on the resin substrate, fine scratches continuous in the lateral direction TD were formed in a cycle of about 377 mm in the longitudinal direction MD.
  • the winding roll 210 It was wound by.
  • the roll of the resin base on which the first gas barrier layer was formed was set again on the unwinding roll 201.
  • the protective film was peeled from the resin base material by the protective film take-up roll 202, and polysilazane was applied by the coater 204 to have a dry layer thickness of 110 nm.
  • a vibration of 4 Hz was applied to the coater 204 using a vibration mechanism (not shown).
  • the coating thickness of the second gas barrier layer changed in a cycle of 4 Hz, and a lateral step unevenness of 12.5 mm pitch was formed in the longitudinal direction MD.
  • drying was performed at a temperature of 80 ° C. for 3.3 minutes, and vacuum ultraviolet light treatment was performed at 4.0 J / cm 2 .
  • the gas barrier layer was formed on the resin base material.
  • the step-like unevenness of 12.5 mm pitch could be confirmed, it could be judged that the water vapor barrier property was not affected.
  • fine scratches continuous in the transverse direction TD with a period of about 377 mm could not be confirmed.
  • the water vapor barrier test region is formed on the back surface of the resin substrate (the surface opposite to the surface on which the gas barrier layer is formed).
  • positioning marking is applied such that there is a configuration in which there is a portion where the ends of the calcium layer to be described later partially overlap with each other when viewed from the lateral direction TD.
  • the laminate of the resin base material and the gas barrier layer was cut, and eight pieces to be a target for forming a water vapor barrier test area portion were cut out. Since each section is marked, it can be determined from which position of the matrix resin base each section is cut out. In addition, each section was cut out so that there was a part overlapping each other when viewed in the lateral direction TD.
  • a glass plate member (first and second water vapor impermeable layers) having an area of 180 mm (longitudinal direction MD) ⁇ 40 mm (lateral direction TD) using a vacuum evaporation apparatus JEE-400 manufactured by Nippon Denshi Co., Ltd.
  • a calcium layer (first and second moisture-reactive metal layers) was vapor-deposited in an area of 152 mm (longitudinal direction MD) ⁇ 20 mm (lateral direction TD) in the central portion of. Eight such glass plate members were produced.
  • gas barrier film 2-2 the area size of the calcium layer is 146 mm (longitudinal direction MD) ⁇ 20 mm (lateral direction TD), and the area size of the glass plate member and the adhesive layer is 174 mm (longitudinal direction MD)
  • a gas barrier film 2-2 was produced in the same manner except that the width of the film was changed to 40 mm (in the width direction TD).
  • the eight water vapor barrier test areas were formed such that there was no overlapping of the calcium layers when viewed in the lateral direction TD.
  • the water vapor barrier test region is formed on the back surface of the resin substrate (the surface opposite to the surface on which the gas barrier layer is formed). Positioning marking was performed at a position corresponding to the region where the end portions of the calcium layer described later partially overlap each other when viewed from the longitudinal direction MD. After marking, the laminate of the resin base material and the gas barrier layer was cut, and eight pieces to be a target for forming a water vapor barrier test area were cut out. Since each section is marked, it can be determined from which position of the matrix resin base each section is cut out. In addition, each section was cut out so that there was a portion overlapping each other when viewed from the longitudinal direction MD.
  • each of the sections prepared above was placed approximately at the center of a 50 mm ⁇ 180 mm glass plate, with the resin base side facing each other, and the four corners of the sections were fixed on the glass plate with Kapton tape. Thereafter, the surface of the gas barrier layer of each section was subjected to UV ozone cleaning.
  • the section on which the calcium layer has been deposited is taken out in a glove box and transferred to a CVD apparatus without being exposed to the air to form a water impermeable layer consisting of three silicon nitride layers with a size of 26 mm ⁇ 158 mm. did.
  • the first silicon nitride layer having a layer thickness of 200 nm was formed on the calcium layer.
  • silane gas flow rate 100 sccm
  • ammonia gas flow rate 300 sccm
  • hydrogen gas flow rate 1000 sccm
  • nitrogen gas flow rate 1000 sccm
  • pressure 200 Pa
  • power supply 13.56 MHz
  • power output 800 W
  • a second silicon nitride layer having a thickness of 400 nm was formed on the first silicon nitride layer.
  • silane gas flow rate 100 sccm
  • ammonia gas flow rate 300 sccm
  • hydrogen gas flow rate 1500 sccm
  • nitrogen gas flow rate 1000 sccm
  • pressure 200 Pa
  • power supply 13.56 MHz
  • power output 1200 W
  • electrode Distance 3.2 cm.
  • a third silicon nitride layer having a thickness of 200 nm was formed on the second silicon nitride layer.
  • the film forming conditions were the same as the film forming conditions at the time of forming the first silicon nitride layer.
  • a water vapor barrier property test area was formed on the gas barrier layer of each section to produce a gas barrier film 3-1.
  • the water vapor barrier property was evaluated in the same manner as in Example 1 using the produced gas barrier film 3-1, and the same result as the gas barrier film 1-1 was obtained.
  • Example 4 Preparation of gas barrier films 4-1 to 4-3 >>
  • the gas barrier film 1-1 when viewed from the longitudinal direction MD, the lengths in the lateral direction TD of the portions where the ends of the calcium layers overlap with each other, and the ends of the glass plate-like members
  • the gas barrier films 4-1 to 4-3 were produced in the same manner except that the length in the lateral direction TD of the overlapping portion of each other was changed as described in Table I.
  • each calcium layer gradually shrinks from its peripheral edge under the influence of water invading from the end of each section, and after a certain time, overlapping portions of the calcium layers in the arrangement before each section is cut out Disappear.
  • the photographed images in each of the above-mentioned standing times it was confirmed whether or not the overlapping portions of the calcium layers disappeared.
  • the results are shown in Table I.
  • the gas barrier film and the water vapor barrier property evaluation test piece of the present invention make it possible to detect with high precision the periodicity of the gas barrier property changes which appear in the form of fine streaks in the form of longitudinal stripes or lateral steps, Is useful as a method for evaluating the water vapor barrier properties of water-repellent films.

Landscapes

  • Laminated Bodies (AREA)

Abstract

L'objectif de la présente invention est de fournir un film formant barrière aux gaz apte à détecter avec une grande précision des rayures fines de type bande longue et la périodicité d'un changement des propriétés de barrière aux gaz apparaissant dans une forme d'étage latéral. Le film formant barrière aux gaz (1) de la présente invention est disposé sur un matériau de base en résine long (4) avec : une couche formant barrière aux gaz (5) ; et des première et seconde parties de région de test de propriétés de barrière à la vapeur d'eau (10) et (20), les première et seconde parties de région de test de propriétés de barrière à la vapeur d'eau (10) et (20) comprenant chacune des première ou seconde couches métalliques réactives à l'humidité (12) et (22), et des première ou seconde couches imperméables à la vapeur d'eau (11) et (21) pour sceller les première et seconde couches métalliques réactives à l'humidité (12) et (22), et lorsque la première couche métallique réactive à l'humidité (12) et la seconde couche métallique réactive à l'humidité (22) sont vues à partir de la direction longitudinale et/ou de la direction de la largeur du matériau de base en résine (4), il y a une partie (L1) dans laquelle la première couche métallique réactive à l'humidité (12) et la seconde couche métallique réactive à l'humidité (22) se chevauchent partiellement.
PCT/JP2018/030332 2017-09-08 2018-08-15 Film formant barrière aux gaz, pièce de test d'évaluation des propriétés de barrière à la vapeur d'eau, et procédé d'évaluation des propriétés de barrière à la vapeur d'un film formant barrière aux gaz Ceased WO2019049618A1 (fr)

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CN201880057076.4A CN111065515B (zh) 2017-09-08 2018-08-15 阻气性膜、水蒸气阻隔性评价试验片及阻气性膜的水蒸气阻隔性评价方法
KR1020207005745A KR102351115B1 (ko) 2017-09-08 2018-08-15 가스 배리어성 필름, 수증기 배리어성 평가 시험편 및 가스 배리어성 필름의 수증기 배리어성 평가 방법

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025117925A1 (fr) * 2023-11-30 2025-06-05 Toray Plastics (America), Inc. Film composite biodégradable à barrière élevée contre l'humidité

Citations (2)

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Publication number Priority date Publication date Assignee Title
WO2015194557A1 (fr) * 2014-06-17 2015-12-23 コニカミノルタ株式会社 Film de barrière contre les gaz et son procédé de production
JP2016190439A (ja) * 2015-03-31 2016-11-10 東レ株式会社 ガスバリア性フィルムおよびガスバリア性フィルムの製造方法およびガスバリア性フィルムの検査方法

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CN102387920B (zh) * 2009-04-09 2015-01-07 住友化学株式会社 气体阻隔性层叠膜

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Publication number Priority date Publication date Assignee Title
WO2015194557A1 (fr) * 2014-06-17 2015-12-23 コニカミノルタ株式会社 Film de barrière contre les gaz et son procédé de production
JP2016190439A (ja) * 2015-03-31 2016-11-10 東レ株式会社 ガスバリア性フィルムおよびガスバリア性フィルムの製造方法およびガスバリア性フィルムの検査方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025117925A1 (fr) * 2023-11-30 2025-06-05 Toray Plastics (America), Inc. Film composite biodégradable à barrière élevée contre l'humidité

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CN111065515B (zh) 2022-02-01
KR102351115B1 (ko) 2022-01-14

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