KR20200035992A - Gas barrier film, water vapor barrier property evaluation test piece, and method for evaluating water vapor barrier property of gas barrier film - Google Patents

Abstract

An object of the present invention is to provide a gas barrier film capable of detecting with high precision the periodicity of changes in gas barrier properties, which are fine stripes of a long stripe type or a transverse type. The gas barrier film 1 of the present invention is provided with a gas barrier layer 5, first and second water vapor barrier test area portions 10, 20 on an elongated resin substrate 4, The first and second water vapor barrier test area portions 10 and 20 seal the first or second water-reactive metal layers 12 and 22 and the first or second water-reactive metal layers 12 and 22, respectively. Having the first or second water vapor impermeable layers 11 and 21, the first water-reactive metal layer 12 and the second water-reactive metal layer 22 are at least one of the longitudinal direction and the width direction of the resin substrate 4 When viewed from one side, it is characterized in that it constitutes a configuration that is arranged such that some overlapping portions (L1) are present.

Description

Gas barrier film, water vapor barrier property evaluation test piece, and method for evaluating water vapor barrier property of gas barrier film

The present invention relates to a gas barrier film, a water vapor barrier property test specimen, and a method for evaluating the water vapor barrier property of a gas barrier film. The present invention provides a gas barrier film, a vapor barrier evaluation test piece, and a gas barrier film which enables to detect with high precision the periodicity of a gas barrier property change, particularly in the form of a long stripe fine scratch or a transverse type. It is related with the water vapor barrier property evaluation method of the used gas barrier film.

Currently, 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 thin televisions.

In recent years, the required performance of these gas barrier films has been further increased. For example, in displays such as electronic paper and organic EL, a glass substrate that does not pass moisture has been conventionally used because a deterioration in image quality or a malfunction occurs due to a small amount of moisture entering from the atmosphere or the outside. However, due to strong demands for device flexibility and weight reduction, development to replace glass substrates with polymer substrates is underway, and the water vapor transmission rate required for polymer substrates is 1.0 × 10 ^-3 g / (m 2 · 24hr) or less. Furthermore, it is very high, such as 1.0 × 10 ^-5 g / (㎡ · 24hr) or less.

Here, as a technique for improving the barrier properties of a gas barrier film that has been widely studied in recent years, a technique in which the gas barrier layer has a multi-layered laminate structure can be cited. In the case of manufacturing this in a roll-to-roll manner, the multi-layer laminate structure is generally formed by conveying a production line multiple times, and laminating an inorganic layer, an intermediate layer, a protective layer, and the like. As a method of forming each constituent layer, a method of forming by vapor phase film formation in vacuum or a method of forming by applying a solution in the air is applied in various ways.

As one of the defects concerned with the gas barrier film having a gas barrier layer having a multi-layered laminate structure, long stripe-like flaws in the transport direction can be mentioned. The long stripe-like scratches take various forms by stacking a plurality of layers in different ways, such as a film formation method, and are buried by lamination, and therefore may not be detected by an optical method. In addition, when a part of the multi-layered laminate structure is formed by application of a solution in the air, a failure originating from solution application, for example, a transverse failure in which a plurality of cycles overlap due to various effects during transport (in the longitudinal direction) There is a concern that periodically formed film thickness unevenness extending in the width direction) may occur.

For example, a gas barrier film roll having an inspection portion provided at a center of a width of a gas barrier film roll manufactured by a roll-to-roll method with a square Ca deposition layer having a side of 10 mm at 4 m intervals is disclosed ( Patent Document 1). Thereby, although the information on the change in the gas barrier properties in the longitudinal direction can be obtained as an evaluation of the quality of the gas barrier film roll, it is a gas barrier that appears in the form of minute scratches of a long stripe type, which is a concern of the roll-to-roll method, or a transverse type. It is not possible to detect the periodicity of sex changes.

In addition, in recent years, displays such as electronic paper and organic EL tend to be large in size, and a gas barrier film is also required to have a width of 1 m or more. Therefore, there is a demand for a method for accurately evaluating changes in gas barrier properties in the longitudinal and width directions of such a wide gas barrier film.

Japanese Patent Publication No. 2016-190439

The present invention has been made in view of the above problems and situations, and the problem to be solved is a gas barrier film capable of accurately detecting the periodicity of minute scratches of a long stripe type or a gas barrier property change in a transverse type, It is to provide a water vapor barrier property evaluation test piece and a method for evaluating water vapor barrier properties of a gas barrier film using them.

In order to solve the above-mentioned problems related to the present invention, as a result of examining the causes of the above problems and the like, it is a gas-barrier film having a gas barrier layer on at least one side of an elongated resin substrate. 1st and 2nd water vapor barrier test area parts are provided, and the 1st water vapor barrier test area part has a 1st water reactive metal layer and a 1st water vapor impermeable layer which seals a 1st water reactive metal layer, and a 2nd water vapor barrier The castle test region portion has a second water-reactive metal layer and a second water-impermeable layer that seals the second water-reactive metal layer, wherein the first water-reactive metal layer and the second water-reactive metal layer are in the longitudinal and width directions of the resin substrate. When viewed from at least one of the above, by forming a configuration that is arranged to partially overlap with each other, fine stripes of long stripes or transverse It has been found that the periodicity of the gas barrier property change appearing in a single form can be detected with high precision.

That is, the subject concerning this invention is solved by the following means.

1. It is a gas barrier film having a gas barrier layer on at least one side of an elongated resin substrate,

On the gas barrier layer, a first water vapor barrier property test area portion and a second water vapor barrier property test area part are provided,

The first water vapor barrier test region portion, in this order, has a first water-reactive metal layer and a first water-impermeable layer sealing the first water-reactive metal layer on the gas barrier layer,

The second water vapor barrier test region portion, in this order, has a second water reactive metal layer and a second water vapor impermeable layer sealing the second water reactive metal layer on the gas barrier layer,

The first water-reactive metal layer and the second water-reactive metal layer, when viewed from at least one of the longitudinal direction and the width direction of the resin substrate, constitutes a configuration that is arranged to partially overlap each other. Gas barrier film.

2. The gas-barrier film according to item 1, wherein the first water-reactive metal layer and the second water-reactive metal layer are arranged to partially overlap each other when viewed in the width direction.

3. The gas-barrier film according to item 1, wherein the first water-reactive metal layer and the second water-reactive metal layer are arranged to partially overlap each other when viewed in the longitudinal direction.

4. The gas barrier film according to any one of items 1 to 3, wherein at least one of the first water vapor impermeable layer and the second water vapor impermeable layer is a vapor deposition layer.

5. The first water vapor barrier test region portion further has a first adhesive layer that fixes the first water vapor impermeable layer to the gas barrier layer,

The gas barrier according to any one of claims 1 to 3, wherein the first water vapor impermeable layer is formed of a plate-shaped member selected from metals, opaque metal compounds, and transparent metal compounds. Sex film.

6. The second water vapor barrier test area portion further has a second adhesive layer that fixes the second water vapor impermeable layer to the gas barrier layer,

The second water vapor impermeable layer is formed of one of a plate-shaped member selected from a metal, an opaque metal compound, and a transparent metal compound. Gas barrier film described in.

7. The length of the first water-reactive metal layer and the second water-reactive metal layer in any one of the length direction and the width direction of portions partially overlapping each other when viewed from either the length direction or the width direction. A gas barrier film according to any one of claims 1 to 6, characterized in that 1.0 mm or more.

8. The first water vapor impermeable layer and the second water vapor impermeable layer are arranged to partially overlap each other when viewed from at least one of the length direction and the width direction,

The length of the first water vapor impermeable layer and the second water vapor impermeable layer in the length direction and the other of the width direction of a portion partially overlapping each other when viewed in one of the length direction and the width direction. (A) The length of the first water-reactive metal layer and the second water-reactive metal layer in the length direction and the other of the width direction of a portion partially overlapping each other when viewed from either the length direction or the width direction. The gas barrier film according to any one of claims 1 to 7, characterized in that it is longer.

9. The first water vapor impermeable layer and the second water vapor impermeable layer are in any one of the length direction and the width direction of a portion partially overlapping each other when viewed from either the length direction or the width direction. The gas barrier film according to claim 8, wherein the length is 3.0 mm or more.

10. A water vapor barrier evaluation test piece 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 side of an elongated resin substrate,

A water-reactive metal layer provided on the gas barrier layer,

And a water vapor impermeable layer sealing the moisture reactive metal layer,

A water vapor barrier evaluation test piece, characterized in that a marker showing coordinates in at least one of the longitudinal direction and the width direction of the gas barrier film is formed.

11. A method for evaluating the water vapor barrier property of a gas barrier film, characterized in that the gas barrier film according to any one of items 1 to 9 or the water vapor barrier evaluation test piece according to item 10 is used.

According to the present invention, a gas barrier film, a water vapor barrier evaluation test piece, and a gas barrier property using the gas barrier property, which enable to accurately detect the periodicity of a gas barrier property change exhibited by a long stripe-like fine scratch or a transverse type A method for evaluating the water vapor barrier property of a film can be provided.

The expression mechanism or mechanism of effect of the present invention is estimated as follows.

In the gas barrier film of the present invention, when the first water-reactive metal layer and the second water-reactive metal layer are disposed in at least one of the longitudinal direction and the width direction of the resin substrate, portions overlapping each other are present. , Water vapor barrier property evaluation can be performed in any one of the length direction and the width direction without a gap. Thereby, when a part overlapping with each other when viewed in the width direction is present, fine scratches of a long stripe type can be detected with high precision, and when a part overlapping with each other when viewed in the longitudinal direction is present, it is transverse. The periodicity of the gas barrier property change can be detected with high precision.

1 is a schematic plan view showing an example of a gas barrier film of the present invention.
Fig. 2 is a cross-sectional view of the plane along line II-II in Fig. 1 seen from the direction of the arrow.
3 is a schematic plan view showing an example of a first water vapor barrier property test area part and a second water vapor barrier property test area part.
4 is a schematic plan view showing another example of the first water vapor barrier property test area part and the second water vapor barrier property test area part.
5 is a schematic plan view showing another example of the gas barrier film of the present invention.
6 is a schematic plan view showing another example of the gas barrier film of the present invention.
7 is a schematic configuration diagram showing an example of a film forming apparatus used for forming a gas barrier layer.
8 is an explanatory diagram showing evaluation results of Example 1;
9 is a schematic configuration diagram showing an example of a coating device used for forming a gas barrier layer.
10 is an explanatory diagram showing evaluation results of Example 2. FIG.

The gas barrier film of the present invention is a gas barrier film having a gas barrier layer on at least one side of an elongated resin substrate, and on the gas barrier layer, a first water vapor barrier test region portion and a second water vapor A barrier test region portion is provided, and the first vapor barrier test region portion comprises: a first moisture-reactive metal layer and a first water vapor-impermeable layer sealing the first moisture-reactive metal layer on the gas barrier layer. And the second water vapor barrier test region portion has a second water vapor impermeable layer on the gas barrier layer and a second water vapor impermeable layer that seals the second water vapor reactive metal layer in this order. 1 The water-reactive metal layer and the second water-reactive metal layer partially overlap each other when viewed from at least one of the length direction and the width direction of the resin substrate. Characterized in that forming a structure which is arranged the part to be present. This feature is a technical feature common to or corresponding to each embodiment.

In the present invention, it is preferable that the first water-reactive metal layer and the second water-reactive metal layer are arranged such that portions overlap with each other when viewed in the width direction.

In addition, in the present invention, it is preferable that the first water-reactive metal layer and the second water-reactive metal layer are arranged so as to partially overlap with each other when viewed in the longitudinal direction.

Moreover, in this invention, it is preferable that at least one of the said 1st water vapor impermeable layer and the said 2nd water vapor impermeable layer is a vapor deposition layer. Thereby, without providing the adhesive layer, the first or second water vapor impermeable layer can be disposed directly on the first or second water-reactive metal layer, and is from the end of the first or second water vapor barrier test area portion. The amount of invading moisture can be reduced.

In addition, in the present invention, the first water vapor barrier test region portion further includes a first adhesive layer that fixes the first water vapor impermeable layer to the gas barrier layer, and the first water vapor impermeable layer is a metal. , It is preferably formed of a plate-like member selected from opaque metal compounds and transparent metal compounds.

In addition, in the present invention, the second water vapor barrier test region portion further includes a second adhesive layer that fixes the second water vapor impermeable layer to the gas barrier layer, and the second water vapor impermeable layer is a metal. , It is preferably formed of a plate-like member selected from opaque metal compounds and transparent metal compounds.

Further, in the present invention, when the first water-reactive metal layer and the second water-reactive metal layer are partially overlapped with each other when viewed in either of the length direction and the width direction, either the length direction or the width direction of the portion It is preferable that the length in the other side is 1.0 mm or more. Thereby, under the influence of water vapor intruding from the ends of the first or second water vapor barrier test area portion, the time until the first or second water-reactive metal layer is corroded from the surroundings and the overlapping parts are lost. It becomes longer, and more detailed evaluation of the water vapor barrier property of the gas barrier film in the overlapping portion can be performed. Moreover, the longitudinal direction or the width direction of the gas barrier film can be more reliably covered without a gap by the first and second water vapor barrier test region portions.

In addition, in the present invention, when the first water vapor impermeable layer and the second water vapor impermeable layer are viewed in at least one of the longitudinal direction and the width direction, portions overlapping each other are disposed, The length of the first water vapor impermeable layer and the second water vapor impermeable layer in the length direction and the other of the width direction of a portion partially overlapping each other when viewed in one of the length direction and the width direction. (A) The length of the first water-reactive metal layer and the second water-reactive metal layer in the length direction and the other of the width direction of a portion partially overlapping each other when viewed from either the length direction or the width direction. Longer is preferred. Thereby, under the influence of water vapor intruding from the ends of the first or second water vapor barrier test area portion, the time until the first or second water-reactive metal layer is corroded from the surroundings and the overlapping parts are lost. By contributing to the elongation, more detailed evaluation of the water vapor barrier property of the gas barrier film in the overlapping portion can be performed.

In addition, in the present invention, the first water vapor impermeable layer and the second water vapor impermeable layer, the longitudinal direction and the width direction of the portion partially overlapping each other when viewed from either one of the length direction and the width direction It is preferable that the length in any of the other is 3.0 mm or more. Thereby, under the influence of water vapor intruding from the ends of the first or second water vapor barrier test area portion, the time until the first or second water-reactive metal layer is corroded from the surroundings and the overlapping parts are lost. By contributing to the elongation, more detailed evaluation of the water vapor barrier property of the gas barrier film in the overlapping portion can be performed.

In addition, the water vapor barrier evaluation test piece of the present invention is a water vapor barrier evaluation test piece 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 an elongated resin substrate, A marker comprising a water-reactive metal layer provided on the gas barrier layer and a water vapor-impermeable layer sealing the water-reactive metal layer, and indicating coordinates in at least one of a longitudinal direction and a width direction of the gas barrier film Characterized in that is formed. Thereby, it is possible to accurately detect the periodicity of the gas barrier property film, which is a long stripe-like fine scratch or a transverse type gas barrier property change.

In addition, the method for evaluating the water vapor barrier property of the gas barrier film of the present invention is characterized by using the gas barrier film or the water vapor barrier evaluation test piece. Thereby, it is possible to accurately detect the periodicity of the gas barrier property film, which is a long stripe-like fine scratch or a transverse type gas barrier property change.

Hereinafter, the present invention and its components, and forms and aspects for carrying out the present invention will be described in detail. In addition, in this application, "-" is used by the meaning including the numerical value described before and after that as a lower limit and an upper limit.

<< gas barrier film >>

The gas barrier film of the present invention is a gas barrier film having a gas barrier layer on at least one side of an elongated resin substrate, and on the gas barrier layer, a first water vapor barrier property test region portion and a second water vapor barrier A first water vapor-impermeable layer for sealing the first moisture-reactive metal layer and a first moisture-reactive metal layer on the gas barrier layer is provided in this order. The 2 water vapor barrier test region portion has a second water-repellent metal layer and a second water-impermeable impermeable layer that seals the second water-reactive metal layer on the gas barrier layer in this order, the first water-reactive metal layer, and the second When the water-reactive metal layer is viewed from at least one of the length direction and the width direction of the resin substrate, a configuration is arranged such that portions overlapping each other exist. The features.

The gas barrier film of the present invention is preferably a gas barrier layer formed on a resin substrate in roll-to-roll, and is usually wound up and stored as a master roll. In this case, the conveyance direction of a roll-to-roll system becomes the longitudinal direction MD of a gas barrier film.

In addition, "gas barrier property" referred to in the present invention is represented by, for example, water vapor permeability measured by a method in accordance with JIS K 7129-1992 or oxygen permeability measured by a method in accordance with JIS K 7126-1987. Generally, it is said to have gas barrier properties 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. Further, if the water vapor transmission rate is 1 × 10 ^-2 g / (m 2 · 24hr) 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 LCDs.

1 to 3, the gas barrier film of the present invention will be described.

1 is a schematic plan view of the gas barrier film 1 having a long shape viewed from the thickness direction. FIG. 2 is a cross-sectional view seen from the direction of the arrow along the line II-II in FIG. 1. 3 is a schematic plan view of a part of the gas barrier film 1 as viewed from the thickness direction.

As shown in FIG. 1, the gas barrier film 1 is a first water vapor barrier property test area portion 10 on a gas barrier layer 5 provided on one side of an elongated resin substrate 4. ) And the 2nd water vapor barrier property test area | region 20 are provided and comprised along the width direction TD. The 1st water vapor barrier test area | region part 10 and the 2nd water vapor barrier test area | region part 20 alternate over the width (product effective width) effective as a product of the gas barrier film 1 in the width direction TD. It is prepared. As a result, when viewed in the longitudinal direction MD, the first water vapor barrier test area portion 10 and the second water vapor barrier test area portion 20 partially overlap each other.

As shown in FIG. 2, the first water vapor barrier property test region 10 includes a first water reactive metal layer 12 and the first water reactive metal layer 12 on the gas barrier layer 5. It has the first water vapor impermeable layer 11 to be sealed in this order, and further has a first adhesive layer 13 that fixes the first water vapor impermeable layer 11 against the gas barrier layer 5. The second water vapor barrier test region 20 is similarly configured, and on the gas barrier layer 5, a second water reactive metal layer 22 and a second water vapor sealing the second water reactive metal layer 22. It has the impermeable layer 21 in this order, and further has a second adhesive layer (not shown) that fixes the second water vapor impermeable layer to the gas barrier layer 5.

In addition, in the example shown in FIG. 1, the first water vapor barrier test area portion 10 and the second water vapor barrier test area portion 20 are each provided with a total of eight, each of which is limited to this. no. Each may be provided with 1 to 3 or may be provided with 5 or more. In addition, the quantity of the 1st water vapor barrier test area | region part 10 and the 2nd water vapor barrier test area | region 20 on the gas barrier layer 5 may differ from each other.

In addition, in the example shown in FIG. 2, the first water-reactive metal layer 12 is formed on the first water vapor impermeable layer 11, and the first water-reactive metal layer 12 is attached to the gas barrier layer 5. The first water vapor impermeable layer 11 is disposed so as to face each other, and this is fixed by the adhesive layer 13, but is not limited to this. That is, the first moisture-reactive metal layer 12 is formed on the gas barrier layer 5, in which the first water vapor impermeable layer 11 is fixed to the gas barrier layer 5 by the adhesive layer 13 You may do it. However, as will be described later, when the first water vapor impermeable layer 11 is a plate-shaped member, since it has a certain degree of stiffness and flatness, the first water reactivity is on the first water vapor impermeable layer 11 Since the metal layer 12 can be formed in a large area by a vapor deposition method and film thickness unevenness can be reduced, the aspect shown in FIG. 2 is preferable.

In addition, in the example shown in FIG. 2, the gas barrier film 1 includes the resin substrate 4, the gas barrier layer 5, and the first and second water vapor barrier property test areas 10 and 20. It is supposed to be provided, but is not limited to this. It is preferable that the gas barrier film 1 further includes various functional layers such as, for example, a hard coat layer, a bleed-out prevention layer, and a smoothing layer. As for these various functional layers, a conventionally well-known structure can be adopted.

Hereinafter, the main structure of the gas barrier film of the present invention will be described in detail.

<< 1st water vapor barrier test area part >>

The 1st water vapor barrier test area | region part has the 1st water reactive metal layer on the gas barrier layer, and the 1st water vapor impermeable layer which seals the said 1st water reactive metal layer in this order. When the first water vapor impermeable layer is a plate-like member, the first water vapor barrier test region portion further has a first adhesive layer that fixes the first water vapor impermeable layer to the gas barrier layer.

The shortest distance from the periphery of the region where the gas barrier layer, the first adhesive layer, and the first water vapor impermeable layer all overlap in the layer thickness direction, that is, the sealed region, to the periphery of the first moisture-reactive metal layer, for example, 1.0 mm It is preferably more than 2.0 mm, more preferably 2.0 mm or more, and even more preferably 3.0 mm or more. If the shortest distance is 1.0 mm or more, the water vapor barrier property evaluation of a portion where the first water-reactive metal layer and the second water-reactive metal layer described later partially overlap each other is intruded from the end of the first water vapor barrier test region portion. Under the influence of water vapor, it is possible to more reliably suppress that the first water-reactive metal is corroded from the surroundings and the overlapping portion disappears.

In addition, as shown in FIG. 1, when a plurality of first water vapor barrier test region parts are provided on the gas barrier layer, the structure (material, layer thickness, formation of each layer constituting the first water vapor barrier test region part) The methods, etc.) may be different for each portion of the first water vapor barrier test region, but from the viewpoint of uniform evaluation of water vapor barrier properties in the plane of the gas barrier film, they are preferably the same.

[First moisture-reactive metal layer]

The first water-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 properties change by reaction with water.

Examples of the metal material used in the first moisture-reactive metal layer include alkali metal, alkaline earth metal, or alloys thereof, and alkali metals such as lithium and potassium, or alkaline earth metals such as calcium, magnesium, and barium are preferred. Do. Especially, it is more preferable that it is calcium which is inexpensive and relatively easy to form a vapor deposition film.

Calcium, when combined with moisture, produces calcium hydroxide and discolors from silver to transparent. For example, by measuring changes in the light reflectance, light transmittance, or luminance value of calcium, the degree of corrosion can be analyzed, and water vapor transmission can be measured.

The method for forming the first water-reactive metal layer is not particularly limited, and may be a vapor deposition method or a coating method. It is preferable to use a vapor deposition method from the viewpoint of control of workability and layer thickness. For example, using a vacuum evaporation apparatus having a metal evaporation source, the metal material is deposited on the surface of the underlying member masked other than the portion to be evaporated. By using a vacuum vapor deposition apparatus, after deposition of the first moisture-reactive metal layer, the sample can be sealed without contacting the atmosphere. The base member may be a gas barrier layer or a first water vapor impermeable layer. When the base member is a gas barrier layer, it is preferable that the resin substrate and the gas barrier layer are fixed to a support substrate such as a glass plate to have flatness. By providing the resin substrate and the gas barrier layer with flatness, it is possible to reduce the film thickness non-uniformity even in the deposition of a large area, and to form a water vapor barrier test region that enables high-accuracy water vapor barrier evaluation.

It is preferable that the layer thickness of the 1st water-reactive metal layer is in the range of 10-500 nm, for example. If it is 10 nm or more, the first water-reactive metal layer is uniformly formed on the surface of the base member. When it is 500 nm or less, when sealing with the first water vapor impermeable layer, the step difference between the portion where the first water-reactive metal layer is formed and the portion where the first water-reactive metal layer is formed can be reduced, and peeling or sealing defects at the boundary portion are prevented. It is difficult to produce.

Although the 1st water-reactive metal layer is arrange | positioned on a gas barrier layer, it is preferable that it is formed in the position spaced apart by a predetermined distance from the peripheral part of a gas barrier layer from a viewpoint of evaluating water vapor barrier property with high precision.

[First water vapor impermeable layer]

The first water vapor impermeable layer is a layer that seals the first moisture reactive metal layer by being provided so as to cover the surface of the first moisture reactive metal layer (excluding the surface contacting the gas barrier layer or the first adhesive layer) without permeating the moisture. to be. That is, the 1st water vapor impermeable layer should just be formed larger than the area of the 1st water-reactive metal layer when it is seen from the layer thickness direction. In addition, in the example shown in FIGS. 1 to 3, the first water vapor impermeable layer is provided separately for each first water-reactive metal layer, and is configured to seal them, respectively, but covers the entire surface of the gas barrier layer. It is good also as what is comprised so that all the 1st moisture-reactive metal layers may be sealed collectively.

Further, the first water vapor impermeable layer may be transparent (light transmissive) or opaque. Here, in the present invention, 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%. When the first water vapor impermeable layer is transparent, by using transmitted light, the corrosion state due to the reaction of water vapor of the first moisture-reactive metal layer on the resin substrate and the gas barrier layer side is observed, and by a known method, the water vapor barrier Evaluate sex. In addition, when the first water vapor impermeable layer is opaque, by using the reflected light, the corrosion state caused by reaction with the water vapor of the first moisture-reactive metal layer is observed on the resin substrate and the gas barrier layer side, by a known method, Water vapor barrier properties can be evaluated. 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 with high sensitivity.

Further, the shortest distance from the periphery of the first water vapor impermeable layer to the periphery of the first moisture-reactive metal layer is preferably 0.5 mm or more, more preferably 1.0 mm or more, and even more preferably 2.0 mm or more. When the shortest distance is 0.5 mm or more, the water vapor barrier property evaluation of a portion where the first water-reactive metal layer and the second water-reactive metal layer, which will be described later, partially overlap each other, enters from the end of the first water vapor barrier test region portion. Under the influence of water vapor, it is possible to more reliably suppress that the first moisture-reactive metal layer is corroded from the surroundings and the overlapping portion disappears.

Here, the 1st water vapor impermeable layer may be formed from 1 type of plate-shaped member selected from a metal, an opaque metal compound, and a transparent metal compound, and 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 moisture-reactive metal layer without providing the first adhesive layer, and from the end of the first water vapor barrier test region portion The amount of invading moisture can be further reduced.

(If the first water vapor impermeable layer is a plate member)

When the first water vapor impermeable layer is formed of a plate-like member selected from a metal, an opaque metal compound, and a transparent metal compound, it is preferable that the first water vapor impermeable layer is, for example, a glass substrate. As a material of a glass base material, soda-lime glass, silicate glass, etc. are mentioned, for example, It is preferable that it is silicate glass, It is more preferable that it is silica glass or borosilicate glass. The thickness of the glass substrate is, for example, in the range of 0.1 to 2 mm.

(When the first water vapor impermeable layer is a vapor deposition layer)

When the first water vapor impermeable layer is a vapor deposition layer, the first water vapor barrier test region portion does not need to have a first adhesive layer, and the vapor vapor impermeable layer, which is a vapor deposition layer, is a gas barrier layer and a first moisture reactivity. It is provided in contact with the metal layer. Further, in this case, after the first water-reactive metal layer is formed on the gas barrier layer, it is preferable that a first water vapor impermeable layer, which is a vapor deposition layer, is formed to cover the first water-reactive metal layer.

In addition, as the first water vapor impermeable layer, a known inorganic compound generally used as a gas barrier layer can be preferably used.

Moreover, as a vapor deposition method, a well-known method of generally forming a gas barrier layer can be used. When forming the first water vapor impermeable layer by vapor deposition, it is preferable to fix the resin substrate and the gas barrier layer to a support substrate such as a glass plate, so as to have flatness. By providing the resin substrate and the gas barrier layer with flatness, it is possible to reduce the film thickness non-uniformity even in the deposition of a large area, and to form a water vapor barrier test area portion that enables high-accuracy water vapor barrier evaluation.

Moreover, it is preferable that the 1st water vapor impermeable layer has a higher water vapor barrier property than the water vapor barrier property of the combination of a resin base material and a gas barrier layer. Therefore, it is preferable that the first water vapor impermeable layer is, for example, a silicon nitride layer, a silicon oxynitride layer, a silicon oxide layer, a silicon oxide oxide layer, or a combination thereof by PECVD. Moreover, when the 1st water vapor impermeable layer is a laminated structure containing multiple layers, you may have a well-known organic layer or plasma polymerization layer as an intermediate layer.

The layer thickness of the first water vapor impermeable layer is not particularly limited, and any layer may be used as long as it can exhibit a desired water vapor barrier property.

[First adhesive layer]

The adhesive used for the first adhesive layer is not particularly limited, and is usually used as an adhesive or an adhesive, for example, an acrylic adhesive, a rubber adhesive, a polyurethane adhesive, a silicone adhesive, etc., acrylic acid oligomer or methacrylic Photocurable or thermosetting adhesives having reactive vinyl groups of acid-based oligomers, thermosetting or chemically curable (two-liquid mixed) adhesives such as epoxy, hot melt polyamides, polyesters, polyolefins, and UV curable epoxy resin adhesives of cationic curing types, etc. Can be preferably used. It is preferable to have water vapor barrier property among these.

As the first adhesive layer, it is preferable to use an adhesive processed into a sheet.

As a sheet adhesive, it is preferable to exhibit non-flowability at room temperature (about 25 ° C), and to exhibit fluidity within a range of 50 to 120 ° C when heated.

The layer thickness of the first adhesive layer is not particularly limited and is appropriately selected depending on the application, but is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, for example. By setting it as 50 micrometers or less, water vapor penetration from the edge part of a 1st adhesive layer can be suppressed. The lower limit of the layer thickness of the first adhesive layer is not particularly defined as long as the necessary adhesiveness is obtained, but is preferably 5 µm or more, and more preferably 10 µm or more.

The water vapor transmission rate in the first adhesive layer having a layer thickness of 50 µm is 40 ° C. and 90% RH, for example, preferably 25 g / (m 2 · 24 hr) or less, more preferably 10 g / (m 2 · 24 hr) ) Or less, and more preferably 8 g / (m 2 · 24 hr) or less. If it is 25 g / (m 2 · 24 hr) or less, it is possible to more reliably prevent moisture intrusion from the end.

The light transmittance of the first adhesive layer is, for example, 80% or more as a total light transmittance, more preferably 85% or more, still more preferably 90% or more. When the total light transmittance is 80% or more, the loss of incident light becomes small, and a suitable first water vapor barrier property test region can be constituted by transmission observation. The total light transmittance can be measured according to JIS K 7375: 2008 "Plastic-total light transmittance and total light reflectance method".

[Method for forming first water vapor barrier property region]

The method for forming the first water vapor barrier property test region is not particularly limited as long as it has the above configuration. For example, to describe the case where the first water vapor impermeable layer is a plate-like member, first, on one side of the first water vapor impermeable layer, an area smaller than the first water vapor impermeable layer when viewed in the layer thickness direction, The first water-reactive metal layer is formed. It is preferable that the first water-reactive metal layer is formed such that an unformed region exists near the periphery of the first water vapor impermeable layer. Subsequently, a first adhesive layer is formed on the gas barrier layer. As the first adhesive layer, it is preferable to form the sheet adhesive by bonding it to the gas barrier layer. Subsequently, the first water vapor impermeable layer is bonded to the gas barrier layer with the first water-reactive metal layer facing the first adhesive layer. For this bonding, for example, a vacuum laminate device can be used. Subsequently, if necessary, the first adhesive layer is cured. As the curing treatment, for example, heating, UV irradiation, a combination of both, and the like are used.

<< second water vapor barrier test area area >>

The second water vapor barrier test region portion has a second water-reactive metal layer, a second water vapor impermeable layer, and the second water vapor impermeable layer is a plate-like member, as in the first water vapor barrier test region portion. It has 2 more adhesive layers. The second moisture-reactive metal layer, the second water vapor impermeable layer, and the second adhesive layer are configured in substantially the same manner as the first water-reactive metal layer, the first water vapor impermeable layer, and the first adhesive layer, respectively.

In addition, although each layer constituting the first water vapor barrier property test region part and each layer constituting the second water vapor barrier test area part may have different configurations (materials, layer thickness, forming method, etc.), the gas barrier properties may be different from each other. It is preferable that they are the same from the viewpoint of performing uniform water vapor barrier evaluation in the plane of the film.

In addition, as shown in FIG. 1, when a plurality of second water vapor barrier test region portions are provided on the gas barrier layer, the structure (material, layer thickness, formation of each layer constituting the second water vapor barrier test region portion) The methods, etc.) may be different from each other for the second water vapor barrier test region, but they are preferably the same from the viewpoint of performing uniform water vapor barrier evaluation in the plane of the gas barrier film.

<< Position relationship of the first water vapor barrier property test area part and the second water vapor barrier property test area part >>

In the gas-barrier film of the present invention, when the first water-reactive metal layer and the second water-reactive metal layer are viewed in at least one of the length direction and the width direction of the resin substrate, portions overlapping each other are present. .

For example, as shown in FIG. 3, the first water-reactive metal layer 12 and the second water-reactive metal layer 22 are arranged such that, when viewed in the longitudinal direction MD, portions L1 partially overlap each other are present. have. The presence of the overlapping portion L1 allows the first water-reactive metal layer 12 and the second water-reactive metal layer 22 to cover the widthwise TD of the gas barrier film without gaps. In addition, when the first water-reactive metal layer 12 and the second water-reactive metal layer 22 are not overlapped with each other when viewed in the longitudinal MD, the first water-reactive metal layer 12 and the second water-reactive metal layer By (22), a wider range of the gas barrier film in the width direction TD can be covered at low cost. Therefore, for example, in the case where fine streak-like defect scratches or the like that extend along the longitudinal MD of the gas-barrier film and cannot be optically detected can be detected more reliably.

Moreover, as the length of the width direction TD of the said overlapping part L1, it is preferable that it is 1.0 mm or more, for example, it is more preferable that it is 1.5 mm or more, and it is still more preferable that it is 2.0 mm or more. When it is set to 1.0 mm or more, the first or second moisture-reactive metal layer is corroded from the surroundings under the influence of water vapor intruding from the end of the first or second water vapor barrier test region, until the overlapping portion L1 disappears. It becomes longer, and it becomes possible to perform more detailed evaluation of the water vapor barrier property of the gas barrier film in the overlapping portion L1. Moreover, when it is 1.0 mm or more, the width direction TD of a gas barrier film can be covered more reliably without a gap.

In addition, the length of the width direction TD of the first water-reactive metal layer 12 and the second water-reactive metal layer 22 is from the viewpoint of covering a wider range of the gas-barrier film at a lower cost. It is preferable that it is 2 times or more of the length of the width direction TD, more preferably 5 times or more, and even more preferably 10 times or more.

In addition, the sum of the areas of the portions L1 where the first water-reactive metal layer 12 and the second water-reactive metal layer 22 overlap each other is, for example, the entire first water-reactive metal layer 12 and the second water-reactive material. The total area of the entire metal layer 22 is preferably 1% or more, more preferably 2% or more, and even more preferably 3% or more. If it is 1% or more, the first or second moisture-reactive metal layer is corroded from the surroundings under the influence of water vapor intruding from the end of the first or second water vapor barrier test region portion, until the overlapping portion L1 disappears. The time becomes longer, and more detailed evaluation of the water vapor barrier property of the gas barrier film in the overlapping portion L1 can be performed.

Here, for example, a configuration in which one water vapor barrier test region portion is formed over the entire product effective width of the gas barrier film in the width direction TD is also considered. However, in recent years, 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 property test region having a length of 1 m or more. And for that, a dedicated device for forming a large water vapor barrier test area portion is required, which is very costly. In addition, it is necessary to form a large size water-reactive metal layer or a water vapor impermeable layer, or a large size water vapor impermeable layer must be bonded on the gas barrier layer, so that the water vapor barrier test region cannot be formed with high precision. However, there is a concern that the measurement accuracy may deteriorate. Therefore, rather than covering the entire area with one water vapor barrier test area part, it is advantageous both in terms of cost and measurement accuracy to cover the entire area with a plurality of water vapor barrier test area parts as in the present invention.

In addition, as shown in FIG. 3, the first water vapor impermeable layer 11 and the second water vapor impermeable layer 21 are arranged such that some overlapping portions L2 exist when viewed from the longitudinal MD. It is desirable. In addition, the length of the width direction TD of the overlapping portion L2 is preferably longer than the length of the width direction TD of the overlapping portion L1, and more preferably 3.0 mm or more. Thereby, under the influence of water vapor intruding from the end of the first or second water vapor barrier test region, the time until the first or second water-reactive metal layer corrodes from the surroundings and the overlapping portion L1 disappears. By contributing to the longer, it is possible to perform more detailed evaluation of the water vapor barrier properties of the gas barrier film in the overlapping portion L1. In addition, in the gas barrier film having a very high barrier property, it is possible to detect a site where the water vapor barrier property is relatively deteriorated.

<< Other examples of the first water vapor barrier test area part and the second water vapor barrier test area part >>

In the above-described embodiment, the first water vapor barrier property test region part and the second water vapor barrier property test region part are assumed to be rectangular in shape extending in the same direction, however, if the overlapping parts are arranged to exist, they are limited to this. It is not. For example, as shown in FIG. 4, the first water vapor barrier test area portion 10 is a rectangular shape extending in the width direction TD, and the second water vapor barrier test area portion 20 is a longitudinal MD It may be a rectangular shape extending to. Even in this case, when viewed from the longitudinal MD, portions L1 partially overlapping each other may exist.

Further, in the above-described embodiment, the first water vapor barrier property test region part and the second water vapor barrier property test region part are assumed to be arranged along the width direction TD, but the first water reactive metal layer and the second water reactive metal layer are It is not limited to this, as long as they are arranged to partially overlap each other when viewed from at least one of the length direction and the width direction.

For example, as shown in FIG. 5, the 1st water vapor barrier test area | region 10 and the 2nd water vapor barrier test area | region 20 may be arrange | positioned along the longitudinal MD. In this case, the first water-reactive metal layer 12 and the second water-reactive metal layer 22 are arranged to partially overlap each other when viewed in the width direction TD, so that a plurality of cycles overlap in the gas barrier film. Crossing faults can be detected. In addition, since the cycle can be accurately detected, the cause of the transverse failure can be specified and coped with this to be resolved.

In addition, as shown in FIG. 6, for example, the first water vapor barrier test area portion 10 and the second water vapor barrier test area portion 20 may be arranged along the arrow direction a. In this case, the first water-reactive metal layer 12 and the second water-reactive metal layer 22 are arranged such that a portion L1 partially overlaps each other when viewed in the longitudinal direction MD and the width direction TD, so as to have a long striped pattern. Both the fine scratches and the periodicity of the gas barrier property change appearing in the transverse form can be detected with high precision.

<< resin description >>

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 φ (diameter) 50mm roll and does not cause cracking or the like before or after winding with a constant tension. More preferably, it is possible to provide a more flexible gas barrier film as long as it is a resin substrate that can be wound on a φ30 mm roll.

The resin substrate is not particularly limited as long as it is a material capable of holding a gas barrier layer or other various functional layers.

As the resin material applicable to the resin substrate, for example, acrylic polymer, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride Resin such as (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyethersulfone, polyimide, polyetherimide A resin film composed of a material, a heat-resistant transparent film based on silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton (product name: Silplus, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), and furthermore, the above-mentioned film material 2 A resin film or the like composed of more than one layer may be used.

Among these resin films, films such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), and polycarbonate (PC) are preferably used from the viewpoint of economical efficiency and availability.

In addition, when a high-temperature treatment is required in the film forming treatment, a transparent polyimide film having both heat resistance and transparency, for example, a transparent polyimide-based film (for example, type HM) manufactured by Toyobo Corporation, or Mitsubishi Gas A transparent polyimide-based film (eg, Neoprem L-3430) manufactured by Kagaku Co., Ltd. can be preferably used.

The thickness of the resin substrate applied to the present invention is preferably in the range of 5 to 500 µm, but is not particularly limited.

The resin substrate using the resin material may be an unstretched film or a stretched film.

<< gas barrier layer >>

[1] Overview of the gas barrier layer

The gas barrier layer according to the present invention is provided on at least one side of the resin substrate, and may be provided on both sides.

The gas barrier layer according to the present invention is not particularly limited, and a layer formed by applying a coating liquid containing polysilazane to a reforming treatment on a dry layer, or at least a layer containing silicon, is vacuum plasma CVD. A gas barrier layer formed by a chemical vapor deposition method (Chemical Vapor Deposition) or a sputtering method may be used.

Among them, the gas barrier film of the present invention is a component of the gas barrier layer from the viewpoint of achieving flexibility (flexibility, bending resistance), mechanical strength, durability during conveyance in roll-to-roll, and gas barrier performance. The film barrier layer is formed by plasma chemical vapor deposition using plasma generated by applying a voltage between opposing roller electrodes containing carbon, silicon, and oxygen, and having a magnetic field generating member that generates a magnetic field. It is preferable to manufacture by the manufacturing method of the gas barrier film which satisfies all the following requirements (i)-(iii).

(i) The ratio of the distance (L) from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) Silicon distribution curve showing the relationship, the oxygen distribution curve showing the relationship of the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of oxygen), and the L and silicon atoms, oxygen In the carbon distribution curve showing the relationship of the ratio of the amount of carbon atoms to the total amount of atoms and carbon atoms (the atomic ratio of carbon), a region of 90% or more (upper limit: 100%) from the surface of the layer thickness of the gas barrier layer In (Atomic Ratio of Carbon), (Atomic Ratio of Silicon), (Atomic Ratio of Oxygen) are many in this order (atomic ratio C <Si <O);

(ii) the carbon distribution curve has at least two extremes;

(iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter also simply referred to as "C _max -C _{min difference} ") is 3 at% or more.

By manufacturing the gas barrier film by this production method, it is possible to obtain a gas barrier film having both the gas barrier properties of the entire surface and the fluctuations in the gas barrier properties, and bending resistance being highly compatible.

The silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve are analyzed by X-ray photoelectron spectroscopy (XPS) and rare gas ion sputter, such as argon, to sequentially analyze the surface composition while exposing the inside of the sample It can be created by so-called XPS depth profile measurement. The distribution curve obtained by such XPS depth profile measurement can be created, for example, using the vertical axis as the atomic ratio (unit: at%) of each element, and the horizontal axis as the etching time (sputter time). In addition, in the distribution curve of the element having the horizontal axis as the etching time, the etching time is generally correlated with the distance L from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer. As the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer ”, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed when measuring the XPS depth profile is adopted as it is. can do. In addition, a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve can be created under the following measurement conditions.

(Measuring conditions)

Etched ion species: Argon (Ar ⁺ )

Etch rate (SiO ₂ thermal oxide film conversion value): 0.05nm / sec

Etching interval (in terms of SiO ₂ ): 10 nm

X-ray photoelectron spectroscopy: Thermo Fisher Scientific, model "VG Theta Probe"

Irradiation X-ray: single crystal spectral AlKα

X-ray spot and its size: 800 μm × 400 μm oval

It is preferable that the gas barrier layer has (ii) a carbon distribution curve having at least two extreme values. The gas barrier layer preferably has a carbon distribution curve having at least three extremes, more preferably at least four extremes, and may have five or more. When the extreme value of the carbon distribution curve is 1 or less, the gas barrier property in the case where the obtained gas barrier film is bent may be insufficient. In addition, although 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. However, it cannot be defined uniformly.

Here, in the case of having at least three extremes, the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer at one extreme value of the carbon distribution curve and at the extreme value adjacent to the extreme value (L) ), The absolute value of the difference (hereinafter also simply referred to as "the distance between the extreme values") is preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably 75 nm or less. If the distance between these extreme values is high, a portion having a large carbon atom ratio (maximum value) in the gas barrier layer is present at a suitable period, thereby providing a suitable flexibility to the gas barrier layer, and effectively generating cracks during bending of the gas barrier film. It can be suppressed and prevented, and the deterioration of the gas barrier property when bending is repeated can be improved.

In addition, in this specification, "the extreme value" means the maximum value or the minimum value of the atomic ratio of the element with respect to the distance L from the surface of the gas barrier layer in the layer thickness direction of a gas barrier layer. In addition, in this specification, the "maximum value" is a point in which the value of the atomic ratio of an element (oxygen, silicon or carbon) changes from increasing to decreasing 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 direction of the layer thickness of the gas barrier layer in the range of 4 to 20 nm is further changed from this point to the atomic ratio of the element is 3 at% It refers to the point of abnormal decrease. That is, when it is changed in the range of 4 to 20 nm, the value of the atomic ratio of the element in any range may be reduced by 3 at% or more.

Similarly, in this specification, the "minimum value" is a point in which the value of the atomic ratio of an element (oxygen, silicon or carbon) changes from decrease to increase when the distance from the surface of the gas barrier layer is changed, and that point The atomic ratio of the element at a position where the distance from the surface of the gas barrier layer in the direction of the layer thickness of the gas barrier layer in the range of 4 to 20 nm is further changed is 3 at least from the value of the atomic ratio of the element of It refers to the point that increases by more than%. That is, when changing in the range of 4 to 20 nm, the value of the atomic ratio of the element in any range may be increased by 3 at% or more. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation during bending of the gas barrier film is high, but is not limited. Considering the flexibility of the barrier layer, the effect of suppressing / preventing cracks, thermal expansion, and the like, it is preferably 10 nm or more, and more preferably 30 nm or more.

In addition, the gas barrier layer preferably has an absolute value (hereinafter, also simply referred to as "C _max -C _{min difference} ") of 3 at% or more of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (iii). Do. When the absolute value is less than 3 at%, the gas barrier property may be insufficient when the obtained gas barrier film is bent. The difference in C _max -C _min 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. In addition, in this specification, "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. Similarly, in this specification, the "minimum value" is the atomic ratio of each element that is the smallest in the distribution curve of each element, and is the lowest value among the minimum values. Here, the upper limit of the difference between C _max -C _min is not particularly limited, but considering the effect of suppressing / preventing crack generation during bending of the gas barrier film, it is preferable that it is 50 at% or less, more preferably 40 at% or less desirable.

The layer thickness (dry layer thickness) of the gas barrier layer formed by the plasma CVD method is not particularly limited as long as the above (i) to (iii) are satisfied. For example, the layer thickness per 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. If it is such a layer thickness, the gas barrier film can exhibit excellent gas barrier properties and a suppression / prevention effect of cracking during bending. In addition, when the barrier layer formed by the plasma CVD method is composed of two or more layers, it is preferable that each gas barrier layer has a layer thickness as described above.

In the present invention, from the viewpoint of forming a barrier layer having uniform and excellent gas barrier properties over the entire film surface, the gas barrier layer is substantially uniform in the film surface direction (direction parallel to the surface of the gas barrier layer). It is preferable that there is little variation.

Here, when the gas barrier layer is substantially uniform in the direction of the film surface, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve are prepared for two measurement points on the film surface of the barrier layer by XPS depth profile measurement. In this case, the number of extreme values of the carbon distribution curves obtained at two arbitrary measurement points is the same, and the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve is the same, or It refers to the difference within 5 at%.

In addition, the details of the composition of the gas barrier layer and the gas barrier properties and the carbon distribution curve are described in Japanese Patent Laid-Open No. 2010-260347 or Japanese Patent Laid-Open No. 2011-73430, and are detailed. Omit the description.

[2] Formation of gas barrier layer by plasma CVD

In order for the gas barrier layer according to the present invention to satisfy all of the above (i) to (iii), it is preferable to use a film forming apparatus capable of performing the plasma CVD method described below.

The film-forming apparatus for forming a gas barrier layer according to the present invention is a film-forming apparatus for forming a thin film layer on the resin substrate, provided with a pair of opposing roller electrodes that oppose the resin substrate in a vacuum chamber, wherein at least 1 It is preferable to have the following means (1) to (5) of the tank.

Means (1): A supply port for supplying a film forming gas to the opposite space between the resin substrates to be arranged oppositely.

Sudan (2): a magnetic field generating device that forms an endless tunnel-type magnetic field that bulges into an opposing space

Sudan (3): power source for generating plasma in the opposite space

Means (4): A pair of opposing roller electrodes forming a thin film layer on the resin substrate

Means (5): An exhaust port for exhausting the deposition gas in the opposite space

Moreover, the manufacturing method of the gas barrier layer which concerns on this invention is a film-forming method which arrange | positions a resin base material in a vacuum chamber and forms a thin film layer on a resin base material, and at least 1 set of following processes (1)-(5) It is preferred to have.

Process (1): Process of supplying film-forming gas to the opposite space between resin substrates which are arranged to face each other

Process (2): A process of forming an endless tunnel type magnetic field that has been swollen into the opposite space

Process (3): process of generating plasma in the opposite space

Step (4): Step of disposing resin substrates oppositely and forming a thin film layer on the resin substrates

Process (5): Process of evacuating the film-forming gas in the opposite space

Incidentally, in the CVD method at atmospheric pressure plasma discharge using a conventional flat electrode (horizontal conveying type) (hereinafter sometimes referred to as atmospheric plasma CVD method), continuous change in the concentration gradient of the carbon atom component in the gas barrier layer Since it does not occur, it is difficult to achieve both gas barrier properties and bending resistance. In a gas barrier layer formed by a plasma chemical vapor deposition method using a plasma generated by applying a voltage between opposing roller electrodes having a magnetic field generating member that generates a magnetic field, the gas barrier is caused by a continuous change in the concentration gradient of carbon atom components Both sex and bending resistance are compatible.

As the apparatus for forming the gas barrier layer according to the present invention, the film forming apparatus 100 shown in Fig. 7 is preferably used. 7 is a schematic configuration diagram showing an example of a film forming apparatus.

As shown in FIG. 7, 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'), winding roll 117, gas supply pipes 118, 118 ', plasma generating power sources 119, 119', and magnetic field generating devices 120, 121, 120 ', 121'), a vacuum chamber 130, vacuum pumps 140, 140 ', and a control unit 141.

Delivery roll 110, conveying rolls 111 to 114, 112 ', 113', first, second, third and fourth film forming rolls 115, 116, 115 ', 116', and winding rolls 117 ) Is accommodated in the vacuum chamber 130.

The delivery roll 110 delivers the resin substrate 1a installed in a pre-wound state toward the transfer roll 111. The dispensing roll 110 is a cylindrical roll extending in a vertical direction with respect to the ground, and is rotated counterclockwise by a drive motor (not shown) (refer to the arrow in FIG. 7), thereby winding the resin on the dispensing roll 110. The base material 1a is sent out toward the conveyance roll 111.

The conveying rolls 111 to 114, 112 ', and 113' are cylindrical rolls configured to be rotatable around a rotation axis substantially parallel to the delivery roll 110. The conveyance roll 111 is a roll for conveying the resin substrate 1a from the delivery roll 110 to the first film forming roll 115 while providing an appropriate tension to the resin substrate 1a. The conveying rolls 112 and 113 transfer the resin substrate 1b from the first film forming roll 115 to the second film forming roll (115) while applying appropriate tension to the resin substrate 1b formed by the first film forming roll 115. 116). The conveying rolls 112 'and 113' remove the resin substrate 1e from the third film forming roll 115 'while applying an appropriate tension to the resin substrate 1e formed by the third film forming roll 115'. 4 This is a roll for conveying to the film forming roll 116 '. In addition, the conveying roll 114 rolls the resin substrate 1c from the fourth film forming roll 116 'while providing an appropriate tension to the resin substrate 1c formed by the fourth film forming roll 116'. 117).

The first film forming roll 115 and the second film forming roll 116 are pairs of film forming rolls having rotation axes that are substantially parallel to the delivery roll 110 and spaced apart from each other by a predetermined distance. Also, the third film forming roll 115 'and the fourth film forming roll 116' are pairs of film forming rolls having rotation axes that are approximately parallel to the delivery roll 110 and spaced apart from each other by a predetermined distance. The 2nd film forming roll 116 forms a film with respect to the resin base material 1b, and conveys the resin base material 1d to the 3rd film forming roll 115 ', providing an appropriate tension to the formed resin base material 1d. . The 4th film forming roll 116 'forms the resin base material 1e, and conveys the resin base material 1c to the conveyance roll 114, providing an appropriate tension to the formed resin base material 1c.

In the example shown in FIG. 7, the separation distance between the first film forming roll 115 and the second film forming roll 116 is a distance connecting points A and B, and the third film forming roll 115 'and the fourth film forming. The separation distance of the roll 116 'is the distance connecting the points A' and B '. The first to fourth film forming rolls 115, 116, 115 ', and 116' are discharge electrodes formed of a conductive material, and the first film forming roll 115, the second film forming roll 116, and the third film forming roll 115 The ') and the fourth film forming roll 116' are each insulated from each other. In addition, the material or configuration of the first to fourth film forming rolls 115, 116, 115 ', and 116' can be appropriately selected to achieve a desired function as an electrode.

In addition, the 1st to 4th film forming rolls 115, 116, 115 ', and 116' may be heated independently, respectively. 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, and the glass transition temperature of the resin substrate 1a. If set to excessively high temperatures in excess of the above, there is a fear that the resin substrate is deformed by heat.

Inside the first to fourth film forming rolls 115, 116, 115 ', and 116', magnetic field generating devices 120, 121, 120 ', and 121' are provided, respectively. The first film forming roll 115 and the second film forming roll 116 are supplied with a plasma generating power source 119, and the third film forming roll 115 'and the fourth film forming roll 116' are supplied with plasma generating power 119. '), A high frequency voltage for plasma generation is applied. Thereby, the film-forming part S between the 1st film-forming roll 115 and the 2nd film-forming roll 116, or the film-forming part between the 3rd film-forming roll 115 'and the 4th film-forming roll 116' An electric field is formed in (S '), and a discharge plasma of the deposition gas supplied from the gas supply pipe 118 or 118' is generated. The voltage applied by the plasma generating power supply 119 and the voltage applied by the plasma generating power supply 119 'may be the same or different. The power source frequency of the plasma generating power source 119 or 119 'can be arbitrarily set, but as an apparatus of this configuration, for example, it is within a range of 60 to 100 kHz, and the applied power is, for example, 1 m of effective film formation width. For example, it is in the range of 1 to 10 kW.

The winding roll 117 has a rotation axis substantially parallel to the delivery roll 110, and the resin base material 1c is wound up and accommodated in a roll shape. The winding roll 117 winds the resin base material 1c by rotating in a counterclockwise direction with a drive motor (not shown) (see arrow in Fig. 7).

The resin base material 1a sent out from the delivery roll 110 is between the delivery roll 110 and the winding roll 117, and the transfer rolls 111 to 114, 112 ', 113', and the first to fourth film formations. It is conveyed by rotation of each of these rolls, while maintaining appropriate tension by being wound around the rolls 115, 116, 115 ', and 116'. In addition, the conveying directions of the resin substrates 1a, 1b, 1c, 1d, 1e are indicated by arrows. The conveyance speed (line speed) of the resin substrates 1a to 1e (for example, the conveyance speed at point C or point C 'in Fig. 7) depends on the type of the source gas, the pressure in the vacuum chamber 130, and the like. Can be adjusted accordingly. The conveyance speed is adjusted by controlling the rotation speeds of the drive motors of the delivery roll 110 and the winding roll 117 by the control unit 141. When the conveying speed is slowed, the thickness of the region to be formed becomes thicker.

In addition, when this film forming apparatus 100 is used, the conveying direction of the resin substrates 1a to 1e is in a direction opposite to that indicated by the arrow in FIG. 7 (hereinafter referred to as a forward direction) (hereinafter referred to as a reverse direction). It is also possible to set the gas barrier film to form a film. Specifically, the control unit 141, in the case where the resin substrate 1c is wound by the winding roll 117, the rotation direction of the drive motor of the delivery roll 110 and the winding roll 117 is described above And controls to rotate in the reverse direction. If controlled in this way, the resin base material 1c sent out from the winding roll 117 is formed between conveyance rolls 111 to 114, 112 ', and 113' between the delivery roll 110 and the winding roll 117. It is conveyed in the reverse direction by rotation of each of these rolls, while maintaining appropriate tension by being wound around the first to fourth film forming rolls 115, 116, 115 ', and 116'.

When the gas barrier layer is formed using the film forming apparatus 100, the gas barrier layer is formed by conveying the resin substrate 1a in the forward and reverse directions to reciprocate the film forming portion S or the film forming portion S '. The (film-forming) process can be repeated multiple times.

The gas supply pipes 118 and 118 'supply film-forming gas such as raw material gas for 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 portion S, and the openings provided in a plurality of places The film forming gas is supplied to the film forming section S from. Likewise, the gas supply pipe 118 'has a tubular shape extending above the film forming portion S' in the same direction as the rotational axes of the third film forming roll 115 'and the fourth film forming roll 116', The film forming gas is supplied from the openings provided in a plurality of places to the film forming section S '. 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. Moreover, the supply gas pressure supplied from these gas supply pipes may be the same or different.

As a raw material gas, a silicon compound can be used. As the silicon compound, for example, hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxanevinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, di Ethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyl Disilazane and the like. In addition, the compound described in paragraph 0075 of JP2008-056967A can also be used. Among these silicon compounds, HMDSO is preferably used in the formation of the gas barrier layer from the viewpoint of ease of handling of the compound and high gas barrier properties of the resulting gas barrier film. Moreover, two or more types of these silicon compounds may be used in combination. Further, the raw material gas may contain a monosilane in addition to the silicon compound.

As the film forming gas, a reactive gas may be used in addition to the raw material gas. As the reaction gas, a gas that is made of a silicon compound such as oxide or nitride by reacting with a source gas is selected. As a reaction gas for forming an oxide as a thin film, oxygen gas or ozone gas can be used, for example. Moreover, you may use these reaction gas in combination of 2 or more type.

As the film forming gas, a carrier gas may be further used to supply the raw material gas into the vacuum chamber 130. Moreover, as a film-forming gas, in order to generate plasma, a gas for discharge may be further used. As the carrier gas and the discharge gas, for example, rare gases such as argon and hydrogen or nitrogen are used.

The magnetic field generating devices 120 and 121 are members for forming a magnetic field in the film forming portion S between the first film forming roll 115 and the second film forming roll 116, and the magnetic field generating devices 120 'and 121' ) Is similarly a member for forming a magnetic field in the film forming portion S 'between the third film forming roll 115' and the fourth film forming roll 116 '. These magnetic field generating devices 120, 120 ', 121, and 121' are stored at a predetermined position without following the rotation of the first to fourth film forming rolls 115, 116, 115 ', and 116'.

The vacuum chamber 130 includes a delivery roll 110, a transfer roll (111 to 114, 112 ', 113'), a first to fourth film forming rolls (115, 116, 115 ', 116') and a winding roll (117) ) To maintain a reduced pressure. The pressure (vacuum degree) in the vacuum chamber 130 can be appropriately adjusted according to the type of raw material gas or the like. It is preferable that the pressure of the film-forming part S or S 'is in the range of 0.1 to 50 Pa.

The vacuum pumps 140 and 140 'are communicatively connected to the control unit 141, and appropriately adjust the pressure in the vacuum chamber 130 according to the command of the control unit 141.

The control unit 141 controls each component of the film forming apparatus 100. The control unit 141 is connected to the drive motors of the delivery roll 110 and the winding roll 117, and controls the rotation speed of these drive motors to adjust the conveyance speed of the resin substrate 1a. Moreover, the conveying direction of the resin base material 1a is changed by controlling the rotation direction of a drive motor. In addition, the control unit 141 is communicatively connected to a supply mechanism of the deposition gas not shown, and controls the supply amount of each component gas of the deposition gas. Further, the control unit 141 is communicatively connected to the plasma generating power sources 119 and 119 ', and controls the output voltage and output frequency of the plasma generating power sources 119 and 119'. Further, the control unit 141 is communicatively connected to the vacuum pumps 140 and 140 ', and controls the vacuum pumps 140 and 140' to maintain the inside of the vacuum chamber 130 in 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). In the HDD, a software program describing a procedure for controlling the components of the film forming apparatus 100 to realize the formation of a gas barrier layer is stored. Then, when the power of the film forming apparatus 100 is turned on, the software program is loaded into the RAM and executed sequentially by the CPU. In addition, various data and parameters used when the CPU executes the software program are stored in the ROM.

[3] Formation of gas barrier layer by coating method

It is also preferable to form a gas barrier layer by providing a coating film of a polysilazane-containing liquid on a resin substrate by a coating method, and irradiating and modifying a vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less.

It is also preferable to form a gas barrier layer by a coating method on the gas barrier layer prepared by the plasma CVD method. In this case, minute defects remaining in the gas barrier layer of the underlying layer can be filled with the gas barrier component of polysilazane, further improving the overall gas barrier properties and bending properties, and reducing fluctuations in gas barrier properties. You can.

The layer thickness of the gas barrier layer 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. If the layer thickness is 1 nm or more, sufficient gas barrier performance can be exhibited, and if it is 500 nm or less, cracks are unlikely to occur in the dense silicon oxynitride film.

Polysilazane is marketed as a solution dissolved in an organic solvent, and commercially available products can be used as it is as a polysilazane-containing coating liquid. As a commercial item of a polysilazane solution, NN120-20, NAX120-20, NL120-20 etc., manufactured by AZ Electronic Materials Co., Ltd. are mentioned, for example. Further, a metal alkoxide compound, a metal chelate compound, or a low molecular silazane / siloxane may be added to the polysilazane solution.

<< Water vapor barrier evaluation test piece >>

The water vapor barrier evaluation test piece of the present invention is a water vapor barrier evaluation test piece 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 an elongated resin substrate, and the gas barrier A water-reactive metal layer provided on the layer and a water vapor-impermeable layer for sealing the water-reactive metal layer are provided, and markers indicating coordinates in at least one of the longitudinal direction and the width direction of the gas barrier film are formed. It is characterized by.

The resin substrate, gas barrier layer, moisture-reactive metal layer, and water vapor impermeable layer constituting the water vapor barrier evaluation test piece of the present invention are the resin substrate, the gas barrier layer, and the first constituting the gas barrier film of the present invention, respectively. And a second moisture-reactive metal layer, and the first and second water vapor impermeable layers.

In the water vapor barrier evaluation test piece of the present invention, markers indicating coordinates in at least one of the longitudinal direction and the width direction of the gas barrier film are formed so that the arrangement before being cut off from the gas barrier film of the mother can be determined. have. It is preferable that the marker is formed in a region that does not overlap the moisture-reactive metal layer. In addition, as a marker, if it does not affect the evaluation of water vapor barrier properties, it may be formed in any form, and may be printed on the back surface of the resin substrate (the surface opposite to the gas barrier layer formation surface) with a predetermined ink, and the resin may be used. It may be engraved on the back side of the base material. In the case of using an ink, in the process of forming a water-reactive metal layer, it is preferable that less outgas is generated.

As a manufacturing method of the water vapor barrier evaluation test piece of this invention, the method of cutting out the area | region which formed the 1st water vapor barrier test area part or the 2nd water vapor barrier test area part from the gas barrier film of this invention mentioned above, or a gas barrier And a method in which a predetermined region of the resin substrate on which the layer is formed is cut off, and a water-reactive metal layer and a water vapor impermeable layer are formed on the gas barrier layer of the cut section.

<< Method for evaluating water vapor barrier properties of gas barrier films >>

The gas barrier property evaluation method of the gas barrier film of the present invention is characterized in that the gas barrier property film or the water vapor barrier evaluation test piece is used.

Specifically, before and after exposing the gas barrier film or the water vapor barrier evaluation test piece, light is incident from one side to confirm or measure a change in the optical properties of the moisture-reactive metal layer.

As a measurement means, a photomultiplier tube or a spectrometer can be used.

In the case of using a spectrometer, light is incident from one side of the gas-barrier film or water vapor barrier evaluation test piece, and the change in the optical properties of the water-reactive metal layer is measured by spot light by reflected light or transmitted light. desirable.

In addition, when photographing a specified range of the water-reactive metal layer as an image, light is incident from one side of the gas barrier film or water vapor barrier evaluation test piece, and reflected light or transmitted light is an area type or line sensor type CCD, or It is possible to take a picture using a CMOS camera, and it is preferable to use an area CCD or a CMOS camera.

In the case of measuring a change in the optical properties, as described above, there is a case where the reflected light of light incident on the gas barrier film or the water vapor barrier evaluation test piece is measured, and sometimes the transmitted light is measured. It is preferable to measure the transmitted light when the gas-barrier film or the water vapor barrier evaluation test piece is transparent, since the influence of noise or the like from the device is small.

It is preferable to perform measurement every predetermined time after exposure to water vapor. Thereby, it is possible to data how the corrosion of the water-reactive metal layer proceeds over time.

The term "exposed to water vapor" means that a gas barrier film or a water vapor barrier evaluation test piece is stored in, for example, a constant temperature and humidity chamber and brought into contact with water vapor. Although the temperature and humidity conditions of the constant temperature and humidity tank are appropriately selected, for example, the temperature is preferably in the range of room temperature to 90 ° C, and the humidity is preferably in the range of 40 to 90% RH. Further, the storage time for the constant temperature and humidity tank is not particularly limited, but is preferably about 10 to 2000 hours, and the sample may be taken out and evaluated at appropriate intervals during the storage time.

<Example>

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these. In addition, although an indication of "part" or "%" is used in Examples, "part by mass" or "mass%" is indicated unless otherwise specified.

[Example 1]

<< Production of gas barrier film 1-1 >>

(1) Preparation of resin substrate

As a resin substrate, a PET film having a thickness of 100 µm having an easy-to-adhesive layer on both sides and Lumirror U403 was prepared.

Subsequently, using a roll-to-roll coating device, the hard coat coating solution HC1 for the surface containing the following composition was applied to one surface of the resin substrate so that the dry film thickness was 4 µm, and after drying, the ultraviolet ray was 500 mJ / It irradiated under the condition of cm <2>, cured, and wound up.

Polymerizable binder: SR368 manufactured by Sartomer 12.0 parts by mass

Polymerizable binder: Arakawa Chemical Co., Ltd. beam set 575 22.0 parts by mass

Polymerization initiator: Irgacure 651 from BASF 1.0 parts by mass

Solvent: Propylene glycol monomethyl ether 65.0 parts by mass

Next, according to Example 2 of Japanese Patent Laid-Open No. 2017-33891, 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 side.

Conductive polymer organic solvent dispersion (solid content 0.5% by mass) 53.5 parts by mass

Polymerizable binder: SR368 manufactured by Sartomer 12.0 parts by mass

Polymerizable binder: Arakawa Chemical Co., Ltd. beam set 575 22.0 parts by mass

Polymerization initiator: Irgacure 651 from BASF 1.0 parts by mass

Silica dispersion: MA-ST-ZL manufactured by Nissan Chemical Co., Ltd. 2.0 parts by mass

Solvent: diacetone alcohol 9.5 parts by mass

Subsequently, the hard coat coating solution HC2 for the back surface was applied to the opposite side of the resin substrate so that the dry film thickness was 4 µm, and after drying, the mixture was cured by irradiation with ultraviolet light at 500 mJ / cm 2. Thereby, an antistatic function and an anti-block function were imparted to the resin substrate.

Subsequently, the said resin base material was slit and wound up to 1200 mm width, and the resin base material roll of 1200 mm width was obtained.

(2) Formation of gas barrier layer

The 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, conveyance speed: 20.0 m / min, raw material gas (HMDSO) supplied in the first film forming section: 150 sccm, oxygen gas supplied in the first film forming section: 500 sccm, vacuum degree in the first film forming section: 1.5 Pa, The applied power of the first film forming section is 4.5kW, the supply of raw material gas (HMDSO) to the second film forming section: 150 sccm, the oxygen gas supply amount of the second film forming section: 1000 sccm, the vacuum degree of the second film forming section: 1.5Pa, the applied power of the second film forming section: 4.5kW Was made. In addition, the power source frequency was 84 kHz, and the temperature of the film forming roll was all set to 30 ° C. In forming the gas barrier layer by passing a plurality of passes through the resin substrate in the film forming apparatus 100, it is conveyed in the direction in which the resin substrate is unwound in the odd passes (1st pass, 3rd pass, 5th pass, ...). In the even-numbered pass (the second pass, the fourth pass, the sixth pass, etc.), the resin substrate is conveyed in the rewinding direction. The film-forming part passing through was made into the 2nd film-forming part. The number of film formations was 10 passes, and a gas barrier layer having a total layer thickness of 300 nm with 20 layers laminated on the resin substrate was formed.

However, in the first pass in the formation of the gas barrier layer, the roll circumferential surface, on which the resin substrate is not wound, of the transfer roll 112 shown in FIG. 7 touching the film-forming surface side of the resin substrate is exposed. The needle-shaped metal member was pressed to the portion where the transfer roll 112 was axially spaced 100 mm apart. Thereby, in 11 places of 100-1100 mm from one end of the resin substrate in the width direction (hereinafter also referred to as a film edge), fine metal powder is generated during film formation, transferred to the film formation surface, and deliberately continuous in the longitudinal direction MD in the form of stripes. Formed an abnormal part of the film formation. Before the second pass was formed, the needle-shaped metal member was separated, and after the second pass, normal film formation was performed, but under the influence of the streak-like film formed on the first pass, 11 places in the width direction TD of the resin substrate In, a stripe-like defect portion extending in the longitudinal direction MD was formed. In addition, by visual observation of the gas barrier layer, it was not possible to confirm the stripe-shaped defect portion.

(3) Formation of first water vapor barrier test area part and second water vapor barrier test area part

First, on the back surface of the resin substrate (opposite surface of the gas barrier layer forming surface), the portion corresponding to the region forming the water vapor barrier test region portion, as viewed in the longitudinal direction MD, the portions of the calcium layers described later partially overlap each other. Positioning marking was performed to achieve this existing configuration. After marking, as shown in Fig. 8, a laminate of the resin substrate and the gas barrier layer was respectively cut, and eight sections to be formed for the water vapor barrier test region were cut out. Since each section is marked, it is possible to determine at which position the section is cut off from the base material. In addition, each section was cut so that some overlapping portions existed when viewed from the longitudinal MD.

Subsequently, using a vacuum deposition apparatus JEE-400 manufactured by Nippon Denshi Co., Ltd., a central portion of a glass plate-like member (first and second water vapor impermeable layers) having an area of 40 mm (longitudinal MD) x 180 mm (wide direction TD). Then, a calcium layer (first and second moisture-reactive metal layers) was deposited in an area of 20 mm (lengthwise MD) x 152 mm (widthwise TD). Eight glass plate-like members were produced.

Subsequently, an adhesive layer (three bonds 1655, first and second adhesive layers) having an area of 33 mm (longitudinal direction) x 165 mm (wide direction TD) was respectively provided on the gas barrier layer of each of the produced sections. This was left in a glove box (GB) day and night to remove moisture from the adhesive layer and adsorbed water from the surface of the gas barrier layer. Thereafter, the glass plate-like member was bonded to each of the adhesive layers of each section so that the calcium layer faced each other, and a total of eight first and second water vapor barrier test regions were formed on the gas barrier layer. Thereby, the gas barrier film 1-1 in which the ends of the calcium layers overlapped with each other as seen in the longitudinal direction MD, in which each section was arranged in the arrangement before cutting out from the base resin substrate, was produced. In addition, the length in the width direction TD of the overlapping portion was set to 1.0 mm.

<< Production of gas barrier film 1-2 >>

In the production of the gas barrier film 1-1, the area size of the calcium layer was 20 mm (MD in the longitudinal direction) x 215 mm (TD in the width direction), and the area size of the glass plate-like member and the adhesive layer was 40 mm (MD in the longitudinal direction), respectively. The gas barrier film 1-2 was produced in the same manner, except that it was changed to 243 mm (width direction TD) and a total of five first and second water vapor barrier test regions were formed. In addition, the length in the width direction TD of the portions where the ends of the calcium layers overlapped each other was set to 5.0 mm.

<< Production of 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 (lengthwise MD) x 20 mm (widthwise TD), and the area size of the glass plate-like member and the adhesive layer is 40 mm (lengthwise MD) x respectively. The gas barrier film 1-3 was produced in the same manner except that it was changed to 40 mm (width direction TD) and a total of four water vapor barrier test area portions were formed. In addition, as shown in FIG. 8, the four water vapor barrier test region portions were formed so that the portions where the calcium layers overlap each other when viewed from the longitudinal MD.

<< Production of gas barrier film 1-4 >>

In the production of the gas barrier film 1-1, the area size of the calcium layer was 20 mm (lengthwise MD) x 146 mm (widthwise TD), and the area sizes of the glass plate-like member and the adhesive layer were respectively 40 mm (lengthwise MD) x A gas barrier film 1-4 was produced in the same manner except that it was changed to 174 mm (width direction TD). In addition, as shown in FIG. 8, the eight water vapor barrier test region portions were formed so that the portions where the calcium layers overlap each other when viewed from the longitudinal MD.

<< Production of gas barrier film 1-5 >>

In the production of the gas barrier film 1-1, the area size of the calcium layer was 20 mm (MD in the longitudinal direction) x 150 mm (TD in the width direction), and the area size of the glass plate-like member and the adhesive layer was 40 mm (MD in the longitudinal direction), respectively. A gas barrier film 1-5 was produced in the same manner except that it was changed to 178 mm (width direction TD). In addition, as illustrated in FIG. 8, the eight water vapor barrier test region portions were formed so that the glass plate-shaped member and the adhesive layer partially overlap each other, but the calcium layer does not overlap with each other when viewed in the longitudinal direction MD.

<< Evaluation of gas barrier films 1-1 to 1-5 >>

Light was incident from the normal direction on the glass plate-shaped member side of each section of the produced gas-barrier film, and photographed with an area-type CCD camera from the opposite side. Thereafter, each section was left in a constant temperature and humidity tank (Yamato Humidic ChamberIG47M) at 85 ° C. and 85% RH for 50 hours, and similarly, imaging was performed with a CCD camera.

The presence or absence of a stripe-like defect was confirmed from the images before and after being placed in the constant temperature and humidity tank. The results are shown in FIG. 8. The case where the stripe type defect portion was detected was evaluated as "○", and the case where the stripe type defect portion was not detected was evaluated as "x".

As shown in Fig. 8, gas barrier films 1-1 and 1-2 are gas barrier films 1-3 to as compared to all of the 11 stripe defects [1] to [11] detected. 1-5, a part of the stripe-like defect portion was not detected. Therefore, it can be said that the gas barrier film 1-1, 1-2 can detect minute scratches of a long stripe type with high precision.

[Example 2]

<< Production of gas barrier film 2-1 >>

(1) Preparation of resin substrate

In the production of the resin base material of the gas barrier film 1-1, after applying and curing the hard coat coating solution HC1 for the surface, a protective film (FTA-mura Chemical Co., Ltd., FSA-020M) is bonded to the hard coat formation surface. A resin substrate was produced in the same manner except that it was done.

(2) Formation of gas barrier layer

A gas barrier layer having a two-layer lamination configuration was formed using the roll-to-roll type coating device 200 shown in FIG. 9.

As shown in FIG. 9, the coating device 200 conveys the resin substrate unwound from the unwinding roll 201 by a plurality of conveying rollers, and the protective film (from the resin substrate by the protective film winding roll 202) 203) is removed and recovered. In addition, after the protective film 203 is peeled off, the coating device 200 applies a coating liquid for forming a gas barrier layer with a coater 204, and after drying it with a dryer 205, vacuum ultraviolet irradiation device ( 206) is applied to the coating film by vacuum ultraviolet irradiation. In addition, after the coating device 200 makes the surface touch roll 207 contact with the layer forming surface after irradiation with vacuum ultraviolet rays, the protective film 209 is bonded to the layer forming surface with the protective film unwinding roll 208. , The resin substrate is wound up by a winding roll 210.

Using the coating device 200, while conveying the resin substrate at a conveying speed of 3.0 m / min, the protective film is peeled from the resin substrate by the protective film winding roll 202, and the dry layer thickness is coated by the coater 204. Polysilazane was applied to be 110 nm. Subsequently, drying treatment 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. Next, the surface touch roll 207 (diameter: 120 mmφ) was brought into contact with the layer forming surface. Here, on the peripheral surface of the surface touch roll 207, one scratch is formed in the width direction TD (axial direction of the surface touch roll 207) by contacting the needle-shaped metal member in advance. As a result, the surface touch roll 207 has fine protrusions by forming the scratch scratches, and by contacting the layer forming surface on the resin substrate, fine scratches leading to the width direction TD are formed on the layer surface. Therefore, in the gas barrier layer formed on the resin substrate, fine scratches leading to the TD in the width direction were formed at a period of about 377 mm in the longitudinal MD.

After the protective film (Futamura Chemical Co., Ltd. make, FSA-020M) is bonded to the resin base material on which the 1st layer gas barrier layer was formed in the above manner by the protective film unwinding roll 208, it is wound up by the winding roll 210. Did.

Subsequently, after separating the surface touch roll 207 from the coating device 200, the roll of the resin substrate on which the first gas barrier layer was formed was set again on the unwinding roll 201.

Subsequently, while conveying the resin substrate at a conveying speed of 3.0 m / min, the protective film was peeled off from the resin substrate by the protective film winding roll 202, and the polysilazane was made so that the dry layer thickness was 110 nm by the coater 204. Applied. Here, a vibration of 4 Hz was applied to the coater 204 using a vibration mechanism (not shown). Thereby, the coating thickness of the second barrier gas barrier layer was changed at a period of 4 Hz, and a transverse non-uniformity of 12.5 mm pitch was formed in the longitudinal direction MD. Next, drying treatment was performed at a temperature of 80 ° C for 3.3 minutes, and vacuum ultraviolet treatment was performed at 4.0 J / cm 2. Next, after the protective film was bonded with the protective film unwinding roll 208, it was wound up with the winding roll 210.

In this way, a gas barrier layer was formed on the resin substrate. In addition, as a visual observation of the gas barrier layer, a 12.5 mm pitch transverse non-uniformity could be confirmed, but it was judged that there was no influence on water vapor barrier properties. Further, no fine scratches leading to the TD in the width direction of about 377 mm period were observed.

(3) Formation of first water vapor barrier test area part and second water vapor barrier test area part

First, on the back surface of the resin substrate (opposite surface of the gas barrier layer forming surface), the portion corresponding to the region forming the water vapor barrier test region portion, as viewed in the width direction TD, the portions of the calcium layers described later partially overlap each other. Positioning marking was performed to achieve this existing configuration. After marking, as shown in Fig. 10, a laminate of the resin substrate and the gas barrier layer was cut respectively, and eight sections to be formed to form the water vapor barrier test region were cut out. Since each section is marked, it is possible to determine at which position the section is cut off from the base material. In addition, each section was cut out so as to partially overlap with each other when viewed in the width direction TD.

Subsequently, using a vacuum deposition apparatus JEE-400 manufactured by Nihon Denshi Co., Ltd., a central portion of a glass plate-like member (first and second water vapor impermeable layers) having an area of 180 mm (MD in the length direction) x 40 mm (TD in the width direction). Then, a calcium layer (first and second water-reactive metal layers) was deposited in an area of 152 mm (MD in the longitudinal direction) x 20 mm (TD in the width direction). Eight glass plate-like members were produced.

Subsequently, an adhesive layer (three bonds 1655, first and second adhesive layers) having an area of 165 mm (longitudinal direction) x 33 mm (wide direction TD) was respectively provided on the gas barrier layer of each of the produced sections. This was left in a glove box (GB) day and night to remove moisture from the adhesive layer and adsorbed water from the surface of the gas barrier layer. Thereafter, the glass plate-like member was bonded to each of the adhesive layers of each section so that the calcium layer faced each other, and a total of eight first and second water vapor barrier test regions were formed on the gas barrier layer. Thereby, the gas barrier film 2-1 in which the ends of the calcium layers overlapped with each other when viewed in the width direction TD, in which each section was arranged in the arrangement before cutting out from the mother resin substrate, was produced. In addition, the length in the longitudinal direction MD of the overlapped portion was set to 1.0 mm.

<< Production of gas barrier film 2-2 >>

In the production of the gas barrier film 2-1, the area size of the calcium layer was 146 mm (MD in the longitudinal direction) x 20 mm (TD in the width direction), and the area sizes of the glass plate-like member and the adhesive layer were 174 mm (MD in the longitudinal direction), respectively. A gas barrier film 2-2 was produced in the same manner except that it was changed to 40 mm (width direction TD). In addition, the eight water vapor barrier test region portions were formed so that there were no portions where the calcium layers overlapped each other when viewed in the width direction TD.

<< Evaluation of gas barrier films 2-1 and 2-2 >>

Light was incident from the normal direction on the glass plate-shaped member side of each section of the produced gas-barrier film, and photographed with an area-type CCD camera from the opposite side. Thereafter, each section was left in a constant temperature and humidity tank (Yamato Humidic ChamberIG47M) at 85 ° C. and 85% RH for 50 hours, and similarly, imaging was performed with a CCD camera.

From the images before and after placing in the constant temperature and humidity tank, the presence or absence of fine scratches leading to the width direction TD was confirmed. The results are shown in FIG. 10. A case where a fine scratch was detected was evaluated as "○", and a case where a fine scratch was not detected was evaluated as "x".

As shown in Fig. 10, since all of the fine scratches [1] to [3] were detected in the gas-barrier film 2-1, it can be seen that fine scratches leading to the TD in the width direction occurred at a period of about 377 mm. The existence of a roll having a diameter of 120 mmφ is suggested as a cause. On the other hand, since the gas barrier film 2-2 did not detect fine scratches [2], there is a fear that the fine scratches leading to the TD in the width direction occurred in a cycle of about 754 mm. Therefore, it can be said that the gas barrier property film 2-1 can detect the periodicity of the gas barrier property change shown in a transverse type with high precision.

[Example 3]

(1) Preparation of resin substrate

A resin base material was produced in the same manner as the production of the resin base material in the gas barrier film 1-1.

(2) Formation of gas barrier layer

A gas barrier layer was formed on the resin substrate in the same manner as the formation of the gas barrier layer in the gas barrier film 1-1.

(3) Formation of first water vapor barrier test area part and second water vapor barrier test area part

First, on the back surface of the resin substrate (opposite surface of the gas barrier layer forming surface), the portion corresponding to the region forming the water vapor barrier test region portion, as viewed in the longitudinal direction MD, the portions of the calcium layers described later partially overlap each other. Positioning marking was performed to achieve this existing configuration. After the marking, the laminate of the resin substrate and the gas barrier layer was respectively cut, and eight sections to be formed for the water vapor barrier test region were cut out. Since each section is marked, it is possible to determine at which position the section is cut off from the base material. In addition, each section was cut so that some overlapping portions existed when viewed from the longitudinal MD.

Subsequently, each of the produced sections was placed at approximately the center of a 50 mm × 180 mm glass plate, with the resin substrate side facing each other, and the four corners of the slices were fixed on a glass plate with Kapton tape. Thereafter, UV ozone cleaning was performed on the surface of the gas barrier layer of each section.

Then, using a vacuum deposition apparatus JEE-400 manufactured by Nihon Denshi Co., Ltd., on the gas barrier layer of each section, a calcium layer (first and first) in an area of 20 mm (longitudinal MD) x 152 mm (wide direction TD). 2 moisture-reactive metal layer). In this way, each calcium layer was formed so that the end portions of the calcium layer overlapped with each other when viewed in the longitudinal direction MD in a state in which each section was arranged in the arrangement before cutting from the mother resin substrate. In addition, the length in the width direction TD of the overlapping portion was set to 1.0 mm.

Subsequently, the fragments on which the calcium layer had been deposited were taken out into a glove box, transferred to a CVD apparatus without exposure to the atmosphere, and a moisture-impermeable layer containing three layers of silicon nitride layers was formed to a size of 26 mm × 158 mm.

That is, first, a first silicon nitride layer having a layer thickness of 200 nm was formed on the calcium layer. As the deposition conditions, the gas flow rate of silane: 100 sccm, the gas flow rate of ammonia: 300 sccm, the gas flow rate of hydrogen: 1000 sccm, the gas flow rate of nitrogen: 1000 sccm, pressure: 200 Pa, power supply: 13.56 MHz, power output: 800 W, distance between electrodes: 2.3 cm.

On the first silicon nitride layer, a second silicon nitride layer having a layer thickness of 400 nm was formed. As the deposition conditions, the gas flow rate of silane: 100 sccm, the gas flow rate of ammonia: 300 sccm, the gas flow rate of hydrogen: 1500 sccm, the gas flow rate of nitrogen: 1000 sccm, pressure: 200 Pa, power supply: 13.56 MHz, power output: 1200 W, distance between electrodes: 3.2 cm.

On the second silicon nitride layer, a third silicon nitride layer having a layer thickness of 200 nm was formed. As the film-forming conditions, the film-forming conditions at the time of formation of the first silicon nitride layer were the same.

As described above, on the gas barrier layer of each section, a water vapor barrier test region was formed to produce a gas barrier film 3-1.

When the vapor barrier property evaluation was performed in the same manner as in Example 1 using the produced gas barrier film 3-1, results similar to those of the gas barrier film 1-1 were obtained.

[Example 4]

<< Production of gas barrier films 4-1 to 4-3 >>

In the production of the gas-barrier film 1-1, when viewed in the longitudinal direction MD, the length in the width direction TD of the portion where the ends of the calcium layers overlap each other and the width of the portion where the ends of the glass plate-like members overlap each other. Gas barrier films 4-1 to 4-3 were produced in the same manner except that the length in the direction TD was changed as described in Table I.

<< Evaluation of gas barrier films 4-1 to 4-3 >>

Among the sections of the produced gas-barrier film, in the sections arranged second and third from the film edge side of the mother gas barrier film, portions where the calcium layers overlap each other (the stripe-like defects [3 (Overlapping part)) was evaluated. That is, light was incident on the glass plate-shaped member side of the section from the normal direction, and photographing was performed with an area-type CCD camera from the opposite side. Thereafter, each section was left in a constant temperature and humidity bath (Yamato Humidic ChamberIG47M) at 85 ° C. and 85% RH for 50 hours, 100 hours, and 200 hours, and was photographed with a CCD camera in the same manner as above for each standing time.

Here, each calcium layer gradually shrinks from its periphery under the influence of moisture entering from the end of each section, and after a certain period of time, the overlapping portion between the calcium layers in the arrangement before each section is cut off is lost.

In the photographed images at each of the above-mentioned standing times, it was confirmed whether or not the overlapping portions between the calcium layers were lost. Table I shows the results.

Table I

As shown in Table I, by lengthening the length in the width direction TD of the portion where the glass plate-like members overlap, the time at which the portions overlapping the calcium layers disappear is also increased. Therefore, it can be said that it is also useful for detection of a stripe-like defect portion that occurs in a gas barrier film having a very high gas barrier property, which is used as a substrate for an organic EL.

The gas barrier film and the water vapor barrier property evaluation test piece of the present invention enable high-accuracy detection of the periodicity of a fine stripe of a long stripe type or a gas barrier property change exhibited in a transverse type, and thereby a water vapor barrier film of the gas barrier film. It is useful as a sex evaluation method.

1: Gas barrier film
4: Resin base material
5: gas barrier layer
10: first water vapor barrier test area
11: First water vapor impermeable layer
12: first water-reactive metal layer
13: first adhesive layer
20: second water vapor barrier test area
21: second water vapor impermeable layer
22: second moisture-reactive metal layer
L1, L2: overlapping part

Claims (11)

It is a gas barrier film having a gas barrier layer on at least one side of an elongated resin substrate,
On the gas barrier layer, a first water vapor barrier property test area portion and a second water vapor barrier property test area part are provided,
The first water vapor barrier test region portion, in this order, has a first water-reactive metal layer and a first water-impermeable layer sealing the first water-reactive metal layer on the gas barrier layer,
The second water vapor barrier test region portion, in this order, has a second water reactive metal layer and a second water vapor impermeable layer sealing the second water reactive metal layer on the gas barrier layer,
The first water-reactive metal layer and the second water-reactive metal layer, when viewed from at least one of the longitudinal direction and the width direction of the resin substrate, constitutes a configuration that is arranged to partially overlap each other. Gas barrier film. The gas-barrier film according to claim 1, wherein the first water-reactive metal layer and the second water-reactive metal layer are arranged to partially overlap each other when viewed in the width direction. The gas-barrier film according to claim 1, wherein the first water-reactive metal layer and the second water-reactive metal layer are arranged to partially overlap each other when viewed in the longitudinal direction. The gas-barrier film according to any one of claims 1 to 3, wherein at least one of the first water vapor impermeable layer and the second water vapor impermeable layer is a vapor deposition layer. According to any one of claims 1 to 3, The first water vapor barrier test region portion further has a first adhesive layer for fixing the first water vapor impermeable layer to the gas barrier layer,
The gas-barrier film, characterized in that the first water vapor impermeable layer is formed of a plate-like member selected from metals, opaque metal compounds, and transparent metal compounds. The said 2nd water vapor barrier test area part has a 2nd adhesive layer which fixes the said 2nd water vapor impermeable layer with respect to the said gas barrier layer. ,
The second water vapor impermeable layer is a gas barrier film, characterized in that it is formed of a plate-shaped member selected from a metal, an opaque metal compound and a transparent metal compound. The length of the portion according to any one of claims 1 to 6, wherein the first water-reactive metal layer and the second water-reactive metal layer partially overlap each other when viewed in one of the length direction and the width direction. The gas barrier film characterized in that the length in any one of the direction and the width direction is 1.0 mm or more. The said 1st water vapor impermeable layer and the said 2nd water vapor impermeable layer partly overlap with each other when viewed from at least one of the said longitudinal direction and the said width direction of any one of Claims 1-7. The parts are arranged to exist,
The length of the first water vapor impermeable layer and the second water vapor impermeable layer in the length direction and the other of the width direction of a portion partially overlapping each other when viewed in one of the length direction and the width direction. (A) The length of the first water-reactive metal layer and the second water-reactive metal layer in the length direction and the other of the width direction of a portion partially overlapping each other when viewed from either the length direction or the width direction. Gas barrier film characterized by being longer. 9. The method of claim 8, wherein the first water vapor impermeable layer and the second water vapor impermeable layer are in the length direction and the width direction of portions partially overlapping each other when viewed in one of the length direction and the width direction. The gas barrier film in which the length in any other side is 3.0 mm or more. It is a water vapor barrier evaluation test piece which evaluates the water vapor barrier property of the cut | disconnected part from the gas barrier film which has a gas barrier layer on at least one side of a long resin base material,
A water-reactive metal layer provided on the gas barrier layer,
And a water vapor impermeable layer sealing the moisture reactive metal layer,
A water vapor barrier evaluation test piece, characterized in that a marker showing coordinates in at least one of the longitudinal direction and the width direction of the gas barrier film is formed. A gas barrier film evaluation method according to any one of claims 1 to 9, or using the water vapor barrier evaluation test piece according to claim 10.

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