WO2021106736A1

WO2021106736A1 - Laminated film

Info

Publication number: WO2021106736A1
Application number: PCT/JP2020/043153
Authority: WO
Inventors: 美保大関; 勝平山川; 山下　恭弘; 花岡　秀典
Original assignee: 住友化学株式会社
Priority date: 2019-11-28
Filing date: 2020-11-19
Publication date: 2021-06-03
Also published as: TW202122262A; JP2021084324A

Abstract

An embodiment of the present invention provides a laminated film exhibiting an excellent warpage suppression effect, and preferably having high gas barrier properties as a result of including a highly dense inorganic thin-film layer.　An embodiment of the present invention provides a laminated film including a base material layer with a flexible base material contained therein, an organic layer, and an inorganic thin-film layer in the stated order, wherein after a laminate composed of the base material layer and the organic layer is heated for 30 minutes at a temperature of 130°C or higher and then left to cool for 10 minutes at 25°C, the measured internal stress of the organic layer is 0.2 GPa or more.

Description

Laminated film

The present invention relates to a laminated film containing a base material layer including a flexible base material, an organic layer and an inorganic thin film layer in this order.

Laminated films with gas barrier properties are widely used in packaging applications for foods, industrial products, pharmaceuticals, etc. (for example, Patent Document 1). In recent years, in flexible substrates of electronic devices such as solar cells, organic EL (electro-luminescence) displays, and organic EL lighting, laminated films having further improved gas barrier properties as compared with the above-mentioned food applications and the like have been demanded. In order to enhance the gas barrier property of such a laminated film, a laminated film in which a thin film layer is laminated via an organic layer on a flexible base material made of polyethylene terephthalate (PET) has been developed (for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2016-68267 Japanese Unexamined Patent Publication No. 2016-68383

In general, laminated films used for electronic devices and the like are required to have higher gas barrier properties than laminated films used for food and pharmaceutical applications. In response to such a request, for example, the laminated film described in Patent Document 2 is a thin film having higher density than the inorganic layer constituting the conventional gas barrier laminated film as described in Patent Document 1. High gas barrier properties are achieved by stacking layers.
However, according to the study by the present inventors, a high compressive stress is likely to occur in the thin film layer having high density, and the entire laminated film is likely to be warped due to the compressive stress generated in the thin film layer. It turned out that there was a problem. In particular, in a laminated film using a flexible base material, the warp of the entire laminated film tends to become larger due to the expansion / contraction change of the flexible base material in the manufacturing process, and the laminated film while ensuring high density. There is a need for technology to suppress warpage.

Therefore, one aspect of the present invention is to provide a laminated film having an excellent warp suppressing effect and preferably having a high gas barrier property by containing an inorganic thin film layer having high density.

The present inventor has completed the present invention as a result of diligent studies to solve the above problems. That is, one aspect of the present invention provides the following suitable aspects.

[1] A laminated film containing a base material layer containing a flexible base material, an organic layer, and an inorganic thin film layer in this order, and a laminate composed of the base material layer and the organic layer is formed at a temperature of 130 ° C. or higher. A laminated film having an internal stress of 0.2 GPa or more, which is measured by heating for 30 minutes and then allowing it to cool at 25 ° C. for 10 minutes.
[2] A laminate composed of the base material layer and an inorganic thin film layer directly laminated on the base material layer at 130 ° C.
The laminated film according to the above [1], wherein the internal stress of the inorganic thin film layer measured by heating at the above temperature for 30 minutes and then allowing to cool at 25 ° C. for 10 minutes is 2.0 GPa or more.
[3] The organic layer and the above-mentioned laminated body composed of the base material layer, the organic layer and the inorganic thin film layer are measured by heating at a temperature of 130 ° C. or higher for 30 minutes and then allowing to cool at 25 ° C. for 10 minutes. The above-mentioned [1] or [2], wherein the internal stress of the laminated film composed of the inorganic thin film layer is 0.030 GPa or less.
] The laminated film described in.
[4] The internal stress of the organic layer measured by heating the laminate composed of the base material layer and the organic layer at 180 ° C. for 30 minutes and then allowing it to cool at 25 ° C. for 10 minutes is 0.8 GPa or more. , Said [1
] To [3].
[5] A laminate composed of the base material layer and an inorganic thin film layer directly laminated on the base material layer at 180 ° C.
The internal stress of the inorganic thin film layer measured by heating at 25 ° C. for 10 minutes after heating for 30 minutes is 3
.. The laminated film according to any one of the above [1] to [4], which is 0 GPa or more.
[6] The laminated film according to any one of [1] to [5] above, wherein the inorganic thin film layer is present only on one surface side of the base material layer.
[7] The laminated film according to any one of [1] to [6] above, further comprising an organic layer on the surface of the base material layer opposite to the organic layer.
[8] The inorganic thin film layer is a layer formed by the plasma chemical vapor deposition method.
7] The laminated film according to any one of.
[9] The inorganic thin film layer contains silicon atoms, oxygen atoms, and carbon atoms, as described in [1] to [8].
]. The laminated film according to any one of.
[10] The atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changes continuously in a region of 90% or more in the film thickness direction of the inorganic thin film layer. The laminated film according to the above [9].
[11] The laminated film according to any one of the above [1] to [10], which has a gas barrier property.

According to one aspect of the present invention, it is possible to provide a laminated film having an excellent warp suppressing effect and a high gas barrier property by including an inorganic thin film layer having high density.

It is sectional drawing which shows an example of the laminated film of one aspect of this invention. It is sectional drawing which shows another example of the laminated film of one aspect of this invention. It is sectional drawing which shows still another example of the laminated film of one aspect of this invention. It is a schematic diagram which shows the manufacturing apparatus of the laminated film used in an Example and a comparative example.

Hereinafter, an embodiment of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

[Laminated film]
The laminated film of the present invention includes a base material layer containing a flexible base material (hereinafter, also simply referred to as “base material layer”), an organic layer, and an inorganic thin film layer in this order.
In the present invention, the laminate consisting of the base material layer and the organic layer constituting the laminated film is heated at a temperature of 130 ° C. or higher for 30 minutes and then allowed to cool at 25 ° C. for 10 minutes for measurement. The internal stress of the organic layer is 0.2 GPa or more. In the inorganic thin film layer whose denseness is increased in order to improve the gas barrier property, convex warpage is likely to occur with respect to the surface forming the inorganic thin film layer due to the high compressive stress generated in the layer. In one aspect of the present invention, the internal stress of the organic layer measured after heating the laminate composed of the base material layer and the organic layer constituting the laminated film to 130 ° C. or higher (hereinafter, “organic layer internal stress A”). By setting the value to 0.2 GPa or more, the organic layer existing between the base material layer and the thin film inorganic layer has an appropriate tensile stress that can eliminate the warpage caused by the high compressive stress generated in the inorganic thin film layer. Is given, and thus the warpage of the entire laminated film can be suppressed. When the internal stress A of the organic layer is less than 0.2 GPa, it becomes difficult to sufficiently suppress the warp of the inorganic thin film layer when the inorganic thin film layer has a high compressive stress, and the gas barrier is highly dense from the viewpoint of the warp suppressing effect. It may not be suitable as a structure of a laminated film having an inorganic thin film layer having excellent properties. The organic layer internal stress A is preferably 0.25 GPa or more, more preferably 0.3 GPa or more. Generally, the higher the internal stress A of the organic layer, the higher the effect of canceling the compressive stress generated in the inorganic thin film layer tends to increase. The internal stress A of the organic layer may be appropriately adjusted according to the compressive stress of the inorganic thin film layer constituting the laminated film, but from the viewpoint of ease of warpage adjustment at the time of forming the inorganic thin film layer and suppression of crack generation of the inorganic thin film layer. Therefore, the upper limit value is usually 7.5 GPa or less, preferably 5.0 GPa or less.

The internal stress A of the organic layer is measured in a laminate composed of a base material layer and an organic layer constituting the target laminated film. When the laminated film of one aspect of the present invention has organic layers on both sides of the base material layer, the organic layer internal stress A is an organic layer (inorganic thin film) located on the side where the base material layer and the inorganic thin film layer are laminated. When the layers are on both sides, it means the internal stress in the laminate consisting of the base material layer and the organic layer located between one inorganic thin film layer). When a plurality of organic layers are present between the base material layer and the inorganic thin film layer, the organic layer internal stress A exists between the base material layer and the base material layer and the inorganic thin film layer. It means the internal stress in the laminate consisting of all organic layers. When an organic layer and an inorganic thin film layer are present on both sides of the base material layer, the organic layer laminated on at least one surface of the base material layer may have an internal stress in the above range, but the base material The organic layers laminated on each side of the layer have sufficient internal stress (tensile stress) to eliminate the warpage caused by the compressive stress generated in the inorganic thin film layer laminated on the layer. It is preferable that the laminated body composed of the organic layer and the base material layer on each side has an internal stress in the above range, because the warp suppressing effect can be exhibited in a well-balanced manner centering on the base material layer.

In one aspect of the present invention, the laminated film is the internal stress of the organic layer measured by heating a laminate composed of a base material layer and an organic layer at 130 ° C. for 30 minutes and then allowing it to cool at 25 ° C. for 10 minutes.
Hereinafter, it is also preferable that the “organic layer internal stress A (130 ° C.)”) is 0.2 GPa or more. When the internal stress A (130 ° C.) of the organic layer is 0.2 GPa or more, it is easy to secure a sufficiently high tensile stress in the organic layer that can eliminate the warp of the inorganic thin film layer caused by the high compressive stress. It is possible to suppress the warp of the entire laminated film. Organic layer internal stress A (13
0 ° C.) is preferably 0.25 GPa or more, more preferably 0.3 GPa or more, and is the upper limit thereof from the viewpoint of ease of warpage adjustment at the time of forming the inorganic thin film layer and suppression of crack generation in the inorganic thin film layer. The value is usually 7.5 GPa or less, preferably 5.0 GPa or less.

In another aspect of the present invention, the laminated film is measured by heating a laminate composed of a base material layer and an organic layer at 180 ° C. for 30 minutes and then allowing it to cool at 25 ° C. for 10 minutes to measure the internal stress of the organic layer. (Hereinafter, also referred to as “organic layer internal stress A (180 ° C.)”) is preferably 0.8 GPa or more. When the internal stress A (180 ° C.) of the organic layer is 0.8 GPa or more, it is easy to secure a sufficiently high tensile stress in the organic layer that can eliminate the warp of the inorganic thin film layer caused by the high compressive stress. It is possible to suppress the warp of the entire laminated film. Organic layer internal stress A (
180 ° C.) is preferably 0.9 GPa or more, more preferably 1.0 GPa or more.
Further, from the viewpoint of ease of warpage adjustment at the time of forming the inorganic thin film layer and suppression of crack generation in the inorganic thin film layer, the upper limit thereof is usually 7.5 GPa or less, preferably 5.0 GPa or less.

Further, in still another aspect of the present invention, the stress A (130 ° C.) inside the organic layer is 0.
It is preferable that the internal stress A (180 ° C.) of the organic layer is 0.8 GPa or more, and the internal stress A (130 ° C.) and (180 ° C.) of the organic layer are in the ranges described in the previous paragraphs, respectively. It is more preferable to have an internal stress inside. Organic layer internal stress A (130 ° C)
When and (180 ° C.) are within the above ranges, it becomes easier to secure a sufficiently high tensile stress in the organic layer that can eliminate the warp of the inorganic thin film layer caused by the high compressive stress, and the warp of the laminated film. The inhibitory effect can be improved more effectively.

The internal stress A of the organic layer is the composition of the organic layer, the composition of the base material layer, the type of flexible base material, the thickness of the organic layer and / or the base material layer, the coating method when forming the organic layer, the tension / temperature. -It can be controlled by appropriately selecting drying conditions such as residence time and curing conditions such as temperature and UV irradiation conditions.

The heating temperature of the laminate when measuring the internal stress A of the organic layer is 130 ° C. or higher. Generally, when a laminated film is used by being bonded to an electronic device such as a solar cell, an organic EL display, or an organic EL lighting, for example, because of moisture adsorbed on the surface of the laminated film and dehydration of an adhesive or an adhesive sheet used for bonding, for example. It may be exposed to a high temperature environment of 130 ° C. or higher, and if a large warp occurs in the process, poor bonding such as air bubbles, wrinkles, and cracks may occur when the film is attached to an electronic device. 130 of the laminate containing the organic layer
If the laminated body has an organic layer internal stress in the above range when heated to ℃ or higher, a high warpage suppressing effect can be expected even in a laminated film that undergoes a process of being exposed to a high temperature environment of 130 ℃ or higher. it can. Therefore, the heating temperature may be 130 ° C. or higher, preferably 130 ° C.
It is 200 ° C. or lower, more preferably 130 ° C. or 180 ° C., 130 ° C. in one aspect of the present invention, and 180 ° C. in another aspect.

In one aspect of the present invention, the internal stress A of the organic layer is 25 after heating the laminate consisting of the base material layer to be measured and the organic layer at a temperature of 130 ° C. or higher from room temperature (25 ° C.) for 30 minutes. It can be calculated based on the amount of deformation of the laminated body when it is allowed to cool at ° C. for 10 minutes. Specifically, the laminate to be measured, which is cut out into a quadrangle of an appropriate size, is heated at a temperature of 130 ° C. or higher for 30 minutes, then allowed to cool at 25 ° C. for 10 minutes, and then placed on a horizontal plane. The distance (height) from to the four corners is measured, and the radius of curvature is calculated from their average value. If the laminated body after cooling is tubular, the diameter inside the cylinder is measured and the radius of curvature is calculated. From the calculated radius of curvature, the thicknesses of the base material layer and the organic layer, the Young's modulus of the base material layer, and the Poison ratio, the following formula (1):
The organic layer internal stress ^{A (GPa) = Eh 2/} 6 (1-v) Rt (1)
[In the formula,
t is the thickness of the organic layer (m), R is the radius of curvature (m), h is the thickness of the base material layer (m), E is the Young's modulus of the base material layer (Pa), and v is the Poisson's ratio of the base material layer. Represent. ]
Therefore, the internal stress of the organic layer can be calculated. More specifically, the organic layer internal stress A can be measured and calculated, for example, according to the method described in Examples described later.

In one aspect of the present invention, a laminate consisting of a base material layer constituting a laminated film and an inorganic thin film layer directly laminated on the base material layer is heated at a temperature of 130 ° C. or higher for 30 minutes and then 25 ° C. The internal stress of the inorganic thin film layer measured by allowing to cool for 10 minutes is preferably 2.0 GPa or more. The internal stress of the inorganic thin film layer measured after heating the laminate composed of the base material layer constituting the laminated film and the inorganic thin film layer directly laminated on the base material layer to 130 ° C. or higher (hereinafter, "" When the (also referred to as “inorganic thin film layer internal stress B”) is 2.0 GPa or more, it is easy to sufficiently increase the density of the inorganic thin film layer, and it is easy to realize a high gas barrier property of the laminated film. The internal stress B of the inorganic thin film layer is more preferably 2.1 GPa or more, still more preferably 2.2 GPa or more. Generally, the higher the internal stress B of the inorganic thin film layer, the higher the denseness of the inorganic thin film layer, and the higher the gas barrier property tends to be. The internal stress B of the inorganic thin film layer usually changes according to the composition of the inorganic thin film layer so as to secure the desired gas barrier property, but it is possible to secure sufficient denseness of the inorganic thin film layer and it is excessive. As a range in which compressive stress is unlikely to occur, the upper limit thereof is usually 15 GPa or less, preferably 10 GPa or less. The internal stress B of the inorganic thin film layer is usually a compressive stress.

In one aspect of the present invention, the laminated film is obtained by heating a laminate consisting of a base material layer and an inorganic thin film layer directly laminated on the base material layer at 130 ° C. for 30 minutes, and then allowing the laminated film to cool at 25 ° C. for 10 minutes. The internal stress of the inorganic thin film layer (hereinafter, also referred to as “inorganic thin film layer internal stress B (130 ° C.)”) measured in the above is preferably 2.0 GPa or more. When the internal stress B (130 ° C.) of the inorganic thin film layer is 2.0 GPa or more, it is easy to sufficiently increase the denseness of the inorganic thin film layer, and it is easy to realize a high gas barrier property of the laminated film. The internal stress B (130 ° C.) of the inorganic thin film layer is more preferably 2.1 GPa or more, further preferably 2.2 GPa or more, and it is possible to secure sufficient denseness of the inorganic thin film layer and excessive compressive stress. From the viewpoint of suppressing the occurrence of the above, the upper limit is usually 10 GPa or less, preferably 15 GPa or less.

In another aspect of the present invention, the laminated film is obtained by heating a laminate consisting of a base material layer and an inorganic thin film layer directly laminated on the base material layer at 180 ° C. for 30 minutes, and then releasing the laminated film at 25 ° C. for 10 minutes. The internal stress of the inorganic thin film layer measured by cooling (hereinafter, "inorganic thin film layer internal stress B (180 ° C.)"
) ”) Is preferably 3.0 GPa or more. Inorganic thin film layer internal stress B (18
When (0 ° C.) is 3.0 GPa or more, it is easy to sufficiently increase the denseness of the inorganic thin film layer, and it is easy to realize high gas barrier properties of the laminated film. The internal stress B (180 ° C.) of the inorganic thin film layer is more preferably 3.2 GPa or more, further preferably 3.5 GPa or more, and it is possible to secure sufficient denseness of the inorganic thin film layer and excessive compressive stress. From the viewpoint of suppressing the occurrence of the above, the upper limit is usually 15 GPa or less, preferably 10 GPa or less.

Further, in still another aspect of the present invention, the inorganic thin film layer internal stress B (130 ° C.) is 2.0 GPa or more, and the inorganic thin film layer internal stress B (180 ° C.) is 3.0 GPa or more. It is preferable that the internal stresses B (130 ° C.) and (180 ° C.) of the inorganic thin film layer have internal stresses within the ranges described in the previous paragraphs, respectively. When the internal stresses B (130 ° C.) and (180 ° C.) of the inorganic thin film layer are within the above ranges, the density of the inorganic thin film layer can be easily increased, and the gas barrier property of the laminated film can be improved more effectively.

The internal stress B of the inorganic thin film layer is the composition of the inorganic thin film layer, the distribution (density) of the inorganic materials / compounds constituting the inorganic thin film layer, the composition of the base material layer, the type of flexible base material, the inorganic thin film layer and / or. It can be controlled by appropriately selecting the thickness of the base material layer, the film forming conditions when forming the inorganic thin film layer, and the like.

The internal stress B of the inorganic thin film layer is measured in a laminate consisting of a base material layer constituting the target laminated film and an inorganic thin film layer directly laminated on the base material layer. In one aspect of the present invention, since the laminated film contains an organic layer between the base material layer and the inorganic thin film layer, the measurement of the internal stress B of the inorganic thin film layer is, for example, the same base material as the laminated film to be measured. The measurement is performed in a laminated body for measurement in which an inorganic thin film layer is formed on the layer in the same manner as the inorganic thin film layer constituting the laminated film to be measured. When the inorganic thin film layers are present on both sides of the base material layer, the internal stress B of the inorganic thin film layer is the internal stress in the laminate composed of the base material layer and the inorganic thin film layer laminated on one side of the base material layer. means. When the laminated film has inorganic thin film layers on both sides of the base material layer, the internal stress B of the inorganic thin film layers of the two inorganic thin film layers may be the same or different from each other, and the inorganic thin film on at least one side may be different. It is preferable that the layer has an internal stress in the above range.

In one aspect of the present invention, the internal stress B of the inorganic thin film layer is obtained after heating a laminate composed of a base material layer to be measured and an inorganic thin film layer at a temperature of room temperature (25 ° C.) to 130 ° C. or higher for 30 minutes. , Can be calculated based on the amount of deformation of the laminated body when allowed to cool at 25 ° C. for 10 minutes. Specifically, according to the same method as the method for measuring the internal stress A of the organic layer described above, the laminate to be measured cut into a quadrangle of an appropriate size is heated at a temperature of 130 ° C. or higher for 30 minutes. Then, after allowing to cool at 25 ° C. for 10 minutes, it is placed on a horizontal plane, the distances (heights) from the horizontal plane to the four corners are measured, and the radius of curvature is calculated from the average value thereof. If the laminated body after cooling is tubular, the diameter inside the cylinder is measured and the radius of curvature is calculated. From the calculated radius of curvature, the thickness of each of the base material layer and the inorganic thin film layer, the Young's modulus of the base material layer, and the Poison ratio, the following formula (2):
Inorganic thin layer internal stress ^{B (GPa) = Eh 2/} 6 (1-v) Rt '(2)
[In the formula,
t'is the thickness of the inorganic thin film layer (m), R is the radius of curvature (m), h is the thickness of the base material layer (m), E is the Young's modulus of the base material layer (Pa), and v is Poisson's ratio of the base material layer. Represents a ratio. ]
Therefore, the internal stress of the inorganic thin film layer can be calculated.

The heating temperature of the laminate when measuring the internal stress B of the inorganic thin film layer is 130 ° C. or higher. The heating temperature may be 130 ° C. or higher, but is preferably 130 ° C. or higher and 200 ° C. or lower, more preferably 130 ° C. or 180 ° C., 130 ° C. in one aspect of the present invention, and another one. In the embodiment, it is 180 ° C. Internal stress (compressive stress) generated in the inorganic thin film layer
By eliminating the warpage of the inorganic thin film layer caused by the internal stress (tensile stress) generated in the organic layer located between the inorganic thin film layer and the base material layer, the effect of suppressing the warp of the laminated film is improved. Therefore, it is preferable that the internal stress B of the inorganic thin film layer in the specific range is generated in the inorganic thin film layer at the same temperature as the internal stress A of the organic layer. Therefore, the internal stress B of the inorganic thin film layer
The heating temperature when measuring the above is preferably the same as the heating temperature applied when measuring the organic layer internal stress A of the organic layer to be measured.
More specifically, the internal stress B of the inorganic thin film layer can be measured and calculated according to, for example, the method described in Examples described later.

In the laminated film of one aspect of the present invention, the organic layer preferably has an organic layer internal stress A (130 ° C.) of 8% or more of the inorganic thin film layer internal stress B (130 ° C.), more preferably 10% or more. More preferably, it has an organic layer internal stress A (130 ° C.) of 12% or more. Further, in one aspect of the present invention, the organic layer preferably has an organic layer internal stress A (180 ° C.) of 15% or more of the inorganic thin film layer internal stress B (180 ° C.), more preferably 20% or more. More preferably, it has an organic layer internal stress A (180 ° C.) of 25% or more. When the organic layer internal stress A is equal to or higher than the above lower limit value with respect to the inorganic thin film layer internal stress B, it is suitable for suppressing the warp of the inorganic thin film layer caused by the internal stress (compressive stress) generated in the inorganic thin film layer. Can be an organic layer. Since the thickness of the organic layer is usually designed to be larger than the thickness of the inorganic thin film layer, the internal stress A of the organic layer is preferably smaller than the internal stress B of the inorganic thin film layer in the laminated film of one aspect of the present invention. The upper limit of the organic layer internal stress A with respect to the inorganic thin film layer internal stress B is usually 50% or less, preferably 40% or less.

In one aspect of the present invention, the laminated film has a relatively high internal stress A of the organic layer, so that the laminated film is formed in the inorganic thin film layer even when it contains an inorganic thin film layer having high density and excellent gas barrier property. It has an excellent effect of suppressing warpage caused by high compressive stress. Therefore, in the laminated film of one aspect of the present invention, a laminate composed of a base material layer, an organic layer and an inorganic thin film layer constituting the laminated film is heated at a temperature of 130 ° C. or higher for 30 minutes, and then heated at 25 ° C. for 10 minutes. The internal stress of the laminated film composed of the organic layer and the inorganic thin film layer (hereinafter, also referred to as “laminated film internal stress C”) measured by allowing to cool is preferably 0.030 GPa or less. When the internal stress C of the laminated film is 0.030 GPa or less, it is considered that the warp of the inorganic thin film layer caused by the high compressive stress is suppressed by the organic layer having an internal stress in a specific range, and the inorganic thin film is considered to be suppressed. It is possible to obtain a laminated film in which warpage is suppressed as a whole laminated film while ensuring high density of layers and excellent gas barrier properties. The internal stress C of the laminated film is more preferably 0.025 GPa or less, and further preferably 0.020 GPa or less. Generally, the smaller the value of the internal stress C of the laminated film, the higher the effect of suppressing the warp of the laminated film. Therefore, the lower limit of the internal stress C of the laminated film is not particularly limited and may be 0 GPa.
When the laminated film contains a plurality of organic layers or other layers between the base material layer and the organic layer and / or the organic layer and the inorganic thin film layer, the internal stress C of the laminated film is the base material layer and the inorganic thin film. It means the internal stress in the laminated body composed of all the layers contained between the base material layer and the inorganic thin film layer located on the side where the layers are laminated and the inorganic thin film layer.

In one aspect of the present invention, the laminated film is obtained by heating a laminated body composed of a base material layer, an organic layer and an inorganic thin film layer constituting the laminated film at 130 ° C. for 30 minutes and then allowing it to cool at 25 ° C. for 10 minutes. The internal stress of the laminated film composed of the organic layer and the inorganic thin film layer to be measured (hereinafter,
The “laminated film internal stress C (130 ° C.)”) is preferably 0.030 GPa or less. When the internal stress C (130 ° C.) of the laminated film is 0.030 GPa or less, it is easy to obtain a laminated film in which warpage is suppressed as a whole while ensuring high density of the inorganic thin film layer and excellent gas barrier properties. .. The internal stress C (130 ° C.) of the laminated film is more preferably 0.
It is 025 GPa or less, more preferably 0.020 GPa or less, and its lower limit value may be 0 GPa or less.

In another aspect of the present invention, the laminated film is obtained by heating a laminate composed of a base material layer, an organic layer and an inorganic thin film layer constituting the laminated film at 180 ° C. for 30 minutes, and then heating at 25 ° C. for 10 minutes.
The internal stress of the laminated film composed of the organic layer and the inorganic thin film layer (hereinafter, also referred to as “laminated film internal stress C (180 ° C.)”) measured by allowing to cool for a minute is 0.020 GPa or less. Is preferable. When the internal stress C (180 ° C.) of the laminated film is 0.020 GPa or less, it is easy to obtain a laminated film in which warpage is suppressed as a whole while ensuring high density of the inorganic thin film layer and excellent gas barrier properties. .. The internal stress C (180 ° C.) of the laminated film is more preferably 0.015 GPa or less, further preferably 0.010 GPa or less, and its lower limit value may be 0 GPa or less.

Further, in still another aspect of the present invention, the internal stress C (130 ° C.) of the laminated film is 0.
It is preferable that the internal stress C (180 ° C.) of the laminated film is 0.020 GPa or less, and the internal stress C (130 ° C.) and (180 ° C.) of the laminated film are the upper limits described in the previous paragraphs, respectively. It is more preferable to have an internal stress equal to or less than the value. Laminated film internal stress C
When (130 ° C.) and (180 ° C.) are each equal to or less than the above upper limit values, the effect of suppressing warpage of the laminated film can be further improved while ensuring high density of the inorganic thin film layer and excellent gas barrier properties.

In one aspect of the present invention, the internal stress C of the laminated film is obtained when the laminated body to be measured is heated at a temperature of 130 ° C. or higher from room temperature (25 ° C.) for 30 minutes and then allowed to cool at 25 ° C. for 10 minutes. It can be calculated based on the amount of deformation of the laminated body. Specifically, the laminate to be measured, which is cut out into a quadrangle of an appropriate size, is heated at a temperature of 130 ° C. or higher for 30 minutes, then allowed to cool at 25 ° C. for 10 minutes, and then placed on a horizontal plane. The distance (height) from to the four corners is measured, and the radius of curvature is calculated from their average value. If the laminated body after cooling is tubular, the diameter inside the cylinder is measured and the radius of curvature is calculated. From the calculated radius of curvature, the thickness of the base material layer, the total thickness of the organic layer and the inorganic thin film layer, the Young's modulus of the base material layer, and the Poison ratio, the following formula (3):
Laminated film internal stress ^{C (GPa) = Eh 2/} 6 (1-v) Rt '' (3)
[In the formula,
t'' is the total thickness (m) of the organic layer and the inorganic thin film layer, R is the radius of curvature (m), h is the thickness of the base material layer (m), E is the Young's modulus of the base material layer (Pa), v. Represents the Poisson's ratio of the substrate layer. ]
Therefore, the internal stress of the laminated film can be calculated.

The heating temperature of the laminated body when measuring the internal stress C of the laminated film is 130 ° C. or higher. The heating temperature may be 130 ° C. or higher, but is preferably 130 ° C. or higher and 200 ° C. or lower, more preferably 130 ° C. or 180 ° C., 130 ° C. in one aspect of the present invention, and another one. In the embodiment, it is 180 ° C. The heating temperature when measuring the internal stress C of the laminated film may be the same as the heating temperature applied when measuring the internal stress A of the organic layer and the internal stress B of the inorganic thin film layer of the laminated film to be measured. preferable.
More specifically, the internal stress C of the laminated film can be measured and calculated according to, for example, the method described in Examples described later.

In one aspect of the present invention, the laminated film is preferably transparent when visually observed. Specifically, the total light transmittance (Tt) of the laminated film is preferably 78.0% or more, more preferably 80.0% or more, still more preferably 83.0% or more, and particularly preferably 85.0%. As mentioned above, it is extremely preferably 87.0% or more. In one aspect of the present invention, when the total light transmittance of the laminated film is at least the above lower limit value, it is easy to secure sufficient visibility when the film is incorporated into an electronic device such as an image display device. In one aspect of the present invention, the upper limit of the total light transmittance of the laminated film is not particularly limited and may be 100% or less.

In one aspect of the present invention, the haze (cloudiness value) of the laminated film is preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less. In one aspect of the present invention, when the haze of the laminated film is not more than the above upper limit value, it is easy to secure sufficient visibility when the film is incorporated into an electronic device such as an image display device. In one aspect of the present invention, the lower limit of the haze of the laminated film is not particularly limited and is usually 0% or more. From the viewpoint of visibility, the smaller the haze is, the more preferable it is. Further, it is preferable that the laminated film after exposure for 250 hours in an environment of 60 ° C. and 90% relative humidity still has a haze in the above range.

The total light transmittance and haze can be measured using, for example, a haze computer. After performing background measurement in the absence of a laminated film, the laminated film is set in a sample holder and measured. The total light transmittance and haze value of the laminated film can be obtained.

In one aspect of the present invention, the thickness of the laminated film may be appropriately determined according to the intended use. From the viewpoint of good handleability of the laminated film and easy improvement of bending characteristics while ensuring an appropriate surface hardness, it may be, for example, 5 to 550 μm, preferably 10 to 250 μm, and more preferably 15 to 200 μm. The thickness of the laminated film can be measured by a film thickness meter.

In a laminated film having an inorganic thin film layer in which a relatively high compressive stress is generated due to high density, for example, an inorganic thin film layer having the same compressive stress is provided on both sides of the base material layer. Warpage of the laminated film can be suppressed by canceling each other's internal stresses between the two inorganic thin film layers existing through the material layer. However, in general, in order to enhance the gas barrier property of the laminated film, it is necessary that the inorganic material is present in the inorganic thin film layer at a high density, and such a highly dense inorganic thin film layer is provided on both sides of the base material layer. In some cases, the laminated film contained in the film may not be sufficiently satisfactory in terms of productivity and production cost. On the other hand, in one aspect of the present invention, the laminated film eliminates the warpage of the organic layer existing between the base material layer and the inorganic thin film layer, which may occur due to the internal stress generated in the inorganic thin film layer. Since it has sufficient internal stress, it has an excellent effect of suppressing warpage of the laminated film even when the inorganic thin film layer is present only on one surface side of the base material layer, and is inorganic only on one side of the base material layer. Since the thin film layer may be formed, it may be advantageous in terms of productivity and production cost. Therefore, in a preferred embodiment of the present invention, the laminated film has an inorganic thin film layer only on one surface side of the base material layer.

Hereinafter, each component of the laminated film according to one aspect of the present invention will be described in detail.

[Base layer]
The base material layer constituting the laminated film of the present invention includes a flexible base material. Flexible substrate means a flexible substrate capable of holding an inorganic thin film layer. For example, a resin film containing at least one kind of resin can be used as the resin component. The flexible base material is preferably a transparent resin base material.

Examples of the resin that can be used in the flexible base material include polyethylene naphthalate (PE).
Polyester resin such as N); Polyethylene (PE), Polypropylene (PP), Polyethylene resin such as cyclic polyolefin; Polyethylene resin; Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Kenzome of ethylene-vinyl acetate copolymer; Polyacrylonitrile Resin; Acetal resin; Polyethylene resin; Polyether sulfide (
PES), biaxially stretched and heat-annealed polyethylene terephthalate (PET)
). As the flexible base material, one of the above resins may be used, or two or more kinds of resins may be used in combination. Among these, polyester resin and polyolefin resin from the viewpoint of easily controlling the internal stress A of the organic layer and the internal stress B of the inorganic thin film layer of the obtained laminated film, easily improving the warp suppressing effect, and having high transparency. It is preferable to use a resin selected from the group consisting of PEN, more preferably a resin selected from the group consisting of PEN and cyclic polyolefin, and even more preferably to use PEN.

The flexible base material may be an unstretched resin base material, or the unstretched resin base material may be uniaxially stretched, tenter-type sequential biaxially stretched, tenter-type simultaneous biaxially stretched, or tubular-type simultaneous biaxially stretched. The stretched resin base material may be stretched in the flow direction (MD direction) of the resin base material and / or in the direction perpendicular to the flow direction of the resin base material (TD direction) by a known method such as stretching. The flexible base material may be a laminate in which two or more layers of the above-mentioned resin are laminated.

The glass transition temperature (Tg) of the flexible substrate is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, from the viewpoint of heat resistance of the laminated film.
The upper limit of the glass transition temperature is preferably 250 ° C. or lower. The glass transition temperature (
Tg) can be measured using a dynamic viscoelasticity measuring (DMA) device or a differential scanning calorimetry (DSC).

The thickness of the flexible base material may be appropriately set in consideration of stability during manufacturing of the laminated film, but it is easy to easily transport the flexible base material in vacuum in the manufacturing process of the laminated film. From the viewpoint, it is preferably 5 to 500 μm. Further, when the inorganic thin film layer is formed by the plasma chemical vapor deposition method (plasma CVD method) as described later, the thickness of the flexible base material is 10.
It is more preferably about 200 μm, and even more preferably 15 to 150 μm. The thickness of the flexible base material can be measured with a film thickness meter.

The flexible substrate may be a retardation film such as a λ / 4 retardation film or a λ / 2 retardation film in which the refractive indexes of the two orthogonal components in the plane are different from each other. As the material of the retardation film, orientation solidification of cellulose-based resin, polycarbonate-based resin, polyarylate-based resin, polyester-based resin, acrylic-based resin, polysulfone-based resin, polyether sulfone-based resin, cyclic olefin-based resin, and liquid crystal compound. Layers and the like can be exemplified. As the film forming method, a solvent casting method or a precision extrusion method capable of reducing the residual stress of the film can be used, but the solvent casting method is preferably used from the viewpoint of uniformity. The stretching method is not particularly limited, and vertical uniaxial stretching between rolls, tenter horizontal uniaxial stretching, and the like that can obtain uniform optical characteristics can be applied.

In-plane retardation Re at a wavelength of 550 nm when the flexible substrate is a λ / 4 retardation film
550) is usually 100 to 180 nm, preferably 110 to 170 nm, and more preferably 120 to 160 nm.

In-plane retardation Re at a wavelength of 550 nm when the flexible substrate is a λ / 2 retardation film
550) is usually 220 to 320 nm, preferably 240 to 300 nm, and more preferably 250 to 280 nm.

When the flexible base material is a retardation film, the retardation value may exhibit an inverse wavelength dispersibility that increases according to the wavelength of the measurement light, and the retardation value decreases according to the wavelength of the measurement light. It may show a positive wavelength dispersion characteristic, or may show a flat wavelength dispersion characteristic in which the phase difference value hardly changes depending on the wavelength of the measurement light.

When the flexible base material is a retardation film exhibiting reverse wavelength dispersibility, when the phase difference of the flexible base material at the wavelength λ is expressed as Re (λ), the flexible base material is Re. (450) / Re (550)
<1 and Re (650) / Re (550)> 1 can be satisfied.

The flexible substrate is preferably colorless and transparent from the viewpoint of being able to transmit and absorb light. More specifically, the total light transmittance is preferably 80% or more, and more preferably 85% or more. Further, the haze value is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less. The total light transmittance and haze of the flexible substrate can be measured by the same method as described above as the method for measuring the total light transmittance and haze in the laminated film.

Flexible base material, from the viewpoint that it either be used on the substrate of the organic devices and energy devices, it is preferable that an insulating, electrical resistivity is preferably 10 ⁶ [Omega] cm or more.

The surface of the flexible base material may be subjected to a surface activation treatment for cleaning the surface from the viewpoint of adhesion to an organic layer or the like. Examples of such surface activation treatment include corona treatment, plasma treatment, and frame treatment.

The flexible base material may or may not be annealed, but it is easy to control the internal stress A of the organic layer and the internal stress B of the inorganic thin film layer, and the warpage of the laminated film is suppressed. From the viewpoint of easily improving the effect, it is preferable to perform an annealing treatment. The annealing treatment involves biaxially stretching the flexible substrate and heating it at a temperature equal to or higher than the upper limit of use temperature (for example, 200 ° C.). After biaxially stretching the flexible substrate, the upper limit of use temperature (for example, 200 ° C.) is offline. ) It can be passed through a heating furnace with a temperature higher than that. The flexible base material may be annealed, or the base material layer in which a primer layer or the like, which will be described later, is laminated on one side or both sides may be annealed.

In one aspect of the present invention, the base material layer constituting the laminated film may consist of only a flexible base material, and in addition to the flexible base material, one side or both sides of the flexible base material. It may contain a primer layer formed in. By having the primer layer, the adhesion between the flexible base material and the organic layer can be improved. Further, when the flexible substrate has primer layers on both sides and there is no layer outside the primer layer on one surface side, that is, when the primer layer is the outermost layer, the primer layer is a laminated film. In addition to functioning as a protective layer for the film, it also functions to improve slipperiness during manufacturing and prevent blocking. In one aspect of the present invention, the laminated film may have an additional primer layer laminated on another portion in addition to the primer layer existing in contact with the flexible base material.

When the base material layer contains a primer layer, the primer layer preferably has a softening temperature of 130 ° C. or higher. By having such a softening temperature, the flexible base material and the organic layer can be sufficiently adhered even in a high temperature environment, and the warp suppressing effect of the laminated film can be sufficiently enhanced. The softening temperature of the primer layer is preferably 130 ° C. or higher, more preferably 160 ° C. or higher.
Above, more preferably 180 ° C. or higher. When the softening temperature of the primer layer is at least the above lower limit value, the warp suppressing effect can be further improved. The upper limit of the softening temperature of the primer layer is usually 250 ° C. or lower.

The primer layer preferably contains at least one selected from urethane resin, acrylic resin, polyester resin, epoxy resin, melamine resin and amino resin. Among these, it is more preferable to contain a polyester resin as a main component.

The primer layer may contain an additive in addition to the above resin. As the additive, a known additive can be used for forming the primer layer, for example, silica particles, alumina particles, calcium carbonate particles, magnesium carbonate particles, barium sulfate particles, aluminum hydroxide particles, titanium dioxide particles. , Zirconium oxide particles, clay, talc and other inorganic particles. Among these, silica particles are preferable from the viewpoint of the effect of suppressing warpage of the laminated film.

When the primer layer contains silica particles, the average primary particle size thereof is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, and particularly preferably 20 n.
It is m or more, preferably 100 nm or less, more preferably 80 nm or less, still more preferably 60 nm or less, and particularly preferably 40 nm or less. When the average primary particle size of the silica particles is in the above range, the aggregation of the silica particles can be suppressed, and the transparency and the warp suppressing effect of the laminated film can be improved. Further, when the primer layer is the outermost layer and the average primary particle size of the silica particles is in the above range, the slipperiness of the laminated film at the time of production can be further improved and blocking can be effectively prevented. The average primary particle size of the silica particles can be measured by the BET method or TEM observation of the particle cross section.

The content of the silica particles is preferably 1 to 50% by mass, more preferably 1.5 to 40% by mass, and further preferably 2 to 30% by mass with respect to the mass of the primer layer. When the content of the silica particles is at least the above lower limit value, the warp suppressing effect of the laminated film is likely to be improved. When the content of the silica particles is not more than the above upper limit value, it is easy to improve optical characteristics such as low haze and high total light transmittance.

The thickness of the primer layer is preferably 1 μm or less, more preferably 500 nm or less, further preferably 200 nm or less, preferably 10 nm or more, and more preferably 20 nm.
Above, more preferably 30 nm or more. When the thickness of the primer layer is within the above range,
It is easy to improve the adhesion between the primer layer and the organic layer and the effect of suppressing warpage of the laminated film. The thickness of the primer layer can be measured with a film thickness meter. When the primer layers are present on both sides of the flexible base material, their thickness may be the same or different, but from the viewpoint of easily improving the warp suppressing effect of the laminated film, the two primer layers are used. It is preferable that the thickness is the same. In one aspect of the present invention, when the laminated film has three or more primer layers, it is preferable that each primer layer has the above thickness.

The primer layer can be obtained by applying a resin composition containing a resin, a solvent and, if necessary, an additive on a flexible base material, and drying the coating film to form a film. When the primer layers are present on both sides of the flexible substrate, the order in which they are formed is not particularly limited.

The solvent is not particularly limited as long as it can dissolve the resin, and is, for example, an alcohol solvent such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol; diethyl ether, diisopropyl ether, tetrahydrofuran, 1 , 4-Dioxane, propylene glycol monomethyl ether and other ether solvents; acetone, 2-butanol, methyl isobutyl ketone and other ketone solvents; N, N-dimethylformamide, N
, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide and other aprotic polar solvents; methyl acetate, ethyl acetate, n acetate
-Ester solvent such as butyl; nitrile solvent such as acetonitrile and benzonitrile; n
-Hydrocarbon solvents such as pentane, n-hexane, n-heptane, octane, cyclohexane, methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene; methylene chloride, chloroform, carbon tetrachloride, 1, 2 -Halogenized hydrocarbon solvents such as dichloroethane, monochlorobenzene and dichlorobenzene can be mentioned. The solvent can be used alone or in combination of two or more.

As a method for applying the primer layer to the flexible substrate, various conventionally used application methods,
For example, spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, reverse roll coating, gravure coating, extraction coating and the like can be mentioned.

Examples of the method for drying the coating film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method, and heat drying can be preferably used. The drying temperature is usually about 50 to 350 ° C., and the drying time is usually about 30 to 300 seconds, although it depends on the type of resin and solvent.

As described above, the primer layer may be formed on one side or both sides of the flexible base material, but a commercially available film having the primer layer on one side or both sides of the flexible base material, for example, manufactured by Teijin Film Solutions Co., Ltd. "Theonex (registered trademark)" or the like can also be used.

When the base material layer has a primer layer, the primer layer may be a single layer or two or more layers. Further, when the flexible substrate has primer layers on both sides, the two primer layers may have the same composition or different compositions from each other, but the effect of suppressing the warp of the laminated film can be easily improved. Therefore, it is preferable that the layers have the same composition. Further, in one aspect of the present invention, when the laminated film has an additional primer layer, the plurality of primer layers may be layers having the same or different compositions.

The base material layer may be a single layer or may be two or more layers as long as it includes a flexible base material. In the present invention, when another layer such as a primer layer is present on the flexible substrate, the layer existing between the flexible substrate and the organic layer closest to the flexible substrate. Is regarded as a layer constituting the base material layer. When other layers such as a primer layer are formed on both sides of the flexible base material, the base material layer for measuring the organic layer internal stress A and the inorganic thin film layer internal stress B is a flexible group. A layer located between the material and the inorganic thin film layer, located between the organic layer closest to the flexible substrate, and a similar layer existing symmetrically or asymmetrically through the flexible substrate. (Primer layer and the above other layers) are included. That is, for example, in FIG. 3, the base material layer 1 is composed of a flexible base material 1-1 and two primer layers 1-2 adjacent to both sides thereof. When the base material layer contains other layers other than the flexible base material, the total thickness of the base material layer is less likely to affect the internal stress of the organic layer and the internal stress of the inorganic thin film layer, and is excellent in the effect of suppressing warpage of the laminated film. From the viewpoint, it may be, for example, 5 to 550 μm, preferably 10 to 250 μm, and more preferably 15 to 200 μm.

[Organic layer]
The laminated film of the present invention is an organic layer located between a base material layer and an inorganic thin film layer, and has the above-mentioned specific organic layer internal stress A (hereinafter, also referred to as “first organic layer”). Has. Further, in one aspect of the present invention, the laminated film further has an organic layer (hereinafter, also referred to as “second organic layer”) on the surface of the base material layer opposite to the first organic layer. By having the second organic layer, for example, precipitation of the resin component of the flexible base material or deformation of the flexible base material is easily suppressed, so that even if the laminated film is exposed to a high temperature environment, its haze Effects such as suppression of the rise can be expected.

In one aspect of the present invention, when the laminated film contains a first organic layer and / or a second organic layer, even if the first organic layer and the second organic layer are layers having a function as a flattening layer, respectively. It may be a layer having a function as an anti-blocking layer, or a layer having both of these functions. In particular, in a laminated film in which the inorganic thin film layer exists only on one side of the base material layer, the second organic layer in which the inorganic thin film layer is not laminated functions as an anti-blocking layer from the viewpoint of ensuring slipperiness during film transportation. The first organic layer has a function as a flattening layer, and the second organic layer has a function as a flattening layer from the viewpoint of improving the gas barrier property by homogenizing the inorganic thin film layer and ensuring slipperiness during film transportation. It is more preferable to have a function as an anti-blocking layer.

In one aspect of the present invention, when the laminated film contains the first organic layer and the second organic layer, if the first organic layer satisfies the organic layer internal stress A in the specific range described above, the second organic layer The value of the internal stress A of the organic layer is not particularly limited, but when the inorganic thin film layer is not present on the side opposite to the base material layer of the second organic layer, the lower the internal stress of the organic layer of the second organic layer is, the more preferable. Further, the first organic layer and the second organic layer may be single layers or may be two or more layers. Further, the first organic layer and the second organic layer may be layers having the same composition or layers having different compositions, but they have the same composition from the viewpoint of easily improving the warp suppressing effect of the laminated film. It is preferably a layer composed of. Further, in one aspect of the present invention, when the laminated film has an organic layer other than the first organic layer and the second organic layer, the plurality of organic layers may be layers having the same composition but different compositions. There may be.
Hereinafter, in the description of the organic layer in the present specification, unless otherwise specified, the “organic layer” means both the first organic layer and the second organic layer.

The organic layer is a layer containing an organic compound, and as long as it satisfies the above-mentioned specific organic layer internal stress A, its constituent components are not particularly limited, and for example, it is photocured having a polymerizable functional group. It can be formed by applying a composition containing a sex compound onto a base material layer and curing the composition. Examples of the photocurable compound contained in the composition for forming the organic layer include an ultraviolet or electron beam curable compound, and such a compound has a polymerizable functional group in the molecule.
Examples of the compound having more than one, for example, a compound having a polymerizable functional group such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group can be mentioned. The composition for forming the organic layer (hereinafter, also referred to as “composition for forming the organic layer”) may contain one kind of photocurable compound.
It may contain two or more photocurable compounds. By curing the photocurable compound having a polymerizable functional group contained in the composition for forming an organic layer, the photocurable compound is polymerized to form an organic layer containing a polymer of the photocurable compound.

The reaction rate of the polymerizable functional group of the photocurable compound having the polymerizable functional group in the organic layer is preferably 70% or more, more preferably 75% or more, still more preferably 80% from the viewpoint of easily improving the appearance quality. That is all. The upper limit of the reaction rate is not particularly limited, but is preferably 95% or less, more preferably 90% or less, from the viewpoint of easily improving the appearance quality. When the reaction rate is equal to or higher than the above lower limit value, colorless and transparent easily occurs. Further, when the reaction rate is not more than the above upper limit value, the bending resistance is likely to be improved. Since the reaction rate increases as the polymerization reaction of the photocurable compound having a polymerizable functional group proceeds, for example, when the photocurable compound is an ultraviolet curable compound, the intensity of the ultraviolet rays to be irradiated may be increased. It can be increased by lengthening the irradiation time. By adjusting the curing conditions as described above, the reaction rate can be kept within the above range.

The reaction rate was determined from the surface of the coating film with respect to the coating film before curing obtained by applying the composition for forming an organic layer on the substrate and drying it if necessary, and the coating film after curing the coating film. The infrared absorption spectrum can be measured using a total reflection type FT-IR, and can be measured from the amount of change in the intensity of the peak derived from the polymerizable functional group. For example, when the polymerizable functional group is a (meth) acryloyl group, the C = C double bond moiety in the (meth) acryloyl group is a group involved in the polymerization, and C = C as the reaction rate of the polymerization increases. The intensity of the peak derived from the double bond decreases. On the other hand, the C = O double bond portion in the (meth) acryloyl group does not participate in the polymerization, and the intensity of the peak derived from the C = O double bond does not change before and after the polymerization. Therefore, the intensity of the peak derived from the C = O double bond in the (meth) acryloyl group in the infrared absorption spectrum measured for the coating film before curing (
The proportion of the intensity of the peak derived from C = C double bond to _{_{_{I CO1) (I CC1) (}}} I CC
₁ / _ICO1 ) and (meth) in the infrared absorption spectrum measured for the cured coating film.
C = C with respect to _{the intensity (ICO2} ) of the peak derived from the C = O double bond in the acryloyl group
By comparing the ratio _{_(I} CC2 _/ I _CO2) of the intensity of a peak derived from the double bond _{(I CC2),} it is possible to calculate the reaction rate. In this case, the reaction rate is calculated by the formula (4) :.
Reaction rate [%] = [1- (I _CC2 / I _CO2 ) / (I _CC1 / I _CO1 )] × 100
(4)
Is calculated by. The infrared absorption peak derived from the C = C double bond is usually 1350 to 1.
Range of 450 cm ^-1, for example, is observed in the vicinity of 1400cm ^-1, C = O double infrared absorption peak attributable to binding in the range of usually 1700 ~ 1800 cm ^-1, for example 1700 cm ^-1
Observed in the vicinity.

The intensity of the infrared absorption peak in the range ^{of 1000 to 1100 cm -1} in the infrared absorption spectrum of the organic layer is _Ia, and the intensity of the infrared absorption peak in the range of 1700 to 1800 cm ^{-1 is I.}
When _b, _{I a} and _{I b} the formula (5):
0.05 ≤ I _b / I _a ≤ 1.0 (5)
It is preferable to satisfy. Here, the infrared absorption peak in the range of 1000 to 1100 cm ^-1 is present in the compound and the polymer (for example, the photocurable compound having a polymerizable functional group and / or the polymer thereof) contained in the organic layer. Infrared absorption peaks derived from Si—O—Si bonds derived from siloxane, and infrared absorption peaks in ^{the range of 1700 to 1800 cm -1} are compounds and polymers contained in the organic layer (for example, polymerizable functional groups). It is considered to be an infrared absorption peak derived from the C = O double bond present in the photocurable compound and / or its polymer). The ratio of the intensities of these peaks (I _b / I _a ) is considered to represent the relative ratio of the C = O double bond to the siloxane-derived Si—O—Si bond in the organic layer. When the peak intensity ratio (I _b / I _a ) is within the above-mentioned predetermined range, it is easy to improve the uniformity of the organic layer, and it is easy to improve the adhesion between layers, particularly the adhesion in a high humidity environment. The peak intensity ratio (I _b / I _a ) is preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.20 or more. When the ratio of peak intensities is equal to or more than the above lower limit value, the uniformity of the organic layer can be easily improved. This is not limited to the following mechanism, but if the amount of siloxane-derived Si—O—Si bonds present in the compound and polymer contained in the organic layer becomes too large, aggregates are generated in the organic layer. It is presumed that this is because the layer may be embrittled and the formation of such agglomerates can be easily reduced. The peak intensity ratio (I _b / I _a ) is preferably 1.0 or less, more preferably 0.8 or less, still more preferably 0.5 or less. When the ratio of peak intensities is not more than the above upper limit value, it is easy to improve the adhesion of the organic layer. This is not limited to the following mechanism, but the hardness of the organic layer is increased by the presence of a certain amount or more of siloxane-derived Si—O—Si bonds in the compounds and polymers contained in the organic layer. It is presumed that this is because it is moderately reduced. The infrared absorption spectrum of the organic layer is A
It can be measured by a Fourier transform infrared spectrophotometer (FT / IR-460Plus manufactured by JASCO Corporation) equipped with a TR attachment (PIKE MIRacle).

The photocurable compound contained in the composition for forming an organic layer is a compound that starts polymerization by ultraviolet rays or the like and proceeds to cure to become a resin which is a polymer. The photocurable compound is preferably a compound having a (meth) acryloyl group from the viewpoint of curing efficiency. The compound having a (meth) acryloyl group may be a monofunctional monomer or oligomer, or may be a polyfunctional monomer or oligomer. In the present specification, "(meth) acryloyl" means acryloyl and / or methacryloyl, and "(meth) acrylic" means acrylic and / or methacrylic.

Examples of the compound having a (meth) acryloyl group include (meth) acrylic compounds, and specifically, alkyl (meth) acrylate, urethane (meth) acrylate, ester (meth) acrylate, epoxy (meth) acrylate, and the like. In addition, the polymer and copolymer thereof and the like can be mentioned. Specifically, methyl (meth) acrylate, butyl (meth)
Acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dipropylene glycol Examples thereof include di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and polymers and copolymers thereof.

The photocurable compound contained in the composition for forming an organic layer may be, for example, in place of the compound having a (meth) acryloyl group or in addition to the compound having a (meth) acryloyl group, for example, metetramethoxysilane. Tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltri It preferably contains ethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, trimethylethoxysilane, triphenylethoxysilane and the like. Alkoxysilanes other than these may be used.

Examples of the photocurable compound other than the photocurable compound having a polymerizable functional group described above include polyester resin, isocyanate resin, ethylene vinyl alcohol resin, vinyl-modified resin, epoxy resin, phenol resin, urea melamine resin, etc. by polymerization. Examples thereof include monomers or oligomers that serve as styrene resins and resins such as alkyl titanates.

The composition for forming an organic layer can contain inorganic particles described as inorganic particles that can be contained in the primer layer, preferably silica particles. The average primary particle size of the silica particles contained in the composition for forming an organic layer is preferably 5 to 100 nm, more preferably 5 to 75 nm. When inorganic particles are contained, the effect of suppressing warpage of the laminated film is likely to be improved.

The content of the inorganic particles, preferably the silica particles, is preferably 20 to 90%, more preferably 40 to 85%, based on the mass of the solid content of the composition for forming the organic layer. When the content of the inorganic particles is in the above range, the warp suppressing effect of the laminated film is likely to be further improved. The solid content of the composition for forming an organic layer means a component excluding volatile components such as a solvent contained in the composition for forming an organic layer.

The composition for forming an organic layer may contain a photopolymerization initiator from the viewpoint of curability of the organic layer.
The content of the photopolymerization initiator is preferably 2 to 15%, more preferably 3 to 11%, based on the mass of the solid content of the composition for forming the organic layer, from the viewpoint of enhancing the curability of the organic layer. Is.

The composition for forming an organic layer may contain a solvent from the viewpoint of coatability. As the solvent, a solvent capable of dissolving the compound can be appropriately selected depending on the type of the photocurable compound having a polymerizable functional group, and for example, a solvent that can be used when forming a primer layer is described above. Examples include solvents. The solvent may be used alone or in combination of two or more.

In addition to the photocurable compound having a polymerizable functional group, the inorganic particles, the photopolymerization initiator and the solvent, if necessary, a thermal polymerization initiator, an antioxidant, an ultraviolet absorber, a plasticizer, and leveling. Additives such as agents and curl inhibitors may be included.

The internal stress A of the organic layer of the organic layer obtained by appropriately selecting the types, blending amounts and combinations thereof of photocurable compounds and inorganic particles, photopolymerization initiators, solvents and the like constituting the composition for forming the organic layer. Can be controlled. For example, when forming an organic layer, the temperature at which the coating film formed from the composition for forming an organic layer is dried is raised, the time for drying the coating film is lengthened, or UV is applied when the coating film is cured by UV irradiation. The internal stress A of the organic layer tends to increase by increasing the degree of curing of the composition for forming the organic layer by increasing the irradiation amount or the like. On the other hand, when the temperature when forming the organic layer is low or the residence time is short, the solvent remains in the organic layer, or when the coating film is cured by UV irradiation, the UV illuminance and UV integration are performed. Due to the small amount of light, the internal stress A of the organic layer tends to be low when the degree of curing of the organic layer cannot be sufficiently increased.

For the organic layer, for example, a composition for forming an organic layer (photocurable composition) containing a photocurable compound is applied onto the base material layer, dried if necessary, and then irradiated with ultraviolet rays or an electron beam. , The photocurable compound can be cured to form.

Examples of the coating method include the same method as the method of coating the primer layer on the flexible substrate.

When the organic layer has a function as a flattening layer, the organic layer may be a (meth) acrylate resin, a polyester resin, an isocyanate resin, an ethylene vinyl alcohol resin, a vinyl-modified resin, an epoxy resin, a phenol resin, a urea melamine resin, or a styrene. It may contain a resin, an alkyl titanate and the like. The organic layer may contain one kind or a combination of two or more kinds of these resins.

When the organic layer has a function as a flattening layer, the organic layer is a rigid pendulum type physical property tester (
For example, when the temperature change of the elastic modulus of the organic layer surface is evaluated by A & D Co., Ltd. (RPT-3000W, etc.), the temperature at which the elastic modulus of the organic layer surface decreases by 50% or more is 150 ° C. or more. It is preferable to have.

When the organic layer has a function as a flattening layer, the surface roughness measured by observing the organic layer with a white interference microscope is preferably 3 nm or less, more preferably 2 nm or less, still more preferably 1 nm or less. .. When the surface roughness of the organic layer is not more than the above upper limit value, the defects of the inorganic thin film layer laminated on the organic layer surface are reduced, and the gas barrier property is further enhanced. The surface roughness is measured by observing the organic layer with a white interference microscope and forming interference fringes according to the unevenness of the sample surface.

When the organic layer has a function as an anti-blocking layer, the organic layer preferably contains the above-mentioned inorganic particles.

In one aspect of the present invention, the thicknesses of the first organic layer and the second organic layer may be appropriately adjusted depending on the intended use, but are preferably 0.1 to 15 μm, more preferably 0.5 to 12 μm, respectively. It is preferably 0.7 to 10 μm. The thickness of the organic layer can be measured with a film thickness meter. When the thickness is at least the above lower limit value, the surface hardness of the laminated film is likely to be improved. Further, when the thickness is not more than the above upper limit value, the flexibility is likely to be improved. The thicknesses of the first organic layer and the second organic layer may be the same or different. When the laminated film of one aspect of the present invention has three or more organic layers, it is preferable that each organic layer has the above-mentioned thickness.

[Inorganic thin film layer]
The laminated film of the present invention has an inorganic thin film layer on a surface opposite to the base material layer of at least the first organic layer. By having the inorganic thin film layer, it is possible to impart excellent gas barrier properties to the laminated film. In one aspect of the present invention, inorganic thin film layers may be provided on both sides of the base material layer constituting the laminated film. In one aspect of the present invention, the organic layer existing between the base material layer and the inorganic thin film layer has an internal stress sufficient to eliminate the warp that may occur due to the internal stress generated in the inorganic thin film layer. Since the film is excellent in the effect of suppressing the warp of the laminated film even when the inorganic thin film layer is present only on one surface side of the base material layer, the inorganic thin film layer is formed only on one side of the base material layer. Therefore, it is advantageous in terms of productivity and production cost. In one aspect of the present invention, when the laminated film has two or more inorganic thin film layers on both sides of the base material layer, these inorganic thin film layers have the same structure but different structures. May be good.

The inorganic thin film layer is preferably configured to satisfy the above-mentioned specific inorganic thin film layer internal stress B, has high density capable of expressing the inorganic thin film layer internal stress B, and serves as a gas barrier layer. It is preferably a layer having a function. The inorganic thin film layer having such a gas barrier property is not particularly limited as long as it is a layer of an inorganic material having a gas barrier property, and a known layer of an inorganic material having a gas barrier property can be appropriately used. Examples of inorganic materials include metal oxides, metal nitrides, metal oxynitrides, metal acid carbides and mixtures containing at least two of these. The inorganic thin film layer may be a single-layer film, or may be a multilayer film in which two or more layers including at least the above thin film layer are laminated.

The inorganic thin film layer is a silicon atom (from the viewpoint of easily exhibiting a higher gas barrier property (particularly water vapor permeation prevention property), and also from the viewpoint of bending resistance, ease of manufacturing, and low manufacturing cost.
It preferably contains at least Si), an oxygen atom (O), and a carbon atom (C).

In this case, the inorganic thin film layer can be mainly composed of a compound whose _{general formula is represented by SiO α} C _β. In the equation, α and β each independently represent a positive number less than 2. Here, "the main component" means that the content of the component is 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more with respect to the mass of all the components of the material. Say. Inorganic thin layer may contain one kind of compound represented by the general formula _SiO α _C β, formula SiO _alpha C
It may contain two or more compounds represented by _β. Α and / or β in the above general formula may be constant values or may change in the film thickness direction of the inorganic thin film layer.

Further, the inorganic thin film layer contains elements other than silicon atom, oxygen atom and carbon atom, for example, one or more atoms of hydrogen atom, nitrogen atom, boron atom, aluminum atom, phosphorus atom, sulfur atom, fluorine atom and chlorine atom. It may be contained.

When the average atomic number ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is represented by C / Si, the inorganic thin film layer has high density and defects such as fine voids and cracks. From the viewpoint of reducing the amount of C / Si, the range of C / Si is the equation (6) :.
0.02 <C / Si <0.50 (6)
It is preferable to satisfy.
From the same viewpoint, C / Si is more preferably in the range of 0.03 <C / Si <0.45, further preferably in the range of 0.04 <C / Si <0.40, and 0. 05 <C / S
It is particularly preferable that it is in the range of i <0.35.

Further, the inorganic thin film layer has high density when the average atomic number ratio of oxygen atoms (O) to silicon atoms (Si) in the thin film layer is represented by O / Si, and has fine voids, cracks, etc. From the viewpoint of reducing defects, it is preferably in the range of 1.50 <O / Si <1.98, and 1.55 <O.
It is more preferably in the range of / Si <1.97, even more preferably in the range of 1.60 <O / Si <1.96, and particularly preferably in the range of 1.65 <O / Si <1.95. preferable.

The average atomic number ratios C / Si and O / Si were measured in XPS depth profile under the following conditions, and from the obtained distribution curves of silicon atoms, oxygen atoms, and carbon atoms, the averages in the thickness direction of each atom were obtained. After determining the atomic concentration, the average atomic number ratio C / Si and O / Si
Can be calculated as.
<XPS depth profile measurement>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film equivalent): 0.027 nm / sec Sputtering time: 0.5 minutes X-ray photoelectron spectrometer: Made by ULVAC-PHI, Ltd., model name "Quantera SX"
M "
Irradiated X-ray: Single crystal spectroscopy AlKα (1486.6 eV)
X-ray spot and its size: 100 μm
Detector: Pass Energy 69eV, Step size 0.125eV
Charge correction: Neutralizing electron gun (1eV), low-speed Ar ion gun (10V)

When infrared spectroscopy (ATR method) is performed on the surface of the inorganic thin film layer, it is 950 to 1050.
cm peak intensities present in the ^-1 and _{(I 1),} the intensity ratio of the peak intensity existing in the ^{_{1240 ~ 1290cm -1 (I2) (}} I 2 / I 1) has the formula (7):
0.01 ≤ I ₂ / I ₁ <0.05 (7)
It is preferable to satisfy.

_{The peak intensity ratio I 2} / I ₁ calculated from infrared spectroscopy (ATR method) is S in the inorganic thin film layer.
It is considered to represent the relative ratio _{of Si—CH 3} to i—O—Si. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (7) has high density and easily reduces defects such as fine voids and cracks, and thus easily enhances gas barrier properties and impact resistance. Peak intensity ratio I ₂
/ I ₁ _{is 0.02 ≤ I 2} / I ₁ <0 from the viewpoint of easily maintaining the high density of the inorganic thin film layer.
.. The range of 04 is more preferable.

When the inorganic thin film layer _{satisfies the peak intensity ratio I 2} / I ₁ , in one aspect of the present invention, the laminated film becomes moderately slippery and blocking is easily reduced. If the peak intensity ratio I ₂ / I ₁ is too large, it means that there is too much SiC, and in this case, the flexibility tends to be poor and slipperiness tends to occur. Further, if the peak intensity ratio I ₂ / I ₁ is too small, the flexibility tends to decrease due to the amount of Si—C being too small.

For infrared spectroscopic measurement of the surface of the inorganic thin film layer, for example, A using a germanium crystal for the prism A
It can be measured by a Fourier transform infrared spectrophotometer (FT / IR-460Plus manufactured by JASCO Corporation) equipped with a TR attachment (PIKE MIRacle).

When infrared spectroscopy (ATR method) is performed on the surface of the inorganic thin film layer, it is 950 to 1050.
intensity ratio of the peaks present in cm ^-1 intensity _{(I 1),} and a peak intensity existing in the ^{_{770 ~ 830cm -1 (I 3)}} (I 3 / I 1) has the formula (87):
0.25 ≤ I ₃ / I ₁ ≤ 0.50 (8)
It is preferable to satisfy.

_{The peak intensity ratio I 3} / I ₁ calculated from infrared spectroscopy (ATR method) is S in the inorganic thin film layer.
It is considered to represent the relative ratio of Si-C, Si-O, etc. to i-O-Si. Equation (8
It is considered that the inorganic thin film layer satisfying the relationship represented by) is easy to improve the bending resistance and the impact resistance because carbon is introduced while maintaining high density. Peak intensity ratio I
₃ / I ₁ _{is 0.25 ≤ I 3} from the viewpoint of maintaining a balance between the compactness and bending resistance of the inorganic thin film layer.
The range of / I ₁ ≤ 0.50 is preferable, and the range of 0.30 ≤ I ₃ / I ₁ ≤ 0.45 is more preferable.

The thin film layer is 770 to 770 to the surface of the thin film layer when infrared spectroscopic measurement (ATR method) is performed.
And the peak intensity _{(I 3)} present in the 830 cm ^-1, the intensity ratio expression between the peak present in the 870 ~ 910 cm ^-1 intensity _{(I 4)} (9):
0.70 ≤ I ₄ / I ₃ <1.00 (9)
It is preferable to satisfy.

_{The peak intensity ratio I 4} / I ₃ calculated from infrared spectroscopy (ATR method) is S in the inorganic thin film layer.
It is considered to represent the ratio of peaks related to iC. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (9) is likely to have high bending resistance and impact resistance because carbon is introduced while maintaining high density. Regarding the range of peak intensity ratio I ₄ / I ₃ _{, 0.70 ≤ I 4} / I ₃ <1 from the viewpoint of maintaining a balance between the compactness and bending resistance of the inorganic thin film layer.
.. The range of 00 is preferable, and the range of 0.80 ≦ I ₄ / I ₃ <0.95 is more preferable.

The thickness of the inorganic thin film layer may be appropriately adjusted depending on the application, but is preferably 5 to 3000 nm.
, More preferably 10 to 2000 nm, still more preferably 50 to 1000 nm. The thickness of the inorganic thin film layer can be measured by a film thickness meter. When the thickness is at least the above lower limit value, the gas barrier property is likely to be improved. Further, when the thickness is not more than the above upper limit value, the flexibility is likely to be improved. In particular, as will be described later, when a thin film layer is formed by a plasma CVD method using glow discharge plasma, the thickness may be 10 to 2000 nm because the inorganic thin film layer is formed while discharging through the base material. It is more preferably 50 to 1000 μm.

The inorganic thin film layer can preferably have a high average density of ^{1.8 g / cm 3 or more.} here,
The "average density" of the inorganic thin film layer is the Rutherford Backscattering method (Rutherford Bac).
The number of silicon atoms determined by kscattering spectroscopy (RBS),
The number of carbon atoms, the number of oxygen atoms, and the hydrogen forward scattering method (Hydrogen Forward)
Calculate the weight of the inorganic thin film layer in the measurement range from the number of hydrogen atoms obtained by scattering spectrum (HFS), and divide by the volume of the inorganic thin film layer in the measurement range (product of ion beam irradiation area and film thickness). It is required by doing. When the average density of the inorganic thin film layer is at least the above lower limit value, the structure is high in density and it is easy to reduce defects such as fine voids and cracks, which is preferable. In a preferred embodiment of the present invention in which the inorganic thin film layer is composed of silicon atoms, oxygen atoms, carbon atoms and hydrogen atoms, the average density of the inorganic thin film layers is preferably less than ^{2.22 g / cm 3.}

In a preferred embodiment of the present invention in which the inorganic thin film layer contains at least silicon atoms (Si), oxygen atoms (O), and carbon atoms (C), from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer. A curve showing the relationship between the distance and the atomic ratio of silicon atoms at each distance is called a silicon distribution curve. Here, the surface of the inorganic thin film layer refers to a surface that becomes the surface of the laminated film of the present invention.
Similarly, a curve showing the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of oxygen atoms at each distance is called an oxygen distribution curve. Further, a curve showing the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of carbon atoms at each distance is called a carbon distribution curve. The atomic ratio of silicon atom, the atomic ratio of oxygen atom, and the atomic ratio of carbon atom mean the ratio of the number of atoms to the total number of silicon atom, oxygen atom, and carbon atom contained in the inorganic thin film layer.

From the viewpoint of easily suppressing the deterioration of the gas barrier property due to bending, the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer is 90 in the film thickness direction of the inorganic thin film layer. It is preferable that the change is continuous in the region of% or more. Here, the fact that the atomic number ratio of the carbon atoms changes continuously in the film thickness direction of the inorganic thin film layer does not include, for example, a portion of the carbon distribution curve in which the atomic ratio of carbon changes discontinuously. Represents.

It is preferable that the carbon distribution curve of the inorganic thin film layer has eight or more extreme values from the viewpoint of flexibility and gas barrier property of the laminated film.

The silicon distribution curve, oxygen distribution curve, and carbon distribution curve of the inorganic thin film layer are subject to the following conditions (i).
) And (ii) are preferable from the viewpoint of flexibility and gas barrier property of the laminated film.
(I) The condition represented by the following formula (10) is satisfied in a region where the atomic number ratio of silicon, the atomic number ratio of oxygen, and the atomic number ratio of carbon are 90% or more in the film thickness direction of the inorganic thin film layer. ,and,
(Atomic number ratio of oxygen)> (Atomic number ratio of silicon)> (Atomic number ratio of carbon) (10)
(Ii) The carbon distribution curve preferably has at least one, more preferably eight or more extrema.

The carbon distribution curve of the inorganic thin film layer is preferably substantially continuous. The fact that the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, when the distance from the surface of the thin film layer in the film thickness direction is x [nm] and the atomic ratio of carbon is C, the formula (11):
| DC / dx | ≤0.01 (11)
It is preferable to satisfy.

Further, the carbon distribution curve of the inorganic thin film layer preferably has at least one extremum, and 8
It is more preferable to have one or more extrema. The extreme value here is the maximum value or the minimum value of the atomic ratio of each element with respect to the distance from the surface of the inorganic thin film layer in the film thickness direction. The extreme value is the atomic ratio at the point where the atomic ratio of the element changes from increasing to decreasing or the atomic ratio of the element changes from decreasing to increasing when the distance from the surface of the inorganic thin film layer in the film thickness direction is changed. Is the value of. The extremum can be determined, for example, based on the atomic ratios measured at a plurality of measurement positions in the film thickness direction. The atomic ratio measurement position is set so that the interval in the film thickness direction is, for example, 20 nm or less. For the positions showing extreme values in the film thickness direction, for discrete data groups including the measurement results at each measurement position, for example, the measurement results at three or more different measurement positions are compared, and the measurement results increase or decrease. It can be obtained by finding the position where it turns to or the position where it turns from decrease to increase. The position showing the extremum can also be obtained, for example, by differentiating the approximate curve obtained from the discrete data group. When the interval where the atomic ratio increases or decreases monotonically from the position showing the extreme value is, for example, 20 nm or more, the atomic ratio at the position moved by 20 nm in the film thickness direction from the position showing the extreme value, and the extreme value The absolute value of the difference is, for example, 0.03 or more.

As described above, the inorganic thin film layer formed so as to satisfy the condition that the carbon distribution curve preferably has at least one, more preferably eight or more extreme values has gas permeation after bending with respect to the gas permeability before bending. The amount of increase in the rate is smaller than that in the case where the above conditions are not satisfied. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier property due to bending can be obtained. When the thin film layer is formed so that the number of extreme values of the carbon distribution curve is two or more, the amount of increase is smaller than that in the case where the number of extreme values of the carbon distribution curve is one. Further, when the thin film layer is formed so that the number of extreme values of the carbon distribution curve is three or more, the amount of increase is small as compared with the case where the number of extreme values of the carbon distribution curve is two. Become. When the carbon distribution curve has two or more extreme values, the distance from the thin film layer surface in the film thickness direction at the position showing the first extreme value and the second extreme value adjacent to the first extreme value. The absolute value of the difference from the distance from the surface of the thin film layer in the film thickness direction at the position indicated by is preferably in the range of 1 nm or more and 200 nm or less, and more preferably in the range of 1 nm or more and 100 nm or less.

Further, it is preferable that 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 of the inorganic thin film layer is larger than 0.01. In the inorganic thin film layer formed so as to satisfy the above conditions, the amount of increase in the gas permeability after bending with respect to the gas permeability before bending is smaller than that in the case where the above conditions are not satisfied. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier property due to bending can be obtained. When the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 0.02 or more, the above effect is high, and when it is 0.03 or more, the above effect is further high.

The lower the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve, the better the gas barrier property of the inorganic thin film layer tends to be. From this point of view, the absolute value is preferably less than 0.05 (less than 5 at%) and less than 0.04 (less than 4 at%).
Is more preferable, and less than 0.03 (less than 3 at%) is particularly preferable.

In addition, in the oxygen carbon distribution curve, when the sum of the atomic ratios of oxygen atoms and the atomic ratios of carbon atoms at each distance is taken as the "total atomic ratio", the absolute value of the difference between the maximum and minimum values of the total atomic ratio The lower the value, the better the gas barrier property of the thin film layer tends to be. From this point of view, the total atomic ratio is preferably less than 0.05, more preferably less than 0.04, and particularly preferably less than 0.03.

When the inorganic thin film layer has a substantially uniform composition in the in-plane direction of the inorganic thin film layer, the gas barrier property of the inorganic thin film layer can be made uniform and improved. The substantially uniform composition means the number of extreme values existing in the film thickness direction at any two points on the surface of the inorganic thin film layer in the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve. Is the same, and the absolute value of the difference between the maximum and minimum values of the atomic ratio of carbon in each carbon distribution curve is the same as or within 0.05.

The inorganic thin film layer formed so as to satisfy the above conditions can exhibit the gas barrier property required for, for example, a flexible electronic device using an organic EL element.

In a preferred embodiment of the present invention in which the inorganic thin film layer contains at least silicon atoms, oxygen atoms, and carbon atoms, the layer of the inorganic material containing such atoms tends to increase the denseness and has fine voids, cracks, and the like. From the viewpoint of easily reducing defects, it is preferably formed by a chemical vapor deposition method (CVD method), and above all, it is formed by a plasma chemical vapor deposition method (PECVD method) using glow discharge plasma or the like. More preferred.

An example of a raw material gas used in the chemical vapor deposition method is an organosilicon compound containing a silicon atom and a carbon atom. Examples of such organic silicon compounds are hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane. , Ppropylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of the handleability of the compound and the gas barrier property of the obtained inorganic thin film layer. As the raw material gas, one kind of these organosilicon compounds may be used alone, or two or more kinds may be used in combination.

Further, a reaction gas capable of reacting with the raw material gas to form an inorganic compound such as an oxide or a nitride can be appropriately selected and mixed with the raw material gas. As the reaction gas for forming the oxide, for example, oxygen or ozone can be used. Further, as the reaction gas for forming the nitride, for example, nitrogen or ammonia can be used. These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and the nitride are formed. Can be used in combination with a reaction gas for The flow rate ratio of the raw material gas and the reaction gas can be appropriately adjusted according to the atomic ratio of the inorganic material to be formed.

If necessary, a carrier gas may be used to supply the raw material gas into the vacuum chamber. Further, a discharge gas may be used, if necessary, in order to generate a plasma discharge. As such a carrier gas and a gas for discharge, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon; hydrogen can be used.

The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of raw material gas and the like, but is preferably in the range of 0.5 Pa to 50 Pa.

For example, the internal stress B of the inorganic thin film layer can be controlled by controlling the degree of vacuum at the time of film formation, the temperature of the base material at the time of film formation, the film formation power, and the magnetic field in the electrode. For example, lowering the degree of vacuum,
The internal stress B of the inorganic thin film layer tends to increase by increasing the substrate temperature at the time of film formation, increasing the film forming power, and increasing the magnetic field density. On the other hand, the internal stress B of the inorganic thin film layer tends to be lowered by increasing the degree of vacuum, lowering the substrate temperature at the time of film formation, lowering the film forming power, or lowering the magnetic flux density.

The configuration of the laminated film of the present invention in one aspect will be described with reference to FIG. 1. The laminated film 4 of the one aspect of the present invention is formed by laminating a base material layer 1, an organic layer 2, and an inorganic thin film layer 3 in this order. ..
If the laminated film of the present invention has a base material layer, an organic layer, and an inorganic thin film layer in this order, it has other layers between each layer and in the outermost layer as long as it does not affect the effect of the present invention. However, in one aspect of the present invention, the base material layer, the organic layer, and the inorganic thin film layer are adjacent to each other in this order. Other layers include, for example, additional organic and inorganic thin film layers, protective layers, easy-to-slip layers, hard coat layers, transparent conductive film layers, color filter layers, easy-adhesion layers, curl adjusting layers, stress relaxation layers, and heat-resistant layers. , Scratch resistant layer, indentation resistant layer and the like.

As a laminated film containing another layer, for example, in the laminated film 4 shown in FIG. 2, which is another aspect of the present invention, the first organic layer 2-1 and the inorganic thin film are formed on one surface of the base material layer 1. Layer 3
Is laminated, and the second organic layer 2-2 is laminated on the surface of the base material layer 1 opposite to the first organic layer 2-1. In the laminated film 4 shown in FIG. 2, the laminated body for measuring the internal stress A of the organic layer in one aspect of the present invention is a laminated body composed of the base material layer 1 and the first organic layer 2-1. .. Further, the laminate for measuring the internal stress B of the inorganic thin film layer in one aspect of the present invention is a laminate composed of the base material layer 1 and the inorganic thin film layer 3 directly formed on the base material layer 1. is there.

Further, the laminated film 4 of one aspect of the present invention shown in FIG. 3 includes a base material layer 1 having primer layers 1-2 on both sides of the flexible base material 1-1. In the laminated film 4, the first organic layer 2-1 is laminated on one of the primer layers 1-2, and the inorganic thin film layer 3 is different from the primer layer 1-2 of the first organic layer 2-1. It is formed on the opposite side. Further, the side of the primer layer 1-2 opposite to the primer layer 1-2 on which the first organic layer 2-1 of the flexible base material 1-1 is laminated is opposite to the flexible base material 1-1. The second organic layer 2-2 is laminated on the surface of the surface. In the laminated film 4 shown in FIG. 3, the laminated body for measuring the internal stress A of the organic layer in one aspect of the present invention is a flexible base material 1-1 and a primer layer 1-laminated on both sides thereof. It is a laminate composed of a base material layer 1 composed of 2 and a first organic layer 2-1. Further, the laminate for measuring the internal stress B of the inorganic thin film layer in one aspect of the present invention is a substrate layer 1 composed of a flexible substrate 1-1 and primer layers 1-2 laminated on both sides thereof. And an inorganic thin film layer 3 directly formed on the base material layer 1.

[Manufacturing method of laminated film]
The method for producing a laminated film of the present invention is not particularly limited as long as each layer can be formed in the above order, but as an example thereof, after forming an organic layer on one surface of a base material layer containing a flexible base material, Examples thereof include a method of forming an inorganic thin film layer on the organic layer. When the base material layer has a primer layer, an organic layer can be formed on the primer layer after forming the primer layer on one surface of the flexible base material. Further, when the laminated film of one aspect of the present invention further contains an organic layer (second organic layer) on the surface of the base material layer opposite to the organic layer (first organic layer), the same method as described above. A second organic layer can be formed on the surface of the base material layer opposite to the first organic layer. The laminated film according to one aspect of the present invention may be produced by separately producing each layer and then laminating them.

From the viewpoint that the density of the inorganic thin film layer can be easily increased and defects such as fine voids and cracks can be easily reduced, the inorganic thin film layer uses glow discharge plasma on the organic layer as described above to form a CV.
It is preferably formed by a known vacuum film forming method such as the D method. The inorganic thin film layer is preferably formed by a continuous film forming process, and more preferably, for example, the inorganic thin film layer is continuously formed on the long laminate while being continuously conveyed. Specifically, the inorganic thin film layer may be formed while transporting the laminated body from the feeding roll to the winding roll. afterwards,
The inorganic thin film layer may be further formed by inverting the feeding roll and the winding roll and transporting the laminated body in the opposite directions.

The laminated film of one aspect of the present invention is excellent in the warp suppressing effect of the laminated film and has a high gas barrier property, and is therefore suitable for, for example, an electronic device application requiring a high gas barrier property. Examples of the electronic device include a liquid crystal display element, a solar cell, an organic EL display, an organic EL microdisplay, an organic EL lighting, and a flexible electronic device (flexible display) such as electronic paper, which are required to have high gas barrier properties. The laminated film of one aspect of the present invention can be suitably used as a flexible substrate of the flexible electronic device. When the laminated film is used as a flexible substrate, the element may be formed directly on the laminated film, or after the element is formed on another substrate, the laminated film is passed through an adhesive layer or an adhesive layer. It may be overlapped from above.

Hereinafter, one aspect of the present invention will be described in more detail with reference to Examples. Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.

1. 1. Example 1
As a base material, a biaxially stretched polyethylene naphthalate film having primer layers on both sides of a flexible base material (manufactured by Teijin Film Solution Co., Ltd., Q65HWA, thickness 100 μm,
Coating composition 1 (Nippon Kako Paint Co., Ltd., TOMAX (registered trademark) FA-3376-2) was applied to the gravure coating method as an organic layer forming composition for forming an organic layer on one side of a width of 350 mm). And applied. After the coating film is dried at 100 ° C. for 1 minute, it is ^{irradiated with ultraviolet rays under the condition of an integrated light amount of 500 mJ / cm 2} using a high-pressure mercury lamp, and an organic layer having a thickness of 4 μm is laminated to form a substrate with an organic layer. Obtained.

An inorganic thin film layer (thickness 400 nm) is laminated on the surface of the obtained base material with an organic layer on the organic layer side according to the method for producing an inorganic thin film layer described below, and the base material layer / organic layer / inorganic thin film layer is laminated. A laminated film 1 made of the above was obtained.

The film thicknesses of the base material layer, the organic layer, and the inorganic thin film layer of the laminated film 1 are measured by a film thickness meter [Co., Ltd.
Using a surf coder ET200 manufactured by Kosaka Laboratory, the step difference between the non-deposited portion and the film-deposited portion was measured, and the film thickness (T) of each layer was determined.

[Manufacturing method of inorganic thin film layer]
An inorganic thin film layer was laminated on a base material with an organic layer using a manufacturing apparatus as shown in FIG. Specifically, in the manufacturing apparatus as shown in FIG. 4 installed in the vacuum chamber, the base film 18 with an organic layer is attached to the delivery roll 10 and the inside of the vacuum chamber is 1 × 10 ^-3.
After the concentration was reduced to Pa or less, an inorganic thin film layer was formed on the organic layer laminated on the base film while the base film 18 was conveyed by the transport roll 11. In the plasma CVD apparatus used for forming the inorganic thin film layer, the base film 18 with an organic layer is conveyed to the surface of a pair of roll-shaped electrodes composed of a film forming roll 12 and a film forming roll 13 while being brought into close contact with each other. Plasma was generated between the pair of electrodes, and the raw material was decomposed in the plasma to form an inorganic thin film layer on the organic layer. In the pair of roll-shaped electrodes, magnets are arranged inside the electrodes so that the magnetic flux density is high on the electrode and the surface of the base material with the organic layer to be conveyed, and when plasma is generated, the magnets are arranged on the electrodes and the base material with the organic layer. The plasma is constrained at high density. In film formation of the inorganic thin film layer, hexamethyldisiloxane (HMDSO) gas and oxygen gas are introduced into the space between the electrodes (deposition roll 12 and film formation roll 13) which are the film formation regions, and between the electrode rolls. AC power was supplied to the film and discharged to generate plasma. Next, after adjusting the exhaust amount so that the pressure around the exhaust port in the vacuum chamber becomes 1 Pa, plasma CVD
A dense inorganic thin film layer was formed on the base material with an organic layer by the method, and the film was wound into a roll by a winding roll 17.

<Film formation condition 1>
Supply amount of raw material gas: 50 sccm (Standard Cubic Centimete)
r per Minute, 0 ° C, 1 atm standard)
Oxygen gas supply: 500 sccm
Vacuum degree in vacuum chamber: 1Pa
Power applied from the plasma generation power supply: 0.8 kW
Frequency of power supply for plasma generation: 70kHz
Film transport speed: 0.6 m / min Number of passes: 2 times

With respect to the obtained laminated film 1, the flatness, internal stress, moisture transmittance and the like were measured and / or evaluated according to the following methods.

[Evaluation of flatness of laminated film]
The laminated film 1 was cut out into a square of 50 mm × 50 mm to obtain a measurement sample. Then, the measurement sample was heated from room temperature (25 ° C.) to 130 ° C. or 180 ° C. in a hot air circulation oven and held for 30 minutes, and then allowed to cool at room temperature (25 ° C.) for 10 minutes. Next, the sample is placed on the horizontal plane so that the central portion of the measurement sample is in contact with the horizontal plane, the distances (heights) from the horizontal plane to the four corners are measured, and the average value is obtained from the four distances obtained. Was calculated. The values calculated in Table 1 are listed as warpage values.

[Measurement of internal stress of organic layer and internal stress of inorganic thin film layer]
Biaxially stretched polyethylene naphthalate film (manufactured by Teijin Film Solution Co., Ltd., Q65HWA, thickness 100μ) in which primer layers are formed on both sides of a flexible base material as a base material layer.
Using m), according to Example 1 above, coating composition 1 (Nippon Kako Paint (Nippon Kako Paint (Nippon Kako Paint)) was applied onto the substrate.
The organic layer formed from TOMAX FA-3376-2) was laminated to obtain a laminate for measuring the internal stress of the organic layer. In the same manner as the above method for evaluating flatness, the measurement sample was placed at room temperature (25).
After heating in a hot air circulation oven from (° C.) to 130 ° C. or 180 ° C. and holding for 30 minutes,
The mixture was allowed to cool at room temperature (25 ° C.) for 10 minutes, and the amount of deformation of the obtained laminate (the average value of each distance from the horizontal plane to the four corners, and the diameter inside the cylinder if it was tubular) was measured. Using the radius of curvature calculated from the measured amount of deformation, the film thickness of the organic layer, the thickness of the base material, the Young's modulus of the base material, and the Poisson's ratio of the base material, the internal stress of the organic layer was calculated from the following equation (12). Calculated. The biaxially oriented polyethylene naphthalate film used as a substrate, the Young's modulus E of the substrate 6.1 × 10 ⁹ Pa, Poisson's ratio v of the substrate was 0.33.
Further, the method for forming the inorganic thin film layer described in Example 1 is the same except that the biaxially stretched polyethylene naphthalate film on which the organic layer is not laminated is conveyed as the base material instead of the base material with the organic layer. Then, the inorganic thin film layer was directly laminated on the base material layer to prepare a laminated body for measuring the internal stress of the inorganic thin film layer. The internal stress of the inorganic thin film layer was calculated by using the amount of deformation of the obtained laminate in the same manner as in the method of measuring and calculating the internal stress of the organic layer.

Internal stress (GPa) = Eh2 / 6 (1-v) Rt (12)
[In the formula (11), t is the thickness (m) of the organic layer or the inorganic thin film layer, R is the radius of curvature (m), h is the thickness of the base material (m), and E is the Young's modulus (Pa) of the base material. , V is the Poisson's ratio of the base material. ]

In the laminated body for measuring the internal stress of the organic layer corresponding to the laminated film 1, the internal stress of the organic layer was calculated according to the above measurement method. The radius of curvature after heating to 130 ° C. is 11.8 mm.
The internal stress was 0.32 GPa. The radius of curvature after heating to 180 ° C is 3.6 m.
It was m and the internal stress was 1.05 GPa.

In the laminated body for measuring the internal stress of the inorganic thin film layer corresponding to the laminated film 1, the internal stress of the inorganic thin film layer was calculated according to the above measurement method. The radius of curvature after heating to 130 ° C is 17.0 mm
The internal stress was 2.23 GPa. The radius of curvature after heating to 180 ° C. was 9.8 mm, and the internal stress was 3.89 GPa.

[Measurement of internal stress of laminated film]
The internal stress of the laminated film 1 (the laminated film composed of the organic layer and the inorganic thin film layer in the laminated film 1) is such that the measurement sample is heated from room temperature (25 ° C.) to 130 ° C. or 180 ° C. in the same manner as in the above method for evaluating flatness. After heating in a circulating oven and holding for 30 minutes, 10 at room temperature (25 ° C)
After allowing to cool for a minute, the amount of deformation of the obtained laminated film 1 (average value of each distance from the horizontal plane to the four corners,
If it was tubular, the diameter inside the cylinder) was measured. Using the radius of curvature calculated from the measured amount of deformation, the total film thickness of the organic layer and the inorganic thin film layer, the thickness of the base material, the Young's modulus of the base material, and the Poisson's ratio of the base material, from the following formula (13) The internal stress of the laminated film 1 was calculated. The biaxially oriented polyethylene naphthalate film used as a substrate, the Young's modulus E of the substrate 6.1 × 10 ⁹ Pa
The Poisson's ratio v of the base material was 0.33.

Internal stress (GPa) = Eh2 / 6 (1-v) Rt (13)
[In formula (13), t is the total film thickness (m) of the organic layer and the inorganic thin film layer, R is the radius of curvature (m), and h.
Is the thickness of the base material (m), E is the Young's modulus of the base material (Pa), and v is the Poisson's ratio of the base material. ]

In the laminated film 1, the radius of curvature after heating to 130 ° C. was 200 mm, and the internal stress was 0.017 GPa. The radius of curvature after heating to 180 ° C is 417 mm.
The internal stress was 0.0083 GPa.

[X-ray photoelectron spectroscopy measurement in the film thickness direction of the inorganic thin film layer]
The atomic number ratio of the inorganic thin film layer of the laminated film 1 in the film thickness direction is determined by X-ray photoelectron spectroscopy using a scanning X-ray photoelectron spectroscopy analyzer (Quantara SXM, manufactured by ULVAC-PHI Co., Ltd.) according to the following measurement conditions. It was measured. Astrophysical X-ray source is AlKα ray (1486.6 eV)
, X-ray spot 100 μm), and for charge correction at the time of measurement, a neutralizing electron gun (1)
eV), low speed Ar ion gun (10V) was used. Analysis after measurement is MultiPak
Spectral analysis was performed using V6.1A (ULVAC PHI Co., Ltd.), and peaks corresponding to the binding energies of 2p of Si, 1s of O, 1s of N, and 1s of C obtained from the measured wide scan spectrum. The surface atomic number ratio of C to Si (C / Si) and the surface atomic number ratio of O to Si (O / Si) were calculated using. As the surface atomic number ratio, the average value of the values measured five times was adopted. From this result, a carbon distribution curve was created.
<XPS depth profile measurement conditions>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film equivalent): 0.027 nm / sec Sputtering time: 0.5 minutes X-ray photoelectron spectrometer: ULVAC-PHI, model name "Quantara SXM"
Irradiated X-ray: Single crystal spectroscopy AlKα (1486.6 eV)
X-ray spot and its size: 100 μm
Detector: Pass Energy 69eV, Step size 0.125eV
Charge correction: Neutralizing electron gun (1eV), low-speed Ar ion gun (10V)

From the results of the XPS depth profile measurement, it was confirmed that in the region of 90% or more in the film thickness direction of the obtained inorganic thin film layer of the laminated film 1, oxygen, silicon and carbon were in order from the one having the largest atomic number ratio. Was done. Further, from the obtained distribution curves of silicon atoms, oxygen atoms, and carbon atoms, the average atomic concentration in the thickness direction of each atom was obtained, and then the average atomic number ratios C / Si and O / Si were calculated. Atomic number ratio C / Si = 0.30, O / S
It was confirmed that i = 1.73. Further, the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changed continuously in the region of 90% or more in the film thickness direction of the inorganic thin film layer.

[Infrared spectroscopic measurement of the surface of the inorganic thin film layer (ATR method)]
Infrared spectroscopic measurement of the surface of the inorganic thin film layer of the laminated film 1 is performed by a Fourier transform infrared spectrophotometer (FT / IR manufactured by Nippon Spectroscopy Co., Ltd.) equipped with an ATR attachment (PIKE MIRacle) using a germanium crystal for the prism. -460Plus) was used.

From the obtained infrared absorption spectrum, the peak intensity existing in ^{950 to 1050 cm -1 (}
Absorption intensity ratio ( _{I 2} ) to the peak intensity (I 2) present in I ₁ ) and 1240 to 1290 cm ^-1.
When I ₂ / I ₁ ) was calculated, it was _{I 2} / I _{1 = 0.03.} Also, 950 to 1050 cm
Peak intensity at ^-1 _{(I 1} ) and peak intensity at ^{770-830 cm -1 (I 1)}
When seeking I ₃₎ and the absorption intensity ratio of the _{_(I} 3 / I _{_1),} it was I ₃ / I 1 = 0.36. Further, a peak exists in the 770 ~ 830 cm ^-1 intensity _{(I 3),} when determining the peak exists in the 870 ~ 910 cm ^-1 intensity _{(I 4)} and the absorption intensity ratio _{_{(I 4 / I 3),}} I 4 / I ₃ = 0
.. It was 84.

[Water vapor permeability of laminated film]
The water vapor permeability is ISO / WD 151 under the conditions of a temperature of 40 ° C. and a humidity of 90% RH.
It was measured by the Ca corrosion test method according to 06-7 (Annex C).

The water vapor permeability of the obtained laminated film 1 under the conditions of a temperature of 40 ° C. and a humidity of 90% RH was 3.5 × 10 ^-3 g / (m ² · day).

2. Comparative Example 1
As a base material layer, a biaxially stretched polyethylene naphthalate film having a primer layer on one side of a flexible base material (manufactured by Teijin Film Solution Co., Ltd., Q65HA, thickness 100 μm,
Using a width of 350 mm), an inorganic thin film layer (400) was applied to one side of the film in the same manner as in Example 1.
nm) was laminated to obtain a laminated film 2 composed of a base material layer / an inorganic thin film layer.

For the obtained laminated film 2, the internal stress of the inorganic thin film layer was calculated by the same method as in Example 1. The radius of curvature after heating to 130 ° C. is 17.0 mm, and the internal stress is 2.23.
It was GPa. The radius of curvature after heating to 180 ° C. was 9.8 mm, and the internal stress was 3.89 GPa. In the laminated film 2, since the measurement sample after heating and cooling became a cylinder, the diameter inside the cylinder was measured and used as the radius of curvature.

Further, the flatness of the laminated film 2 was evaluated according to the same method as in Example 1, and the diameter inside the obtained cylinder was shown in Table 1 as a warp value.

3. 3. Comparative Example 2
As a base material layer, a biaxially stretched polyethylene naphthalate film having primer layers on both sides of a flexible base material (manufactured by Teijin Film Solution Co., Ltd., Q65HWA, thickness 100 μm)
, Width 350 mm), coating composition 2 (Nippon Kako Paint Co., Ltd., TOMAX FA-3298-1) was applied by the gravure coating method as an organic layer forming composition for forming an organic layer. .. After the coating film is dried at 100 ° C. for 1 minute, it is ^{irradiated with ultraviolet rays under the condition of an integrated light amount of 500 mJ / cm 2} using a high-pressure mercury lamp, and an organic layer having a thickness of 4 μm is laminated to form a substrate with an organic layer. Obtained.
On the surface of the obtained base material with an organic layer on the organic layer side, an inorganic thin film layer (4) was applied in the same manner as in Example 1.
00 nm) was laminated to obtain a laminated film 3 composed of a base material layer / an organic layer / an inorganic thin film layer.

When the water vapor permeability of the obtained laminated film 3 was measured by the same method as in Example 1, 3.7 × 10 ^-3 g / (m ² · day) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH.
)Met.

Biaxially stretched polyethylene naphthalate film (manufactured by Teijin Film Solution Co., Ltd., Q65HWA, thickness 100μ) in which primer layers are formed on both sides of a flexible base material as a base material layer.
Using m), according to Example 3 above, coating composition 2 (Nippon Kako Paint (Nippon Kako Paint)
The organic layer formed from TOMAX FA-3298-1) was laminated to obtain a laminate for measuring the internal stress of the organic layer.
In the laminated body for measuring the internal stress of the organic layer corresponding to the laminated film 3, the internal stress of the organic layer was calculated according to the same measurement method as in Example 1. The radius of curvature after heating to 130 ° C is 23.8
It was mm and the internal stress was 0.16 GPa. The radius of curvature after heating to 180 ° C. was 7.5 mm, and the internal stress was 0.51 GPa.

The laminate for measuring the internal stress of the inorganic thin film layer corresponding to the laminated film 3 is the same as the laminate for measuring the internal stress of the inorganic thin film layer of Example 1, and the radius of curvature after heating to 130 ° C. is 17.0 mm. The internal stress was 2.23 GPa. The radius of curvature after heating to 180 ° C is 9
.. It was 8 mm and the internal stress was 3.89 GPa.

Further, the flatness of the laminated film 3 was evaluated according to the same method as in Example 1, and the average value of the obtained distances (heights) to the four corners was shown in Table 1 as a warp value.

As shown in Table 1, the laminated film obtained in Example 1 is laminated with an inorganic thin film layer having high density and a large internal stress, but the organic layer has a high internal stress and is either 130 ° C. or 180 ° C. It was excellent in the effect of suppressing the warp of the laminated film even when heated at a temperature. On the other hand, in the laminated films obtained in Comparative Examples 1 and 2 which did not contain the organic layer or the internal stress of the organic layer was not sufficient, a large warp of the laminated film occurred under any temperature condition.

1: Base material layer 1-1: Flexible base material 1-2: Primer layer 2: Organic layer 2-1: First organic layer 2-2: Second organic layer 3: Inorganic thin film layer 4: Laminated film 10 : Feeding roll 11: Conveying roll 12: Film forming roll 13: Film forming roll 14: Gas supply pipe 15: Power source for plasma generation 16: Magnetic field generator 17: Winding roll 18: Base film

Claims

A laminated film containing a base material layer containing a flexible base material, an organic layer, and an inorganic thin film layer in this order, and the laminate composed of the base material layer and the organic layer is heated at a temperature of 130 ° C. or higher for 30 minutes. rear,
A laminated film having an internal stress of 0.2 GPa or more measured by allowing it to cool at 25 ° C. for 10 minutes.
The inorganic thin film measured by heating a laminate composed of the base material layer and an inorganic thin film layer directly laminated on the base material layer at a temperature of 130 ° C. or higher for 30 minutes and then allowing it to cool at 25 ° C. for 10 minutes. The laminated film according to claim 1, wherein the internal stress of the layer is 2.0 GPa or more.
The organic layer and the inorganic thin film layer are measured by heating the laminate composed of the base material layer, the organic layer and the inorganic thin film layer at a temperature of 130 ° C. or higher for 30 minutes and then allowing the laminate to cool at 25 ° C. for 10 minutes. The laminated film according to claim 1 or 2, wherein the internal stress of the laminated film made of the above is 0.030 GPa or less.
After heating the laminate composed of the base material layer and the organic layer at 180 ° C. for 30 minutes, 10 at 25 ° C.
The laminated film according to any one of claims 1 to 3, wherein the internal stress of the organic layer measured by allowing to cool for 1 minute is 0.8 GPa or more.
A laminate composed of the base material layer and an inorganic thin film layer directly laminated on the base material layer is formed at 180 ° C. 3
The internal stress of the inorganic thin film layer measured by heating for 0 minutes and then allowing it to cool at 25 ° C for 10 minutes is 3.0 GP.
The laminated film according to any one of claims 1 to 4, which is a or more.
The laminated film according to any one of claims 1 to 5, wherein the inorganic thin film layer is present only on one surface side of the base material layer.
The laminated film according to any one of claims 1 to 6, further comprising an organic layer on the surface of the base material layer opposite to the organic layer.
The laminated film according to any one of claims 1 to 7, wherein the inorganic thin film layer is a layer formed by a plasma chemical vapor deposition method.
The laminated film according to any one of claims 1 to 8, wherein the inorganic thin film layer contains a silicon atom, an oxygen atom and a carbon atom.
9. Claim 9 in which the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changes continuously in a region of 90% or more in the film thickness direction of the inorganic thin film layer. The laminated film described in.
The laminated film according to any one of claims 1 to 10, which has a gas barrier property.