TW201834850A - Gas barrier film and organic EL device - Google Patents

Abstract

The purpose of the present invention is to provide a gas barrier film that has low retardation, is highly transparent, and has favorable flexibility. In order to achieve the foregoing, the present invention has the following configuration. Namely, a gas barrier film having a gas barrier layer composed of a single inorganic membrane directly on at least one surface of a cyclic olefin resin film, wherein the inorganic membrane comprises at least zinc oxide, silicon dioxide, and aluminum oxide.

Description

 Gas barrier film and organic EL device  

The present invention relates to a gas barrier film suitable for use in packaging materials for foods and pharmaceutical products which are required to have gas barrier properties, solar cells, electronic papers, organic electroluminescence (EL) devices, and the like, and gas barrier properties. Thin film organic EL device.

The gas barrier film is generally formed by laminating a gas barrier layer on a base film.

The gas barrier layer is known as an inorganic oxide, for example, a vapor deposited film of alumina, cerium oxide, magnesium oxide or the like.

As the substrate film, various plastic films are known, for example, saponified materials including polyolefin, polyester, polyamide, polycarbonate, polystyrene, polyvinyl alcohol, ethylene vinyl acetate copolymer, polyacrylonitrile, poly A plastic film of a resin such as acetal.

On the other hand, as a gas barrier film of an electronic device such as an organic electroluminescence (EL) or a liquid crystal, a cyclic olefin resin film having a low hysteresis amount (small birefringence) and high transparency is known as a base film. A gas barrier film (Patent Documents 1 to 3).

In addition, in order to improve the adhesion between the base film and the gas barrier layer, it has been proposed to dispose a hard coat layer between the base film and the gas barrier layer (Patent Documents 3 and 4).

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2007-83644

Patent Document 2 Japanese Patent Laid-Open Publication No. 2013-103373

Patent Document 3 Japanese Patent Laid-Open No. 2015-24536

Patent Document 4 Japanese Patent Laid-Open Publication No. 2006-224577

In recent years, gas barrier films have been required to be extended to flexible electronic devices such as flexible solar cell devices, organic electroluminescence (EL) devices, and liquid crystal display devices. That is, the gas barrier film is gradually required to withstand the flexibility of bending, bending, or a complicated planar shape.

However, in the gas barrier film described in Patent Documents 1 to 3, a cyclic olefin resin film is used as the base film, and an inorganic film such as ruthenium dioxide is laminated as a gas barrier film of the gas barrier layer, and has flexibility. Low problem. Further, in the gas barrier film described in Patent Documents 3 and 4, the gas barrier film in which the hard coat layer is disposed between the base film and the gas barrier layer has a problem that flexibility is low.

Therefore, in view of the above problems, an object of the present invention is to provide a gas barrier film which has a low hysteresis amount, high transparency, and good flexibility. Another object of the present invention is to provide an organic EL device comprising the gas barrier film of the present invention.

The above object of the present invention can be achieved by the following invention:

[1] A gas barrier film which is a gas barrier film having a gas barrier layer containing a single inorganic film directly on at least one of a side surface of a cyclic olefin resin film, wherein the inorganic film contains at least zinc oxide, cerium oxide, and Alumina.

[2] The gas barrier film according to [1], wherein the inorganic film has a Zn atom concentration of 20 to 40 atom% and an atomic concentration of 5 to 20 atom by X-ray photoelectron spectroscopy (XPS method). The atomic concentration of % and Al is 0.5 to 5 atom%, and the concentration of O atom is 35 to 70 atom%.

[3] The gas barrier film of [1] or [2], wherein the cyclic olefin resin film has a retardation amount (Re550) in the in-plane direction of light having a wavelength of 550 nm of 500 nm or less.

[4] The gas barrier film according to any one of [1] to [3] wherein the cyclic olefin resin film has a function as a retardation film.

[5] The gas barrier film according to any one of [1] to [4] wherein the cyclic olefin resin film has a thickness of less than 100 μm.

[6] The gas barrier film according to any one of [1] to [5] wherein the thickness of the inorganic film is in the range of 30 to 60 nm or in the range of 120 to 170 nm.

[7] The gas barrier film according to [5] or [6] wherein the thickness of the cyclic olefin resin film is less than 50 μm, and the thickness of the inorganic film is in the range of 30 to 60 nm.

[8] The gas barrier film according to any one of [1] to [7], wherein the surface of the cyclic olefin resin film having a gas barrier layer has a cured resin layer.

[9] The gas barrier film according to [8], wherein the hardened resin layer contains particles, and a ratio of an average particle diameter (r: μm) of the particles to a thickness (d: μm) of the cured resin layer (r/d) ) is 0.7 or less.

[10] The gas barrier film according to [8] or [9], wherein the surface roughness (Ra) of the cured resin layer measured by an atomic force microscope is 2.0 nm or more and 10.0 nm or less.

[11] An organic EL device comprising the gas barrier film according to any one of [1] to [10].

According to the present invention, it is possible to provide a gas barrier film which has a low hysteresis amount, high transparency, and good flexibility. Moreover, the gas barrier film of the present invention is suitable for use in an organic EL device.

1‧‧‧Wind-sputtering ‧CVD device

4‧‧‧ gas barrier film

6‧‧‧Winding room

7‧‧‧Rolling shaft

8, 9, ‧ ‧ rolled out side guide rolls

11‧‧‧Cooling roller

12‧‧‧ Sputtering electrode

13,14,15‧‧‧Winding side guide roller

16‧‧‧Winding shaft

100‧‧‧Organic EL device

101‧‧‧Back substrate

102‧‧‧Organic EL components

103‧‧‧ Sealing adhesive layer

104‧‧‧ gas barrier film

105‧‧‧Optical film

106‧‧‧Surface protection film

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL device including the gas barrier film of the present invention.

Fig. 2 is a schematic view schematically showing a wound sputtering apparatus for producing a gas barrier film of the present invention.

Form of implementing the invention

The gas barrier film of the present invention directly has a gas barrier layer containing a single inorganic film on at least one side of the cyclic olefin resin film. The inorganic film system contains at least zinc oxide, cerium oxide, and aluminum oxide. Hereinafter, an inorganic film containing at least zinc oxide, cerium oxide, and aluminum oxide is referred to as "an inorganic film of the film of the present invention".

The gas barrier layer of the present invention contains only a single inorganic film, and the single inorganic film contains at least zinc oxide, cerium oxide, and aluminum oxide. In the present invention, as long as it is an inorganic film containing at least zinc oxide, cerium oxide, and aluminum oxide, for example, two or more inorganic films having different composition ratios of zinc oxide, cerium oxide, and aluminum oxide are also defined as A single inorganic membrane. In other words, only one or more inorganic membranes belonging to the "inorganic film of the film of the present invention" are also defined as a single inorganic film.

The gas barrier layer of the present invention does not contain an inorganic film other than the inorganic film of the film of the present invention as described below. For example, it does not include: an inorganic film containing only a cerium compound (for example, cerium oxide, cerium nitride, cerium oxynitride), an inorganic film containing only an aluminum compound (for example, alumina), and only a zinc compound (for example, zinc oxide, zinc sulfide). The inorganic film or an inorganic film containing only the above-described ruthenium compound and the above-described aluminum compound, an inorganic film containing only the above ruthenium compound and the above zinc compound, and an inorganic film containing only the above-described aluminum compound and the above zinc compound. Further, the gas barrier layer of the present invention does not contain a gas barrier organic film such as an organic film containing an organic ruthenium compound. The organic film containing the organic ruthenium compound may, for example, be an organic film containing a ruthenium compound having a polyazirane skeleton, or a plasma CVD film using hexamethyldioxane (HMDSO) gas.

In the gas barrier layer, in addition to the inorganic film or the organic film described above, in addition to the inorganic film of the film of the present invention, the flexibility or transparency of the gas barrier film is lowered.

Moreover, the gas barrier film of the present invention is an inorganic film which directly has the film of the present invention on at least one side of the cyclic olefin resin film. That is, the gas barrier film of the present invention does not have an undercoat layer such as a hard coat layer between the cyclic olefin resin film and the inorganic film of the film of the present invention.

When a hard coat layer having a high hardness is present between the cyclic olefin resin film and the inorganic film of the film of the present invention, the flexibility of the gas barrier film is lowered.

Further, when a hard coat layer having a high hardness is provided, when the gas barrier film is cut into a predetermined size, minute cracks are generated in the hard coat layer. Once a small crack is formed in the hard coat layer, it will extend to the gas barrier layer laminated on the hard coat layer, and the gas barrier layer will also generate minute cracks. When a micro crack occurs in the cut portion of the gas barrier layer, and the gas barrier film is applied to the flexible organic EL device to be bent or folded, the gas barrier property is lowered. The details are described later.

[Inorganic film containing at least zinc oxide, cerium oxide and aluminum oxide]

The gas barrier layer of the present invention is composed of a single layer of an inorganic film (an inorganic film of the film of the present invention) containing at least zinc oxide, cerium oxide and aluminum oxide.

The composition of the inorganic film of the film of the present invention is preferably a concentration of Zn atom of 20 to 40 atom% and a concentration of Si atom of 5 to 20 atom% as measured by X-ray photoelectron spectroscopy (XPS method). The Al atom concentration is 0.5 to 5 atom%, and the O atom concentration is 35 to 70 atom%.

When the Zn atom concentration is more than 40 atom% or the Si atom concentration is less than 5 atom%, the oxide which inhibits the crystal growth of zinc oxide tends to be insufficient, and therefore the void portion or the defective portion is increased, and sufficient gas barrier properties cannot be obtained. When the Zn atom concentration is less than 20 atom% or the Si atom concentration is more than 20 atom%, the amorphous component of the cerium oxide inside the inorganic film is likely to increase, and the flexibility of the inorganic film is deteriorated.

When the Al atom concentration is more than 5 atom%, the affinity between zinc oxide and ceria is likely to be too high. Therefore, the hardness of the inorganic film is likely to increase, and cracks are likely to occur with heat or stress from the outside. When the Al atom concentration is less than 0.5 atom%, the affinity between zinc oxide and cerium oxide is insufficient, and the binding force between the particles forming the inorganic film is not easily improved, and the flexibility is deteriorated.

When the concentration of the O atom is more than 70 atom%, the amount of defects inside the inorganic film is likely to increase, and high gas barrier properties cannot be obtained. When the concentration of the O atom is less than 35 atom%, the oxidation state of zinc, bismuth, and aluminum is liable to be insufficient, and crystal growth cannot be suppressed, and the particle diameter tends to be large, resulting in deterioration of gas barrier properties.

Based on the above viewpoint, it is more preferable that the Zn atom concentration is 25 to 35 atom%, the Si atom concentration is 10 to 15 atom%, the Al atom concentration is 1 to 3 atom%, and the O atom concentration is 50 to 64 atom%.

Since the above composition is formed by the same composition as that of the mixed sintered material used in the formation of the inorganic film, it can be adjusted by using a mixed sintered material which satisfies the composition of the composition of the target inorganic film.

The method of forming the inorganic film of the film of the present invention is not particularly limited, and it can be formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like using a mixed sintered material of zinc oxide, cerium oxide, and aluminum oxide. In the case of using a simple material of zinc oxide, cerium oxide and aluminum oxide, each of zinc oxide, cerium oxide and aluminum oxide may be simultaneously formed from individual vapor deposition sources or sputtering electrodes to form a desired composition. It is formed by mixing. Among these methods, a sputtering method using a mixed sintered material is more preferable from the viewpoint of composition reproducibility of the inorganic film.

When the inorganic film is formed by a sputtering method or the like, it is preferred to laminate a heat-resistant protective film on the opposite side of the surface of the cyclic olefin resin film on which the inorganic film is formed, for example, in polyethylene terephthalate ( The PET film has a micro-adhesive PET protective film. Further, it is also preferable to laminate a cured resin layer described later in place of the protective film.

The inorganic film of the film of the present invention may contain other metals such as titanium, tin, copper, indium, gallium, zirconium, hafnium, molybdenum, insofar as it does not impair the effects (gas barrier properties, flexibility, transparency) of the present invention. A metal such as ruthenium or an oxide, a nitride or a sulfide of such a metal.

The thickness of the inorganic film of the film of the present invention is preferably 10 nm or more, more preferably 20 nm or more, and particularly preferably 30 nm or more from the viewpoint of obtaining good gas barrier properties. On the other hand, the upper limit of the thickness is preferably 500 nm or less, more preferably 300 nm or less, and particularly preferably 200 nm or less from the viewpoint of suppressing curl of the gas barrier film.

Further, when the inorganic film of the film of the present invention is laminated on the film of the cyclic olefin resin, the thickness of the inorganic film of the film of the present invention is preferably in the range of 30 to 60 nm from the viewpoint of obtaining high transparency (high total light transmittance). Or a range of 120 to 170 nm. The relationship between the visible light refractive index (about 1.70) of the inorganic film of the film of the present invention and the visible light refractive index (about 1.53) of the cyclic olefin resin film, when the inorganic film of the film of the present invention is laminated on the cyclic olefin resin film The transmittance is relatively high in the above two ranges (the thickness of the inorganic film is in the range of 30 to 60 nm or in the range of 120 to 170 nm).

The inorganic film of the film of the present invention has such a characteristic that cracks do not occur at the time of cutting, or even cracks are extremely small. On the other hand, this feature has the effect that the gas barrier film of the present invention is cut into a predetermined size and applied to a flexible organic EL device, and the gas barrier property can be suppressed even if it is bent or folded. The details are described later.

In order to suppress the occurrence of cracks at the time of cutting of the inorganic film, the thickness of the inorganic film is preferably as small as possible; from this viewpoint, the thickness of the inorganic film is more preferably in the range of 30 to 60 nm.

[Ring olefin resin film]

The cycloolefin-like hydrocarbon resin film of the present invention is a resin film containing a cyclic olefin resin (COP) or a cyclic olefin copolymer resin (COC) as a main component. In the resin component constituting the resin film, the composition ratio of COP or COC is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, and still more preferably 90%. The mass% or more is particularly preferably 95% by mass or more.

The cyclic olefin resin film has a relatively small moisture permeability and high transparency as compared with a polyester film which has been widely used, especially a polyethylene terephthalate film, and is used in an organic EL device. It can improve the characteristics of luminous efficiency. Further, it has an advantage that the degree of hysteresis is low (the birefringence is small) and the viewing angle dependence of color is small when used in an organic EL device.

The cyclic olefin resin (COP) means a resin composed of a homopolymer of a cyclic olefin. The cyclic olefin copolymer resin (COC) is a resin composed of a copolymer of a cyclic olefin and a monomer other than a cyclic olefin.

Examples of the cyclic olefin which can be used in order to obtain COP and COC include cyclobutene, cyclopentene, cycloheptene, cyclohexene, cyclooctene, cyclopentadiene, and 1,3-cyclohexane. Diene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, 3a,5,6,7a-tetrahydro- Monocyclic olefin such as 4,7-methylene-1H-indole; norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylene tetracyclododecene a polycyclic olefin such as tetracyclo [7.4.0.110, 13.02, 7] thirteen-2,4,6,11-tetraene; These cyclic olefins can be used individually or in combination of 2 or more types.

Examples of the monomer other than the cyclic olefin which can be used in order to obtain a cyclic olefin copolymer resin (COC) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3- Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4, 4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1 - terpene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like.

The cyclic olefin resin film of the present invention can also be obtained in the form of a commercially available product. As a commercial item, for example, "ZEONEX (registered trademark)", "ZEONOR (registered trademark)", and "Esshina (registered trademark)", JSR (share) of Sekisui Chemical Industry Co., Ltd., manufactured by Japan ZEON Co., Ltd. "ARTON (registered trademark)", "Optolet" of Hitachi Chemical Co., Ltd., "Apel (registered trademark)" of Mitsui Chemicals Co., Ltd., etc.

The thickness of the cyclic olefin resin film is not particularly limited, and the thickness is preferably as small as possible from the viewpoint of ensuring high flexibility; specifically, it is preferably less than 100 μm, more preferably less than 80 μm, and particularly preferably less than 50 μm. The lower limit thickness is preferably 5 μm or more, more preferably 10 μm or more, and particularly preferably 20 μm or more, from the viewpoint of ensuring the strength against stretching or impact.

Moreover, when the gas barrier film of the present invention is applied to an organic EL device, the thickness of the gas barrier film of the present invention is preferably smaller as compared with the viewpoint of reducing the thickness of the organic EL device. From this point of view, the thickness of the cyclic olefin resin film is preferably less than 50 μm, more preferably less than 40 μm, and particularly preferably less than 35 μm. The lower limit thickness is preferably 5 μm or more, and more preferably 10 μm or more.

In the cyclic olefin resin film having a thickness of less than 50 μm, the gas barrier film in which only one of the inorganic films of the film of the present invention is laminated is likely to be curled. In order to suppress this curl, the thickness of the inorganic film of the film of the present invention is preferably in the range of 30 to 60 nm, more preferably in the range of 40 to 55 nm. That is, in the gas barrier film of the present invention, it is preferred that the thickness of the cyclic olefin resin film is less than 50 μm, and the thickness of the inorganic film is in the range of 30 to 60 nm, more preferably the cyclic olefin. The thickness of the resin film is less than 50 μm, and the thickness of the inorganic film is in the range of 40 to 55 nm. By laminating the inorganic film of the film of the present invention having a thickness of 30 to 60 nm, preferably 40 to 55 nm, to a cyclic olefin resin film having a thickness of less than 50 μm, it is possible to maintain good gas barrier properties while easily obtaining high transparency (high Total light transmittance).

The cyclic olefin resin film of the present invention preferably has a low hysteresis amount. Specifically, the amount of retardation (Re550) in the in-plane direction of light having a wavelength of 550 nm is preferably 500 nm or less, preferably 400 nm or less, and particularly preferably 300 nm or less. The lower limit is 0 nm.

When the gas barrier film is used to protect the organic EL device of the organic EL device from water vapor, the retardation amount Re550 of the cyclic olefin resin film is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 10 nm. the following. The gas barrier film using such a low hysteresis amount of the cyclic olefin resin film has an advantage that the viewing angle dependence of the luminescent color of the organic EL element is small.

Further, the gas barrier film of the present invention can also serve as a retardation film (λ/4 plate) constituting a circularly polarizing plate of an organic EL display device (organic EL display). At this time, it is preferred that the cyclic olefin resin film has a function as a retardation film (λ/4 plate). Here, the term "the cyclic olefin resin film has a function as a retardation film" means that the cyclic olefin resin film has a retardation amount Re550 of 110 to 170 nm. The retardation amount Re550 at this time is more preferably in the range of 120 to 150 nm, and particularly preferably in the range of 130 to 145 nm.

The amount of hysteresis (Re550) of the cyclic olefin resin film in the in-plane direction of light having a wavelength of 550 nm is a value represented by the following formula: | nx-ny | × d

(wherein nx represents a refractive index in the slow axis direction in the plane of the cyclic olefin resin film, ny represents a refractive index in the fast axis direction in the plane of the cyclic olefin resin film, and d represents a film thickness (nm)).

The term "in the surface" as used herein means the in-plane of the cyclic olefin resin film, and means the surface perpendicular to the thickness direction of the film. The amount of hysteresis can be determined by a parallel Nicols rotation method using a birefringence meter as used in the examples.

The amount of hysteresis of the cyclic olefin resin film can be controlled, for example, by adjusting the extending direction or the stretching ratio at the time of production (at the time of film formation). Further, it can be suitably selected from the above-mentioned commercial products.

[Gas barrier film]

The gas barrier film of the present invention has a gas barrier layer on at least one side of the cyclic olefin resin film. The gas barrier layer may be provided only on one side of the cyclic olefin resin film, or may be provided on both sides, but it is preferably provided only on one side.

In the form in which the gas barrier layer is provided only on one side of the cyclic olefin resin film, it is preferable to provide hardening on the opposite surface of the surface of the cyclic olefin resin film on which the gas barrier layer is provided (hereinafter referred to as "back surface"). Resin layer. The details of the hardened resin layer will be described later.

The gas barrier film of the present invention is preferably highly flexible. That is, it is preferable that the bending property is good. In the present invention, as an index for evaluating the above flexibility, a cylindrical mandrel method (JIS K5600-5-1: 1999) is employed.

The cylindrical mandrel method is a method of observing and evaluating the occurrence of cracks and the like when the gas barrier film is wound around a cylindrical mandrel (cylindrical rod) having a diameter of 2 mm to 10 mm. Specifically, it is preferable that the gas barrier film is wound around a cylindrical mandrel having a diameter of 2 mm so that the gas barrier layer is formed outside, according to the cylindrical mandrel method (JIS K5600-5-1: 1999). The gas barrier layer of the wound portion thereof is not cracked.

The gas barrier properties of the gas barrier film of the present invention are evaluated by the water vapor transmission rate. The gas barrier film of the present invention preferably has a water vapor transmission rate of less than 5.0 × 10 ^-3 g / m ² /day, more preferably less than 3.0 × 10 ^-3 g / m ² /day, particularly preferably less than 1.0. ×10 ^-3 g/m ² /day.

Further, the gas barrier film of the present invention preferably has high transparency. Specifically, the gas barrier film of the present invention preferably has a total light transmittance of 88% or more.

[hardened resin layer]

It is preferred to have a hardened resin layer on the opposite side (back surface) of the surface of the cyclic olefin resin film having the gas barrier layer. By having a hardened resin layer, the scratch resistance of the gas barrier film can be improved. From this point of view, the pencil hardness of the cured resin layer (the pencil hardness specified by JIS K5600-5-4 (1999)) is preferably F or more, more preferably H or more. When the pencil hardness of the upper limit is too high, the flexibility described later is deteriorated, so it is preferably 3H or less, and particularly preferably 2H or less.

The hardened resin layer is preferably a thermosetting resin layer or an active energy ray-curable resin layer, and particularly preferably an active energy ray-curable resin layer. The active energy ray-curable resin layer is preferably an ultraviolet-curable resin layer.

Further, the cured resin layer preferably contains particles. Further, the hardened resin layer preferably has minute projections generated by particles on its surface. Thereby, the slidability or blocking resistance of the gas barrier film can be improved.

From the viewpoint of ensuring high transparency and improving slidability, when the gas barrier film is provided with a hardened resin layer containing particles, it is preferred to contain particles having an average particle diameter much smaller than the thickness of the cured resin layer, and on the surface of the cured resin layer. The protrusions generated by the particles are formed. For example, the ratio (r/d) of the average particle diameter (r: μm) of the particles contained in the cured resin layer to the thickness (d: μm) of the cured resin layer is preferably 0.7 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less. When the lower limit ratio is too small, good slidability cannot be obtained, so it is preferably 0.01 or more, more preferably 0.02 or more, and particularly preferably 0.03 or more.

For a gas barrier film in which a hardened resin layer is laminated, it is also preferable to use a gas barrier film as a hardening resin in accordance with a cylindrical mandrel method (JIS K5600-5-1:1999) based on the viewpoint of ensuring high flexibility. When the layer is wound on the outer side of the cylindrical mandrel having a diameter of 2 mm (when the gas barrier layer of the gas barrier film is wound in contact with the cylindrical mandrel), the hardened resin layer of the wound portion is not produced. crack.

For example, the pressing hardness measured by the nanoindentation method of the cured resin layer is preferably in the range of 200 to 600 N/mm ² , more preferably 250 to 250, based on the viewpoint of imparting high flexibility to the cured resin layer. range of 550N / mm ^2, and particularly preferably in a range of 300 ~ 500N / mm ² of.

From the above viewpoints, as the resin component of the cured resin layer, a urethane-based resin is preferably used. That is, the cured resin layer is preferably an active energy ray-curable resin layer containing a urethane-based resin (urethane (meth) acrylate monomer or oligomer). The urethane-based resin is preferably a 1-5-functional urethane-based resin, more preferably a 1-4-functional urethane-based resin, and particularly preferably a 1-3 functional group. A urethane resin.

The thickness of the cured resin layer is preferably less than 4 μm, more preferably less than 3 μm, and particularly preferably less than 2 μm from the viewpoint of ensuring good flexibility and suppressing curl of the gas barrier film. The lower limit thickness is preferably 0.3 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.7 μm or more, from the viewpoint of imparting good slidability.

The average particle diameter (r) of the particles contained in the cured resin layer is preferably in the range of 0.02 to 0.5 μm, more preferably in the range of 0.03 to 0.4 μm, and particularly preferably in the range of 0.04 to 0.2 μm.

When the average particle diameter (r) of the particles contained in the cured resin layer is less than 0.02 μm, good slidability cannot be obtained. On the other hand, if the average particle diameter (r) is more than 0.5 μm, the haze value is increased. The transparency is reduced.

The content of the particles contained in the cured resin layer is preferably in the range of 2 to 40% by mass, more preferably in the range of 2 to 40% by mass based on 100% by mass of the total solid content of the cured resin layer, from the viewpoint of ensuring high transparency and improving slidability. It is in the range of 3 to 30% by mass, and particularly preferably in the range of 5 to 20% by mass.

Examples of the particles contained in the cured resin layer include organic particles or inorganic particles.

Examples of the resin constituting the organic particles include an acrylic resin, a styrene resin, a polyester resin, a polyurethane resin, a polycarbonate resin, a polyamide resin, and a polyoxyn resin. A fluorine-based resin or a copolymer resin of two or more kinds of monomers used for the synthesis of the above resins. Among these, acrylic resin particles are preferably used.

Examples of the acrylic resin particles include acrylic resin particles, methacrylic resin particles, acrylic monomers or methacrylic monomers and other monomers such as styrene, urethane acrylate, and urethane. Copolymer resin particles such as methacrylate, polyester acrylate, polyester methacrylate, polyoxy acrylate, polyfluorene methacrylate, and the like.

These organic particles are preferably synthesized by an emulsion polymerization method. By synthesizing by an emulsion polymerization method, organic particles having an average particle diameter of 0.5 μm or less can be obtained.

Examples of the inorganic particles include inorganic particles such as cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, and zeolite. Among these, cerium oxide particles are preferred, and colloidal cerium oxide or fumed cerium oxide (also known as dry cerium oxide or fumed cerium oxide) is particularly preferred.

The inorganic particles, such as cerium oxide particles, are preferably modified with an organic compound (surface treatment). By surface-treating the inorganic particles with an organic compound, the particles can be locally present in a large amount (floating) on the surface side of the cured resin layer (opposite side of the cyclic olefin resin film). Thereby, high slidability can be imparted with a small particle content.

Examples of the organic compound used for the modification (surface treatment) of the inorganic particles include the following general formulae (1) to (3), and these organic compounds can be used singly or in combination; C _n F _2n+1 -(CH) ₂ ) _m -Si(Q) ₃ ... general formula (1)

(In the formula (1), n represents an integer of 1 to 10, m represents an integer of 1 to 5; and Q represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom).

BR ⁴ -SiR ⁵ _n (OR ⁶ ) _3-n ... Formula (2)

DR ⁷ -Rf ² ...general (3)

(In the general formulae (2) and (3), B and D each independently represent a reactive moiety, and R ⁴ and R ⁷ each independently represent an alkylene group having 1 to 3 carbon atoms or derived from the aforementioned alkylene group. The ester structure, R ⁵ and R ⁶ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, Rf ² represents a fluoroalkyl group, and n represents an integer of 0 to 2.

Specific examples of the compound of the formula (1) include the following compounds: C ₄ F ₉ CH ₂ CH ₂ Si(OCH ₃ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ Si(OCH ₃ ) ₃

C ₈ F ₁₇ CH ₂ CH ₂ Si(OCH ₃ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ Si(OC ₂ H ₅ ) ₃

C ₈ F ₁₇ CH ₂ CH ₂ CH ₂ Si(OC ₂ H ₅ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ CH ₂ CH ₂ Si(OC ₂ H ₅ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ SiCl ₃

C ₆ F ₁₃ CH ₂ CH ₂ SiBr ₃

C ₆ F ₁₃ CH ₂ CH ₂ CH ₂ SiCl ₃

C ₆ F ₁₃ CH ₂ CH ₂ Si(OCH ₃ )Cl ₂ .

Specific examples of the general formula (2) include propylene oxime oxyethyl trimethoxy decane, propylene oxypropyl trimethoxy decane, propylene oxybutyl trimethoxy decane, and propylene oxiranyl trimethoxy hydride. Base alkane, propylene oxyhexyl trimethoxy decane, propylene oxiranyl heptyl trimethoxy decane, methacryl oxiranyl trimethoxy decane, methacryl oxiranyl trimethoxy decane, methacryl oxime Oxybutyl butyl trimethoxy decane, methacryl oxiranyl trimethoxy decane, methacryl oxiranyl trimethoxy decane, methacryl oxiranyl methyl dimethoxy decane, methacryl oxime Oxypropylmethyldimethoxydecane and a compound containing a methoxy group in these compounds substituted with another alkoxy group and a hydroxyl group.

Specific examples of the general formula (3) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, and 2-perfluorobutyl B. Acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctyl Acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro 3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate , 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorodecyl acrylate , hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl Methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropylmethyl Oleate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxyl Propyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro- 7-Methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, eight Fluoryl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorodecyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, etc. .

The surface roughness (Ra) measured by atomic force microscopy (AFM) on the surface of the cured resin layer is preferably 2.0 nm or more and 10.0 nm or less from the viewpoint of ensuring high transparency and improving slidability. . When the surface roughness (Ra) of the cured resin layer is less than 2.0 nm, the slidability is lowered. Further, when the surface roughness (Ra) exceeds 10.0 nm, the transparency is lowered. From the above viewpoints, the surface roughness (Ra) measured by atomic force microscopy (AFM) on the surface of the cured resin layer is more preferably 2.5 nm or more and 7.0 nm or less, and particularly preferably 3.0 nm or more and 6.0 nm or less.

[Sealing Adhesive Layer]

When the gas barrier film of the present invention is applied to an organic EL device to be described later, the gas barrier film of the present invention is preferably bonded to the organic EL device via a sealing adhesive layer. That is, in the gas barrier film of the present invention, it is preferred to seal the adhesive layer in the area layer of the gas barrier layer.

The sealing adhesive layer preferably contains a polymer selected from the group consisting of polyisobutylene, butyl rubber, polyisoprene, styrene-isobutylene modified resin, styrene-isoprene-styrene block copolymer, styrene- At least one resin of a group of a butadiene-styrene block copolymer, a styrene-isoprene rubber, a polybutadiene rubber, a styrene-butadiene rubber, and a polybutene is used as a sealing resin. Among these, it is more preferable to contain polyisobutylene or butyl rubber.

The sealing adhesive layer preferably further contains a tackifying resin. Examples of the tackifier resin include an alicyclic petroleum resin, an alicyclic hydrogenated petroleum resin, an aromatic petroleum resin, and a rosin-based resin. Among these tackifier resins, preferred are alicyclic petroleum resins, and among the alicyclic hydrogenated petroleum resins, hydrogenated terpene resins, hydrogenated ester resins, hydrogenated resins of C5 petroleum resins, and C9 are preferred. A hydrogenated resin of petroleum resin.

The mass ratio of the sealing resin to the tackifying resin (sealing resin/tackifying resin) is preferably from 10/90 to 100/0, more preferably from 20/80 to 90/10.

Further, the sealing adhesive layer may further contain an ultraviolet absorber, an antioxidant, an antistatic agent, a plasticizer, a filler, a flame retardant, a crosslinking agent, and a rust preventive agent.

The thickness of the sealing adhesive layer is preferably in the range of 5 to 150 μm, more preferably in the range of 10 to 100 μm, and particularly preferably in the range of 20 to 80 μm. Further, the sealing adhesive layer preferably has a water vapor permeability of 40 g/m ² /day or less, more preferably 30 g/m ² /day or less, and particularly preferably 20 g/m ² /day or less.

The sealing adhesive layer can be formed by coating on the gas barrier layer of the gas barrier film, and the sealing adhesive layer can be applied to the release film, and then the surface of the sealing adhesive layer and the gas barrier film can be bonded. The face of the gas layer.

[Application examples of gas barrier film]

The gas barrier film of the present invention can be suitably used for packaging materials such as pharmaceuticals, organic EL illumination, organic EL devices, and electronic devices such as solar cells.

In particular, since the gas barrier film of the present invention has high flexibility, it is suitable for a flexible (bendable or foldable) organic EL device. Further, the gas barrier film of the present invention is suitable as a retardation film (λ/4 plate).

Examples of the flexible organic EL device include flexible displays such as a foldable display (foldable display), a bent display (a bendable display), and a reel display (a rollable display). The gas barrier film of the present invention is suitable for use in a flexible display as described above.

The gas barrier film is cut into a predetermined size when applied to an organic EL device or the like. At this time, minute cracks may occur in the cut portion of the gas barrier layer. Even if a crack is generated only in the cut portion of the gas barrier layer cut into a slice of the gas barrier film of a predetermined size, generally, the gas barrier performance is not problematic. However, when a slice having a micro crack in the cut portion of the gas barrier layer is applied to a flexible display, when the flexible display is bent or folded, it is present in the cut portion of the gas barrier layer of the slice. The crack will extend in the center direction to lower the gas barrier properties.

The inorganic film of the gas barrier film of the present invention does not cause cracks at the time of cutting, or is extremely small or extremely rare even if cracks are generated. When the slice of the gas barrier film of the present invention is applied to a flexible organic EL device and is bent or folded, the decrease in gas barrier properties can be suppressed.

That is, the chip of the gas barrier film of the present invention is suitable for a flexible organic EL device such as a flexible organic EL display. Especially suitable for folding organic EL displays or bent organic EL displays.

The organic EL device of the present invention comprises the gas barrier film of the present invention.

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL device including a gas barrier film (slice) of the present invention. However, the invention is not limited thereto. The organic EL device 100 has an organic EL element 102 on a back substrate 101 (polyimine substrate). The organic EL element 102 is covered with the gas barrier film 104 via the sealing adhesive layer 103.

An optical film 105 (a polarizing film, a retardation film, a touch panel, or the like) is laminated on the gas barrier film 104, and a surface protective film 106 (a hard coat film, an antireflection film, or the like) is further laminated thereon. When the optical film 105 has both surface protection functions, the surface protection film 106 can be omitted.

[Slice of gas barrier film]

As described above, the slice of the gas barrier film of the present invention (hereinafter simply referred to as "slice") has a feature that the water vapor permeability does not increase even if it is bent or folded. Specifically, the water vapor permeability after the folding test of the slice is preferably less than 5.0 × 10 ^-3 g / m ² /day, more preferably less than 3.0 × 10 ^-3 g / as in the case of the folding test. m ² /day, particularly preferably less than 1.0 × 10 ^-3 g / m ² /day. The details of the folding test are described later.

The slice of the gas barrier film of the present invention preferably has substantially no microscopic cracks in the cut portion of the gas barrier layer. Thereby, the increase in the water vapor permeability after the folding test of the slice can be suppressed, and the water vapor permeability after the folding test of the slice can be made into the above range.

Here, the microcrack means a crack having a length of 30 μm or more. In addition, it is said that there is substantially no micro-crack in the cut portion of the gas barrier layer, and it is a cut-off portion for the slice at a magnification of 200 times using a digital microscope ("VHX-1000" manufactured by KEYENCE Co., Ltd.). For example, when the slice is a rectangle, the four sides thereof are observed at intervals of about 10 mm, and the number of minute cracks per 200 mm of the length of the cut portion is less than 50. The number of the micro cracks in the method for measuring the micro cracks is preferably less than 30 (the length of the cut portion is 200 mm), more preferably less than 10 (the length of the cut portion is 200 mm), and particularly preferably 0 (cut/cut) The length of the broken part is 200mm).

The gas barrier film according to the present invention has a gas barrier layer directly composed of a single film of an inorganic film containing zinc oxide, cerium oxide and aluminum oxide. With this configuration, it is possible to suppress the occurrence of minute cracks during cutting.

 [Examples]  

Hereinafter, the present invention will be specifically described based on examples. However, the invention is not limited by the following examples.

 [Assessment method]  

First, the evaluation methods in the respective examples and comparative examples will be described. The number of n is evaluated, and unless otherwise specified, n=5 is set and the average value is obtained.

(1) Evaluation of the flexibility (A) of the gas barrier layer of the gas barrier film

According to the cylindrical mandrel method (JIS K5600-5-1:1999), the gas barrier layer of the gas barrier film was wound around a cylindrical mandrel having a diameter of 2 mm so as to be visually observed to be wound. Whether or not some of the gas barrier layer is cracked is evaluated according to the following criteria.

A: No cracks can be seen.

B: I saw the crack.

(2) Evaluation of flexibility (B) of the cured resin layer of the gas barrier film

The gas barrier film provided with the cured resin layer was evaluated in the same manner as in the above (1). In the meantime, the hardened resin layer on the opposite side of the gas barrier layer of the gas barrier film was wound around a cylindrical mandrel having a diameter of 2 mm to evaluate whether or not the cured resin layer was cracked.

(3) Determination of the hardness of the hardened resin layer by the nanoindentation method

The measurement was carried out using a nanoindenter "ENT-2100" manufactured by ELIONIX. The opposite side of the measurement surface (hardened resin layer) of the gas barrier film was fixed to a dedicated sample fixing table via an adhesive (Aron Alpha (registered trademark) manufactured by Toagos Corporation, and a ridge angle of 115° was used. The triangular cone diamond indenter (Berkovich indenter) measures the pressing hardness (H _IT (N/mm ² )) of the cured resin layer under the following conditions. The measurement data is a dedicated analysis software of "ENT-2100". 6.18) to deal with.

 <Measurement conditions>  

‧ Measurement mode: load-unloading test

‧Maximum load: 100mN

‧ Hold time at maximum load: 1 second

‧Load speed, unloading speed: 10mN/sec

‧Pushing depth: 1/10 of the film thickness.

(4) Thickness of each layer

Using a micro-sampling system (Hitachi FB-2000A), the gas barrier property is produced by the FIB method (specifically, the method described in "Polymer Surface Processing" (Iwate), p. 118-119) A sample for cross-section observation of a film. The cross section of the sample for cross-section observation was observed by a transmission electron microscope (H-9000 UHRII manufactured by Hitachi Ltd.) at an acceleration voltage of 300 kV, and the thickness of the gas barrier layer and the cured resin layer was measured.

(5) Measurement of average particle diameter of particles contained in the cured resin layer

The cross section (about 10,000 to 300,000 times) of the cured resin layer was observed by a TEM (transmission electron microscope), and the width of the cross-sectional photograph (the length orthogonal to the thickness direction of the cured resin layer) of 1 μm was measured. The maximum length of the particles is arithmetically averaged, and the obtained value is taken as the average particle diameter of the particles.

(6) Determination of surface roughness (Ra) measured by atomic force microscopy

The surface roughness (Ra) of the cured resin layer was measured according to the following conditions using an atomic force microscope "AFM5100N" manufactured by Hitachi High-Tech Science.

‧ Scan mode: DFM

‧Scanning range: 5μm×5μm

‧Number of data: 256×256

‧ Measurement environment: 25 ° C, in the atmosphere.

(7) Determination of water vapor transmission rate of gas barrier film

The measurement was carried out using a water vapor permeability measuring apparatus (model name: "DELTAPERM (registered trademark)") manufactured by Technolox, UK under the conditions of a temperature of 40 ° C, a humidity of 90% RH, and a measurement area of 50 cm ² . The number of samples was taken to be two samples per level, and the number of measurements was set to five times for each sample, and the average value of the obtained ten points was used as the water vapor transmission rate (g/m ² /day).

(8) Composition analysis of gas barrier layer (inorganic membrane)

The composition analysis of the gas barrier layer (whether or not the inorganic film contains zinc oxide, cerium oxide, aluminum oxide, and the content ratio of each element) is carried out by X-ray photoelectron spectroscopy (XPS method). That is, the outermost layer was etched and removed by about 5 nm by sputtering using argon ions, and then the content ratio of each element was measured. The measurement conditions of the XPS method are as follows:

‧Device: ESCA 5800 (manufactured by ULVAC-PHI)

‧Inspire X-ray: monochromatic AlKα

‧X-ray power: 300W

‧X-ray diameter: 800μm

‧Photoelectron detachment angle: 45°

‧Ar ion etching: 2.0kV, 10mPa.

(9) Evaluation of the slidability of gas barrier film

The slidability of the gas barrier film provided with the hardened resin layer on the back side was evaluated in the following manner.

Two sheets (20 cm × 15 cm) were cut by cutting the gas barrier film. The two sheets are overlapped with a slight gap between the two gas barrier layers and the hardened resin layer, and placed on a smooth table, by fixing the lower sheet to the table with a finger, and by hand to make the upper portion The method of sliding the sheet to determine whether the slidability is good or not. The measurement environment was 23 ° C and 55% RH.

A: The upper sheet can slide.

B: The upper sheet cannot slide.

(10) Determination of hysteresis amount of substrate film (Re550)

The hysteresis amount (Re550) of the base film in the in-plane direction of light having a wavelength of 550 nm was measured by a parallel Nicols rotation method using a birefringence meter KOBRA-WR manufactured by Oji Scientific Co., Ltd.

(11) Determination of total light transmittance

It is measured based on JIS K7361 (1997) using a turbidity meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

(12) Determination of pencil hardness of hardened resin layer

It was measured using a pencil hardness tester HEIDON-14 (New East Science Co., Ltd.) in accordance with JIS K5600-5-4 (1999).

(13) Observation of micro cracks in the cut portion of the slice of the gas barrier film

The gas barrier layer cut portion on the four sides of the slice was observed at a magnification of 200 times using a digital microscope ("VHX-1000" manufactured by KEYENCE Co., Ltd.), and the number of minute cracks having a length of 30 μm or more was measured. The cut portions of the four sides were observed at intervals of approximately 10 mm, and the total number of the micro cracks was determined, and the number of the cut portions per 200 mm was converted according to the following formula, and the evaluation was performed based on the following criteria.

The number of the cut portions per 200 mm = the total number / (200 mm / the total length of the cut portions)

(In addition, the total length of the cut portions in the present embodiment is 640 mm)

A: The number of micro cracks per cut of the cut portion is less than ten.

B: The number of micro cracks per 10 mm in the cut portion is 10 or more and less than 30.

C: The number of micro cracks per 30 mm in the cut portion is 30 or more and less than 50.

D: The number of micro cracks per 50 mm in the cut portion is 50 or more and less than 100.

E: The number of micro cracks per 100 mm in the cut portion is 100 or more.

(14) Determination of water vapor transmission rate after folding test and folding test

Using a Gardner type mandrel bending tester ("No. 550 Gardner type mandrel bending tester" manufactured by Yasuda Seiki Co., Ltd.) according to ASTM-D522, the sliced inorganic film was rolled outward. Wrap around a 3 mm diameter rod and fold it 180 degrees in about 1 second. Repeat this operation 10 times. A sample for measuring a water vapor permeability was prepared so that the portion abutting on the rod in the bending test was slightly centered, and the water vapor permeability was measured in the same manner as in the above (7).

[Example 1]

A cyclic olefin resin film having a thickness of 50 μm (Zeonor Film (registered trademark) ZF14-050 of Japan ZEON Co., Ltd.: hysteresis amount Re550=3 nm; a single-sided pre-laminated PET protective film) is not laminated with a protective film. The area layer contains a gas barrier layer of the following inorganic film to form a gas barrier film. The thickness of the inorganic film was adjusted to 130 nm.

<Lamination of inorganic film>

Using a wound sputter ‧ CVD apparatus 1 having the structure shown in FIG. 2, a sputtering target of a mixed sintered material composed of zinc oxide, cerium oxide and aluminum oxide is placed on the sputtering electrode 12, and argon gas and oxygen gas are used. In the sputtering, an inorganic film is laminated on one surface of the cyclic olefin resin film to obtain a gas barrier film 4.

The specific operation is as follows. First, the sputter electrode 12 is provided with a sputter-plated CVD apparatus 1 having a sputter target sintered at a mass ratio of zinc oxide/ceria/alumina of 77/20/3. In the winding chamber 6, the surface of one side of the inorganic film provided with the annular olefin resin film is attached to the winding shaft 7 so as to face the sputtering electrode 12, and is wound up, and the winding side guide roller 8 is 9, 10, through the cooling drum 11. Argon gas and oxygen gas were introduced at a partial pressure of oxygen of 10% by a pressure of 2 × 10 ^-1 Pa, and an input power of 4000 W was applied by a DC power source to generate an argon gas/oxygen plasma to form an inorganic film. The thickness is adjusted according to the film transport speed. Thereafter, the winding shaft 16 is wound around the winding side guide rolls 13, 14, and 15.

With respect to the composition of the inorganic film, the Zn atom concentration was 27.5 atom%, the Si atom concentration was 13.1 atom%, the Al atom concentration was 2.3 atom%, and the O atom concentration was 57.1 atom%.

[Embodiment 2]

In addition, it was changed to a cyclic olefin resin film having a thickness of 23 μm (Zeonor Film (registered trademark) ZF14-023 of Japan ZEON Co., Ltd.: hysteresis amount Re550=3 nm: a single-sided pre-laminated PET protective film), and an inorganic film A gas barrier film was produced in the same manner as in Example 1 except that the thickness was changed to 50 nm.

[Example 3]

A gas barrier film having a function as a retardation film (λ/4 plate) was produced in the following manner. In other words, a cyclic olefin resin film having a thickness of 28 μm and a hysteresis amount of Re550 of 140 nm (Zeonor Film (registered trademark) ZM14-140 of Japan ZEON Co., Ltd.: a PET protective film laminated on one side) has an unstacked layer. On the surface of the protective film, an inorganic film was laminated in the same manner as in Example 1 to form a gas barrier film. However, the thickness of the inorganic film was adjusted to 50 nm.

[Comparative Example 1]

A 50-m thick cyclic olefin resin film (Zeonor Film (registered trademark) ZF14-050 of Japan ZEON Co., Ltd.: hysteresis amount Re550=3 nm: a single-sided pre-laminated PET protective film) The surface was subjected to a corona treatment, and the coating liquid for a hard coat layer described below was applied as a primer layer by a gravure coater, dried at 90 ° C, and then irradiated with ultraviolet rays at 400 mJ/cm ² to be hardened to form a hard coat layer. This hard coat layer has a thickness of 2 μm.

<Undercoat layer (coating solution for hard coat layer)>

The ultraviolet curable resin coating liquid containing the urethane acrylate oligomer ("Synthesis Chemical Co., Ltd." "UV-1700B") was diluted with an organic solvent (MEK) to have a solid content concentration of 20% by mass.

<Layer of gas barrier layer>

On the surface of the hard coat layer of the cyclic olefin resin film in which the hard coat layer was laminated, the inorganic film was formed in the same manner as in Example 1 to obtain a gas barrier film.

[Comparative Example 2]

A 50-m thick cyclic olefin resin film (Zeonor Film (registered trademark) ZF14-050 of Japan ZEON Co., Ltd.: hysteresis amount Re550=3 nm: a single-sided pre-laminated PET protective film) On the surface, an inorganic film having a thickness of 100 nm was laminated in the same manner as in Example 1. Next, on the inorganic film, a SiO ₂ film was deposited by chemical vapor deposition (CVD) using hexamethyldiaziridine as a raw material by a roll-type sputtering CVD apparatus 1 having the structure shown in Fig. 2 . This SiO ₂ film had a thickness of 120 nm.

[Comparative Example 3]

A gas barrier was produced in the same manner as in Example 1 except that the base film was changed to a polyethylene terephthalate film ("Lumirror (registered trademark)" U48) manufactured by TORAY Co., Ltd., having a thickness of 50 μm. Film.

[Comparative Example 4]

The same procedure as in Comparative Example 1 except that the base film in Comparative Example 1 was changed to a polyethylene terephthalate film ("Lumirror (registered trademark)" U48) manufactured by TORAY Co., Ltd., having a thickness of 50 μm. The method is to form a gas barrier film.

[Comparative Example 5]

A laminated olefin resin film having a thickness of 50 μm (Zeonor Film (registered trademark) ZF14-050, manufactured by Japan ZEON Co., Ltd.: hysteresis amount Re550 = 3 nm; a single-sided pre-laminated PET protective film) On the surface, a ruthenium dioxide film (SiO ₂ film) having a thickness of 200 nm was laminated using a wound sputter ‧ CVD apparatus 1 having the structure shown in FIG. 2 .

[Comparative Example 6]

A laminated olefin resin film having a thickness of 50 μm (Zeonor Film (registered trademark) ZF14-050, manufactured by Japan ZEON Co., Ltd.: hysteresis amount Re550 = 3 nm; a single-sided pre-laminated PET protective film) On the surface, a tantalum nitride film (SiN film) having a thickness of 200 nm was laminated using a wound sputter ‧ CVD apparatus having the structure shown in FIG. The tantalum nitride film is produced by causing plasma to be generated in a mixed gas containing SiH ₄ , NH ₃ , and N ₂ .

[assessment]

The above-described measurement and evaluation were carried out for the gas barrier films obtained in the above examples and comparative examples. The results are shown in Table 1. Further, the above measurement and evaluation were carried out in a state where the protective film was peeled off.

In the table, COP represents a cyclic olefin resin film, and PET represents a polyethylene terephthalate film. HC represents a hard coat layer.

As is clear from Table 1, Examples 1 to 3 were excellent in water vapor permeability, gas barrier properties, and total light transmittance.

On the other hand, in Comparative Example 1, since the undercoat layer (hard coat layer) was disposed between the cyclic olefin resin film and the gas barrier layer, the flexibility (A) of the gas barrier layer was lowered.

In Comparative Example 2, as the gas barrier layer, since the inorganic film of the film of the present invention and the other film (SiO ₂ film) were laminated, the flexibility (A) of the gas barrier layer was lowered.

In Comparative Example 3, the inorganic film of the film of the present invention was directly laminated on a polyethylene terephthalate film (PET film), but the gas barrier property (water vapor transmission rate) was poor. The reason for this is presumed to be that the PET film is less affected by the smoothness than the cyclic olefin resin film. Moreover, since a PET film is used as a base film, the total light transmittance is lowered.

In Comparative Example 4, a polyethylene terephthalate film (PET film) was laminated with a gas barrier layer (an inorganic film of the film of the present invention) via an undercoat layer (hard coat layer) to block gas. Although the properties (water vapor transmission rate) are good, the flexibility (A) of the gas barrier layer is lowered, and the total light transmittance is also lowered.

In the case of Comparative Examples 5 and 6, it is a gas barrier film in which an inorganic film of the film of the present invention is provided instead of a ruthenium dioxide film (SiO ₂ film) or a tantalum nitride film (SiN film), but gas barrier properties, Flexibility and total light transmittance are poor.

Further, in the sections of the gas barrier film of Examples 1 to 3, substantially no micro-cracks were generated in the cut portion of the gas barrier layer, and the increase in the water vapor permeability after the folding test was suppressed.

On the other hand, Comparative Examples 1 and 4 in which an undercoat layer (hard coat layer) was provided, Comparative Example 2 in which an inorganic film of a film of the present invention was laminated and another film (SiO ₂ film), and a ruthenium dioxide film (SiO) were provided. ₂ film) or tantalum nitride film (SiN film) instead of the inorganic film of the film of the present invention, the gas barrier film of Comparative Examples 5 and 6 all produced micro cracks in the cut portion of the gas barrier layer, and the folding test The subsequent water vapor transmission rate has increased significantly.

[Example 11]

Before the gas barrier film of Example 1 was produced, the protective film of the cyclic olefin resin film was peeled off, and the following coating liquid a1 for the cured resin layer was applied to the release surface by a gravure coater, and dried at 90 ° C. 400 mJ/cm ^{2 was} irradiated with ultraviolet rays to be hardened to form a cured resin layer.

The thickness of the cured resin layer was 1.5 μm, the average particle diameter of the particles was 0.08 μm, and the ratio (r/d) of the average particle diameter (r: μm) of the particles to the thickness (d: μm) of the cured resin layer was 0.05. Further, the hardened resin layer has a pencil hardness of F.

<Coating liquid a1 for a resin layer)

The following oxidizing agent was added to the AICA Kogyo Co., Ltd. UV-curable coating agent "AICAAITRON (registered trademark)" Z-850-3 in terms of solid content in a manner of 10% by mass based on the total solid content of the coating liquid. The cerium particle dispersion b1 was diluted with an organic solvent (MEK) to prepare a coating liquid having a solid content concentration of 20% by mass.

(cerium oxide particle dispersion b1)

The vapor phase cerium oxide ("AEROSIL (registered trademark)" OX50) of AEROSIL (Japan) was dispersed in an organic solvent (MEK) to obtain a dispersion having a cerium oxide concentration of 15% by mass. A bead mill is used as the dispersing device.

Next, 8 parts by mass of fluoroalkyl alkoxy decane ("KBM7103" manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 300 parts by mass of this dispersion, and the mixture was heated and stirred at 50 ° C for 1 hour to obtain a surface-treated two. A dispersion of cerium oxide particles.

<Layer of gas barrier layer (inorganic film)>

On the opposite side to the surface of the cured resin layer of the cyclic olefin resin film in which the cured resin layer was laminated, a gas barrier layer (inorganic film) was laminated in the same manner as in Example 1 to form a gas barrier film.

[Embodiment 12]

Before the gas barrier film of Example 2 was produced, the protective film of the cyclic olefin resin film was peeled off, and the cured resin layer was laminated in the same manner as in Example 11 on the release surface. Then, a gas barrier layer (inorganic film) was laminated in the same manner as in Example 2 on the opposite side to the surface of the cured resin layer of the cyclic olefin resin film in which the cured resin layer was laminated to form a gas barrier film.

[Example 13]

Before the gas barrier film of Example 3 was produced, the protective film of the cyclic olefin resin film was peeled off, and the cured resin layer was laminated in the same manner as in Example 11 on the release surface. Then, a gas barrier layer (inorganic film) was laminated in the same manner as in Example 3 on the opposite side to the surface of the cured resin layer of the cyclic olefin resin film in which the cured resin layer was laminated to form a gas barrier film.

[Comparative Example 11]

The protective film of the cyclic olefin resin film was peeled off before the production of the gas barrier film of Comparative Example 1, and the coating liquid a2 for the cured resin layer described below was applied to the release surface by a gravure coater, and dried at 90 ° C. 400 mJ/cm ^{2 was} irradiated with ultraviolet rays to be hardened to form a cured resin layer.

The thickness of the cured resin layer was 1.5 μm, the average particle diameter of the particles was 0.08 μm, and the ratio (r/d) of the average particle diameter (r: μm) of the particles to the thickness (d: μm) of the cured resin layer was 0.05. The hardened resin layer has a pencil hardness of H.

Then, the hard coat layer and the gas barrier layer (inorganic film) were sequentially laminated in the same manner as in Comparative Example 1 on the opposite side to the surface of the cured resin layer of the cyclic olefin resin film in which the cured resin layer was laminated. Gas film.

<Coating liquid for hardened resin layer a2>

The ultraviolet curable resin coating liquid containing the urethane acrylate oligomer ("UV-1700B" of Nippon Synthetic Chemical Co., Ltd.) is 8 mass based on the total solid content of the coating liquid in terms of solid content. The above-described ceria particle dispersion b1 was added in an amount of %, and diluted with an organic solvent (MEK) to prepare a coating liquid having a solid content concentration of 20% by mass.

[Comparative Example 12]

Before the gas barrier film of Comparative Example 2 was produced, the protective film of the cyclic olefin resin film was peeled off, and the following coating liquid a3 for the cured resin layer was applied to the release surface by a gravure coater, and dried at 90 ° C. 400 mJ/cm ^{2 was} irradiated with ultraviolet rays to be hardened to form a cured resin layer.

The thickness of this hardened resin layer was 1.5 μm. The hardened resin layer has a pencil hardness of H.

Then, the hard coat layer and the gas barrier layer (inorganic film) were sequentially laminated in the same manner as in Comparative Example 2 on the opposite side to the surface of the cured resin layer of the cyclic olefin resin film in which the cured resin layer was laminated. Gas film.

<Coating liquid for hardened resin layer a3>

The ultraviolet curable resin coating liquid containing the urethane acrylate oligomer ("Synthesis Chemical Co., Ltd." "UV-1700B") was diluted with an organic solvent (MEK) to prepare a solid content concentration of 20% by mass. Coating solution.

[assessment]

The above-described measurement and evaluation were carried out for the gas barrier films obtained in the above examples and comparative examples. The results are shown in Table 2.

In the table, COP represents a cyclic olefin resin film. HC represents a hard coat layer.

Claims (11)

 A gas barrier film which is a gas barrier film having a gas barrier layer containing a single inorganic film directly on at least one side of a cyclic olefin resin film, wherein the inorganic film contains at least zinc oxide, cerium oxide, and aluminum oxide .    The gas barrier film according to claim 1, wherein the inorganic film has a Zn atom concentration of 20 to 40 atom%, an atomic concentration of 5 to 20 atom%, and Al measured by X-ray photoelectron spectroscopy (XPS method). The atomic concentration is 0.5 to 5 atom%, and the O atom concentration is 35 to 70 atom%.    The gas barrier film according to claim 1 or 2, wherein the cyclic olefin resin film has a retardation amount (Re550) in the in-plane direction of light having a wavelength of 550 nm of 500 nm or less.    The gas barrier film according to any one of claims 1 to 3, wherein the cyclic olefin resin film has a function as a retardation film.    The gas barrier film according to any one of claims 1 to 4, wherein the cyclic olefin resin film has a thickness of less than 100 μm.    The gas barrier film according to any one of claims 1 to 5, wherein the thickness of the inorganic film is in the range of 30 to 60 nm or in the range of 120 to 170 nm.    The gas barrier film according to claim 5 or 6, wherein the cyclic olefin resin film has a thickness of less than 50 μm, and the inorganic film has a thickness of 30 to 60 nm.    The gas barrier film according to any one of claims 1 to 7, which has a cured resin layer on a surface opposite to a surface of the cyclic olefin resin film having a gas barrier layer.    The gas barrier film according to claim 8, wherein the hardened resin layer contains particles, and a ratio (r/d) of an average particle diameter (r: μm) of the particles to a thickness (d: μm) of the cured resin layer is 0.7. the following.    The gas barrier film according to claim 8 or 9, wherein the surface roughness (Ra) of the cured resin layer measured by atomic force microscopy is 2.0 nm or more and 10.0 nm or less.    An organic EL device comprising the gas barrier film according to any one of claims 1 to 10.