KR102446746B1 - Gas barrier film and device comprising same - Google Patents

Abstract

The purpose of providing light resistance to a moisture-proof gas barrier film used for a flexible display is to suppress UV deterioration inside the device lower than the gas barrier film, and/or suppress UV deterioration of the gas barrier film itself. .
A gas barrier film having a base layer comprising at least a flexible substrate, an inorganic thin film layer, and an organic layer containing an ultraviolet absorber in this order, wherein the inorganic thin film layer contains silicon atoms, oxygen atoms and carbon atoms, A gas barrier film having a light transmittance of 20% or less at 380 nm is provided.

Description

Gas barrier film and device comprising same

The present invention relates to a gas barrier film and a device comprising the same.

BACKGROUND ART Gas barrier films used for organic EL displays and the like have been proposed.

Japanese Patent Laid-Open No. Hei 8-187825 Japanese Patent Laid-Open No. 2006-297737 Japanese Patent Laid-Open No. 2011-194766 Japanese Patent Laid-Open No. 2012-6154 Japanese Patent Laid-Open No. 2013-154584 Japanese Patent Laid-Open No. 2012-6154 Japanese Patent Laid-Open No. 2014-189585 Japanese Patent Laid-Open No. 2014-226894

However, the light resistance of the gas barrier film was not satisfactory. Therefore, the present invention provides light resistance to a gas barrier film for moisture-proof purposes used for devices such as flexible displays, suppressing UV deterioration inside the device lower than the gas barrier film, and/or UV of the gas barrier film itself It aims at suppression of deterioration.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, when the present inventors repeated examination in detail about a gas barrier film, it came to complete this invention.

That is, this invention includes the following suitable aspects.

[1] A gas barrier film having a substrate layer including at least a flexible substrate, an inorganic thin film layer, and an organic layer containing an ultraviolet absorber in this order, comprising:

The inorganic thin film layer contains a silicon atom, an oxygen atom and a carbon atom,

The gas barrier film whose light transmittance in 380 nm of the said gas barrier film is 20 % or less.

[2] The gas barrier film according to [1], wherein an additional inorganic thin film layer is provided on the surface of the substrate layer on the opposite side to the ultraviolet absorber-containing organic layer side.

[3] The gas barrier film according to [1] or [2], wherein the substrate layer has the organic layer (A) on at least one surface of the flexible substrate.

[4] The gas barrier film according to any one of [1] to [3], wherein the organic layer (A) is a layer selected from the group consisting of a lubricity layer and a flat layer.

[5] Any of [1] to [4], wherein the atomic ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer continuously changes in the thickness direction of the inorganic thin film layer The gas-barrier film as described in it.

[6] The inorganic thin film layer is the gas barrier according to any one of [1] to [5], wherein the average atomic ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is in the range of formula (1). sex film.

0.10<C/Si<0.50 (1)

[7] The distance from the surface of the inorganic thin film layer in the thickness direction of the inorganic thin film layer and the silicon to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer at each distance In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve respectively showing the relationship between the atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio, [1] to [6] satisfying conditions (i) and (ii) The gas barrier film according to any one of ].

(i) the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfies the condition represented by formula (5) in a region of 90% or more in the thickness direction of the inorganic thin film layer;

Atomic ratio of oxygen > Atomic ratio of silicon > Atomic ratio of carbon (5)

(ii) the carbon distribution curve has at least one extreme value.

[8] A device comprising the gas barrier film according to any one of [1] to [7] so that a coating layer containing an ultraviolet absorber becomes an outermost layer.

[9] When the surface of the inorganic thin film layer is measured by the ATR method of infrared spectroscopy, the peak intensity (I ₁ ) at 950 to 1050 cm ^-1 and the peak intensity at 1240 to 1290 cm ^-1 (I) The gas barrier film according to any one of [1] to [7], wherein the strength ratio of ₂ ) is in the range of formula (2).

0.01≤I ₂ /I ₁ <0.05 (2)

[10] When the surface of the inorganic thin film layer was measured by the ATR method of infrared spectroscopy, the peak intensity at 950 to 1050 cm ^-1 (I ₁ ) and the peak intensity at 770 to 830 cm ^-1 (I ₃ ) ), the gas barrier film according to any one of [1] to [7] and [9], wherein the strength ratio is in the range of formula (3).

0.25≤I ₃ /I ₁ ≤0.50 (3)

[11] When the surface of the inorganic thin film layer was measured by the ATR method of infrared spectroscopy, the peak intensity (I ₃ ) at 770 to 830 cm ^-1 and the peak intensity at 870 to 910 cm ^-1 (I ₄ ) ), the gas barrier film according to any one of [1] to [7], [9] and [10], wherein the strength ratio is in the range of formula (4).

0.70≤I ₄ /I ₃ <1.00 (4)

Since the gas barrier film of this invention has sufficient light resistance and flexibility, it can be used suitably for a device.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the manufacturing apparatus for manufacturing the gas-barrier film in an Example.

The gas barrier film of the present invention has a substrate layer having at least a flexible substrate, an inorganic thin film layer, and a coating layer containing an ultraviolet absorber in this order, wherein the inorganic thin film layer contains silicon atoms, oxygen atoms and carbon atoms, The light transmittance in 380 nm of a gas barrier film is 20 % or less.

(substrate layer)

A base material layer has a flexible base material at least. A single layer or multiple layers may be sufficient as a base material layer. When a base material layer is a single|mono layer, it is preferable that the base material layer is comprised by the flexible base material. When the substrate layer is a plurality of layers, it is preferable that the substrate layer has at least a flexible substrate and the substrate layer exhibits flexibility, and it is more preferable that the surface of the substrate layer on which the inorganic thin film layer is laminated is a flexible substrate, It is more preferable that the plurality of layers are each composed of a flexible substrate.

(Flexible base material)

As a flexible base material, the resin film containing at least 1 sort(s) of resin can be used as a resin component, A colorless and transparent resin film is preferable. As resin which can be used for a resin film, For example, polyester resins, such as a polyethylene terephthalate (PET) and a polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; polyamide resin; polycarbonate resin; polystyrene resin; polyvinyl alcohol resin; saponified products of ethylene-vinyl acetate copolymers; polyacrylonitrile resin; acetal resin; polyimide resin; Polyether sulfide (PES) is mentioned, You can also use them combining 2 or more types as needed. Among these, it is preferable to select and use from polyester resin and polyolefin resin according to required characteristics, such as transparency, heat resistance, and linear expansion property, and it is more preferable to use PET, PEN, and a cyclic polyolefin.

The flexible substrate may be an unstretched resin film, and the unstretched resin substrate is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. by a known method, The resin film extended|stretched in the flow direction (MD direction) of a resin base material and/or the flow direction of a resin base material and the direction perpendicular|vertical (TD direction) may be sufficient.

The thickness of the flexible substrate can be appropriately set in consideration of production of a stable gas barrier film. For example, from a viewpoint that a film can be conveyed also in vacuum, it is preferable that it is 5-500 micrometers, It is more preferable that it is 10-200 micrometers, It is more preferable that it is 50-100 micrometers. When a base material layer is a single layer of a flexible base material, the thickness of a base material layer becomes like the above, Preferably it is 5-500 micrometers, More preferably, it is 10-200 micrometers, More preferably, it is 50-100 micrometers. When a base material layer is multiple, the thickness of the sum total of all the layers which comprise the base material layer containing a flexible base material becomes like this. Preferably it is 5-500 micrometers, More preferably, it is 10-200 micrometers, More preferably, 50 to 100 μm.

The layer constituting the flexible substrate may be a retardation film in which the refractive indices of two orthogonal components in the plane, such as a λ/4 retardation film and a λ/2 retardation film, differ from each other. As a material of the retardation film, a cellulose-based resin, a polycarbonate-based resin, a polyarylate-based resin, a polyester-based resin, an acrylic resin, a polysulfone-based resin, a polyethersulfone-based resin, a cyclic olefin-based resin, an alignment-solidified layer of a liquid crystal compound etc. can be exemplified. Among them, a polycarbonate-based resin film is preferably used because a uniform film can be obtained at a low cost. As a film forming method, although the solvent casting method, the precision extrusion method which can make small the residual stress of a film, etc. can be used, the solvent casting method is used preferably from a point of uniformity. The stretching method is not particularly limited, and can be applied such as longitudinal uniaxial stretching between rolls, or transverse uniaxial stretching between rolls in which uniform optical properties are obtained.

When the layer constituting the flexible substrate is a λ/4 retardation film, the in-plane retardation (Re(550)) at a wavelength of 550 nm is preferably 100 to 180 nm, more preferably 110 to 170 nm, , more preferably 120 to 160 nm.

When the layer constituting the flexible substrate is a λ/2 retardation film, the in-plane retardation (Re(550)) at a wavelength of 550 nm is preferably 220 to 320 nm, more preferably 240 to 300 nm. , more preferably 250 to 280 nm.

When the flexible substrate is a retardation film, the retardation value may exhibit reverse wavelength dispersion, which increases with the wavelength of the measurement light, or it may exhibit a positive wavelength dispersion characteristic in which the retardation value decreases with the wavelength of the measurement light. , a flat wavelength dispersion characteristic in which the phase difference value hardly changes even with the wavelength of the measurement light may be exhibited.

When the flexible substrate is a retardation film exhibiting reverse wavelength dispersion and the retardation at the wavelength λ of the flexible substrate is expressed as Re(λ), the flexible substrate 10 is Re(450)/Re(550) )<1 and Re(650)/Re(550)>1 may be satisfied.

The flexible substrate is preferably colorless and transparent from the viewpoint of being able to transmit or absorb light. More specifically, it is preferable that a total light transmittance is 80 % or more, and it is more preferable that it is 85 % or more. Moreover, it is preferable that a cloudiness value (haze) is 5 % or less, It is more preferable that it is 3 % or less, It is more preferable that it is 1 % or less.

It is preferable that a flexible base material is insulating from a viewpoint that it can be used for the base material of an organic device or an energy device, and it is preferable that electrical resistivity is 10 ⁶ Ωcm or more.

The surface of the flexible substrate may be subjected to a surface active treatment from the viewpoint of adhesion to an inorganic thin film layer or the like. Examples of the surface active treatment include corona treatment, plasma treatment, frame treatment, and liquid cleaning treatment.

(organic layer (A))

A base material layer may also contain the organic layer (A) of the same or different kind on the at least one surface of a flexible base material for the purpose of improving adhesiveness with an inorganic thin film layer and/or flatness. When a base material layer is a multiple layer, you may also contain the organic layer (A) of the same or different kind in the at least one surface of the flexible base material which comprises a base material layer similarly. As an example of a preferred embodiment, the surface of the substrate layer on which the inorganic thin film layer can be laminated (that is, at least one surface of the surface of the substrate layer) is a flexible substrate, and at least one surface of the flexible substrate, more preferably The embodiment which has an organic layer (A) on the surface on which an inorganic thin film layer is laminated|stacked is mentioned. As an example of another preferable embodiment, both surfaces of a base material layer are a flexible base material, At least one surface of this flexible base material, More preferably, the embodiment which has an organic layer (A) on the surface on which an inorganic thin film layer is laminated|stacked is mentioned. can The thickness of an organic layer becomes like this. Preferably it is 0.5-10 micrometers, More preferably, it is 0.8-5 micrometers, More preferably, it is 1-3 micrometers. As an organic layer (A), a planarization layer, a lubricity layer, and an anti-blocking layer are mentioned, for example.

When a base material layer contains an organic layer (A), a base material layer has an organic layer only on one surface of a flexible base material, What has a different kind of organic layer on both surfaces of a flexible base material, for example, one It may have a flat layer on the surface of , and may have a lubricity layer on the other surface.

The organic layer (A) is usually coated with a resin composition containing a monomer and/or an oligomer of a photocurable resin such as an ultraviolet or electron beam curable resin on a flexible substrate, dried if necessary, and then subjected to ultraviolet or electron beam irradiation. It can be formed by curing. The resin composition may contain additives, such as a solvent, a photoinitiator, a thermal polymerization initiator, antioxidant, a ultraviolet absorber, and a plasticizer, as needed.

Examples of the coating method include various coating methods conventionally used, for example, spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, reverse roll coating, gravure coating. , extrusion coating, and the like.

A planarization layer is formed by apply|coating a UV curable resin on a base material, and making it UV harden. For example, UV curable urethane acrylate resin, UV curable epoxy acrylate resin, UV curable polyester acrylate resin, UV curable epoxy resin, UV curable polyol acrylate resin, etc. are mentioned.

As the flattening layer, when the temperature change of the elastic modulus of the flattening layer surface is evaluated by a rigid pendulum type physical property tester (for example, A&D Co., Ltd. RPT-3000W, etc.), the flattening layer surface It is preferable that the temperature at which the elastic modulus of is reduced by 50% or more is 150°C or more.

The lubricity layer is formed by, for example, applying a UV curable resin containing inorganic particles on a substrate and UV curing. Examples of the UV curable resin include UV curable urethane acrylate resin, UV curable epoxy acrylate resin, UV curable polyester acrylate resin, UV curable epoxy resin, and UV curable polyol acrylate resin. Examples of the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, and zirconium oxide. When an organic layer (A) is a lubricity layer, it can make it easy to roll convey a gas barrier film.

(Inorganic thin film layer)

The inorganic thin film layer has at least a silicon atom (Si), an oxygen atom (O) and carbon Contains atom (C). As an inorganic thin film layer, the layer of the inorganic material which has well-known gas-barrier property can be used suitably. One layer may be sufficient as an inorganic thin film layer, and multiple layers may be sufficient as it. In addition, the process of forming an inorganic thin film layer may be one time, and may be performed multiple times. When performing multiple times, it may be performed under the same conditions, and may be performed under different conditions.

Examples of the inorganic material are metal oxides, metal nitrides, metal oxynitrides, metal oxycarbides, and mixtures containing at least two of them. Moreover, as a layer of an inorganic material, the multilayer film which laminated|stacked the above-mentioned inorganic thin film layer in two or more layers can also be used. In addition, an inorganic thin film layer can be provided in one or both surfaces of a base material layer.

The inorganic thin film layer may be a main component of a compound represented by the general formula SiO _α C _β [wherein α and β each independently represent a positive number less than 2]. Here, "it is a main component" means that the content of the component is 50 mass % or more, preferably 70 mass % or more, more preferably 90 mass % or more with respect to the mass of all components constituting the inorganic thin film layer. The inorganic thin film layer may contain one type of compound represented by the general formula SiO _α C _β , or may contain two or more types of compounds represented by the general formula SiO _α C _β . 1 or more of (alpha) and (beta) in the said General formula may be a fixed value in the thickness direction of an inorganic thin film layer, and may change.

In addition, the inorganic thin film layer contains one or more atoms of an element other than a silicon atom, an oxygen atom and a carbon atom, for example, a hydrogen atom, a nitrogen atom, a boron atom, an aluminum atom, a phosphorus atom, a sulfur atom, a fluorine atom, and a chlorine atom. may be doing

When the inorganic thin film layer contains a hydrogen atom in addition to a silicon atom, an oxygen atom and a carbon atom, the general formula is SiO _α C _β H _γ [wherein α and β are synonymous with the above, and γ is less than 6 It is preferable that the compound represented by ] is the main component. Here, "it is a main component" means that the content of the component is 50 mass % or more, preferably 70 mass % or more, more preferably 90 mass % or more with respect to the mass of all components constituting the inorganic thin film layer. The inorganic thin film layer may contain one type of compound represented by the general formula SiO _α C _β H _γ , or may contain two or more types of compounds represented by the general formula SiO _α C _β H _γ . One or more of α, β, and γ in the general formula may be a constant value in the thickness direction of the thin film layer, or may change.

In the inorganic thin film layer, when the average atomic ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is expressed as C/Si, the density is increased, and defects such as fine voids and cracks are reduced. The range of C/Si preferably satisfies the formula (1).

0.10<C/Si<0.50 (1)

Further, more preferably in the range of 0.15<C/Si<0.45, more preferably in the range of 0.20<C/Si<0.40, and particularly preferably in the range of 0.25<C/Si<0.35.

In addition, when the average atomic ratio of oxygen atoms (O) to silicon atoms (Si) in the inorganic thin film layer is expressed as O/Si, the inorganic thin film layer increases the compactness and reduces defects such as fine voids and cracks. , preferably in the range of 1.50<O/Si<1.90, more preferably in the range of 1.55<O/Si<1.85, more preferably in the range of 1.60<O/Si<1.80, and more preferably in the range of 1.65<O/Si<1.80. It is especially preferable to exist in the range of Si<1.75.

In addition, the average atomic ratio C/Si and O/Si is the average atomic concentration in the thickness direction of each atom from the distribution curve of the silicon atom, oxygen atom, and carbon atom obtained by performing XPS depth profile measurement under the following conditions. After obtaining , the average atomic ratio C/Si and O/Si can be calculated.

<XPS Depth Profile Measurement>

Etching ion species: Ar (Ar ⁺ )

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

Etching gap (SiO ₂ conversion value): 10 nm

X-ray photoelectron spectroscopy device: manufactured by Thermo Fisher Scientific, model name "VG Theta Probe"

Irradiation X-ray: single crystal spectroscopy AlKα

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

The inorganic thin film layer has a peak intensity (I 1 ) present at 950 to 1050 cm ^-1 and a peak intensity (I ₁ ) present at 1240 to 1290 cm ^-1 when infrared spectroscopy (ATR method) is performed on the surface of the inorganic thin film layer. The intensity ratio of ₂ ) may exist in the range which satisfy|fills Formula (2).

0.01≤I ₂ /I ₁ <0.05 (2)

The peak intensity ratio (I ₂ /I ₁ ) calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si-CH ₃ to Si-O-Si in the inorganic thin film layer. Since the inorganic thin film layer satisfying the relationship expressed by the formula (2) has high compactness and fewer defects such as fine voids and cracks, it is considered to be excellent in gas barrier properties and excellent in impact resistance. With respect to the range of the peak intensity ratio (I ₂ /I ₁ ), the range of 0.02≤I ₂ /I ₁ <0.04 is preferable from the viewpoint of maintaining high density of the inorganic thin film layer.

Moreover, when the range _of the said peak intensity ratio ( _I2 /I1) is satisfy|filled, a gas barrier film becomes easy to slide moderately, and it becomes more difficult to block. Conversely, when I ₂ /I ₁ is large, that is, when there is too much Si-C, there exists a tendency for a flexibility to become bad and to become slippery. Moreover, even when I2/I1 is small, ie, Si _{- C} is too small, there exists a tendency for a flexibility to fall.

Infrared spectroscopy of the surface of the inorganic thin film layer can be measured with a Fourier transform infrared spectrophotometer (manufactured by Nippon Spectroscopy Co., Ltd., FT/IR-460Plus) equipped with an ATR attachment (PIKE MIRacle) using a germanium crystal to a prism. have.

The inorganic thin film layer has a peak intensity (I ₁ ) present at 950 to 1050 cm ⁻¹ and a peak intensity (I ) present at 770 to 830 cm ⁻¹ when infrared spectroscopy (ATR method) is performed on the surface of the inorganic thin film layer. The intensity ratio of ₃ ) may exist in the range of Formula (3).

0.25≤I ₃ /I ₁ ≤0.50 (3)

It is considered that the peak intensity ratio (I ₃ /I ₁ ) calculated from infrared spectroscopy (ATR method) represents a relative ratio of Si-C or Si-O to Si-O-Si in the inorganic thin film layer. It is thought that the inorganic thin film layer which satisfy|fills the relationship represented by Formula (3) is excellent in bending resistance at the point which carbon is introduce|transduced, maintaining high compactness, and is excellent in impact resistance. With respect to the range of the peak intensity ratio (I ₃ /I ₁ ), the range of 0.25≤I ₃ /I ₁ ≤0.50 is preferable, and 0.30≤I ₃ / The range of I ₁ ≤ 0.45 is more preferable.

The inorganic thin film layer has a peak intensity (I ₃ ) at 770 to 830 cm ⁻¹ and a peak intensity at 870 to 910 cm ⁻¹ (I) when infrared spectroscopy (ATR method) is performed on the surface of the inorganic thin film layer. The intensity ratio of ₄ ) may be in the range of Formula (4).

0.70≤I ₄ /I ₃ <1.00 (4)

The peak intensity ratio (I ₄ /I ₃ ) calculated from infrared spectroscopy (ATR method) is considered to represent the ratio of peaks related to Si-C in the inorganic thin film layer. It is thought that the inorganic thin film layer which satisfy|fills the relationship represented by Formula (4) is excellent in bending resistance at the point which carbon is introduce|transduced, maintaining high compactness, and is excellent in impact resistance. With respect to the range of the peak intensity ratio (I ₄ /I ₃ ), from the viewpoint of maintaining the balance between the compactness and bending resistance of the inorganic thin film layer, the range of 0.70≤I ₄ /I ₃ <1.00 is preferable, and 0.80≤I ₄ / The range of I ₃ <0.95 is more preferable.

It is preferable that the thickness of an inorganic thin film layer is 5-3000 nm from a viewpoint of making it hard to break when an inorganic thin film layer is bent. In the case of forming the inorganic thin film layer by plasma CVD using glow discharge plasma, from the viewpoint of forming the inorganic thin film layer while discharging through the substrate, it is more preferably 10 to 2000 nm, and 100 to 1000 nm. More preferably, it is nm.

The inorganic thin film layer may have an average density of 1.8 g/cm 3 or more. In addition, the "average density" of the inorganic thin film layer is the number of silicon atoms, the number of carbon atoms, the number of oxygen atoms, and the hydrogen forward scattering spectrometry method (Hydrogen Forward scattering Spectrometry: HFS), the weight of the inorganic thin film layer in the measurement range is calculated from the number of hydrogen atoms, and divided by the volume of the inorganic thin film layer in the measurement range (the product of the ion beam irradiation area and the film thickness). When the inorganic thin film layer has a density of 1.8 g/cm 3 or more, the inorganic thin film layer has a high density and has a structure with few defects such as fine voids and cracks. Moreover, when the inorganic thin film layer consists of a silicon atom, an oxygen atom, a carbon atom, and a hydrogen atom, it is preferable that the average density of an inorganic thin film layer is less than 2.22 g/cm<3>.

A curve showing the relationship between the distance from the surface of the inorganic thin film layer in the thickness direction of the inorganic thin film layer and the atomic ratio of silicon atoms at each distance is called a silicon distribution curve. 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. In addition, the curve which shows the relationship between the distance from the said inorganic thin film layer surface in the film thickness direction, and the atomic ratio of carbon atoms in each distance is called a carbon distribution curve. The atomic ratio of silicon atoms, the atomic ratio of oxygen atoms and the atomic ratio of carbon atoms is each atom at each distance from the surface of the inorganic thin film layer with respect to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer. means the ratio of numbers.

From the viewpoint of easily suppressing a decrease in gas barrier properties due to bending, the atomic ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer continuously changes in the thickness direction of the inorganic thin film layer. it is preferable Here, that the atomic ratio of carbon atoms continuously changes in the thickness direction, for example, in the carbon distribution curve, the atomic ratio of carbon atoms gives a plurality of extreme values within a predetermined displacement range. indicates that the increase and decrease are continuously repeated, and that the atomic ratio of carbon does not include a discontinuous change, that is, that the atomic ratio of carbon atoms does not increase or decrease monotonically.

It is preferable from the viewpoint of gas barrier properties and flexibility that the atomic ratio and carbon distribution curve obtained from the silicon distribution curve, the oxygen distribution curve and the carbon distribution curve in the inorganic thin film layer satisfy the conditions (i) and (ii). .

(i) the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfies the condition represented by formula (5) in a region of 90% or more in the thickness direction of the inorganic thin film layer;

Atomic ratio of oxygen > Atomic ratio of silicon > Atomic ratio of carbon (5)

(ii) the carbon distribution curve has at least one extreme value.

It is preferable that the carbon distribution curve of an inorganic thin film layer is substantially continuous. That the carbon distribution curve is substantially continuous does not include the part in which the atomic ratio of carbon in the carbon distribution curve changes discontinuously. Specifically, when the distance from the surface of the inorganic thin film layer in the film thickness direction is x [nm] and the carbon atom ratio is C, it is preferable to satisfy the formula (6).

|dC/dx|≤0.01 (6)

In addition, it is preferable that the carbon distribution curve of the inorganic thin film layer has at least one extreme value. The extreme value here is the maximum value or minimum value of the atomic ratio of each element with respect to the distance from the said inorganic thin film layer surface in a film thickness direction. The extreme value is the atomic ratio at a point where the atomic ratio of an element changes from an increase to a decrease when the distance from the surface of the inorganic thin film layer in the film thickness direction is changed, or at a point where the atomic ratio of an element changes from a decrease to an increase is the value The extreme value can be calculated|required based on the atomic ratio measured in the some measurement position in the film thickness direction, for example. At the measurement position of the atomic ratio, the interval in the film thickness direction is set to, for example, 20 nm or less. In the position showing the extreme value in the film thickness direction, for example, the measurement results at three or more different measurement positions are compared with respect to a discrete data group including the measurement results at each measurement position, and the measurement result decreases from the increase. It can be obtained by finding the position at which it changes to , or the position at which it changes from decreasing to increasing. The position showing the extreme value can also be obtained, for example, by differentiating the approximate curve obtained from the discrete data group described above. When the section where the atomic ratio monotonically increases or monotonically decreases from the position showing the extreme value is, for example, 20 nm or more, the difference between the atomic ratio and the extreme value at the position moved by 20 nm in the film thickness direction from the position showing the extreme value The absolute value of is, for example, 0.03 or more.

As described above, in the inorganic thin film layer formed to satisfy the condition that the carbon distribution curve has at least one extreme value, the increase in the gas permeability after bending with respect to the gas permeability before bending is smaller compared to the case where the above condition is not satisfied . That is, the effect of suppressing the fall of the gas barrier property by bending|flexion is acquired by satisfy|filling the said condition. When the inorganic 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 reduced compared with the case where the number of extreme values of the carbon distribution curve is one. In addition, when the inorganic 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 reduced compared with the case where the number of extreme values of the carbon distribution curve is two. When the carbon distribution curve has two or more extreme values, the distance from the surface of the inorganic thin film layer in the film thickness direction at the position showing the first extreme value and the film thickness at the position showing the second extreme value adjacent to the first extreme value It is preferable that the absolute value of the difference of the distance from the said inorganic thin film layer surface in a direction exists in the range of 1 nm or more and 200 nm or less, and it is more preferable that it exists in the range of 1 nm or more and 100 nm or less.

Moreover, 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 said inorganic thin film layer is 0.01 or more. In the inorganic thin film layer formed to satisfy the above conditions, the increase in the gas permeability after bending with respect to the gas permeability before bending is small compared to the case where the above conditions are not satisfied. That is, the effect of suppressing the fall of the gas barrier property by bending|flexion is acquired by satisfy|filling the said condition. 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 increased.

The gas barrier property of the inorganic thin film layer tends to improve as 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 decreases. From such a viewpoint, the above absolute value is preferably less than 0.05 (less than 5 at%), more preferably less than 0.04 (less than 4 at%), and still more preferably less than 0.03 (less than 3 at%).

In addition, in the oxygen-carbon distribution curve, when the sum of the atomic ratio of oxygen atoms and the atomic ratio of carbon atoms at each distance is "total atomic ratio", the absolute value of the difference between the maximum value and the minimum value of the total atomic ratio It tends to improve the gas barrier property of the said inorganic thin film layer, so that this becomes low. From such a viewpoint, the said total atomic ratio becomes like this. Preferably it is less than 0.05, More preferably, it is less than 0.04, More preferably, it is less than 0.03.

When the inorganic thin film layer has substantially the same composition in the surface direction of the inorganic thin film layer, the gas barrier properties of the inorganic thin film layer can be made uniform and improved. Substantially the same composition means that, in the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon distribution curve, the number of extreme values present in each film thickness direction at two arbitrary points on the surface of the inorganic thin film layer is the same, and each carbon It means that the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in a distribution curve is mutually the same or it is a difference within 0.05.

The inorganic thin film layer formed so as to satisfy the above conditions can exhibit gas barrier properties required for, for example, flexible electronic devices using organic EL elements.

The inorganic thin film layer containing silicon atoms, oxygen atoms and carbon atoms is preferably formed by a chemical vapor deposition method (CVD method), and particularly, it is formed by a plasma chemical vapor deposition method (PECVD method) using glow discharge plasma or the like. It is more preferable to be

As an example of a raw material gas, the organosilicon compound containing a silicon atom and a carbon atom is mentioned. Examples of the organosilicon compound include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of characteristics such as handling properties of the compound and gas barrier properties of the inorganic thin film layer obtained. In addition, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more type.

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

By adjusting the flow rate ratio of the source gas and the reaction gas, the C/Si value can be controlled. For example, when using hexamethyldisiloxane (HMDSO) as the source gas and oxygen as the reaction gas, respectively, if the ratio of the oxygen flow rate to the HMDSO flow rate (O ₂ /HMDSO) is in the range of 5 to 25, C The value of /Si can be controlled within the above range.

In order to supply the said source gas in a vacuum chamber, you may use carrier gas as needed. In addition, in order to generate a plasma discharge, you may use the gas for discharge as needed. As such carrier gas and gas for discharge, a well-known thing can be used suitably, For example, Rare gases, such as helium, argon, neon, and xenon; Hydrogen can be used.

Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5-50 Pa.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the manufacturing apparatus used for manufacture of the inorganic thin film layer contained in a gas barrier film, It is a schematic diagram of the apparatus which forms an inorganic thin film layer by the plasma chemical vapor deposition method. In Fig. 1, in order to make the drawing easier to see, the dimensions, ratios, and the like of each component are appropriately different. The manufacturing apparatus shown in FIG. 1 includes a feed roll 11 , a take-up roll 71 , conveyance rolls 21 to 24 , a gas supply pipe 41 , a power supply for plasma generation 51 , and a film forming roll 31 . and magnetic field forming devices 61 and 62 respectively provided inside the 32). In the apparatus of FIG. 1, the film-forming rolls 31 and 32 also serve as an electrode, and are made into the roll-shaped electrode mentioned later.

Among the components of the manufacturing apparatus, at least a film forming roll, a gas supply pipe, and a magnetic field forming apparatus are disposed in a vacuum chamber (not shown) when forming the inorganic thin film layer. This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

By using this apparatus, by controlling the power supply for generating plasma, it is possible to generate discharge plasma of the film forming gas supplied from the gas supply pipe in the space between the two film forming rolls, and use the generated discharge plasma to form a continuous film. Plasma CVD film formation can be performed by the process.

The film 100 before film formation is installed on the delivery roll in the wound state, and is sent out, unwinding the film in the elongate direction. Moreover, a winding roll is provided in the edge part side of a film, and it winds up, pulling the film after film-forming, and accommodates it in roll shape.

It is preferable that the said two film-forming rolls extend in parallel and are opposingly arranged. Both rolls are formed of a conductive material, and each rotates to convey the film. It is preferable to use the thing of the same diameter as two film-forming rolls, for example, it is preferable to use the thing of 5 cm or more and 100 cm or less.

When the inorganic thin film layer is formed, the substrate layer is transported while closely adhering to the surface of the pair of roll-shaped electrodes, plasma is generated between the pair of electrodes, the raw material is decomposed in plasma, and the inorganic thin film layer is formed on the flexible substrate. It is preferable to form In the pair of electrodes, a magnet is preferably disposed inside the electrode so that the magnetic flux density becomes high at the electrode and the flexible substrate surface. Thereby, the plasma tends to be confined at a high density on the electrode and the flexible substrate at the time of plasma generation.

(Organic layer containing UV absorber)

The organic layer containing the ultraviolet absorber is formed on the inorganic thin film layer. When the ultraviolet absorber-containing organic layer is formed on the inorganic thin film layer, that is, when the gas barrier film of the present invention is bonded to the device, the ultraviolet absorber-containing organic layer is formed outside the inorganic thin film layer, so that the ultraviolet rays contained in electrical or electronic devices, natural light, etc. This absorption and/or shielding is carried out, and deterioration of an inorganic thin film layer or a device can be suppressed. Therefore, the gas barrier film of this invention is comprised so that it may bond with a device so that an ultraviolet absorber containing organic layer may become outside. Here, in the laminate in which the gas barrier film is bonded to the device, that the ultraviolet absorber-containing organic layer is formed "outside" of the inorganic thin film layer, the ultraviolet absorber-containing organic layer is on the opposite side to the surface side on which the device of the base layer is laminated. means to be formed. In addition, even when an inorganic thin film layer is formed on both sides of a base material layer, the organic layer containing a ultraviolet absorber should just be formed on the inorganic thin film layer on the opposite side to the surface to be bonded with a device, Preferably, the device of a gas barrier film is bonded together. It is formed in the outermost layer on the opposite side to the surface to be used.

The ultraviolet absorber-containing organic layer has a light transmittance at 380 nm of preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, still more preferably 5% or less. The light transmittance in 380 nm was measured using the spectrophotometer (Nippon Spectroscopy Co., Ltd. product ultraviolet-visible near-infrared spectrophotometer V-670).

Although there is no restriction|limiting in particular as a ultraviolet absorber, An organic ultraviolet absorber and a fine powder type sunscreen are mentioned.

As an organic ultraviolet absorber, a benzotriazole type, a triazine type, an acrylonitrile type, a benzophenone type, an aminobutadiene type, a salicylate type, etc. are mentioned.

As the benzotriazole type, for example, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6[(2H-benzotriazol-2-yl)phenol]], 2- (2H-Benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4- and methyl-6-(tert-butyl)phenol.

Typical commercial products of benzotriazole-based organic UV absorbers include Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350, Sumisorb 400, TINUVIN PS, TINUVIN 99-2, and TINUVIN 384-2 manufactured by BASF manufactured by Sumika Chemtex. , TINUVIN 900, TINUVIN 928, TINUVIN 1130, ADEKA STAB LA-24, ADEKA STAB LA-29, ADEKA STAB LA-31, ADEKA STAB LA-32, ADEKA STAB LA-36, etc. (Sumisorb, TINUVIN, and Adecastab are all registered trademarks).

Examples of the triazine type include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol.

Typical commercial products of the triazine-based organic ultraviolet absorber include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 479 manufactured by BASF, ADEKA STAB LA-46, ADEKA STAB LA-F70, etc. .

Moreover, you may use a hindered amine etc. as an optical stabilizer. As the hindered amine, for example, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, poly[[6-(1,1,3,3-tetramethylbutyl)amino- 1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetra methyl-4-piperidyl)imino]], dibutylamine/1,3,5-triazine N,N-bis(2,2,6,6-tetramethyl-4-piperidyl-1 and polycondensate of 6-hexamethylenediamine/N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine.

Representative commercial products made by HALS include TINUVIN 111, TINUVIN 123, TINUVIN 144, TINUVIN 292, TINUVIN 5100 manufactured by BASF, ADEKA STAB LA-52, ADEKA STAB LA-57, ADEKA STAB LA-63P, ADEKASTAVE LA-68, ADEKASTAVE LA-72, ADEKASTAVE LA-77, ADEKASTAVE LA-81, ADEKASTAVE LA-82, ADEKASTAVE LA-87, ADEKASTAVE LA-402, ADEKASTAB Castab LA-502 etc. are mentioned.

As a fine powder type sunscreen agent, fine particle metal oxide is preferable, and it is the range whose average primary particle diameter is 1-100 nm, and it is more preferable that it has an ultraviolet protective effect. Examples of the metal oxide include titanium oxide, zinc oxide, cerium oxide, iron oxide, and magnesium oxide. One or more of these particulate metal oxides, preferably two or more, may be combined.

In addition, the shape of the fine particle metal oxide is not particularly limited, such as spherical shape, needle shape, rod shape, spindle shape, indeterminate shape, plate shape, etc., and the crystal form is also particularly limited, such as amorphous, rutile, anatase, etc. doesn't happen

The fine particle metal oxide is treated with a conventionally known surface treatment, for example, fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil treatment, N-acylated lysine treatment, polyacrylic acid It is preferable that the surface is treated in advance by treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, etc., in particular, one selected from silicone, silane, fluorine compound, amino acid compound, and metallic soap. It is preferable that the water-repellent treatment is carried out with more than one type of surface treatment agent.

As a typical commercial item of fine particle metal oxide, Sumitomo Osaka Cement Co., Ltd. product HMZD-50 etc. are mentioned.

It is preferable that the ultraviolet absorber containing organic layer is a layer which, after apply|coating a ultraviolet absorber containing coating agent, dried as needed, and hardened by irradiation of an ultraviolet-ray or an electron beam.

The UV absorber-containing coating agent contains a UV absorber, a monomer and/or oligomer of a photocurable resin such as an UV or electron beam curable resin as a resin component, and, if necessary, an additive, for example, a photopolymerization initiator, a solvent and a dispersing agent. do. The ultraviolet absorber-containing coating agent can be obtained by dissolving or dispersing the ultraviolet absorber and optionally additives in the resin component by a known method. The ultraviolet absorber or sunscreen agent in the ultraviolet absorber-containing coating agent is contained in an appropriate amount from the viewpoint of adjusting the ultraviolet transmittance, but is preferably 0.1 to 50% by mass based on the amount of the ultraviolet absorber-containing coating agent, more preferably 1 -30 mass %.

The UV-curable monomer or oligomer, or the electron beam-curable monomer or oligomer is not particularly limited as long as it is a monomer or oligomer having a group that can be crosslinked by irradiation with UV or electron beam, but an acryloyl group, a methacryloyl group, and an oxetane group It is preferable to use a monomer or oligomer having a group selected from The ultraviolet absorber-containing organic layer is epoxy (meth)acrylate, urethane (meth)acrylate, isocyanuric acid (meth)acrylate, pentaerythritol (meth)acrylate, trimethylolpropane (meth)acrylate, ethylene glycol ( Among meth)acrylates, polyester (meth)acrylates, and the like, it is preferable to have a polymer obtained by crosslinking a monomer having a bifunctional or higher acryloyl group or a methacryloyl group as a main component. Two or more types may be mixed and used for the monomer which has such a bifunctional or more than bifunctional acryloyl group or methacryloyl group, and may mix and use monofunctional (meth)acrylate.

Representative commercial products of the UV absorber-containing coating agent include Lioduras (registered trademark) TYN manufactured by Dongyang Ink Co., Ltd., Z-735-27L (containing particles) manufactured by Aika Industrial Co., Ltd., KRX-705-6 manufactured by ADEKA Co., Ltd. can be heard

As a formation method of an ultraviolet absorber containing organic layer, the method etc. by application|coating are mentioned, for example. Examples of the coating method include various coating methods conventionally used, for example, spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, reverse roll coating, gravure coating, Methods, such as extrusion application|coating, are mentioned. It is preferable to form after apply|coating a ultraviolet absorber containing coating agent on an inorganic thin film layer, drying as needed, and hardening by irradiation of an ultraviolet-ray or an electron beam.

The thickness of the ultraviolet absorber containing organic layer becomes like this. Preferably it is 10-10000 nm. The upper limit of the thickness of the ultraviolet absorber containing organic layer becomes like this. More preferably, it is 8000 nm, More preferably, it is 7000 nm. The lower limit of the thickness of the ultraviolet absorber-containing organic layer is more preferably 50 nm, still more preferably 100 nm. The thickness of the ultraviolet absorber-containing organic layer, depending on the contained ultraviolet absorber, resin component, or ultraviolet absorber-containing coating agent, etc., is preferably 10 to 5000 nm, more preferably 50 to 5000 nm, further preferably 100 to 5000 nm. is nm.

(organic layer (B))

The gas barrier film may have an organic layer (B) in the outermost layer of the gas barrier film. The organic layer (B) may be formed in only one surface of the gas barrier film, or may be formed in both surfaces. Examples of the organic layer (B) include a mat layer, a protective layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light shielding layer, an antireflection layer, a hard coat layer, a stress relaxation layer, an antifogging layer, an antifouling layer. , a to-be-printed layer, an easily adhesive layer, etc. are mentioned.

(gas barrier film)

The gas barrier film of the present invention has a light transmittance of 20% or less at a wavelength of 380 nm. Thereby, light resistance can be provided to a gas barrier film, and UV deterioration inside a device lower than a gas barrier film can be suppressed, or UV deterioration of gas barrier film itself can be suppressed. The gas barrier film of the present invention has a light transmittance of preferably 15% or less at a wavelength of 380 nm, more preferably 10% or less, still more preferably 5% or less. In this invention, the light transmittance in wavelength 380nm was measured using the spectrophotometer (Nippon Spectroscopy Co., Ltd. product ultraviolet-visible near-infrared spectrophotometer V-670).

The layer structure of the gas barrier film of this invention will not be specifically limited if a base material layer, an inorganic thin film layer, and the organic layer containing a ultraviolet absorber are laminated|stacked in this order, It is not limited to the illustration of the following layer structure, either. Specifically, as an example of layer structure, 3-layer structure of a base material layer/inorganic thin film layer/ultraviolet absorber containing organic layer; flexible substrate/organic layer (A)/inorganic thin film layer/ultraviolet absorber containing organic layer, organic layer (A)/flexible substrate/inorganic thin film layer/ultraviolet absorber containing organic layer, inorganic thin film layer/flexible substrate/inorganic thin film layer/ultraviolet absorber containing organic layer; Four-layer configuration of flexible substrate/inorganic thin film layer/ultraviolet absorber-containing organic layer/organic layer (B), organic layer (B)/flexible substrate/inorganic thin film layer/ultraviolet absorber-containing organic layer; Five-layer configuration of flexible substrate/organic layer (A)/inorganic thin film layer/ultraviolet absorber containing organic layer/organic layer (B), inorganic thin film layer/flexible substrate/organic layer (A)/inorganic thin film layer/ultraviolet absorber containing organic layer; Organic layer (B) / inorganic thin film layer / flexible substrate / organic layer (A) / inorganic thin film layer / ultraviolet absorber containing organic layer, inorganic thin film layer / organic layer (A) / flexible substrate / organic layer (A) / inorganic thin film layer / ultraviolet absorber containing organic layer; Inorganic thin film layer / organic layer (A) / flexible substrate / organic layer (A) / inorganic thin film layer / ultraviolet absorber containing organic layer / organic layer (B), organic layer (B) / inorganic thin film layer / organic layer (A) / flexible substrate / organic layer (A) ) / inorganic thin film layer / ultraviolet absorber containing organic layer, organic layer (B) / inorganic thin film layer / organic layer (A) / flexible substrate / organic layer (A) / inorganic thin film layer / ultraviolet absorber containing organic layer / organic layer (B), etc. may be You may have an additional layer (C) other than said layer. As such a layer (C), a colorant containing organic layer, a bleed-out prevention layer, an antireflection layer, an adhesion layer, a transparent conductive layer, an infrared rays blocking layer, a vacuum ultraviolet curing organic layer, etc. are mentioned, for example.

The gas barrier film has a coefficient of static friction between one surface of the gas barrier film and the other surface of 0.85 or more and 2.0 or less.

The static friction coefficient is obtained by dividing the gas barrier film having an upper surface and a lower surface into two sheets, and bringing the upper surface of the first gas barrier film and the lower surface of the second gas barrier film into contact with each other, so that the static friction coefficient is you just have to measure The static friction coefficient can be measured in an environment of a temperature of 23°C and a humidity of 50 RH% in accordance with the gradient method of JIS P 8147.

In order to adjust a static friction coefficient, what is necessary is just to adjust the surface roughness of both surfaces of a gas barrier film. For example, when the inorganic thin film layer is provided on only one surface of the base layer, the surface roughness of the exposed surface of the inorganic thin film layer and the surface roughness of the exposed surface of the base layer may be adjusted. When an inorganic thin film layer is provided in both surfaces of a base material layer, what is necessary is just to adjust the surface roughness of the exposed surface of one inorganic thin film layer, and the surface roughness of the exposed surface of the other inorganic thin film layer. When the surface roughness of at least one surface of a gas barrier film is made large, there exists a tendency for the static friction coefficient between front and back surfaces to become small.

The surface roughness of the inorganic thin film layer can be changed according to, for example, conditions such as the pressure (vacuum degree) and the film thickness in the vacuum chamber in the film formation conditions of the inorganic thin film layer, and the composition of the inorganic film formation layer. In addition, the surface roughness of the inorganic thin film layer can also be adjusted by adjusting the surface roughness of the flexible base material used as a base, and the surface roughness of the intermediate|middle layer arrange|positioned between the inorganic thin film layer and the flexible base material.

In order to adjust the surface roughness of the flexible substrate, treatment such as corona treatment may be performed.

The arithmetic mean roughness (Ra) of the surface of the inorganic thin film layer may be 3 nm or more. Arithmetic mean roughness Ra can be obtained by observing the surface with a white interference microscope, after affixing a gas barrier film to the epoxy board which has an adhesive. Arithmetic mean roughness Ra is arithmetic mean roughness according to JIS B 0601:2001.

Further, in the gas barrier film according to the present embodiment, when the 50 mm square part cut out from the gas barrier film is mounted so that the center part of the part is in contact with the horizontal plane, from the horizontal plane to the four corners bent upward. The average value of the distance is 2 mm or less.

This average value can be measured as follows. First, a gas barrier film is hold|maintained on the conditions of temperature 23 degreeC, and humidity 50RH% for 48 hours. Next, a 50 mm square part is cut out from the said gas barrier film, and a sample is obtained. The sample is mounted on a horizontal plane so that the center part of the sample is in contact with the horizontal plane, and a total of 4 points is obtained from the horizontal plane to the four corners. Finally, the average value of these four points is obtained.

In order to reduce warpage of the gas barrier film and improve planarity, the stress of each inorganic thin film layer on the front and back surfaces is balanced, or the stress of the inorganic thin film layer on one surface and the coating layer below it is balanced, or the residual inorganic thin film layer itself What is necessary is just to reduce stress, or to balance the stress of both surfaces by combining these. The stress can be adjusted according to the film-forming pressure at the time of forming the inorganic thin film layer, the film thickness, the degree of curing shrinkage at the time of forming the coating layer, and the like.

The water vapor transmission rate in 40 degreeC 90 %RH of a gas barrier film may be 0.1 g/m<2>/day or less, and may be 0.001 g/m<2>/day or less. Water vapor transmission rate can be measured by the Ca corrosion test method based on ISO/WD 15106-7 (Annex C).

The gas barrier film of the present invention can be produced by a method in which a base layer, an inorganic thin film layer, and an organic layer containing an ultraviolet absorber are respectively prepared and bonded, or a method in which an inorganic thin film layer and an organic layer containing an ultraviolet absorber are formed on the base layer. The inorganic thin film layer is preferably produced by forming on the flexible substrate or on the organic layer (A) laminated on the surface of the flexible substrate by a known vacuum film forming method such as CVD using glow discharge plasma. You may form the ultraviolet absorber containing organic layer and an additional organic layer (B) in the laminated|multilayer film obtained in this way by a well-known method. It is preferable to form an inorganic thin film layer by a continuous film-forming process, For example, it is more preferable to continuously form an inorganic thin film layer on it, conveying a long base material continuously. You may form an inorganic thin film layer, conveying a flexible base material from a sending roll to a take-up roll specifically,. Then, you may form an inorganic thin film layer further from above by inverting a sending roll and a take-up roll, and conveying a base material in a reverse direction.

The gas-barrier film of this invention is a film excellent in gas-barrier property and light resistance by which the fall of gas-barrier property was suppressed especially even when it bends after a light resistance test. The gas barrier film of the present invention can be used for packaging applications requiring gas barrier properties, such as food, industrial products, and pharmaceuticals. Moreover, this invention also provides the flexible electronic device which has the gas barrier film of this invention. The gas barrier film of this invention can be used also as a flexible substrate of flexible electronic devices (for example, a flexible display), such as a liquid crystal display element by which higher gas barrier property is requested|required, a solar cell, and an organic electroluminescent display. When the gas barrier film of the present invention is used as a flexible substrate for an electronic device, the element may be formed directly on the gas barrier film of the present invention, or after forming the element on another substrate, the gas barrier property of the present invention The films may be superimposed from above.

Hereinafter, the present invention will be described in more detail by way of specific examples.

[Example]

<Film thickness of inorganic thin film layer, organic layer (A) and organic layer containing ultraviolet absorber>

An inorganic thin film layer, an organic layer (A), or an organic layer containing an ultraviolet absorber is formed on a flexible substrate, and the step difference between the non-film-forming part and the film-forming part is measured using Kosaka Lab Co., Ltd. Surfcoder ET200, and the film thickness of each layer ( T) was found.

<Measurement of XPS depth profile in thickness direction of inorganic thin film layer>

The atomic ratio in the thickness direction of the inorganic thin film layer of the gas barrier film was measured by X-ray photoelectron spectroscopy.

Etching ion species: Ar (Ar ⁺ )

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

Etching gap (SiO ₂ conversion value): 10 nm

X-ray photoelectron spectroscopy device: manufactured by Thermo Fisher Scientific, model name "VG Theta Probe"

Irradiation X-ray: single crystal spectroscopy AlKα

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

<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 was measured with a Fourier transform infrared spectrophotometer (manufactured by Nippon Spectroscopy Co., Ltd., FT/IR-460Plus) equipped with an ATR attachment (PIKE MIRacle) using a germanium crystal to a prism. did. Moreover, the laminated|multilayer film for infrared spectroscopy was obtained by using a cyclic cycloolefin film (Nippon Zeon Co., Ltd. product, Zeonoa ZF16) as a base material as a flexible base material, and forming an inorganic thin film layer on the said base material.

<Gas barrier properties>

Gas barrier property was measured by the calcium corrosion method (the method described in Unexamined-Japanese-Patent No. 2005-283561) in conditions of temperature 40 degreeC and humidity 90%RH, and the water vapor transmission rate of the gas barrier film was calculated|required.

(Preparation Example 1 of Inorganic Thin Film Layer)

The flexible base material was mounted on the delivery roll in the vacuum chamber, and the inside of the vacuum chamber was set to 1×10 ^-3 Pa or less, and then an inorganic thin film layer was formed on the flexible base material. In the plasma CVD apparatus used to form an inorganic thin film layer, the base material layer is conveyed while closely contacting each of the surfaces of a pair of roll-shaped electrodes, plasma is generated between the pair of electrodes, and the raw material is decomposed in plasma to decompose the flexible base material. An inorganic thin film layer was formed thereon. In the pair of electrodes, a magnet is disposed inside the electrode so that the magnetic flux density becomes high at the surface of the electrode and the flexible substrate, and the plasma is confined at high density on the electrode and the flexible substrate when plasma is generated. In the film formation of the inorganic thin film layer, 100 sccm of hexamethyldisiloxane gas (Standard Cubic Centimeter per Minute, 0°C, 1 atm) and 1400 sccm of oxygen gas were introduced toward the space between the electrodes serving as the film formation zone, and between the electrode rolls. An AC power of 1.2 kW and a frequency of 70 kHz was supplied and discharged to generate plasma. Next, after adjusting the exhaust amount so that the pressure in the vicinity of the exhaust port in the vacuum chamber was 5 Pa, a dense inorganic thin film layer was formed on the flexible substrate by plasma CVD.

About the inorganic thin film layer of the obtained gas barrier film, infrared spectroscopy was performed on the said conditions. From the obtained infrared absorption spectrum, the absorption intensity ratio (I ₂ /I ₁ ) of the peak intensity (I ₁ ) present at 950 to 1050 cm ^-1 and the peak intensity (I ₂ ) present at 1240 to 1290 cm ^-1 ) When calculated, I ₂ /I ₁ =0.04. In addition, if the absorption intensity ratio (I ₃ /I ₁ ) of the peak intensity (I ₁ ) present at 950 to 1050 cm ⁻¹ and the peak intensity (I ₃ ) present at 770 to 830 cm ⁻¹ is obtained, I ₃ /I ₁ =0.40.

In addition, if the absorption intensity ratio (I ₄ /I ₃ ) of the peak intensity (I ₃ ) present at 770 to 830 cm ^-1 and the peak intensity (I ₄ ) present at 870 to 910 cm ^-1 is obtained, I ₄ /I ₃ =0.88.

In addition, the infrared absorption spectrum showed said absorption intensity ratio without a change even if it performed the corona treatment mentioned later. The obtained gas-barrier film (1) has oxygen, silicon, and carbon in the order of oxygen, silicon, and carbon in the region of 90% or more in the film thickness direction of the inorganic thin film layer from the one with the largest atomic ratio, and the carbon distribution in the film thickness direction The extreme value of the curve was 10 or more, and 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 was 0.02 or more.

In addition, after performing XPS depth profile measurement and obtaining the average atomic concentration in the thickness direction of each atom from the obtained distribution curves of silicon atoms, oxygen atoms and carbon atoms, the average atomic ratios C/Si and O/Si As a result of the calculation, the average atomic ratio was C/Si=0.27 and O/Si=1.76.

The thickness of the inorganic thin film layer in the obtained gas barrier film was 320 nm.

(Production Example 2 of Inorganic Thin Film Layer)

In the same manner as in Production Example 1, except that the oxygen gas supply amount was 900 sccm, the AC power supplied between the electrode rolls was 0.6 kW, and the exhaust amount was adjusted so that the pressure around the exhaust port in the vacuum chamber was 1 Pa, An inorganic thin film layer was formed on the base layer.

About the inorganic thin film layer of the obtained gas barrier film, infrared spectroscopy was performed on the said conditions. From the obtained infrared absorption spectrum, the absorption intensity ratio (I ₂ /I ₁ ) of the peak intensity (I ₁ ) present at 950 to 1050 cm ^-1 and the peak intensity (I ₂ ) present at 1240 to 1290 cm ^-1 ) When calculated, I ₂ /I ₁ =0.03. In addition, if the absorption intensity ratio (I ₃ /I ₁ ) of the peak intensity (I ₁ ) present at 950 to 1050 cm ^-1 and the peak intensity (I ₃ ) present at 770 to 830 cm ^-1 is obtained, I ₃ /I ₁ =0.36.

In addition, if the absorption intensity ratio (I ₄ /I ₃ ) of the peak intensity (I ₃ ) present at 770 to 830 cm ^-1 and the peak intensity (I ₄ ) present at 870 to 910 cm ^-1 is obtained, I ₄ /I ₃ =0.84.

In addition, the infrared absorption spectrum showed said absorption intensity ratio without a change even if it performed the corona treatment mentioned later. The obtained gas-barrier film (1) has oxygen, silicon, and carbon in the order of oxygen, silicon, and carbon in the region of 90% or more in the film thickness direction of the inorganic thin film layer from the one with the largest atomic ratio, and the carbon distribution in the film thickness direction The extreme value of the curve was 10 or more, and 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 was 0.02 or more.

In addition, after performing XPS depth profile measurement and obtaining the average atomic concentration in the thickness direction of each atom from the obtained distribution curves of silicon atoms, oxygen atoms and carbon atoms, the average atomic ratios C/Si and O/Si As a result of the calculation, the average atomic ratio was C/Si=0.30 and O/Si=1.73.

The thickness of the inorganic thin film layer in the obtained gas barrier film was 250 nm.

(Example 1)

After corona treatment on the cycloolefin polymer film (COP film, Nippon Zeon Co., Ltd., ZF16, 100 μm thick), the coating agent (1) (Toyochem Co., Ltd., Rioduras (registered trademark) TYAB500LC3NS, particles) was applied by gravure coating method, dried at 100° C. for 3 minutes, and then irradiated with ultraviolet rays (Ushio Electric Co., Ltd., SP-9) under the condition of an accumulated light amount of 500 mJ/cm 2 , and an organic layer with a thickness of 1.5 μm ( A lubricity layer was formed as A1). Subsequently, after corona treatment is performed on the COP substrate on the opposite side to the coated surface of the organic layer (A1), the coating agent (2) (Dong-A Synthetic Co., Ltd., Aronix (registered trademark) UV3701) is applied by a gravure coating method, After drying at 100 degreeC for 3 minutes, it irradiated with ultraviolet-ray under the conditions of 500 mJ/cm<2> of accumulated light amount, the planarization layer was formed as an organic layer (A2) with a thickness of 1.8 micrometers, and the flexible base material was obtained.

On the organic layer (A1) of the obtained flexible base material, the inorganic thin film layer was formed on the conditions of manufacture example 1, and the inorganic thin film layer was formed on the organic layer (A2) under the conditions of manufacture example 2. Next, the ultraviolet absorber containing organic layer was formed in the outermost surface of the organic layer (A1) side of the film in which the inorganic thin film layer was formed, and the gas barrier film was manufactured. In the formation of the organic layer containing the ultraviolet absorber, after corona treatment on the lubricious layer surface side of the film on which the inorganic thin film layer is formed, the coating agent (3) (manufactured by ADEKA, KRX-705-6) is applied by a wet coating method, 80 After drying at 占폚 for 3 minutes, ultraviolet irradiation (Ushio Electric Co., Ltd., SP-9) was carried out under conditions of an accumulated light amount of 500 mJ/cm 2 to form an organic layer containing an ultraviolet absorber having a thickness of 5.5 µm.

Moreover, in the obtained gas barrier film, the water vapor transmission rate in the conditions of a temperature of 40 degreeC, the humidity of 0%RH on the low-humidity side, and the humidity of 90%RH on the high-humidity side was 2x10 ^-3 g/(m<2>*day) it was

(Example 2)

A gas barrier film was produced in the same manner as in Example 1 except that the thickness of the ultraviolet absorber-containing organic layer was set to 6.5 µm.

Moreover, in the obtained gas barrier film, the water vapor transmission rate in the conditions of a temperature of 40 degreeC, the humidity of 0%RH on the low-humidity side, and the humidity of 90%RH on the high-humidity side was 2x10 ^-3 g/(m<2>*day) it was

(Comparative Example 1)

After corona treatment on the COP film (Nippon Zeon Co., Ltd., Zeonoa (registered trademark) ZF16, thickness 100 μm), the coating agent (4) (manufactured by Aika Kogyo Co., Ltd., Z-735-27L, containing particles) ) was applied by a gravure coating method, dried at 100° C. for 2 minutes, and then irradiated with ultraviolet rays under the conditions of an accumulated light amount of 150 mJ/cm 2 to form an organic layer containing a UV absorber having a thickness of 3.5 μm as a lubricity layer. Subsequently, after corona treatment is performed on the COP substrate on the opposite side to the coated surface of the organic layer containing the ultraviolet absorber, the coating agent (2) (Dong-A Synthetic Co., Ltd., Aronix (registered trademark) UV3701) is applied by a gravure coating method, After drying at 100 degreeC for 3 minutes, it irradiated with ultraviolet-ray under the conditions of 500 mJ/cm<2> of accumulated light quantity, and formed the planarization layer as 1.8-micrometer-thick organic layer A2.

On the organic layer containing the ultraviolet absorber of the obtained substrate, an inorganic thin film layer was formed under the conditions of Production Example 1, and an inorganic thin film layer was formed on the organic layer (A2) under the conditions of Production Example 2 to prepare a gas barrier film.

(Comparative Example 2)

A gas barrier film was produced in the same manner as in Comparative Example 1 except that the thickness of the ultraviolet absorber-containing organic layer was set to 4.5 µm.

(Comparative Example 3)

Except not forming the ultraviolet absorber containing organic layer, it carried out similarly to Example 1, and produced the gas barrier film.

For the gas barrier films obtained in Examples 1 to 2 and Comparative Examples 1 to 3, the light transmittance at 380 nm ( Tt) was measured. The obtained results are shown in Table 1.

The gas barrier films obtained in Examples 1 to 2 and Comparative Examples 1 to 3 were left to stand for 168 hours in a light resistance tester (Dypla Wintess Co., Ltd., SWM-03F) at a temperature of 40°C and an illuminance of 765 W/m2. By doing so, a light resistance test was performed. The test was performed by arranging the gas barrier film so that light was incident from the lubricious layer surface side of the gas barrier film.

In addition, with respect to the gas barrier film after the light resistance test, after winding once on a mandrel with a radius of 4 mm, deterioration such as peeling, cracking, and coloring does not occur in the barrier layer, and the area in which no change in appearance is seen is 100% The case was evaluated as "A", the case where it was 80% or more and less than 100% was evaluated as "B", and the case where it was less than 80% was evaluated as "C". The results are shown in Table 1.

As shown in Table 1, since the gas barrier film of the present invention shown in Examples 1 and 2 has the ultraviolet absorber-containing organic layer on the inorganic thin film layer, the inorganic thin film layer does not deteriorate even after the light resistance test, and good adhesion after bending have Although Comparative Examples 1 and 2 had low light transmittance at a wavelength of 380 nm, the inorganic thin film layer deteriorated after the light resistance test, and the adhesiveness after bending was low. Therefore, it is understood that the gas barrier film of this invention is used suitably in devices, such as a display apparatus.

11: sending roll
21, 22, 23, 24: transfer roll
31, 32: film forming roll
41: gas supply pipe
51: power for plasma generation
61, 62: magnetic field generator
71: winding roll
100: film

Claims (11)

A gas barrier film having in this order a substrate layer including at least a flexible substrate, an organic layer (A) present on the surface of the flexible substrate, an inorganic thin film layer, and an organic layer containing an ultraviolet absorber,
The inorganic thin film layer contains a silicon atom, an oxygen atom and a carbon atom,
The light transmittance at 380 nm of the gas barrier film is 20% or less,
The organic layer (A) is a gas barrier film, which is a lubricating layer formed by applying a UV curable resin containing inorganic particles on a substrate and UV curing. The method of claim 1,
The gas barrier film which has an additional inorganic thin film layer on the surface of the base material layer on the opposite side to the ultraviolet absorber containing organic layer side. The method of claim 1,
The gas barrier film in which a base material layer has an additional organic layer (A) on the other surface of a flexible base material. 4. The method of claim 3,
The further organic layer (A) is a gas barrier film which is a flat layer. The method of claim 1,
A gas barrier film, wherein a ratio of the atomic ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer continuously changes in the thickness direction of the inorganic thin film layer. The method of claim 1,
The inorganic thin film layer is a gas barrier film, wherein the average atomic ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is in the range of formula (1).
0.10<C/Si<0.50 (1) The method of claim 1,
In the thickness direction of the inorganic thin film layer, the distance from the surface of the inorganic thin film layer and the ratio of silicon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer at each distance; A gas barrier film satisfying conditions (i) and (ii) in a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve each showing the relationship between the oxygen atomic ratio and the carbon atomic ratio.
(i) the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfies the condition represented by formula (5) in a region of 90% or more in the thickness direction of the inorganic thin film layer;
Atomic ratio of oxygen > Atomic ratio of silicon > Atomic ratio of carbon (5)
(ii) the carbon distribution curve has at least one extreme value. The device which contains the gas barrier film in any one of Claims 1-7 so that the coating layer containing an ultraviolet absorber may become an outermost layer. 8. The method according to any one of claims 1 to 7,
When the surface of the inorganic thin film layer is measured by the ATR method of infrared spectroscopy, the peak intensity (I ₁ ) at 950 to 1050 cm ^-1 and the peak intensity at 1240 to 1290 cm ^-1 (I ₂ ) A gas barrier film, wherein the strength ratio is in the range of formula (2).
0.01≤I ₂ /I ₁ <0.05 (2) 8. The method according to any one of claims 1 to 7,
When the surface of the inorganic thin film layer was measured by the ATR method of infrared spectroscopy, the peak intensity (I ₁ ) present at 950 to 1050 cm ^-1 and the peak intensity (I ₃ ) present at 770 to 830 cm ^-1 were the intensity of A gas barrier film, wherein the ratio is in the range of formula (3).
0.25≤I ₃ /I ₁ ≤0.50 (3) 8. The method according to any one of claims 1 to 7,
When the surface of the inorganic thin film layer is measured by the ATR method of infrared spectroscopy, the peak intensity (I ₃ ) present at 770 to 830 cm ^-1 and the peak intensity (I ₄ ) present at 870 to 910 cm ^-1 are the intensity of A gas barrier film, wherein the ratio is in the range of formula (4).
0.70≤I ₄ /I ₃ <1.00 (4)

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