JPWO2015186434A1 - Gas barrier film - Google Patents

Abstract

The subject of this invention is providing the gas barrier film which is excellent in the adhesiveness of a clear hard-coat layer and a gas barrier layer, hold | maintaining gas barrier property. The gas barrier film (F) of the present invention is a distribution curve of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the clear hard coat layer (4) and the gas barrier layer (6). The distance from the surface of the gas barrier layer (6) opposite to the clear hard coat layer (4) in the layer thickness direction of the gas barrier layer (6) and the total number of atoms of carbon atoms, silicon atoms and oxygen atoms (100 at %) Carbon distribution curve showing the relationship with the ratio of carbon atoms (carbon atom ratio), or the ratio of oxygen atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (oxygen atom ratio) The width of the composition gradient region of the oxygen distribution curve showing the relationship between and is in the range of 7 to 20 nm.

Description

  The present invention relates to a gas barrier film. More specifically, the present invention relates to a gas barrier film having excellent adhesion between a clear hard coat layer and a gas barrier layer while maintaining gas barrier properties.

Conventionally, in the fields of food, packaging materials, pharmaceuticals, etc., in order to prevent the permeation of gases such as water vapor and oxygen, it is relatively simple to provide an inorganic film such as a metal or metal oxide vapor deposition film on the surface of a resin substrate. Gas barrier films having a structure have been used.
In addition to packaging applications, flexible solar devices, organic electroluminescence (EL) devices, liquid crystal display (LCD) devices and other flexible electronic devices such as liquid crystal display devices are required, and many studies have been made. Has been made.

By the way, when an inorganic film such as a gas barrier layer is directly formed on a resin substrate, the affinity is small due to the difference in chemical composition between the organic film and the inorganic film, and physical properties (hardness, elastic modulus, density) Clear hard coat with stress relaxation function and affinity (adhesion) improvement function between the resin substrate and the gas barrier layer because the interface stress caused by the difference in the It is known to provide a layer (CHC layer).
In general, an organic polymer such as an acrylic resin is used for the clear hard coat layer, but the interface adhesion with the inorganic film is often insufficient. Even if the initial adhesion is obtained, in the high-temperature and high-humidity test (85 ° C., relative humidity 85% RH), moisture enters the interface due to poor adhesion, resulting in deterioration of gas barrier properties (water vapor permeability). There was a problem that.

For example, Patent Document 1 discloses an optical film having a layer made of a coating composition containing inorganic fine particles having an average particle diameter of 1 to 100 nm, an ionizing radiation curable binder forming material, a photopolymerization initiator, and an organic solvent. . However, the layer made of the coating composition is insufficient in terms of adhesion with the gas barrier layer formed by the plasma CVD method.
Patent Document 2 discloses a gas barrier laminate having an organic layer and an inorganic layer, and the pencil hardness of the organic layer is HB or higher. The organic layer material is a polyfunctional acrylate or a polyfunctional urethane acrylate. Is used. However, in Patent Document 2, although the organic layer is a hard layer, it is difficult to be damaged during film formation, but the adhesion between the organic film and the inorganic film is insufficient.
Patent Document 3 discloses a laminate containing urethane (meth) acrylate, but is flexible, but has strong damage during film formation by the plasma CVD method and sufficiently exhibits gas barrier properties. I couldn't.
Patent Document 4 discloses a gas barrier laminated film having a gas barrier layer composed of an anchor layer and SiO _x C _y on a base material. The thermal expansion coefficient in the gas barrier layer, the base material, the anchor layer, and the gas are disclosed. It defines the relationship between the tensile modulus of the barrier layer. However, the laminated film disclosed in Patent Document 4 is flexible, like the laminated body disclosed in Patent Document 3, but has strong damage during film formation by the plasma CVD method, and has a gas barrier property. It was not possible to fully demonstrate.

JP 2011-208102 A JP2012-020516A JP 2011-208096 A JP 2012-166499 A

  The present invention has been made in view of the above problems and situations, and a solution to the problem is to provide a gas barrier film having excellent adhesion between the clear hard coat layer and the gas barrier layer while maintaining gas barrier properties. That is.

  In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, etc., each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the clear hard coat layer and the gas barrier layer Among the distribution curves, the distance from the surface of the gas barrier layer opposite to the clear hard coat layer in the thickness direction of the gas barrier layer and the total number of atoms of carbon atoms, silicon atoms and oxygen atoms (100 at%) Carbon distribution curve indicating the relationship with the ratio of carbon atoms (carbon atom ratio), or the relationship with the ratio of oxygen atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (oxygen atom ratio) Clear hard coat layer and gas barrier layer while maintaining the gas barrier property by setting the width of the composition gradient region of the oxygen distribution curve to be within a specific range It found that can provide excellent gas-barrier film adhesion, leading to the invention.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A clear hard coat layer made of UV curable resin and at least one gas barrier layer containing silicon oxide carbide formed by a roll-to-roll CVD apparatus are sequentially laminated on at least one surface of the resin base material. Gas barrier film,
Among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the clear hard coat layer and the gas barrier layer, the clear hard coat layer in the thickness direction of the gas barrier layer and Is a carbon distribution curve showing the relationship between the distance from the surface of the gas barrier layer on the opposite side and the ratio of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio) Or the width of the composition gradient region of the oxygen distribution curve showing the relationship with the ratio of oxygen atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (oxygen atom ratio) is in the range of 7 to 20 nm A gas barrier film characterized by being inside.

  2. The oxygen atom ratio in the clear hard coat layer is in the range of 25 to 45 at%, and the ratio of the number of silicon atoms (silicon atom ratio) to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) is 10 to 10%. 2. The gas barrier film according to item 1, which is in a range of 30 at%.

3. The gas barrier film according to item 1 or 2, wherein the clear hard coat layer contains SiO ₂ fine particles.

4). 4. The gas barrier film according to item 3, wherein the SiO ₂ fine particles are surface-modified with a reaction product of pentaerythritol (meth) acrylate and isophorone diisocyanate.

  5. The gas barrier film according to any one of Items 1 to 4, wherein the clear hard coat layer contains urethane (meth) acrylate.

  6). 6. The gas barrier film according to item 5, wherein the urethane (meth) acrylate is a reaction product of pentaerythritol (meth) acrylate and isophorone diisocyanate.

  7). The gas barrier film according to claim 5 or 6, wherein the clear hard coat layer further contains isocyanuric acid tri (meth) acrylate.

  8). The carbon distribution curve in the gas barrier layer has at least two extreme values, and the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is 3 at% or more. The gas barrier film according to any one of Items 7 to 7.

  By the above means of the present invention, it is possible to provide a gas barrier film having excellent adhesion between the clear hard coat layer and the gas barrier layer while maintaining gas barrier properties.

  The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.

In the gas barrier film of the present invention, the width of the composition gradient region in the carbon distribution curve or oxygen distribution curve of the gas barrier layer made of silicon oxide carbide and the clear hard coat layer made of UV curable resin, that is, the constituent atoms of each layer are mixed. The width of the region to be performed is in the range of 7 to 20 nm.
By making the width of the composition gradient region within the above range, it is possible to prevent delamination between the gas barrier layer and the clear hard coat layer even under severe conditions, and to ensure a sufficient thickness of the gas barrier layer. Therefore, it is considered that the gas barrier property can be maintained.

Schematic sectional view showing an example of the basic configuration of the gas barrier film of the present invention The graph which shows an example of the carbon distribution curve of the clear hard-coat layer which concerns on this invention, and a gas barrier layer, a silicon distribution curve, and an oxygen distribution curve The graph which shows an example of the carbon distribution curve of the clear hard-coat layer of a comparative example, and a gas barrier layer, a silicon distribution curve, and an oxygen distribution curve The schematic diagram which shows an example of the manufacturing apparatus used for formation of the gas barrier layer which concerns on this invention

  The gas barrier film of the present invention contains, on at least one surface of a resin base material, a clear hard coat layer made of a UV curable resin and at least one layer of silicon oxide carbide formed by a roll-to-roll CVD apparatus. Gas barrier layers are laminated in order, and among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the clear hard coat layer and the gas barrier layer, the thickness direction of the gas barrier layer Between the distance from the surface of the gas barrier layer on the opposite side of the clear hard coat layer and the ratio of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio) Or a ratio of the number of oxygen atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (oxygen atom) The width of the composition gradient region of the oxygen distribution curve showing the relationship with the child ratio) is in the range of 7 to 20 nm. This feature is a technical feature common to the inventions according to claims 1 to 8.

  As an embodiment of the present invention, from the viewpoint of improving the affinity between the clear hard coat layer and the gas barrier layer and improving the adhesion between the clear hard coat layer and the substrate, the oxygen atomic ratio in the clear hard coat layer is 25 to 45 at%. Preferably, the ratio of the number of silicon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (silicon atom ratio) is in the range of 10 to 30 at%.

In addition, from the viewpoint of the affinity between the clear hard coat layer and the gas barrier layer and the stress relaxation effect, and the improvement in adhesion between the clear hard coat layer and the substrate, the clear hard coat layer may contain SiO ₂ fine particles. preferable.

In addition, from the viewpoint of improving the affinity and stress relaxation effect between the clear hard coat layer and the gas barrier layer and improving the adhesion between the clear hard coat layer and the gas barrier layer, the SiO ₂ fine particles are converted to pentaerythritol (meth) acrylate and isophorone diisocyanate. It is preferable that the surface is modified with the above reaction product.

  Further, from the viewpoint of weather resistance and hydrolysis resistance, it is preferable that urethane (meth) acrylate is contained in the clear hard coat layer.

  From the viewpoint of the affinity between the clear hard coat layer and the gas barrier layer and the stress relaxation effect, the urethane (meth) acrylate is preferably a reaction product of pentaerythritol (meth) acrylate and isophorone diisocyanate.

  Moreover, it is preferable that isocyanuric acid tri (meth) acrylate is further contained in the clear hard coat layer from the viewpoint of the affinity between the clear hard coat layer and the gas barrier layer and the stress relaxation effect.

  Furthermore, from the viewpoint of suppressing the deterioration of gas barrier properties when the gas barrier film is bent, the carbon distribution curve in the gas barrier layer has at least two extreme values, and the maximum and minimum carbon atom ratios. The absolute value of the difference from the value is preferably 3 at% or more.

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

The “gas barrier property” as used in the present invention is a water vapor permeability (temperature: 60 ± 0.5 ° C., relative humidity (RH): 90 ± 2%) measured by a method according to JIS K 7129-1992. ) Is 1 × 10 ⁻¹ g / (m ² · 24 h) or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻¹ ml / (m ² · 24 h · atm. ) Means the following.

≪Gas barrier film≫
As shown in FIG. 1, the gas barrier film F of the present invention is configured by sequentially laminating a clear hard coat layer 4 and a gas barrier layer 6 on a resin substrate 2.

  In addition, the gas barrier film F of the present invention includes the gas barrier layer 6 among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by the X-ray photoelectron spectroscopy of the clear hard coat layer 4 and the gas barrier layer 6. The distance from the surface of the gas barrier layer 6 on the opposite side of the clear hard coat layer 4 in the layer thickness direction and the ratio of the number of carbon atoms to the total number of atoms (100 at%) of carbon atoms, silicon atoms and oxygen atoms (carbon Composition of the oxygen distribution curve indicating the relationship with the ratio of the number of oxygen atoms (oxygen atom ratio) to the total number of atoms (100 at%) of carbon atoms, silicon atoms and oxygen atoms. The width of the inclined region is in the range of 7 to 20 nm. When the width of the composition gradient region is less than 7 nm, delamination occurs under severe conditions, resulting in deterioration of water vapor barrier properties (WVTR). When the width of the composition gradient region exceeds 20 nm, the thickness of the gas barrier layer capable of exhibiting the gas barrier property becomes thin, and the water vapor barrier property (WVTR) becomes insufficient.

  The gas barrier film F of the present invention may have other various functional layers used for conventional gas barrier films on the other surface of the resin base material 2 on which the gas barrier layer 6 is not formed. Specific examples of the functional layer include a smooth layer, an anchor coat layer, a bleed-out prevention layer, and a functional layer such as a protective layer, a moisture absorption layer, and an antistatic layer.

  The total light transmittance in the gas barrier film F of the present invention is preferably as high as possible, but is preferably higher than 90%, more preferably 92% or more, and still more preferably 94% or more. In addition, let the total light transmittance be the value measured using Tokyo Denshoku Co., Ltd. haze meter NDH5000.

<X-ray photoelectron spectroscopy>
Carbon distribution curve (distance (L) from the gas barrier layer surface in the thickness direction of the gas barrier layer and the ratio of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio) ), A silicon distribution curve (curve showing the relationship between the distance L and the ratio of silicon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (silicon atom ratio) ) And oxygen distribution curve (curve showing the relationship between the distance L and the ratio of the number of oxygen atoms (oxygen atom ratio) to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%)) is X-ray photoelectron spectroscopy. By using the X-ray Photoelectron Spectroscopy (XPS) measurement in combination with rare gas ion sputtering such as argon, Issued sequentially performing surface composition analysis while, it can be produced by so-called XPS depth profile measurement.
A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve having the horizontal axis as the etching time in this way, the etching time generally correlates with the distance (L) from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer in the layer thickness direction. , “Distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer” as calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement (That is, SiO ₂ equivalent layer thickness (nm) = (etching time (sec) × etching rate (nm / sec)) can be employed.

Examples of measurement results based on the XPS depth profile are shown in FIGS.
The discrimination of the gas barrier layer, the clear hard coat layer and the composition gradient region is clear from the graph obtained from the XPS depth profile. For example, in the gas barrier film of the present invention shown in FIG. It turns out that it is 8 nm. In contrast, in the gas barrier film shown in FIG. 3, the width of the composition gradient region 10 is about 6 nm, which is outside the scope of the present invention.
2 and 3, the symbol A represents a carbon distribution curve, the symbol B represents a silicon distribution curve, and the symbol C represents an oxygen distribution curve.

<Composition gradient region>
In the gas barrier film of the present invention, a composition gradient region where the composition increases or decreases with a constant gradient (gradient) continuously or stepwise exists at the interface between the gas barrier layer and the clear hard coat layer. It is characterized by that.
The composition in the composition gradient region is the composition of the gas barrier layer itself at the end on the gas barrier layer side, and as the clear hard coat layer is approached, the ratio of carbon atoms and oxygen atoms gradually increases or decreases, At the end of the composition gradient region on the clear hard coat layer side, the composition of the clear hard coat layer itself is obtained.
The width of the composition gradient region is defined as the distance between the end portion on the gas barrier layer side in the composition gradient region and the end portion on the clear hard coat layer side.

More specifically, the “width of the composition gradient region” means the composition inflection point at one end of the composition gradient region in the carbon distribution curve or oxygen distribution curve obtained by XPS depth profile measurement. The distance between the composition inflection points shall be indicated.
Here, the “compositional inflection point at the end of the composition gradient region” means that the gas barrier layer itself or the clear hard coat layer itself increases from the decrease in the portion where the increase or decrease is clearly recognized rather than the change in each composition. A change point that turns into a point, a change point that goes from an increase to a decrease, or a change point that becomes constant from an increase or a decrease.
The width of the composition gradient region (mixed region) between the carbon atom ratio derived from the gas barrier layer component and the carbon atom ratio derived from the clear hard coat layer component, or the oxygen atom ratio derived from the gas barrier layer component and the clear hard coat layer component The width of the composition gradient region (mixed region) with respect to the oxygen atomic ratio was determined as follows.

Width of composition gradient region (nm) =
Distance (depth) from the surface of the end (inflection point) on the clear hard coat layer side where the composition gradient region ends (nm)-Surface of the end (inflection point) on the gas barrier layer side where the composition gradient region begins Distance (depth) from (nm)

  In the above formula, the distance from the surface means the distance from the surface of the gas barrier layer on the opposite side to the clear hard coat layer in the thickness direction of the gas barrier layer.

  The composition of the composition gradient region according to the present invention can be adjusted by gradually changing the amount of the raw material supplied when forming the components of the clear hard coat layer and / or the gas barrier layer with the passage of time.

  In the gas barrier film of the present invention, the absolute value of the rate of change (gradient) of the oxygen distribution curve in the composition gradient region is preferably 0.6 at% / nm or more. The rate of change (slope) of the oxygen distribution curve in the composition gradient region was determined as follows.

Change rate (gradient) of oxygen distribution curve in composition gradient region (at% / nm) =
(Oxygen atom ratio (at%) at the end (inflection point) on the clear hard coat layer side where the composition gradient region ends-oxygen atom ratio at the end (inflection point) on the gas barrier layer side where the composition gradient region starts ( at%)) / width of composition gradient region (nm)

  In the gas barrier film of the present invention, the absolute value of the change rate (gradient) of the carbon distribution curve in the composition gradient region is preferably 1.7 at% / nm or more. The rate of change (slope) of the carbon distribution curve in the composition gradient region was determined as follows.

Change rate (gradient) of carbon distribution curve in composition gradient region (at% / nm) =
(Carbon atom ratio (at%) at the end (inflection point) on the clear hard coat layer side where the composition gradient region ends)-Carbon atom ratio at the end (inflection point) on the gas barrier layer side where the composition gradient region begins ( at%)) / width of composition gradient region (nm)

  In the present invention, the carbon distribution curve, silicon distribution curve and oxygen distribution curve were prepared under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 μm × 400 μm oval

≪Resin base material (2) ≫
A resin film is used as the resin substrate of the gas barrier film of the present invention. The resin film to be used is not particularly limited in material, thickness and the like as long as it can hold the gas barrier layer, and can be appropriately selected depending on the purpose of use and the like.
Specifically, as the resin constituting the resin film, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, Polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin And thermoplastic resins such as an alicyclic modified polycarbonate resin, a fluorene ring modified polyester resin, and an acryloyl compound.

When the gas barrier film is used as a substrate for an electronic device such as an organic EL element, the resin base material is preferably made of a material having heat resistance. Specifically, a resin base material having a linear expansion coefficient in the range of 15 to 100 ppm / K and a glass transition temperature Tg in the range of 100 to 300 ° C. is used. The resin base material satisfies the necessary conditions as a laminated film for electronic parts and displays.
That is, when using a gas barrier film for these uses, the gas barrier film may be exposed to a process of 150 ° C. or higher. In this case, when the linear expansion coefficient of the base material in the gas barrier film is in the range of 15 to 100 ppm / K, the heat resistance is high and the flexibility is good. The linear expansion coefficient and Tg of the base material can be adjusted by an additive or the like.

  More preferable specific examples of the thermoplastic resin that can be used as the resin substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic ring. Polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C., manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C.), polyether sulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cyclo Olefin copolymer (COC: compound described in JP-A No. 2001-150584: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C., manufactured by Mitsubishi Gas Chemical Company, Inc.), fluorene ring-modified polycarbonate (BCF-PC) : JP 2000-227603 Compound described in the publication: 225 ° C., alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205 ° C.), acryloyl compound (compound described in JP 2002-80616 A: (The numerical value in parentheses indicates Tg.). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

Since the gas barrier film is used as an electronic device such as an organic EL element, the resin base material is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
The light transmittance is determined by measuring the total light transmittance and the amount of scattered light using the method described in JIS K 7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. Can be calculated.

  However, even when the gas barrier film is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the resin base material. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.

  The thickness of the resin substrate used for the gas barrier film is not particularly limited because it is appropriately selected depending on the application, but is typically in the range of 1 to 800 μm, preferably in the range of 10 to 200 μm. . These resin films may have a functional layer such as a known transparent conductive layer or smooth layer used in conventional gas barrier films. As the functional layer, in addition to those described above, those described in paragraphs 0036 to 0038 of JP-A-2006-289627 can be preferably employed.

  In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The resin base material can be manufactured by a conventionally known general method. For example, an unstretched resin base material that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, an unstretched resin base material is uniaxially stretched, a tenter-type sequential biaxial stretch, a tenter-type simultaneous biaxial stretch, a tubular-type simultaneous biaxial stretch, and the like in a flow direction (vertical axis) direction of the resin base material. Alternatively, a stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the resin substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably in the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  On both sides of the resin substrate, at least the side where the gas barrier layer is provided, various known treatments for improving adhesion, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, lamination of smooth layers, etc. are necessary. It can be done in combination.

≪Clear hard coat layer (CHC layer) (4) ≫
The clear hard coat layer according to the present invention improves the adhesion between the resin base material and the gas barrier layer, alleviates internal stress resulting from the difference between expansion and contraction of the resin base material and the gas barrier layer under high temperature and high humidity, It has a function of preventing bleeding out of low molecular weight components such as monomers and oligomers from the substrate.
The oxygen atom ratio relative to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) in the clear hard coat layer is preferably in the range of 25 to 45 at%. The ratio of the number of silicon atoms to the total number of carbon atoms, silicon atoms, and oxygen atoms (100 at%) (silicon atom ratio) is preferably in the range of 10 to 30 at%.
The oxygen atomic ratio and silicon atomic ratio in the clear hard coat layer were determined as average values in the clear hard coat layer excluding the composition gradient region.

  The clear hard coat layer is formed by applying an ultraviolet (UV) curable resin on a resin substrate and then curing it.

<Ultraviolet (UV) cured resin>
The UV curable resin refers to a UV curable resin cured by irradiating UV.
Examples of the UV curable resin for obtaining the UV curable resin include a UV curable urethane acrylate resin, a UV curable polyester acrylate resin, a UV curable epoxy acrylate resin, a UV curable polyol acrylate resin, and a UV curable epoxy resin. Is preferably used. Among these, UV curable acrylate resins are preferable.

  The UV curable urethane acrylate resin is generally obtained by reacting a polyester polyol with a product obtained by reacting an isocyanate monomer or a prepolymer with 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate (hereinafter referred to as methacrylate for acrylate). Only acrylates are indicated as being included.), And can be easily obtained by reacting an acrylate monomer having a hydroxy group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used. For example, a mixture of 100 parts by mass of Unidic (registered trademark) 17-806 (manufactured by DIC Corporation) and 1 part by mass of Coronate (registered trademark) L (manufactured by Nippon Polyurethane Co., Ltd.) is preferably used.

  Examples of the UV curable polyester acrylate resin include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are reacted with a polyester polyol. Those described in the publication can be used.

  Specific examples of the UV curable epoxy acrylate resin include an epoxy acrylate as an oligomer, and a reactive diluent and a photopolymerization initiator added thereto to react with each other. Can be used.

  Specific examples of the UV curable polyol acrylate resin include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like. be able to.

  Specific examples of photopolymerization initiators for these UV curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. These may be used together with a photosensitizer, and the photopolymerization initiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The amount of the photopolymerization initiator or photosensitizer used in the UV curable resin composition is in the range of 0.1 to 15 parts by mass, preferably 1 with respect to 100 parts by mass of the composition. It is in the range of -10 parts by mass.

  As a monomer of the UV curable resin, for example, a monomer having an unsaturated double bond is a common monomer such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, or styrene. Can be mentioned. In addition, as monomers having two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, trimethylolpropane triacrylate And pentaerythritol tetraacrylic ester. As commercial products, Adekaoptomer (registered trademark) KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by ADEKA Corporation), Koei Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8 MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.), Seika Beam (registered trademark) PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10 , DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, Dainichi Chemical Industries KRM7033, KRM7033, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, manufactured by Daicel UC Corporation), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC- 5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by DIC Corporation), Aulex No. 340 clear (above, manufactured by China Paint Co., Ltd.), Sun Rad (registered trademark) H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (Sanyo Chemical Industries, Ltd.) ), SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.), RCC-15C (above, made by Grace Japan KK), Aronix (registered trademark) M-6100, M-8030, M- 8060 (manufactured by Toagosei Co., Ltd.), NK hard B-420, NK ester A-DOG, NK ester A-IBD-2E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be appropriately selected and used.

  Furthermore, specific examples of compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dioxane glycol acrylate, ethoxylated acrylate, alkyl-modified diester. A pentaerythritol pentaacrylate etc. can be mentioned.

  Moreover, as curable resin, for example, thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, brominated epoxy resin, glycidyl ester type Epoxy resins such as epoxy resins and biphenyl type epoxy resins, and thermosetting resins such as unsaturated polyester resins and silicon resins are also used.

The clear hard coat layer according to the present invention preferably contains urethane (meth) acrylate, among which urethane (meth) acrylate which is a reaction product of pentaerythritol (meth) acrylate and isophorone diisocyanate. It is more preferable.
Furthermore, it is preferable that isocyanuric acid tri (meth) acrylate is contained in the clear hard coat layer.

  The solvent for dissolving the UV curable resin is not particularly limited, but alcohols such as methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol, and propylene glycol, terpenes such as α- or β-terpineol, acetone, and methyl ethyl ketone. , Cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone and other ketones, toluene, xylene, tetramethylbenzene and other aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carb Tolu, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, propylene Lenglycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, triethylene glycol monomethyl ether, triethylene Glycol ethers such as glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether ace Esters, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, methyl benzoate, N, N-dimethylacetamide, N, N- Amides such as dimethylformamide may be mentioned. These solvents may be used alone or in combination of two or more.

The clear hard coat layer may contain SiO ₂ fine particles. The surface of the SiO ₂ fine particles may be surface-modified with another composition, and is more preferably surface-modified with a reaction product of pentaerythritol (meth) acrylate and isophorone diisocyanate.

The method for applying the UV curable resin to the resin substrate is not particularly limited, and examples thereof include a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as a vapor deposition method. .
As a method of irradiating the formed clear hard coat layer with ultraviolet rays, ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, etc. It can be performed by a known method.

  The layer thickness of the clear hard coat layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm. It is preferable that the thickness of the clear hard coat layer is 1 μm or more because the heat resistance of the gas barrier film is improved. On the other hand, when the thickness of the clear hard coat layer is 10 μm or less, the optical properties of the gas barrier film are preferably adjusted, and curling of the gas barrier film is preferably suppressed.

≪Gas barrier layer (6) ≫
The gas barrier layer according to the present invention includes at least one layer, and includes silicon oxide silicon carbide represented by SiC _x O _y . For example, a first gas barrier layer is formed on a clear hard coat layer by chemical vapor deposition (CVD), and a second gas barrier layer is formed by applying a solution containing a silicon compound. Also good.

  The gas barrier layer according to the present invention preferably satisfies the following requirements (i) and (ii).

(I) The distance (L) from the gas barrier layer surface in the layer thickness direction of the gas barrier layer and the ratio of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio) Distribution curve showing the relationship between the above-mentioned distance (L) and the silicon distribution showing the relationship between the ratio of silicon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (ratio of silicon atoms) Among the oxygen distribution curves showing the relationship between the curve and the distance (L) and the ratio of the number of oxygen atoms (oxygen atom ratio) to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) The distribution curve has at least two extreme values.
(Ii) The absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio in the carbon distribution curve is 3 at% or more.

  Since the gas barrier layer has the above composition, gas barrier properties and flexibility can be highly compatible.

  Furthermore, in the region of 90% or more of the total thickness of the gas barrier layer, the average atomic ratio of each atom to the total number of carbon atoms, silicon atoms, and oxygen atoms (100 at%) is expressed by the following formula (A) or (B It is preferable to have an order of magnitude relationship represented by

Formula (A)
(Carbon average atomic ratio) <(silicon average atomic ratio) <(oxygen average atomic ratio)
Formula (B)
(Oxygen average atomic ratio) <(silicon average atomic ratio) <(carbon average atomic ratio)

  By having an order of magnitude relationship represented by the above formula (A) or (B), the bending resistance is further improved, which is more preferable.

  The preferred embodiment will be described below.

Relationship between the distance (L) from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer and the ratio of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio) A carbon distribution curve showing the relationship between the distance (L) and the ratio of the number of silicon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (silicon atom ratio), and Of the oxygen distribution curves showing the relationship between the distance (L) and the ratio of the number of oxygen atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (oxygen atom ratio), the carbon distribution curve is Preferably it has at least two extreme values. The gas barrier layer preferably has a carbon distribution curve having at least three extreme values, particularly preferably at least four extreme values, but may have five or more extreme values.
When the carbon distribution curve has at least two extreme values, the carbon atom ratio continuously changes with a concentration gradient, and the gas barrier performance during bending is enhanced.
The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 at% or less, more preferably 25 at% or less, for example. Since the number of extreme values is also caused by the thickness of the gas barrier layer, it cannot be specified unconditionally.

Here, in the case of having at least three extreme values, the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value ( The absolute value of the difference in L) (hereinafter also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably 75 nm or less. preferable. With such a distance between extreme values, there are portions with a high carbon atom ratio (maximum value) in the gas barrier layer at an appropriate period, so that the gas barrier layer is provided with an appropriate flexibility, and the gas barrier Generation of cracks when the film is bent can be more effectively suppressed / prevented.
In the present invention, the extreme value means the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer.

Here, the maximum value is a point where the value of the atomic ratio of the element (carbon, silicon or oxygen) changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed, and The value of the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer from the point is further changed within the range of 4 to 20 nm, rather than the value of the atomic ratio of the element. It means a point that decreases by 3 at% or more. That is, when changing within the range of 4 to 20 nm, the atomic ratio value of the element should be reduced by 3 at% or more within any range.
This varies depending on the thickness of the gas barrier layer. For example, when the thickness of the gas barrier layer is 300 nm, the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer is changed by 20 nm decreases by 3 at% or more. A point is preferable.

  The local minimum is the point where the atomic ratio of an element (carbon, silicon or oxygen) changes from decreasing to increasing when the distance from the surface of the gas barrier layer is changed, and the atomic ratio of the element at that point The atomic ratio of the element at the position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer from the above point is further changed within the range of 4 to 20 nm is increased by 3 at% or more. The point to do. That is, when changing within the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range.

  Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly limited because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent. Not.

  Further, in the gas barrier layer, the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio in the carbon distribution curve is preferably 3 at% or more, more preferably 5 at% or more, and 7 at% or more. More preferably it is. When the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio in the carbon distribution curve is 3 at% or more, the gas barrier performance during bending is enhanced. The “maximum value” is the maximum atomic ratio of each element in the distribution curve of each element, and is the highest value among the maximum values. Similarly, the “minimum value” is the atomic ratio of each element that is the smallest in the distribution curve of each element, and is the lowest value among the minimum values.

  Further, in the region of 90% or more (upper limit: 100%) of the thickness of the gas barrier layer, (oxygen atomic ratio), (silicon atomic ratio), (carbon atomic ratio) increase in this order (atomic ratio is O> Si > C). By satisfying such a condition, the gas barrier film obtained has sufficient gas barrier properties and flexibility. Here, the relationship of (oxygen atomic ratio), (silicon atomic ratio) and (carbon atomic ratio) is satisfied in a region of at least 90% (upper limit: 100%) of the thickness of the gas barrier layer. More preferably, at least 93% or more (upper limit: 100%) is satisfied. Here, the term “at least 90% or more of the thickness of the gas barrier layer” does not need to be continuous in the gas barrier layer, and it is only necessary to satisfy the above-described relationship in a portion of 90% or more.

  Further, the gas barrier layer according to the present invention is formed in a film surface direction (a direction parallel to the surface of the gas barrier layer) from the viewpoint of forming a layer having a uniform and excellent gas barrier property over the entire film surface. ) Is substantially uniform. Here, that the gas barrier layer is substantially uniform in the film surface direction means that a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement. The difference between the maximum value and the minimum value of the carbon atom ratio in each carbon distribution curve is the same as the number of extreme values of the carbon distribution curve obtained at any two measurement locations. Are the same or different within 5 at%.

  Furthermore, the carbon distribution curve is preferably substantially continuous. Here, the carbon distribution curve being substantially continuous means that it does not include a portion where the carbon atom ratio in the carbon distribution curve changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. In the relationship between the distance (x, unit: nm) from the surface of the gas barrier layer in the layer thickness direction of at least one of the gas barrier layers and the carbon atom ratio (C, unit: at%), Satisfying the condition expressed by the formula (1).

  When the gas barrier layer has a sublayer, a plurality of sublayers that satisfy all of the above conditions (i) to (ii) may be stacked to form the gas barrier layer. When two or more sublayers are provided, the materials of the plurality of sublayers may be the same or different.

<Method for forming gas barrier layer>
The gas barrier layer according to the present invention is formed by a plasma CVD (PECVD) method. More specifically, the substrate is formed by a plasma CVD method in which a substrate is disposed on a pair of film forming rollers, and plasma is generated by discharging between the pair of film forming rollers. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  When generating plasma in the plasma CVD method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and a substrate is provided for each of the pair of film forming rollers. It is more preferable that a plasma is generated by disposing and discharging between a pair of film forming rollers. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller. The film formation rate can be doubled compared to the plasma CVD method using no roller, and a film having substantially the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled, and the above can be efficiently performed. It is possible to form a gas barrier layer that satisfies all the conditions (i) and (ii).

  Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the oxygen content in the film forming gas is the total amount of the organic silicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount required for complete oxidation. In the gas barrier film of the present invention, the gas barrier layer is preferably a layer formed by a continuous film forming process.

  Further, from the viewpoint of productivity, a gas barrier layer is formed on the surface of the substrate by a roll-to-roll method. An apparatus that can be used when producing a gas barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and a pair of film forming processes. It is preferable that the apparatus has a configuration capable of discharging between rollers. For example, when the manufacturing apparatus shown in FIG. 4 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It becomes possible.

  Hereinafter, the method for forming the gas barrier layer will be described in more detail with reference to FIG. FIG. 4 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing a gas barrier layer. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  4 includes a feed roller 32, transport rollers 33, 34, 35, and 36, film forming rollers 39 and 40, a gas supply pipe 41, a plasma generating power source 42, and a film forming roller. Magnetic field generators 43 and 44 installed inside 39 and 40 and a winding roller 45 are provided. Further, in such a manufacturing apparatus 31, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are arranged in a vacuum chamber (not shown). Has been. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by such a vacuum pump. Details regarding the apparatus can be referred to conventionally known documents, for example, Japanese Patent Application Laid-Open No. 2011-73430.

  As described above, the gas barrier layer according to the present invention is formed by the plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roller electrode shown in FIG. This is excellent in flexibility (flexibility) when mass-produced using a plasma CVD apparatus having a counter roller electrode, mechanical strength, particularly durability during transport from roll to roll, and gas barrier performance. This is because it is possible to efficiently produce a gas barrier layer compatible with the above. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce a gas barrier film that is required for durability against temperature changes used in solar cells, electronic parts, and the like.

<Gas barrier layer formed by applying a solution containing a silicon compound (second gas barrier layer)>
The gas barrier film according to the present invention may further have a second gas barrier layer on the gas barrier layer (first gas barrier layer). The method for forming the second gas barrier layer is not particularly limited. For example, the layer containing a silicon compound is heated to modify the layer, and the layer containing the silicon compound is irradiated with active energy rays for modification. The method of quality is mentioned.
The layer containing a silicon compound is formed by applying a coating solution containing a silicon compound.

(Silicon compound)
The silicon compound is not particularly limited as long as a coating solution containing the silicon compound can be prepared. Of these, polysilazane such as perhydropolysilazane and organopolysilazane, and polysiloxane such as silsesquioxane are preferable because of their low film-forming properties, few defects such as cracks, and low residual organic matter, and high gas barrier performance. Polysilazane is more preferable, and perhydropolysilazane is particularly preferable because gas barrier performance is maintained even when bent and under high temperature and high humidity conditions.

Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a coating solution for forming a polysilazane layer. As a commercial item of polysilazane solution, AZ Electronic Materials Co., Ltd. Aquamica (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110 NP140, SP140 and the like.
The method for forming the second gas barrier layer is not particularly limited, and a known method can be applied. For forming a gas barrier layer containing a silicon compound, a compound containing an additive element in an organic solvent, and a catalyst as necessary. A method of applying a coating solution (hereinafter also simply referred to as “coating solution”) by a known wet coating method, removing the solvent by evaporation, and then performing a modification treatment is preferable.

(Gas barrier layer forming coating solution)
Hereinafter, the coating liquid using a polysilazane compound will be described.

(Polysilazane compound)
A polysilazane compound is a polymer having a bond such as Si—N, Si—H, or N—H in its structure, and an inorganic precursor such as SiO ₂ , Si ₃ N ₄ , or an intermediate solid solution thereof such as SiO _x N _y. Functions as a body.
The polysilazane compound is not particularly limited, but is preferably a compound that is converted to silica by being converted to silica at a relatively low temperature in consideration of the modification treatment described later, and is described in, for example, JP-A-8-112879. It is preferable that it is a compound which has the main frame | skeleton which consists of a unit represented by following General formula (1).

In the general formula (1), R ¹ , R ² and R ³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. At this time, R ¹ , R ² and R ³ may be the same or different.
Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.
Examples of the aryl group include aryl groups having 6 to 30 carbon atoms. More specifically, non-condensed hydrocarbon group such as phenyl group, biphenyl group, terphenyl group, pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. Can be mentioned.
Examples of the (trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specifically, 3- (triethoxysilyl) propyl group, 3- (trimethoxysilyl) propyl group and the like can be mentioned.

The substituent optionally present in R ^{1 to} R ³ is not particularly limited. For example, an alkyl group, a halogen atom, a hydroxy group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxy group (—COOH), a nitro group (—NO ₂ ), and the like. In addition, the substituent which exists depending on the case does not become the same as R < ¹ > -R < ³ > to substitute. For example, when R ^{1 to} R ³ are alkyl groups, they are not further substituted with an alkyl group. Of these, R ¹ , R ² and R ³ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group. Perhydropolysilazane (PHPS) in which all of R ¹ , R ² and R ³ are hydrogen atoms is particularly preferred. A gas barrier layer formed from such polysilazane exhibits high density.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. The molecular weight is a number average molecular weight (Mn) of about 600 to 2000 (polystyrene conversion), and can be a liquid or solid substance (depending on the molecular weight). A commercially available product may be used as the perhydropolysilazane, and examples of commercially available products include AQUAMICA NN120, NN120-10, NN120-20, NN110, NAX120, NAX120-20, NAX110, NL120A, NL120-20, NL110A, NL150A. NP110, NP140 (all manufactured by AZ Electronic Materials Co., Ltd.) and the like.

The content of the polysilazane compound in the coating solution varies depending on the layer thickness of the desired gas barrier layer, the pot life of the coating solution, etc., but is within the range of 0.2 to 35% by mass with respect to the total amount of the coating solution. Preferably there is.
The coating solution may further contain an amine catalyst, a metal and a solvent.

(Amine catalyst and metal)
The amine catalyst and the metal can promote the conversion of the polysilazane compound to the silicon oxide compound in the modification treatment described later.
The amine catalyst used is not particularly limited, but N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′— Examples include tetramethyl-1,3-diaminopropane and N, N, N ′, N′-tetramethyl-1,6-diaminohexane.
The metal used is not particularly limited, and examples thereof include platinum compounds such as platinum acetylacetonate, palladium compounds such as palladium propionate, and rhodium compounds such as rhodium acetylacetonate.

  The amine catalyst and the metal are preferably contained within a range of 0.05 to 10% by mass, and more preferably within a range of 0.1 to 5% by mass with respect to the polysilazane compound. More preferably, it is contained in the range of 0.5 to 2% by mass. When the amount of the catalyst added is within the above range, it is preferable because excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like can be prevented.

(solvent)
The solvent contained in the coating solution is not particularly limited as long as it does not react with the polysilazane compound, and a known solvent is used. Specific examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons, and ether solvents such as aliphatic ethers and alicyclic ethers. More specifically, examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, methylene chloride, trichloroethane, and the like. Examples of ether solvents include dibutyl ether, dioxane, and tetrahydrofuran.
These solvents are used alone or in combination of two or more. These solvents can be appropriately selected according to the purpose in consideration of the solubility of the polysilazane compound and the evaporation rate of the solvent.

(Formation of coating film)
As a method for applying the coating solution, a known method is appropriately employed. Examples of coating methods include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, casting film formation, bar coating, wireless bar coating, and gravure printing. Law.

  The coating thickness is appropriately set according to the purpose. For example, the thickness of the coating after drying is preferably in the range of 10 to 1000 nm, more preferably in the range of 20 to 600 nm, and still more preferably in the range of 40 to 400 nm. . If the layer thickness is 10 nm or more, sufficient gas barrier properties can be obtained, and if it is 1000 nm or less, stable coating properties can be obtained at the time of layer formation, and high light transmittance can be realized.

After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed.
Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it exists in the range of 20-200 degreeC. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.

(Coating film modification treatment)
The modification treatment of the second gas barrier layer formed by the coating method refers to a conversion reaction of a silicon compound to silicon oxide, silicon oxynitride, or the like. Specifically, the gas barrier film as a whole has gas barrier properties. The process which forms the inorganic thin film of the level which can contribute to expressing.
The conversion reaction of the silicon compound to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). In the treatment by vacuum ultraviolet irradiation, the wavelength to be used needs to be 200 nm or less from the viewpoint of efficiently performing the modification, and light energy of 100 to 200 nm larger than the interatomic bonding force in the polysilazane compound may be used. Uses light energy with a wavelength of 100 to 180 nm, and by the action of only photons called photon processes, the bonding of atoms proceeds directly through an oxidation reaction with active oxygen or ozone, so that the temperature is relatively low (about 200 ° C. The following is a method for forming a silicon oxide film. Here, the modification of the polysilazane compound means that the polysilazane compound is converted into a silicon oxide compound and / or a silicon oxynitride compound.

The light source of vacuum ultraviolet light is not particularly limited, and a known light source is used. For example, a low pressure mercury lamp, an excimer lamp, etc. are mentioned. Of these, it is preferable to use an excimer lamp, particularly a xenon (Xe) excimer lamp.
Such an excimer light (vacuum ultraviolet light) irradiation apparatus can use a commercially available lamp (for example, manufactured by USHIO INC., Manufactured by M.D.Com Co., Ltd.).
The excimer lamp is characterized in that the excimer light is concentrated at one wavelength, and only the necessary light is hardly emitted, and is highly efficient. Moreover, since excess light is not radiated | emitted, the temperature of a target object can be kept low. Further, since no time is required for starting and restarting, lighting and blinking can be performed instantaneously. In particular, the Xe excimer lamp is excellent in luminous efficiency because it emits short wavelength 172 nm vacuum ultraviolet light at a single wavelength. Since the Xe excimer lamp has a short wavelength of 172 nm and a high energy, it is known that the bond breaking ability of organic compounds is high.

Irradiation intensity of the vacuum ultraviolet light irradiation, the composition of the resin substrate and the gas barrier layer to be used also varies depending concentrations, ^etc., is preferably in the range of ^{1mW / cm 2 ~100kW / cm 2} , 1mW / cm 2 and more preferably in a range of ~10W / cm ^2.

  Although the time of vacuum ultraviolet light irradiation changes also with a base material to be used, a composition, density | concentration, etc. of a gas barrier layer, it is preferable to exist in the range of 0.1 second-10 minutes, 0.5 second-3 minutes More preferably within the range.

Integrated light quantity of vacuum ultraviolet light is not particularly limited, is preferably in the range of 200~5000mJ / cm ^2, and more preferably in a range of 500~3000mJ / cm ^2. It is preferable that the integrated light quantity of vacuum ultraviolet light is 200 mJ / cm ² or more because high gas barrier properties can be obtained by sufficient modification. On the other hand, when the cumulative amount of vacuum ultraviolet light is 5000 mJ / cm ² or less, it is preferable because a gas barrier layer having high smoothness is formed without deformation of the substrate.

  Moreover, the irradiation temperature of vacuum ultraviolet light changes with resin base materials to apply, and is suitably determined. The irradiation temperature of the vacuum ultraviolet light is preferably in the range of 50 to 200 ° C, and more preferably in the range of 80 to 150 ° C. It is preferable for the irradiation temperature to be within the above-mentioned range since deformation of the base material, deterioration of strength, etc. are unlikely to occur and the characteristics of the base material are not impaired.

  Furthermore, the irradiation atmosphere of the vacuum ultraviolet light is not particularly limited, but it is preferably performed in an atmosphere containing oxygen from the viewpoint of generating active oxygen and ozone and efficiently modifying. The oxygen concentration of the vacuum ultraviolet irradiation is preferably in the range of 10 to 10000 volume ppm (0.001 to 1 volume%), and in the range of 50 to 5000 volume ppm (0.005 to 0.5 volume%). It is more preferable that It is preferable that the oxygen concentration is 10 ppm by volume or more because the reforming efficiency is increased. On the other hand, when the oxygen concentration is 10,000 ppm by volume or less, the substitution time between the atmosphere and oxygen is preferably shortened.

  The coating film to be irradiated with ultraviolet rays is mixed with oxygen and a small amount of water at the time of application, and adsorbed oxygen and adsorbed water may also exist in the base material and adjacent layers. If oxygen or the like is used, an oxygen source required for generation of active oxygen or ozone for performing the reforming treatment is sufficient even if oxygen is not newly introduced into the irradiation chamber. In addition, since the vacuum ultraviolet light of 172 nm like the Xe excimer lamp is absorbed by oxygen, the amount of vacuum ultraviolet light reaching the coating film may be decreased. Therefore, the oxygen concentration is set low when the vacuum ultraviolet light is irradiated. In addition, it is preferable that the vacuum ultraviolet light be able to efficiently reach the coating film.

  The layer thickness, density, and the like of the second gas barrier layer obtained by the above-described modification treatment can be controlled by appropriately selecting application conditions, vacuum ultraviolet light irradiation conditions, and the like. For example, the thickness of the second gas barrier layer can be appropriately selected by appropriately selecting the irradiation method of vacuum ultraviolet light from continuous irradiation, irradiation divided into a plurality of times, and so-called pulse irradiation in which the plurality of times of irradiation is short. Density and the like are controlled.

  The thickness (application thickness) of the second gas barrier layer is appropriately set according to the purpose. For example, the thickness (application thickness) of the second gas barrier layer is preferably in the range of 1 nm to 100 μm, more preferably in the range of 10 nm to 10 μm, as the thickness after drying. More preferably, it is in the range of 50 nm to 1 μm, and particularly preferably in the range of 20 nm to 2 μm. If the dry thickness of the second gas barrier layer is 1 nm or more, sufficient gas barrier properties can be obtained, and if it is 100 μm or less, stable coating properties can be obtained when forming the second gas barrier layer. And high light transmittance can be realized.

The second gas barrier layer preferably has appropriate surface smoothness. Specifically, as the smoothness of the surface of the second gas barrier layer, the center line average roughness (Ra) of the second gas barrier layer is preferably 50 nm or less, and preferably 10 nm or less. More preferred. The lower limit of the center line average roughness (Ra) of the second gas barrier layer is not particularly limited, but is practically 0.01 nm or more and preferably 0.1 nm or more.
If it is such a gas barrier layer having Ra, another gas barrier layer can be formed on the second gas barrier layer corresponding to the unevenness in the gas barrier layer. For this reason, another gas barrier layer can more efficiently coat defects such as cracks and dangling bonds generated in the gas barrier layer, and a dense surface can be formed. Therefore, it is possible to more effectively suppress and prevent a decrease in gas barrier properties (for example, low oxygen permeability and low water vapor permeability) under high temperature and high humidity conditions. In the present invention, the centerline average roughness (Ra) of the gas barrier layer is measured by using an atomic force microscope (AFM), performing an automatic tilt correction process on the AFM topography image obtained by measuring the surface of the sample, It can be obtained by performing a three-dimensional roughness analysis.

≪Smooth layer (underlayer, primer layer) ≫
In the gas barrier film of the present invention, a smooth layer (underlying layer, primer layer) may be provided between the surface of the base material having the gas barrier layer, preferably between the base material or the clear hard coat layer and the gas barrier layer. The smooth layer is provided to flatten the rough surface of the substrate on which protrusions and the like exist, or to fill the unevenness and pinholes generated in the gas barrier layer with the protrusions existing on the substrate and flatten the surface. It is done.

Such a smooth layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer.
The smooth layer also contains a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material with an active energy ray such as ultraviolet ray to be cured is heated. The thermosetting resin etc. which are obtained by curing by the above method. The curable resins may be used alone or in combination of two or more.

  Examples of the active energy ray-curable material used for forming the smooth layer include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, and polyester. Examples include compositions containing polyfunctional acrylate monomers such as acrylates, polyether acrylates, polyethylene glycol acrylates, and glycerol methacrylates. Specifically, it is possible to use a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series (compound obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) manufactured by JSR Corporation. it can.

  The method for forming the smooth layer is not particularly limited, but a coating solution containing a curable material is applied to a spin coating method, a spray method, a blade coating method, a dipping method, a wet coating method such as a gravure printing method, or a dry method such as a vapor deposition method. After applying the coating method to form a coating film, the coating film is cured by irradiation and / or heating with active energy rays such as visible light, infrared rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, and electron beams. A method of forming them is preferable. As a method of irradiating active energy rays, for example, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp, etc. are used, preferably 100 to 400 nm, more preferably 200 to 400 nm. Or a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nitto Boseki Co., Ltd. Inorganic / organic nanocomposite material SSG coating, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicon resin, polyamidoamine-epichlorohydrin resin And the like.

The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably in the range of 10 to 30 nm.
The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times.

  The thickness of the smooth layer is not particularly limited, but is preferably in the range of 0.1 to 10 μm.

≪Anchor coat layer≫
On the surface of the base material according to the present invention, an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). As an anchor coat agent used for this anchor coat layer, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, alkyl titanate, etc. One type or two or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.
The layer thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

≪Bleed-out prevention layer≫
In the base material having a smooth layer, the surface of the base material may be contaminated due to migration of unreacted oligomers from the base material to the surface during heating. The bleed-out prevention layer has a function of suppressing contamination of the substrate surface.
The bleed-out prevention layer is usually provided on the surface opposite to the smooth layer of the substrate having the smooth layer.
The bleed-out prevention layer may have the same configuration as the smooth layer as long as it has the above function. That is, the bleed-out prevention layer can be formed by applying a UV curable resin on a substrate and then curing it.

  When at least one functional layer selected from the group consisting of the above-mentioned smooth layer, anchor coat layer, and bleed-out prevention layer is formed on the substrate, the total thickness of the substrate and the functional layer is 5 to The thickness is preferably in the range of 500 μm, and more preferably in the range of 25 to 250 μm.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.
Hereinafter, materials used in this example will be shown.

<Base material>
A polyethylene terephthalate film (manufactured by Teijin DuPont: KFL12W) having a thickness of 23 μm was used as a roll base made of a resin film.

<Clear hard coat material>
Urethane acrylate A: Kyoeisha Chemical Co., Ltd. UA-306I (reaction product of pentaerythritol triacrylate and isophorone diisocyanate)
Urethane acrylate B: UA-306H (reacted product of pentaerythritol triacrylate and hexamethylene diisocyanate) manufactured by Kyoeisha Chemical
Acrylate monomer C: Light acrylate PE-4A (pentaerythritol tetraacrylate) manufactured by Kyoeisha Chemical
Acrylate monomer D: Shin-Nakamura Chemical A-9300 (ethoxylated isocyanuric acid triacrylate)
Photopolymerization initiator: Irgacure 819 manufactured by BASF Japan
SiO ₂ fine particle E: colloidal silica (Nissan Chemical “Snowtex O”)
・ SiO ₂ fine particle F: Colloidal silica (Nissan Chemical “Snowtex O”) 10 parts by mass treated with 50 parts by mass of pentaerythritol triacrylate and 20 parts by mass of isophorone diisocyanate ・ Fluorine-based activator: manufactured by AGC Seimi Chemical S651

≪Preparation of base material for gas barrier film≫
<Preparation of gas barrier film substrate 1>
A clear hard coat layer coating solution 1 having the following composition was applied onto the substrate and dried, followed by curing with ultraviolet light to form a clear hard coat layer, thereby preparing a gas barrier film substrate 1. . The drying conditions, dry layer thickness and curing conditions are shown below.

<Clear hard coat layer coating solution 1>
Urethane acrylate A: 70 parts by weight acrylate monomer D: 20 parts by mass Photopolymerization initiator: 1 parts by weight SiO ₂ particles F: 10 parts by mass Fluorine-based active agent: 0.03 parts by diluting solvent: propylene Adjusted to 35% solids with glycol monomethyl ether

Drying conditions: 90 ° C., 90 seconds,
Dry layer thickness: 3 μm,
Curing conditions: high pressure mercury lamp, 500 mJ / cm ²

<Preparation of Gas Barrier Film Substrates 2-12>
In the production of the gas barrier film substrate 1, the urethane acrylate, acrylate monomer, and SiO ₂ fine particles of the clear hard coat layer coating liquid 1 are mixed into the materials and parts by mass (clear hard coat layer coating liquids 2 to 12) shown in Table 1. Except having changed, the base materials 2-12 for gas barrier films were produced similarly.

≪Production of gas barrier film≫
<Formation of gas barrier layer by plasma CVD method>
The gas barrier film base materials 1 to 12 on which the clear hard coat layer was formed were set in a plasma CVD film forming apparatus 31 shown in FIG. Next, a magnetic field is applied between the film forming roller 39 and the film forming roller 40, and electric power is supplied to the film forming roller 39 and the film forming roller 40, respectively. During the discharge, plasma was generated. Thereafter, a film-forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a raw material gas and oxygen gas (which also functions as a discharge gas) as a source gas) is supplied to the formed discharge region, and clear hard On the surface on which the coating layer was formed, a gas barrier layer having a layer thickness of 120 nm was formed by the plasma CVD method under the following conditions, and gas barrier films 1 to 12 were produced.

(Deposition conditions)
Feed rate of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Reaction gas (O ₂ ) supply amount: 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.8 m / min

≪Evaluation of gas barrier film≫
<Measurement of element distribution profile in clear hard coat layer and gas barrier layer>
About each produced gas barrier film, XPS depth profile measurement was performed on condition of the following, and carbon atom distribution, silicon atom distribution, and oxygen atom distribution in the distance from the surface of the gas barrier layer of the layer thickness direction were obtained.
As a result, in all the gas barrier films, the carbon distribution curve had at least two extreme values, and the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio was 3 at% or more.
For each gas barrier film, the width of the composition gradient region (nm), the change rate (gradient) of the oxygen distribution curve and carbon distribution curve in the composition gradient region, and the oxygen atomic ratio (at%) in the clear hard coat layer (average value) ) And silicon atomic ratio (at%) (average value) are shown in Table 2.

Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 μm × 400 μm oval

<Evaluation of water vapor barrier properties (water vapor permeability, WVTR)>
About each produced gas barrier film, the water vapor | steam barrier property of 100 hours after an initial stage and 85 degreeC and 85% RH environment was evaluated. The evaluation of the water vapor barrier property was carried out using AQUATRAN manufactured by MOCON, and the water vapor transmission rate (WVTR) (g / m ² · day) was measured after the numerical value was stabilized at 38 ° C. and 90% RH.
The measurement results are shown in Table 2.

<Evaluation of adhesion>
About each produced gas barrier film, adhesiveness was evaluated according to the test method described in JISK5600-5-6 at the initial stage and after 100 hours in 85 degreeC and 85% RH environment. Specifically, 100 grid-shaped cuts were made using a cutter guide with a gap interval of 1 mm. Next, an 18 mm wide tape (Cello Tape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) was applied to the cut surface on the grid, and the 2.0 kg roller was reciprocated 20 times to completely adhere to it. The peeled surface after being peeled off rapidly at the peel angle was observed, and the rank was evaluated based on the peeled area according to the following evaluation criteria. It was confirmed by TEM observation that the peeled portion was generated between the clear hard coat layer and the gas barrier layer.
The evaluation results are shown in Table 2.

A: Peeling area: less than 3% B: Peeling area: 3% or more and less than 10% Δ: Peeling area: 10% or more and less than 50% ×: Peeling area: 50% or more

<Summary>
As is clear from Table 2, the gas barrier film of the present invention is superior in adhesion between the clear hard coat layer and the gas barrier layer while maintaining the water vapor barrier property as compared with the gas barrier film of the comparative example. I understand that.
From the above, among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the clear hard coat layer and the gas barrier layer, with the clear hard coat layer in the layer thickness direction of the gas barrier layer A carbon distribution curve showing the relationship between the distance from the surface of the opposite gas barrier layer and the ratio of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio), or The composition gradient region of the oxygen distribution curve indicating the relationship with the ratio of the number of oxygen atoms (oxygen atom ratio) to the total number of carbon atoms, silicon atoms, and oxygen atoms (100 at%) may be within a range of 7 to 20 nm. It turns out that it is useful.

  The present invention can be particularly suitably used for providing a gas barrier film having excellent adhesion between the clear hard coat layer and the gas barrier layer while maintaining gas barrier properties.

2 Resin base material 4 Clear hard coat layer 6 Gas barrier layer 8, 10 Composition gradient region 31 Manufacturing device 32 Delivery rollers 33, 34, 35, 36 Transport rollers 39, 40 Film forming rollers 41 Gas supply pipe 42 Power source for generating plasma 43, 44 Magnetic field generator 45 Winding roller A Carbon distribution curve B Silicon distribution curve C Oxygen distribution curve F Gas barrier film

Claims (8)

A clear hard coat layer made of UV curable resin and at least one gas barrier layer containing silicon oxide carbide formed by a roll-to-roll CVD apparatus are sequentially laminated on at least one surface of the resin base material. Gas barrier film,
Among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the clear hard coat layer and the gas barrier layer, the clear hard coat layer in the thickness direction of the gas barrier layer and Is a carbon distribution curve showing the relationship between the distance from the surface of the gas barrier layer on the opposite side and the ratio of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio) Or the width of the composition gradient region of the oxygen distribution curve showing the relationship with the ratio of oxygen atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (oxygen atom ratio) is in the range of 7 to 20 nm A gas barrier film characterized by being inside.   The oxygen atom ratio in the clear hard coat layer is in the range of 25 to 45 at%, and the ratio of the number of silicon atoms (silicon atom ratio) to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) is 10 to 10%. The gas barrier film according to claim 1, wherein the gas barrier film is in a range of 30 at%. The gas barrier film according to claim 1 or 2, wherein the clear hard coat layer contains SiO ₂ fine particles. The gas barrier film according to claim 3, wherein the SiO ₂ fine particles are surface-modified with a reaction product of pentaerythritol (meth) acrylate and isophorone diisocyanate.   The gas barrier film according to any one of claims 1 to 4, wherein the clear hard coat layer contains urethane (meth) acrylate.   The gas barrier film according to claim 5, wherein the urethane (meth) acrylate is a reaction product of pentaerythritol (meth) acrylate and isophorone diisocyanate.   The gas barrier film according to claim 5 or 6, wherein the clear hard coat layer further contains isocyanuric acid tri (meth) acrylate.   The carbon distribution curve in the gas barrier layer has at least two extreme values, and the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is 3 at% or more. The gas barrier film according to claim 7.

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