JP6354302B2 - Gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film.

  Conventionally, a gas barrier film formed by laminating a plurality of layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film is used to block various gases such as water vapor and oxygen. For example, it is widely used for packaging of articles that require the use of, for example, packaging for preventing deterioration of foods, industrial products, pharmaceuticals, and the like. In addition to packaging applications, development to flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, etc. has been demanded, and many studies have been made.

  Patent Document 1 includes a first chemical vapor deposition layer formed by a plasma CVD method and containing silicon element and having an oxygen concentration of 0 element% or more and less than 10 element%; and formed by plasma CVD method and containing silicon element And a second chemical vapor deposition layer having an oxygen concentration of greater than 35 element% and less than or equal to 70 element%, and a laminate comprising a substrate and a substrate.

  Patent Document 2 has at least one silicon hydronitride layer and at least one silicon nitride layer on the surface of a flexible support substrate, and the composition between these adjacent layers is continuous. A gas barrier film that has changed in nature and does not have a clear interface is disclosed.

  Patent Document 3 includes a base film, a weather-resistant coat layer, and an inorganic thin film layer formed on the surface of the coat layer, and the weather-resistant coat layer includes an ultraviolet-stable group, an ultraviolet-absorbing group, and a cycloalkyl. A gas barrier film containing an acrylic copolymer having at least one group selected from the group consisting of groups is disclosed.

Patent Document 4 has at least one barrier layer composed of a ceramic material, and the barrier layer is coated with a solution of perhydropolysilazane (PHPS) and then cured to form silicon oxide (SiO _x ). A gas barrier film having a layer formed thereon is disclosed.

  Patent Document 5 discloses a gas barrier film comprising a base material and at least one thin film layer formed on at least one surface of the base material, and a region of 90% or more of the thickness of the thin film layer. Discloses a gas barrier laminate film in which the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are in a specific relationship.

JP 2013-185207 A Japanese Patent No. 5139153 JP 2009-202589 A Special table 2008-536711 gazette JP 2011-73430 A

  However, the techniques described in Patent Documents 1 to 5 have a problem that gas barrier performance and adhesion that are stable for a long time cannot be exhibited even in a high temperature and high humidity environment.

  Accordingly, an object of the present invention is to provide a gas barrier film having gas barrier performance and adhesion that are stable for a long time even in a high temperature and high humidity environment.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by the following gas barrier film, and the present invention has been completed.

  That is, the present invention is a gas barrier film comprising a resin base material and a gas barrier layer containing a silicon atom, an oxygen atom, and a carbon atom formed on at least one surface side of the resin base material, The gas barrier layer has a change rate of Si—C bond before and after storage for 300 hours in an environment of 85 ° C. and 85% RH of 15% or less, and the composition of the gas barrier layer continuously changes in the layer thickness direction. The gas barrier film satisfies the requirements (1) and (2).

(1) Among the distribution curves of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the gas barrier layer, the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer; In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (100 at%) (referred to as “carbon atom ratio (at%)”), at least one extreme value And the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5 at% or more:
(2) In the region of 90% or more of the total thickness of the gas barrier layer, the average atomic ratio of each atom with respect to the total amount (100 at%) of silicon atoms, oxygen atoms, and carbon atoms is expressed by the following formula (A) or ( It has the order of magnitude relationship represented by B).

  ADVANTAGE OF THE INVENTION According to this invention, the gas barrier film which has the gas barrier performance and adhesiveness which were stable for a long period of time also in high temperature, high humidity environment can be provided.

It is a schematic diagram which shows an example of the plasma CVD apparatus used for formation of the gas barrier layer which concerns on this invention.

  The gas barrier film of the present invention is a gas barrier film comprising a resin substrate and a gas barrier layer containing silicon atoms, oxygen atoms, and carbon atoms formed on at least one surface side of the resin substrate. The gas barrier layer has a change rate of Si—C bonds of about 15% or less before and after storage for 300 hours in an environment of 85 ° C. and 85% RH, and the composition of the gas barrier layer continuously changes in the layer thickness direction. The following requirements (1) and (2) are satisfied.

(1) Among the distribution curves of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the gas barrier layer, the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer; In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (100 at%) (referred to as “carbon atom ratio (at%)”), at least one extreme value And the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5 at% or more:
(2) In the region of 90% or more of the total thickness of the gas barrier layer, the average atomic ratio of each atom with respect to the total amount (100 at%) of silicon atoms, oxygen atoms, and carbon atoms is expressed by the following formula (A) or ( It has the order of magnitude relationship represented by B).

  The gas barrier film of the present invention having such a configuration has gas barrier performance and adhesion that are stable for a long period of time even in a high temperature and high humidity environment.

  The details of why the above-described effects can be obtained by the gas barrier film of the present invention are unknown, but the gas barrier layer containing silicon atoms, oxygen atoms, and carbon atoms is composed of -Si-O-Si- (siloxane). (Bonded) network has a structure such as -Si-C-Si- bond. Since the Si—O bond is about 444 kJ / mol and the Si—C bond is about 337 kJ / mol, the Si—O bond is a stronger bond. However, the bond angles of the Si—O—Si bond and the Si—C—Si bond are about 134 ° for the Si—O—Si bond and about 120 ° for the Si—C—Si bond. The bonding is considered to have a high gas barrier property (small gas permeability) because the rotation barrier is large and the fluidity is poor. That is, the main part of the bond that deteriorates in a high-temperature and high-humidity environment is a Si-C bond whose bond energy is smaller than that of the Si-O bond, but it is considered that the Si-C bond contributes to the gas barrier property. It is done. Therefore, by densifying the film and improving the degree of cross-linking of the gas barrier layer, the rate of change of Si—C bond before and after storage for 300 hours in an 85 ° C. and 85% RH environment is set to 15% or less, so that a high temperature and high humidity environment Under this condition, the gas barrier performance is stable for a long time.

  The gas barrier layer according to the present invention satisfies the requirements (1) and (2). By adopting such a configuration, a stress relaxation layer exists in the gas barrier layer in which many carbon atoms exist and glassiness is lowered. Therefore, the gas barrier film of the present invention exhibits stable adhesion between the resin substrate and the gas barrier layer for a long period of time even in a high temperature and high humidity environment.

  In addition, said mechanism is based on presumption and this invention is not bound to the said mechanism at all.

  Hereinafter, although preferable embodiment of this invention is described, this invention is not limited only to the following embodiment. In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

In addition, the “gas barrier property” in the present invention means that the permeated water amount measured by the method described in Examples is less than 1 × 10 ⁻³ g / m ² / day.

[Resin substrate]
As the resin substrate according to the present invention, a plastic film or a plastic sheet is preferably used, and a film or sheet made of a colorless and transparent resin is more preferably used. The plastic film used is not particularly limited in material, thickness and the like as long as it can hold a gas barrier layer or the like, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and 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, Alicyclic Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  When the gas barrier film of the present invention 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 of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C. or more and 300 ° C. or less is used.

  Since the gas barrier film of the present invention is used as an electronic device such as an organic EL element, the resin substrate 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 calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.

  However, even when the gas barrier film of the present invention is used for display applications, 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 in the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the application, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer, a primer layer, and a clear hard coat layer. As the functional layer, in addition to those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably employed.

  The resin base material preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. The lower limit is not particularly limited, but is practically 0.01 nm or more. If necessary, both surfaces of the resin substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.

  In addition, the resin base listed above may be an unstretched film or a stretched film.

  The resin base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched resin substrate 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. After producing an unstretched resin base material, it is preferable to perform a stretching treatment or a heat treatment by a conventionally known method as described above, if necessary.

  At least on the side of the resin substrate on which the gas barrier layer is provided, various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, lamination of a clear hard coat layer described later, etc. May be performed, and it is preferable to combine the above treatments as necessary.

[Gas barrier layer]
The gas barrier layer according to the present invention contains silicon atoms, oxygen atoms, and carbon atoms, and the rate of change of Si—C bonds before and after storage for 300 hours in an environment of 85 ° C. and 85% RH is 15% or less. When the rate of change of the Si-C bond exceeds 15%, for example, gas barrier performance and adhesion after storage in a high-temperature and high-humidity environment such as 85 ° C. and 85% RH deteriorate. The rate of change of the Si—C bond is preferably 5 to 10%.

  The rate of change of the Si-C bond is determined by, for example, a plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied using a source gas containing an organosilicon compound, oxygen gas, and carrier gas, which will be described later. In the formation of the gas barrier layer used, a low molecular weight hydrocarbon gas such as methane or ethylene is added to control the flow rate ratio between the source gas and the carrier gas (helium gas, argon gas, etc., preferably argon gas). It can be controlled by a method such as a low pressure during film formation or a large amount of raw material gas.

  In addition, the composition of the gas barrier layer according to the present invention continuously changes in the layer thickness direction, and simultaneously satisfies the following requirements (1) and (2).

  (1) Among the distribution curves of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the gas barrier layer, the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer, and silicon In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of atoms, oxygen atoms, and carbon atoms (100 at%) (referred to as “carbon atom ratio (at%)”), at least one extreme value is And the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5 at% or more.

  (2) In a region of 90% or more of the total thickness of the gas barrier layer, the average atomic ratio of each atom to the total amount (100 at%) of silicon atoms, oxygen atoms, and carbon atoms is expressed by the following formula (A) or (B ) In the order of magnitude.

  In addition, since the measurement accuracy in the resin base material interface region is slightly lowered due to noise of constituent atoms of the resin base material, the region satisfying the relationship defined by the above formula (A) or formula (B) is a gas barrier. A region in the range of 90 to 95% of the total layer thickness is preferred.

  Details of the gas barrier layer according to the present invention will be described below.

(Carbon atom distribution profile in gas barrier layer)
The gas barrier layer according to the present invention contains silicon atoms, oxygen atoms, and carbon atoms as constituent elements of the gas barrier layer, the composition continuously changes in the layer thickness direction, and the element distribution in the depth direction by X-ray photoelectron spectroscopy Of the distribution curve of each constituent element based on the measurement, the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer and the carbon atoms relative to the total amount (100 at%) of silicon atoms, oxygen atoms, and carbon atoms In a carbon distribution curve showing a relationship with a ratio of amounts (also referred to as “carbon atom ratio (unit: at%)”), the carbon curve has at least one extreme value, and the maximum extreme value (maximum value) of the carbon atom ratio And the absolute value of the difference between the minimum extreme value (minimum value) is 5 at% or more. When the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio in the carbon distribution curve is less than 5 at%, the resulting gas barrier film is bent. Gas barrier properties and adhesion are insufficient.

  The absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is more preferably 6 at% or more, and further preferably 7 at% or more.

  In the gas barrier layer according to the present invention, the gas barrier film has a configuration in which the carbon atom ratio continuously changes with a concentration gradient in a specific region of the gas barrier layer. This is a preferred embodiment from the viewpoint of providing.

  In the gas barrier layer according to the present invention having such a carbon atom distribution profile, the carbon distribution curve in the layer has at least one extreme value, and more preferably has at least two extreme values, and at least 3 More preferably, it has two extreme values. When the carbon distribution curve does not have an extreme value, the gas barrier property when the obtained gas barrier film is bent is insufficient. Further, in the case of having at least two or three extreme values in this way, one extreme value of the carbon distribution curve and an extreme value adjacent to the extreme value of the gas barrier layer in the layer thickness direction of the gas barrier layer. The absolute value of the difference in distance from the surface is preferably 200 nm or less, and more preferably 100 nm or less.

  In the present invention, the extreme value of the distribution curve means a measured value of the maximum value or the minimum value of the atomic ratio of the element to the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer.

  In the present invention, the maximum value is a point where the value of the atomic ratio of an element changes from increase to decrease when the distance from the surface of the gas barrier layer is changed, and is more than the value of the atomic ratio of the element at that point. This means that the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the thickness direction of the gas barrier layer is further changed by 20 nm is reduced by 3 at% or more.

  Furthermore, in the present invention, the minimum value is a point where the value of the atomic ratio of the element changes from decreasing to increasing when the distance from the surface of the gas barrier layer is changed, and from the value of the atomic ratio of the element at that point This also means that 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 is further changed by 20 nm from that point increases by 3 at% or more.

  In the above description regarding the carbon atom distribution profile, “the total amount of silicon atoms, oxygen atoms, and carbon atoms” means the total at% of silicon atoms, oxygen atoms, and carbon atoms, and “the amount of carbon atoms” "Means the number of carbon atoms. The term “at%” in the present invention means the atomic ratio of each atom when the total number of silicon atoms, oxygen atoms, and carbon atoms is 100 at%. The same applies to the amount of silicon atoms and the amount of oxygen atoms for the silicon distribution curve, oxygen distribution curve, and carbon distribution curve.

(Each element profile in the gas barrier layer)
The gas barrier layer according to the present invention contains silicon atoms, oxygen atoms, and carbon atoms as constituent elements, but preferred embodiments of the ratio of each of silicon atoms and oxygen atoms, the maximum value, and the minimum value Is described below.

<Relationship between maximum and minimum values of silicon atom ratio>
In the gas barrier layer according to the present invention, the absolute value of the difference between the maximum value and the minimum value in the silicon distribution curve is preferably less than 5 at%, more preferably less than 4 at%, and more preferably less than 3 at%. Particularly preferred. When the absolute value is less than 5 at%, the gas barrier property and mechanical strength of the obtained gas barrier film are sufficient. The silicon distribution curve here refers to the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the gas barrier layer. Of silicon atoms indicating the relationship between the distance from the surface and the ratio of the amount of silicon atoms to the total amount (100 at%) of carbon atoms, silicon atoms, and oxygen atoms (also referred to as “silicon atom ratio (unit: at%)”) Refers to the distribution curve.

<Relationship between maximum and minimum oxygen atom ratio>
In the gas barrier layer according to the present invention, the absolute value of the difference between the maximum value and the minimum value in the oxygen distribution curve is preferably 5 at% or more, more preferably 6 at% or more, and preferably 7 at% or more. Further preferred. When the absolute value is 5 at% or more, the gas barrier property when the obtained gas barrier film is bent is sufficient. The oxygen distribution curve here refers to the distribution curve of each constituent element based on the measurement of the element distribution in the depth direction by X-ray photoelectron spectroscopy for the gas barrier layer, of the gas barrier layer in the layer thickness direction of the gas barrier layer. Oxygen indicating the relationship between the distance from the surface and the ratio of the amount of oxygen atoms to the total amount (100 at%) of silicon atoms, oxygen atoms, and carbon atoms (also referred to as “oxygen atom ratio (unit: at%)”) Refers to the distribution curve of elements.

  In the gas barrier layer according to the present invention, the total amount of oxygen atoms and carbon atoms with respect to the distance from the surface of the layer in the layer thickness direction and the total amount (100 at%) of silicon atoms, oxygen atoms, and carbon atoms. In an oxygen-carbon total distribution curve (also referred to as oxygen-carbon distribution curve), which is a ratio (also referred to as an oxygen-carbon total atomic ratio), the absolute value of the difference between the maximum value and the minimum value of the oxygen-carbon total atomic ratio. Is preferably less than 5 at%, more preferably less than 4 at%, and particularly preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is sufficient.

  In the gas barrier layer according to the present invention, 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 amount of silicon atoms, oxygen atoms, and carbon atoms (100 at%) is expressed by the above formula. (A) or (B) has an order of magnitude relationship represented by (B). By satisfying such requirements, the gas barrier film of the present invention has gas barrier performance and adhesion that are stable for a long time even in a high temperature and high humidity environment.

The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen-carbon total distribution curve in the thickness direction of the gas barrier layer described above are measured by X-ray photoelectron spectroscopy (XPS) and measured by argon or the like. By using together with rare gas ion sputtering, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time in this way, the etching time generally correlates with the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer in the layer thickness direction. As the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement may be adopted. it can. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value). More specifically, the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon total distribution curve can be measured by the methods described in Examples.

  In the present invention, the gas barrier layer is substantially in the film surface direction (direction parallel to the surface of the gas barrier layer) from the viewpoint of forming a gas barrier layer having a uniform and excellent gas barrier property over the entire film surface. Preferably it is uniform. In the present invention, that the gas barrier layer is substantially uniform in the film surface direction means that the carbon distribution curve, the silicon distribution curve, and the oxygen at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement. When the distribution curve and the distribution curve of the oxygen-carbon total are prepared, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the carbon in each carbon distribution curve The absolute value of the difference between the maximum value and the minimum value of the atomic ratio is the same or within 5 at%.

  The gas barrier film according to the present invention is indispensable to have at least one gas barrier layer that simultaneously satisfies the requirements (1) and (2) defined in the present invention. Two or more layers may be provided. Furthermore, when two or more such gas barrier layers are provided, the materials of the plurality of gas barrier layers may be the same or different. In addition, when two or more such gas barrier layers are provided, such a gas barrier layer may be formed on one surface of the resin base material, and formed on both surfaces of the resin base material. May be.

  In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve in the gas barrier layer, the silicon atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms is in the range of 20 to 45 at%. It is preferable that the range is 25 to 40 at%. In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve in the gas barrier layer, the oxygen atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms is in the range of 45 to 75 at%. It is preferable that it is in the range of 50 to 70 at%. Furthermore, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve in the gas barrier layer, the carbon atom ratio to the total amount of silicon atoms, oxygen atoms, and carbon atoms is in the range of 1 to 25 at%. It is preferable that it is in the range of 2 to 20 at%.

<Gas barrier layer thickness>
The thickness of the gas barrier layer according to the present invention is preferably in the range of 5 to 1000 nm, more preferably in the range of 10 to 1000 nm, and still more preferably in the range of 100 to 1000 nm. When the thickness of the gas barrier layer is within the above range, curling is small, gas barrier properties against various gases such as water vapor and oxygen are excellent, and deterioration of gas barrier properties due to bending is not observed. In particular, even when the thickness of the gas barrier layer is increased within the above range, it is excellent in that the increase in film curl can be effectively suppressed.

  Even when there are two or more gas barrier layers, the total thickness of the gas barrier layers is preferably in the range of 5 to 1000 nm, more preferably in the range of 10 to 1000 nm, and in the range of 100 to 1000 nm. It is particularly preferred that If the total thickness of the gas barrier layers is within the above range, desired flatness can be achieved, curl is small, gas barrier properties against various gases such as water vapor and oxygen, etc. There is no decline. Furthermore, when the total thickness of the gas barrier layers is increased within the above range, the film curl can be effectively prevented from increasing.

<Method for forming gas barrier layer>
The method for forming the gas barrier layer according to the present invention is not particularly limited, but it is easy to form a gas barrier layer in which the element distribution is precisely controlled so as to satisfy the above requirements (1) and (2). From the viewpoint, plasma chemical vapor deposition (plasma CVD, plasma-enhanced chemical vapor deposition (PECVD), hereinafter, also simply referred to as “plasma CVD method”) is preferable.

  Although it does not specifically limit as a plasma CVD method, The plasma CVD method using the plasma CVD method of the atmospheric pressure or the atmospheric pressure described in the international publication 2006/033233, and the plasma CVD apparatus with a counter roll electrode is mentioned. .

  Especially, since productivity is high, it is preferable to form a 1st layer by the plasma CVD method using the plasma CVD apparatus which has a counter roll electrode. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  Hereinafter, a method for forming a gas barrier layer by a plasma CVD method using a plasma CVD apparatus having a counter roll electrode will be described.

  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 resin base is used for each of the pair of film forming rollers. A material (here, the resin base material includes a form in which the resin base material is processed or has a functional layer on the resin base material) is disposed, and discharge is generated between a pair of film forming rollers to generate plasma. More preferably. In this way, by using a pair of film forming rollers, placing a resin base on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller at the time of film forming While forming the surface portion of the resin substrate existing above, the surface portion of the resin substrate existing on the other film forming roller can be formed at the same time, so that a thin film can be produced efficiently. In addition, the film formation rate can be doubled compared to the normal plasma CVD method that does not use a roller, and a film with substantially the same structure can be formed, so it is possible to at least double the extreme value in the carbon distribution curve. Thus, it is possible to efficiently form a gas barrier layer that satisfies the requirements (1) and (2).

  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 includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary 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.

  Moreover, it is preferable that the gas barrier film which concerns on this invention forms a gas barrier layer on the surface of a resin base material by a roll-to-roll system from a viewpoint of productivity. Further, 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 formation rollers and a plasma power source, and the pair of film formations. It is preferable that the apparatus has a configuration capable of discharging between rollers. For example, when the manufacturing apparatus shown in FIG. 1 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible.

  Hereinafter, the manufacturing method of the gas barrier layer which comprises the gas barrier film which concerns on this invention is demonstrated in detail, referring FIG. FIG. 1 is a schematic view showing an example of a plasma CVD apparatus to which a magnetic field that can be suitably used in the production of the gas barrier layer constituting the gas barrier film according to the present invention is applied.

  The plasma CVD apparatus shown in FIG. 1 mainly includes a delivery roller 14, transport rollers 15, 16, 17 and 18, film formation rollers 19 and 20, a gas supply pipe 21, a plasma generation power source 22, Magnetic field generators 23 and 24 installed inside the film forming rollers 19 and 20 and a winding roller 25 are provided. In such a plasma CVD apparatus, at least the film forming rollers 19 and 20, the gas supply pipe 21, the plasma generation power source 22, and the magnetic field generators 23 and 24 are contained in a vacuum chamber (not shown). Has been placed. Further, in such a plasma CVD apparatus, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by this vacuum pump.

  In such a plasma CVD apparatus, each film-forming roller is for plasma generation so that a pair of film-forming rollers (film-forming roller 19 and film-forming roller 20) can function as a pair of counter electrodes. Connected to a power source 22. By supplying electric power to the pair of film forming rollers (the film forming roller 19 and the film forming roller 20) from the power source 22 for generating plasma, the space between the film forming roller 19 and the film forming roller 20 can be discharged. Accordingly, plasma can be generated in a space (also referred to as a discharge space) between the film formation roller 19 and the film formation roller 20. In addition, since the film-forming roller 19 and the film-forming roller 20 are used as electrodes in this way, materials and designs that can be used as electrodes may be appropriately changed. In such a plasma CVD apparatus, the pair of film forming rollers (film forming rollers 19 and 20) are preferably arranged so that their central axes are substantially parallel on the same plane. In this way, by arranging a pair of film forming rollers (film forming rollers 19 and 20), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled. And according to such a manufacturing apparatus, it is possible to form a gas barrier layer on the surface of the resin base material 12 by CVD method, and the gas barrier layer component on the surface of the resin base material 12 on the film-forming roller 19 Further, the gas barrier layer component can be deposited on the surface of the resin base material 12 also on the film forming roller 20, so that the gas barrier layer can be efficiently formed on the surface of the resin base material 12. .

  The film forming roller 19 and the film forming roller 20 are characterized in that magnetic field generators 23 and 24 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  The magnetic field generators 23 and 24 provided on the film forming roller 19 and the film forming roller 20 respectively are a magnetic field generator 23 provided on one film forming roller 19 and a magnetic field generator provided on the other film forming roller 20. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between the magnetic field generators 24 and the magnetic field generators 23 and 24 form a substantially closed magnetic circuit. By providing such magnetic field generators 23 and 24, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surface of each of the film forming rollers 19 and 20, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

  The magnetic field generators 23 and 24 provided on the film forming roller 19 and the film forming roller 20 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generating device 23 and the other magnetic field generating device. It is preferable to arrange the magnetic poles 24 so that the opposite magnetic poles have the same polarity. For example, in the magnetic field generators 23 and 24 shown in FIG. 1, the racetrack-shaped magnetic poles (one for each film-forming roller, two in total) are provided on the long protrusion at the center of the cross-sectional chevron. It is arranged so as to be polar (N pole or S pole), and the racetrack-shaped magnetic poles (two for each film-forming roller, four in total) are also provided on the short protrusions on both sides of the center of the mountain-shaped cross section. All of these magnetic poles are arranged so as to have the same polarity (S pole or N pole) as the counter pole of the magnetic pole of the central long protrusion. However, the magnetic poles (N pole and S pole) may be arranged in reverse. By providing such magnetic field generators 23 and 24, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 23 and 24 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so a wide resin wound around the roller width direction. The substrate 12 is excellent in that a gas barrier layer that is a vapor deposition film can be efficiently formed.

  Furthermore, as the film forming rollers 19 and 20, known rollers can be used as appropriate. As the film forming rollers 19 and 20, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. The diameters of the film forming rollers 19 and 20 are preferably in the range of 100 to 1000 mmφ, particularly in the range of 100 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter is 100 mmφ or more, the plasma discharge space will not be reduced, so there will be no deterioration in productivity, and it will be possible to avoid applying the total amount of heat of the plasma discharge to the film (resin substrate 12) in a short time, and the residual stress Is preferable because it is difficult to increase. On the other hand, a diameter of 1000 mmφ or less is preferable because practicality can be maintained in terms of device design including uniformity of the plasma discharge space.

  Further, as the feed roller 14 and the transport rollers 15, 16, 17 and 18 used in such a plasma CVD apparatus, known rollers can be appropriately selected and used. The winding roller 25 is not particularly limited as long as it can wind the resin base material 12 on which the gas barrier layer 26 is formed, and a known roller can be used as appropriate.

  As the gas supply pipe 21 and the vacuum pump, those capable of supplying or discharging the source gas and the oxygen gas at a predetermined rate can be appropriately used.

  The gas supply pipe 21 serving as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 19 and the film formation roller 20 and is a vacuum serving as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. In this way, by providing the gas supply pipe 21 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 19 and the film formation roller 20. It is excellent in that the film formation efficiency can be improved.

  Further, as the plasma generation power source 22, a power source of a conventionally known plasma generation apparatus can be used. Such a power source 22 for generating plasma supplies power to the film forming roller 19 and the film forming roller 20 connected thereto, and makes it possible to use them as a counter electrode for discharging. Such a plasma generation power source 22 can perform the plasma CVD method more efficiently, and can alternately reverse the polarity of a pair of film forming rollers (AC power source or the like). Is preferably used. Moreover, as such a plasma generating power source 22, it is possible to perform the plasma CVD method more efficiently, so that the applied power can be in the range of 100 W to 10 kW, and the AC frequency is 50 Hz. It is more preferable that it can be in the range of ˜500 kHz. As the magnetic field generators 23 and 24, known magnetic field generators can be used as appropriate.

  Using the plasma CVD apparatus as shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the strength of the magnetic field generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the resin The gas barrier film according to the present invention can be produced by appropriately adjusting the conveyance speed of the substrate. That is, using the plasma CVD apparatus shown in FIG. 1, a magnetic field is generated between a pair of film forming rollers (film forming rollers 19 and 20) while supplying a film forming gas (raw material gas) into the vacuum chamber. By performing plasma discharge, the film forming gas (raw material gas or the like) is decomposed by plasma, and on the surface of the resin base material 12 on the film forming roller 19 and on the surface of the resin base material 12 on the film forming roller 20. The gas barrier layer according to the present invention is formed by the plasma CVD method. In such film formation, the resin base material 12 is transported by the delivery roller 14 and the film formation roller 19, respectively, so that the resin base material 12 is formed by a roll-to-roll continuous film formation process. A gas barrier layer is formed on the surface.

  As the film forming gas (such as source gas) supplied from the gas supply pipe 21 to the facing space, source gas, reaction gas, carrier gas, discharge gas, or the like can be used alone or in combination of two or more. The source gas in the film forming gas used for forming the gas barrier layer can be appropriately selected and used according to the material of the gas barrier layer to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used.

  Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane.

  Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of properties such as the handleability of the compound and the gas barrier properties of the resulting gas barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. Especially, since it can adjust to the film | membrane composition of this embodiment easily, it is preferable that an organosilicon compound is included as source gas.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide can be appropriately selected and used. As the reactive gas, for example, oxygen and ozone can be used, and oxygen is preferably used from the viewpoint of simplicity. In addition, a reactive gas for forming a nitride may be used. For example, nitrogen or ammonia can be used. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

  When such a film forming gas contains a raw material gas and a reactive gas, the ratio of the raw material gas and the reactive gas is a reaction that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive as compared with the ratio of the amount of gas. By not making the ratio of the reaction gas excessive, the gas barrier layer formed is excellent in that excellent gas barrier properties and bending resistance can be obtained. Moreover, when the film-forming gas contains an organosilicon compound and oxygen, the amount is preferably less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film-forming gas.

Hereinafter, as the film forming gas, hexamethyldisiloxane (organosilicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a raw material gas and oxygen (O ₂ ) as a reactive gas are used. Taking a case of producing a silicon-oxygen-based thin film as an example, a suitable ratio of the raw material gas and the reactive gas in the film forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen system When the thin film is produced, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and silicon dioxide is generated.

  In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, a uniform silicon dioxide film is formed when oxygen is contained in the film forming gas in an amount of 12 moles or more per mole of hexamethyldisiloxane and a uniform silicon dioxide film is formed (a carbon distribution curve exists). Therefore, it becomes impossible to form a gas barrier layer containing carbon. Therefore, when the gas barrier layer is formed, the oxygen amount is less than the stoichiometric ratio of 12 moles with respect to 1 mole of hexamethyldisiloxane so that the reaction of the reaction formula (1) does not proceed completely. It is preferable to reduce it. In the actual reaction in the plasma CVD chamber (film formation chamber), the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film. Even if the molar amount (flow rate) of oxygen is 12 times the molar amount (flow rate) of hexamethyldisiloxane as a raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when the oxygen content is supplied in a large excess compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is changed). (It may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material). Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. .

  By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer. From the viewpoint of use as a flexible substrate for devices that require transparency, such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas The lower limit of (flow rate) is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.

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

  In order to obtain the gas barrier layer according to the present invention, it is preferable to appropriately select the type and flow rate of the carrier gas. A rare gas such as argon has high ionization properties, and when used as a carrier gas, activates a gas phase reaction in forming the gas barrier layer, resulting in densification of the gas barrier layer and improvement in the degree of crosslinking. More preferably, argon gas is used. The flow ratio is preferably argon gas: organosilicon compound = 0.1: 1 to 2: 1, more preferably argon gas: organosilicon compound = 0.2: 1 to 2: 1. preferable.

  Although the pressure (degree of vacuum) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-100 Pa.

  In the plasma CVD method using a plasma CVD apparatus or the like as shown in FIG. 1, the electric power applied to the electrode drum connected to the plasma generating power source 22 for discharging between the film forming rollers 19 and 20 is a raw material. Although it can adjust suitably according to the kind of gas, the pressure in a vacuum chamber, etc. and it cannot say generally, it is preferable to set it as the range of 0.1-10 kW. When the applied power is in such a range, no generation of particles (illegal particles) is observed, and the amount of heat generated during film formation is within the control range, so that the surface temperature of the resin base material during film formation increases. In addition, there is no thermal deformation of the resin base material, performance deterioration due to heat, and generation of wrinkles during film formation. In addition, damage to the film forming roller due to melting of the resin base material by heat and generation of a large current discharge between the bare film forming rollers can be prevented.

  Although the conveyance speed (line speed) of the resin base material 12 can be suitably adjusted according to the kind of raw material gas, the pressure in a vacuum chamber, etc., it is preferable to set it as the range of 0.25-100 m / min. More preferably, it is in the range of 0.5 to 20 m / min. If the line speed is within the above range, wrinkles due to the heat of the resin base material hardly occur, and the thickness of the formed gas barrier layer can be sufficiently controlled.

  The gas barrier layer may be a single layer or a laminated structure of two or more layers. When the gas barrier layer has a laminated structure of two or more layers, the gas barrier layers may have the same composition or different compositions.

  In the gas barrier layer according to the present invention obtained by the above manufacturing method, the critical load measured based on ASTM D718705 is preferably 2.0 μN or more, and more preferably 4.0 μN or more. By having a critical load in such a range, the mechanical strength of the gas barrier film is improved. Such a critical load can be controlled by controlling the flow rate, vacuum degree, power, etc. of the argon gas.

[Each functional layer]
In the gas barrier film according to the present invention, each functional layer can be provided as necessary in addition to the gas barrier layer described above.

<Overcoat layer>
An overcoat layer may be formed on the gas barrier layer according to the present invention for the purpose of improving flexibility. As the organic material used for the formation of the overcoat layer, organic resins such as organic monomers, oligomers and polymers, and organic / inorganic composite resins using siloxane and silsesquioxane monomers, oligomers and polymers having organic groups are preferably used. be able to. These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed from the organic resin composition coating solution to be cured.

[Undercoat layer (smooth layer)]
The support according to the present invention may have an undercoat layer (smooth layer) between the surface of the resin substrate having the gas barrier layer, preferably between the resin substrate and the gas barrier layer. The undercoat layer (smooth layer) is flattened to flatten the rough surface of the resin base material where protrusions and the like exist, or by filling the irregularities and pinholes generated in the gas barrier layer with the protrusions existing on the resin base material. It is provided to Further, it is provided for the purpose of improving the adhesion (adhesion) between the resin substrate and the gas barrier layer.

  Such an undercoat layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, the gas barrier film according to the present invention preferably further includes an undercoat layer containing a carbon-containing polymer between the support and the gas barrier layer.

  The undercoat 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 or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These 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 undercoat 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, Examples thereof include compositions containing polyfunctional acrylate monomers such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate. Specifically, an organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series (compound formed by bonding an organic compound having a polymerizable unsaturated group to silica fine particles), which is an ultraviolet curable material manufactured by JSR Corporation. Can be used. It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no restriction in particular.

  The method for forming the undercoat layer is not particularly limited, but a coating liquid containing a curable material is applied to a spin coating method, a spray method, a blade coating method, a die coating method, a dip coating method, a gravure printing method, or a wet coating method. After applying by a dry coating method such as vapor deposition to form a coating film, irradiation with active energy rays such as visible light, infrared rays, ultraviolet rays, X rays, α rays, β rays, γ rays, electron rays and / or heating A method of forming the coating film by curing is preferred. 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 or the like is used. 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.

  The smoothness of the undercoat layer is a value expressed by the surface roughness specified by JIS B0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 3 nm or more and 30 nm or less.

  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.

  Although it does not restrict | limit especially as a film thickness of an undercoat layer, The range of 0.1-10 micrometers is preferable.

<Clear hard coat layer (CHC layer)>
The gas barrier film of the present invention may or may not have a clear hard coat layer. However, from the viewpoint of improving gas barrier performance and adhesion, the gas barrier film of the present invention preferably has a clear hard coat layer. The clear hard coat layer improves the adhesion between the resin substrate and the gas barrier layer, relieves internal stress caused by the difference in expansion and contraction between the resin substrate and the gas barrier layer under high temperature and high humidity, and flats the lower layer on which the gas barrier layer is provided. And functions such as prevention of bleeding out of low molecular weight components such as monomers and oligomers from the resin substrate. Therefore, the gas barrier film having a clear hard coat layer has gas barrier performance and adhesion that are stable for a long period of time even in a high temperature and high humidity environment. The clear hard coat layer is preferably provided on the surface of the resin substrate having the gas barrier layer, more preferably between the resin substrate and the gas barrier layer.

  Specifically, the clear hard coat layer can be formed by applying a photosensitive resin composition on a resin base material and then curing it. Moreover, the gas barrier film of the present invention also has a clear hard coat layer by using a resin base with a clear hard coat layer as the resin base. The hard coat layer may use the same material as the undercoat layer.

  The photosensitive resin composition usually contains a photosensitive resin, a photopolymerization initiator, and a solvent. The photosensitive resin is not particularly limited as long as it is a photosensitive resin containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule, and is a known resin that is used alone or in combination of two or more. Things are used. As a photoinitiator, the well-known thing used individually or in mixture of 2 or more types according to the photosensitive resin to be used is used. The solvent is not particularly limited as long as it can dissolve or disperse the photosensitive resin to be used, and a known solvent may be used alone or in combination of two or more. For example, photosensitive resins, photopolymerization initiators, solvents and the like disclosed in paragraphs “0170” to “0173” of JP2013-226673A are appropriately employed.

  Moreover, additives, such as antioxidant, ultraviolet absorber, a plasticizer, an inorganic particle, resin other than photosensitive resin, may further be added to the photosensitive resin composition as needed.

  Among these, one of the preferred additives is reactive silica particles having a photosensitive group having photopolymerization reactivity introduced on the surface (hereinafter also simply referred to as “reactive silica particles”). Although it does not restrict | limit especially as the photosensitive group which has the said photopolymerizability, For example, the polymerizable unsaturated group represented by the (meth) acryloyloxy group is mentioned. Adhesiveness with the gas barrier layer can be improved by the reaction of the photopolymerizable photosensitive group of the reactive silica particles with the polymerizable unsaturated group of the photosensitive resin.

  As the reactive silica particles, for example, reactive silica particles disclosed in paragraphs “0175” to “0178” of JP2013-226673A are appropriately employed.

  The photosensitive resin composition may contain a matting agent. By containing a matting agent, the optical properties can be adjusted. As the matting agent, for example, matting agents disclosed in paragraphs “0180” to “0182” of JP2013-226673A are appropriately employed.

  Furthermore, the photosensitive resin composition may contain a resin other than the photosensitive resin. The resin other than the photosensitive resin is not particularly limited, and examples thereof include a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin.

  Moreover, a commercial item may be used for the photosensitive resin composition. Examples of commercially available products include, but are not limited to, the OPSTAR (registered trademark) series (compounds obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) manufactured by JSR Corporation.

  The method for applying the photosensitive resin composition 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. It is done.

A clear hard coat layer can be formed by irradiating the coating film obtained by coating with ionizing radiation and curing it. The ionizing radiation is preferably emitted from an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp, or the like, preferably vacuum ultraviolet light in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm, or scanning. An electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator can be used. Moreover, although irradiation conditions differ with each lamp | ramp, the irradiation amount of an ultraviolet light is the range of 0.05-3 J / cm < ² > normally, and it is preferable that it is the range of 0.8-2 J / cm < ² >.

  The film thickness (dry film thickness) of the clear hard coat layer is preferably 1 to 10 μm, more preferably 2 to 7 μm. The arithmetic average surface roughness (Ra) of the clear hard coat layer is preferably 1 μm or less.

  Moreover, you may use the commercially available resin base material in which the clear hard-coat layer is formed previously as mentioned above. Examples of such a resin base material include, for example, a product name “KB film GSAB” manufactured by Kimoto Co., Ltd.

[Usage]
The gas barrier film of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Examples of the device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Example 1: Production of gas barrier film 1]
(Preparation of resin base material)
A transparent polyethylene terephthalate film with a clear hard coat layer (abbreviation: PET film, thickness: 125 μm, width: 350 mm, manufactured by Kimoto Co., Ltd., trade name “KB film GSAB”) was used as a resin base material. The thickness of the clear hard coat layer was 4 μm, and the arithmetic average surface roughness (Ra) of the clear hard coat layer was 0.4 to 0.5 μm.

(Formation of gas barrier layer: Roller CVD method)
Using the inter-roller discharge plasma CVD apparatus (roller CVD method) to which the magnetic field shown in FIG. 1 is applied, the surface (AB layer) opposite to the surface having the clear hard coat layer of the resin substrate is in contact with the film forming roller. As described above, the resin base material was mounted on the apparatus, and the gas barrier layer was formed under the following film formation conditions (plasma CVD condition 1) under the condition that the layer thickness was 300 nm. A 27.12 MHz high frequency power source was used as a power source for applying a voltage to the cathode electrode.

<Plasma CVD condition 1>
Supply amount of raw material gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Argon gas supply rate: 40 sccm
Degree of vacuum in the vacuum chamber: 2Pa
Applied power from power supply for plasma generation: 1 kW
Frequency of power source for plasma generation: 84 kHz
Distance between electrodes: 20mm
Roll temperature: 30 ° C
Transport speed of resin substrate: 2 m / min.

<Measurement of element distribution profile>
For the gas barrier layer formed under the above film formation conditions, XPS depth profile measurement was performed under the following conditions to obtain a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction. .

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 name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval.

  From the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve in the entire gas barrier layer measured as described above, the presence or absence of a continuous change region, the presence or absence of an extreme value, the maximum value of the atomic ratio of carbon in each elemental composition And the minimum value, and the average atomic ratio of silicon atoms, oxygen atoms, and carbon atoms.

  As a result, there are continuous change regions and extreme values in the composition, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 7 at%, and the average atomic ratio of silicon atoms, oxygen atoms, and carbon atoms is It was confirmed that the relationship defined by the formulas (A) and (B) was satisfied in a region of 90% or more of the total layer thickness.

[Change rate of Si-C bond]
IR of the gas barrier layer using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, Herchel FT-IR610) equipped with a multiple reflection (ATR) measuring device (manufactured by JASCO Corporation, ATR-300 / H) Measurements were performed. The prism used was a Ge crystal and was measured at an incident angle of 45 °.

The peak appearing at 810 to 825 cm ^{−1 of} the IR spectrum obtained by the measurement was defined as Si—C bond stretching vibration, and the absorption intensity was measured. Further, the absolute film thickness was calculated from the TEM cross section. Using the measured IR absorption intensity and the calculated absolute film thickness, IR intensity / absolute film thickness was calculated, and the IR absorption intensity per unit film thickness was calculated. About the gas barrier film preserve | saved for 300 hours in 85 degreeC85% RH environment, and the gas barrier film before a preservation | save, the absorption intensity of a Si-C bond is measured by the same method, Si before and behind preservation | save by the following formula | equation The rate of change of -C bond [%] was calculated. As a result, the change rate of the Si—C bond was 8%.

[Example 2: Production of gas barrier film 2]
A gas barrier film 2 was produced in the same manner as in Example 1 except that the supply amount of argon gas was 50 sccm.

  In the same manner as described above, XPS depth profile measurement was performed to obtain a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction.

  As a result, there is a continuous change region and an extreme value in the composition, and the average atomic ratio of silicon atoms, oxygen atoms, and carbon atoms is defined by the formulas (A) and (B) in a region where 90% or more of the total layer thickness is present. Confirmed that the relationship is satisfied. The change rate of the Si—C bond was 5%.

[Example 3: Production of gas barrier film 3]
A gas barrier film 3 was produced in the same manner as in Example 1 except that the supply amount of argon gas was 25 sccm.

  In the same manner as described above, XPS depth profile measurement was performed to obtain a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction.

  As a result, there is a continuous change region and an extreme value in the composition, and the average atomic ratio of silicon atoms, oxygen atoms, and carbon atoms is defined by the formulas (A) and (B) in a region where 90% or more of the total thickness is Confirmed that the relationship is satisfied. The rate of change of the Si—C bond was 10%.

[Example 4: Production of gas barrier film 4]
A gas barrier film 4 was produced in the same manner as in Example 1 except that the supply amount of argon gas was 12.5 sccm.

  In the same manner as described above, XPS depth profile measurement was performed to obtain a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction.

  As a result, there is a continuous change region and an extreme value in the composition, and the average atomic ratio of silicon atoms, oxygen atoms, and carbon atoms is defined by the formulas (A) and (B) in a region where 90% or more of the total layer thickness is present. Confirmed that the relationship is satisfied. The rate of change of the Si—C bond was 13%.

[Example 5: Production of gas barrier film 5]
A gas barrier film 5 was produced in the same manner as in Example 1 except that the supply amount of argon gas was 75 sccm.

  In the same manner as described above, XPS depth profile measurement was performed to obtain a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction.

  As a result, there is a continuous change region and an extreme value in the composition, and the average atomic ratio of silicon atoms, oxygen atoms, and carbon atoms is 90% or more of the total layer thickness, and in the formulas (A) and (B) Confirmed that the specified relationship was satisfied. The rate of change of the Si—C bond was 4%.

[Comparative Example 1: Production of gas barrier film 6]
A gas barrier film 6 was produced in the same manner as in Example 1 except that the supply amount of argon gas was 4 sccm.

  In the same manner as described above, XPS depth profile measurement was performed to obtain a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction. The change rate of the Si—C bond was 25%.

[Comparative Example 2: Production of gas barrier film 7]
The resin base material is mounted on the apparatus so that the surface (AB layer) opposite to the surface on which the clear hard coat layer of the resin base material is formed is in contact with the roll, and the following film formation conditions (plasma CVD condition 2) ), A gas barrier layer was formed under the condition that the layer thickness was 300 nm, and a gas barrier film 7 was produced. As a power source for applying a voltage to the cathode electrode, an 84 MHz high frequency power source was used.

<Plasma CVD condition 2>
Supply amount of raw material gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Argon gas supply rate: 40 sccm
Degree of vacuum in the film forming apparatus: 2 Pa
Electric power applied to the electrode drum: 3 kW
Distance between electrodes: 50mm
Roll temperature: 40 ° C
Power supply frequency: 90 kHz
Transport speed of resin substrate: 2 m / min.

  In the same manner as described above, XPS depth profile measurement was performed to obtain a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction. As a result, there were no continuously changing regions and extreme values in the composition (carbon distribution curve, silicon distribution curve, and oxygen distribution curve), and the difference between the maximum value and the minimum value of the carbon atom ratio was 0 at%. The rate of change of the Si—C bond was 20%.

[Comparative Example 3: Production of gas barrier film 8]
A gas barrier film 8 was produced in the same manner as in Example 1 except that argon gas was not used.

  In the same manner as described above, XPS depth profile measurement was performed to obtain a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction. The change rate of the Si—C bond was 21%.

[Comparative Example 4: Production of gas barrier film 9]
A gas barrier film 9 was produced in the same manner as in Comparative Example 2 except that argon gas was not used.

  In the same manner as described above, XPS depth profile measurement was performed to obtain a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction. As a result, there were no continuously changing regions and extreme values in the composition (carbon distribution curve, silicon distribution curve, and oxygen distribution curve), and the difference between the maximum value and the minimum value of the carbon atom ratio was 0 at%. The change rate of the Si—C bond was 25%.

<< Evaluation of gas barrier film sample >>
About the gas barrier film samples 1-9 produced above, the following physical properties were evaluated before and after storage at 85 ° C. and 85% RH for 300 hours.

[Evaluation of gas barrier properties (permeated water content (WVTR))]
According to the following measurement method, the permeated water amount of each gas barrier film sample was measured, and the water vapor barrier property was evaluated according to the following criteria.

  Using the vacuum vapor deposition device (manufactured by JEOL Ltd., vacuum vapor deposition device JEE-400) on the gas barrier layer surface of the sample, the portion of the gas barrier film sample to be vapor-deposited before attaching the transparent conductive film (9 locations of 12 mm x 12 mm) The metal calcium (granular form) was vapor-deposited (deposition film thickness 80 nm). Then, the mask was removed in a vacuum state, and metal aluminum (φ3 to 5 mm, granular), which is a water vapor impermeable metal, was deposited on the entire surface of one side of the sheet from another metal deposition source. After aluminum sealing, the vacuum state is released, and the aluminum sealing side is quickly passed through a UV-curable resin (manufactured by Nagase ChemteX Corporation) to 0.2 mm thick quartz glass in a dry nitrogen gas atmosphere. And an evaluation cell was produced by irradiating with ultraviolet rays.

  The obtained sample was stored under high temperature and high humidity of 60 ° C. and 90% RH, and the amount of moisture permeated into the cell was calculated from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. .

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample Was stored under the same high temperature and high humidity conditions of 85 ° C. and 85% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 300 hours.

  The permeated water amount of each gas barrier film measured as described above was evaluated by the Ca method and ranked as follows. In addition, if it is rank 3 or more, there is no problem in actual use and it is a pass product.

(Rank evaluation)
Less than 5: 1 × 10 ⁻⁴ g / m ² / day 4: 1 × 10 ⁻⁴ g / m ² / day or more and less than 5 × 10 ⁻⁴ g / m ² / day 3: 5 × 10 ⁻⁴ g / day m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 2: 1 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g / m ² / day or more [Adhesion]
Based on JIS K5600-5-6: 1999, the adhesiveness between the resin base material and the gas barrier layer was evaluated according to the following criteria by a cross-cut method. If the evaluation standard is 3 or more, there is no practical problem.

(Evaluation criteria)
5: 90 or more squares after peeling 4: 90 or less squares after peeling 3: 50 or less squares after peeling 2: 30 or more squares after peeling 1: less than 50 1: After peeling The square is less than 30.

[Measurement of nano-scratch test critical load (film strength)]
The critical load of the gas barrier layer was measured based on ASTM D718705. A “Triboscope system” manufactured by Hystron was used, and a 60 ° conical (cone) made of diamond having a tip radius of curvature of about 1 μm was used as the indenter. When the SiO ₂ thermal oxide film 25 nm / Si wafer manufactured by ULVAC-PHI Co., Ltd. was measured as a standard, the indenter state was 57 μN in the vertical direction (Normal Force) when the vertical displacement (Normal Displacement) was 4 nm. Measurement is performed by adsorbing and fixing a gas barrier film on a sample stage (support), measuring n = 3 or more under a continuous load test condition with a load speed of about 1 μN / sec and a scratch speed of about 133 nm / sec. The average value was calculated.

(Evaluation criteria)
5: The average value of critical loads is 5.0 μN or more 4: The average value of critical loads is 3.0 μN or more and less than 5.0 μN 3: The average value of critical loads is 1.5 μN or more and less than 3.0 μN 2: The average of critical loads Value is 0.7 μN or more and less than 1.5 μN 1: The average value of critical loads is less than 0.7 μN.

  The composition and evaluation results of each gas barrier film are shown in Table 1 below. In addition, the term of requirement (1) and (2) in Table 1 shows that the requirement is satisfied if it is ◯, and that the requirement is not satisfied if it is x.

  As is clear from Table 1 above, it was found that the gas barrier film of the present invention has stable gas barrier performance and adhesion for a long period of time even in a high temperature and high humidity environment of 85 ° C. and 85% RH.

11 Gas barrier film,
12 resin base material,
13 Manufacturing equipment,
14 Feeding roller,
15, 16, 17, 18 Transport roller,
19, 20 Deposition roller,
21 gas supply pipe,
22 Power source for plasma generation,
23, 24 Magnetic field generator,
25 take-up roller,
26 Gas barrier layer.

Claims (3)

A resin substrate;
A gas barrier layer containing silicon atoms, oxygen atoms, and carbon atoms formed on at least one side of the resin substrate;
A gas barrier film comprising
The gas barrier layer has a change rate of the Si—C bond before and after storage for 300 hours in an environment of 85 ° C. and 85% RH of 15% or less, and the composition continuously changes in the layer thickness direction. And a gas barrier film satisfying (2):
(1) Among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the gas barrier layer, the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer; In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount (100 at%) of silicon atoms, oxygen atoms, and carbon atoms (referred to as “carbon atom ratio (at%)”), at least one pole The absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5 at% or more:
(2) In the region of 90% or more of the total thickness of the gas barrier layer, the average atomic ratio of each atom with respect to the total amount (100 at%) of silicon atoms, oxygen atoms, and carbon atoms is expressed by the following formula (A) or ( It has the order of magnitude relationship represented by B).
  2. The gas barrier film according to claim 1, wherein a change rate of Si—C bonds before and after storage for 300 hours in the 85 ° C. and 85% RH environment is 5 to 10%. The gas barrier film according to claim 1 or 2 , wherein a critical load measured based on ASTM D718705 of the gas barrier layer is 2.0 µN or more.