JP2014141055A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having a low steam permeability.SOLUTION: There is provided a gas barrier film which comprises a substrate, a barrier layer which is formed an at least one surface of the substrate and contains silicon, oxygen and carbon and an inorganic-organic hybrid polymer layer. The inorganic-organic hybrid polymer layer (ORMOCER layer) is composed of a material containing a polymethoxysiloxane of the following formula (1) in an amount of 20 to 40 mol% based on the total number of moles of the material constituting the inorganic-organic hybrid polymer layer and the barrier layer satisfies the following conditions (i) to (iii).

Description

  The present invention relates to a gas barrier film. More specifically, the present invention relates to a gas barrier film having a low water vapor transmission rate.

  Conventionally, various studies have been made on a film having a property of blocking permeation of water vapor and oxygen, that is, a so-called gas barrier property. In such examination, in order to improve the gas barrier property of a film, the technique which forms an inorganic layer by methods, such as sputtering and a plasma CVD method, is proposed (patent document 1).

  In recent years, in addition to demands for weight reduction and size increase, long-term reliability, high degree of freedom in shape, and the ability to display curved surfaces have been added, resulting in a glass substrate that is heavy, easily broken, and difficult to increase in area. Instead, film base materials such as transparent plastics are beginning to be adopted.

  However, a film substrate such as a transparent plastic has a problem that the gas barrier property is inferior to glass. If a base material with inferior gas barrier properties is used, water vapor or air will permeate, and for example, the function in the electronic device will be degraded.

As gas barrier films used for packaging materials and liquid crystal display elements, those obtained by depositing silicon oxide or aluminum oxide on plastic films are known. However, in those techniques, only a water vapor barrier property of about 1 g / m ² / day is obtained. On the other hand, in recent years, the liquid crystal display has been increased in size, developed as a high-definition display, etc., and the gas barrier performance to the film substrate is about 0.1 g / m ² / day for water vapor permeability. ^The demand has risen to the order of ⁻⁵ to 10 ⁻⁶ g / m ² / day.

  In order to solve the above problem, Patent Document 2 describes a polymer multilayer (PML) technique. This technique applies a coating consisting of a polymer layer and an aluminum oxide layer to a flexible substrate and seals the substrate. Both deposition processes can be operated at very high speeds using web processing equipment. It has been disclosed that the resistance to water and oxygen permeability is improved by 3 to 4 orders of magnitude compared to uncoated PET membranes.

  In such polymer multilayer techniques, the polymer layer may work to mask any defects in adjacent ceramic layers and reduce the diffusion rate of oxygen and water vapor through the channels created by these defects in the barrier layer. Has been suggested. However, since the interface between the polymer layer and the aluminum oxide layer is generally weak due to the incompatibility of adjacent materials, there is a problem that it is easy to peel off and sufficient barrier ability cannot be obtained during long-term storage. It was.

  On the other hand, Patent Document 3 reports an organic EL device having a gas barrier layer containing silicon, oxygen, and carbon with a specific composition. It is disclosed that the gas barrier layer has a high gas barrier property, and the gas barrier property is hardly lowered even when the film is bent, and can be formed in a short time by a simple process.

JP-A-6-234186 JP 2005-288851 A JP 2012-84306 A

  However, even with the gas barrier layer described in Patent Document 3, it cannot be said that a water vapor transmission rate sufficient for application to organic electroluminescence can be achieved. Moreover, cracks are generated under severe conditions in which the temperature and humidity are greatly changed, and a decrease in gas barrier properties is induced. Therefore, there is still a need for a gas barrier film that has a higher water vapor permeability, can suppress and prevent generation of cracks even under severe conditions, and can maintain high gas barrier properties.

  Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a gas barrier film having a low water vapor transmission rate.

  Another object of the present invention is to provide a gas barrier film capable of maintaining a high gas barrier property even under severe conditions.

  As a result of intensive studies to solve the above problems, the present inventors have combined the barrier layer containing silicon, oxygen, and carbon with a specific composition with a specific inorganic / organic hybrid polymer layer, thereby The present inventors have found that the problem can be solved and have completed the present invention.

That is, the above-mentioned objects are to provide a gas barrier film having a substrate, a barrier layer containing silicon, oxygen, and carbon and an inorganic / organic hybrid polymer layer (ORMOCER layer) formed on at least one surface of the substrate. Because
The inorganic / organic hybrid polymer layer (ORMOCER layer) has the following formula (1):

However, n is 2-20.
Of the polymethoxysiloxane in an amount of 20 to 40 mol% with respect to the total number of moles of the material constituting the inorganic / organic hybrid polymer layer (ORMOCER layer), and the barrier layer The following conditions (i) to (iii):
(I) The distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) A silicon distribution curve showing a relationship, an oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and the L and silicon atoms In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of oxygen atoms, and carbon atoms (the atomic ratio of carbon),
In the region of 90% or more of the film thickness of the barrier layer, the order is (atomic ratio of oxygen), (atomic ratio of silicon), (atomic ratio of carbon) from the largest.
(Ii) the carbon distribution curve has at least two extreme values;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.
It can be achieved by a gas barrier film that satisfies the above.

  According to the present invention, a gas barrier film having a low water vapor transmission rate can be provided.

It is a schematic diagram which shows an example of the manufacturing apparatus which can be utilized suitably in order to manufacture the barrier layer which concerns on this invention. It is the glass of the carbon distribution curve, oxygen distribution curve, and silicon distribution curve of the barrier layer of Example 1.

  The present invention relates to a base material, a barrier layer containing silicon, oxygen, and carbon (hereinafter, also simply referred to as “barrier layer”) and an inorganic / organic hybrid polymer layer (which is formed on at least one surface of the base material). It is a gas barrier film having an “ORMOCER layer” (hereinafter also simply referred to as “inorganic / organic hybrid polymer layer” or “ORMOCER layer”). Here, the inorganic / organic hybrid polymer layer (ORMOCER layer) has the above formula (1):

However, n is an integer of 2-20.
The polymethoxysiloxane is formed using a material containing 20 to 40 mol% with respect to the total number of moles of the material constituting the inorganic / organic hybrid polymer layer (ORMOCER layer). Further, the barrier layer satisfies all the following conditions (i) to (iii):
(I) The distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) A silicon distribution curve showing a relationship, an oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and the L and silicon atoms In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of oxygen atoms, and carbon atoms (the atomic ratio of carbon),
In the region of 90% or more of the film thickness of the barrier layer, the order is (oxygen atomic ratio), (silicon atomic ratio), (carbon atomic ratio) in descending order;
(Ii) the carbon distribution curve has at least two extreme values; and (iii) the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.

The present invention is characterized in that a specific barrier layer that satisfies all of the above conditions (i) to (iii) is combined with an ORMOCER layer. Barrier layer according to the present invention, when used alone, in the order of water vapor transmission rate of ^{10 -4 g / m 2 / day} ( see below Comparative Example 1), ¹⁰ -5 to 10 required for the organic electroluminescent ⁻⁶ g / m ² / day cannot be reached at all. In addition, if the barrier layer according to the present invention is placed under severe conditions in which the temperature and humidity greatly change, cracks are generated (see Comparative Example 1 below), which causes a decrease in gas barrier properties. On the other hand, when the ORMOCER layer according to the present invention is combined with the barrier layer according to the present invention, it is surprisingly up to the order of 10 ⁻⁵ to 10 ⁻⁶ g / m ² / day required for organic electroluminescence. It can be improved. Further, according to such a combination, the occurrence of cracks can be suppressed / prevented even under severe conditions where the temperature and humidity greatly change. Here, the mechanism for exerting the above-described effects by the configuration of the present invention is presumed as follows. The present invention is not limited to the following. That is, in the barrier layer according to the present invention, carbon atoms are present in addition to silicon atoms and oxygen atoms. Among these, gas barrier properties can be imparted by the presence of silicon atoms and oxygen atoms, and by the presence of carbon atoms. Flexibility can be imparted to the barrier layer. For this reason, the barrier layer according to the present invention has gas barrier properties and flexibility. On the other hand, as described above, since only the barrier layer according to the present invention cannot satisfy the requirement of low water vapor transmission rate including organic electroluminescence, it is necessary to further improve the gas barrier property. Here, as the above purpose, it is conceivable to increase the thickness or to provide another barrier layer. Of these, the former may cause curling and is not practical. Further, the latter has insufficient adhesion with different barrier layers and has a problem of peeling. However, according to the present invention, when the carbon part existing in the barrier layer and the organic part in the ORMOCER layer according to the present invention are brought into contact with each other, the barrier layer and the ORMOCER layer are in close contact with each other, Even when these layers are stacked, gas (for example, water vapor or oxygen) does not enter between both layers. For this reason, the gas barrier film of the present invention can synergistically improve the gas barrier property (for example, low water vapor transmission rate) as compared with the case where the barrier layer and the ORMOCER layer are used alone. In addition, when the barrier layer according to the present invention is present alone, cracks are generated because the shape change (shrinkage / expansion) of the base material due to changes in temperature and humidity is repeated together. As a result, gas barrier properties are reduced. On the other hand, although the ORMOCER layer according to the present invention has a network structure although it has a low gas barrier property, it is less likely to be affected by a change in the shape of the substrate due to a change in temperature or humidity. For this reason, the gas barrier film of the present invention reduces the shape change of the base material and the barrier layer even when the gas barrier film of the present invention is left standing for a long time under severe conditions in which the temperature and humidity greatly change. Therefore, the gas barrier film of the present invention can maintain excellent gas barrier properties (for example, low water vapor permeability) for a long period of time.

  Therefore, the gas barrier film of the present invention has excellent gas barrier properties (for example, low water vapor transmission rate and oxygen transmission rate). Further, the gas barrier film of the present invention suppresses and prevents the occurrence of cracks even under severe conditions such as temperature and humidity greatly changing, and has excellent gas barrier properties (for example, low water vapor permeability and (Oxygen permeability) can be maintained. For this reason, the gas barrier film of the present invention can be suitably applied to packages such as electronic devices that require high gas barrier properties, and electronic devices such as photoelectric conversion elements, organic electroluminescence (EL) elements, and liquid crystal display elements.

  Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  In the present specification, “X to Y” indicating a range means “X or more and Y or less”, and “weight” and “mass”, “wt%” and “mass%”, “part by weight” and “ “Part by mass” is treated as a synonym. 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%.

<Gas barrier film>
The gas barrier film of the present invention has a barrier layer and an ORMOCER layer on a substrate. Here, the stacking order of the barrier layer and the ORMOCER layer is not particularly limited, but the barrier layer and the ORMOCER layer are preferably stacked in this order on the substrate. With such a structure, the gas barrier property due to the barrier layer is more effectively exhibited, and the ORMOCER layer is easy to relieve the shape change (shrinkage / expansion) of the substrate due to changes in temperature and humidity. It can be effectively suppressed / prevented.

  Moreover, although the gas barrier film of this invention has a base material, a barrier layer, and an ORMOCER layer essential, it may further contain another member. The gas barrier film of the present invention is, for example, between a substrate and a barrier layer or an ORMOCER layer; between the barrier layer and the ORMOCER layer; or on the other surface where the barrier layer or the ORMOCER layer is not formed. You may have another member. Here, the other members are not particularly limited, and members used for conventional gas barrier films can be used similarly or appropriately modified. Specific examples include a base layer, an anchor coat layer, a bleed-out prevention layer, a protective layer, a functional layer of a hygroscopic layer and an antistatic layer, and the like.

  In the present invention, each of the barrier layer and the ORGOCER layer may exist as a single layer or may have a laminated structure of two or more layers. In the latter case, one or more barrier layers or ORMOKER layers may exist as one unit, or two or more of the above units may be laminated.

  Furthermore, in the present invention, the barrier layer and the ORMOCER layer may be formed on at least one surface of the substrate. For this reason, the gas barrier film of the present invention includes both a form in which the barrier layer and the ORMOCER layer are formed on one side of the substrate, and a form in which the barrier layer and the ORMOCER layer are formed on both sides of the substrate.

[Base material]
In the gas barrier film according to the present invention, a plastic film or a sheet is usually used as a substrate, and a film or sheet made of a colorless and transparent resin is preferably used. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a barrier layer, a hard coat layer and the like, and can be appropriately selected according to the purpose of use and the like. 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 according to the present invention is used as a substrate of an electronic device such as an organic EL element, the 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. The base material satisfies the requirements for use as a laminated film for electronic parts and displays. That is, when the gas barrier film of the present invention is used for these applications, the gas barrier film may be exposed to a process at 150 ° C. or higher. In this case, when the coefficient of linear expansion of the base material in the gas barrier film exceeds 100 ppm / K, the substrate dimensions are not stable when the gas barrier film is passed through the temperature process as described above, and thermal expansion and contraction occur. Inconvenience that the shut-off performance is deteriorated or a problem that the thermal process cannot withstand is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.

  The Tg and the linear expansion coefficient of the substrate can be adjusted with an additive or the like. More preferable specific examples of the thermoplastic resin that can be used as the substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic. Polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin 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 Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: JP In 2000-227603 Listed compound: 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: 300 ° C.) And the like) (Tg is shown in parentheses).

  When the gas barrier film according to the present invention is used in combination with a polarizing plate, it is preferably arranged so that the barrier layer of the gas barrier film faces the inside of the cell. More preferably, the ORMOKER layer of the gas barrier film is disposed on the innermost side of the cell (adjacent to the element). At this time, since the gas barrier film is disposed inside the cell from the polarizing plate, the retardation value of the gas barrier film is important. The usage form of the gas barrier film in such an embodiment includes a gas barrier film using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (¼ wavelength plate + (½ wavelength plate) + straight line. The polarizing plate is preferably used in combination with a linear polarizing plate in combination with a gas barrier film using a base film having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate. .

  Examples of the base film having a retardation of 10 nm or less include, for example, cellulose triacetate (Fuji Film Co., Ltd .: Fujitac (registered trademark)), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace (registered trademark), Kaneka Corporation): Elmec (registered trademark)), cycloolefin polymer (manufactured by JSR Corporation: Arton (registered trademark), Nippon Zeon Corporation: ZEONOR (registered trademark)), cycloolefin copolymer (manufactured by Mitsui Chemicals, Inc .: APPEL (registered trademark)) (Pellets), manufactured by Polyplastics Co., Ltd .: Topas (registered trademark) (pellets)), polyarylate (manufactured by Unitika Co., Ltd .: U100 (pellets)), transparent polyimide (manufactured by Mitsubishi Gas Chemical Co., Ltd .: Neoprim (registered trademark)) Etc.

  Moreover, as a quarter wavelength plate, the film adjusted to the desired retardation value by extending | stretching said film suitably can be used.

  Since the gas barrier film according to the present invention is used as an electronic device such as an organic EL element, the plastic film 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 according to 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 plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.

  The thickness of the plastic film used for the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the use, 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 and a primer 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 substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.

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

  The base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched 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. Further, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

At least on the side of the substrate on which the barrier layer according to the present invention is provided, various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and lamination of a primer layer described later Etc. are preferably performed, and it is more preferable to perform the above treatment in combination as necessary.
[Barrier layer]
The barrier layer according to the present invention is a layer formed on one surface of the substrate and is a layer containing silicon, oxygen, and carbon. The barrier layer satisfies the above conditions (i) to (iii).

  First, the barrier layer comprises (i) a distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer, and a ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon An oxygen distribution curve indicating the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), And 90% or more of the thickness of the barrier layer in a carbon distribution curve showing a relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (carbon atomic ratio) ( In the range of (upper limit: 100%), (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in this order (atomic ratio is O> Si> C). When the above condition (i) is not satisfied, the gas barrier property and flexibility of the obtained gas barrier film are insufficient. Here, in the carbon distribution curve, the relationship of the above (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more (upper limit: 100%) of the thickness of the barrier layer. ) And more preferably at least 93% or more (upper limit: 100%). Here, “at least 90% or more of the thickness of the barrier layer” does not need to be continuous in the barrier layer, and only needs to satisfy the above-described relationship at a portion of 90% or more.

  In the barrier layer, (ii) the carbon distribution curve has at least two extreme values. The barrier layer preferably has at least three extreme values in the carbon distribution curve, more preferably at least four extreme values, but may have five or more extreme values. When the extreme value of the carbon distribution curve is 1 or less, the gas barrier property when the obtained gas barrier film is bent is insufficient. The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. Since the number of extreme values is also caused by the film thickness of the 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 barrier layer in the film thickness direction of the 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 of (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 having a large carbon atom ratio (maximum value) in the barrier layer at an appropriate period, so that appropriate flexibility is imparted to the barrier layer, and the gas barrier film Generation of cracks during bending can be more effectively suppressed / prevented. In this specification, the “extreme value” refers to the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer. Further, in this specification, the “maximum value” is a point where the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from an increase to a decrease when the distance from the surface of the barrier layer is changed, And the value of the atomic ratio of the element at the position where the distance from the surface of the barrier layer in the thickness direction of the barrier layer from the point is further changed within the range of 4 to 20 nm than the value of the atomic ratio of the element at that point. It means a point that decreases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element should be reduced by 3 at% or more in any range. Similarly, the “minimum value” in this specification is a point in which the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from decrease to increase when the distance from the surface of the barrier layer is changed. In addition, the value of the atomic ratio of the element at a position where the distance from the point in the film thickness direction of the barrier layer from the point in the thickness direction of the barrier layer is further changed in the range of 4 to 20 nm. Is a point that increases by 3 at% or more. That is, when changing in 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 high 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. Although not limited, in consideration of the flexibility of the barrier layer, the effect of suppressing / preventing cracks, thermal expansion, and the like, the thickness is preferably 10 nm or more, and more preferably 30 nm or more.

Further, the barrier layer has (iii) the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter, also simply referred to as “C _max −C _min difference”) of 3 at% or more. . When the absolute value is less than 3 at%, the gas barrier property is insufficient when the obtained gas barrier film is bent. The C _max -C _min difference is preferably 5 at% or more, more preferably 7 at% or more, and particularly preferably 10 at% or more. By setting the C _max −C _min difference, the gas barrier property can be further improved. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values. Here, the upper limit of the C _max -C _min difference is not particularly limited, but it is preferably 50 at% or less, and 40 at% or less in consideration of the effect of suppressing / preventing crack generation when the gas barrier film is bent. It is more preferable that

  In the present invention, the oxygen distribution curve of the barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and more preferably has at least three extreme values. When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved. The upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the thickness of the barrier layer, and it cannot be defined unconditionally. In the case of having at least three extreme values, a difference in distance from the surface of the barrier layer in the film thickness direction of the barrier layer at one extreme value of the oxygen distribution curve and an extreme value adjacent to the extreme value. Are preferably 200 nm or less, more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, but considering the improvement effect of crack generation suppression / prevention when the gas barrier film is bent, the thermal expansion property, etc. The thickness is preferably 10 nm or more, and more preferably 30 nm or more.

In addition, in the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the barrier layer (hereinafter also simply referred to as “O _max −O _min difference”) is 3 at% or more. It is preferably 5 at% or more, more preferably 6 at% or more, and particularly preferably 7 at% or more. When the absolute value is 3 at% or more, the gas barrier property when the obtained gas barrier film is bent is further improved. Here, the upper limit of the O _max -O _min difference is not particularly limited, but it is preferably 50 at% or less, and 40 at% or less in consideration of the effect of suppressing / preventing crack generation when the gas barrier film is bent. It is more preferable that

In the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the barrier layer (hereinafter also simply referred to as “Si _max -Si _min difference”) is 10 at% or less. Is preferable, 7 at% or less is more preferable, and 3 at% or less is further preferable. When the absolute value is 10 at% or less, the gas barrier property of the obtained gas barrier film is further improved. The lower _limit of Si max _{-Si min difference,} because the effect of improving the crack generation suppression / prevention during bending of Si max _{-Si min} as gas barrier property difference is small film is high, is not particularly limited, and gas barrier property In consideration, it is preferably 1 at% or more, and more preferably 2 at% or more.

In the present invention, the total amount of carbon and oxygen atoms with respect to the thickness direction of the barrier layer is preferably substantially constant. Thereby, a barrier layer exhibits moderate flexibility, and the crack generation at the time of bending of a gas barrier film can be more effectively suppressed / prevented. More specifically, the ratio of the total amount of oxygen atoms and carbon atoms to the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms ( In the oxygen-carbon distribution curve showing a relationship with the atomic ratio of oxygen and carbon, the absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the oxygen-carbon distribution curve (hereinafter simply referred to as “OC _max ”). -OC _min difference ") is preferably less than 5 at%, more preferably less than 4 at%, and even more 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 further improved. _The lower limit of the OC max _{-OC min difference,} since preferably as OC max _{-OC min} difference is small, but is 0 atomic%, it is sufficient if more than 0.1 at%.

  The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. Thus, 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 (L) from the surface of the barrier layer in the film thickness direction of the barrier layer in the film thickness direction. Therefore, “Distance from the surface of the barrier layer in the film thickness direction of the barrier layer” is the distance from the surface of the barrier layer calculated from the relationship between the etching rate and the etching time adopted in the XPS depth profile measurement. can do. In the present invention, the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve were prepared under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ );
Etching rate (converted to SiO ₂ thermal oxide film): 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.

  In the present invention, the thickness (dry film thickness) of the barrier layer is not particularly limited as long as the above (i) to (iii) are satisfied. The thickness of the barrier layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 100 to 1000 nm. With such a thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending. In addition, when a barrier layer is comprised from 2 or more layers, it is preferable that each barrier layer has thickness as mentioned above. In addition, the thickness of the entire barrier layer when the barrier layer is composed of two or more layers is not particularly limited, but the thickness of the entire barrier layer (dry film thickness) is preferably about 1000 to 2000 nm. With such a thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending.

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

  Furthermore, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, 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 barrier layer in the film thickness direction of at least one of the barrier layers, and the atomic ratio of carbon (C, unit: at%), It means satisfying the condition represented by the following formula (1).

In the gas barrier film according to the present invention, the barrier layer satisfying all of the above conditions (i) to (iii) may include only one layer or may include two or more layers. Furthermore, when two or more such barrier layers are provided, the materials of the plurality of barrier layers may be the same or different.

  In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio are in the region of 90% or more of the thickness of the barrier layer (i ), The atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer is preferably 20 to 40 at%, It is more preferable that it is 25-35at%. Further, the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer is preferably 45 to 75 at%, and more preferably 50 to 70 at%. . Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer is preferably 0.5 to 25 at%, and preferably 1 to 20 at%. More preferred.

  In the present invention, the method for forming the barrier layer is not particularly limited, and the conventional method and the method can be applied in the same manner or appropriately modified. The barrier layer is preferably formed by a chemical vapor deposition (CVD) method, particularly a plasma chemical vapor deposition method (plasma CVD, PECVD (plasma-enhanced chemical vapor deposition), hereinafter, also simply referred to as “plasma CVD method”). It is more preferable that the substrate is formed by a plasma CVD method in which a base material is disposed on a pair of film forming rollers and a plasma is generated by discharging between the pair of film forming rollers. Hereinafter, a method for forming a barrier layer using the plasma CVD method preferably used in the present invention will be described below.

[Method for forming barrier layer]
Next, a preferred method for forming the barrier layer according to the present invention will be described. The gas barrier film of the present invention can be produced by forming a barrier layer on at least one surface of the substrate and further forming an OMOCER layer on the barrier layer. As a method for forming the barrier layer according to the present invention on the surface of the substrate, it is preferable to employ a plasma CVD method from the viewpoint of gas barrier properties. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  Further, when plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and each of the pair of film forming rollers is used. More preferably, the substrate is disposed and discharged between a pair of film forming rollers to generate plasma. 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. Compared with the plasma CVD method using no roller, the film formation rate can be doubled, 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 it is efficient. It is possible to form a layer that satisfies all of the above conditions (i) to (iii).

  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 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 the said barrier layer on the surface of the said base material by a roll-to-roll system from a viewpoint of productivity. Further, an apparatus that can be used when manufacturing the 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 the 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. 1 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible.

  Hereinafter, the method for forming a barrier layer according to the present invention will be described in more detail with reference to FIG. FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the barrier layer according to the present invention. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  1 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 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, 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). ing. 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 the vacuum pump.

  In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 39 and 40) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), 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 the barrier layer 3 on the surface of the base material 2 by the CVD method, and the barrier layer component is formed on the surface of the base material 2 on the film forming roller 39. While depositing, the barrier layer component can also be deposited on the surface of the substrate 2 also on the film forming roller 40, so that the barrier layer can be efficiently formed on the surface of the substrate 2.

  Inside the film forming roller 39 and the film forming roller 40, magnetic field generators 43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit. By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell near the opposing surface of each film forming roller 39 and 40, 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 43 and 44 provided on the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such magnetic field generators 43 and 44, 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 43 and 44 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 that a wide base wound around the roller width direction can be obtained. The material 2 is excellent in that the barrier layer 3 that is a deposited film can be efficiently formed.

  As the film forming roller 39 and the film forming roller 40, known rollers can be appropriately used. As such film forming rollers 39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameters of the film forming rollers 39 and 40 are preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

  In such a manufacturing apparatus 31, the base material 2 is arrange | positioned on a pair of film-forming roller (The film-forming roller 39 and the film-forming roller 40) so that the surface of the base material 2 may respectively oppose. By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present. Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, a barrier layer component is deposited on the surface of the substrate 2 on the film forming roller 39 and further deposited on the film forming roller 40 by plasma CVD. Therefore, the barrier layer can be efficiently formed on the surface of the substrate 2.

  As the feed roller 32 and the transport rollers 33, 34, 35, and 36 used in such a manufacturing apparatus, known rollers can be appropriately used. The winding roller 45 is not particularly limited as long as it can wind the gas barrier film 1 having the barrier layer 3 formed on the substrate 2, and a known roller may be used as appropriate. it can.

  Further, as the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used.

  The gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, by providing the gas supply pipe 41 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 39 and the film formation roller 40. It is excellent in that the film formation efficiency can be improved.

  Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. Moreover, as such a plasma generating power source 42, it becomes possible to perform plasma CVD more efficiently, so that the applied power can be set to 100 W to 10 kW, and the AC frequency is set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the magnetic field generators 43 and 44, known magnetic field generators can be used as appropriate. Furthermore, as the base material 2, in addition to the base material used in the present invention, a material in which the barrier layer 3 is previously formed can be used. As described above, the barrier layer 3 can be thickened by using the substrate 2 having the barrier layer 3 formed in advance.

  Using such a manufacturing apparatus 31 shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport of the film (base material) The barrier layer according to the present invention can be produced by appropriately adjusting the speed. That is, using the manufacturing apparatus 31 shown in FIG. 1, a discharge is generated between a pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. Thus, the film-forming gas (raw material gas or the like) is decomposed by plasma, and the barrier layer 3 is formed on the surface of the base material 2 on the film-forming roller 39 and the surface of the base material 2 on the film-forming roller 40 by plasma CVD. Formed by law. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 39 and 40, and the plasma is converged on the magnetic field. For this reason, when the base material 2 passes through the point A of the film forming roller 39 and the point B of the film forming roller 40 in FIG. 1, the maximum value of the carbon distribution curve is formed in the barrier layer. On the other hand, when the base material 2 passes through the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. It is formed. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between the extreme values of the barrier layer (the difference between the distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (Absolute value) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (base material transport speed). In such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. Thus, the barrier layer 3 is formed.

  As the film forming gas (such as source gas) supplied from the gas supply pipe 41 to the facing space, source gas, reaction gas, carrier gas, and discharge gas may be used alone or in combination of two or more. The source gas in the film-forming gas used for forming the barrier layer 3 can be appropriately selected and used according to the material of the barrier layer 3 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 characteristics such as handling of the compound and gas barrier properties of the resulting 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. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the barrier layer 3.

  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 or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. 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.

  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.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not excessively increasing the ratio of the reactive gas, the barrier layer 3 formed is excellent in that excellent barrier properties and bending resistance can be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

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 barrier layer that satisfies all of the above conditions (i) to (iii). Therefore, in the present invention, when the barrier layer is formed, the stoichiometric ratio of oxygen amount to 1 mol of hexamethyldisiloxane is set so that the reaction of the reaction formula (1) does not proceed completely. The amount is preferably less than 12 moles. In the actual reaction in the plasma CVD 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, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced. It is considered that the reaction is completed only when a large excess is supplied 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 to the hexamethyldioxide raw material. (It may be about 20 times or more the molar amount (flow rate) of siloxane). 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 barrier layer, and the above conditions (i) to (iii) It is possible to form a barrier layer satisfying all of the above) and to exhibit excellent gas barrier properties and flex resistance in the obtained gas barrier film. 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.

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

  In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The electric power to be applied to the power source can be adjusted as appropriate according to the type of the raw material gas, the pressure in the vacuum chamber, etc. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed, and if it is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the substrate during film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.

  Although the conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of raw material gas, the pressure in the vacuum chamber, and the like, it is preferably in the range of 0.25-100 m / min, More preferably, it is in the range of 5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient thickness as a barrier layer, without impairing productivity.

  As described above, as a more preferable aspect of the present embodiment, the barrier layer according to the present invention is formed by plasma CVD using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is characterized by doing. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently produce a barrier layer having both the barrier performance and the barrier performance. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

[ORMOCER layer]
The gas barrier film of the present invention is formed by forming an ORMOCER layer on a substrate in addition to the barrier layer. Here, the stacking order of the barrier layer and the ORMOCER layer is not particularly limited, but the barrier layer and the ORMOCER layer are preferably stacked in this order on the substrate. With such a structure, the ORMOCER layer can further relieve the shape change (shrinkage / expansion) of the base material due to changes in temperature and humidity, and more effectively suppress / prevent cracks.

  In the present invention, the ORMOCER layer has the following formula (1):

However, n is an integer of 2-20.
Polymethoxysiloxane (hereinafter also simply referred to as “polymethoxysiloxane”) with respect to the total number of moles of the material constituting the inorganic / organic hybrid polymer layer (ORMOCER layer) (hereinafter also simply referred to as “ORMOCER constituent material”) And a material containing 20 to 40 mol%. In the present specification, “ORMOCER” means an inorganic substance obtained by mixing (i) an organosilicon compound and (c) an aluminum compound, and (d) other metal compound if necessary, followed by hydrolysis and polycondensation.・ It means organic hybrid polymer. “ORMOCER” is described in, for example, EP-A-0 792 846, Japanese Patent Laid-Open No. 2-160836, and the like.

  The ORMOCER layer according to the present invention has a uniform network structure (silicate network structure) in the layer by adding a specific amount of the polymethoxysiloxane of the above formula (1). Therefore, the ORMOCER layer according to the present invention has gas barrier properties and can flexibly absorb changes in shape due to changes in temperature and humidity. For this reason, even if the base material or barrier layer undergoes a shape change (shrinkage / expansion) under severe conditions where the temperature or humidity changes greatly, the ORMOCER layer is not subject to a shape change. Little or no generation occurs, and excellent gas barrier properties (for example, low water vapor transmission rate) can be maintained for a long time.

  The ORMOCER layer according to the present invention is formed from (a) polymethoxysiloxane, (b) an organosilicon compound and (c) an aluminum compound, and (d) other metal compounds if necessary.

(A) Polymethoxysiloxane Polymethoxysiloxane is represented by the following formula (1).

  In said formula (1), n represents the average degree of polymerization of polymethoxysiloxane, and is 2-20. The polymethoxysiloxane may have a single structure or may be in the form of a mixture of two or more. In the former case, n is an integer, but in the latter case, n is not necessarily an integer, and in this case, n is an average value of n of each polymethoxysiloxane component of the mixture. , May be a decimal point. In consideration of the gas barrier property, the effect of suppressing / preventing crack generation, etc., n is preferably 2 to 9, more preferably 3 to 7, and particularly preferably 4 to 6. By using polymethoxysiloxane having such a structure, a uniform silicate stitch structure can be introduced into the ORMOCER layer to improve the gas barrier property, and the safety is excellent.

  The polymethoxysiloxane is an amount of 20 to 40 mol% based on the total number of moles of the ORMOCER constituent material (= total number of moles of polymethoxysiloxane, organosilicon compound, aluminum compound and other metal compound when added). Included. If the amount of polymethoxysiloxane is below the lower limit, a sufficiently uniform silicate stitch structure cannot be introduced into the ORMOKER layer. Conversely, if the amount exceeds the upper limit, the amount of the organosilicon compound or aluminum compound is too small and the gas barrier Inferior to sex. Preferably, the polymethoxysiloxane is 25 to 35 moles relative to the total number of moles of the ORMOCER component (= total moles of polymethoxysiloxane, organosilicon compound, aluminum compound and other metal compounds if added). Contained in an amount of%.

(I) Organosilicon compound The organosilicon compound is not particularly limited, but is preferably a compound represented by the following formula (2) or an oligomer thereof.

In the above formula (2), R ¹ may have a hydrogen atom, a halogen atom, an alkoxy group that may have a substituent, an acyloxy group that may have a substituent, or a substituent. The alkylcarbonyl group, the alkoxycarbonyl group which may have a substituent, or the amine group (—N (R ₃ ) ₂ and R ₃ may each independently have a hydrogen atom or a substituent. Represents an alkyl group). When a plurality of R ¹ are present (that is, m is 2 or 3), each R ¹ may be the same or different.

  Here, the halogen atom is not particularly limited, and may be any of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), and an iodine atom (I). Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable, and a chlorine atom is more preferable.

  The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 24 carbon atoms. Examples of such an alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, n-octyloxy group, n Examples include -decyloxy group, n-dodecyloxy group, n-hexadecyloxy group, 2-ethylhexyloxy group, 2-hexyldecyloxy group, and 2-decyltetradecyloxy group. Among these, a linear or branched alkoxy group having 1 to 20 carbon atoms is preferable, a linear or branched alkoxy group having 1 to 10 carbon atoms is more preferable, and a linear chain having 1 to 8 carbon atoms. Or a branched alkoxy group is still more preferable, and a C1-C4 linear alkoxy group is especially preferable.

  The acyl group in the acyloxy group (—O-acyl group) is not particularly limited, but is preferably a linear or branched acyl group having 1 to 24 carbon atoms. Examples of such acyl groups include formyl group, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, A naphthyl carbonyl group, a pyridyl carbonyl group, etc. are mentioned.

The alkylcarbonyl group (—C (═O) -alkyl group) is not particularly limited, but is an alkylcarbonyl group having 2 to 25 carbon atoms (—C (═O) —C _1-24 alkyl group). It is preferable. Examples of such an alkylcarbonyl group include an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an isopropylcarbonyl group, and a cyclohexylcarbonyl group.

The alkoxycarbonyl group (—C (═O) -alkoxy group) is not particularly limited, but is an alkoxycarbonyl group having 2 to 25 carbon atoms (—C (═O) —C _1-24 alkoxy group). It is preferable. Examples of such alkoxycarbonyl groups include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group.

The amine group is represented by the formula: —N (R ³ ) ₂ . Here, R ³ represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. In this case, R ³ may be the same or different.

  Here, the alkyl group is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 24 carbon atoms. Examples of such an alkyl group include a 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, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1- Isopropylbutyl group, 2-methyl-1-isopropyl group, 1-t-butyl-2-methylpropyl group, n-nonyl group, 3 5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group , N-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group and the like. Among these, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a linear chain having 1 to 8 carbon atoms. Or a branched alkyl group is still more preferable, and a linear alkyl group having 1 to 3 carbon atoms is particularly preferable.

In the above formula (2), R ² is a group represented by the formula (3): — (R ⁴ ) _n —X—R ⁵ . When a plurality of R ² are present (that is, m is 1 or 2), each R ² may be the same or different.

In the above formula (3), R ⁵ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. An aryl group which may have

  Here, although the said alkyl group does not have a restriction | limiting in particular, Since it is the same as that of the said Formula (1), description is abbreviate | omitted here.

  The alkenyl group is not particularly limited, but is preferably a linear or branched alkenyl group having 2 to 24 carbon atoms. Examples of such an alkenyl group include a vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 5-heptenyl group, 1-octenyl group, 3-octenyl group, and 5-octenyl group Etc.

  The alkynyl group is not particularly limited, but is preferably a linear or branched alkynyl group having 2 to 24 carbon atoms. Examples of such an alkynyl group include acetylenyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentethyl group, 2-pentethyl group, 3- Pentetyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 1-heptynyl group, 2-heptynyl group, 5-heptynyl group, 1-octynyl group, 3-octynyl group, 5-octynyl group, etc. Can be mentioned.

  The aryl group is not particularly limited, but is preferably an aryl group having 6 to 24 carbon atoms. Examples of such aryl groups include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, an anthryl group, a pyrenyl group, an azulenyl group, an acenaphthylenyl group, a terphenyl group, and a phenanthryl group. Among these, a phenyl group, a naphthyl group, and a biphenyl group are preferable, and a phenyl group is more preferable.

In the above formula (3), X is a single bond, an oxygen atom (—O—), a sulfur atom (—S—), or a nitrogen atom (—N (Y ¹ ) —; Y ¹ is a hydrogen atom or an alkyl group ). The alkyl group as the substituent “Y ¹ ” when X is a nitrogen atom (—N (Y ¹ ) —; Y ¹ is a hydrogen atom or an alkyl group) is not particularly limited. Since it is the same as the alkyl group of (1), description is abbreviate | omitted here.

In the above formula (3), R ⁴ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent.

  Here, the alkylene group is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 24 carbon atoms. Examples of such an alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a propylene group.

  The alkenylene group is not particularly limited, but is preferably a linear or branched alkenylene group having 2 to 25 carbon atoms. Examples of such alkenylene groups include vinylene groups and propenylene groups.

  The arylene group is not particularly limited, but is preferably an arylene group having 6 to 24 carbon atoms. Examples of such an arylene group include a phenylene group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthrylene group, a pyrenylene group, an azlenylene group, an acenaphthylene group, a terphenylene group, and a phenanthrylene group. Among these, a phenylene group and a naphthylene group are preferable, and a phenylene group is more preferable.

In the above formula (3), n is 0 or 1. Here, n is 0 means that R ⁴ is a single bond, that is, —X—R ⁵ is directly bonded to a silicon atom (Si).

The “substituent” that may be present in the above formulas (1) to (3) is not particularly limited. Specifically, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a linear or branched alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 1 to 24 carbon atoms (for example, Cyclopentyl group, cyclohexyl group), hydroxyalkyl group having 1 to 24 carbon atoms (for example, hydroxymethyl group, hydroxyethyl group), alkoxyalkyl group having 2 to 24 carbon atoms (for example, methoxyethyl group), carbon atom An alkoxy group of 1 to 24 (for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, dodecyloxy group, etc.), A cycloalkoxy group having 3 to 24 carbon atoms (for example, cyclopentyloxy group, cyclohexane Siloxy group) alkenyl group, alkynyl group, amine group, aryl group, aryloxy group having 6 to 24 carbon atoms (for example, phenoxy group, naphthyloxy group), alkylthio group having 1 to 24 carbon atoms (for example, methylthio group) , Ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group), cycloalkylthio group having 3 to 24 carbon atoms (for example, cyclopentylthio group, cyclohexylthio group), arylthio having 6 to 24 carbon atoms Group (for example, phenylthio group, naphthylthio group), alkoxycarbonyl group having 1 to 24 carbon atoms (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group), carbon An aryloxycarbonyl group having 7 to 24 moles (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group), amide group (—C═O) —N (R) (R ′); wherein R and R ′ are Each independently an alkyl group having 1 to 24 carbon atoms which may have a substituent), a hydroxyl group (—OH), a carboxyl group (—COOH), a thiol group (—SH), a cyano group. (-CN), mercapto group (-SH), amino group _(-NH 2), an epoxy group, and the like. In addition, since an alkyl group, an alkenyl group, an alkynyl group, an amine group, and an aryl group have the same definition as described above, description thereof is omitted here. The number of substituents is not particularly limited and can be appropriately selected in consideration of a desired effect. In the above, it is not substituted with the same substituent. That is, a substituted alkyl group is not substituted with an alkyl group. Among these, it is preferably substituted with at least one of a halogen atom, an alkyl having 1 to 3 carbon atoms, an alkoxy group, a nitro group, an amino group (—NH ₂ ), and an epoxy group, and a halogen atom (for example, F, Cl, Br), an amino group (—NH ₂ ), and an epoxy group are more preferable. In view of excellent resistance to the hydrophobicity (especially condensed water) of the final product, fluorine atoms (fluorinated silane) are particularly preferable. On the other hand, in view of gas barrier properties and the effect of suppressing / preventing crack generation, amino groups (—NH ₂ ) and epoxy groups are particularly preferable.

  Specifically, the organosilicon compound includes an epoxy group, an amino group, an amide group, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a (meth) acryloxy group, a vinyl group and the like from the viewpoint of the formation of a crosslinked structure. The compound which has is preferable. Preferable specific examples of the organosilicon compound include 3-gridoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-aminopropyltriethoxy. Silane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyl Trimethoxysilane or the like is preferable, and 3-glycoxypropyltrimethoxysilane or 3-glycidoxypropylmethyldimethoxysilane having an epoxy group is particularly preferable. The organosilicon compound may be used alone or in the form of a mixture of two or more.

  Further, the content of the organosilicon compound in the starting material is not particularly limited, but relative to the total number of moles of the starting compound (= the total number of moles of the organosilicon compound, the aluminum compound and other metal compounds when added). The content is preferably 25 to 95 mol%, more preferably 35 to 90 mol%. Further, the content of the organosilicon compound relative to the total number of moles of the starting compound (= total number of moles of polymethoxysiloxane, organosilicon compound, aluminum compound and other metal compound when added) is not particularly limited, It is preferably 30 to 60 mol%, and more preferably 40 to 55 mol%.

(C) Aluminum compound The aluminum compound is not particularly limited, but is preferably a compound represented by the following formula (4), an oligomer thereof, or an aluminum salt of an inorganic or organic acid thereof.

In the above formula (4), R ⁶ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an acyloxy group which may have a substituent, Or represents a hydroxyl group. At this time, each R ⁶ may be the same or different. The “halogen atom”, “alkyl group optionally having substituent (s)”, and “alkoxy group optionally having substituent (s)” are the same as defined above. Omitted.

  That is, preferable specific examples of the aluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum triisopropoxide, aluminum-sec- Butoxide, Aluminum-isopropoxide, Methyl aluminum dichloride, Ethyl aluminum dichloride, Dimethyl aluminum methoxide, Diethyl aluminum methoxide, Dimethyl aluminum ethoxide, Diethyl aluminum ethoxide, Methyl aluminum dimethoxide, Ethyl aluminum dimethoxide, Methyl aluminum diethoxy And ethylaluminum diethoxide; These and acetylacetone Rabbi, ethyl acetoacetate, alkanolamines, and the like complexes with glycols and derivatives thereof. The said aluminum compound may be used independently or may be used with the form of a 2 or more types of mixture.

  Further, the content of the aluminum compound in the starting material is not particularly limited, but with respect to the total number of moles of the starting compound (= the total number of moles of the organosilicon compound, the aluminum compound and other metal compounds when added). 5 to 75 mol% is preferable, and 10 to 65 mol% is more preferable. Further, the content of the aluminum compound relative to the total number of moles of the starting compound (= total number of moles of polymethoxysiloxane, organosilicon compound, aluminum compound and other metal compound when added) is also not particularly limited. It is preferably ˜30 mol%, more preferably 10 to 20 mol%.

(D) Other metal compounds Other metal compounds are not particularly limited, but include Group 1 to 3 elements, Group 4 to 10 elements, Group 12 elements, Group 13 to 15 elements (excluding aluminum), and lanthanoids. And an oxide containing at least one element selected from the group consisting of actinides, particularly a low-volatile oxide. More preferably, the other metal compound is Mg, alkaline earth metal (especially Ca), B, Si, Sn, Pb, P, As, Sb, Bi, Ti, Zr, Hf, V, Nb, Ta, An oxide containing at least one element selected from the group consisting of Cr, Mo, W, Mn, Fe, Co, Ni, and Zn, particularly a low-volatile oxide (eg, alkoxide), B, Si, Particularly preferred is an oxide containing at least one element selected from the group consisting of Sn, Zn, and P, particularly a low-volatile oxide (eg, alkoxide).

  That is, preferred specific examples of other metal compounds include tetra n-propoxy zirconium (IV), tetra n-butoxy zirconium (IV), tetra sec-butoxy titanium (IV), tetramethoxy titanium (IV), and tetraethoxy. Titanium (IV); and complexes of these with acetylacetone, ethyl acetoacetate, alkanolamine, glycol and derivatives thereof. The other metal compounds may be used alone or in the form of a mixture of two or more.

  In addition, the content of other metal compounds in the starting material is not particularly limited, but the total number of moles of the starting compound (= the total number of moles of the organosilicon compound, aluminum compound and other metal compound when added). On the other hand, it is preferably 0 to 70 mol%, more preferably 5 to 60 mol%. Further, the content of other metal compounds relative to the total number of moles of the starting compound (= polymethoxysiloxane, organosilicon compound, aluminum compound and the total number of other metal compounds when added) is also not particularly limited. 5-30 mol% is preferable, and 10-20 mol% is more preferable.

  In the present invention, the thickness (dry film thickness) of the ORMOCER layer is not particularly limited, but is preferably 30 to 7000 nm, more preferably 35 to 6000 nm, and particularly preferably 250 to 2000 nm. With such a thickness, the OMOCER layer can exhibit gas barrier properties and excellent adhesion to the barrier layer. In addition, when an ORMOCER layer is comprised from 2 or more layers, it is preferable that an ORMOCER layer has thickness as mentioned above. Further, the thickness of the entire barrier layer when the ORMOCER layer is composed of two or more layers is not particularly limited, but the thickness (dry film thickness) of the entire ORMOCER layer is preferably about 300 to 3000 nm. With such a thickness, the OMOCER layer can exhibit gas barrier properties and excellent adhesion to the barrier layer.

  Further, in the present invention, the ratio of the thickness (dry film thickness) between the barrier layer and the ORMOCER layer is not particularly limited. The thickness ratio of the barrier layer to the ORMOCER layer (the thickness of the barrier layer (nm): the thickness of the ORMOKER layer (nm)) is preferably 1: 0.01 to 60, and 1: 0.1 Is more preferably ˜20, even more preferably 1: 0.15 to 10, particularly preferably 1: 1 to 10. With such a ratio, the obtained gas barrier film can exhibit further excellent gas barrier properties, crack generation suppressing / preventing effects during bending, and excellent adhesion to the barrier layer.

[Formation method of ORMOCER layer]
Next, a preferred method for forming the ORMOKER layer according to the present invention will be described. For example, after mixing the components (A) to (U) and (D) if necessary, water is added and stirred to prepare an ORMOCER layer forming solution. Here, you may add a solvent at the time of mixing of said each component. Here, the solvent is not particularly limited as long as it can dissolve the respective components to be added, and can be appropriately selected depending on the types (a) to (c) and (d) if necessary. Specifically, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), normal propyl alcohol, butanol, isobutanol, tertiary butanol, butanediol, ethylhexanol, benzyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone Ketone solvents such as cyclohexanone and diacetone alcohol; hydrocarbon solvents such as toluene, xylene, solvent naphtha, normal hexane, isohexane, cyclohexane, methylcyclohexane, normal heptane, isooctane and normal decane; ethyl acetate, methyl acetate, acetic acid Butyl, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, lactate ester And ester solvents such as butyl ether, isopropyl ether, methyl cellosolve, cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether (MTBE), butyl carbitol and the like; N-methyl-2-pyrrolidone (NMP), Examples thereof include amine solvents such as dimethylformamide (DMF) and N, N-dimethylacetamide (DMAC), and water.

  Here, the mixing order of the components (a) to (c) and, if necessary, (d) is not particularly limited. For example, (a) to (c) and if necessary, each component of (e) is added and mixed at once; (a) to (c) and if necessary, a part of each component of (d) After adding / mixing, any of the methods of adding / mixing the remaining components; (a) to (c) and, if necessary, the method of sequentially adding each component of (e) may be used.

  In addition, water is added after mixing the above components, but the water in this case is not particularly limited, and is pure water, ultrapure water, industrial pure water, tap water (water), ground water, distilled water, ions Exchange water etc. are mentioned. The amount of water added is not particularly limited, but is preferably less than the stoichiometric amount necessary to completely hydrolyze the hydrolyzable group.

  The liquid for forming the ORMOKER layer prepared as described above is applied on a predetermined layer (for example, a base material, a barrier layer, etc., preferably a barrier layer), and then heated. As a result, the ORMOCER layer is formed on a predetermined layer (for example, a substrate, a barrier layer, etc., preferably a barrier layer). Here, the coating method is not particularly limited, and known methods such as a spray coating method, a spin coating method, a bar coating method, a doctor blade method, a squeegee method, and a screen printing method can be used. Further, the heating condition is not particularly limited as long as the ORMOCER layer is cured. For example, heating temperature is 25-250 degreeC normally, and 50-200 degreeC is preferable. Moreover, heating time is 1 to 60 minutes normally, and 3 to 20 minutes are preferable.

  Further, the thickness (dry film thickness) of the ORMOCER layer is not particularly limited. However, the ORMOCER layer has a thickness as described above, more preferably a thickness as described above, and a thickness ratio with the barrier layer as described above. It is preferably formed on a predetermined layer (for example, a base material, a barrier layer, etc., preferably a barrier layer).

[Underlayer (smooth layer, primer layer)]
The gas barrier film of the present invention may have a base layer (smooth layer, primer layer) between the surface of the substrate having the barrier layer, preferably between the substrate and the barrier layer. The underlayer is provided in order to flatten the rough surface of the substrate on which the protrusions and the like exist, or to fill the unevenness and pinholes generated in the barrier layer with the protrusions existing on the substrate and to flatten the surface. Such an underlayer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, it is preferable that the gas barrier film of the present invention further has an underlayer containing a carbon-containing polymer between the base material and the barrier layer.

  The underlayer 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 underlayer 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. 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.

  Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene Oxide modified pentaerythritol triacrylate, propylene oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

  It is preferable that the composition containing an active energy ray-curable material contains a photopolymerization initiator.

  Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride , Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide And combinations of photoreducing dyes such as eosin and methylene blue and reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more. .

  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 formation method of the underlayer is not particularly limited, but a coating solution containing a curable material is applied to a dry coating method such as a spin coating method, a spray method, a blade coating method, a dipping method, a gravure printing method, or a vapor deposition method. After applying the coating method 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 beams, and / or heating, the coating films are formed. A method of forming 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 preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm. Alternatively, 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 can be used.

  Solvents used when forming the underlayer using a coating solution in which a curable material is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol Terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carb Acetic esters such as tall acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate , Diethylene glycol dialkyl ether, dipropylene Glycol dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  In addition to the above-mentioned materials, the underlayer can contain additives such as a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a plasticizer as necessary. In addition, an appropriate resin or additive may be used for improving the film formability and preventing the occurrence of pinholes in the film. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof and the like. Examples include resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, and polycarbonate resins.

  The smoothness of the underlayer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 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 thickness of a base layer, The range of 0.1-10 micrometers is preferable.

[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). Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. 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.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). A commercially available base material with an easy-adhesion layer may be used.

  Alternatively, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

[Bleed-out prevention layer]
The gas barrier film of the present invention can further have a bleed-out preventing layer. The bleed-out prevention layer is a smooth layer for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film base material to the surface when the film having the base layer is heated and contaminate the contact surface. It is provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  Compounds that can be included in the bleed-out prevention layer include polyunsaturated organic compounds having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated group in the molecule. Hard coat agents such as unitary unsaturated organic compounds can be mentioned.

  Here, as the polyunsaturated organic compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane Tiger (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of unit unsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl. (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-eth Ciethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by weight or more, preferably 4 parts by weight or more, more preferably 6 parts by weight or more and 20 parts by weight or less, preferably 100 parts by weight of the solid content of the hard coating agent. It is desirable that they are mixed in a proportion of 18 parts by weight or less, more preferably 16 parts by weight or less.

  In addition, the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl formal, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicon resin etc. are mentioned.

  In addition, as an ionizing radiation curable resin, an ionizing radiation (ultraviolet ray or electron beam) is irradiated to an ionizing radiation curable coating material in which one or more of a photopolymerizable prepolymer or a photopolymerizable monomer is mixed. Those that cure can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl). ) -1-propane, α-acyloxime ester, thioxanthone and the like.

  The bleed-out prevention layer as described above is prepared as a coating solution by blending a hard coat agent and other components as necessary, and appropriately using a diluting solvent as necessary. After coating by a conventionally known coating method, it can be formed by irradiating with ionizing radiation and curing. As a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, 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 are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer is one of the transparent polymer films. When it is provided on this surface, curling of the barrier film can be easily suppressed.

  As the gas barrier film of the present invention, those described in paragraphs “0036” to “0038” of JP-A No. 2006-289627 can be preferably employed in addition to the above-mentioned ones.

<Electronic device>
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.

  The gas barrier film of the present invention can also be used for device film sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support. The device may be covered with a protective layer before providing the gas barrier film.

  The gas barrier film of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

(Organic EL device)
An example of an organic EL element using a gas barrier film is described in detail in Japanese Patent Application Laid-Open No. 2007-30387.

(Liquid crystal display element)
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has the structure which consists of a film | membrane. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a B type. OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), and CPA type (Continuous Pinwheel Alignment) are preferable.

(Solar cell)
The gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element. The solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type. Amorphous silicon-based solar cell elements, III-V compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I / III- such as copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur system (so-called CIGS system) Group VI compound semiconductor solar cell element, dye-sensitized solar cell element, organic solar cell element, etc. And the like. In particular, in the present invention, the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur. It is preferable that it is an I-III-VI group compound semiconductor solar cell element, such as a system (so-called CIGSS system).

(Other)
As other application examples, the thin film transistor described in JP-A-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., described in JP-A-2000-98326. Electronic paper and the like.

<Optical member>
The gas barrier film of the present invention can also be used as an optical member. Examples of the optical member include a circularly polarizing plate.

(Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate is 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Further, in the examples, the display of “part” or “%” is used, but “part by weight” or “% by weight” is expressed unless otherwise specified. Moreover, in the following operation, unless otherwise specified, the measurement of the operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

  Each characteristic value of the gas barrier film is measured according to the following method.

[Adhesion evaluation method]
As an evaluation of barrier adhesion, the obtained gas barrier film is subjected to a cross-cut test based on JIS K5400 under the conditions of 40 ° C. and 80%. That is, incisions of 90 ° with respect to the film surface are made at intervals of 1 mm on the surface of the gas barrier film, respectively, and 100 grids at intervals of 1 mm are produced. A Mylar tape having a width of 2 cm [manufactured by Nitto Denko, polyester tape (No. 31B)] is applied thereto, and the tape attached using a tape peeling tester is peeled off. Of the 100 grids on the gas barrier film, the number (n) of cells remaining without peeling is counted. The results are expressed as ranks 1-5 as follows.

[Evaluation method of water vapor transmission rate (water vapor barrier property)]
On the barrier layer surface of each gas barrier film sample, using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400), mask the gas barrier film sample except for the portion to be vapor deposited (12 mm × 12 mm 9 locations), and metal Calcium was deposited. Thereafter, the mask is removed in a vacuum state, and aluminum is vapor deposited from another metal vapor deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere Then, by irradiating with ultraviolet rays, a water vapor barrier property evaluation cell is produced.

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

  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 Is stored under the same high temperature and high humidity conditions of 60 ° C. and 90% RH, and it is confirmed that corrosion of metallic calcium does not occur even after 1000 hours.

(Devices and materials used)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
[Crack evaluation method]
Each gas barrier film sample was allowed to stand for 12 hours in an environment of 23 ± 2 ° C. and 55 ± 5% RH, then left for 12 hours under conditions of 85 ± 3 ° C. and 90 ± 2% RH, and again 23 ± 2 ° C. , 55 ± 5% RH for 12 hours, 85 ± 3 ° C., 90 ± 2% RH for 12 hours. This operation is performed 30 times. Finally, the sample is allowed to stand for 12 hours in an environment of 23 ± 2 ° C. and 55 ± 5% RH. The sample is then observed for cracks with an optical microscope and evaluated according to the following criteria. In the following criteria, C and D are not suitable for practical use.

Example 1
1. Base material A biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) was used as the base material.

2. Formation of Underlayer After applying UV curable organic / inorganic hybrid hard coat material OPSTARZ7501 by JSR Co., Ltd. with a wire bar so that the film thickness after drying becomes 4 μm on the easy-adhesion surface of the base material, 80 ° C. After drying in 3 minutes, under air atmosphere, using a high-pressure mercury lamp, curing conditions; curing was performed at 1.0 J / cm ² to form an underlayer. The maximum cross-sectional height Rt (p) representing the surface roughness at this time was 16 nm. The surface roughness is calculated from an uneven sectional curve continuously measured with a detector having a stylus having a minimum tip radius using an AFM (Atomic Force Microscope AFM: manufactured by Digital Instruments), and the minimum tip radius is calculated. Was measured many times in the section having a measurement direction of 30 μm with the stylus of No. 1 and obtained from the average roughness with respect to the amplitude of fine irregularities.

3. Formation of barrier layer 2. The base material with the base layer formed on the surface is mounted on a Kobelco plasma CVD roll coater W35 series apparatus so that the base layer is on top, and hexamethyldisiloxane (HMDSO) is used. Then, a film was formed under the following film forming conditions (plasma CVD conditions), and a barrier layer was formed on the base layer with a thickness of 300 nm.

  The obtained sample was subjected to XPS depth profile measurement under the following conditions to obtain silicon element distribution, oxygen difference element distribution, and carbon element distribution. The results are shown in FIG.

  As is clear from FIG. 2, the obtained carbon distribution curve has a plurality of (5) distinct extreme values, and the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 3 at% or more. In addition, in the region where the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon are 90% or more of the film thickness of the barrier layer, the largest (oxygen atomic ratio), (silicon atomic ratio) , (Atomic ratio of carbon).

4). Formation of ORMOCER layer 27.7 g (30 mol%) of polymethoxysiloxane (Mitsubishi Chemical Corporation, trade name: MS51, average molecular weight 500-700), 212.7 g (45 mol%) of 3-glycidoxy Propyltrimethoxysilane, 22.1 g (5 mol%) 3-aminopropyltriethoxysilane, 49.2 g (10 mol%) aluminum sec-butoxide was added to the flask and cooled with ice while adding 5 Stir for minutes. To this mixture, 7.6 g of distilled water was slowly added dropwise and the mixture was stirred for an additional 5 minutes. Next, 65.5 g (10 mol%) of tetra-n-propoxyzirconium (IV) was added to the mixture obtained above and stirred for 5 minutes, and then 15.3 g of distilled water was further added to the mixture. And continued stirring for 15 minutes. Finally, 122.5 g of distilled water was added to the mixture, and the mixture was stirred at room temperature (25 ° C.) for 2 hours to obtain a transparent ORMOCER layer forming liquid.

  Next, the above 3. Apply the above-prepared ORMOCER layer forming solution on the barrier layer of the base material having the base layer and the barrier layer formed on the surface by the bar coating method, and heat at 130 ° C. for 10 minutes. The gas barrier film 1 in which an ORMOCER layer (thickness after drying: 0.25 μm) was formed on the barrier layer by thermosetting was produced.

Comparative Example 1
In Example 1, 4. Comparative gas barrier film 1 was produced in the same manner as in Example 1 except that the ORMOCER layer was not formed.

Comparative Example 2
With reference to Example 2 of Japanese Patent No. 4821610, a comparative gas barrier film 2 in which the carbon element concentration in the composition continuously changed was produced by an atmospheric pressure plasma apparatus.

  The gas barrier film 1 produced in Example 1 and the comparative gas barrier films 1 and 2 produced in Comparative Examples 1 and 2 were evaluated for cracks and water vapor permeability, and the results are shown in Table 1 below.

  From Table 1 above, it is shown that the gas barrier film of the present invention exhibits excellent water vapor barrier properties and crack generation suppression / prevention effects.

Examples 2-9
In Example 1, except that the thickness of the barrier layer and the ORMOCER layer (film thickness after drying) was changed as shown in Table 2 below, in the same manner as in Example 1, the gas barrier films 2 to 2 were used. 9 was produced. In addition, about the barrier layer formed at the formation process of each barrier layer, XPS depth profile measurement was performed like Example 1, and silicon element distribution, oxygen difference element distribution, carbon element distribution, and oxygen carbon distribution were obtained. However, the silicon atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio in all the barrier layers are more than 90% of the thickness of the barrier layer thickness (atomic ratio of oxygen). It was confirmed that the order was (atomic ratio) and (atomic ratio of carbon).

Comparative Example 3
With reference to JP 2005-537963 A, a comparative gas barrier film 3 in which a gradient composition coating having a thickness of about 500 nm was formed on a polycarbonate substrate having a thickness of about 10 cm × 10 cm and a thickness of 200 μm was produced using PECVD technology. . That is, a gradient coating made of silicon, carbon, oxygen, and nitrogen is produced using silane (maximum flow rate of about 500 sccm / min), ammonia (maximum flow rate of about 60 sccm / min), and propylene oxide (maximum flow rate of about 500 sccm / min). did. The rate of reactant gas was varied during deposition such that the composition of the coating changed continuously in its thickness direction. The power supplied to the RF electrode was 100 W when plasma was generated from propylene oxide and 200 W when a mixture of silane and ammonia was supplied to the reactor. The vacuum level in the reactor was 0.2 mmHg and the average temperature was about 55 ° C.

Comparative Example 4
A comparative gas barrier film 4 was produced with reference to Example 3-3 of JP-A-7-178860. That is, on the PET film (Toyobo Co., Ltd .: E5001) having a thickness of 12 μm by EB heating vapor deposition using particulate SiO (purity 99.7%) having a size of about 3 to 5 mm as a vapor deposition source. A silicon oxide (SiOx) gas barrier thin film was formed. A barrier layer having a thickness of 80 nm was produced at a film feed rate of 100 m / min and an applied power of 5 kw. Further, propylene gas was used as a reaction gas, and a high-frequency voltage was applied to an electrode installed in the vicinity of the chill roll so that carbon substitution proceeded smoothly, so that the propylene gas was brought into a plasma state. The flow rate was changed, and the sinusoidal curve was changed with an amplitude of 500 V around the excitation voltage of 1 KV. Thereby, a gas barrier film (SiO _1.7 ) ₉₀ -C ₁₀ ) was obtained. The amount of carbon substitution and the change in the thickness direction of the film thus obtained were measured using an ESCA apparatus. As measurement conditions, Mg-Kα rays were used as a light source, the output was 8 kV × 30 mA, and the degree of vacuum was constant 5 × 10 ⁻⁶ Pa. As a result, silicon (Si) atoms change by 34.4 to 36.6 at% in the thickness direction, and carbon (C) atoms have an average concentration of 27.5 at% and 3.0 to 3.0 in the thickness direction. The change was 5.0 at%, and the period of the change was 5 times.

Comparative Example 5
In Example 1, 3. A comparative gas barrier film 5 was produced in the same manner as in Example 1 except that the barrier layer was not formed.

  About the gas barrier film 2-9 produced in the said Examples 2-9 and the comparative gas barrier film 3-5 produced in Comparative Examples 3-5, a crack, adhesiveness, and water-vapor-permeation rate were evaluated, and a result is shown below. It shows in Table 2.

  From the above Table 2, it is shown that the gas barrier film of the present invention exhibits superior water vapor barrier properties, adhesion, and crack generation suppressing / preventing effects as compared with the comparative gas barrier film.

Examples 10-22
In Example 1, the gas barrier films 10 to 10 were prepared in the same manner as in Example 1 except that the thicknesses (film thicknesses after drying) of the barrier layer and the ORMOCER layer were changed as shown in Table 3 below. 22 was produced. In addition, about the barrier layer formed at the formation process of each barrier layer, XPS depth profile measurement was performed like Example 1, and silicon element distribution, oxygen difference element distribution, carbon element distribution, and oxygen carbon distribution were obtained. However, the silicon atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio in all the barrier layers are more than 90% of the thickness of the barrier layer thickness (atomic ratio of oxygen). It was confirmed that the order was (atomic ratio) and (atomic ratio of carbon).

  Gas barrier films 2 to 3 produced in Examples 2 to 3, Gas barrier films 6 to 9 produced in Examples 6 to 9 and Gas barrier films 10 to 10 produced in Examples 10 to 22 For No. 22, cracks, adhesion and water vapor transmission rate were evaluated, and the results are shown in Table 3 below.

  From Table 3 above, it is shown that the gas barrier film of the present invention exhibits excellent water vapor barrier properties, adhesion, and crack generation suppressing / preventing effects.

1 ... Gas barrier film,
2 ... base material,
3 ... barrier layer,
31 ... Manufacturing equipment,
32 ... feed roller,
33, 34, 35, 36 ... transport rollers,
39, 40 ... film forming roller,
41 ... gas supply pipe,
42 ... Power source for plasma generation,
43, 44 ... Magnetic field generator,
45: Winding roller.

Claims (4)

A gas barrier film having a substrate, a barrier layer containing silicon, oxygen, and carbon and an inorganic / organic hybrid polymer layer (ORMOCER layer) formed on at least one surface of the substrate,
The inorganic / organic hybrid polymer layer (ORMOCER layer) has the following formula (1):
However, n is 2-20.
Of the polymethoxysiloxane in an amount of 20 to 40 mol% with respect to the total number of moles of the material constituting the inorganic / organic hybrid polymer layer (ORMOCER layer), and the barrier layer The following conditions (i) to (iii):
(I) The distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) A silicon distribution curve showing a relationship, an oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and the L and silicon atoms In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of oxygen atoms, and carbon atoms (the atomic ratio of carbon),
In the region of 90% or more of the film thickness of the barrier layer, the order is (atomic ratio of oxygen), (atomic ratio of silicon), (atomic ratio of carbon) from the largest.
(Ii) the carbon distribution curve has at least two extreme values;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.
Satisfying gas barrier film.   The gas barrier film according to claim 1, wherein the ORMOCER layer has a thickness of 0.03 to 7 μm.   3. The film thickness ratio between the barrier layer and the ORMOCER layer (the thickness of the barrier layer (nm): the thickness of the ORMOCER layer (nm)) is 1: 0.01 to 60. 4. Gas barrier film.   The gas barrier film according to any one of claims 1 to 3, further comprising an underlayer containing a carbon-containing polymer between the substrate and the barrier layer.