JP6507493B2 - Method of manufacturing gas barrier film - Google Patents

Description

The present invention relates to the production how the gas barrier film having a hard coat layer having a gradient structure of the silicon dioxide particles content.

  An organic electroluminescent element (hereinafter, also referred to as an organic EL element) using electroluminescence (hereinafter referred to as EL) of an organic material can emit light at a low voltage of several volts to several tens of volts. It is a thin film type completely solid element, and has many excellent features such as high luminance, high luminous efficiency, thinness and light weight. For this reason, in recent years, attention has been focused on surface light sources such as backlights of various displays, display boards such as billboards and emergency lights, and illumination light sources.

  Although an organic EL element using a resin base material as a base material has been studied for the purpose of making the element thin and light and flexible, the resin base material is used for the inside of the organic EL element. A gas barrier film may be provided to block the entry of various gases such as water vapor and oxygen. By providing the gas barrier film in the organic EL element, the influence of harmful gases and the like from the external environment is blocked, and the deterioration of the function of the organic EL element is suppressed.

  The organic EL element with flexibility can maintain the curved state as a shape because of its features, but if it is maintained for such a curved state for a long time, the adhesion deterioration of the gas barrier film provided or There is a problem that the gas barrier property is lowered. One of the causes is the deterioration of the adhesion between the resin substrate and the gas barrier film provided thereon. This is because the gas barrier film has a laminated structure in which a plurality of organic layers, inorganic layers, and the like are laminated, and when the curved surface state lasts for a long time, cracks occur in a specific constituent layer or is subjected to bending stress. At the same time, it is presumed that peeling is caused due to the difference in the expansion ratio between the resin base material and the constituent layer.

  To solve such problems, Patent Document 1 discloses physical vapor deposition (PVD), low temperature plasma vapor deposition, chemical deposition (CVD) on a polyethylene terephthalate (hereinafter abbreviated as PET) substrate. Method), inorganic-organic hybrid polymer layer (ORMOCER) formed by applying a silicon oxide metal alkoxide or its derivative, an aluminum compound, and a compound containing another metal element if necessary. It is described that the gas barrier film which improved bending resistance can be provided by laminating (layer). Patent Document 1 also proposes a gas barrier film in which the bending resistance is improved by setting the thickness of the inorganic-organic hybrid polymer layer in the range of 0.05 to 0.95 μm.

  However, although the gas barrier film described in the above-mentioned Patent Document 1 exhibits excellent characteristics with respect to bending resistance, when exposed to a long time in a high temperature and high humidity environment, the metal oxide layer and the inorganic / organic layer There is a problem that the adhesion between the layers with the hybrid polymer layer is lowered and the gas barrier property is deteriorated. In addition, since polyethylene terephthalate is applied as the resin substrate, there is a problem that the transparency is a little low, the birefringence (retardation value) is high, and the angle dependency of color is large.

  Therefore, when a gas barrier film using polyethylene terephthalate as a resin substrate is applied to an organic EL element, the durability of the gas barrier film is lowered in addition to the problems such as transparency, birefringence and visibility as described above. There is a problem that the light emission performance of the organic EL element is also deteriorated due to the

  Further, in Patent Document 2, a gas barrier formed by subjecting a polysilazane film formed by applying a polysilazane-containing liquid to a resin base material, for example, at least one surface of a PET film, to a modification treatment by plasma irradiation. A gas barrier film having a layer is disclosed.

  According to the method disclosed in Patent Document 2, it is believed that a gas barrier film can be provided which exhibits excellent gas barrier properties, has a short production time, and is excellent in the selectivity of the resin substrate. However, as described above, when exposed to a high temperature and high humidity environment for a long time, there is a problem that the adhesion between the resin base and the gas barrier layer is not sufficient.

  Furthermore, in the Patent Document 1 and the Patent Document 2, although a PET film or the like is mainly used as a resin substrate, the PET film has the above-mentioned transparency, birefringence, and visibility. In addition to problems such as the above, the barrier property against moisture etc. is low, so when forming a gas barrier film, it is necessary to design the gas barrier layer to be applied to exhibit a high degree of gas barrier performance. Constraint on layer configuration and quality requirements are growing.

On the other hand, Patent Document 3 discloses a method of manufacturing a gas barrier laminate film having a water vapor transmission rate of 1 × 10 ⁻⁴ g / m ² · day level by a roll-to-roll method using a plasma CVD apparatus. It is disclosed. The method used for the production of the gas barrier film produced by the method described in Patent Document 3 is a discharge plasma chemical vapor deposition method in which a large number of carbon atoms can be arranged around the substrate, but At the time of film formation, foreign particles may be generated in the plasma discharge space, and the generated foreign particles form the surface of the resin substrate used in film formation, the interface between the resin substrate and the gas barrier layer, or the gas barrier layer formed It has the problem of being easy to adhere or deposit on the surface. When such foreign particles are present in the gas barrier film, the foreign particles act as a starting point when exposed to a high temperature and high humidity environment for a long time or when they are bent and subjected to a stretching stress. It was found that the barrier layer was likely to be broken, cracked or peeled off, and the gas barrier properties were likely to be deteriorated.

Japanese Patent Application Laid-Open No. 2002-046208 JP 2007-237588 A International Publication No. 2012/046767

The present invention has been made in view of the above problems, and the problem to be solved is the adhesion between the resin base and the constituent layer (for example, gas barrier layer) even after being stored for a long time in a high temperature and high humidity environment. it is to provide a manufacturing how the gas barrier film to produce a good gas-barrier film sex.

  As a result of intensive investigations in view of the above problems, the present inventor is a method for producing a gas barrier film having at least a hard coat layer and a gas barrier layer on a resin substrate, wherein the hard coat layer is at least silicon dioxide. A particle is contained, the silicon dioxide particle content rate (mass%) in the hard coat layer has a concentration gradient structure, and the gas barrier layer uses an oxygen gas and a source gas containing an organosilicon compound, According to the method for producing a gas barrier film formed by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied, even after being stored for a long time in a high temperature and high humidity environment, See that it is possible to provide a method for producing a gas barrier film that produces a gas barrier film with excellent adhesion between the material and the constituent layers. However, the present invention has been accomplished.

  That is, the above-mentioned subject of the present invention is solved by the following means.

1. A method for producing a gas barrier film having at least a hard coat layer and a gas barrier layer on a resin substrate,
The hard coat layer contains at least silicon dioxide particles, and the silicon dioxide particle content 2 (mass%) in the surface area T on the gas barrier layer side of the hard coat layer and the surface area B on the resin substrate side The concentration gradient structure is such that the content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) with the silicon dioxide particle content 1 (mass%) is 10 mass% or more and 30.6 mass% or less Have
The hard coat layer satisfies the following condition 1 or 2:
And the gas barrier layer is formed by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied, using a raw material gas containing an organosilicon compound and an oxygen gas. How to make a film.

  2. The method for producing a gas barrier film according to claim 1, wherein the resin substrate is a resin film containing triacetyl cellulose.

3. The silicon dioxide particle content 2 (mass%) in the surface area T on the gas barrier layer side of the hard coat layer, and the silicon dioxide particle content 1 (mass%) in the surface area B on the resin substrate surface side The content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) is 20% by mass or more and 30.6% by mass or less , according to the first or second aspect. Method for producing a gas barrier film.

  4. The method for producing a gas barrier film according to any one of claims 1 to 3, wherein the hard coat layer contains an active energy ray-curable resin and is formed by a wet coating method.

  5. The gas barrier layer contains carbon atoms, silicon atoms and oxygen atoms as constituent elements, and is formed to satisfy all of the following (1) to (4): The manufacturing method of the gas barrier film as described in any one of these.

  (1) The carbon atom ratio of the gas barrier layer changes continuously in the layer thickness direction within the distance from the surface of the gas barrier layer to 89% of the layer thickness in accordance with the distance from the surface .

  (2) The maximum value of the carbon atom ratio of the gas barrier layer is less than 20 at% within the distance from the surface of the gas barrier layer to 89% of the layer thickness in the layer thickness direction.

  (3) The carbon atom ratio of the gas barrier layer continuously increases in the layer thickness direction from the surface of the gas barrier layer to 90 to 95% of the layer thickness.

  (4) The maximum value of the carbon atom ratio of the gas barrier layer is at least 20 at% within the range of 90 to 95% of the layer thickness from the surface of the gas barrier layer in the layer thickness direction.

6 . The hard coat layer, a gas barrier film according to any one of the first term, characterized in that configured in the silicon dioxide particles content (mass%) of different two or more layers to the fifth term Manufacturing method.

7 . A polysilazane-containing liquid is applied and dried on the gas barrier layer, and the formed coating film is reformed by irradiating vacuum ultraviolet light having a wavelength of 200 nm or less to form a second gas barrier layer. method for producing gas barrier film according to any one of the first term to the sixth term to.

By the means of the present invention is excellent in flatness, a manufacturing how the gas barrier film that can be excellent in adhesion even after stored for a long period of time in the environment of high temperature and high humidity, it maintains a high gas barrier property can do.

  The mechanism for expressing the effects of the present invention or the mechanism of action is not clear but is presumed as follows.

In the present invention, at least a hard coat layer and a gas barrier layer are formed on a resin substrate, and the method for forming the hard coat layer contains at least silicon dioxide particles (hereinafter also referred to as silica particles) and is hard. The silicon dioxide particles content (mass%) in the coating layer is the silicon dioxide particles in the surface area T on the gas barrier layer surface relative to the silicon dioxide particles content 1 (mass%) in the surface region B on the resin substrate surface side Silicon dioxide particles having a content gradient of 2 (mass%) in a concentration gradient pattern in a range of 10 mass% or more and 30.6 mass% or less, and the hard coat layer surface-modified as silicon dioxide particles, or normal pressure boiling point containing a high boiling point solvent of a polyhydric alcohol of more than 0.99 ° C. in, and as a method for forming the gas barrier layer comprises an organic silicon compound By using the material gas and oxygen gas, it is a feature formed by a discharge plasma chemical vapor deposition with a discharge space between the rollers applying a magnetic field.

  A conventional gas barrier film has a structure in which a gas barrier layer is formed on a flexible resin substrate, so that the resin substrate is bent in a severe environment, for example, in a high temperature and high humidity environment for a long time When stored in a bent state, the film peels off at the interface between the resin base material and the gas barrier layer, etc., and breakage, cracks, etc. of the gas barrier layer subjected to excessive stress occur. And the deterioration of the gas barrier properties. When a gas barrier layer is formed by discharge plasma chemical vapor deposition having a discharge space between rollers to which a magnetic field is applied, using a raw material gas containing an organosilicon compound and oxygen gas, foreign matter in the plasma discharge space Particles (particle growth in the discharge space) may be generated, and the generated foreign particles are deposited on the surface of the resin substrate or the formed gas barrier layer, so that the foreign particles become a nucleus of foreign particle failure, It has been a factor of deterioration of the gas barrier properties.

  In the present invention, in consideration of the above problems, a gas barrier film which is excellent in adhesion and can maintain high gas barrier properties even when stored for a long time in a high temperature and high humidity environment in a bent or curved state As a result of intensive studies toward development, a hard coat layer containing at least silicon dioxide particles (silica particles) was provided between the resin substrate and the gas barrier layer, and the silicon dioxide particle content in the hard coat layer By providing the inclined structure at (mass%), when the resin base and the gas barrier layer are subjected to stress due to bending or bending under a high temperature and high humidity environment, in particular, between the resin base and the gas barrier layer By compensating the stress and developing the stress relaxation action, it is possible to dramatically reduce the delamination of the layers and the film breakage of the gas barrier layer, and as a result, it is possible to save under various environments. It was always higher realized a method of manufacturing a gas barrier film capable of maintaining the gas barrier properties even when.

  In the case of forming the gas barrier layer by the discharge plasma chemical vapor deposition method having the discharge space between the rollers to which the magnetic field is applied, using the source gas containing the organosilicon compound and the oxygen gas as described above, the plasma discharge In the space, foreign particles (particle growth in the discharge space) may be generated, and the generated foreign particles are deposited on the surface of the resin substrate or the formed gas barrier layer, so that the foreign particles act as nuclei of foreign matter failure. It becomes a factor of deterioration of the gas barrier property, but it has a graded structure in the silicon dioxide particle content rate according to the present invention with a large stress relaxation effect between the resin base material and the gas barrier layer formed by the above method. By providing the hard coat layer, it is possible to alleviate excessive stress concentration originating from the generated foreign matter, and as a result, it is possible to reduce film breakage and film peeling. It is possible to prevent manner.

Schematic sectional drawing which shows an example of a structure of the gas barrier film of this invention The schematic diagram which shows an example of the inclined structure of the silicon dioxide particle content rate in the hard-coat layer which concerns on this invention The schematic diagram which shows an example of the inclined structure of the silicon dioxide particle content comprised from the several hard-coat layer which concerns on this invention The schematic diagram which shows another example of the inclined structure of the silicon dioxide particle content rate comprised from the several hard-coat layer which concerns on this invention The schematic diagram which shows an example of a structure of a discharge plasma processing apparatus suitable for formation of the gas barrier layer which concerns on this invention Graph showing silicon distribution curve, oxygen distribution curve and carbon distribution curve in gas barrier layer The schematic diagram which shows an example of the production line applicable to manufacture of the gas barry film of this invention The schematic block diagram which shows an example of a structure of the organic EL element which comprised the gas barrier film of this invention

The method for producing a gas barrier film of the present invention is a method for producing a gas barrier film having at least a hard coat layer and a gas barrier layer on a resin substrate, wherein the hard coat layer contains at least silicon dioxide particles, Silicon dioxide particle content 2 (mass%) in the surface area T on the gas barrier layer side of the hard coat layer and silicon dioxide particle content 1 (mass%) in the surface area B on the resin substrate surface side The hard coat layer has a concentration gradient structure in which the ratio difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) is 10% by mass or more and 30.6% by mass or less , and the hard coat layer has a surface as silicon dioxide particles. modified silicon dioxide particles, or boiling point at normal pressure is containing a high boiling point solvent of a polyhydric alcohol of more than 0.99 ° C., and the gas barrier But by using the raw material gas and the oxygen gas containing an organic silicon compound, and forming a discharge plasma chemical vapor deposition with a discharge space between the rollers applying a magnetic field. This feature is a technical feature common to the inventions of the respective claims .

  As an embodiment of the present invention, adhesion with a hard coat layer and bending can be achieved by applying a resin film containing triacetyl cellulose as the resin base material from the viewpoint that the effects aimed by the present invention can be further expressed. It is preferable from the point which can set resistance highly and can obtain the gas barrier film provided with the low retardation characteristic.

  Moreover, the silicon dioxide particle content 2 (mass%) in the surface area T on the gas barrier layer side of the hard coat layer according to the present invention and the silicon dioxide particle content 1 in the surface area B on the resin substrate side By setting the content difference ΔC with (mass%) (silicon dioxide particle content 2-silicon dioxide particle content 1) to 20 mass% or more, it is possible to obtain more excellent adhesion and failure resistance. Preferred.

  In addition, the hard coat layer according to the present invention contains an active energy ray-curable resin, and it is possible to stably form a high quality hard coat layer by a simple manufacturing facility to be formed by a wet coating method. Is preferable in that

  In addition, it is preferable that the gas barrier layer be formed so as to satisfy all of the above (1) to (4) as a profile of carbon element from the viewpoint of forming a gas barrier layer having a minute structure.

The hard coat layer according to the present invention is characterized in that surface-modified silicon dioxide particles are used as the contained silicon dioxide particles, and the silicon dioxide in the hard coat layer of the silicon dioxide particles specified in the present invention. the gradient structure of the content of the particles, Ru can be stably obtained.

In addition, the hard coat layer according to the present invention is characterized by containing a polyhydric alcohol high-boiling point solvent having a boiling point of 150 ° C. or higher at normal pressure , and the hard coat of silicon dioxide particles specified in the present invention Ru can achieve concentration gradient in the layer.

  Further, in the hard coat layer according to the present invention, it is preferable that the silicon dioxide particles in the layer defined in the present invention be constituted of two or more layers having different silicon dioxide particle contents (% by mass). It is preferable from the viewpoint that a concentration gradient can be obtained.

  Further, a polysilazane-containing liquid is further applied and dried on the gas barrier layer, and the formed coating film is reformed by irradiating vacuum ultraviolet light having a wavelength of 200 nm or less to form a second gas barrier layer. It is preferable from the viewpoint of achieving more excellent gas barrier properties.

  BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in the following description uses the numerical value described before and after that in the meaning included as a lower limit and an upper limit. In the following description, numerals shown in parentheses after each component represent symbols in each figure.

<< Basic composition of gas barrier film >>
FIG. 1 is a schematic cross-sectional view showing an example of a typical configuration of the gas barrier film of the present invention. In addition, the number shown in the parenthesis after each component represents the code | symbol in each figure.

  As shown in FIG. 1, the gas barrier film (1) of the present invention contains at least silicon dioxide particles on one side of the resin substrate (2), and the silicon dioxide particle content (mass%) in the layer The silicon dioxide particle content (mass%) in the surface area (3T) on the gas barrier layer (4) side is lower than the surface area (3B) on the resin base (2) side with a concentration gradient as A discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied, using a hard coat layer (3) having a high structure, and a source gas containing an organic silicon compound and an oxygen gas thereon Gas barrier layer (4) formed by The definition of the surface area (3B) on the resin base (2) side and the surface area (3T) on the gas barrier layer (4) side according to the present invention will be described later with reference to FIG. .

  In the present invention, if necessary, a polysilazane-containing liquid is applied and dried on the gas barrier layer (4), and the formed coating film is reformed by irradiating vacuum ultraviolet light having a wavelength of 200 nm or less. It can be set as the structure which has the 2nd gas barrier layer (5) formed.

The gas barrier layer (4) and the second gas barrier layer (5) according to the present invention have gas barrier properties. Specifically, the gas barrier layer (4) and the second gas barrier layer (5) have a water vapor permeability (25. +-. 0.5.degree. C.) measured by a method according to JIS-K-7129-1992. It is preferable to exhibit a gas barrier property having a relative humidity of 90 ± 2%) of 0.01 g / (m ² · 24 hours) or less. Moreover, the oxygen permeability measured by the method according to JIS-K-7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the water vapor permeability is 1 × 10 ⁻⁵ It is preferable to exhibit a gas barrier property of not more than g / (m ² · 24 hours).

<Silicon dioxide concentration distribution in hard coat layer>
In the gas barrier film of the present invention, at least silicon dioxide particles are contained between the resin substrate and the gas barrier layer, and the silicon dioxide particle content 2 in the surface region T on the gas barrier layer side of the hard coat layer is 2 (mass %) And the content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) of silicon dioxide particle content 1 (mass%) in the surface region B on the side of the resin base material is 10 mass% As described above , it is characterized by having a concentration gradient structure of 30.6 mass% or less .

More preferably, the silicon dioxide particle content 2 (mass%) in the surface area T on the gas barrier layer surface side of the hard coat layer according to the present invention and the silicon dioxide particle content 1 in the surface area B on the resin substrate surface side The content difference with (mass%) (silicon dioxide particle content 2-silicon dioxide particle content 1) is 20 mass% or more and 30.6 mass% or less .

  The method of forming the hard coat layer according to the present invention is not particularly limited, but in the present invention, it is preferable to contain an active energy ray-curable resin together with silicon dioxide particles and to form by a wet coating method. As another constitution, it is formed by a wet coating method using a coating solution for forming a hard coat layer composed of a photopolymerization initiator, a surfactant, a solvent and the like in addition to silicon dioxide particles and an active energy ray curable resin. Method is preferred.

  Hereinafter, the silicon dioxide particle content (% by mass) of the hard coat layer according to the present invention will be described with reference to the drawings.

  FIG. 2 is a schematic view showing an example of the silicon dioxide particle content gradient structure in the hard coat layer according to the present invention.

  FIG. 2A shows a partial cross-sectional view in which the hard coat layer (3) and the gas barrier layer (4) are laminated on the resin base material (2).

  In the present invention, the surface side in contact with the resin base material (2) is referred to as a surface area B (3B), and the content of silicon dioxide particles (hereinafter also referred to as silica particles) in the surface area B (3B) is referred to. The silicon dioxide particle content is 1 (mass%). Similarly, the surface side in contact with the gas barrier layer (4) is a surface area T (3T), and the content of silicon dioxide particles in the surface area T (3T) is the silicon dioxide particle content 2 (mass%) Do.

When the total layer thickness of the hard coat layer (3) is hd, as shown in the left drawing of FIG. 2, the depth is from the surface side of the hard coat layer (3) in contact with the resin substrate (2) A layer thickness region of 0.1 hd (region of 10% of the total layer thickness) is defined as the surface region B (3B) in the present invention, and the average silicon dioxide particle content (mass%) in the surface region B (3B) is The silicon dioxide particle content is 1 (mass%). At this time, in the thickness direction of the surface area B (3B), the silicon content in the surface area B (3B) with a thickness of 0.1 hd is measured by X-ray photoelectron spectroscopy (abbreviation: XPS) described below. The silicon content is converted to a silicon dioxide (SiO ₂ ) content to obtain an average value of silicon dioxide particle content 1 (mass%) in a surface area B (3B) with a thickness of 0.1 hd.

  Similarly, the area from the surface of the hard coat layer (3) in contact with the gas barrier layer (4) to 0.1 hd in the depth direction (10% of the total layer thickness) is referred to as the surface area in the present invention T (3T), silicon dioxide particle content (mass%) in the surface region T (3T) is silicon dioxide particle content 2 (mass%), X-ray photoelectron spectroscopy (abbreviation: XPS) in the same manner as described above ) Is used to determine the average value of silicon dioxide particle content 2 (mass%).

That is, in the present invention, as shown by the graph on the right side of FIG. 2, the content of silicon dioxide particles is 1 (mass%) with respect to the silicon dioxide particle content 1 (mass%) in the surface region B (3B) on the resin substrate (2) It has a concentration gradient structure in which the silicon dioxide particle content 2 (mass%) in the surface region T (3T) on the gas barrier layer (4) side is high, specifically, the silicon dioxide particle content 2 (mass%) It is characterized in that the content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) between and the silicon dioxide particle content 1 (mass%) is 10 mass% or more and 30.6 mass% or less I assume. More preferably, the content difference ΔC between the silicon dioxide particle content 2 (mass%) and the silicon dioxide particle content 1 (mass%) is 20 mass% or more and 30.6 mass% or less , and more preferably 20. It is in the range of -30 mass%.

  The silicon dioxide particle content 2 (% by mass) in the surface region T (3T) is preferably in the range of approximately 30 to 80% by mass, and more preferably in the range of 40 to 70% by mass. The silicon dioxide particle content 1 (mass%) in the surface region B (3B) is preferably in the range of approximately 10 to 50 mass%, more preferably in the range of 15 to 40 mass%. .

<Measurement of silicon dioxide particle content in hard coat layer: XPS measurement method>
The silicon dioxide particle content in the layer thickness direction of the hard coat layer is measured by using X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering by argon etc. in combination to sequentially expose the hard coat layer surface. Meanwhile, the surface elemental composition analysis can be performed by so-called XPS depth profile measurement. The distribution curve of the silicon element obtained by such XPS depth profile measurement can be created, for example, with the vertical axis representing the number of silicon atoms (unit: at%) and the horizontal axis representing the etching time (sputtering time). In the distribution curve of silicon in which the horizontal axis represents the etching time, the etching time is the distance from the surface of the hard coat layer in the layer thickness direction of the hard coat layer in the layer thickness direction, ie, the layer thickness of the hard coat layer Generally correlate with

In the present invention, the silicon element content in the surface area T (3T) and the surface area B (3B) in the layer thickness direction of the hard coat layer is determined, and converted to the content as silicon dioxide particles (SiO ₂ ) By separately measuring the mass of the hard coat layer in the region, the silicon dioxide particle content 2 in the surface region T (3T) and the silicon dioxide particle content 1 in the surface region B (3B) can be determined. Further, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set sec (SiO ₂ thermal oxide film equivalent value).

  In addition, the mass of the hard coat layer in the surface area T (3T) and the surface area B (3B) is the surface area T (3T) and the surface area B while trimming the hard coat layer in the horizontal direction by the ultrathin section method. It can be easily determined by measuring the total mass of the thin film section in the range of 0.1 hd corresponding to (3B).

  Below, an example of the concrete conditions of a XPS measurement method is shown.

Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film conversion value): 0.05 nm / sec
Etching interval (SiO ₂ conversion value): 10 nm
X-ray photoelectron spectrometer: manufactured by Thermo Fisher Scientific, model name "VG Theta Probe"
Irradiated X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: oval of 800 × 400 μm <other silicon dioxide particle content measurement method>
In addition to the method described above, while trimming the formed hard coat layer in the horizontal direction by the ultra-thin section method, 0.1 hd corresponding to the surface area T (3T) and the surface area B (3 B) A thin film of a range is prepared and the total mass is measured, then the binder resin is dissolved with an acid, an alkali, an organic solvent or the like, the silicon dioxide particles are separated and dried, and the mass is measured to measure silicon dioxide. Particle content (mass%) can also be determined.

<< Composition requirements of gas barrier film >>
Then, the detail of the specific component of the gas barrier film of this invention is demonstrated one by one.

[Resin base material]
The resin substrate applicable to the present invention is not particularly limited, but is preferably a transparent resin film having flexibility. For example, as a resin component, polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (Abbreviation: PEN) polyester, polyethylene, polypropylene, cellophane, diacetylcellulose, triacetylcellulose (abbreviation: TAC), cellulose acetate butyrate, cellulose acetate propionate (abbreviation: CAP), cellulose acetate phthalate, cellulose nitrate Cellulose esters or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene tree , Polymethylpentene, polyether ketone, polyimide, polyether sulfone (abbreviation: PES), polyphenylene sulfide, polysulfones, polyether imide, polyether ketone imide, polyamide, fluorocarbon resin, nylon, polymethyl methacrylate, acrylic or polyarylate And cycloolefin resins such as ARTON (trade name, manufactured by JSR Corporation) or APEL (trade name, manufactured by Mitsui Chemicals, Inc.).

  In the present invention, among the above resin substrates, the adhesion to the hard coat layer and the bending resistance can be set high, and a gas barrier film having low retardation characteristics can be obtained. It is particularly preferred to apply a resin film containing triacetyl cellulose.

  The triacetyl cellulose (TAC) applicable to the present invention preferably has an acetyl group substitution degree in the range of 2.6 to 3.0, more preferably in the range of 2.7 to 2.95. It is. The degree of acetyl group substitution can be determined according to ASTM D-817-91.

  Further, the film thickness of the triacetyl cellulose film according to the present invention is preferably in the range of 15 to 150 μm, more preferably in the range of 30 to 120 μm, and still more preferably in the range of 40 to 100 μm. is there. If the film thickness of the triacetyl cellulose film is 15 μm or more, it has sufficient rigidity, can be excellent in handleability and can obtain characteristics, and if it is 150 μm or less, it becomes easy to prepare a thin gas barrier film.

  The number average molecular weight (Mn) of the triacetyl cellulose is preferably in the range of 125000 to 155000, and more preferably in the range of 129000 to 152000. The weight average molecular weight (Mw) is preferably in the range of 200,000 to 300,000.

  The average molecular weight (Mn, Mw) can be measured by gel permeation chromatography, respectively. The measurement conditions are as follows.

Solvent: Methylene Chloride Column: Shodex K 806, K 805, K 803 G (three columns of Showa Denko KK were connected and used)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Science)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard A calibration curve with 13 samples of polystyrene (manufactured by Tosoh Corp.) Mw = 500 to 280,000 was used. The 13 samples are preferably used at approximately equal intervals.

  Raw materials used for producing triacetyl cellulose are not particularly limited, and cotton linter, wood pulp (derived from softwood and hardwood), kenaf and the like can be mentioned. Moreover, the triacetyl cellulose obtained from them can be mixed and used in arbitrary ratios, respectively. Moreover, the triacetyl cellulose which concerns on this invention can be synthesize | combined also with reference to the method as described in Unexamined-Japanese-Patent No. 10-45804, Unexamined-Japanese-Patent No. 2005-281645 etc., for example.

  The triacetyl cellulose which concerns on this invention can be manufactured by the conventionally well-known general film-forming method. For example, a substantially amorphous non-oriented unstretched triacetyl cellulose film is produced by melting a material triacetyl cellulose resin with an extruder, extruding with an annular die or T die and quenching it. Can. In addition, the triacetylcellulose resin as a material is dissolved in an organic solvent or the like, cast (casted) on an endless metal resin support, dried and peeled off, so that it is substantially amorphous and not oriented. Stretched triacetyl cellulose films can also be produced.

  Transport of triacetyl cellulose film by known methods such as uniaxial stretching, tenter type sequential biaxial stretching, tenter type simultaneous biaxial stretching, tubular type simultaneous biaxial stretching, etc. of unstretched triacetyl cellulose film (longitudinal axis, MD) A stretched triacetyl cellulose film can be produced by stretching in the direction perpendicular to the transport direction of the triacetyl cellulose film or the transport direction of the triacetyl cellulose film (horizontal axis, TD). The stretch ratio in this case can be selected appropriately, but is preferably in the range of 2 to 10 times in each of the vertical axis direction (MD direction) and the horizontal axis direction (TD direction).

  In addition, the triacetyl cellulose according to the present invention can be obtained as a commercial product, for example, Konica Minolta Tac KC8UX, KC5UX, KC4UX, KC8UY, KC6UY, KC4UY, KC4UE, KC8UE, KC2UA, KC4UA, etc. (above, Konica Minolta) Fujitac T40UZ, Fujitac T60UZ, Fujitac T80UZ, Fujitac TD80UL, Fujitac TD60UL, Fujitac TD40UL, etc. (all manufactured by Fujifilm Corp.) are preferably used.

[Hard coat layer]
In the gas barrier film (1) of the present invention, a hard coat layer having a concentration gradient as a silicon dioxide particle content ratio as illustrated in FIG. 2 between the resin substrate (2) and the gas barrier layer (4). It has (3), silicon dioxide particle content rate 2 (mass%) in surface field T (3T) of the gas barrier layer side of hard court layer 3 (3), and surface field B (3 B) of resin substrate side Characterized in that the content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) with the silicon dioxide particle content 1 (mass%) in 10 is 10 mass% or more, more preferably 20 It is mass% or more.

  The hard coat layer according to the present invention is not particularly limited as long as it contains silicon dioxide particles, but in addition to the silicon dioxide particles, an active energy ray-curable resin is used as a binder resin constituting the hard coat layer. Containing, preferably formed by a wet coating method, and further, for forming a hard coat layer composed of a photopolymerization initiator, a surfactant, a solvent, etc. in addition to the silicon dioxide particles and the active energy ray curable resin It is preferable to form by a wet coating method using a coating solution.

[Method for applying graded structure of silicon dioxide particle content]
Next, a method of giving a graded concentration structure of silicon dioxide particles to the hard coat layer according to the present invention will be described.

  In the present invention, silicon dioxide particle content 1 (mass%) in the surface area B (3B) on the resin substrate (2) side and silicon dioxide in the surface area T (3T) on the gas barrier layer (4) side It is characterized in that the content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) with the particle content 2 (mass%) is 10 mass% or more, and this condition can be satisfied. There is no particular limitation as long as it is a method, but it is preferable to appropriately select or combine each method shown below from the viewpoint of stably achieving the graded concentration structure of silicon dioxide particles specified in the present invention.

  The first method can impart a desired silicon dioxide particle concentration gradient in the layer by forming a hard coat layer using surface modified silicon dioxide particles (surface modified silica particles) as silicon dioxide particles. .

  In the present invention, the reason why the concentration gradient of silicon dioxide particles can be provided in the layer by forming the hard coat layer according to the first method is presumed as follows.

  In the case of a coating film containing silicon dioxide particles as in the hard coat layer according to the present invention, convection (also called a Benard cell) in a coating solution is accompanied by evaporation of the solvent contained in the coating film during coating film formation. And a partial difference in surface tension difference on the surface of the coating film. In the thickness direction after drying, due to the nonuniformity of surface tension during such coating-drying-film-forming, and the difference in the mobility of each component (for example, silicon dioxide particles etc.) in the coating film, etc. It is estimated that the bias of the component ratio is expressed.

  The second method is desired by forming a hard coat layer using a coating liquid for forming a hard coat layer containing a polyhydric alcohol high boiling point solvent having a boiling point of 150 ° C. or higher at a predetermined amount under normal pressure. Silicon dioxide particle concentration gradient can be applied.

  In the present invention, by forming the hard coat layer according to the second method, the concentration gradient of the silicon dioxide particles can be provided in the layer as a reason similar to that of the first method. In particular, mixing of a high boiling point solvent in the solvent affects changes in the evaporation rate of the solvent at the time of coating film formation, convection, and drying of the coating film, and each component of the coating film (for example, It is presumed that the difference in the mobility of the silicon dioxide particles etc. causes a bias of the component ratio in the thickness direction.

  The third method is not a single layer configuration as illustrated in FIG. 2 as a hard coat layer but a plurality of layers of two or more layers having different silicon dioxide particle concentrations as shown in FIG. 3 and FIG. By constructing the coating layer unit (3U), it is possible to stably form a concentration gradient structure of any silicon dioxide particles from the surface side.

  In addition, as another method, after a coating solution for forming a hard coat layer is applied on a resin substrate, drying conditions are slower drying conditions, that is, it takes a long time to finish drying, and drying slowly. By doing this, the silicon dioxide particles in the hard coat layer are more oriented to the upper side of the hard coat layer, and a concentration gradient structure of silicon dioxide particles can be formed.

  As a reason for the concentration gradient structure of the silicon dioxide particles to be developed by the above-mentioned drying conditions, convection in the coating, non-uniformity of surface tension during drying-film formation, and each component of the coating (for example, dioxide) It is presumed that the effect is due to the influence of the mobility of silicon particles etc.).

  FIG. 3 is a schematic view showing an example of a silicon dioxide particle content (mass%) inclined structure composed of a plurality of hard coat layers corresponding to the third method.

  In FIG. 3, by laminating five layers of hard coat layers 3-1A to 3-5A having different silicon dioxide particle contents on the resin base material (2), as shown in the graph on the right side. A hardcoat layer unit (3U) having a silicon dioxide particle content profile is formed.

  In the configuration shown in FIG. 3, the silicon dioxide particle concentration is uniform in each hard coat layer, and a hard coat layer 3- corresponding to the surface region T (3T) on the gas barrier layer (4) side is provided. The silicon dioxide particle content difference ΔC between 5A and the hard coat layer 3-1A corresponding to the surface region B (3B) on the resin base (2) side is 10% by mass or more.

  On the other hand, FIG. 4 is a schematic view showing another example of the graded structure of silicon dioxide particle content (mass%) composed of a plurality of hard coat layers according to the present invention, similarly to FIG. Although five layers of hard coat layers 3-1B to 3-5B different in content of particles are laminated on the resin base material (2), even in each hard coat layer, for example, the first to second The method of (1) is applied, and the composition having a graded structure as the content of silicon dioxide particles is shown. Therefore, the graph described on the right side is not the stepped silicon dioxide particle content profile as shown in FIG. 3 but the surface region T (3T) on the gas barrier layer (4) side to the resin base material (2) The hard coat layer unit (3U) having a continuous silicon dioxide particle-containing concentration profile is formed up to the surface area B (3B) on the surface side.

[Material of hard coat layer]
In the present invention, as the material constituting the hard coat layer, in addition to silicon dioxide particles, a curable resin, a photopolymerization initiator, a surfactant, a solvent and the like can be mentioned.

(Silicon dioxide particles: silica particles)
Examples of the silica particles applicable to the present invention include particles having an average particle diameter in the range of 0.01 to 1 μm. For example, Aerosil 200, 200 V, 300 manufactured by Nippon Aerosil Co., Ltd., manufactured by Degussa, Aerosil Trade names such as OX50, TT600, etc., KEP-10, KEP-50, KEP-100, etc. manufactured by Nippon Shokubai Co., Ltd. can be mentioned. In addition, colloidal silica may be used. Colloidal silica is obtained by dispersing silicon dioxide in the form of colloid in water or an organic solvent, and is not particularly limited, and is spherical, needle-like or bead-like. Such colloidal silica is commercially available, and examples thereof include Snowtex series manufactured by Nissan Chemical Industries, Ltd., Cataloid-S series manufactured by Catalyst Chemical Industries, and Revasil series manufactured by Bayer. In addition, colloidal silica in which primary particles of alumina sol, cationic silica modified with aluminum hydroxide, or primary particles of silica are bound with particles by metal ions of divalent or higher and connected in a bead shape is also preferably used. Examples of beaded colloidal silica include Snowtex-AK series, Snowtex-PS series, Snowtex-UP series manufactured by Nissan Chemical Industries, Ltd. Specifically, IPS-ST-L (isopropanol silica sol, particle diameter MEK-ST (methyl ethyl ketone silica sol, particle diameter 10-15 nm, silica concentration 30%), MEK-ST-MS (methyl ethyl ketone silica sol, particle diameter 17-23 nm, silica concentration 35%), etc. , MEK-ST-L (methyl ethyl ketone silica sol, particle diameter 40 to 50 nm, silica concentration 30%), MEK-ST-UP (methyl ethyl ketone silica sol, particle diameter 9 to 15 nm (chain structure), silica concentration 20%) and the like Be

Surface-Modified Silicon Dioxide Particles: Surface-Modified Silica Particles
In the present invention, as a means for effectively forming a graded structure of silicon dioxide particle content in the hard coat layer, it is one of applying silicon dioxide particles surface-modified as silicon dioxide particles (surface modified silica particles) . It is a feature .

  Hereinafter, the surface-modified silicon dioxide particles (surface-modified silica particles) suitable for the present invention will be described.

  Since the silica particles are inorganic compounds, there was a problem that the affinity with the binder resin constituting the hard coat layer and the organic solvent used for preparation of the coating liquid for forming the hard coat layer is poor. As a method of solving this problem, the affinity with the binder resin or the organic solvent can be enhanced by setting the surface of the silica particle to, for example, a surface modified silica particle surface-treated with a surface modifying agent of a silicone compound.

  Examples of surface modifiers used for surface treatment of silica particles include silane coupling agents, silicone oil based, titanate based, aluminate based and zirconate based coupling agents. Although these are not specifically limited, it is possible to select suitably according to the kind of silica particle and binder resin. Also, two or more different types of surface treatments may be performed simultaneously or at different times.

  Examples of the silane coupling agent include vinyl silazane trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, trimethylalkoxysilane, dimethyldialkoxysilane, methyltrialkoxysilane, hexamethyldisilazane and the like, and the surface of the inorganic fine particles is selected. Hexamethyldisilazane or the like is preferably used for wide coverage.

  As the silicone oil-based coupling agent, straight silicone oils such as dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone Oil, methacryl modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, one-end reactive modified silicone oil, heterofunctional modified silicone oil, polyether modified silicone oil, methylstyryl modified silicone oil, alkyl modified silicone oil, high grade Fatty acid ester modified silicone oil, hydrophilic special modified silicone oil, higher alkoxy modified silicone oil , It is possible to use a higher fatty acid containing modified silicone oil and modified silicone oil and fluorine-modified silicone oil.

  These surface treating agents may be suitably diluted with hexane, toluene, methanol, ethanol, acetone, water or the like.

  Examples of the method of surface treatment with the above surface modifier include a wet heating method, a wet filtration method, a dry stirring method, an integral blending method, a granulation method and the like. In the case of performing surface modification of 100 nm or less, the dry stirring method is suitably used from the viewpoint of particle aggregation suppression, but is not limited thereto.

  These surface modifiers may be used alone or in combination of two or more.

  The surface-modified silica particles can be obtained as commercial products, for example, Aerosil R7200 (a primary average particle diameter of 12 nm, silica fine particles having (meth) acryloyl group on the particle surface) manufactured by Nippon Aerosil Co., Ltd., Aerosil R711 manufactured by Nippon Aerosil Co., Ltd. (silica fine particles having a primary average particle diameter of 12 nm and having (meth) acryloyl groups on the particle surface), ELCOM V-8804 (manufactured by JGC Co., Ltd.) Silica fine particles having a group, etc. can be mentioned.

  The content of the silica particles or surface modified silica particles in the hard coat layer according to the present invention can be appropriately selected in the range satisfying the silicon dioxide particle content specified in the present invention, for example, the total solid content of the hard coat layer On the other hand, it can be in the range of 10 to 80% by mass, preferably in the range of 20 to 75% by mass.

(Resin binder: Cured resin)
Although a thermosetting resin and an active energy ray curable resin are mentioned as a curable resin used for formation of the hard-coat layer which concerns on this invention, Since shaping | molding is easy, active energy ray curable resin is preferable. It can be used.

<Thermosetting resin>
The thermosetting resin is not particularly limited, and specifically, various thermosetting resins such as epoxy resin, cyanate ester resin, phenol resin, bismaleimide-triazine resin, polyimide resin, acrylic resin, vinyl benzyl resin, etc. It can be mentioned.

  The epoxy resin may be one having an average of 2 or more epoxy groups per molecule, and specifically, bisphenol A epoxy resin, biphenyl epoxy resin, biphenyl aralkyl epoxy resin, naphthol epoxy Resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidyl amine type epoxy resin (specifically, tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, Diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin Epoxy resin having butadiene structure, phenol aralkyl type epoxy resin, epoxy resin having dicyclopentadiene structure, diglycidyl etherate of bisphenol, diglycidyl etherate of naphthalenediol, glycidyl etherate of phenols, diglycidyl of alcohols Ethers and alkyl-substituted products, halides and hydrogenates of these epoxy resins are listed. These may be used alone or in combination of two or more.

<Active energy ray curable resin>
The active energy ray-curable resin that can be suitably used in the present invention refers to a resin that is cured through a crosslinking reaction or the like by irradiation with actinic radiation such as ultraviolet light or electron beam. As the active energy ray-curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray-curable resin is cured by irradiation with an actinic ray such as an ultraviolet ray or an electron beam. A resin layer is formed. As the active energy ray curable resin, an ultraviolet curable resin, an electron beam curable flag resin and the like can be mentioned as a typical one, but an ultraviolet curable resin which is cured by ultraviolet irradiation is preferable.

<UV curable resin>
The UV curable resin suitable for the hard coat layer according to the present invention will be described below.

  Examples of UV curable resins include UV curable urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, and UV curable epoxy resins. be able to.

  UV-curable acrylic urethane resins generally contain hydroxy groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, etc. and products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a group. For example, the resin described in JP-A-59-151110 can be used.

  Examples of UV-curable polyester acrylate resins include those which can be easily formed by reacting polyester polyol with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, as disclosed in JP-A-59-151112. The resin described in the publication can be used.

  Specific examples of the UV curable epoxy acrylate resin include epoxy acrylate as an oligomer, to which a reactive diluent and a photoreaction initiator are added and reacted to form an epoxy resin. The thing as described in 105738 gazette can be used.

  Further, in the present invention, it is preferable to use an ultraviolet-curable polyol acrylate resin, and as such a compound, for example, a polyfunctional acrylate resin and the like can be mentioned. Here, the polyfunctional acrylate resin is a compound having two or more acryloyloxy groups or methacroyloxy groups in the molecule.

  As a monomer of polyfunctional acrylate resin, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylol methane Triacrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate , Dippen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylolmethane trimethacrylate, tetramethylolmethane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate. These compounds may be used alone or in combination of two or more. In addition, oligomers such as dimers and trimers of the above monomers may be used.

Commercially available ultraviolet curable resins applicable in the present invention include, for example, Adeka Optomer KR · BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B ( As described above, manufactured by ADEKA Corporation); Koei Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D -102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (all available from Hiroei Chemical Co., Ltd.); SEEKA beam PHC2210 (S), PHC X-9 (K- 3), PHC2213, DP-10, DP-20,
DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR 900 (all available from Dainichi Seika Kogyo Co., Ltd.); RC-5015, RC-5016, RC-5020, RC-501, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (above, DIC Corporation); 340 KRYA (above, made by China Paint Co., Ltd.); San Rad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, Sanyo Chemical Industries, Ltd.) SP-1509, SP-1507 (above, Showa Highpolymer Co., Ltd.); RCC-15C (from Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd. product) can be appropriately selected and used.

<Photoinitiator>
In the present invention, in order to accelerate the curing of the ultraviolet curable resin described above, it is preferable to contain a photopolymerization initiator in the range of 2 to 30% by mass with respect to the ultraviolet curable resin. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is preferable.

  As such an onium salt, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator, in particular, as described in JP-A 50-151996, JP-A 50-158680, etc. Group VIA aromatic onium salts described in JP-A-50-151997, JP-A-52-30899, JP-A-59-50420, JP-A-55-125105, etc., JP-A-56-8428 Nos. 56-149402 and 57-192429, etc., an aromatic diazonium salt described in JP-B-49-17040, etc., and U.S. Pat. No. 4,139,655 etc. The thiopyrylium salt of is preferable. Moreover, an aluminum complex, a photodegradable silicon compound type polymerization initiator, etc. can be mentioned. The above-mentioned cationic polymerization initiator and photosensitizers such as benzophenone, benzoin isopropyl ether and thioxanthone can be used in combination.

<High-boiling point solvent>
In the hard coat layer according to the present invention, as a method of obtaining a gradient structure of the silicon dioxide particles content defined in the present invention, a boiling point at atmospheric pressure it is preferable to use a high-boiling point solvent of a polyhydric alcohol of more than 0.99 ° C. one One feature .

  As a high boiling point solvent applicable to the present invention, a polyhydric alcohol organic solvent having a boiling point of 150 ° C. or higher is preferable, and, for example, ethylene carbonate (238 ° C.), ethylene glycol (197 ° C.), ethylene glycol diacetate (191 ° C.), ethylene glycol dibutyl ether (195 ° C.), ethylene glycol monoacetate (182 ° C.), ethylene glycol monoethyl ether acetate (156 ° C.), ethylene glycol monophenyl ether (245 ° C.), ethylene glycol monobutyl ether (171 ° C), ethylene glycol monobutyl ether acetate (192 ° C), ethylene glycol monohexyl ether (208 ° C), 1,3-octylene glycol (244 ° C), glycerin triacetate (259 ° C), Glycol (244 ° C.), diethylene glycol ethyl methyl ether (179 ° C.), diethylene glycol chlorohydrin (199 ° C.), diethylene glycol diacetate (250 ° C.), diethylene glycol diethyl ether (187 ° C.), diethylene glycol dibutyl ether (254 ° C.), Diethylene glycol dimethyl ether (162 ° C.), diethylene glycol monoethyl ether (202 ° C.), diethylene glycol monoethyl ether acetate (217 ° C.), diethylene glycol monobutyl ether (231 ° C.), diethylene glycol monobutyl ether acetate (247 ° C.), diethylene glycol monomethyl ether (194 ° C), dipropylene glycol (232 ° C), dipropylene glycol Diethyl ether (198 ° C), dipropylene glycol monobutyl ether (231 ° C), dipropylene glycol monomethyl ether (189 ° C), triethylene glycol (287 ° C), triethylene glycol dimethyl ether (216 ° C), triethylene glycol monomethyl ether (245 ° C.), 1,2-butanediol (195 ° C.), 1,3-butane diol (208 ° C.), propylene glycol (187 ° C.), propylene glycol monobutyl ether (170 ° C.), and the like. In addition, the numerical value described in the parenthesis after each high boiling point solvent name illustrated above is a boiling point.

  The high boiling point solvent according to the present invention is in the range of 5 to 30% by mass, preferably in the range of 10 to 20% by mass, with respect to the total solid content of the hard coat layer. In the present invention, when calculating the total mass of the hard coat layer after drying, the mass of the high boiling point solvent is included.

<Various additives>
In order to enhance the heat resistance of the hard coat layer, an antioxidant which does not suppress the photocuring reaction can be selected and used.

  In addition to the high boiling point solvent described above, the hard coat layer forming coating solution used for forming the hard coat layer may contain a low boiling point solvent, for example, an organic solvent having a boiling point of less than 150 ° C. at normal pressure. Good. As an organic solvent contained in the coating liquid for hard-coat layer formation, for example, hydrocarbons (for example, toluene, xylene etc.), alcohols (for example, methanol, ethanol, isopropanol, butanol, cyclohexanol etc.), ketones (For example, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like), esters (for example, methyl acetate, ethyl acetate, methyl lactate and the like), and other organic solvents can be appropriately selected or mixed and used. 5% by mass or more, preferably 5 to 50% by mass of propylene glycol monoalkyl ether (1 to 4 as carbon number of alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 as carbon atom of alkyl group) It is to contain in the range of%.

  The hard coat layer may further contain a silicone surfactant, a fluorine surfactant or a polyoxyether compound. Alternatively, the overcoat layer may contain a fluorine-siloxane graft polymer.

  Preferred examples of surfactants include Kaoh Co., Ltd .: Emulgen 102 Kg, Emulgen 103, Emulgen 104 P, Emulgen 105, Emulgen 106, Emulgen 108, etc. Emulgen series, Latemul PD-420, Latemul PD-430, Latemul PD-430S, etc. Latemule series, Leodol SP-L10, Leodol SP-P10 etc., Emazole L-10 V, Emazole P-10 V, Emazole S-10 V etc. Emazole series, Exel T-95, Exel VS-95, Exel series such as Exel O-95R, Emmanon 1112, Emmanon 4110, Emmanon CH-25 etc., Emanoon series, Ameat 102, Ameat 105, Ameat 105A etc., Ameto series, Nisshinka Industrial Co., Ltd .: Surfynol 104 E, Surfynol 104 H, Surfynol 104 A, etc. Surfynol series, Olfin STG, Olfin E 1004, Orphine E1010 etc., Olfin series, Shin-Etsu Chemical Co., Ltd .: X-22-4272, X -22-6266, KF-351A, KF-352, KF-353L, KF- 355A, KF-615A, KF-945, KF-618, KF-6011, KF-6015, KF-6004, etc. It can be mentioned.

  These hard coat layers may be a single layer or two layers by a known wet coating method such as a gravure coater, dip coater, reverse coater, wire bar coater, die coater, or ink jet method using a hard coat layer forming coating solution. The plurality of layers described above can be formed by simultaneous lamination coating.

(Layer thickness of hard coat layer)
The coating amount of the hard coat layer coating solution as a wet film thickness is suitably in the range of 0.1 to 40 μm as a total thickness, and preferably in the range of 0.5 to 30 μm. The layer thickness after drying is preferably in the range of 0.1 to 30 μm, more preferably in the range of 1 to 10 μm.

(Hardening method of hard coat layer)
After the hard coat layer is formed on the resin substrate, the hard coat layer is irradiated with active energy rays, preferably ultraviolet rays to finally cure the hard coat layer.

As a light source used to cure an ultraviolet-curable resin by a photo-curing reaction and to form a cured hard coat layer, any light source that generates ultraviolet can be used without limitation. For example, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps and the like can be used. Although the irradiation conditions differ depending on each lamp, the irradiation dose of the active energy ray is preferably in the range of 5 to 100 mJ / cm ² , and particularly preferably in the range of ^{20 to} 80 mJ / cm ² .

[Gas barrier layer]
The gas barrier film of the present invention is characterized in that as shown in FIG. 1, the gas barrier layer (4) is provided on the hard coat layer (3) described above.

  As a material for forming the gas barrier layer (4), a material having a function to suppress the entry of an element such as water or oxygen which causes the performance deterioration of the resin substrate (2) or the organic EL element provided with the gas barrier film 1 For example, silicon oxide, silicon oxynitride, silicon dioxide, silicon nitride and the like can be used.

  As a method for forming the gas barrier layer (4) according to the present invention, a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied using a raw material gas containing an organosilicon compound and an oxygen gas It is characterized by forming. Furthermore, as a constituent element of the gas barrier layer (4), a carbon atom, a silicon atom and an oxygen atom are preferably contained.

  Specifically, a film forming gas is formed by winding a pair of film forming rollers (roller electrodes) on the hard coat layer (3) of the resin base material (2) and applying the magnetic field to the pair of film forming rollers. Is a method of forming a gas barrier layer on a resin substrate by plasma chemical vapor deposition in which plasma discharge is performed while supplying

  The gas barrier layer according to the present invention uses a raw material gas containing an organosilicon compound as a film forming gas and an oxygen gas, contains carbon, silicon and oxygen as constituent elements of the gas barrier layer, and shows the following (1) to It is a more preferable aspect that all the conditions of the carbon atom distribution profile defined in (4) are satisfied.

  (1) The carbon atom ratio of the gas barrier layer changes continuously corresponding to the distance from the surface within the distance range from the surface of the gas barrier layer to 89% of the layer thickness in the layer thickness direction Do.

  (2) The maximum value of the carbon atom ratio of the gas barrier layer is less than 20 at% within the distance from the surface of the gas barrier layer to 89% of the layer thickness in the layer thickness direction.

  (3) The carbon atom ratio of the gas barrier layer continuously increases in the layer thickness direction from the surface of the gas barrier layer to 90 to 95% of the layer thickness.

  (4) The maximum value of the carbon atom ratio of the gas barrier layer is at least 20 at% within the range of 90 to 95% of the layer thickness from the surface of the gas barrier layer in the layer thickness direction.

  In the present invention, the average value of the content ratio of carbon atoms in the gas barrier layer (4) according to the present invention can be determined by the measurement of the XPS depth profile described as the method for quantifying the silicon element in the hard coat layer.

  Hereinafter, the details of the gas barrier layer (4) according to the present invention will be further described.

(Elemental carbon profile in gas barrier layer)
The gas barrier layer (4) according to the present invention contains carbon atoms, silicon atoms and oxygen atoms as constituent elements of the gas barrier layer, and the distance from the surface in the layer thickness direction of the gas barrier layer, silicon atoms, oxygen atoms And in the carbon distribution curve showing the relationship with the ratio of the amount of carbon atoms to the total amount of carbon atoms (carbon atom ratio), the carbon atom content profile corresponds to all the conditions of the above items (1) to (4) It is preferable from the viewpoint of being able to obtain a gas barrier film further excellent in flexibility (flexibility) and adhesion by satisfying the conditions.

  Moreover, it is a preferable aspect from a viewpoint which makes gas barrier property and flexibility compatible, having a structure which has a concentration gradient and changes continuously in the specific area | region of a gas barrier layer in a carbon atom ratio.

  In the gas barrier layer (4) according to the present invention having such a carbon atom distribution profile, the carbon distribution curve in the layer preferably has at least one extreme value. Furthermore, it is more preferred to have at least two extrema, and particularly preferred to have at least three extrema. When the carbon distribution curve does not have an extreme value, the gas barrier properties in the case of bending the obtained gas barrier film become insufficient. In addition, in the case of having at least two or three extreme values in this manner, the thickness direction of the gas barrier layer (4) at one extreme value of the carbon distribution curve and at the extreme value adjacent to the extreme value. The absolute value of the difference in distance from the surface of the gas barrier layer in the above is preferably 200 nm or less, and more preferably 100 nm or less.

  In the present invention, the extreme value means the maximum value or the minimum value of the atomic ratio of each element.

<Maximum value and minimum value>
In the present invention, the maximum value is a point at which the atomic ratio of elements changes from an increase to a decrease when the distance from the surface of the gas barrier layer (4) is changed, and the atomic ratio of the elements at that point The point at which the value of the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer is further changed by 20 nm from that point is decreased by 3 at% or more.

  Furthermore, in the present invention, the minimum value is a point at which the value of the atomic ratio of elements changes from a decrease to an increase when the distance from the surface of the gas barrier layer (4) is changed, and the atoms of the elements of that point The point at which the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer (4) is further changed by 20 nm from the value of the ratio increases by 3 at% or more It means that.

  In the gas barrier layer (4) according to the present invention, the maximum value of the carbon element ratio in the range up to 89% in the vertical direction from (1) surface (surface opposite to the surface in contact with the resin substrate) is 20 at% It is a preferred embodiment that it is less and (3) the range of 90 to 95% in the vertical direction (the maximum value of the carbon element ratio in the vertical direction is 20 at% or more).

<Continuous change of concentration gradient>
In the present invention, the gas barrier layer (4) has a region in which the carbon element ratio has a concentration gradient and the concentration changes continuously in the range from 89% in the vertical direction from the surface (2). And (4) It is a preferable aspect that the carbon elemental ratio in the range of 90 to 95% in the vertical direction from the surface is continuously increased.

  In the present invention, "Continuously changing the concentration gradient of the carbon element ratio" means that the carbon distribution ratio in the carbon distribution curve does not include a portion that changes discontinuously, specifically, the etching rate and etching In relation to the distance (x, unit: nm) from the surface in the layer thickness direction of the gas barrier layer according to the present invention calculated from time and the carbon atom ratio (C, unit: at%), It means that the condition represented by F1) is satisfied.

Formula (F1)
(DC / dx) ≦ 0.5
(Each element profile in the gas barrier layer)
In the gas barrier layer (4) according to the present invention, it is preferable to contain carbon atoms, silicon atoms and oxygen atoms as constituent elements, but preferred embodiments for the ratio of the respective atoms and the maximum value and the minimum value are It will be described below.

<Relationship between maximum value and minimum value of carbon atom ratio>
In the gas barrier layer (4) according to the present invention, it is further preferable that the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio in the carbon distribution curve is 5 at% or more. In such a gas barrier layer, the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is more preferably 6 at% or more, particularly preferably 7 at% or more. When the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is 5 at% or more, the gas barrier properties at the time of bending the produced gas barrier film become sufficient.

<Relationship between maximum value and minimum value of oxygen atom ratio>
In the gas barrier layer (4) according to the present invention, the absolute value of the difference between the maximum value and the minimum value in the oxygen distribution curve is preferably at% or more, more preferably 6 at% or more, and 7 at% or more Is particularly preferred. When the absolute value is 5 at% or more, the gas barrier property in the case where the obtained gas barrier film is bent is sufficient.

<Relationship between maximum value and minimum value of silicon atomic ratio>
In the gas barrier layer (4) according to the present invention, the absolute value of the difference between the maximum value and the minimum value in the silicon distribution curve is preferably less than 5 at%, more preferably less than 4 at%, less than 3 at% Is particularly preferred. If the said absolute value is less than 5 at%, the gas barrier property and mechanical strength of the gas barrier film obtained will become enough.

<Ratio of total amount of oxygen atom + carbon atom>
In the gas barrier layer (4) according to the present invention, the ratio from the distance from the surface of the layer in the layer thickness direction to the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (oxygen In an oxygen-carbon total distribution curve (also referred to as an oxygen-carbon total distribution curve) which is an atomic ratio of carbon total, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of the oxygen-carbon total is 5 at It is preferably less than%, more preferably less than 4 at%, particularly preferably less than 3 at%. If the said absolute value is less than 5 at%, the gas barrier property of the gas barrier film obtained will become enough.

  In the carbon atom distribution profile (silicon distribution curve, oxygen distribution curve and carbon distribution curve) whose details are shown in FIG. 6 described later, “total amount of silicon atoms, oxygen atoms and carbon atoms” means silicon atoms, oxygen The sum of atoms and carbon atoms means at, and the "amount of carbon atoms" means the number of carbon atoms. The term "at%" as used in the present invention means the atomic ratio of each atom when the total number of silicon atoms, oxygen atoms and carbon atoms is 100%. The same applies to “amount of silicon atoms” and “amount of oxygen atoms” for the silicon distribution curve, the oxygen distribution curve and the oxygen carbon distribution curve as shown in FIG. 6 described later.

(About XPS depth profile)
In the gas barrier layer according to the present invention, a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, a distribution curve of oxygen-carbon total, etc. in the layer thickness direction are measured by X-ray photoelectron spectroscopy (XPS), argon, etc. By using together with the rare gas ion sputtering, it is possible to create by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. In the distribution curve obtained by such XPS depth profile measurement, for example, as illustrated in FIG. 6, the ordinate represents the atomic ratio (unit: at%) of each element, and the abscissa represents the etching time (sputtering time) Can be created. In addition, in the distribution curve of the element in which the horizontal axis represents the etching time, the etching time generally correlates with the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer in the layer thickness direction. "The distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer", the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement Can be adopted. Further, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set sec (SiO ₂ thermal oxide film equivalent value).

  In the present invention, from the viewpoint of forming a gas barrier layer having uniform and excellent gas barrier properties over the entire film surface, the gas barrier layer is in the film surface direction (direction parallel to the surface of the gas barrier layer) Preferably substantially uniform. In the present invention, if the gas barrier layer is substantially uniform in the film surface direction, the oxygen distribution curve and the carbon distribution curve are measured for any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement. And when the oxygen-carbon total distribution curve is created, the number of extremums possessed by the carbon distribution curve obtained at any two measurement points is the same, and the carbon atoms in each carbon distribution curve The absolute value of the difference between the maximum value and the minimum value of the ratio is the same as or within 5 at% of each other.

  The gas barrier film of the present invention preferably comprises at least one gas barrier layer satisfying all the above (1) to (4) defined in the present invention, but two or more layers satisfying such conditions are preferably used. You may have. Furthermore, when two or more such gas barrier layers are provided, the materials of the plurality of gas barrier layers may be the same or different. When two or more such gas barrier layers are provided, such a gas barrier layer may be formed on one surface of the substrate, and is formed on both surfaces of the substrate. It may be done. In addition, such a plurality of gas barrier layers may include a gas barrier layer that does not necessarily have gas barrier properties.

(Thickness of gas barrier layer)
The thickness of the gas barrier layer according to the present invention is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and particularly preferably in the range of 100 to 1000 nm. If the thickness of the gas barrier layer is within the above range, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are excellent, and no decrease in the gas barrier properties due to bending is observed.

  Moreover, when the gas barrier film of the present invention comprises a plurality of gas barrier layers, the total value of the thickness of the gas barrier layer is usually in the range of 10 to 10000 nm, and in the range of 10 to 5000 nm. Is preferable, and the range of 100 to 3000 nm is more preferable, and the range of 200 to 2000 nm is particularly preferable. When the total value of the thickness of the gas barrier layer is within the above range, gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are sufficient, and the gas barrier properties also tend to be less likely to be deteriorated by bending.

(Method of forming gas barrier layer)
The gas barrier layer according to the present invention is characterized in that it is formed on a resin substrate by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied.

  More specifically, in the gas barrier layer according to the present invention, a resin base material is wound around a pair of film forming rollers using a roller-to-roller discharge plasma treatment apparatus to which a magnetic field is applied, and a film forming gas is interposed between the pair of film forming rollers. It is a layer formed by plasma chemical vapor deposition with plasma discharge while being supplied. Further, when discharging while applying a magnetic field between the pair of film forming rollers as described above, it is preferable to alternately reverse the polarity between the pair of film forming rollers. Furthermore, as a film forming gas used in such a plasma chemical vapor deposition method, a source gas containing an organic silicon compound and an oxygen gas are used, and the content of the oxygen gas in the film forming gas is equal to that in the film forming gas. It is preferable that the theoretical amount of oxygen necessary for complete oxidation of the total amount of the organosilicon compound of In the gas barrier film of the present invention, it is a preferred embodiment that the gas barrier layer is formed by a continuous film forming process.

  Next, the manufacturing method of the gas barrier film of this invention is demonstrated.

  The gas barrier film of the present invention forms a gas barrier layer on a hard coat layer having a silicon concentration gradient structure formed on the surface of a resin substrate using a discharge plasma processing apparatus having a discharge space between rollers to which a magnetic field is applied. Manufactured by

  In the gas barrier layer according to the present invention, in order to form a layer in which the carbon atom ratio has a concentration gradient and continuously changes in the layer, a discharge plasma chemical gas having a discharge space between rollers to which a magnetic field is applied. It is characterized by using the phase growth method.

  In the discharge plasma chemical vapor deposition method (hereinafter, also referred to as plasma CVD method) having a discharge space between rollers to which a magnetic field according to the present invention is applied, a magnetic field is generated between a plurality of film forming rollers when generating plasma. Is a method of generating plasma discharge in the formed discharge space while applying a voltage, and in the present invention, a pair of film forming rollers are used, and a resin base material having a hard coat layer is wound around each of the pair of film forming rollers. Preferably, plasma is generated by discharging in a state where a magnetic field is applied between the pair of film forming rollers. In this manner, the resin base material is wound on the pair of film forming rollers using the pair of film forming rollers, and plasma discharge is performed between the pair of film forming rollers to form the resin base material and the film forming roller. By changing the distance between them, it is possible to form a gas barrier layer in which the carbon atom ratio has a concentration gradient and continuously changes in the layer.

  In addition, while forming a film on the hard coat layer surface portion of the resin base existing on one film forming roller at the time of film formation, on the hard coat layer surface portion of the resin base existing on the other film forming roller As well as being able to form a film simultaneously, not only can thin films be produced efficiently, it is also possible to double the film forming rate, and films of the same structure can also be formed, so at least the extremum in the carbon distribution curve. It becomes possible to double, and it becomes possible to form a layer which satisfy | fills the said conditions (1)-(4) efficiently efficiently.

  In the gas barrier film of the present invention, it is preferable to form the gas barrier layer on the surface of the hard coat layer of the resin substrate by a roll-to-roll method from the viewpoint of productivity.

  Also, an apparatus applicable when manufacturing a gas barrier film by such a plasma chemical vapor deposition method is not particularly limited, but a film forming roller equipped with an apparatus for applying at least a pair of magnetic fields, a plasma power source And is configured to be capable of discharging between a pair of film forming rollers. For example, when using the manufacturing apparatus shown in FIG. 5, plasma chemical vapor deposition is preferable. The hard coat layer, the gas barrier layer and the second gas barrier layer are formed on the resin base material by using a continuous process as shown in FIG. A gas barrier film can be manufactured by sequentially laminating.

  Hereinafter, the method for producing the gas barrier film of the present invention will be described in detail with reference to FIG. In addition, FIG. 5 is a schematic diagram which shows an example of the discharge plasma CVD apparatus between rollers which applied the magnetic field which can be utilized suitably when manufacturing the gas barrier film of this invention. The resin base material (F2) in the following description refers to a resin base material (2) having a hard coat layer (3) according to the present invention.

  A discharge plasma CVD apparatus (30, hereinafter also referred to as a plasma CVD apparatus) having a discharge space between rollers to which a magnetic field is applied as shown in FIG. 5 mainly includes a delivery roller (11), a transport roller (21), (22), (23) and (24), film forming rollers (31) and (32), film forming gas supply pipe (41), power source for plasma generation (51), film forming roller (31) And (32), and includes a magnetic field generator (61) and (62) installed inside, and a take-up roller (71). Further, in such a plasma CVD manufacturing apparatus (30), at least the film forming rollers (31) and (32), the film forming gas supply pipe (41), the plasma generating power supply (51), and the magnetic field generating apparatus (61) and (62) are disposed in a vacuum chamber (72) as shown in FIG. 7 described later. Furthermore, in such a plasma CVD manufacturing apparatus (30), as shown in FIG. 7, the vacuum chamber (72) is connected to a vacuum pump (72), and the vacuum chamber (72) is connected by the vacuum pump (73). It is possible to adjust the pressure in) properly.

  In such a plasma CVD manufacturing apparatus (30), each film forming roller (film forming roller (31) and film forming roller (32)) can be functioned as a pair of opposed electrodes. The film forming rollers are connected to the plasma generation power source 51, respectively. The film forming roller (31) and the film forming roller (32) are supplied with power from the plasma generation power supply (51) to the pair of film forming rollers (film forming roller (31) and film forming roller (32)). It is possible to discharge into the space between them, thereby generating plasma in the space between the film forming roller (31) and the film forming roller (32) (hereinafter, this space is also referred to as a discharge space). be able to. In addition, since a pair of film-forming roller (31) and film-forming roller (32) will be used as an electrode in this way, the material and design that can be used as an electrode may be changed appropriately. Further, in such a plasma CVD manufacturing apparatus (30), the pair of film forming rollers (film forming rollers (31) and (32)) are arranged such that their central axes are substantially parallel on the same plane Is preferred. By thus arranging the pair of film forming rollers (film forming rollers (31) and (32)), the film forming rate can be doubled, and a film having the same structure can be formed, so the carbon distribution It is possible to at least double the extrema in the curve.

  In addition, even when the film forming roller rotates, the film forming roller (31) and the film forming roller (32) are fixed so that they do not rotate themselves. Are provided respectively.

  Furthermore, the film-forming roller (31) and the film-forming roller (32) can use a well-known roller suitably. The film forming rollers (31) and (32) are preferably rollers having the same diameter from the viewpoint of being able to form a thin film more efficiently. Further, the diameters of the film forming rollers (31) and (32) are preferably in the range of 300 to 1000 mm in diameter, particularly preferably in the range of 300 to 700 mm in diameter, from the viewpoint of discharge conditions, chamber space and the like. If the diameter of the roller is 300 mmφ or more, the plasma discharge space does not become small, there is no deterioration in productivity, and it is possible to avoid that the total heat of plasma discharge is applied to the film in a short time, residual stress does not easily increase preferable. On the other hand, if the diameter of the roller is 1000 mmφ or less, the size of the apparatus is not increased, and practicability can be maintained including the uniformity of the plasma discharge space and the like, which is preferable.

  Also, as the delivery roller (11) and the transport rollers (21), (22), (23) and (24) used for such a plasma CVD production apparatus (30), known rollers should be appropriately selected and used. Can. In addition, the winding roller (71) may be any roller capable of winding up the resin base material (F3) on which the gas barrier layer is formed, and is not particularly limited, and a known roller can be appropriately used. .

  As the film forming gas supply pipe (41), one capable of supplying or discharging a source gas and an oxygen gas at a predetermined speed can be used. Furthermore, as a power supply (51) for plasma generation, the power supply of a conventionally well-known plasma generation apparatus can be used. Such a plasma generation power source (51) supplies electric power to the film forming roller (31) and the film forming roller (32) connected thereto, and uses them as an opposing electrode for discharge. To be possible. As the power source for plasma generation (51), it is possible to carry out the plasma CVD method more efficiently, and therefore, it is possible to alternately reverse the polarity of the pair of film forming rollers (AC power source etc.) It is preferred to use. Further, since the plasma generation power source (51) can perform the plasma CVD method more efficiently, the applied power can be in the range of 100 W to 10 kW, and the frequency of the alternating current is 50 Hz to More preferably, it can be in the range of 500 kHz. Further, as the magnetic field generators (61) and (62), known magnetic field generators can be used as appropriate.

  Using a plasma CVD apparatus (30) as shown in FIG. 5, for example, type of source gas, power of electrode drum of plasma generator, strength of magnetic field generator, pressure in vacuum chamber, diameter of film forming roller, And the gas barrier film of this invention can be manufactured by adjusting the conveyance speed of a resin base material suitably. That is, using the plasma CVD apparatus (30) shown in FIG. 5, a film forming gas (raw material gas etc.) is supplied from the film forming gas supply pipe (41) into the vacuum chamber, and a pair of film forming rollers (film forming By applying a magnetic field between the rollers (31) and (32) and generating plasma discharge, the film forming gas (raw material gas etc.) is decomposed by plasma, and the resin base on the film forming roller (31) The gas barrier layer according to the present invention is formed on the surface of (F2) and the surface of the resin base (F2) on the film forming roller (32) by plasma CVD. In addition, in the case of such film formation, the resin base material (F2) is conveyed by the delivery roller (11), the film formation roller (31), etc., so that a continuous film formation process of roll-to-roll method is performed. The gas barrier layer can be formed on the surface of the resin base (F2).

Raw material gas
The raw material gas which comprises the film-forming gas used for formation of the gas barrier layer which concerns on this invention is characterized by using the organosilicon compound containing at least silicon.

  Examples of the organosilicon compound applicable to the present invention include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethyl. Silane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like can be mentioned. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of handling during film formation and gas barrier properties of the gas barrier layer to be obtained. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition to the source gas, the film formation gas is characterized in that it contains an oxygen gas as a reaction gas. The oxygen gas is a gas that reacts with the source gas and becomes an inorganic compound such as an oxide.

  As a film forming gas, a carrier gas may be used as needed to supply the source gas into the vacuum chamber. Furthermore, as a film-forming gas, a discharge gas may be used as necessary to generate plasma discharge. As such carrier gas and discharge gas, known ones can be appropriately used. For example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.

  When such a film forming gas is composed of a source gas containing an organosilicon compound containing silicon and an oxygen gas, the source gas and the oxygen gas are completely reacted with each other as the ratio of the source gas and the oxygen gas. It is preferable not to make the ratio of the oxygen gas too much excess over the ratio of the amount of oxygen gas that is theoretically required. If the ratio of oxygen gas is excessive, it is difficult to obtain the gas barrier layer aimed in the present invention. Therefore, in order to obtain a barrier film having a desired elemental profile, it is preferable that the oxygen gas ratio be equal to or less than the theoretical oxygen amount necessary to completely oxidize the total amount of the organosilicon compound in the film forming gas.

Hereinafter, as a representative example, a system of hexamethyldisiloxane (organic silicon compound, abbreviated: HMDSO, chemical formula: (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas will be described. .

A film forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a raw material gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to obtain silicon-oxygen When forming a thin film of a system, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and a thin film made of silicon dioxide SiO ₂ is formed.

Reaction formula (1)
(CH ₃ ) ₆ Si ₂ O + 12 O ₂ → ₆ CO ₂ + 9 H ₂ O + ₂ SiO ₂
In such a reaction, the amount of oxygen required to completely oxidize one mole of hexamethyldisiloxane is 12 moles. Therefore, if 12 moles or more of oxygen is contained in the film forming gas with respect to 1 mole of hexamethyldisiloxane and a complete reaction is caused, a uniform silicon dioxide film is formed, so the gas flow rate of the raw material The ratio is controlled to a flow rate equal to or less than the theoretical reaction ratio of the complete reaction to carry out the incomplete reaction. That is, it is necessary to set the amount of oxygen to less than 12 moles of the stoichiometric ratio with respect to 1 mole of hexamethyldisiloxane.

  In the actual reaction in the chamber of the plasma CVD apparatus (30), since the raw material hexamethyldisiloxane and the oxygen as the reaction gas are supplied from the gas supply unit to the film formation region, the reaction gas is formed. Even if the molar amount (flow rate) of oxygen is 12 times the molar amount (flow rate) of the molar amount (flow rate) of the raw material hexamethyldisiloxane, the reaction can not actually be completely advanced. It is considered that the reaction is completed only when the oxygen content is supplied in a large excess relative to the stoichiometric ratio. For example, in order to form a silicon oxide film by complete oxidation by plasma CVD, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material. . Therefore, it is preferable that the molar amount (flow rate) of oxygen to the molar amount (flow rate) of hexamethyldisiloxane as the raw material is 12 times or less (more preferably, 10 times or less) as the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane not completely oxidized are taken into the gas barrier layer, and a gas having a desired elemental profile It becomes possible to form a barrier layer, and it becomes possible to obtain a gas barrier film excellent in barrier property and bending resistance.

  If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, carbon atoms and hydrogen atoms which are not oxidized are excessively taken into the gas barrier layer. become. In this case, the transparency of the gas barrier film is reduced, and the gas barrier film is used for a flexible substrate for an electronic device, for example, a device requiring transparency such as an organic EL device or an organic thin film solar cell. It will not be possible.

  From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane Preferably, the amount is more than 0.5 times.

<Degree of vacuum>
The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the source gas and the like, but is preferably in the range of 0.5 to 100 Pa.

<Roller deposition>
In the discharge plasma chemical vapor deposition method using a plasma CVD apparatus or the like as shown in FIG. 5, a plasma discharge is generated between the film forming rollers (31) and (32) to form a discharge space. The power applied to the electrode drum (which is installed on the film forming rollers (31) and (32) in FIG. 5) connected to (51) depends on the type of source gas, the pressure in the vacuum chamber, etc. Although it can adjust suitably according to, and it can not generally say, it is preferable to carry out within the range of 0.1-10 kW.

  If the applied power in such a range, it is possible to suppress the generation of particles (illegal particles) to some extent, but when there is a specific applied power condition or resin resin temperature range, there are cases where particles are generated, In such a case, by applying a resin base having a hard coat layer having a graded structure of silicon dioxide particle concentration according to the present invention, for example, even when particles are generated, under a high temperature and high humidity environment It is possible to prevent the decrease in adhesion after storage and the occurrence of dark spots when applied to an organic EL element. Further, it is possible to prevent damage to the film forming roller due to the fact that the resin base material is melted by heat and a large current discharge occurs between the naked film forming rollers.

  The conveyance speed (line speed) of the resin base material (F2) can be appropriately adjusted according to the type of raw material gas, the pressure in the vacuum chamber, etc., but should be in the range of 0.25 to 100 m / min. Is preferable, and it is more preferable to set it in the range of 0.5 to 20 m / min. If the transport speed is within the range specified above, wrinkles due to the heat of the resin base and the like are not easily generated, and the thickness of the formed gas barrier layer can be sufficiently controlled.

  As an example of the gas barrier layer according to the present invention formed as described above, each element profile in the thickness direction of the layer according to the XPS depth profile is shown in FIG.

  FIG. 6 is a graph showing an example of a silicon distribution curve, an oxygen distribution curve and a carbon distribution curve of the gas barrier layer according to the present invention.

  In FIG. 6, symbols A to D represent a carbon distribution curve, B a silicon distribution curve, C an oxygen distribution curve, and D an oxygen carbon distribution curve.

  As the carbon gas ratio of the gas barrier layer according to the present invention, the maximum value of the carbon element ratio in the range up to 89% in the vertical direction from the surface is less than 20 at. It is a preferred embodiment that the carbon element ratio in the range of up to 89% in the vertical direction from the surface has a concentration gradient and has a structure in which the concentration changes continuously (claim of the present invention) It corresponds to (1) and (2) as defined in paragraph 5.)

  In addition, as the carbon atom ratio of the gas barrier layer, the maximum value of the carbon element ratio is 20 at% or more in the range of 90 to 95% in the direction perpendicular to the surface, and the carbon element ratio increases continuously. It is preferable to have the characteristics (applies to the items (3) and (4) defined in claim 5 of the present invention).

[Second gas barrier layer]
In the gas barrier film of the present invention, a polysilazane-containing liquid is applied and dried by the wet coating method on the above-described gas barrier layer according to the present invention, and vacuum ultraviolet light of a wavelength of 200 nm or less It is preferable to form the second gas barrier layer by irradiating VUV light and modifying the formed coating film.

  In the present invention, the second gas barrier layer is formed on the gas barrier layer (hereinafter also referred to as the first gas barrier layer) provided by the inter-roller discharge plasma CVD method to which the magnetic field according to the present invention is applied. By the second gas barrier layer component composed of polysilazane to be applied from the upper side by leveling and filling the minute defect portion generated in the formation of the first gas barrier layer already formed It is preferable from the viewpoint of being able to efficiently prevent gas purge and the like and to further improve the gas barrier properties and flexibility.

  The thickness of the second gas barrier layer is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. If the thickness of the second gas barrier layer is 1 nm or more, desired gas barrier performance can be exhibited, and if it is 500 nm or less, film quality deterioration such as generation of cracks in a dense silicon oxynitride film It can be prevented.

<Polysilazane>
The polysilazane used to form the second gas barrier layer according to the present invention is a polymer having a silicon-nitrogen bond in the molecular structure and is a polymer to be a precursor of silicon oxynitride, and as polysilazane to be applied, in particular, Although there is no limitation, it is preferable to be a compound having a structure represented by the following general formula (1).

In the above general formula (1), R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

In the present invention, perhydropolysilazane (abbreviation: PHPS) in which all of R ¹ , R ² and R ³ are composed of hydrogen atoms is particularly preferable from the viewpoint of the denseness as the second gas barrier layer to be obtained. .

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring, and its molecular weight is about 600 to 2000 (number of molecular weight (Mn)) (gel It is a liquid or solid substance in terms of polystyrene by permeation chromatography).

  Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution. As a commercial item of polysilazane solution, NN120-20 made from AZ Electronic Materials Co., Ltd., NAX120-20, NL120-20 etc. are mentioned, for example.

  The second gas barrier layer can be formed by applying and drying a coating solution containing polysilazane on the first gas barrier layer and then irradiating vacuum ultraviolet light (excimer light) having a wavelength of 200 nm or less.

  As an organic solvent for preparing a coating solution containing polysilazane, it is preferable to avoid using an alcohol type or one containing water so as to easily react with polysilazane. Examples of applicable organic solvents include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers. Specific examples thereof include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, Solvesso, and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane, and tetrahydrofuran. These organic solvents may be selected in accordance with the purpose such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

  The concentration of polysilazane in the second gas barrier layer-forming coating solution containing polysilazane varies depending on the layer thickness of the second gas barrier layer and the pot life of the coating solution, but is preferably 0.2 to 35% by mass Within the scope of

  In order to promote modification to silicon oxynitride, an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as Pd propionate, a Rh acetylacetonate or the like in the second gas barrier layer forming coating solution Metal catalysts such as Rh compounds can also be added. In the present invention, it is particularly preferable to use an amine catalyst. Specific amine catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ', N'-tetramethyl-1 And 3-diaminopropane, N, N, N ', N'-tetramethyl-1,6-diaminohexane and the like.

  The amount of these catalysts added to polysilazane is preferably in the range of 0.1 to 10% by mass, and in the range of 0.2 to 5% by mass, based on the total mass of the second gas barrier layer-forming coating solution. It is more preferable that it is, and it is still more preferable that it is in the range of 0.5-2 mass%. By setting the amount of catalyst added within the range defined above, excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects and the like can be avoided.

  Any appropriate wet coating method may be employed as a method of applying the second gas barrier layer forming coating solution containing polysilazane. Specific examples thereof include a roller coating method, a flow coating method, an inkjet method, a spray coating method, a printing method, a dip coating method, a cast film forming method, a bar coating method, and a gravure printing method.

  The thickness of the second gas barrier layer can be appropriately set according to the purpose. For example, the thickness of the second gas barrier layer is preferably in the range of 50 nm to 2 μm, more preferably in the range of 70 nm to 1.5 μm, and in the range of 100 nm to 1 μm. It is further preferred that it be inside.

<Excimer processing>
In the second gas barrier layer according to the present invention, at least a part of polysilazane is modified to silicon oxynitride in the step of irradiating the layer containing polysilazane with vacuum ultraviolet (VUV) light.

Here, the coating film containing a polysilazane modified with vacuum ultraviolet irradiation step, for estimating the mechanism comprising a specific composition of the SiO _x N _y, illustrating the perhydropolysilazane as an example.

Perhydropolysilazane can be represented by the composition of _{"- -} (SiH 2 _{-NH) n".} When the second gas barrier layer has a structure represented by SiO _x N _y , x = 0 and y = 1. An external oxygen source is required to achieve x> 0.
(I) Oxygen and moisture contained in the polysilazane coating solution
(Ii) oxygen and moisture taken into the coating from the atmosphere during the coating and drying process,
(Iii) Oxygen, moisture, ozone, singlet oxygen, etc. taken into the coating from the atmosphere in the vacuum ultraviolet irradiation step
(Iv) Oxygen or moisture moving from the substrate side into the coating film as outgassing due to heat applied in the vacuum ultraviolet irradiation step, etc.
(V) When the vacuum ultraviolet irradiation step is carried out in a non-oxidative atmosphere, oxygen or moisture taken from the atmosphere into the coating when the non-oxidative atmosphere is transferred to the oxidative atmosphere
Etc are oxygen sources.

  On the other hand, with regard to y, basically, 1 is the upper limit because it is considered that the conditions under which nitriding proceeds more than oxidation of Si is very special.

  Moreover, basically, x and y are in the range of 2x + 3y ≦ 4 because of the relationship between Si, O and N bonds. In the state of y = 0 where oxidation has completely proceeded, the coating film may contain silanol groups, and may be in the range of 2 <x <2.5.

  The reaction mechanism which is presumed to generate silicon oxynitride and further silicon oxide from perhydropolysilazane in the vacuum ultraviolet irradiation step is described below.

(1) Dehydrogenation and the formation of Si-N bond accompanying it Dehydrogenation of Si-H bond and N-H bond in perhydropolysilazane is relatively easily broken by excitation by vacuum ultraviolet radiation etc. It is considered that they recombine as N (Si dangling bonds may be formed in some cases). That is, it cures as a SiN _y composition without oxidation. In this case no cleavage of the polymer backbone occurs. Cleavage of Si-H bond and N-H bond is promoted by the presence of a catalyst and heating. The cleaved H is released out of the membrane as H ₂ .

(2) Formation of Si-O-Si Bond by Hydrolysis and Dehydration Condensation Si-N bond in perhydropolysilazane is hydrolyzed by water and the polymer main chain is cleaved to form Si-OH. The two Si-OHs are dehydrated and condensed to form Si-O-Si bonds and cure. Although this is a reaction that occurs in the atmosphere, it is considered that, during vacuum ultraviolet irradiation under an inert atmosphere, water vapor generated as an outgas from the resin substrate by the heat of irradiation becomes the main water source. When water is excessive, Si-OH, which can not be condensed by dehydration remains _and the gas barrier properties of low cured film represented by a composition of _SiO 2.1 ~SiO _2.3.

(3) Direct oxidation by singlet oxygen, formation of Si-O-Si bond During vacuum ultraviolet irradiation, when an appropriate amount of oxygen is present in the atmosphere, singlet oxygen having a very strong oxidizing power is formed. H and N in perhydropolysilazane replace O to form a Si-O-Si bond and cure. It is believed that cleavage of the polymer backbone may result in recombination of bonds.

(4) Oxidation accompanied by cleavage of Si-N bond by vacuum ultraviolet irradiation and excitation The energy of vacuum ultraviolet ray is higher than the bond energy of Si-N in perhydropolysilazane, so the Si-N bond is broken and oxygen around it In the presence of an oxygen source such as ozone and water, it is considered that oxidation occurs to form Si-O-Si bond and Si-O-N bond. It is believed that cleavage of the polymer backbone may result in recombination of bonds.

  The composition of silicon oxynitride in the layer obtained by vacuum ultraviolet irradiation of the layer containing polysilazane can be adjusted by controlling the oxidation state by appropriately combining the above-mentioned oxidation mechanisms (1) to (4). .

In vacuum ultraviolet ray irradiation process of the present invention, it is preferable that the illuminance of the vacuum ultraviolet rays in the coated film surface for receiving the polysilazane coating film is in the range of 30~200mW / cm ^2, in the range of 50~160mW / cm ² It is more preferable that If the illuminance is 30 mW / cm ² or more, there is no concern about a decrease in the modification efficiency, and if 200 mW / cm ² or less, no abrasion occurs in the coating film and the resin substrate is not damaged, which is preferable. .

Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in the range of 200~10000mJ / cm ^2, and more preferably in a range of 500~5000mJ / cm ^2. If the irradiation energy amount is 200 mJ / cm ² or more, reforming can be sufficiently performed, and if it is 10000 mJ / cm ² or less, excessive reforming does not result and generation of cracks and thermal deformation of the resin substrate are prevented. can do.

  As a vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. The atoms of noble gases such as Xe, Kr, Ar, Ne, etc. are called inert gases because they do not chemically combine to form molecules.

However, the excited atoms of the rare gas that have obtained energy by discharge can be combined with other atoms to form molecules. If the noble gas is xenon,
e + Xe → Xe ^*
Xe ^* + ₂ Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
Thus, when the excited excimer molecule Xe ₂ ^* transits to the ground state, it emits an excimer of 172 nm.

  The characteristic of the excimer lamp is that the efficiency is high because the radiation is concentrated at one wavelength and almost no light is emitted. In addition, since the extra light is not emitted, the temperature of the object can be kept low. Furthermore, since it does not take time for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. A dielectric barrier discharge is generated by arranging a gas space between both electrodes via a dielectric such as transparent quartz, and applying a high frequency high voltage of several tens of kHz to the electrodes, which is very similar to lightning. The discharge is called fine micro discharge, and when the stream of micro discharge reaches the tube wall (derivative), the electric charge is accumulated on the surface of the dielectric, and the micro discharge disappears.

  This microdischarge spreads over the entire wall of the tube and is a discharge which is repeatedly generated and annihilated. For this reason, the flicker of the light which can be confirmed with the naked eye is produced. In addition, since a very high temperature streamer locally and directly reaches the pipe wall, there is a possibility that the deterioration of the pipe wall may be accelerated.

  As a method of obtaining excimer emission efficiently, electrode-less electric field discharge is also possible besides dielectric barrier discharge. Electrodeless field discharge with capacitive coupling, also known as RF discharge. The lamp and the electrodes and the arrangement thereof may be basically the same as the dielectric barrier discharge, but the high frequency applied between both electrodes is lit at several MHz. Since the electrodeless electric field discharge can thus obtain a spatially and temporally uniform discharge, a lamp with a long life without flicker can be obtained.

  In the case of dielectric barrier discharge, since microdischarge occurs only between the electrodes, the outer electrode covers the entire outer surface to transmit discharge throughout the discharge space and transmits light to extract light to the outside It must be a thing.

  For this reason, the electrode which made the thin metal wire reticulate is used. This electrode is likely to be damaged by ozone or the like generated by vacuum ultraviolet light in an oxygen atmosphere because a thin wire is used as thin as possible so as not to block light. In order to prevent this, it is necessary to make the surroundings of the lamp, that is, the inside of the irradiation apparatus, an atmosphere of an inert gas such as nitrogen, and provide a window of synthetic quartz to take out the irradiation light. Not only is a synthetic quartz window an expensive consumable, it also results in light loss.

  Since the outer diameter of the double cylindrical lamp is about 25 mm, the difference in the distance to the irradiation surface can not be ignored immediately below the lamp axis and the lamp side surface, and a large difference occurs in the illuminance. Therefore, even if the lamps are closely arranged, uniform illuminance distribution can not be obtained. By using an irradiation apparatus provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the outer electrode mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. For the external electrode, an electrode serving as a light reflector made of an aluminum block is generally used on the back of the lamp. However, since the outer diameter of the lamp is large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The greatest feature of the capillary excimer lamp is its simple structure. Both ends of the quartz tube are closed, and a gas for performing excimer light emission is enclosed inside.

  The outer diameter of the tube of the capillary lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  As a form of discharge, either dielectric barrier discharge or electrodeless electric field discharge can be used. The shape of the electrode may be a flat surface in contact with the lamp, but if the shape conforms to the curved surface of the lamp, the lamp can be firmly fixed and the discharge will be more stable because the electrode adheres to the lamp. Also, if the curved surface is made of aluminum, it will be a light reflector.

  The Xe excimer lamp emits a short wavelength of 172 nm ultraviolet light at a single wavelength, and thus is excellent in luminous efficiency. Since this light has a large absorption coefficient of oxygen, it can generate radical oxygen atom species and ozone at high concentration with a small amount of oxygen.

  In addition, it is known that the energy of 172 nm light having a short wavelength has a high ability to dissociate the binding of an organic substance. The high energy possessed by the active oxygen and ozone and the ultraviolet radiation can realize the modification of the polysilazane layer in a short time.

  Therefore, it is possible to shorten the process time and reduce the installation area with high throughput compared to the low pressure mercury lamp emitting 185 nm wavelength and 254 nm, and plasma cleaning, and to irradiate organic materials and plastic substrates that are easily damaged by heat. .

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power input. In addition, since light having a long wavelength causing temperature rise due to light is not emitted, energy is irradiated in the ultraviolet region, that is, at a short wavelength, so that the rise of the surface temperature of the object to be deciphered is suppressed. Therefore, it is suitable for heat-sensitive flexible film materials.

  The reaction at the time of ultraviolet irradiation requires oxygen, but vacuum ultraviolet radiation is absorbed by oxygen and the efficiency in the ultraviolet irradiation process is likely to be reduced. It is preferable to carry out in the low state. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm, and still more preferably in the range of 100 to 4500 ppm.

  It is preferable to set it as dry inert gas as gas which satisfy | fills irradiation atmosphere used at the time of vacuum ultraviolet irradiation, and it is preferable to set it as dry nitrogen gas especially from a viewpoint of cost. The adjustment of the oxygen concentration can be performed by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation storage and changing the flow ratio.

<< On-line manufacturing method of gas barrier film >>
In the gas barrier film of the present invention, as described above, the hard coat layer (3), the gas barrier layer (4) and, if necessary, the second gas barrier layer (5) are formed on the resin substrate (2). Can be formed individually in independent manufacturing steps, but as shown in FIG. 7, the step of forming the hard coat layer (3), the step of forming the gas barrier layer (4) and if necessary The process of forming the second gas barrier layer (5) is arranged on-line, and a method of manufacturing a gas barrier film by roll-to-roll method is a preferred embodiment from the viewpoint of obtaining high productivity. .

  FIG. 7 is a schematic view showing an example of an on-line production process applicable to the production of the gas-rolled film of the present invention.

  The manufacturing process of the gas barrier film shown in FIG. 7 mainly includes station 1 (S1) which forms a hard coat layer (3) having a graded structure as a silicon concentration according to the present invention on a resin substrate (F1); A station 2 (S2) for forming a first gas barrier layer using an inter-roller discharge plasma CVD apparatus having a discharge space between rollers to which a magnetic field is applied, using a raw material gas containing an organosilicon compound and an oxygen gas; The coated film formed by applying and drying a polysilazane-containing liquid is irradiated with vacuum ultraviolet light having a wavelength of 200 nm or less for modification to form a second gas barrier layer, which is an on-line method. It is arranged continuously.

  In station 1 (S1), a hard coat layer (3) having a graded structure as a silicon concentration is formed on a resin base (F1).

  In the case of forming the hard coat layer having the layer configuration exemplified in FIG. 2 by feeding out the roll-shaped resin base material (F1) from the delivery roller (11), for example, the preparation pots (12A) to (12E) In one of the preparation pots, a coating solution for forming a hard coat layer for forming a hard coat layer having a graded structure as a silicon concentration is stored. As a coating solution for forming a hard coat layer, for example, a coating solution containing silica particles surface-modified as silicon dioxide particles and an ultraviolet-curable urethane acrylate resin is prepared, and this coating solution is wetted by a coater (13). It supplies on a resin base material (F1) so that it may become a film thickness, and forms the hard-coat layer of a single layer structure. Further, as another method, coating solutions for forming a hard coat layer having different silicon dioxide particles are stored in preparation pots (12A) to (12E), respectively, using a coater (13) capable of performing multilayer simultaneous coating, A plurality of hard coat layer forming coating solutions are simultaneously applied in multiple layers to form, for example, a hard coat layer unit (3U) configured as illustrated in FIG. 3 or FIG. 4. Next, in the drying step (14), the hard coat layer in the wet state is dried, and then the ultraviolet ray (18) is irradiated on the hard coat layer from the ultraviolet irradiation lamp (17) using the ultraviolet irradiation device (15). And cure to form a hard coat layer.

  Next, while continuously transporting the resin base material (F2) on which the hard coat layer is formed in station 1, using station 2 (S2), using plasma CVD manufacturing apparatus (30) described in detail using FIG. A gas barrier layer having a discharge space between rollers to which a magnetic field is applied using a raw material gas containing an organosilicon compound and an oxygen gas on a hard coat layer of a resin substrate (F2) by a discharge plasma chemical vapor deposition method Form

  Next, while continuously transporting the resin base material (F3) on which the gas barrier layer is formed, the polysilazane-containing coating solution stored in the preparation pot (81) is used as a gas barrier of the resin base material (F3) using a coater (82). After coating on the layer, the coated film is dried in the drying step (83) and then irradiated with vacuum ultraviolet light (92) having a wavelength of 200 nm or less from the excimer lamp (91) in the modification step (90) The polysilazane-containing layer is reformed into a gas barrier layer to produce a gas barrier film (F4), and the film is wound into a roll by a winding roller (93).

<< Organic electroluminescent device >>
[Schematic Configuration of Organic EL Element]
Then, the specific structure of the organic electroluminescent element which comprises the gas barrier film of this invention is demonstrated.

  FIG. 8 is a schematic configuration view showing an example of the configuration of the organic EL element provided with the gas barrier film of the present invention.

As shown in FIG. 8, the organic EL element (101) mainly includes the gas barrier film (1), the first electrode (116), the organic functional layer unit (117), and the second electrode (118) of the present invention. And a sealing resin layer (119) and a sealing member (120). The gas barrier film (1) of the present invention comprises a hard coat layer (3) having a silicon concentration gradient structure on a film substrate (2), a first gas barrier layer (4) and, if necessary, a second The gas barrier layer (5) is laminated in this order .

  In the organic EL element (101) shown in FIG. 8, an organic functional layer unit (117) having a light emitting layer and a second electrode (118) as a cathode are stacked on a first electrode (116) as an anode, Furthermore, it is the structure solid-sealed by the gas barrier film (1), the sealing resin layer (119), and the sealing member (120). Among these, the first electrode (116) used as an anode is configured as a translucent electrode. In such a configuration, only the portion in which the organic functional layer unit (117) is sandwiched between the first electrode (116) and the second electrode (118) is the light emitting region in the organic EL element (101). And, in the example shown in FIG. 8, the organic EL element (101) is configured as a bottom emission type in which the generated light (hereinafter referred to as emitted light (h)) is taken out at least from the gas barrier film (1) side. ing.

  The organic EL element (101) is a sealing resin layer (119) covering the first electrode (116), the organic functional layer unit (117) and the second electrode (118) on one surface of the gas barrier film (1). The sealing member (120) is solid-sealed by pasting together the sealing member (120). The solid sealing type organic EL element (101) is formed on the bonding surface of the sealing member (120) or at a plurality of locations of the gas barrier layer (4) of the gas barrier film (1) and the second electrode (118). An uncured resin material is applied, and the gas barrier film (1) and the sealing member (120) are integrated by thermocompression bonding with each other with the resin material interposed therebetween.

  The organic EL element (101) of the present invention is not limited to the bottom emission type, but has a top emission type configuration in which light is extracted from the second electrode (118) side or a double emission type configuration in which light is extracted from both sides It may be If the organic EL element (101) is a top emission type, the light emitting light h is extracted from the second electrode (118) side by using a transparent material for the second electrode (118). Further, if the organic EL element (101) is a double-sided light emitting type, a transparent material is used for the second electrode (118), and the emitted light h is extracted from both sides.

[Component of organic EL element]
Next, for the first electrode (116), the second electrode (118), the organic functional layer unit (117), the sealing resin layer (119), and the sealing member (120) excluding the gas barrier film 1 described above, The detailed configuration will be described. In addition, in the organic EL element (101) of this invention, light transmittance means that the light transmittance in wavelength 550nm is 50% or more.

(First electrode)
In the organic EL element (101) shown in FIG. 8, the first electrode (116) is a substantial anode. The organic EL element (101) is a bottom emission type element which transmits the first electrode (116) and takes out light from the film base 2 side. Therefore, the first electrode (116) needs to be formed of a light-transmitting conductive layer.

  The first electrode (116) is preferably a layer configured using, for example, silver or an alloy containing silver as a main component. Examples of an alloy containing silver (Ag) as a main component of the first electrode (116) include, for example, silver-magnesium (Ag-Mg), silver-copper (Ag-Cu), silver-palladium (Ag-Pd) And silver-palladium-copper (Ag-Pd-Cu), silver-indium (Ag-In) and the like. The main component in the first electrode (116) means that the content in the first electrode is 98% by mass or more.

  The first electrode (116) may be configured by laminating a plurality of layers of silver or an alloy containing silver as a main component.

  As a method of forming such a first electrode (116), a method using a wet process such as a coating method, an ink jet method, a coating method, a dip method, an evaporation method (resistance heating, EB method etc.), a sputtering method, CVD The method etc. which use dry processes, such as a method, are mentioned. Above all, the vapor deposition method is preferably applied.

  Furthermore, the first electrode (116) preferably has a thickness in the range of 4 to 12 nm. If the thickness is 12 nm or less, it is preferable because the light absorption component and the reflection component can be suppressed low and the light transmittance can be secured. In addition, when the thickness is 4 nm or more, it is preferable because sufficient conductivity as an electrode can be secured.

  The upper part of the first electrode (116) may be covered with a protective film, and another conductive layer may be stacked. In this case, it is preferable that the protective film and the conductive layer have light transmittance so as not to impair the light transmittance of the organic EL element (101).

  A layer according to need may be provided also under the first electrode (116), that is, between the gas barrier layer (4) and the first electrode (116). For example, it may have a base layer or the like for improving the characteristics of the first electrode (116) or facilitating the formation.

  In addition, the first electrode (116) may have a configuration other than the above-described silver as a main component. For example, various transparent conductive substance thin films such as other metals or alloys, ITO, zinc oxide, tin oxide and the like may be used.

  In addition, in the case where the organic EL element (101) is a top emission type in which emitted light h is extracted from the second electrode (118) side, the first electrode (116) may not have translucency. .

(Second electrode)
The second electrode (118) is an electrode layer functioning as a cathode for supplying electrons to the organic functional layer unit (117), and a metal, an alloy, a conductive compound of organic or inorganic, and a mixture thereof are constituted. It is used as a material. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO _And oxide semiconductors such as SnO ₂ .

  The second electrode (118) can be formed by depositing or sputtering these conductive materials. In addition, the sheet resistance as the second electrode (118) is several hundreds Ω / sq. The following is preferable, and the thickness is usually selected in the range of 5 to 5000 nm, preferably 5 to 200 nm.

  In the case where the organic EL element (101) is of the top emission type or double-sided emission type in which the emitted light h is extracted from the second electrode (118) side, the conductive material having good light transmittance among the above-mentioned conductive materials Material is selected to constitute the second electrode (118).

(Organic functional layer unit)
The organic functional layer unit (117) is, for example, a hole injection layer (117) a / a hole transport layer (117b) / a light emitting layer (117c) / an electron transport layer on the first electrode (116) which is an anode. Although the structure which laminated | stacked (117d) / electron injection layer (117e) in this order can be illustrated, it is a necessary condition to have the light emitting layer (117c) comprised using an organic material at least among these. The hole injection layer (117a) and the hole transport layer (117b) may be provided as a single hole transport / injection layer having hole transportability and hole injectability. The electron transport layer (117d) and the electron injection layer (117e) may be provided as a single layer electron transport / injection layer having electron transportability and electron injectability. Further, among these organic functional layer units (117), for example, the electron injection layer (117e) may be made of an inorganic material.

  Further, in addition to these layers, the organic functional layer unit (117) may be, for example, a hole blocking layer, an electron blocking layer, etc., may be laminated at necessary places as necessary. Furthermore, the light emitting layer (117c) has a plurality of light emitting layers for emitting light of each wavelength range, and the light emitting layers of these colors are stacked by laminating a plurality of layers via the non-light emitting intermediate layer to emit light. It may be formed as a layer unit. The intermediate layer may function as a hole blocking layer or an electron blocking layer.

<Light emitting layer>
The light emitting layer (117c) contains, for example, a phosphorescent compound as a light emitting material. This light emitting layer (117c) is a layer in which electrons emitted from the electrode or the electron transport layer (117d) recombine with holes injected from the hole transport layer (117b) to emit light. The portion may be in the layer of the light emitting layer (117c) or an interface between the light emitting layer (117c) and the adjacent layer.

  There is no particular limitation on the configuration of such a light emitting layer (117c) as long as the contained light emitting material satisfies the light emitting requirements. In addition, a plurality of layers having the same emission spectrum or emission maximum wavelength may be provided. In this case, it is preferable to have a non-luminescent intermediate layer (not shown) between the light emitting layers (117c).

  The total thickness of the light emitting layer (117c) is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because it can be driven at a lower voltage. In addition, with the sum total of the layer thickness of a light emitting layer (117c), when the nonluminous intermediate layer exists between light emitting layers (117c), it is displayed by the layer thickness also including the said intermediate layer.

  When the light emitting layer (117c) is composed of a plurality of layers, the thickness of each light emitting layer is preferably adjusted in the range of 1 to 50 nm, and more preferably adjusted in the range of 1 to 20 nm preferable. When the plurality of stacked light emitting layers correspond to the respective blue, green and red light emitting colors, there is no particular limitation on the relationship of the layer thicknesses of the blue, green and red light emitting layers.

  The light emitting layer (117c) as described above is formed by using a light emitting material or a host compound described later, for example, by a known thin film forming method such as a vacuum evaporation method, a spin coating method, a casting method, an LB method, or an inkjet method. Can.

  The light emitting layer (117c) may contain a plurality of light emitting materials, and a phosphorescent light emitting material and a fluorescent light emitting material (also referred to as a fluorescent dopant or a fluorescent compound) are mixed in the same light emitting layer (117c). You may use it.

  As a configuration of the light emitting layer (117c), a host compound (also referred to as a light emitting host) and a light emitting material (also referred to as a light emitting dopant compound or a guest material) are contained, and light is preferably emitted from the light emitting material.

(1) Host Compound The host compound contained in the light emitting layer (117c) is preferably a compound having a phosphorescence quantum yield of phosphorescence at room temperature (25 ° C.) of less than 0.1. Furthermore, compounds having a phosphorescent quantum yield of less than 0.01 are preferred. Further, among the compounds contained in the light emitting layer (117c), the host compound preferably has a volume ratio of 50% or more in the layer.

  As the host compound, known host compounds may be used alone or in combination of two or more. By using a plurality of host compounds, charge transfer can be adjusted, and the efficiency of the organic EL element (101) can be increased. In addition, by using a plurality of light emitting materials described later, it is possible to mix different light emissions, and thereby it is possible to obtain any light emission color including white light emission.

  The host compound to be used may be a conventionally known low molecular weight compound or a high molecular weight compound having a repeating unit, or may be a low molecular weight compound having a polymerizable group such as a vinyl group or an epoxy group (vapor deposition polymerizable light emitting host) .

  As a known host compound, a compound having a hole transporting ability and an electron transporting ability, preventing a long wavelength of light emission and having a high Tg (glass transition temperature) is preferable. The glass transition point (Tg) as used herein is a value determined by a method in accordance with JIS-K-7121 using differential scanning colorimetry (DSC).

(2) Light Emitting Material As a light emitting material which can be used for the organic EL element (101), a phosphorescent compound (also referred to as a phosphorescent compound or a phosphorescent material) and a fluorescent compound can be mentioned.

  The phosphorescent compound is a compound in which light emission from the excitation triplet is observed, and specifically, a compound which emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. Although it is defined as a compound of .01 or more, a preferable phosphorescence quantum yield is 0.1 or more.

  The above-mentioned phosphorescence quantum yield can be measured by the method described on page 398 (1992 edition, Maruzen) of Spectrum II of Fourth Experimental Chemistry Course 7. The phosphorescence quantum yield in solution can be measured using various solvents, but in the case of using a phosphorescent compound in this example, the phosphorescence quantum yield (0.01 or more) in any of the optional solvents is It should be achieved.

  There are two kinds of principles of light emission of the phosphorescent compound. First, carrier recombination occurs on the host compound to which the carrier is transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound to emit light from the phosphorescent compound Energy transfer type to obtain The other is a carrier trap type in which a phosphorescent compound acts as a carrier trap, and carrier recombination occurs on the phosphorescent compound to cause light emission from the phosphorescent compound. In any case, it is a condition that the energy of the excited state of the phosphorescent compound is lower than the energy of the excited state of the host compound.

  The phosphorescent compound can be appropriately selected from known ones used in the light emitting layer of a general organic EL device, but preferably contains a metal of group 8 to 10 in the periodic table of the element Complex compounds. More preferable are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and among these, iridium compounds are most preferable.

  In the organic EL element (101), at least one light emitting layer (117c) may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer (117c) is It may be changed in the layer thickness direction of the light emitting layer (117c).

  The phosphorescent compound is preferably in the range of 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer (117c).

  Moreover, as a fluorescent light emitting material used for the light emitting layer (117c), for example, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzthracene dyes, fluorescein dyes, rhodamine dyes Dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, rare earth complex phosphors, etc. may be mentioned.

Injection layer
The injection layer is a layer provided between the electrode and the light emitting layer (117c) to lower the driving voltage and to improve the light emission luminance, and the “injection layer of the organic EL element and its industrialization (November 30, 1998 2), “Electrode materials” (pages 123 to 166), and there are a hole injection layer (117a) and an electron injection layer (117e).

  The injection layer can be provided as needed. In the case of the hole injection layer (117a), between the anode and the light emitting layer (117c) or the hole transport layer (117b), in the case of the electron injection layer (117e) the cathode and the light emitting layer (117c) or the electron transport layer ( 117d).

  The details of the hole injection layer (117a) are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc. As a specific example, copper phthalocyanine is exemplified. Phthalocyanine layers, oxide layers represented by vanadium oxide, amorphous carbon layers, polymer layers using conductive polymers such as polyaniline (emeraldine) and polythiophene, and the like.

  The details of the electron injection layer (117e) are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, etc. Specifically, representative examples are strontium, aluminum, etc. Metal layers, alkali metal halide layers represented by potassium fluoride, alkaline earth metal compound layers represented by magnesium fluoride, oxide layers represented by molybdenum oxide, and the like. The electron injection layer 17 e is preferably a very thin layer, and the thickness is preferably in the range of 0.001 to 10 μm, depending on the material.

<Hole transport layer>
The hole transport layer (117b) is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer (117a) and the electron blocking layer are also included in the hole transport layer (117b). . The hole transport layer (117b) can be provided as a single layer or a plurality of layers.

  The hole transport material has any function of hole injection or transport and electron barrier property, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  As the hole transport material, those described above can be used, but in addition, it is preferable to use a porphyrin compound, an aromatic tertiary amine compound, a styrylamine compound, and particularly an aromatic tertiary amine compound.

Representative examples of aromatic tertiary amine compounds and styrylamine compounds are
N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl,
N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (abbreviation: TPD),
2,2-bis (4-di-p-tolylaminophenyl) propane,
1,1-bis (4-di-p-tolylaminophenyl) cyclohexane,
N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl,
1,1-bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane,
Bis (4-di-p-tolylaminophenyl) phenylmethane,
N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl,
N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether,
4,4'-bis (diphenylamino) quadriphenyl,
N, N, N-tri (p-tolyl) amine,
4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene,
4-N, N-diphenylamino- (2-diphenylvinyl) benzene,
3-methoxy-4'-N, N-diphenylaminostilbenzene,
N-phenylcarbazole,
Further, those having two fused aromatic rings in the molecule as described in US Pat. No. 5,061,569, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] Biphenyl (abbreviation: NPD), 4,4 ′, 4 ′ ′-tris [N- (3-methylphenyl) described in JP-A-4-308688 in which triphenylamine units are linked in a three-star burst form ) -N-phenylamino] triphenylamine (abbreviation: MTDATA) and the like.

  Furthermore, it is also possible to use a polymer material in which these materials are introduced into a polymer chain, or in which these materials are used as a polymer main chain. Inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  In the hole transport layer (117b), JP-A-11-251067, J.-P. Huang et. al. , Applied Physics Letters, 80 (2002), p. It is also possible to use so-called p-type hole transport materials as described in 139. It is preferable to use these materials because a light emitting element with high efficiency can be obtained.

  The hole transport layer (117b) is formed by thinning the above hole transport material by a known method such as vacuum evaporation, spin coating, casting, printing including inkjet, LB, etc. It can be formed.

  Although there is no restriction | limiting in particular about the layer thickness of a positive hole transport layer (117b), Usually, about 5-5000 nm, Preferably it exists in the range of 5-200 nm. The hole transport layer (117b) may have a single-layer structure composed of one or more of the above materials.

  In addition, the material of the hole transport layer (117b) can be doped with an impurity to enhance p-type. Examples thereof are disclosed in JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, and J.-A. Appl. Phys. , 95, 5773 (2004) and the like.

  Thus, it is preferable to increase the p property of the hole transport layer (117b) because a device with lower power consumption can be manufactured.

Electron Transport Layer
The electron transport layer (117d) is made of a material having a function of transporting electrons, and in a broad sense, the electron injection layer (117e) and the hole blocking layer (not shown) are also included in the electron transport layer (117d). The electron transporting layer (117d) can be provided as a single layer structure or a stacked structure of a plurality of layers.

  An electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer (117c) in the electron transport layer (117d) of a single layer structure and the electron transport layer (117d) of a laminated structure It suffices to have a function of transmitting the more injected electrons to the light emitting layer (117c). As such a material, it can be arbitrarily selected and used from conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethanes, anthrone derivatives, oxadiazole derivatives and the like can be mentioned. Furthermore, in the above-mentioned oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted by sulfur atoms, and quinoxaline derivatives having a quinoxaline ring known as an electron withdrawing group are also used as materials for the electron transport layer (117d). It can be used. Furthermore, it is also possible to use a polymer material in which these materials are introduced into a polymer chain, or a polymer material in which these materials have a polymer main chain.

In addition, metal complexes of 8-quinolinol derivatives, for example, tris (8-quinolinol) aluminum (abbreviation: Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-) Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc., and central metals of these metal complexes A metal complex in which In is replaced by In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as a material of the electron transport layer (117d).

  In addition, even if metal free or metal phthalocyanine, or the terminal thereof is substituted by an alkyl group, a sulfonic acid group or the like, it can be preferably used as a material of the electron transport layer (117d). In addition, distyrylpyrazine derivatives exemplified as the material of the light emitting layer (117c) can also be used as the material of the electron transporting layer (117d), similarly to the hole injecting layer (117a) and the hole transporting layer (117b). Inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the material of the electron transport layer (117d).

  The electron transport layer (117d) may be formed by thinning the above-mentioned material by a known method such as vacuum evaporation, spin coating, casting, printing including inkjet, LB, etc. it can. The thickness of the electron transport layer (117d) is not particularly limited, but is usually in the range of about 5 to 5000 nm, preferably 5 to 200 nm. The electron transport layer (117d) may have a single-layer structure composed of one or more of the above materials.

  In addition, the electron transporting layer (117d) can be doped with an impurity to increase n-type. Examples thereof are disclosed in JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, and J.-A. Appl. Phys. , 95, 5773 (2004) and the like. Furthermore, it is preferable to make a potassium, a potassium compound, etc. contain in an electron carrying layer (117d). As a potassium compound, potassium fluoride etc. can be used, for example. When the n property of the electron transport layer (117d) is increased as described above, a device with lower power consumption can be manufactured.

<Blocking layer>
The blocking layer is optionally provided in addition to the basic constituent layer of the organic compound thin film as described above. For example, they are described in JP-A-11-204258, JP-A-11-204359, and page 237 of "Organic EL element and its forefront of industrialization (issued on November 30, 1998)". There is a hole blocking (hole blocking) layer.

  The hole blocking layer has a function of the electron transport layer (117d) in a broad sense. The hole blocking layer is made of a hole blocking material having an extremely small ability to transport holes while having the function of transporting electrons, and the electron-hole recombination by stopping the holes while transporting the electrons. The probability can be improved. In addition, the configuration of the electron transport layer (117d) described later can be used as a hole blocking layer, if necessary. The hole blocking layer is preferably provided adjacent to the light emitting layer (117c).

  On the other hand, the electron blocking layer has a function of the hole transport layer (117b) in a broad sense. The electron blocking layer is made of a material having an ability to transport electrons while having a function of transporting holes, and improves the probability of recombination of electrons and holes by transporting electrons while blocking holes. be able to. In addition, the above-described configuration of the hole transport layer (117b) can be used as an electron blocking layer as needed.

  The layer thickness of the blocking layer is preferably 3 to 100 nm, more preferably 5 to 30 nm.

(Sealing member)
The sealing member (120) covers the organic EL element (101), and the plate-like (film-like) sealing member (120) is a film base of the gas barrier film by the sealing resin layer (119). It is fixed to the material (2) side. The sealing member (120) is provided so as to cover at least the organic functional layer unit (117), and provided so as to expose the terminal portions (not shown) of the organic EL element (101) and the second electrode (118). It is done. In addition, an electrode may be provided on the sealing member (120), and the electrode and the terminal portion of the second electrode (118) may be electrically connected.

  Specific examples of the plate-like (film-like) sealing member (120) include a glass substrate and a polymer substrate, and these substrate materials may be used in the form of a thinner film. Examples of the glass substrate include soda lime glass, glass containing barium and strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like. In addition, as the polymer substrate, polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like can be mentioned.

  Among them, since the organic EL element can be thinned, a thin film-like polymer substrate can be preferably used as the sealing member (120).

Furthermore, the polymer substrate in the form of a film has an oxygen permeability of 1 × 10 ^-3 ml / (m ² · 24 h · atm) or less, which is measured by a method according to JIS-K-7126-1987, JIS-K Water vapor transmission rate (25 ± 0.5 ° C, relative humidity (90 ± 2)%) measured by the method according to –7129-1992 is less than 1 × 10 ⁻³ g / m ² · 24 h Is preferred.

  Also, the substrate material as described above may be processed into a concave plate shape and used as a sealing member (120). In this case, the substrate member described above is subjected to processing such as sand blast processing and chemical etching processing to form a concave shape.

  Moreover, you may use not only this but a metal material. Examples of the metal material include one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicone, germanium and tantalum. By making such a metal material into a thin film shape and using it as a sealing member (120), the whole light emitting panel provided with the organic EL element (101) can be thinned.

封 止 Sealing resin layer》
The sealing resin layer (119) for fixing the sealing member (120) on the gas barrier film (1) side is an organic EL element (in which the sealing member (120) and the gas barrier film (1) 101) used for sealing. The encapsulating resin layer (119) is, for example, a photocurable or thermosetting adhesive having a reactive vinyl group of an acrylic acid oligomer or a methacrylic acid oligomer, a thermosetting or chemical curing agent such as an epoxy resin ( Adhesives of two-component mixtures), polyamides of hot melt type, polyesters, polyolefins, and adhesives of UV curable epoxy resin of cationic curing type can be mentioned.

  From the viewpoint of simplicity of the manufacturing process, it is preferable to form the sealing resin layer (119) with a thermosetting adhesive. Moreover, as a form of the sealing resin layer (119), it is preferable to use a thermosetting adhesive processed into a sheet shape. In the case of using a sheet-like thermosetting adhesive, it is non-flowable at normal temperature (about 25 ° C.), and is an adhesive that develops fluidity at a temperature within the range of 50 to 130 ° C. when heated. (Sealing material) is used.

  Any adhesive can be used as the thermosetting adhesive. From the viewpoint of improving the adhesion with the sealing member (120) adjacent to the sealing resin layer (119), the gas barrier film 1 and the like, a suitable thermosetting adhesive is appropriately selected. For example, as the thermosetting adhesive, a resin having a compound having an ethylenic double bond at an end or a side chain of a molecule and a thermal polymerization initiator as main components can be used. More specifically, a thermosetting adhesive composed of an epoxy resin, an acrylic resin or the like can be used. Moreover, you may use a thermosetting type thermosetting adhesive according to the bonding apparatus and hardening treatment apparatus which are used at the manufacturing process of organic EL element (101).

  Further, as the adhesive, a mixture of two or more of the above-described adhesives may be used, or an adhesive having both thermosetting and ultraviolet curing properties may be used.

<< Application of Organic Electroluminescent Device >>
Since the organic EL element (101) is a surface light emitter as described above, it can be used as various light emission sources. For example, lighting devices such as home lighting and car lighting, backlights for watches and liquid crystals, lights for advertising billboards, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copiers, light sources for optical communication processors, The light source of an optical sensor etc. are mentioned. Moreover, it is not limited to these light emission light sources, It can use also as another light source.

  In particular, it can be effectively used as a backlight of a liquid crystal display combined with a color filter, and an application as a light source for illumination.

  In addition, the organic EL element (101) may be used as a kind of lamp such as illumination or exposure light source, a projection device of a type which projects an image, or a type of which a still image or a moving image is directly viewed. You may use as a display apparatus (display). In this case, the light emitting surface may be enlarged by so-called tiling in which the light emitting panels provided with the organic EL element (101) are planarly joined with increase in size of the lighting device and display in recent years.

  When used as a display device for moving image reproduction, a driving method may be a simple matrix (passive matrix) method or an active matrix method. Moreover, it is possible to produce a color or a full color display by using 2 or more types of organic EL elements 10 which have different luminescent colors.

<< Method of manufacturing organic electroluminescent device >>
A method of manufacturing the organic EL device (101) shown in FIG. 8 will be described as one example of the method of manufacturing the organic EL device of the present invention.

  First, the first electrode (116) is formed on the second gas barrier layer (5) of the gas barrier film (1) of the present invention produced by the method described above. The first electrode (116) is formed of a transparent conductive material. For example, an electrode having a thickness of about 3 to 15 nm containing silver as a main component, or a transparent conductive material such as ITO having a thickness of about 100 nm is formed. As a method of forming the first electrode (116), for example, spin coating method, casting method, ink jet method, vapor deposition method, sputtering method, printing method etc. can be used, but it is easy to obtain a homogeneous layer and pin The vacuum evaporation method is particularly preferable from the viewpoint that holes are hardly generated. Before and after the formation of the first electrode (116), the pattern formation of the auxiliary electrode is performed as needed.

Next, a hole injection layer (117a), a hole transport layer (117b), a light emitting layer (117c), an electron transport layer (117d), and an electron injection layer (117e) are formed in this order, and an organic functional layer is formed. Form a unit (117). As a method of forming these layers, for example, spin coating method, casting method, ink jet method, vapor deposition method, sputtering method, printing method and the like can be used, but it is easy to obtain a homogeneous layer and pin holes are generated. Vacuum evaporation or spin coating is particularly preferred in view of the difficulty of adhesion. Furthermore, different formation methods may be used for each layer. When a vapor deposition method is employed to form these layers, the vapor deposition conditions vary depending on the type of compound used, etc., but generally within the range of 50 to 450 ° C. as a boat heating temperature at which the compounds are stored, 1 × 10 as a vacuum degree. Within the range of ⁻⁶ to 1 × 10 ⁻² Pa, within the range of 0.01 to 50 nm / sec as the deposition rate, within the range of −50 to 300 ° C. as the resin substrate temperature It is desirable to select each condition appropriately in the range.

  Next, a second electrode (118) to be a cathode is formed by a film formation method such as evaporation or sputtering. At this time, while maintaining the insulating state with respect to the first electrode (116) by the organic functional layer unit (117), the terminal portion was drawn out to the peripheral edge of the gas barrier film (1) from the upper side of the organic functional layer unit (117). Pattern in shape.

  Next, solid sealing of the first electrode (116), the organic functional layer unit (117) and the second electrode (118) provided on the gas barrier film (1) is performed. A sealing resin layer (119) is formed on one side of the sealing member (120). Then, the sealing resin layer (119) of the sealing member (120) is set so that the end portions of the lead wires of the first electrode (116) and the second electrode (118) come out of the sealing resin layer (119). The formation surface is superimposed on the gas barrier film (1) via the first electrode (116), the organic functional layer unit (117) and the second electrode (118). After laminating the gas barrier film (1) and the sealing member (120), pressure is applied to the gas barrier film (1) and the sealing member (120). Furthermore, in order to cure the sealing resin layer (119), the sealing resin layer (119) is heated. At this time, the sealing resin layer (119) is sufficiently cured so that there is no problem in the adhesion between the gas barrier layer (4) and the sealing resin layer (119).

  Thus, the solid sealing is performed by the gas barrier film (1) provided with the hard coat layer (3), the first gas barrier layer (4) and the second gas barrier layer (5) on the film substrate (2). The obtained organic EL element (101) is obtained. In the production of such an organic EL element (101), a production process is preferable in which the first electrode (116) to the second electrode (118) are consistently produced by one evacuation, but in the middle of the vacuum atmosphere It is possible to take out and use different formation methods. At this time, it is necessary to take into consideration that the operation is performed in a dry inert gas atmosphere.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, although the display of "%" and "part" is used in an Example, unless otherwise indicated, "mass%" and "mass part" are represented.

<< Preparation of gas barrier film >>
[Preparation of gas barrier film 1]
(Preparation of resin base material)
A triacetyl cellulose film KC6UY (thickness: 60 μm, abbreviated as TAC in Table 1) manufactured by Konica Minolta Co., Ltd. was prepared as a resin substrate.

(Surface treatment of resin base material)
The surface of the TAC film prepared above was subjected to corona treatment. AGI-080 manufactured by Kasuga Denki Co., Ltd. was used as a corona discharge device, the gap between the discharge-like electrode of the corona discharge treatment device and the TAC surface was set to 1 mm, and surface corona for 10 seconds under the condition of 600 mW / cm ² processing power. I did the processing.

(Formation of hard coat layer)
Next, a hard coat layer 1 was formed on the corona-treated TAC film using a coating solution for forming a hard coat layer 1 composed of the following additives.

Preparation of Coating Solution for Forming Hard Coat Layer 1
The following constituent materials were sequentially added, mixed and dissolved to prepare a coating solution for forming a hard coat layer 1.

Silicon dioxide particles: non-surface modified silica (average particle diameter 6 nm, 47.3 parts of colloidal silica Snowtex AK manufactured by Nissan Chemical Industries, Ltd.) binder resin 1: urethane acrylate (UA-1100H-LC manufactured by Shin-Nakamura Chemical Co., Ltd.) 28.4 Part Binder resin 2: Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 18.9 parts Alkylphenone photopolymerization initiator 1: Irgacure 907 (2-methyl-1- (4-methylthio) Phenyl) -2-morpholinopropan-1-one BASF Japan Ltd.)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF Japan Ltd.) 2.55 parts Modified silicone oil: KF-351A (polyether modified by Shin-Etsu Chemical Co., Ltd.) )
0.95 parts surfactant: EMULGEN 404 (polyoxyethylene oleyl ether Kao Corporation)
0.26 parts Organic solvent: methyl ethyl ketone 100 parts The solid content concentration of the coating solution for forming the above hard coat layer 1 is 50% by mass, and the solid content ratio of silicon dioxide particles to the total solid content is 47.3% by mass .

Coating and curing treatment
The above-prepared hard coat layer 1 forming coating solution is filtered through a polypropylene filter with a pore diameter of 0.4 μm, and then coated on a TAC film using a wet coater under the condition that the layer thickness after drying becomes 4 μm. After drying at a constant rate drying zone temperature of 80 ° C. and a reduction rate drying zone temperature of 80 ° C., the hard coat layer 1 is cured under a condition of 1.0 J / cm ² using a high pressure mercury lamp under the atmosphere. It formed.

  As a result of measuring the silicon content rate and the silicon dioxide particle content rate (mass%) by the below-mentioned XPS method, the surface area T (thickness 1/10) of the surface side in contact with the gas barrier layer is formed here In the above, the silicon dioxide particle content 2 (mass%) is 48.2 mass%, and the silicon dioxide particle content 1 (mass%) in the surface area B in contact with the TAC film as the resin substrate is 46. At 4% by mass, the content difference ΔC between the silicon dioxide particle content 2 (mass%) and the silicon dioxide particle content 1 (mass%) (silicon dioxide particle content 2-silicon dioxide particle content 1) is 1. It was 8% by mass.

  The silicon dioxide particle content was measured according to the following method.

<Measurement of silicon dioxide particle content>
The silicon dioxide particle content 2 (mass%) in the surface area T and the surface on the resin substrate surface side of a sample in which the hard coat layer is formed on the TAC film using the coating solution for forming the hard coat layer 1 The silicon dioxide particle content rate 1 (mass%) in the region B is a combination of X ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon to expose the inside of the hard coat layer. It measured by the method of performing surface composition analysis one by one.

The content of silicon dioxide particles (SiO ₂ ) calculated from the silicon element content in the surface area T (3T) and the surface area B (3B) in the layer thickness direction of the hard coat layer, and the mass of the hard coat layer in the area The silicon dioxide particle content 1 and the silicon dioxide particle content 2 were measured. The content of silicon element and the content of silicon oxide particles (SiO ₂ ) determined thereby in the region concerned are the surface of the hard coat layer calculated from the relationship between the etching rate and the etching time adopted in the measurement of the XPS depth profile It calculated by adopting the distance from.

  In addition, the mass of the surface area T (3T) and the surface area B (3B) is in the surface area T (3T) and the surface area B (3B) while trimming the hard coat layer in the horizontal direction by the ultrathin section method. It was determined by measuring the total mass of the corresponding thin film in the range of 0.1T.

  As a result of measurement according to the above method, in the surface area T (layer thickness: 0.4 μm) on the upper surface side of the hard coat layer 1, the average content 2 (mass%) of silicon dioxide particles is 48.2 mass%, TAC The average content 1 of silicon dioxide particles in the surface area B (layer thickness: 0.4 μm) in contact with the film is 46.4% by mass, and the content difference ΔC (silicon dioxide particles content 2-dioxide The silicon particle content 1) was 1.8% by mass.

  Specific conditions of the XPS measurement method are as follows.

Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film conversion value): 0.05 nm / sec
Etching interval (SiO ₂ conversion value): 10 nm
X-ray photoelectron spectrometer: manufactured by Thermo Fisher Scientific, model name "VG Theta Probe"
Irradiated X-ray: Single crystal spectroscopy AlKα
X-ray spots and their sizes: 800 × 400 μm oval (formation of first gas barrier layer: discharge plasma treatment method)
Then, the first gas barrier layer 1 was formed on the hard coat layer 1 according to the following method.

  Using the discharge plasma processing apparatus capable of forming a discharge space between the rollers to which the magnetic field having the configuration described in FIG. 5 described above is applied, using the TAC film on which the hard coat layer 1 is formed, a film substrate (F The TAC film on which the above hard coat layer is formed is mounted, and the first gas barrier layer 1 is formed with a thickness of 300 nm on the hard coat layer of the TAC film under the following film forming conditions (plasma CVD conditions) did. The method of forming the first gas barrier layer 1 is referred to as a CVD method 1.

<Deposition conditions>
Feed gas (hexamethyldisiloxane, HMDSO) supply rate: 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3 Pa
Applied power from plasma power supply: 0.8 kW
Power supply frequency for plasma generation: 70 kHz
Film transport speed: 0.8 m / min
The carbon atom, silicon atom and oxygen atom profiles of the first gas barrier layer 1 prepared above are measured by the XPS method, and as a result, they are element profiles shown in FIG. It confirmed that all the conditions of 1)-(4) were satisfy | filled.

(Formation of second gas barrier layer: excimer method)
The second gas barrier layer 1 having a thickness of 300 nm was formed on the first gas barrier layer 1 of the produced TAC film according to the PHPS-excimer method, to produce the gas barrier film 1. This film formation method is referred to as the PHPS-excimer method (in Table 1, simply described as the excimer method).

Preparation of Coating Solution for Forming Polysilazane Layer
A 10% by mass dibutyl ether solution of perhydropolysilazane (PHPS, AQUAMICA NN 120-10, non-catalytic type, manufactured by AZ Electronic Materials, Inc.) was used as a coating liquid for forming a polysilazane layer.

<Formation of polysilazane layer>
The coating solution for forming the polysilazane layer prepared above is applied with a wireless bar so that the (average) layer thickness after drying is 300 nm, and treated for 1 minute in an atmosphere at a temperature of 85 ° C. and a relative humidity of 55%. It was dried and further held for 10 minutes in an atmosphere of temperature 25 ° C. and relative humidity 10% (dew point temperature −8 ° C.) for dehumidifying treatment to form a polysilazane layer.

<Formation of gas barrier layer: silica conversion treatment of polysilazane layer by ultraviolet light>
Subsequently, with respect to the formed polysilazane layer, the following ultraviolet device was installed in a vacuum chamber, the pressure in the device was adjusted, and silica conversion treatment was performed.

<UV irradiation device>
Device: Excimer irradiation device manufactured by M.D.COM MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filling gas: Xe
<Reforming conditions>
The resin base material 2 with a conductive layer on which a polysilazane layer fixed on an operation stage was formed was subjected to a modification treatment under the following conditions to form a gas barrier layer, and a gas barrier film 5 was produced.

Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1 mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer lamp irradiation time: 5 seconds [Preparation of gas barrier film 2]
A gas barrier film 2 was produced in the same manner as in the production of the gas barrier film 1 except that the method for forming the hard coat layer was changed to the following method.

(Formation of hard coat layer 2)
Hard coat layer 2A and hard coat layer 2B were laminated in this order on the resin base according to the following method to form hard coat layer 2 composed of two layers.

Preparation of Coating Solution for Forming Hard Coat Layer 2A
The following constituent materials were sequentially added, mixed and dissolved to prepare a coating solution for forming a hard coat layer 2A.

Silicon dioxide particles: 51.3 parts of non-surface modified silica (average particle diameter: 6 nm, manufactured by Nissan Chemical Co., Ltd., colloidal silica Snowtex AK) Binder resin 1: Urethane acrylate (UA-1100H-LC, manufactured by Shin-Nakamura Chemical Co., Ltd.) 26.4 Part Binder resin 2: Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 16.9 parts Alkylphenone photopolymerization initiator 1: Irgacure 907 (2-methyl-1- (4-methylthio) Phenyl) -2-morpholinopropan-1-one BASF Japan Ltd.)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF Japan Ltd.) 2.55 parts Modified silicone oil: KF-351A (polyether modified by Shin-Etsu Chemical Co., Ltd.) )
0.95 parts surfactant: EMULGEN 404 (polyoxyethylene oleyl ether Kao Corporation)
0.26 parts Organic solvent: methyl ethyl ketone 100 parts The solid content concentration of the coating solution for forming the hard coat layer 2A is 50% by mass, and the solid content ratio of silicon dioxide particles to the total solid content is 51.3% by mass .

Preparation of Coating Solution for Forming Hard Coat Layer 2B
The following constituent materials were sequentially added, mixed and dissolved to prepare a coating solution for forming a hard coat layer 2B.

Silicon dioxide particles: non-surface modified silica (average particle diameter 6 nm, 43.3 parts of Nissan Chemical Co., Ltd. colloidal silica Snowtex AK) Binder resin 1: Urethane acrylate (UA-1100H-LC, Shin-Nakamura Chemical Co., Ltd.) 30.4 Part Binder resin 2: Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 20.9 parts Alkylphenone photopolymerization initiator 1: Irgacure 907 (2-methyl-1- (4-methylthio) Phenyl) -2-morpholinopropan-1-one BASF Japan Ltd.)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF Japan Ltd.) 2.55 parts Modified silicone oil: KF-351A (polyether modified by Shin-Etsu Chemical Co., Ltd.) )
0.95 parts surfactant: EMULGEN 404 (polyoxyethylene oleyl ether Kao Corporation)
0.26 parts Organic solvent: methyl ethyl ketone 100 parts The solid content concentration of the coating solution for forming the hard coat layer 2B is 50% by mass, and the solid content ratio of silicon dioxide particles to the total solid content is 43.3% by mass .

Coating and curing treatment
The above-prepared coating solution for forming hard coat layer 2A and the coating solution for forming hard coat layer 2B are filtered with a polypropylene filter having a pore diameter of 0.4 μm, respectively, and then the lower portion using a coater capable of double layer simultaneous multilayer coating The coating solution for hard coat layer 2B formation and the coating solution for hard coat layer 2A formation on the top are supplied and coated on the TAC film under the condition that the layer thickness after drying becomes 2 μm, respectively, and then the constant rate drying is performed. The drying is performed under drying conditions of a section temperature of 80 ° C. and a reduction rate drying section temperature of 80 ° C., followed by curing under a condition of 1.0 J / cm ² using a high pressure mercury lamp under the atmosphere to obtain a hard coat layer 2A and Formed 2B.

  In the surface area T on the side of the hard coat layer 2A formed in contact with the gas barrier layer (area with a thickness of 0.4 μm from the surface with respect to the total layer thickness of 4 μm of the hard coat layer) The silicon dioxide particle content 1 (mass%) in the surface area B of the hard coat layer 2B which is 51.5 mass% (mass%) and is in contact with the TAC film which is a resin base material is 43.1 mass% The difference in content ΔC between silicon dioxide particle content 2 (mass%) and silicon dioxide particle content 1 (mass%) (silicon dioxide particle content 2-silicon dioxide particle content 1) is 8.4 mass% there were.

[Preparation of gas barrier film 3]
In the preparation of the gas barrier film 1, a gas barrier film 3 was prepared in the same manner as the hard coat layer 1 except that the hard coat layer 3 was formed according to the following method.

(Formation of hard coat layer 3)
The hard coat layer 3 was formed on the corona-treated TAC film using a coating solution for forming a hard coat layer 3 composed of the following additives.

Preparation of Coating Solution for Forming Hard Coat Layer 3
The following constituent materials were sequentially added, mixed and dissolved to prepare a coating solution for forming a hard coat layer 3.

Silicon dioxide particles: Surface-modified silica (average particle size 12 nm ELCOM V-8804 Silica fine particles having (meth) acryloyl group on the particle surface manufactured by JGC Corporation)
59.6 parts Binder resin 1: Urethane acrylate (UA-1100H-LC, manufactured by Shin-Nakamura Chemical Co., Ltd.) 22.7 parts Binder resin 2: Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 12.3 parts alkylphenone photopolymerization initiator 1: Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one manufactured by BASF Japan Ltd.)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF Japan Ltd.) 2.55 parts Modified silicone oil: KF-351A (polyether modified by Shin-Etsu Chemical Co., Ltd.) )
0.95 parts surfactant: EMULGEN 404 (polyoxyethylene oleyl ether Kao Corporation)
0.26 parts Organic solvent 1: methyl ethyl ketone (boiling point: 79 ° C.) 20 parts Organic solvent 2: propylene glycol monomethyl ether (boiling point: 120 ° C.) 80 parts The solid content concentration of the coating solution for forming the hard coat layer 3 is 50% by mass The solid content ratio of silicon dioxide particles (surface modified silica particles) to the total solid content is 59.6% by mass.

Coating and curing treatment
The above-prepared hard coat layer 3 forming coating solution is filtered through a polypropylene filter having a pore size of 0.4 μm, and then coated on a TAC film using a wet coater under the condition that the layer thickness after drying becomes 4 μm. After drying under slow drying conditions of constant rate drying zone temperature 65 ° C and decreasing rate drying zone temperature 65 ° C, using a high pressure mercury lamp under the atmosphere, cure under the condition of 1.0 J / cm ² to obtain hard The coat layer 3 was formed.

  As a result of measuring the silicon content rate and the silicon dioxide particle content rate (mass%) by the XPS method, the hard coat layer 3 formed here has a surface area T (thickness 1/10) on the side in contact with the gas barrier layer The silicon dioxide particle content rate 2 (mass%) is 71.2 mass%, and the silicon dioxide particle content rate 1 (mass%) in the surface area B in contact with the TAC film as the resin substrate is 47.8 mass % Difference in content between silicon dioxide particle content 2 (mass%) and silicon dioxide particle content 1 (mass%) ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1): 23.4 mass %Met.

[Preparation of gas barrier film 4]
In the production of the gas barrier film 3 described above, the first method of forming the gas barrier layer is replaced with the CVD method 1 using a discharge plasma processing apparatus capable of forming a discharge space between rollers to which a magnetic field is applied. A gas barrier film 4 was produced in the same manner except that the first gas barrier layer 2 having a uniform composition was formed using a parallel flat type electrode according to the method of 5.

(Formation of gas barrier layer 2: CVD method 2)
A gas barrier layer 2 with a thickness of 300 nm was formed by plasma discharge according to the following conditions. This film formation method is referred to as CVD method 2.

<Mixed Gas Composition for Forming Gas Barrier Layer 2>
Discharge gas: nitrogen gas 94.9% by volume
Thin film forming gas: Tetraethoxysilane 0.5% by volume
Additive gas: oxygen gas 5.0% by volume
<Deposition condition of gas barrier layer 2)
First electrode side Power supply type 80 kHz
Frequency 80kHz
Power density 8 W / cm ²
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl industry 13.56 MHz CF-5000-13M
Frequency 13.56 MHz
Power density 10 W / cm ²
Electrode temperature 90 ° C
The first gas barrier layer 2 formed above has a substantially uniform elemental composition (Si, C, O) in the layer, and satisfies all the conditions (1) to (4) defined in claim 5 It was not.

[Preparation of gas barrier film 5]
A gas barrier film 5 was produced in the same manner as in the preparation of the gas barrier film 3 except that the hard coat layer 4 was formed by changing the coating and curing treatment conditions when forming the hard coat layer 3 as follows.

(Formation of Hard Coat Layer 4: Coating and Curing Conditions)
The hard coat layer 3 forming coating solution used for producing the gas barrier film 3 is filtered with a polypropylene filter having a pore size of 0.4 μm, and then the layer thickness after drying becomes 4 μm using a wet coater. After applying on a TAC film, after drying under rapid drying conditions of constant rate drying zone temperature 85 ° C and decreasing rate drying zone temperature 85 ° C, using a high pressure mercury lamp under the atmosphere, 1.0 J / cm ² It hardened | hardened on conditions and the hard-coat layer 4 was formed.

  As a result of measuring the silicon content rate and the silicon dioxide particle content rate (mass%) by the XPS method, the hard coat layer 4 formed here has a surface area T (thickness 1/10) on the side in contact with the gas barrier layer The silicon dioxide particle content rate 2 (mass%) is 65.3 mass%, and the silicon dioxide particle content rate 1 (mass%) in the surface area B in contact with the TAC film as the resin substrate is 54.1 mass % Difference in content between silicon dioxide particle content 2 (mass%) and silicon dioxide particle content 1 (mass%) ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) %Met.

[Preparation of gas barrier film 6]
A gas barrier film 6 was produced in the same manner as in the preparation of the gas barrier film 3 except that the hard coat layer 5 was formed by changing the coating and curing conditions when forming the hard coat layer 3 as follows.

(Formation of hard coat layer 5: application and curing conditions)
The hard coat layer 3 forming coating solution used for producing the gas barrier film 3 is filtered with a polypropylene filter having a pore size of 0.4 μm, and then the layer thickness after drying becomes 4 μm using a wet coater. After being applied on a TAC film, after drying under drying conditions of constant rate drying zone temperature 75 ° C. and decreasing rate drying zone temperature 75 ° C., using a high pressure mercury lamp under the atmosphere, a condition of 1.0 J / cm ² The hard coat layer 5 was formed.

  As a result of measuring the silicon content rate and the silicon dioxide particle content rate (mass%) by the XPS method, the hard coat layer 4 formed here has a surface area T (thickness 1/10) on the side in contact with the gas barrier layer The silicon dioxide particle content 2 (mass%) is 68.8 mass%, and the silicon dioxide particle content 1 (mass%) in the surface region B in contact with the TAC film as the resin substrate is 50.3 mass % Difference in content between silicon dioxide particle content 2 (mass%) and silicon dioxide particle content 1 (mass%) ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) is 18.5 mass %Met.

[Preparation of gas barrier film 7]
In the preparation of the gas barrier film 3, the surface modified silica 1 used in the formation of the hard coat layer 3 is the same as the surface modified silica 1 except that the following surface modified silica 2 is used in place of ELCOM V-8804. A gas barrier film 7 was produced.

Surface modified silica 2: Aerosil R711 (manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 12 nm, fine silica particles having (meth) acryloyl group on the particle surface)
[Preparation of gas barrier film 8]
A gas barrier film 8 was produced in the same manner as in the production of the gas barrier film 3 except that the second gas barrier layer was not formed.

[Preparation of gas barrier film 9]
A gas barrier film 9 was produced in the same manner as in the production of the gas barrier film 3 except that the hard coat layer 3 was changed to the following hard coat layer 7.

(Formation of hard coat layer 7)
A hard coat layer 7 was formed on the corona-treated TAC film using a coating solution for forming a hard coat layer 7 composed of the following additives.

Preparation of Coating Solution for Forming Hard Coat Layer 7
The following constituent materials were sequentially added, mixed and dissolved to prepare a coating solution for forming a hard coat layer 7.

Silicon dioxide particles: non-surface modified silica (average particle diameter 6 nm, 47.3 parts of colloidal silica Snowtex AK manufactured by Nissan Chemical Industries, Ltd.) binder resin 1: urethane acrylate (UA-1100H-LC manufactured by Shin-Nakamura Chemical Co., Ltd.) 28.4 Part Binder resin 2: Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 18.9 parts Alkylphenone photopolymerization initiator 1: Irgacure 907 (2-methyl-1- (4-methylthio) Phenyl) -2-morpholinopropan-1-one BASF Japan Ltd.)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF Japan Ltd.) 2.55 parts Modified silicone oil: KF-351A (polyether modified by Shin-Etsu Chemical Co., Ltd.) )
0.95 parts surfactant: EMULGEN 404 (polyoxyethylene oleyl ether Kao Corporation)
0.26 parts Organic solvent: methyl ethyl ketone (boiling point: 79 ° C.) 80 parts High boiling point solvent: HBS1 Propylene glycol (boiling point: 188 ° C.) 20 parts The solid content concentration of the coating liquid for forming the hard coat layer 7 is 60 mass% The solid content ratio of silicon dioxide particles to the total solid content is 39.4% by mass. In addition, in the hard-coat layer after drying, since propylene glycol (boiling point: 188 degreeC) which is a high boiling point solvent exists, it is added to calculation of a total solid.

Coating and curing treatment
The above-prepared coating solution for forming hard coat layer 7 is filtered with a polypropylene filter having a pore diameter of 0.4 μm, and then coated on a TAC film under the condition that the layer thickness after drying becomes 4 μm using a wet coater. After drying at a constant rate drying zone temperature of 65 ° C. and a reduction rate drying zone temperature of 65 ° C., the hard coat layer 7 is cured under the condition of 1.0 J / cm ² using a high pressure mercury lamp under the atmosphere. It formed.

  As a result of measuring the silicon content rate and the silicon dioxide particle content rate (mass%) by the below-mentioned XPS method, the surface area T (thickness 1/10) of the surface side in contact with the gas barrier layer is formed here In the above, the silicon dioxide particle content 2 (mass%) is 49.8 mass%, and the silicon dioxide particle content 1 (mass%) in the surface region B in contact with the resin base material TAC film is 28. The content difference ΔC between the silicon dioxide particle content 2 (mass%) and the silicon dioxide particle content 1 (mass%) at 4% by mass (silicon dioxide particle content 2-silicon dioxide particle content 1) is 21. It was 4% by mass.

[Preparation of gas barrier film 10]
In the production of the gas barrier film 9 described above, the first gas barrier layer is formed by a gas instead of the CVD method 1 using a discharge plasma processing apparatus capable of forming a discharge space between rollers to which a magnetic field is applied. A gas barrier film 10 was produced in the same manner except that the first bus barrier layer having a uniform composition was formed by the CVD method 2 used for producing the barrier film 4.

[Preparation of gas barrier film 11]
In the preparation of the gas barrier film 9 described above, the gas barrier film was prepared in the same manner except that the high boiling point solvent (HBS1: propylene glycol (boiling point: 188 ° C.)) used for forming the hard coat layer 3 was used and Film 11 was produced.

HBS2: diethylene glycol monomethyl ether (boiling point: 194 ° C)
[Preparation of gas barrier film 12]
A gas barrier film 12 was produced in the same manner as in the production of the gas barrier film 9 except that the second gas barrier layer was not formed.

[Preparation of gas barrier film 13]
In the preparation of the gas barrier film 3, a gas barrier film is similarly prepared except that the hard coat layer 9 is formed by using the following hard coat layer 9 forming coating solution instead of the hard coat layer 3 forming coating solution. 13 was produced.

Preparation of Coating Solution for Forming Hard Coat Layer 9
The following constituent materials were sequentially added, mixed and dissolved to prepare a coating solution for forming a hard coat layer 9.

Silicon dioxide particles: Surface-modified silica (average particle size 12 nm ELCOM V-8804 Silica fine particles having (meth) acryloyl group on the particle surface manufactured by JGC Corporation)
59.6 parts Binder resin 1: Urethane acrylate (UA-1100H-LC, manufactured by Shin-Nakamura Chemical Co., Ltd.) 22.7 parts Binder resin 2: Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 12.3 parts alkylphenone photopolymerization initiator 1: Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one manufactured by BASF Japan Ltd.)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF Japan Ltd.) 2.55 parts Modified silicone oil: KF-351A (polyether modified by Shin-Etsu Chemical Co., Ltd.) )
0.95 parts surfactant: EMULGEN 404 (polyoxyethylene oleyl ether Kao Corporation)
0.26 parts Organic solvent 1: methyl ethyl ketone (boiling point: 79 ° C.) 80 parts Organic solvent 2: HBS 1 propylene glycol (boiling point: 188 ° C.) 20 parts [Preparation of gas barrier film 14]
In the preparation of the gas barrier film 3 described above, the following five types of coating solutions for forming a hard coat layer are used instead of the hard coat layer 3, and in the configuration illustrated in FIG. A gas barrier film 14 was produced in the same manner except that a hard coat layer (unit) 10 composed of five layers having the above was formed.

The hard coat layer coating solution for forming each layer is changed to the following amount of surface modification silica content with respect to the hard coat layer 3 forming coating solution used for producing the gas barrier film 3, and the increase or decrease thereof is Hard coating layer coating liquid for forming the first layer (3-1B in FIG. 4) was prepared with the same amount of binder resin and the same as the other additive materials: Surface modified silica content = 53% by mass
Hard coat layer coating solution for forming the second layer (3-2B in FIG. 4): Surface modified silica content = 56% by mass
Hard coat layer coating solution for forming the third layer (3-3B in FIG. 4): Surface modified silica content = 59% by mass
Hard coat layer coating solution for forming the fourth layer (3-4B in FIG. 4): Surface modified silica content = 62% by mass
Hard coat layer coating solution for forming the fifth layer (3-5B in FIG. 4): Surface modified silica content = 68% by mass
Coating and curing treatment
The above-prepared hard coat layer forming coating solution is filtered with a polypropylene filter having a pore size of 0.4 μm, and then a hard coat layer forming for the first layer formation is applied from the bottom using a coater capable of applying five layers simultaneously. Solution to a fifth layer formation hard coat layer coating solution on a TAC film under the conditions that the layer thickness of each layer after drying is 0.8 μm and the total layer thickness is 4 μm; After drying at a temperature reduction rate of 75 ° C. and a reduction rate drying zone temperature of 75 ° C., a hard coat layer 10 was formed by curing under the condition of 1.0 J / cm ² using a high pressure mercury lamp under the atmosphere.

  As a result of measuring the silicon content rate and the silicon dioxide particle content rate (mass%) by the XPS method, the hard coat layer 10 formed here shows that the surface region T (surface) in the fifth layer which is the side in contact with the gas barrier layer Surface region B (the TAC film surface) in which the silicon dioxide particle content rate 2 (mass%) is 72.5 mass% and which is in contact with the TAC film as the resin substrate Silicon dioxide particle content 1 (mass%) in the range of 400 nm is 51.3 mass%, and the content difference ΔC between silicon dioxide particle content 2 (mass%) and silicon dioxide particle content 1 (mass%) The (silicon dioxide particle content 2-silicon dioxide particle content 1) was 21.2% by mass.

[Preparation of gas barrier film 15]
A gas barrier film 15 was produced in the same manner as in the production of the gas barrier film 14 except that the second gas barrier layer was not formed.

[Preparation of gas barrier film 16]
In the production of the gas barrier film 14 described above, the first gas barrier layer is formed by a gas instead of the CVD method 1 using a discharge plasma processing apparatus capable of forming a discharge space between rollers to which a magnetic field is applied. A gas barrier film 16 was produced in the same manner except that the barrier film 4 was formed by the CVD method 2 used for the production of the barrier film 4.

[Preparation of gas barrier film 17]
In the preparation of the gas barrier film 1 described above, silicon dioxide particle concentrations are obtained in the step-like concentration configuration illustrated in FIG. 3 using the following five types of hard coat layer forming coating solutions in place of the hard coat layer 1 A gas barrier film 14 was produced in the same manner except that a hard coat layer (unit) 11 composed of five different layers was formed.

  The hard coat layer coating solution for forming each layer is changed in the colloidal silica content to the following addition amount with respect to the hard coat layer 1 forming coating solution used for producing the gas barrier film 1, and the increase or decrease thereof is The amount of binder resin was prepared, and the other additive materials were the same.

Hard coat layer coating solution for forming the first layer (3-1A in FIG. 3): Colloidal silica content = 35% by mass
Hard coat layer coating solution for forming the second layer (3-2A in FIG. 3): Colloidal silica content = 39% by mass
Hard coat layer coating solution for forming the third layer (3-3A in FIG. 3): Colloidal silica content = 44% by mass
Hard coat layer coating solution for forming the fourth layer (3-4A in FIG. 3): Colloidal silica content = 49% by mass
Hard coat layer coating solution for forming the fifth layer (3-5A in FIG. 3): Colloidal silica content = 54% by mass
Coating and curing treatment
The above-prepared hard coat layer forming coating solution is filtered with a polypropylene filter having a pore size of 0.4 μm, and then a hard coat layer forming for the first layer formation is applied from the bottom using a coater capable of applying five layers simultaneously. Solution to a fifth layer formation hard coat layer coating solution on a TAC film under the conditions that the layer thickness of each layer after drying is 0.8 μm and the total layer thickness is 4 μm; After drying at a temperature reduction rate of 75 ° C. and a reduction rate drying zone temperature of 75 ° C., a hard coat layer 11 was formed by curing under the condition of 1.0 J / cm ² using a high pressure mercury lamp under the atmosphere.

  As a result of measuring the silicon content rate and the silicon dioxide particle content rate (mass%) by the XPS method, the hard coat layer 11 formed here shows that the surface region T in the fifth layer which is the surface side in contact with the gas barrier layer Surface region B (the TAC film surface) in the first layer in which the silicon dioxide particle content 2 (mass%) is 54.8 mass% and the resin base material is in contact with the TAC film) Silicon dioxide particle content 1 (mass%) in the range of 400 nm is 34.1 mass%, and the content difference ΔC between silicon dioxide particle content 2 (mass%) and silicon dioxide particle content 1 (mass%) The (silicon dioxide particle content 2-silicon dioxide particle content 1) was 20.7% by mass.

[Preparation of gas barrier film 18]
In the preparation of the gas barrier film 9 described above, the following five types of coating solutions for forming a hard coat layer are used in place of the hard coat layer 7, and in the configuration illustrated in FIG. A gas barrier film 18 was produced in the same manner except that the hard coat layer (unit) 12 composed of five layers having the above was formed.

  The hard coat layer coating solution for forming each layer is changed to the following addition amount of colloidal silica content to the hard coat layer 7 forming coating solution used for producing the gas barrier film 9, and the increase or decrease thereof is The amount of binder resin was prepared, and the other additive materials were the same.

Hard coat layer coating solution for forming the first layer (3-1B in FIG. 4): Colloidal silica content = 30% by mass
Hard coat layer coating solution for forming the second layer (3-2B in FIG. 4): Colloidal silica content = 34% by mass
Hard coat layer coating solution for forming the third layer (3-3B in FIG. 4): Colloidal silica content = 38% by mass
Hard coat layer coating solution for forming the fourth layer (3-4B in FIG. 4): Colloidal silica content = 42% by mass
Hard coat layer coating solution for forming the fifth layer (3-5B in FIG. 4): Colloidal silica content = 46% by mass
Coating and curing treatment
The above-prepared hard coat layer forming coating solution is filtered with a polypropylene filter having a pore size of 0.4 μm, and then a hard coat layer forming for the first layer formation is applied from the bottom using a coater capable of applying five layers simultaneously. Solution to a fifth layer formation hard coat layer coating solution on a TAC film under the conditions that the layer thickness of each layer after drying is 0.8 μm and the total layer thickness is 4 μm; After drying at a reduction rate drying zone temperature of 75 ° C. and a high-pressure mercury lamp under the atmosphere, the hard coat layer 12 was formed by curing under a condition of 1.0 J / cm ² .

  As a result of measuring the silicon content rate and the silicon dioxide particle content rate (mass%) by the XPS method, the hard coat layer 12 formed here shows that the surface region T in the fifth layer which is the surface side in contact with the gas barrier layer Surface region B (the TAC film surface) in the first layer in which the silicon dioxide particle content 2 (mass%) is 49.1 mass% and the resin base material is in contact with the TAC film) Silicon dioxide particle content 1 (mass%) in the range of 400 nm is 28.4 mass%, and the content difference ΔC between silicon dioxide particle content 2 (mass%) and silicon dioxide particle content 1 (mass%) The (silicon dioxide particle content 2-silicon dioxide particle content 1) was 20.7% by mass.

[Preparation of gas barrier film 19]
In the production of the gas barrier film 18 described above, the first gas barrier layer is formed by a gas instead of the CVD method 1 using a discharge plasma processing apparatus capable of forming a discharge space between rollers to which a magnetic field is applied. A gas barrier film 19 was produced in the same manner except that the barrier film 4 was formed by the CVD method 2 used for the production of the barrier film 4.

[Preparation of gas barrier films 20 and 21]
In the preparation of the gas barrier film 3, the gas barrier films 20 and 21 were prepared in the same manner except that the resin substrate was replaced with a TAC film, and the following PET film and COP film were used respectively.

PET film: biaxially stretched polyethylene terephthalate film, manufactured by Teijin DuPont Films KEL 86 W film thickness: 125 μm
COP film: cycloolefin polymer film, manufactured by Nippon Zeon, Zeonea ZF 14 film thickness: 100 μm
[Preparation of gas barrier film 22]
A gas barrier film 22 was produced in the same manner as in the production of the gas barrier film 3 except that the hard coat layer 3 was not formed.

[Preparation of gas barrier film 23]
A gas barrier film 23 was produced in the same manner as in the preparation of the hard coat layer 3 used for forming the hard coat layer 3 except that the surface modified silica was removed in the preparation of the gas barrier film 3.

<< Production of Organic EL Device >>
Subsequently, using the gas barrier films 1 to 23 produced above, organic EL elements 101 to 123 were produced according to the following method.

  Each gas barrier film was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus, and the following compound No. 1 was obtained. 10 was placed in a resistance heating boat made of tungsten, and the gas barrier film holder and the heating boat were mounted in a first vacuum tank of a vacuum deposition apparatus. In addition, silver (Ag) was put in a tungsten resistance heating boat and mounted in a second vacuum tank of a vacuum evaporation system.

After reducing the pressure of the first vacuum tank of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, the compound No. 1 was obtained. The heating boat containing 10 was energized to be heated, and the underlayer of the first electrode was provided with a layer thickness of 10 nm at a deposition rate of 0.1 to 0.2 nm / sec. The gas barrier film on which the underlayer was formed was transferred to a second vacuum tank under vacuum, and the second vacuum tank was depressurized to 4 × 10 ⁻⁴ Pa, and then a heating boat containing silver was energized to heat. Thereby, the 1st electrode which consists of silver with a thickness of 8 nm was formed at vapor deposition rate of 0.1-0.2 nm / sec.

Next, after reducing the pressure to a vacuum degree of 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, the following compound HT-1 was deposited at a deposition rate of 0 on the first electrode formed while moving the gas barrier film. Evaporated at 1 nm / sec and provided a hole transport layer (HTL) of 20 nm.

  Next, using the following compound A-3 (blue light emitting dopant), the following compound A-1 (green light emitting dopant), the following compound A-2 (red light emitting dopant) and the following compound H-1 (host compound), Compound A -3 changes the deposition rate so that the content is linear from 35% to 5% in the layer thickness direction, and the compound A-1 and the compound A-2 do not depend on the layer thickness At a deposition rate of 0.0002 nm / sec, the compound H-1 has a gradient concentration of 64.6% to 94.6% in the layer thickness direction so that each has a constant concentration of 0.2% by mass. The deposition rate was changed as described above to form a co-deposited light emitting layer with a layer thickness of 70 nm.

  Then, the following compound ET-1 was vapor-deposited on the light emitting layer to form an electron transporting layer having a layer thickness of 30 nm, and potassium fluoride (KF) was further vapor deposited to form an electron injecting layer having a layer thickness of 2 nm. Furthermore, aluminum was vapor deposited to form a second electrode having a thickness of 110 nm.

  Compound No. 1 used in the formation of each organic functional layer described above. 10, compound HT-1, compounds A-1 to 3, compound H-1, and compound ET-1 are compounds shown below.

Next, a 25 μm thick aluminum foil is used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) is bonded to a single surface of this aluminum foil as a sealing resin layer at a thickness of 20 μm. The stop member was used to overlap the resin base material produced up to the second electrode. At this time, the adhesive-formed surface of the sealing member and the organic functional layer surface of the element were continuously superposed so that the end portions of the lead wires of the first electrode and the second electrode would come out.

  Next, the sample containing the gas barrier film was placed in a decompression apparatus, and held under pressure at 90 ° C. and 0.1 MPa under pressure for 5 minutes in a state where pressure was applied to the superposed sample and the sealing member. Subsequently, the sample containing the gas barrier film was returned to the atmospheric pressure environment, and heated at 120 ° C. for 30 minutes to cure the adhesive.

  The sealing step is performed under atmospheric pressure, under a nitrogen atmosphere having a water content of 1 ppm or less, in accordance with JIS B 9920, with a cleanliness of class 100, a dew point temperature of -80 ° C. or less, an oxygen concentration of 0.8 ppm or less At atmospheric pressure.

  The organic EL elements 101 to 123 were manufactured by the above steps. The area of the light emitting region was 5 cm × 5 cm.

<< Evaluation of gas barrier film and organic EL element >>
[Evaluation of gas barrier film]
(Evaluation of adhesion)
The above-prepared gas barrier films were stored in an environment of 50 ° C. and 80% RH for 1 week in a metal roll-wound state, and then adhesion was evaluated according to the following evaluation method for cross-cut adhesion. .

  For evaluation of cross-cut adhesion, according to the description of JIS K 5600, 5.6 (2004 edition), the gas barrier layer and the hard coat layer are formed on the gas barrier layer side of each gas barrier film with a cutter knife. 100 pieces of 1 mm square cross-cuts that penetrate and reach the resin substrate are attached using a cutter guide with 1 mm intervals, and a cellophane adhesive tape (“Nichiban Co., Ltd.“ CT405AP-18 ”; 18 mm width) is attached to the cut surface After the tape is completely rubbed with an eraser and rubbed from above, the tape is peeled off in the vertical direction to visually confirm how much the gas barrier layer and the hard coat layer remain on the substrate surface, out of 100 The number of peelings was examined, and the adhesion was evaluated according to the following criteria.

5: The number of peelings was 5 or less in the grid test 4: The number of peelings was 6 or more and 10 or less in the grid test 3: The number of peelings was 11 in the grid test The number of peels was 16 or more and 20 or less in the cross-cut test 1: The number of peels was 21 or more in the cross-cut test [Organic EL Evaluation of element]
A current of 1 mA / cm ² was applied to the organic EL elements 101 to 123 to emit light. Then, immediately after the application and as light emission time in an environment of 50 ° C. and 80% RH, the light emission state after continuous light emission for 300 hours and 500 hours is 100 × optical microscope (Molitex Co., Ltd. MS-804, A part of the organic EL element was enlarged and photographed with a lens MP-ZE 25-200). Next, the photographed image was cut into 2 mm squares, and the presence or absence of dark spots was observed for each image. From the observation results, the generation area ratio of dark spots to the light emission area was determined, and the dark spot resistance was evaluated according to the following criteria.

No generation of dark spots is observed at all for the samples after 5: 500 hours of light emission 4: The occurrence of dark spots is not observed at all for the samples after 4 hours of light emission; Occurrence of dark spots is observed (the occurrence area is 0.1% or more and less than 3.0%)
3: A slight dark spot is observed in the sample after 300 hours of light emission (the generation area is 0.1% or more and less than 3.0%)
2: In the sample after luminescence for 300 hours, the occurrence of a distinct dark spot is observed (the occurrence area is 3.0% or more and less than 6.0%)
1: Occurrence of many dark spots is observed in the sample after luminescence for 300 hours (the occurrence area is 6.0% or more)
The results obtained by the above are shown in Table 2.

As is clear from the results described in Table 2, the gas barrier film produced by the method defined in the present invention, compared to the comparative example, shows close adhesion between the layers even when stored for a long time in a high temperature and high humidity environment. There is no deterioration of sex. In addition, it is understood that generation of dark spots due to film peeling and the like in a high temperature and high humidity environment is suppressed by providing the organic EL element with a gas barrier film having such characteristics.

DESCRIPTION OF SYMBOLS 1 gas barrier film 2, F, F1-F4 resin base material 3 hard-coat layer 3-1A-3-5A, 3-1B- 3-5B lamination type hard-coat layer 3T surface area T
3B Surface area B
3U hard coat layer unit 4 gas barrier layer, first gas barrier layer 5 second gas barrier layer 11 delivery roller 12A to 12E, 81 preparation kettle 13, 82 coater 14, 83 drying process 15 ultraviolet irradiation device 17 ultraviolet irradiation lamp DESCRIPTION OF SYMBOLS 18 Ultraviolet rays 21, 22, 23, 24 Conveying roller 30 Plasma CVD manufacturing apparatus 31, 32 Film-forming roller 41 Gas supply pipe 51 Power supply for plasma generation 61, 62 Magnetic field generator 71, 93 Take-up roller 72 Vacuum chamber 73 Vacuum pump 90 Modification step 91 excimer lamp 92 vacuum ultraviolet light 101 organic EL element 116 first electrode 117 organic functional layer unit 117 a hole injection layer 117 b hole transport layer 117 c light emitting layer 117 d electron transport layer 117 e electron injection layer 118 second electrode 119 sealing Deoki Layer 120 sealing member 201 device chamber 204 content difference of the sample stage 206 shielding plate ΔC dioxide particles h emitting light S1 station 1
S2 station 2
S3 station 3

Claims (7)

A method for producing a gas barrier film having at least a hard coat layer and a gas barrier layer on a resin substrate,
The hard coat layer contains at least silicon dioxide particles, and the silicon dioxide particle content 2 (mass%) in the surface area T on the gas barrier layer side of the hard coat layer and the surface area B on the resin substrate side Concentration gradient structure in which the content difference ΔC with silicon dioxide particle content 1 (mass%) (silicon dioxide particle content 2-silicon dioxide particle content 1) is 10 mass% or more and 30.6 mass% or less Have
The hard coat layer satisfies the following condition 1 or 2:
And the gas barrier layer is formed by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied, using a raw material gas containing an organosilicon compound and an oxygen gas. How to make a film.
Condition 1: Silicon dioxide particles contained in the hard coat layer are surface-modified silicon dioxide particles Condition 2: The hard coat layer is a polyhydric alcohol high boiling point solvent having a boiling point of 150 ° C. or higher at normal pressure Containing   The method for producing a gas barrier film according to claim 1, wherein the resin base material is a resin film containing triacetyl cellulose.   The silicon dioxide particle content 2 (mass%) in the surface area T on the gas barrier layer side of the hard coat layer, and the silicon dioxide particle content 1 (mass%) in the surface area B on the resin substrate surface side The content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) of 20% or more and 30.6% or less by mass is set as described in claim 1 or 2. Method for producing a gas barrier film.   The method for producing a gas barrier film according to any one of claims 1 to 3, wherein the hard coat layer contains an active energy ray-curable resin and is formed by a wet coating method. The said gas barrier layer contains a carbon atom, a silicon atom, and an oxygen atom as a constitutent element, It forms so that all of following (1)-(4) may be satisfy | filled. The manufacturing method of the gas barrier film as described in any one of these.
(1) The carbon atom ratio of the gas barrier layer changes continuously in the layer thickness direction within the distance from the surface of the gas barrier layer to 89% of the layer thickness in accordance with the distance from the surface .
(2) The maximum value of the carbon atom ratio of the gas barrier layer is less than 20 at% within the distance from the surface of the gas barrier layer to 89% of the layer thickness in the layer thickness direction.
(3) The carbon atom ratio of the gas barrier layer continuously increases in the layer thickness direction from the surface of the gas barrier layer to 90 to 95% of the layer thickness.
(4) The maximum value of the carbon atom ratio of the gas barrier layer is at least 20 at% within the range of 90 to 95% of the layer thickness from the surface of the gas barrier layer in the layer thickness direction.   The gas barrier film according to any one of claims 1 to 5, wherein the hard coat layer is composed of two or more layers having different silicon dioxide particle contents (% by mass). Manufacturing method.   A polysilazane-containing liquid is applied and dried on the gas barrier layer, and the formed coating film is reformed by irradiating vacuum ultraviolet light having a wavelength of 200 nm or less to form a second gas barrier layer. The manufacturing method of the gas barrier film as described in any one of Claim 1- Claim 6 set to.