JP2015229317A - Production method of gas barrier film, and organic electroluminescence device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a gas barrier film having excellent adhesiveness between a resin substrate and a constituent layer even after stored for a long time in a high-temperature and high-humidity environment, a gas barrier film, and an organic EL device including the gas barrier film and having excellent dark spot resistance.SOLUTION: The production method of a gas barrier film aims to produce a gas barrier film having a hard coat layer and a gas barrier layer on a resin substrate, in which the hard coat layer contains silicon dioxide particles and has such a density gradient structure that a difference between a content percentage 2 of the silicon dioxide particles in a surface region T on the gas barrier layer surface side and a content percentage 1 of the silicon dioxide particles in a surface region B on the resin substrate surface side is 10 mass% or more. The gas barrier layer is formed by a discharge plasma chemical vapor phase growth method using oxygen gas and a raw material gas containing an organic silicon compound, in a system having a discharge space formed between rollers to which a magnetic field is applied.

Description

  The present invention relates to a method for producing a gas barrier film provided with a hard coat layer having an inclined structure having a silicon dioxide particle content, and an organic electroluminescence device comprising the gas barrier film produced by the production method.

  An organic electroluminescence element (hereinafter also referred to as an organic EL element) using an organic material electroluminescence (hereinafter abbreviated as EL) can emit light at a low voltage of several V to several tens V. It is a thin film type complete solid-state device and has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, in recent years, it has attracted attention as a backlight for various displays, a display plate such as a signboard or emergency light, and a surface light emitter such as an illumination light source.

  For the purpose of making the device thin and light and flexible, an organic EL device using a resin substrate as a substrate has been studied. In some cases, a gas barrier film that blocks intrusion of various gases such as water vapor and oxygen may be provided. By providing the organic EL element with the gas barrier film, the influence of harmful gas from the external environment is blocked, and the deterioration of the function of the organic EL element is suppressed.

  The organic EL element having flexibility can maintain a curved surface state as a shape due to its characteristics, but if maintained in such a curved surface state for a long time, in the gas barrier film provided, adhesion deterioration and There is a problem that the gas barrier property is lowered. One of the causes is deterioration of adhesion between the resin base material 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, etc. are laminated, and the curved surface state lasts for a long time, causing cracks in specific constituent layers or bending stress. In this case, it is assumed that peeling occurs due to a difference in expansion / contraction ratio between the resin base material and the constituent layers.

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

  However, the gas barrier film described in Patent Document 1 exhibits excellent properties with respect to bending resistance, but when exposed to a long time in a high temperature and high humidity environment, the metal oxide layer and the inorganic / organic There was a problem that the adhesion between the hybrid polymer layer and the gas barrier property was deteriorated. In addition, since polyethylene terephthalate is applied as a resin base material, there are problems that transparency is slightly low, birefringence (retardation value) is high, and color angle dependency is large.

  For this reason, when a gas barrier film using polyethylene terephthalate as a resin base material is applied to an organic EL element, in addition to the problems such as transparency, birefringence, visibility, etc., the durability of the gas barrier film is lowered. Due to the above, there has been a problem that the light emitting performance of the organic EL element is also deteriorated.

  In Patent Document 2, a gas barrier formed by subjecting a polysilazane film formed by applying a polysilazane-containing liquid to at least one surface side of a resin base material, for example, a PET film, is subjected 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 said that it is possible to provide a gas barrier film that exhibits excellent gas barrier properties, has a short manufacturing time, and is excellent in resin substrate selectivity. However, as described above, there is a problem that the adhesion between the resin base material and the gas barrier layer is not sufficient when exposed to a high temperature and high humidity environment for a long time.

  Furthermore, in Patent Document 1 and Patent Document 2, a PET film or the like is mainly used as the resin base material, but the PET film has the above-described transparency, birefringence, and visibility. In addition to problems such as the above, since the barrier property against moisture etc. is low, when forming a gas barrier film, it is necessary to design the gas barrier layer to be applied in order to exhibit advanced gas barrier performance. The restrictions on the composition of layers and the required quality are increasing.

On the other hand, Patent Document 3 discloses a production method for producing 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. During film formation, foreign particles may be generated in the plasma discharge space, and the generated foreign particles are generated on the surface of the resin substrate used in the film formation, the interface between the resin substrate and the gas barrier layer, or the formed gas barrier layer. There is a problem that it easily adheres to or deposits on the surface. If such foreign particles are present in the gas barrier film, the foreign particles become the starting point when exposed to high-temperature and high-humidity environment for a long time, or when bent and subjected to stretching stress. It has been found that the barrier layer is easily broken, cracked or peeled off, and the gas barrier property is easily deteriorated.

Japanese Patent 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 substrate and the constituent layer (for example, a gas barrier layer) even after being stored for a long time in a high temperature and high humidity environment. A gas barrier film manufacturing method for producing a gas barrier film having excellent properties, a gas barrier film obtained therefrom, and an organic electroluminescence device having the gas barrier film and excellent in failure resistance (dark spot resistance) It is to be.

  As a result of intensive studies in view of the above problems, the present inventor has obtained a gas barrier film production method 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. Containing particles, the silicon dioxide particle content (% by mass) in the hard coat layer has a concentration gradient structure, and the gas barrier layer uses a source gas containing an organosilicon compound and an oxygen gas, A gas barrier film is formed by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied. It can be seen that a method for producing a gas barrier film for producing a gas barrier film having excellent adhesion between the material and the constituent layers can be provided. However, the present invention has been accomplished.

  That is, the said subject of this 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, the silicon dioxide particle content 2 (mass%) in the surface region T on the gas barrier layer surface side of the hard coat layer, and the surface region B on the resin substrate surface side. A concentration gradient structure in which the content difference ΔC (silicon dioxide particle content 2−silicon dioxide particle content 1) with respect to the silicon dioxide particle content 1 (mass%) is 10% by mass or more,
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 source gas containing an organic silicon compound and oxygen gas. A method for producing a film.

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

  3. The silicon dioxide particle content 2 (mass%) in the surface region T on the gas barrier layer side of the hard coat layer, and the silicon dioxide particle content 1 (mass%) in the surface region B on the resin substrate surface side, The method for producing a gas barrier film according to Item 1 or 2, wherein a content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) is 20 mass% or more.

  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 so as 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 continuously changes in the layer thickness direction corresponding to the distance from the surface within a distance range from the surface of the gas barrier layer to 89% of the layer thickness. .

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

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

  6). The method for producing a gas barrier film according to any one of Items 1 to 5, wherein the silicon dioxide particles contained in the hard coat layer are surface-modified silicon dioxide particles.

  7). The gas barrier film according to any one of items 1 to 6, wherein the hard coat layer contains a polyhydric alcohol-based high boiling point solvent having a boiling point of 150 ° C. or higher at normal pressure. Manufacturing method.

  8). The gas barrier film according to any one of items 1 to 7, wherein the hard coat layer is composed of two or more layers having different silicon dioxide particle content (mass%). Manufacturing method.

  9. A polysilazane-containing liquid is applied and dried on the gas barrier layer, and the formed coating film is irradiated with vacuum ultraviolet light having a wavelength of 200 nm or less to form a second gas barrier layer. The method for producing a gas barrier film according to any one of items 1 to 8 above.

  10. An organic electroluminescence device comprising a gas barrier film produced by the method for producing a gas barrier film according to any one of items 1 to 9.

  By the above means of the present invention, a method for producing a gas barrier film that has excellent flatness, has excellent adhesion even after being stored for a long time in a high temperature and high humidity environment, and can maintain high gas barrier properties, and It is possible to provide a gas barrier film obtained and an organic electroluminescence device having the gas barrier film and excellent in failure resistance (dark spot resistance).

  The expression mechanism or action mechanism of the effect of the present invention 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 includes at least silicon dioxide particles (hereinafter also referred to as silica particles) and hard. The silicon dioxide particles in the surface region T on the gas barrier layer surface side with respect to the silicon dioxide particle content 1 (mass%) in the surface region B on the resin base material surface side with respect to the silicon dioxide particle content rate (mass%) in the coating layer The content rate 2 (mass%) is composed of a concentration gradient pattern that increases by 10 mass% or more, and a gas barrier layer is formed by applying a magnetic field using a source gas containing an organosilicon compound and oxygen gas. It is characterized in that it is formed by a discharge plasma chemical vapor deposition method having a discharge space between rollers.

  In the conventional gas barrier film, since the gas barrier layer is formed on the flexible resin base material, the resin base material is bent in a harsh environment, for example, in a high temperature and high humidity environment for a long time. When stored in a bent state, due to the difference in expansion and contraction between the resin substrate and the gas barrier layer, the film peels off at the interface between them, or the gas barrier layer is damaged or cracked due to excessive stress. However, it was a cause of deterioration of gas barrier properties. In addition, when a 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 source gas containing an organic silicon compound and oxygen gas, foreign matter is generated in the plasma discharge space. Particles (particle growth in the discharge space) may occur, 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 the core of the foreign matter failure. It was a cause of deterioration of gas barrier properties.

  In the present invention, based on the above problems, a gas barrier film that has excellent adhesion and can maintain high gas barrier properties even when stored in a bent or curved state for a long time in a high temperature and high humidity environment. As a result of diligent research for development, a hard coat layer containing at least silicon dioxide particles (silica particles) is provided between the resin substrate and the gas barrier layer, and the silicon dioxide particle content in the hard coat layer By providing an inclined structure in (% by mass), especially when the resin base material and the gas barrier layer are subjected to stress due to bending or bending in a high temperature and high humidity environment, the resin base material and the gas barrier layer By compensating for stress and exerting a stress relaxation effect, delamination between layers and film breakdown of gas barrier layers can be drastically reduced. As a result, they can be stored in 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 addition, when a 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 source gas containing an organosilicon compound and oxygen gas as described above, plasma discharge Foreign particles (particle growth in the discharge space) may occur in the space, and the generated foreign particles are deposited on the surface of the resin base material or the formed gas barrier layer. It was a deterioration factor of gas barrier properties, but between the resin base material and the gas barrier layer formed by the above method, the silicon dioxide particle content rate according to the present invention having a large stress relaxation effect has an inclined structure. By providing a hard coat layer, it is possible to alleviate excessive stress concentration starting from the generated foreign matter, and as a result, film breakage and film peeling are effective. It is possible to prevent manner.

Schematic sectional view showing an example of the configuration of the gas barrier film of the present invention The schematic diagram which shows an example of the gradient structure of the silicon dioxide particle content rate in the hard-coat layer based on this invention The schematic diagram which shows an example of the gradient structure of the silicon dioxide particle content rate comprised from the some hard-coat layer based on this invention The schematic diagram which shows another example of the gradient structure of the silicon dioxide particle content rate comprised from the some hard-coat layer based on this invention The schematic diagram which shows an example of a structure of the discharge plasma processing apparatus suitable for formation of the gas barrier layer based 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, Content of silicon dioxide particle content 2 (mass%) in the surface region T on the gas barrier layer surface side of the hard coat layer and silicon dioxide particle content 1 (mass%) in the surface region B on the resin substrate surface side A rate difference ΔC (silicon dioxide particle content 2−silicon dioxide particle content 1) has a concentration gradient structure of 10% by mass or more, and the gas barrier layer includes a source gas containing an organosilicon compound, oxygen gas, And using a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied. This feature is a technical feature common to the inventions according to claims 1 to 10.

  As an embodiment of the present invention, from the viewpoint of more manifesting the intended effect of the present invention, by applying a resin film containing triacetyl cellulose as the resin base material, adhesion to the hard coat layer and bending. This is preferable because the gas barrier film having high resistance and low retardation characteristics can be obtained.

  Further, the silicon dioxide particle content 2 in the surface region T on the gas barrier layer surface side of the hard coat layer according to the present invention is 2 (% by mass), and the silicon dioxide particle content 1 in the surface region B on the resin substrate surface side. By making the content rate difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) with (mass%) 20 mass% or more, more excellent adhesion and failure resistance can be obtained. Is preferable.

  In addition, the hard coat layer according to the present invention contains an active energy ray-curable resin and can be formed by a wet coating method, and a high-quality hard coat layer can be stably formed with simple manufacturing equipment. It is preferable at the point which can do.

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

  In the hard coat layer according to the present invention, it is possible to use surface-modified silicon dioxide particles as the silicon dioxide particles to be contained, so that the content of silicon dioxide particles in the hard coat layer of silicon dioxide particles defined in the present invention The inclined structure is preferable from the viewpoint that it can be stably obtained.

  Further, in the hard coat layer according to the present invention, the concentration of the silicon dioxide particles defined in the present invention in the hard coat layer includes a polyhydric alcohol-based high boiling point solvent having a boiling point of 150 ° C. or higher at normal pressure. This is preferable from the viewpoint of achieving a gradient.

  In addition, in the hard coat layer according to the present invention, it is constituted by two or more layers having different silicon dioxide particle content (mass%), so that the particle content in the silicon dioxide particle layer defined in the present invention This is preferable from the viewpoint of obtaining a concentration gradient.

  Further, a polysilazane-containing liquid is further applied and dried on the gas barrier layer, and the formed coating film is irradiated with vacuum ultraviolet light having a wavelength of 200 nm or less to form a second gas barrier layer. It is preferable from the viewpoint that a more excellent gas barrier property can be realized.

  By providing the organic EL device with a gas barrier film obtained by the method for producing a gas barrier film of the present invention, excellent adhesion and failure resistance even after being stored for a long period of time in a high temperature and high humidity environment, for example, dark An organic EL element having spot resistance can be obtained.

  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 is used with the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit. In the following description, numerals shown in parentheses after each component represent a reference in each figure.

《Basic structure 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 surface side of the resin substrate (2), and the silicon dioxide particle content (mass%) in the layer. ), And the silicon dioxide particle content (% by mass) in the surface region (3T) on the gas barrier layer (4) surface side with respect to the surface region (3B) on the resin substrate (2) surface side is 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 configuration and a source gas containing oxygen and an organic gas on the hard coat layer (3) It has the gas barrier layer (4) formed by. The definition and details of the surface region (3B) on the resin base material (2) surface side and the surface region (3T) on the gas barrier layer (4) surface side in 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 irradiated with vacuum ultraviolet light having a wavelength of 200 nm or less for modification treatment. It can be set as the structure which has the 2nd gas barrier layer (5) formed in this way.

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) were measured by a method according to JIS-K-7129-1992, water vapor permeability (25 ± 0.5 ° C., It is preferable that the gas barrier property is 0.01 g / (m ² · 24 hours) or less at a relative humidity of 90 ± 2%. Moreover, the oxygen permeability measured by the method based on 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 that the gas barrier property is 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 rate 2 (mass) in the surface region T on the gas barrier layer surface side of the hard coat layer. %) And the content difference ΔC (silicon dioxide particle content 2−silicon dioxide particle content 1) in the surface region B on the resin substrate surface side is 10% by mass. It has the above-described concentration gradient structure.

  More preferably, the silicon dioxide particle content 2 (mass%) in the surface region 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 region B on the resin base material surface side. The content difference (silicon dioxide particle content 2-silicon dioxide particle content 1) with respect to (mass%) is 20 mass% or more.

  The method for forming a hard coat layer according to the present invention is not particularly limited, but in the present invention, it contains an active energy ray-curable resin together with silicon dioxide particles, and is preferably formed by a wet coating method. In addition to silicon dioxide particles and active energy ray curable resins, other configurations include 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. 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 diagram showing an example of a gradient structure of silicon dioxide particle content in the hard coat layer according to the present invention.

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

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

When the total thickness of the hard coat layer (3) is hd, as shown in the left diagram of FIG. 2, the depth is from the surface side of the hard coat layer (3) in contact with the resin base material (2). The 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 (% by 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 region B (3B), the silicon content in the surface region B (3B) having a thickness of 0.1 hd is measured by the X-ray photoelectron spectroscopy (abbreviation: XPS) described below. The silicon content is converted into the silicon dioxide (SiO ₂ ) content, and the average value of the silicon dioxide particle content 1 (mass%) is obtained in the surface region B (3B) having a thickness of 0.1 hd.

  Similarly, a region 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 a surface region referred to in the present invention. T (3T), the silicon dioxide particle content (mass%) in the surface region T (3T) is the silicon dioxide particle content 2 (mass%), and X-ray photoelectron spectroscopy (abbreviation: XPS) is the same as above. ) To obtain an average value of silicon dioxide particle content 2 (mass%).

  That is, in the present invention, as shown in the graph on the right side of FIG. 2, the silicon dioxide particle content 1 (mass%) in the surface region B (3B) on the resin base material (2) surface side is described above. 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 increases, specifically, the silicon dioxide particle content 2 (mass%). And a content difference ΔC (silicon dioxide particle content 2−silicon dioxide particle content 1) between the silicon dioxide particle content 1 and the silicon dioxide particle content 1 (mass%) is 10 mass% or more. 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 more preferably within the range of 20 to 30 mass%. It is.

  The silicon dioxide particle content 2 (mass%) in the surface region T (3T) is preferably approximately in the range of 30 to 80 mass%, more preferably in the range of 40 to 70 mass%. Moreover, as silicon dioxide particle content rate 1 (mass%) in the surface area | region B (3B), it is preferable to exist in the range of about 10-50 mass% in general, More preferably, it exists in the range of 15-40 mass%. .

<Measurement of silicon dioxide particle content in hard coat layer: XPS measurement method>
The measurement of the silicon dioxide particle content in the layer thickness direction of the hard coat layer uses X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering with argon or the like to expose the hard coat layer surface in sequence. However, the surface element composition analysis can be performed by so-called XPS depth profile measurement. The silicon element distribution curve 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 silicon distribution curve with the horizontal axis as 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, that is, the layer thickness of the hard coat layer. It is mostly correlated.

In the present invention, the silicon element content in the surface region T (3T) and surface region B (3B) in the layer thickness direction of the hard coat layer is determined, and this is converted into 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 obtained. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

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

  An example of specific conditions for the XPS measurement method is shown below.

Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval <Other methods for measuring silicon dioxide particle content>
In addition to the above-described method, the formed hard coat layer is trimmed in the horizontal direction by the ultrathin slice method, and 0.1 hd corresponding to the surface region T (3T) and the surface region B (3B). After preparing a thin film in the range and measuring its total mass, silicon dioxide is dissolved by dissolving the binder resin with an acid, alkali, or organic solvent, etc., separating and drying the silicon dioxide particles, and measuring the mass. The particle content (% by mass) can also be determined.

<Construction requirements for gas barrier film>
Subsequently, the detail of the specific component of the gas barrier film of this invention is demonstrated sequentially.

[Resin substrate]
The resin substrate applicable to the present invention is not particularly limited, but is preferably a transparent resin film having flexibility. Examples of the resin component include polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate. Polyester such as (abbreviation: PEN), polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose (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, polyetherketone, polyimide, polyethersulfone (abbreviation: PES), polyphenylene sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate And cycloolefin-based resins such as Arton (trade name, manufactured by JSR) or Apel (trade name, manufactured by Mitsui Chemicals).

  In the present invention, among the above resin base materials, it is possible to set a high adhesion and bending resistance with the hard coat layer, and from the point that it is possible to obtain a gas barrier film with low retardation characteristics, It is particularly preferable to apply a resin film containing triacetyl cellulose.

  The triacetyl cellulose (TAC) applicable to the present invention preferably has a degree of acetyl group substitution 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.

  Moreover, it is preferable that the film thickness of the triacetylcellulose film which concerns on this invention exists in the range of 15-150 micrometers, More preferably, it exists in the range of 30-120 micrometers, More preferably, it exists in the range of 40-100 micrometers. is there. If the film thickness of the triacetyl cellulose film is 15 μm or more, the film has sufficient rigidity and can be obtained with excellent handleability, and if it is 150 μm or less, a thin gas barrier film can be easily produced.

  The number average molecular weight (Mn) of the triacetyl cellulose is preferably in the range of 125,000 to 155000, and more preferably in the range of 129000 to 152000. Moreover, it is preferable that a weight average molecular weight (Mw) exists in the range of 200000-300000.

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

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three columns manufactured by Showa Denko KK)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 500 to 2800000 13 calibration curves were used. The 13 samples are preferably used at approximately equal intervals.

  The raw material used for the production of triacetyl cellulose is not particularly limited, and examples thereof include cotton linters, wood pulp (derived from conifers and hardwoods), kenaf and the like. Moreover, the triacetyl cellulose obtained from them can be mixed and used in arbitrary ratios, respectively. The triacetyl cellulose according to the present invention can be synthesized with reference to the methods described in, for example, JP-A Nos. 10-45804 and 2005-281645.

  The triacetyl cellulose according to the present invention can be produced by a conventionally known general film forming method. For example, an unstretched triacetyl cellulose film that is substantially amorphous and not oriented is manufactured by melting a raw material triacetyl cellulose resin with an extruder, extruding it with an annular die or a T-die, and quenching. Can do. In addition, the triacetyl cellulose resin used as a material is dissolved in an organic solvent, cast on an endless metal resin support, dried, and peeled off. A stretched triacetyl cellulose film can also be produced.

  The triacetyl cellulose film is conveyed (vertical axis, MD) by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, and tubular simultaneous biaxial stretching. ) Direction, or a stretched triacetylcellulose film can be produced by stretching in the direction perpendicular to the conveying direction of the triacetylcellulose film (horizontal axis, TD). The draw ratio in this case can be selected as appropriate, but is preferably in the range of 2 to 10 times in the vertical axis direction (MD direction) and the horizontal axis direction (TD direction).

  The triacetyl cellulose according to the present invention can also be obtained as a commercial product. For example, Konica Minoltack KC8UX, KC5UX, KC4UX, KC8UY, KC6UY, KC4UAY, KC4UE, KC8UE, KC2UA, KC4UA, etc. Fujitac T40UZ, Fujitac T60UZ, Fujitac T80UZ, Fujitac TD80UL, Fujitac TD60UL, Fujitac TD40UL, etc. (above, manufactured by Fuji Film Co., Ltd.) 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 the silicon dioxide particle content as exemplified in FIG. 2 between the resin substrate (2) and the gas barrier layer (4). (3), the silicon dioxide particle content 2 (mass%) in the surface region T (3T) on the gas barrier layer surface side of the hard coat layer (3), and the surface region B (3B) on the resin substrate surface side The difference in content ΔC (silicon dioxide particle content 2−silicon dioxide particle content 1) with respect to silicon dioxide particle content 1 (mass%) is 10 mass% or more, more preferably 20%. It is at least mass%.

  The constitution of 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. Preferably, it is formed by a wet coating method. Furthermore, in addition to the silicon dioxide particles and the active energy ray-curable resin, for forming a hard coat layer composed of a photopolymerization initiator, a surfactant, a solvent, etc. It is preferable to form by a wet coating method using a coating solution.

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

  In the present invention, the silicon dioxide particle content 1 (mass%) in the surface region B (3B) on the resin substrate (2) surface side and the silicon dioxide in the surface region T (3T) on the gas barrier layer (4) surface side It is characterized in that the content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) with respect to the particle content 2 (mass%) is 10 mass% or more, and this condition can be satisfied. The method is not particularly limited, but from the viewpoint of stably achieving the gradient concentration structure of silicon dioxide particles defined in the present invention, it is preferable to appropriately select or combine the following methods.

  A 1st method can provide a desired silicon dioxide particle density | concentration gradient in a layer by forming a hard-coat layer using a surface modification silicon dioxide particle (surface modification silica particle) as a silicon dioxide particle. .

  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 a coating film containing silicon dioxide particles as in the hard coat layer according to the present invention, convection (also referred to as Benard cell) in the coating liquid is accompanied with evaporation of the solvent contained in the coating film during coating film formation. ) And partial surface tension unevenness on the coating surface. Due to such non-uniformity of surface tension during coating-drying-film formation, and further due to differences in the mobility of each component (for example, silicon dioxide particles) in the coating film, It is speculated that a bias in the proportion of the ingredients has developed.

  In the second method, a hard coat layer is formed by using a hard coat layer-forming coating solution containing a polyhydric alcohol-based high boiling point solvent having a boiling point of 150 ° C. or higher at a predetermined amount of normal pressure. A silicon dioxide particle concentration gradient can be provided.

  In the present invention, the reason why the concentration gradient of silicon dioxide particles can be imparted in the layer by forming the hard coat layer according to the second method is expressed by the same mechanism as in the first method. In particular, the high boiling point solvent mixed in the solvent affects the change in the evaporation rate of the solvent and convection during coating film formation, and the coating film drying. The difference in the mobility of the silicon dioxide particles, etc.) is presumed to cause an uneven proportion of the constituent components in the thickness direction.

  The third method is not a single layer structure as illustrated in FIG. 2 as a hard coat layer, but a hard layer formed by laminating two or more layers having different silicon dioxide particle concentrations as shown in FIGS. By constituting the coat layer unit (3U), a concentration gradient structure of arbitrary silicon dioxide particles can be stably formed from the surface side.

  As another method, after coating the hard coat layer-forming coating solution on the resin substrate, the drying conditions are slower, i.e., slowly drying over a long time until the end of drying. By doing so, the silicon dioxide particles in the hard coat layer are more oriented on the upper side of the hard coat layer, and a concentration gradient structure of the silicon dioxide particles can be formed.

  The reason why the concentration gradient structure of the silicon dioxide particles appears due to the above drying conditions is that the convection in the coating film, the non-uniformity of the surface tension during the drying-film formation, and each component of the coating film (for example, dioxide dioxide) This is presumed to be due to the influence of mobility of silicon particles.

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

  In FIG. 3, by laminating 5 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 described on the right side. A hard coat 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 the hard coat layer 3- corresponding to the surface region T (3T) on the gas barrier layer (4) surface side. 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 substrate (2) surface side is 10% by mass or more.

  On the other hand, FIG. 4 is a schematic view showing another example of a gradient structure of silicon dioxide particle content (mass%) composed of a plurality of hard coat layers according to the present invention. Five layers of hard coat layers 3-1B to 3-5B having different particle contents are laminated on the resin base material (2). This method is applied, and the structure having an inclined structure as the content of silicon dioxide particles is shown. Therefore, even in the graph shown on the right side, not the step-like silicon dioxide particle content profile as shown in FIG. 3, but the resin base material (2) from the surface region T (3T) on the gas barrier layer (4) surface side. The hard coat layer unit (3U) having a continuous silicon dioxide particle-containing concentration profile is formed up to the surface region B (3B) on the surface side.

[Constituent material of hard coat layer]
In the present invention, examples of the material constituting the hard coat layer include curable resins, photopolymerization initiators, surfactants, solvents and the like in addition to silicon dioxide particles.

(Silicon dioxide particles: silica particles)
Examples of 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, 200V, 300 manufactured by Nippon Aerosil Co., Ltd., Aerosil Product names such as OX50, TT600, etc., and KEP-10, KEP-50, KEP-100 manufactured by Nippon Shokubai Co., Ltd. can be mentioned. Colloidal silica may also be used. Colloidal silica is obtained by dispersing silicon dioxide in water or an organic solvent in a colloidal form, and is not particularly limited but is spherical, acicular or beaded. Such colloidal silica is commercially available, and examples thereof include the Snowtex series manufactured by Nissan Chemical Industries, the Cataloid-S series manufactured by Catalytic Chemical Industry, and the Rebacil series manufactured by Bayer. Also, beaded colloidal silica in which primary particles of cation-modified with alumina sol or aluminum hydroxide are bonded in a bead shape by bonding the particles with divalent or higher metal ions. Examples of beaded colloidal silica include SNOWTEX-AK series, SNOWTEX-PS series, SNOWTEX-UP series, etc., manufactured by Nissan Chemical Industries, Ltd. Specifically, IPS-ST-L (isopropanol silica sol, particle size) 40-50 nm, silica concentration 30%), MEK-ST-MS (methyl ethyl ketone silica sol, particle size 17-23 nm, silica concentration 35%), etc. MEK-ST (methyl ethyl ketone silica sol, particle size 10-15 nm, silica concentration 30%) MEK-ST-L (methyl ethyl ketone silica sol, particle size 40-50 nm, silica concentration 30%), MEK-ST-UP (methyl ethyl ketone silica sol, particle size 9-15 nm (chain structure), silica concentration 20%), etc. It is done.

<Surface-modified silicon dioxide particles: surface-modified silica particles>
In the present invention, as a means for effectively forming a gradient structure having a silicon dioxide particle content in the hard coat layer, a method in which silicon dioxide particles surface-modified as silicon dioxide particles (surface-modified silica particles) is applied is preferable. It is.

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

  Since silica particles are an inorganic compound, there is a problem that the affinity for the binder resin constituting the hard coat layer and the organic solvent used for preparing the coating liquid for forming the hard coat layer is poor. As a method for solving this problem, affinity of the surface of the silica particles with, for example, surface-modified silica particles treated with a surface modifier of a silicone compound can be increased.

  Examples of the surface modifier used for the 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 vinylsilazane trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, trimethylalkoxysilane, dimethyldialkoxysilane, methyltrialkoxysilane, and hexamethyldisilazane. In order to cover widely, hexamethyldisilazane or the like is preferably used.

  Examples of the silicone oil coupling agent include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, and carbinol-modified silicone. Oil, methacryl-modified silicone oil, mercapto-modified silicone oil, phenol-modified silicone oil, one-end reactive modified silicone oil, heterogeneous functional group-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 treatment agents may be appropriately diluted with hexane, toluene, methanol, ethanol, acetone, water, or the like.

  Examples of the surface treatment method using the surface modifier include a wet heating method, a wet filtration method, a dry stirring method, an integral blend method, and a granulation method. When surface modification of 100 nm or less is performed, the dry stirring method is preferably used from the viewpoint of suppressing particle aggregation, but is not limited thereto.

  Only one kind of these surface modifiers may be used, or a plurality of kinds may be used in combination.

  Further, as the surface-modified silica particles, it can be obtained as a commercial product, for example, Aerosil R7200 manufactured by Nippon Aerosil Co., Ltd. (silica fine particles having a primary average particle diameter of 12 nm and a (meth) acryloyl group on the particle surface), Aerosil R711 manufactured by Nippon Aerosil Co., Ltd. (silica fine particles having a primary average particle size of 12 nm and (meth) acryloyl group on the particle surface), ELCOM V-8804 manufactured by JGC Catalysts Co., Ltd. ((meth) acryloyl on the particle surface) And silica fine particles having a group).

  The content of the silica particles or the surface-modified silica particles in the hard coat layer according to the present invention can be appropriately selected within the range satisfying the silicon dioxide particle content defined 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, and preferably in the range of 20 to 75% by mass.

(Resin binder: curable resin)
Examples of the curable resin used for the formation of the hard coat layer according to the present invention include a thermosetting resin and an active energy ray curable resin. However, an active energy ray curable resin is preferable because of easy molding. Can be used.

<Thermosetting resin>
The thermosetting resin is not particularly limited. Specifically, various thermosetting resins such as epoxy resin, cyanate ester resin, phenol resin, bismaleimide-triazine resin, polyimide resin, acrylic resin, and vinylbenzyl resin can be used. Can be mentioned.

  As an epoxy resin, those having an average of two or more epoxy groups per molecule may be used. Specifically, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, and naphthol type epoxy are used. Resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (specifically, tetraglycidyldiaminodiphenylmethane, 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 etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, glycidyl etherified product of phenol, and diglycidyl alcohol Examples include etherified products, and alkyl-substituted products, halides, and hydrogenated products of these epoxy resins. 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 cures through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used. The active energy ray curable resin is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. A resin layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable flag resin, but an ultraviolet curable resin that is cured by ultraviolet irradiation is preferable.

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

  Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

  In general, UV-curable acrylic urethane-based resins are produced by reacting a polyester polyol with an isocyanate monomer or a prepolymer and further adding a hydroxy group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, or 2-hydroxypropyl acrylate. 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 are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 The resin described in the publication can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added to the oligomer, and a reaction. Those described in Japanese Patent No. 105738 can be used.

  Further, in the present invention, it is preferable to use an ultraviolet curable polyol acrylate resin, and examples of such a compound include a polyfunctional acrylate resin. Here, the polyfunctional acrylate resin is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate resin include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane. Triacrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate , Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

Examples of commercially available ultraviolet curable resins applicable in the present invention include, for example, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B ( As described above, manufactured by ADEKA Corporation); KEIHARD A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D -102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K- 3), PHC2213, DP-10, DP-20,
DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.); KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by DIC Corporation); 340 clear (above, manufactured by China Paint Co., Ltd.); Sunrad 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 Polymer Co., Ltd.); RCC-15C (Grace Japan, Inc.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.) can be selected as appropriate.

<Photopolymerization initiator>
In this invention, it is preferable to contain a photoinitiator in the range of 2-30 mass% with respect to an ultraviolet curable resin in order to accelerate | stimulate hardening of the ultraviolet curable resin demonstrated above. The photopolymerization initiator is preferably a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization upon light irradiation.

  As such an onium salt, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator, and among them, the fragrances described in JP-A Nos. 50-151996, 50-158680, etc. Group VIA aromatic onium salts described in JP-A-50-151997, JP-A-52-30899, JP-A-59-55420, JP-A-55-125105, etc., JP-A-56-8428 Oxosulfonium salts described in Japanese Patent Publication Nos. 56-149402 and 57-192429, aromatic diazonium salts described in Japanese Patent Publication No. 49-17040, US Pat. No. 4,139,655, and the like. Of these, thiopyrylium salts are preferred. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

<High boiling point solvent>
In the hard coat layer according to the present invention, it is preferable to use a polyhydric alcohol-based high-boiling solvent having a boiling point of 150 ° C. or higher at normal pressure as a method for obtaining a gradient structure having a silicon dioxide particle content specified in the present invention. .

  The high boiling point solvent applicable to the present invention is preferably a polyhydric alcohol organic solvent having a boiling point of 150 ° C. or higher, 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.), die Ren 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) ° C), dipropylene glycol (232 ° C), dipropylene glycol Noethyl 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-butanediol (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, based on the total solid content of the hard coat layer. In addition, in this invention, when calculating the total mass of the hard-coat layer after drying, the mass of the said high boiling point solvent shall be included.

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

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

  Further, the hard coat layer can contain a silicone-based surfactant, a fluorine-based surfactant or a polyoxyether compound. Alternatively, the coat layer may contain a fluorine-siloxane graft polymer.

  As a preferable example of the surfactant, manufactured by Kao Corporation: Emulgen 102KG, Emulgen 103, Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108, etc., Emulgen series, Latemu PD-420, Latemul PD-430, Latemu PD-430S, etc. Latemule series, Rhedol SP-L10, Rheodor series such as Rhedol SP-P10, Emazole L-10V, Emazole P-10V, Emazole series such as Emazole S-10V, Excel T-95, Excel VS-95, Excel series such as Excel O-95R, Emanon series such as Emanon 1112, Emanon 4110, Emanon CH-25, Amit series such as Amete 102, Amete 105, Amete 105A, etc. Manufactured by Kogyo Co., Ltd .: Surfinol series such as Surfinol 104E, Surfinol 104H, Surfinol 104A, etc., Olphine series such as Olphine STG, Olphin E1004, Olphine E1010, Shin-Etsu Chemical Co., Ltd .: X-22-4272, X -22-6266, KF-351A, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011, KF-6015, KF-6004, etc. Can be mentioned.

  These hard coat layers are formed in a single layer or two layers by a known wet coating method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method using a coating liquid for forming a hard coat layer. The above plural layers can be formed by simultaneous lamination coating.

(Hard coat layer thickness)
The coating amount of the hard coat layer coating solution is suitably in the range of 0.1 to 40 μm as the total thickness, and preferably in the range of 0.5 to 30 μm as the total thickness. 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.

(Hard coat layer curing method)
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.

The light source used for curing the ultraviolet curable resin by a photocuring reaction to form a cured hard coat layer can be used without limitation as long as it is a light source that generates ultraviolet rays. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Although the irradiation conditions differ depending on each lamp, the irradiation amount of the active energy ray is preferably in the range of 5 to 100 mJ / cm ² , particularly preferably in the range of ^{20 to} 80 mJ / cm ² .

[Gas barrier layer]
As shown in FIG. 1, the gas barrier film of the present invention is characterized in that 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 of suppressing intrusion of elements such as moisture and oxygen that cause performance deterioration of the resin substrate (2) and the organic EL element provided with the gas barrier film 1 For example, silicon oxide, silicon oxynitride, silicon dioxide, silicon nitride, or the like can be used.

  The gas barrier layer (4) according to the present invention is formed by a discharge plasma chemical vapor deposition method using a source gas containing an organosilicon compound and an oxygen gas and having a discharge space between rollers to which a magnetic field is applied. It is characterized by forming. Furthermore, as a constituent element of the gas barrier layer (4), it is a preferred embodiment that contains a carbon atom, a silicon atom and an oxygen atom.

  Specifically, a film forming gas is wound between a pair of film forming rollers (roller electrodes) on the hard coat layer (3) of the resin base material (2) and applied with the pair of magnetic fields. In this method, a gas barrier layer is formed on a resin base material by a plasma chemical vapor deposition method in which plasma discharge is performed while supplying water.

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

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

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

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

  In the present invention, the average value of the carbon atom content ratio in the gas barrier layer (4) according to the present invention can be determined by measuring 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.

(Carbon element 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 a carbon distribution curve showing a 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 satisfies all the conditions of items (1) to (4) above. By satisfy | filling, it is preferable from a viewpoint which can obtain the gas barrier film which was further excellent in flexibility (flexibility) and adhesiveness.

  In addition, it is a preferable embodiment that the carbon atom ratio has a configuration in which the carbon atom ratio continuously changes with a concentration gradient in a specific region of the gas barrier layer from the viewpoint of achieving both gas barrier properties and flexibility.

  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 preferable to have at least two extreme values, and it is particularly preferable to have at least three extreme values. When the carbon distribution curve does not have an extreme value, the gas barrier property when the obtained gas barrier film is bent is insufficient. In the case of having at least two or three extreme values as described above, the thickness direction of the gas barrier layer (4) at one extreme value and the extreme value adjacent to the extreme value that the carbon distribution curve has. The absolute value of the difference in distance from the surface of the gas barrier layer is preferably 200 nm or less, and more preferably 100 nm or less.

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

<Maximum and minimum values>
In the present invention, the maximum value is a point where the value of the atomic ratio of an element changes from increasing to decreasing when the distance from the surface of the gas barrier layer (4) is changed, and the atomic ratio of the element at that point. Than the above value, the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer is further changed by 20 nm from this point is reduced by 3 at% or more.

  Further, in the present invention, the minimum value is a point where the value of the atomic ratio of the element changes from decreasing to increasing when the distance from the surface of the gas barrier layer (4) is changed, and the atomic atom of the element at that point 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 (4) in the thickness direction of the gas barrier layer (4) is further changed by 20 nm from the point increases by 3 at% or more. That means.

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

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

  In the present invention, “the concentration gradient of the carbon element ratio is continuously changed” means that the carbon distribution curve does not include a portion in which the carbon atom ratio changes discontinuously. In the relationship between 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 the time, and the carbon atom ratio (C, unit: at%), the following formula ( 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 a carbon atom, a silicon atom and an oxygen atom as constituent elements, but preferred embodiments of the ratio of each atom and the maximum and minimum values are as follows: This will be described below.

<Relationship between maximum and minimum 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, and particularly preferably 7 at% or more. By setting the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio to 5 at% or more, the gas barrier property when the produced gas barrier film is bent is sufficient.

<Relationship between maximum and minimum 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. It is particularly preferred that When the absolute value is 5 at% or more, the gas barrier property when the obtained gas barrier film is bent is sufficient.

<Relationship between maximum and minimum values of silicon 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 silicon distribution curve is preferably less than 5 at%, more preferably less than 4 at%, and less than 3 at%. It is particularly preferred that If the absolute value is less than 5 at%, the gas barrier film obtained has sufficient gas barrier properties and mechanical strength.

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

  In addition, 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 atom, oxygen atom and carbon atom” means silicon atom, oxygen It means the total at of atoms and carbon atoms, and “amount of carbon atoms” means the number of carbon atoms. The term “at%” in the present invention means the atomic ratio of each atom when the total number of silicon atoms, oxygen atoms and carbon atoms is 100%. The same applies to “amount of silicon atoms” and “amount of oxygen atoms” for a silicon distribution curve, an oxygen distribution curve, and an oxygen carbon distribution curve as shown in FIG.

(About XPS depth profile)
In the gas barrier layer according to the present invention, the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen-carbon total distribution curve 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 prepare by so-called XPS depth profile measurement in which the surface composition analysis is sequentially performed while exposing the inside of the sample. The distribution curve obtained by such XPS depth profile measurement is, for example, as illustrated in FIG. 6, where the vertical axis is the atomic ratio (unit: at%) of each element and the horizontal axis is the etching time (sputtering time). Can be created. In the element distribution curve with the horizontal axis as the etching time in this way, the etching time generally correlates with the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer in the layer thickness direction. , “Distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer” as calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement Can be adopted. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

  In the present invention, from the viewpoint of forming a gas barrier layer that is uniform over the entire film surface and has excellent gas barrier properties, the gas barrier layer is in the film surface direction (direction parallel to the surface of the gas barrier layer). Is substantially uniform. In the present invention, that the gas barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon distribution curve are measured at 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 prepared, the carbon distribution curves obtained at any two measurement locations have the same number of extreme values, and the carbon atoms in the respective carbon distribution curves. The absolute value of the difference between the maximum value and the minimum value of the ratio is the same or within 5 at%.

  The gas barrier film of the present invention preferably includes at least one gas barrier layer that satisfies all of the above (1) to (4) defined in the present invention. 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. Further, when two or more such gas barrier layers are provided, such a gas barrier layer may be formed on one surface of the base material, and is formed on both surfaces of the base material. May be. Moreover, as such a plurality of gas barrier layers, a gas barrier layer not necessarily having a gas barrier property may be included.

(Gas barrier layer thickness)
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. When the thickness of the gas barrier layer is within the above range, the gas barrier properties such as oxygen gas barrier property and water vapor barrier property are excellent, and the gas barrier property is not deteriorated by bending.

  When the gas barrier film of the present invention includes a plurality of gas barrier layers, the total value of the thicknesses of the gas barrier layers is usually in the range of 10 to 10,000 nm, and in the range of 10 to 5000 nm. It is more preferable, it is more preferable that it is the range of 100-3000 nm, and it is especially preferable that it is the range of 200-2000 nm. When the total thickness of the gas barrier layers 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 tend not to be lowered by bending.

(Method for forming gas barrier layer)
The gas barrier layer according to the present invention 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, the gas barrier layer according to the present invention uses an inter-roller discharge plasma processing apparatus to which a magnetic field is applied, winds a resin base material around a pair of film forming rollers, and forms a film forming gas between the pair of film forming rollers. It is a layer formed by plasma chemical vapor deposition by plasma discharge while being supplied. Further, when discharging while applying a magnetic field between the pair of film forming rollers, it is preferable to reverse the polarity between the pair of film forming rollers alternately. Further, as a film forming gas used in such a plasma chemical vapor deposition method, a source gas containing an organosilicon compound and an oxygen gas are used, and the content of the oxygen gas in the film forming gas is within the film forming gas. It is preferable that the amount is less than the theoretical oxygen amount necessary for complete oxidation of the total amount of the organosilicon compound. Moreover, in the gas barrier film of this invention, it is a preferable aspect that a gas barrier layer forms with 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. To make it.

  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 vapor having a discharge space between rollers to which a magnetic field is applied. It is characterized by using a 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 is applied according to the present invention, a magnetic field is generated between a plurality of film forming rollers when generating plasma. In the present invention, a pair of film forming rollers is used, and a resin base material having a hard coat layer is wound around each of the pair of film forming rollers. Thus, it is preferable to generate plasma by discharging in a state where a magnetic field is applied between the pair of film forming rollers. Thus, by using a pair of film forming rollers, winding the resin base material on the pair of film forming rollers, and performing plasma discharge between the pair of film forming rollers, the resin base material and the film forming roller By changing the distance between the gas barrier layer and the gas barrier layer, 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, when forming a film on the hard coat layer surface portion of the resin substrate existing on one film forming roller during film formation, on the hard coat layer surface portion of the resin substrate existing on the other film forming roller. In addition, it is possible not only to produce a thin film efficiently, but also to double the film formation rate and to form a film having the same structure. It is possible to double the number, and it is possible to efficiently form a layer that satisfies all of the above conditions (1) to (4).

  Moreover, it is preferable that the gas barrier film of this invention forms the said gas barrier layer on the surface of the hard-coat layer of the said resin base material by a roll-to-roll system from a viewpoint of productivity.

  Further, an apparatus applicable when producing a gas barrier film by such a plasma chemical vapor deposition method is not particularly limited, but a film forming roller having at least a pair of magnetic field applying apparatuses, a plasma power source, and the like. And is configured to be capable of discharging between a pair of film forming rollers. For example, when the manufacturing apparatus shown in FIG. 5 is used, plasma chemical vapor deposition is performed. In a roll-to-roll method using a method, for example, a hard coat layer, a gas barrier layer, and a second gas barrier layer are formed on a resin substrate using a continuous process as shown in FIG. A gas barrier film can be manufactured by sequentially laminating.

  Hereinafter, the manufacturing method of the gas barrier film of the present invention will be described in detail with reference to FIG. FIG. 5 is a schematic view showing an example of an inter-roller discharge plasma CVD apparatus to which a magnetic field that can be suitably used when producing the gas barrier film of the present invention is applied. The resin base material (F2) in the following description refers to the resin base material (2) having the 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 shown in FIG. 5 is applied mainly includes a delivery roller (11), a transport roller (21), (22), (23) and (24), film formation rollers (31) and (32), film formation gas supply pipe (41), power source for plasma generation (51), film formation roller (31) And the magnetic field generator (61) and (62) installed in the inside of (32), and the winding roller (71) are provided. Further, in such a plasma CVD manufacturing apparatus (30), at least film forming rollers (31) and (32), a film forming gas supply pipe (41), a plasma generating power source (51), and a magnetic field generating apparatus. (61) and (62) are arranged in a vacuum chamber (72) as shown in FIG. Further, 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 to the vacuum pump (73). ) Can be adjusted as appropriate.

  In such a plasma CVD manufacturing apparatus (30), each of the pair of film forming rollers (the film forming roller (31) and the film forming roller (32)) can function as a pair of counter electrodes. The film forming rollers are each connected to a plasma generating power source 51. By supplying power from a plasma generation power source (51) to a pair of film forming rollers (film forming roller (31) and film forming roller (32)), the film forming roller (31) and the film forming roller (32) It is possible to discharge into the space between the film and the plasma, thereby generating plasma in the space between the film formation roller (31) and the film formation roller (32) (hereinafter, this space is also referred to as discharge space). be able to. In addition, since a pair of film-forming roller (31) and film-forming roller (32) are used as electrodes in this way, materials and designs that can be used as electrodes may be appropriately changed. Further, in such a plasma CVD manufacturing apparatus (30), the pair of film forming rollers (film forming rollers (31) and (32)) are arranged so that their central axes are substantially parallel on the same plane. It is preferable that Thus, by arranging a 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. It is possible to at least double the extreme values in the curve.

  In addition, the magnetic field generators (61) and (62) fixed inside the film forming roller (31) and the film forming roller (32) so as not to rotate even when the film forming roller rotates. Are provided.

  Furthermore, a well-known roller can be used suitably for the film-forming roller (31) and the film-forming roller (32). The film forming rollers (31) and (32) are preferably rollers having the same diameter from the viewpoint of forming a thin film more efficiently. The diameters of the film forming rollers (31) and (32) are preferably in the range of 300 to 1000 mmφ, particularly preferably in the range of 300 to 700 mmφ, 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 will not become small, so there will be no deterioration in productivity, and it will be possible to avoid applying the total amount of heat of the plasma discharge to the film in a short time, and the residual stress will not increase easily. preferable. On the other hand, if the diameter of the roller is 1000 mmφ or less, the apparatus does not increase in size, and it is preferable because practicality can be maintained in apparatus design including uniformity of the plasma discharge space.

  In addition, as the feed roller (11) and the transport rollers (21), (22), (23), and (24) used in such a plasma CVD manufacturing apparatus (30), known rollers are appropriately selected and used. Can do. The winding roller (71) is not particularly limited as long as it can wind the resin base material (F3) on which the gas barrier layer is formed, and a known roller can be used as appropriate. .

  As the film forming gas supply pipe (41), one capable of supplying or discharging the source gas and the oxygen gas at a predetermined rate can be used. Furthermore, as the plasma generating power source (51), a conventionally known power source for a plasma generating apparatus can be used. Such a plasma generating power source (51) supplies power to the film forming roller (31) and the film forming roller (32) connected thereto, and uses them as a counter electrode for discharge. Make it possible. As the power source for generating plasma (51), a plasma CVD method can be carried out more efficiently, so that the polarity of a pair of film forming rollers can be alternately reversed (such as an AC power source). It is preferable to use it. Further, since the power source for plasma generation (51) can perform the plasma CVD method more efficiently, the applied power can be set within a range of 100 W to 10 kW, and the AC frequency can be set to 50 Hz to More preferably, it can be within the range of 500 kHz. As the magnetic field generators (61) and (62), known magnetic field generators can be used as appropriate.

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

<Raw gas>
The source gas constituting the deposition gas used for forming the gas barrier layer according to the present invention is characterized by using an 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. Examples thereof include silane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling in film formation and gas barrier properties of the obtained gas barrier layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  Further, the film formation gas contains oxygen gas as a reaction gas in addition to the source gas. The oxygen gas is a gas that reacts with the raw material gas to become an inorganic compound such as an oxide.

  As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and 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 ratio of the source gas to the oxygen gas is such that the source gas and the oxygen gas are completely reacted. It is preferable that the oxygen gas ratio is not excessively larger than the theoretically required oxygen gas ratio. If the ratio of oxygen gas is excessive, it is difficult to obtain the target gas barrier layer in the present invention. Therefore, in order to obtain a barrier film having a desired element profile, the oxygen gas ratio is preferably set to be equal to or less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas.

Hereinafter, as a representative example, a system of hexamethyldisiloxane (organosilicon compound, abbreviation: 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 source gas and oxygen (O ₂ ) as a reaction gas is reacted by a plasma CVD method to form silicon-oxygen. When forming a thin film of the type, 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 + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. The ratio is controlled to a flow rate equal to or less than the raw material ratio of the complete reaction, which is the theoretical ratio, and the incomplete reaction is performed. 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 hexamethyldisiloxane as a raw material and oxygen as a reactive gas are supplied from a gas supply unit to a film formation region, a reaction gas is formed. Even if the molar amount (flow rate) of oxygen is 12 times the molar amount (flow rate) of hexamethyldisiloxane as a raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when the oxygen content is supplied in a large excess compared to the stoichiometric ratio. For example, in order to 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 the raw material hexamethyldisiloxane. . Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By including hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer and have a desired element profile. A barrier layer can be formed, and a gas barrier film excellent in barrier properties and bending resistance can be obtained.

  If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas is too small, unoxidized carbon atoms and hydrogen atoms will be 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 electronic devices such as organic EL devices and organic thin film solar cells that require transparency. It becomes impossible.

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

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

<Roller film formation>
In the discharge plasma chemical vapor deposition method using a plasma CVD apparatus or the like as shown in FIG. 5, a plasma discharge power source is formed by plasma discharge between the film forming rollers (31) and (32). The power applied to the electrode drum connected to (51) (installed in the film forming rollers (31) and (32) in FIG. 5) depends on the type of source gas, the pressure in the vacuum chamber, and the like. Depending on the situation, it can be adjusted as appropriate, and it cannot be generally stated, but it is preferably in the range of 0.1 to 10 kW.

  With this range of applied power, the generation of particles (illegal particles) can be suppressed to some extent, but there are cases where particles are generated when the specific applied power condition or resin substrate temperature range is reached, In such a case, by applying a resin base material having a hard coat layer having a gradient structure of silicon dioxide particle concentration according to the present invention, for example, even when particles are generated, in a high temperature and high humidity environment Decrease in adhesion after storage and generation of dark spots when applied to an organic EL element can be prevented. In addition, damage to the film forming roller due to melting of the resin base material by heat and generation of a large current discharge between the bare film forming rollers can be prevented.

  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 within the range of 0.5 to 20 m / min. If the conveyance speed is within the range specified above, wrinkles due to heat of the resin base material 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 based on 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 as a carbon distribution curve, B as a silicon distribution curve, C as an oxygen distribution curve, and D as an oxygen carbon distribution curve.

  As shown in the graph of FIG. 6, the gas barrier layer according to the present invention has a maximum carbon element ratio in the range of 89% in the vertical direction from the surface as the carbon atom ratio of the gas barrier layer, which is less than 20 at%. It is preferable 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 continuously changes (claims of the present invention). (Applicable to the items (1) and (2) defined in Item 5.)

  Further, 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 vertical direction with respect to the surface, and the carbon element ratio continuously increases. It preferably has a characteristic (corresponding 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 on the above-described gas barrier layer according to the present invention by a wet coating method, and vacuum ultraviolet light having a wavelength of 200 nm or less ( It is preferable to form a 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. Thus, the minute defect portion generated when forming the already formed first gas barrier layer can be leveled and filled with the second gas barrier layer component composed of polysilazane applied from above. It is preferable from the viewpoint of efficiently preventing gas purge and improving 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, the desired gas barrier performance can be exhibited, and if it is 500 nm or less, film quality degradation such as generation of cracks in a dense silicon oxynitride film can be achieved. Can be prevented.

<Polysilazane>
The polysilazane used for forming the second gas barrier layer according to the present invention is a polymer having a silicon-nitrogen bond in its molecular structure and is a polymer that is a precursor of silicon oxynitride. Although there is no restriction | limiting, It is preferable that it is a compound which has a structure represented by following General formula (1).

In the 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 obtained second gas barrier layer. .

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

  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. Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials Co., Ltd.

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

  As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts 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 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 according to purposes 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. Is within the range.

  In order to promote the modification to silicon oxynitride, the second gas barrier layer forming coating solution contains an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, Rh acetylacetonate, etc. A metal catalyst such as an Rh compound 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 , 3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane and the like.

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

  Any appropriate wet coating method may be employed as a method for applying the second gas barrier layer forming coating solution containing polysilazane. Specific examples include a roller coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting 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 as the thickness after drying, more preferably in the range of 70 nm to 1.5 μm, and in the range of 100 nm to 1 μm. More preferably, it is within.

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

Here, perhydropolysilazane will be described as an example of the presumed mechanism in which the coating film containing polysilazane is modified in the vacuum ultraviolet irradiation step and becomes a specific composition of SiO _x N _y .

Perhydropolysilazane can be represented by a composition of “— (SiH ₂ —NH) _n —”. When the second gas barrier layer has a configuration represented by SiO _x N _y , x = 0 and y = 1. An external oxygen source is required for x> 0,
(I) oxygen and moisture contained in the polysilazane coating solution,
(Ii) oxygen and moisture taken into the coating film from the atmosphere of the coating and drying process,
(Iii) oxygen, moisture, ozone, singlet oxygen taken into the coating film from the atmosphere in the vacuum ultraviolet irradiation process,
(Iv) Oxygen and moisture moving into the coating film as outgas from the substrate side by heat applied in the vacuum ultraviolet irradiation process,
(V) When the vacuum ultraviolet ray irradiation step is performed in a non-oxidizing atmosphere, when moving from the non-oxidizing atmosphere to the oxidizing atmosphere, oxygen and moisture taken into the coating film from the atmosphere,
Etc. become oxygen sources.

  On the other hand, for y, the condition under which nitriding proceeds rather than the oxidation of Si is considered to be very special, so basically 1 is the upper limit.

  Also, from the relationship of Si, O, and N bond, x and y are basically in the range of 2x + 3y ≦ 4. In the state of y = 0 where the oxidation has progressed completely, the coating film contains silanol groups, and there are cases where 2 <x <2.5.

  The reaction mechanism presumed to produce silicon oxynitride and further silicon oxide from perhydropolysilazane in the vacuum ultraviolet irradiation step will be described below.

(1) Dehydrogenation and associated Si—N bond formation Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation, etc., and in an inert atmosphere, Si— It is considered that they are recombined as N (a dangling bond of Si may be formed). That is, the cured as SiN _y composition without oxidizing. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H ₂ .

(2) Formation of Si—O—Si bond by hydrolysis and dehydration condensation The Si—N bond in perhydropolysilazane is hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. Two Si—OHs are dehydrated and condensed to form Si—O—Si bonds and harden. This is a reaction that occurs even in the atmosphere, but during vacuum ultraviolet irradiation in an inert atmosphere, it is considered that water vapor generated as outgas from the resin base material by the heat of irradiation becomes the main moisture source. When the water becomes excessive, Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO _2.1 to SiO _2.3 is obtained.

(3) Direct oxidation by singlet oxygen, formation of Si-O-Si bond When a suitable amount of oxygen is present in the atmosphere during irradiation with vacuum ultraviolet rays, singlet oxygen having a very strong oxidizing power is formed. H or N in perhydropolysilazane is replaced with O to form a Si—O—Si bond and is cured. It is considered that recombination of the bond may occur due to cleavage of the polymer main chain.

(4) Oxidation with Si-N bond cleavage by vacuum ultraviolet irradiation and excitation Since the energy of vacuum ultraviolet light is higher than the bond energy of Si-N in perhydropolysilazane, the Si-N bond is broken and oxygen is surrounded by oxygen. When an oxygen source such as ozone or water is present, it is considered that the substrate is oxidized to form a Si—O—Si bond or a Si—O—N bond. It is considered that recombination of the bond may occur due to the cleavage of the polymer main chain.

  Adjustment of the composition of the silicon oxynitride of the layer subjected to vacuum ultraviolet irradiation on the layer containing polysilazane can be performed by appropriately controlling the oxidation state by appropriately combining the oxidation mechanisms (1) to (4) described above. .

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 the reduction of the reforming efficiency, and if it is 200 mW / cm ² or less, the coating film is not ablated, and the resin base material is not damaged. .

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, the modification can be sufficiently performed, and if it is 10000 mJ / cm ² or less, cracking and thermal deformation of the resin base material are prevented without being over-modified. can do.

  As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.

However, excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms. When the rare gas is xenon,
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, an excimer having a wavelength of 172 nm is emitted.

  A feature of the excimer lamp is that the radiation is concentrated at one wavelength, and only the necessary light is hardly emitted, so that the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required 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. Dielectric barrier discharge is a gas space created by placing 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 electrode. It is a discharge called a thin micro discharge. When the micro discharge streamer reaches the tube wall (derivative), the electric charge is accumulated on the dielectric surface, and the micro discharge disappears.

  This micro discharge spreads over the entire tube wall and repeats generation and extinction. For this reason, flickering of light that can be confirmed with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge is possible in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as those of dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, microdischarge occurs only between the electrodes, so the outer electrode covers the entire outer surface and allows light to pass through to extract light to the outside in order to cause discharge throughout the discharge space. Must be a thing.

  For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is 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 external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the lamp outer surface. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.

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

  As the form of discharge, both dielectric barrier discharge and electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

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

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane layer can be modified in a short time.

  Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and 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. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials that are easily affected by heat.

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a low state. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays 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.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

《Online manufacturing method of gas barrier film》
As described above, the gas barrier film of the present invention has a hard coat layer (3), a gas barrier layer (4) and, if necessary, a second gas barrier layer (5) on the resin substrate (2). ) Can be formed individually by independent manufacturing processes, but as shown in FIG. 7, the hard coating layer (3) forming process, the gas barrier layer (4) forming process and as required The method for producing the gas barrier film by the roll-to-roll method in which the formation process of the second gas barrier layer (5) is arranged on-line is a preferable embodiment from the viewpoint of obtaining high productivity. .

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

  The manufacturing process of the gas barrier film shown in FIG. 7 mainly includes a station 1 (S1) for forming a hard coat layer (3) having an inclined structure as a silicon concentration according to the present invention on the resin substrate (F1), 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 source gas containing an organosilicon compound and oxygen gas; Station 3 (S3), in which a polysilazane-containing liquid is applied and dried, and the formed coating film is irradiated with vacuum ultraviolet light having a wavelength of 200 nm or less to form a second gas barrier layer by an on-line method, It is arranged continuously.

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

  When the roll-shaped resin base material (F1) laminated from the delivery roller (11) is fed out, for example, when the hard coat layer having the layer configuration illustrated in FIG. 2 is formed, the preparation kettles (12A) to (12E) A hard coat layer forming coating solution for forming a hard coat layer having an inclined structure as a silicon concentration is stored in one of the preparation kettles. As a coating liquid for forming a hard coat layer, for example, a coating liquid containing silica particles surface-modified as silicon dioxide particles and an ultraviolet curable urethane acrylate resin is prepared, and this coating liquid is predetermined wetted by a coater (13). It supplies on a resin base material (F1) so that it may become a film thickness, and the hard-coat layer of a single layer structure is formed. Further, as another method, a coating liquid for forming a hard coat layer having different silicon dioxide particles is stored in each of the preparation kettles (12A) to (12E), and a coater (13) capable of simultaneous multi-layer coating is used. A plurality of hard coat layer forming coating solutions are applied simultaneously to form a hard coat layer unit (3U) having a configuration as illustrated in FIG. 3 or FIG. Next, after the wet hard coat layer is dried in the drying step (14), the hard coat layer is irradiated with ultraviolet rays (18) from the ultraviolet irradiation lamp (17) using the ultraviolet irradiation device (15). And hardened to form a hard coat layer.

  Next, while continuously transporting the resin base material (F2) on which the hard coat layer is formed at station 1, using the plasma CVD manufacturing apparatus (30) described in detail with reference to FIG. 5 at station 2 (S2), On the hard coat layer of the resin substrate (F2), a 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 source gas containing an organic silicon compound and oxygen gas. Form.

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

《Organic electroluminescence device》
[Schematic configuration of organic EL element]
Subsequently, 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 diagram 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. , 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 gradient structure of silicon concentration, a first gas barrier layer (4), and a second if necessary, on a film substrate (2). These gas barrier layers (5) are 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) serving as a cathode are stacked on a first electrode (116) serving as an anode, Further, the gas barrier film (1), the sealing resin layer (119), and the sealing member (120) are solid-sealed. Among these, the 1st electrode (116) used as an anode is comprised as a translucent electrode. In such a configuration, only a portion where the organic functional layer unit (117) is sandwiched between the first electrode (116) and the second electrode (118) is a light emitting region in the organic EL element (101). In the example shown in FIG. 8, the organic EL element (101) is configured as a bottom emission type in which generated light (hereinafter referred to as emitted light (h)) is extracted from at least the gas barrier film (1) side. ing.

  The organic EL element (101) includes 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). ) Through which the sealing member (120) is bonded. The solid-sealed organic EL element (101) is attached to the bonding surface of the sealing member (120) or the gas barrier layer (4) and the second electrode (118) of the gas barrier film (1). An uncured resin material is applied, and the gas barrier film (1) and the sealing member (120) are integrated by thermocompression bonding with the resin material interposed therebetween.

  The organic EL element (101) of the present invention is not limited to the bottom emission type, but a top emission type configuration in which light is extracted from the second electrode (118) side, or a dual emission type configuration in which light is extracted from both sides. It is good. If the organic EL element (101) is a top emission type, a transparent material is used for the second electrode (118), and the emitted light h is extracted from the second electrode (118) side. Further, when 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.

[Components of organic EL elements]
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 already described, The detailed configuration will be described. In addition, in the organic EL element (101) of this invention, translucency 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 that passes through the first electrode (116) and extracts light from the film base 2 side. For this reason, the first electrode (116) needs to be formed of a conductive layer having translucency.

  The first electrode (116) is preferably a layer formed using, for example, silver or an alloy containing silver as a main component. Examples of the alloy mainly composed of silver (Ag) constituting the first electrode (116) include silver-magnesium (Ag-Mg), silver-copper (Ag-Cu), and silver-palladium (Ag-Pd). 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 formed by laminating a plurality of layers of silver or an alloy containing silver as a main component.

  As a method for forming such a first electrode (116), a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, or the like. And a method using a dry process such as a method. Of these, the vapor deposition method is preferably applied.

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

  The first electrode (116) may be covered with a protective film at the top, or may be laminated with another conductive layer. 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).

  Moreover, it is good also as a structure which provided the layer according to the necessity under the 1st electrode (116), ie, between the gas barrier layer (4) and the 1st electrode (116). For example, the first electrode (116) may have an improvement in characteristics and an underlayer for facilitating the formation.

  Further, the first electrode (116) may have a configuration other than that containing silver as a main component. For example, various transparent conductive material thin films such as other metals and alloys, ITO, zinc oxide, tin oxide and the like may be used.

  Further, when the organic EL element (101) is a top emission type in which the 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 that functions as a cathode for supplying electrons to the organic functional layer unit (117), and is composed of a metal, an alloy, an organic or inorganic conductive compound, and a mixture thereof. Used as 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 ₂ and oxide semiconductors such as SnO ₂ .

  The second electrode (118) can be formed of these conductive materials by a method such as vapor deposition or sputtering. The sheet resistance as the second electrode (118) is several hundred 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 addition, when the organic EL element (101) is a top emission type or a 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-described conductive materials. A second material (118) is formed by selecting a conductive material.

(Organic functional layer unit)
The organic functional layer unit (117) has, 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. A configuration in which (117d) / electron injection layer (117e) are stacked in this order can be exemplified, but it is a necessary condition that at least a light emitting layer (117c) formed using an organic material is included. The hole injection layer (117a) and the hole transport layer (117b) may be provided as a single layer hole transport / injection layer having a hole transport property and a hole injection property. The electron transport layer (117d) and the electron injection layer (117e) may be provided as a single-layer electron transport / injection layer having electron transport properties and electron injection properties. Of these organic functional layer units (117), for example, the electron injection layer (117e) may be made of an inorganic material.

  In addition to these layers, the organic functional layer unit (117) may have, for example, a hole blocking layer, an electron blocking layer, and the like laminated as necessary. Further, the light emitting layer (117c) has a plurality of light emitting layers for emitting light of each wavelength region, and the light emitting layers emit light by laminating a plurality of layers through a non-light emitting intermediate layer. It may be formed as a layer unit. The intermediate layer may function as a hole blocking layer and an electron blocking layer.

<Light emitting layer>
The light emitting layer (117c) contains, for example, a phosphorescent light emitting compound as a light emitting material. The light emitting layer (117c) is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer (117d) and holes injected from the hole transport layer (117b). The portion may be in the layer of the light emitting layer (117c) or may be the interface between the light emitting layer (117c) and the adjacent layer.

  The light emitting layer (117c) is not particularly limited in its configuration as long as the light emitting material contained satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting 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. Note that the sum of the layer thicknesses of the light emitting layer (117c) is displayed in a layer thickness including the intermediate layer when a non-light emitting intermediate layer exists between the light emitting layers (117c).

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

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

  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). May be used.

  The light-emitting layer (117c) preferably includes 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) and emits light from the light-emitting material.

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

  As a host compound, a well-known host compound may be used independently, or multiple types may be used. By using a plurality of types of host compounds, the movement of charges can be adjusted, and the organic EL element (101) can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining any light emission color including white light emission.

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

  As the known host compound, a compound that has a hole transporting ability and an electron transporting ability, prevents light emission from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable. The glass transition point (Tg) here is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

(2) Light-Emitting Material Examples of the light-emitting material that can be used for the organic EL element (101) include phosphorescent compounds (also referred to as phosphorescent compounds and phosphorescent materials) and fluorescent compounds.

  A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, in the case where a phosphorescent compound is used in this example, the phosphorescence quantum yield (0.01 or more) is obtained in any solvent. It only has to be achieved.

  There are two types of light emission principles of the phosphorescent compound. One is that recombination of carriers occurs on the host compound to which carriers are 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. The other is a carrier trap type in which the phosphorescent compound becomes a carrier trap, and recombination of carriers occurs on the phosphorescent compound, and light emission from the phosphorescent compound is obtained. In either case, the condition is that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of a general organic EL device, but preferably contains a group 8-10 metal in the periodic table of elements. It is a complex compound. More preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.

  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 change in the layer thickness direction of the light emitting layer (117c).

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

  Examples of the fluorescent light emitting material used for the light emitting layer (117c) include a coumarin dye, a pyran dye, a cyanine dye, a croconium dye, a squalium dye, an oxobenzanthracene dye, a fluorescein dye, and a rhodamine dye. Examples thereof include dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

<Injection layer>
The injection layer is a layer provided between the electrode and the light-emitting layer (117c) in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its industrialization front line (November 30, 1998 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of the second edition of “TS Co., Ltd.”, which has a hole injection layer (117a) and an electron injection layer (117e).

  The injection layer can be provided as necessary. 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 described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like, and a specific example is represented by copper phthalocyanine. Phthalocyanine layers, oxide layers typified 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 described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, representative examples thereof include strontium and aluminum. Metal layers, alkali metal halide layers typified by potassium fluoride, alkaline earth metal compound layers typified by magnesium fluoride, oxide layers typified by molybdenum oxide, and the like. The electron injection layer 17e is desirably a very thin layer, and its thickness is preferably within a range of 0.001 to 10 μm, although it depends on the material.

<Hole transport layer>
The hole transport layer (117b) is made of a hole transport material having a function of transporting holes. 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 a function of hole injection or transport or 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 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, particularly an aromatic tertiary amine compound.

As representative examples of aromatic tertiary amine compounds and styrylamine compounds,
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,
Furthermore, those having two condensed aromatic rings described in US Pat. No. 5,061,569 in the molecule, for example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] Biphenyl (abbreviation: NPD), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) in which triphenylamine units described in JP-A-4-308688 are linked in a three star burst type ) -N-phenylamino] triphenylamine (abbreviation: MTDATA).

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, 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 addition, in the hole transport layer (117b), JP-A-11-251067, J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p. A so-called p-type hole transport material as described in 139 can also be used. These materials are preferably used because a highly efficient light-emitting element can be obtained.

  The hole transport layer (117b) is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. 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.

  Alternatively, the material of the hole transport layer (117b) can be doped with impurities to increase the p property. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, 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 an element 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, an electron injection layer (117e) and a hole blocking layer (not shown) are also included in the electron transport layer (117d). The electron transport layer (117d) can be provided as a single-layer structure or a stacked structure of a plurality of layers.

  As 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) having a single layer structure and the electron transport layer (117d) having a multilayer structure, a cathode is used. It is only necessary to have a function of transmitting more injected electrons to the light emitting layer (117c). Such a material can be arbitrarily selected from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Further, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group are also used as the material for the electron transport layer (117d). Can be used. Furthermore, a polymer material in which these materials are introduced into a polymer chain, or a polymer material having these materials as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as 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 the central metal of these metal complexes A metal complex in which In, Mg, Cu, Ca, Sn, Ga, or Pb is substituted can also be used as the material of the electron transport layer (117d).

  In addition, even if it is metal-free or metal phthalocyanine, or even if the terminal thereof is substituted with an alkyl group or a sulfonic acid group, it can be preferably used as a material for the electron transport layer (117d). A distyrylpyrazine derivative exemplified also as a material for the light emitting layer (117c) can also be used as a material for the electron transport layer (117d), and is similar to the hole injection layer (117a) and the hole transport layer (117b). In addition, inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the material for the electron transport layer (117d).

  The electron transport layer (117d) can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can. Although there is no restriction | limiting in particular about the layer thickness of an electron carrying layer (117d), Usually, it is about 5-5000 nm, Preferably it exists in the range of 5-200 nm. The electron transport layer (117d) may have a single layer structure composed of one or more of the above materials.

  Further, the electron transport layer (117d) can be doped with an impurity to increase n property. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. Furthermore, it is preferable that potassium, a potassium compound, or the like is contained in the electron transport layer (117d). As the potassium compound, for example, potassium fluoride can be used. Thus, when the n property of the electron transport layer (117d) is increased, a device with lower power consumption can be manufactured.

<Blocking layer>
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  In a broad sense, the hole blocking layer has a function of an electron transport layer (117d). The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of the electron carrying layer (117d) mentioned later can be used as a hole-blocking layer as needed. 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 a hole transport layer (117b) in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes but has a very small ability to transport electrons, and improves the probability of recombination of electrons and holes by blocking electrons while transporting holes. be able to. The structure of the hole transport layer (117b) described above can be used as an electron blocking layer as necessary.

  The 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-shaped (film-shaped) sealing member (120) is covered with the sealing resin layer (119) to form the film base of the gas barrier film. 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 is provided so as to expose the terminal portions (not shown) of the organic EL element (101) and the second electrode (118). It has been. Further, an electrode may be provided on the sealing member (120), and the electrode may be electrically connected to the terminal portion of the second electrode (118).

  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, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

  Especially, since an organic EL element can be made thin, the polymer substrate made into the thin film form as a sealing member (120) can be used preferably.

Furthermore, the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS-K-7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, JIS-K. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)%) measured by a method based on −7129-1992 is 1 × 10 ⁻³ g / (m ² · 24 h) or less. Preferably there is.

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

  Moreover, not only this but a metal material may be used. 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 using such a metal material as a sealing member (120) in the form of a thin film, the entire light-emitting panel provided with the organic EL element (101) can be thinned.

<Sealing resin layer>
The sealing resin layer (119) for fixing the sealing member (120) to the gas barrier film (1) side is an organic EL element (sandwiched between the sealing member (120) and the gas barrier film (1)). 101). The sealing resin layer (119) is, for example, a photocurable or thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer or a methacrylic acid-based oligomer, an epoxy-based thermosetting or chemical curable ( Two-component mixed adhesives, hot-melt polyamides, polyesters, polyolefins, and cationic curing type ultraviolet curable epoxy resins.

  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. When a sheet-like thermosetting adhesive is used, the adhesive exhibits non-fluidity at room temperature (about 25 ° C.) and exhibits fluidity at a temperature in the range of 50 to 130 ° C. when heated. (Sealant) is used.

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

  Moreover, what mixed two or more types of above-mentioned adhesives may be used as an adhesive agent, and the adhesive agent provided with both thermosetting property and ultraviolet-ray-curing property may be used.

<< Application of organic electroluminescence element >>
Since the organic EL element (101) is a surface light emitter as described above, it can be used as various light sources. For example, lighting devices such as home lighting and interior lighting, backlights for clocks and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, Examples include a light source of an optical sensor. 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 for a backlight of a liquid crystal display device combined with a color filter and a light source for illumination.

  The organic EL element (101) may be used as a kind of lamp for illumination or an exposure light source, a projection device that projects an image, or a type that directly recognizes a still image or a moving image. It may be used as a display device (display). In this case, with the recent increase in the size of lighting devices and displays, the light emitting surface may be enlarged by so-called tiling, in which light emitting panels provided with the organic EL elements (101) are joined together in a plane.

  A driving method when used as a display device for reproducing a moving image may be a simple matrix (passive matrix) method or an active matrix method. In addition, a color or full-color display device can be manufactured by using two or more kinds of organic EL elements 10 having different emission colors.

<< Method for Manufacturing Organic Electroluminescent Element >>
As an example of the method for producing the organic EL element of the present invention, a method for producing the organic EL element (101) shown in FIG. 8 will be described.

  First, the 1st electrode (116) is formed on the 2nd gas barrier layer (5) of the gas barrier film (1) of this invention produced by the above-mentioned method. The first electrode (116) is formed from a transparent conductive material. For example, an electrode having a thickness of about 3 to 15 nm mainly composed of silver or a transparent conductive material such as ITO of about 100 nm is formed. As a method for forming the first electrode (116), for example, a spin coating method, a casting method, an ink jet method, a vapor deposition method, a sputtering method, a printing method, or the like can be used. The vacuum deposition method is particularly preferable from the viewpoint that holes are hardly generated. In addition, before and after the formation of the first electrode (116), an auxiliary electrode pattern is formed as necessary.

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 on the organic functional layer. A unit (117) is formed. As a method for forming each of these layers, for example, a spin coating method, a casting method, an ink jet method, a vapor deposition method, a sputtering method, a printing method, or the like can be used, but a homogeneous layer is easily obtained and a pinhole is generated. From the standpoint of difficulty, it is particularly preferable to use vacuum deposition or spin coating. Furthermore, different formation methods may be used for each layer. When a vapor deposition method is employed for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, etc., but generally the boat heating temperature storing the compound is within a range of 50 to 450 ° C., and the degree of vacuum is 1 × 10. Within the range of ⁻⁶ to 1 × 10 ⁻² Pa, the deposition rate within the range of 0.01 to 50 nm / second, the resin substrate temperature within the range of −50 to 300 ° C., and the formation layer thickness of 0.01 to 5 μm. It is desirable to appropriately select each condition within a range.

  Next, a second electrode (118) to be a cathode is formed by a film forming method such as an evaporation method or a sputtering method. At this time, the organic functional layer unit (117) was insulated from the first electrode (116), and the terminal portion was drawn from above the organic functional layer unit (117) to the periphery of the gas barrier film (1). Pattern the shape.

  Next, solid sealing of the 1st electrode (116), organic functional layer unit (117), and 2nd electrode (118) which were provided on the gas barrier film (1) is performed. A sealing resin layer (119) is formed on one surface of the sealing member (120). Then, the sealing resin layer (119) of the sealing member (120) is arranged 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) through the first electrode (116), the organic functional layer unit (117), and the second electrode (118). After superposing the gas barrier film (1) and the sealing member (120), pressure is applied to the gas barrier film (1) and the sealing member (120). Further, 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).

  By the above, solid sealing by the gas barrier film (1) provided with the hard-coat layer (3), the 1st gas barrier layer (4), and the 2nd gas barrier layer (5) on a film base material (2). The obtained organic EL element (101) is obtained. In the production of such an organic EL element (101), a production process in which production from the first electrode (116) to the second electrode (118) is consistently performed by a single evacuation is preferable. Different forming methods may be used after taking out. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

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

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

(Surface treatment of resin base material)
The prepared TAC film surface was subjected to corona treatment. AGI-080 manufactured by Kasuga Denki Co., Ltd. was used as the 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 the surface corona for 10 seconds under the condition of a treatment output of 600 mW / cm ^2. Processed.

(Formation of hard coat layer)
Next, the hard coat layer 1 was formed on the TAC film subjected to the corona treatment using a hard coat layer 1 forming coating solution 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 the hard coat layer 1.

Silicon dioxide particles: non-surface-modified silica (average particle diameter 6 nm, colloidal silica Snowtex AK, manufactured by Nissan Chemical Co., Ltd.) 47.3 parts 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 (manufactured by BASF Japan)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone BASF Japan) 2.55 parts modified silicone oil: KF-351A (polyether modified Shin-Etsu Chemical Co., Ltd.) )
0.95 parts Surfactant: Emulgen 404 (Polyoxyethylene Oleille Ether Kao)
0.26 parts Organic solvent: 100 parts of methyl ethyl ketone The solid content concentration of the coating liquid for forming the hard coat layer 1 is 50% by mass, and the solid content ratio of the silicon dioxide particles to the total solid content is 47.3% by mass. .

<Coating and curing treatment>
After filtering the prepared coating liquid for forming the hard coat layer 1 through a polypropylene filter having a pore size of 0.4 μm, and then applying it on a TAC film under a condition that the layer thickness after drying is 4 μm using a wet coater. After drying at a constant rate drying zone temperature of 80 ° C. and a reduced rate drying zone temperature of 80 ° C., the hard coat layer 1 is cured under conditions of 1.0 J / cm ² using a high-pressure mercury lamp in the atmosphere. Formed.

  As a result of measuring the silicon content and silicon dioxide particle content (mass%) by the XPS method described later, the hard coat layer 1 formed here was a surface region T (thickness 1/10) on the side in contact with the gas barrier layer. ), The silicon dioxide particle content 2 (mass%) is 48.2 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 46. At 4 mass%, the content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) between the silicon dioxide particle content 2 (mass%) and the silicon dioxide particle content 1 (mass%) is 1. It was 8 mass%.

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

<Measurement of silicon dioxide particle content>
About the sample which formed the hard-coat layer on the TAC film using the said coating liquid for hard-coat layer 1 formation, the silicon dioxide particle content rate 2 (mass%) in the surface region T, and the surface by the side of the resin base material The silicon dioxide particle content 1 (% by mass) in the region B is obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon, and exposing the inside of the hard coat layer. It was measured by the method of sequentially performing surface composition analysis.

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

  The masses of the surface region T (3T) and the surface region B (3B) are divided into the surface region T (3T) and the surface region 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 by the above method, in the surface region 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 was 48.2 mass%, and TAC The average content 1 (mass%) of silicon dioxide particles in the surface region B (layer thickness: 0.4 μm) in contact with the film is 46.4 mass%, and the content difference ΔC (silicon dioxide particle content 2−dioxide 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 equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval (formation of first gas barrier layer: discharge plasma treatment method)
Next, 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 which can form a discharge space between the roller which applied the magnetic field which consists of the structure of FIG. ), 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. This method for forming the first gas barrier layer 1 is referred to as a CVD method 1.

<Film formation conditions>
Feed rate of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.8 m / min
As a result of measuring the carbon atom, silicon atom, and oxygen atom profiles of the first gas barrier layer 1 produced by the XPS method, the element profile shown in FIG. 6 is obtained, which is defined in claim 5 of the present invention ( It was confirmed that all the conditions of 1) to (4) were satisfied.

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

<Preparation of coating solution for forming polysilazane layer>
A 10 mass% dibutyl ether solution of perhydropolysilazane (PHPS, Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as a coating liquid for forming a polysilazane layer.

<Formation of polysilazane layer>
The prepared polysilazane layer-forming coating solution 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%. The polysilazane layer was formed by drying and further holding in an atmosphere of a temperature of 25 ° C. and a relative humidity of 10% (dew point temperature −8 ° C.) for 10 minutes to perform dehumidification.

<Formation of gas barrier layer: Silica conversion of polysilazane layer by ultraviolet light>
Next, the following ultraviolet device was installed in the vacuum chamber for the polysilazane layer formed above, and the pressure in the device was adjusted to carry out a silica conversion treatment.

<Ultraviolet irradiation device>
Apparatus: M.com Co., Ltd. excimer irradiation apparatus MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
<Reforming treatment conditions>
The resin base material 2 with a conductive layer on which the polysilazane layer fixed on the operation stage was subjected to a modification treatment under the following conditions to form a gas barrier layer, thereby producing a gas barrier film 5.

Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
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]
In the production of the gas barrier film 1, a gas barrier film 2 was produced in the same manner except that the method for forming the hard coat layer was changed to the following method.

(Formation of hard coat layer 2)
In accordance with the following method, the hard coat layer 2A and the hard coat layer 2B were laminated in this order on the resin base material to form a hard coat layer 2 composed of two layers.

<Preparation of coating liquid 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: Non-surface-modified silica (average particle size 6 nm, colloidal silica Snowtex AK, manufactured by Nissan Chemical Co., Ltd.) 51.3 parts 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 (manufactured by BASF Japan)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone BASF Japan) 2.55 parts modified silicone oil: KF-351A (polyether modified Shin-Etsu Chemical Co., Ltd.) )
0.95 parts Surfactant: Emulgen 404 (Polyoxyethylene Oleille Ether Kao)
0.26 parts Organic solvent: 100 parts of methyl ethyl ketone 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 the 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 the hard coat layer 2B.

Silicon dioxide particles: non-surface-modified silica (average particle size 6 nm, colloidal silica Snowtex AK, manufactured by Nissan Chemical Co., Ltd.) 43.3 parts binder resin 1: urethane acrylate (UA-1100H-LC, manufactured by 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 (manufactured by BASF Japan)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone BASF Japan) 2.55 parts modified silicone oil: KF-351A (polyether modified Shin-Etsu Chemical Co., Ltd.) )
0.95 parts Surfactant: Emulgen 404 (Polyoxyethylene Oleille Ether Kao)
0.26 parts Organic solvent: 100 parts of methyl ethyl ketone The solid content concentration of the coating liquid for forming the hard coat layer 2B is 50% by mass, and the solid content ratio of the silicon dioxide particles to the total solid content is 43.3% by mass. .

<Coating and curing treatment>
The above-prepared coating liquid for forming the hard coat layer 2A and the coating liquid for forming the hard coat layer 2B are filtered through a polypropylene filter having a pore diameter of 0.4 μm, respectively, The coating solution for forming the hard coat layer 2B and the coating solution for forming the hard coat layer 2A on the top are supplied and applied on the TAC film under the condition that the layer thickness after drying is 2 μm, and then dried at a constant rate. Drying was performed under the drying conditions of a section temperature of 80 ° C. and a reduced rate drying section temperature of 80 ° C., and then cured under a condition of 1.0 J / cm ² using a high-pressure mercury lamp in the atmosphere, and the hard coat layer 2A and 2B was formed.

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

[Preparation of gas barrier film 3]
In the production of the gas barrier film 1, the gas barrier film 3 was produced in the same manner except that the hard coat layer 3 was formed according to the following method instead of the hard coat layer 1.

(Formation of hard coat layer 3)
The hard coat layer 3 was formed on the TAC film subjected to the corona treatment by using a hard coat layer 3 forming coating solution 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 the 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 Catalysts & Chemicals)
59.6 parts Binder resin 1: Urethane acrylate (UA-1100H-LC, Shin-Nakamura Chemical Co., Ltd.) 22.7 parts Binder resin 2: Dipentaerythritol hexaacrylate (NK ester A-DPH, 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 BASF Japan) 2.55 parts modified silicone oil: KF-351A (polyether modified Shin-Etsu Chemical Co., Ltd.) )
0.95 parts Surfactant: Emulgen 404 (Polyoxyethylene Oleille Ether Kao)
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 concentration of the coating liquid for forming the hard coat layer 3 is 50% by mass. The solid content ratio of silicon dioxide particles (surface-modified silica particles) with respect to the total solid content is 59.6% by mass.

<Coating and curing treatment>
After the prepared coating liquid for forming the hard coat layer 3 is filtered through a polypropylene filter having a pore size of 0.4 μm, and then applied onto a TAC film using a wet coater under a condition that the layer thickness after drying is 4 μm. After drying under slow drying conditions at a constant rate drying zone temperature of 65 ° C. and a decreasing rate drying zone temperature of 65 ° C., it is hardened under a condition of 1.0 J / cm ² using a high-pressure mercury lamp in the atmosphere. Coat layer 3 was formed.

  As a result of measuring the silicon content and silicon dioxide particle content (mass%) by the XPS method, the hard coat layer 3 formed here was a surface region T (thickness 1/10) on the surface side in contact with the gas barrier layer. The silicon dioxide particle content 2 (mass%) is 71.2 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 47.8 mass. %, The difference in content ΔC (silicon dioxide particle content 2−silicon dioxide particle content 1) between the silicon dioxide particle content 2 (mass%) and the silicon dioxide particle content 1 (mass%) is 23.4 mass. %Met.

[Preparation of gas barrier film 4]
In the production of the gas barrier film 3, the first gas barrier layer forming method 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. According to the above method, a gas barrier film 4 was produced in the same manner except that the parallel gas type electrode was used and the first gas barrier layer 2 having a uniform composition was formed.

(Formation of gas barrier layer 2: CVD method 2)
In accordance with the following conditions, a 300 nm thick gas barrier layer 2 was formed by a plasma discharge method. This film forming method is referred to as CVD method 2.

<A mixed gas composition for forming the 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
<Gas barrier layer 2 deposition conditions>
1st electrode side Power supply type
Frequency 80kHz
Output density 8W / cm ²
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 90 ° C
The formed first gas barrier layer 2 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 wasn't.

[Preparation of gas barrier film 5]
In the production of the gas barrier film 3, a gas barrier film 5 was produced in the same manner 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)
After filtering the coating solution for forming the hard coat layer 3 used for the production of the gas barrier film 3 through a polypropylene filter having a pore diameter of 0.4 μm, using a wet coater, the layer thickness after drying is 4 μm, After being coated on the TAC film, it was dried under a rapid drying condition of a constant rate drying section temperature of 85 ° C. and a decreasing rate drying section temperature of 85 ° C., and then using a high pressure mercury lamp in the atmosphere, 1.0 J / cm ² The hard coat layer 4 was formed by curing under conditions.

  As a result of measuring the silicon content and the silicon dioxide particle content (mass%) by the XPS method, the hard coat layer 4 formed here is a surface region T (thickness 1/10) on the side in contact with the gas barrier layer. The silicon dioxide particle content 2 (mass%) is 65.3 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 54.1 mass%. %, The content difference ΔC (silicon dioxide particle content 2 -silicon dioxide particle content 1) between the silicon dioxide particle content 2 (mass%) and the silicon dioxide particle content 1 (mass%) is 11.2 mass. %Met.

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

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

  As a result of measuring the silicon content and the silicon dioxide particle content (mass%) by the XPS method, the hard coat layer 4 formed here is a surface region 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%. %, The content difference ΔC (silicon dioxide particle content 2-silicon dioxide particle content 1) between the silicon dioxide particle content 2 (mass%) and the silicon dioxide particle content 1 (mass%) is 18.5 mass %Met.

[Preparation of gas barrier film 7]
In the production of the gas barrier film 3, the surface modified silica used for forming the hard coat layer 3 was replaced with the surface modified silica 1: ELCOM V-8804, except that the following surface modified silica 2 was used. A gas barrier film 7 was produced.

Surface-modified silica 2: Aerosil R711 (manufactured by Nippon Aerosil Co., Ltd., primary average particle size: 12 nm, silica fine particles having a (meth) acryloyl group on the particle surface)
[Production 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)
The hard coat layer 7 was formed on the TAC film subjected to the corona treatment by using a coating liquid for forming a hard coat layer 7 composed of the following additives.

<Preparation of coating liquid for forming hard coat layer 7>
The following constituent materials were sequentially added, mixed and dissolved to prepare a coating solution for forming the hard coat layer 7.

Silicon dioxide particles: non-surface-modified silica (average particle diameter 6 nm, colloidal silica Snowtex AK, manufactured by Nissan Chemical Co., Ltd.) 47.3 parts 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 (manufactured by BASF Japan)
1.70 parts alkylphenone photopolymerization initiator 2: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone BASF Japan) 2.55 parts modified silicone oil: KF-351A (polyether modified Shin-Etsu Chemical Co., Ltd.) )
0.95 parts Surfactant: Emulgen 404 (Polyoxyethylene Oleille Ether Kao)
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% by mass The solid content ratio of the silicon dioxide particles to the total solid content is 39.4% by mass. Note that propylene glycol (boiling point: 188 ° C.), which is a high boiling point solvent, is present in the hard coat layer after drying, and therefore is taken into account in the calculation of the total solid content.

<Coating and curing treatment>
After the prepared coating liquid for forming the hard coat layer 7 is filtered through a polypropylene filter having a pore size of 0.4 μm, and then coated on a TAC film under a condition that the layer thickness after drying is 4 μm using a wet coater. Then, after drying at a constant rate drying zone temperature of 65 ° C. and a decreasing rate drying zone temperature of 65 ° C., the hard coat layer 7 is hardened under conditions of 1.0 J / cm ² using a high-pressure mercury lamp in the atmosphere. Formed.

  As a result of measuring the silicon content and silicon dioxide particle content (mass%) by the XPS method described later, the hard coat layer 1 formed here was a surface region T (thickness 1/10) on the side in contact with the gas barrier layer. ), 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 TAC film as the resin substrate is 28. The content difference ΔC (silicon dioxide particle content 2−silicon dioxide particle content 1) between the silicon dioxide particle content 2 (mass%) and the silicon dioxide particle content 1 (mass%) at 4% by mass is 21. It was 4% by mass.

[Production of Gas Barrier Film 10]
In the production of the gas barrier film 9, the first gas barrier layer is formed by replacing 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 production of the gas barrier film 9, a gas barrier was similarly obtained except that the following HBS2 was used instead of the high boiling point solvent (HBS1: propylene glycol (boiling point: 188 ° C.)) used for forming the hard coat layer 3. Film 11 was produced.

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

[Production of gas barrier film 13]
In the production of the gas barrier film 3, the gas barrier film was formed in the same manner except that the hard coat layer 9 was 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 the 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 Catalysts & Chemicals)
59.6 parts Binder resin 1: Urethane acrylate (UA-1100H-LC, Shin-Nakamura Chemical Co., Ltd.) 22.7 parts Binder resin 2: Dipentaerythritol hexaacrylate (NK ester A-DPH, 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 BASF Japan) 2.55 parts modified silicone oil: KF-351A (polyether modified Shin-Etsu Chemical Co., Ltd.) )
0.95 parts Surfactant: Emulgen 404 (Polyoxyethylene Oleille Ether Kao)
0.26 parts organic solvent 1: methyl ethyl ketone (boiling point: 79 ° C) 80 parts organic solvent 2: HBS1 propylene glycol (boiling point: 188 ° C) 20 parts [Preparation of gas barrier film 14]
In the production of the gas barrier film 3, instead of the hard coat layer 3, the following five types of hard coat layer forming coating liquids were used, and the gradient concentrations with different silicon dioxide particle concentrations were used in the configuration illustrated in FIG. 4. A gas barrier film 14 was produced in the same manner except that a hard coat layer (unit) 10 composed of five layers having a thickness of 10 was formed.

In addition, the hard coat layer coating solution for forming each layer is obtained by changing the surface-modified silica content to the following addition amount with respect to the coating solution for forming the hard coat layer 3 used for the production of the gas barrier film 3, The first layer (3-1B in FIG. 4) forming hard coat layer coating solution: surface-modified silica content = 53 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>
After each of the prepared coating liquids for forming a hard coat layer is filtered through a polypropylene filter having a pore size of 0.4 μm, a hard coat layer for forming a first layer is applied from the bottom using a coater capable of simultaneous five-layer coating. After applying the liquid to the fifth layer forming hard coat layer coating solution on the 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, the constant rate drying section temperature 75 After drying at a temperature of 75 ° C. and a decreasing drying temperature of 75 ° C., the hard coat layer 10 was formed by curing under a condition of 1.0 J / cm ² using a high-pressure mercury lamp in the atmosphere.

  The hard coat layer 10 formed here was measured for the silicon content and silicon dioxide particle content (mass%) by XPS, and as a result, the surface region T (surface) in the fifth layer on the surface side in contact with the gas barrier layer To 400 nm), the silicon dioxide particle content 2 (mass%) is 72.5 mass%, and the surface area B (from the TAC film surface) of the first layer in contact with the TAC film as the resin base material The silicon dioxide particle content 1 (mass%) in the range of 400 nm is 51.3% by mass, and 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) 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, the first gas barrier layer is formed by replacing 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 it was formed by the CVD method 2 used for producing the barrier film 4.

[Production of gas barrier film 17]
In the production of the gas barrier film 1, instead of the hard coat layer 1, the following five kinds of hard coat layer forming coating liquids were used, each having a step-like concentration configuration illustrated in FIG. 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.

  In addition, the hard coat layer coating solution for forming each layer is changed from the colloidal silica content to the following addition amount with respect to the coating solution for forming the hard coat layer 1 used for the production of the gas barrier film 1, The amount of the binder resin was adjusted, 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 mass%
Hard coat layer coating solution for forming the fourth layer (3-4A in FIG. 3): Colloidal silica content = 49 mass%
Hard coat layer coating solution for forming the fifth layer (3-5A in FIG. 3): Colloidal silica content = 54 mass%
<Coating and curing treatment>
After each of the prepared coating liquids for forming a hard coat layer is filtered through a polypropylene filter having a pore size of 0.4 μm, a hard coat layer for forming a first layer is applied from the bottom using a coater capable of simultaneous five-layer coating. After applying the liquid to the fifth layer forming hard coat layer coating solution on the 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, the constant rate drying section temperature 75 After drying at a temperature of 75 ° C. and a reduced drying temperature of 75 ° C., the hard coat layer 11 was formed by curing under a condition of 1.0 J / cm ² using a high-pressure mercury lamp in the atmosphere.

  As a result of measuring the silicon content and the silicon dioxide particle content (mass%) by XPS method, the hard coat layer 11 formed here was the surface region T (surface) in the fifth layer on the side in contact with the gas barrier layer. To 400 nm), the silicon dioxide particle content 2 (mass%) is 54.8 mass%, and the surface area B (from the TAC film surface) in the first layer in contact with the TAC film as the resin substrate In the range of 400 nm, the silicon dioxide particle content 1 (mass%) is 34.1 mass%, and 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) was 20.7% by mass.

[Preparation of gas barrier film 18]
In the production of the gas barrier film 9, instead of the hard coat layer 7, the following five types of hard coat layer forming coating solutions were used, and the gradient concentrations with different silicon dioxide particle concentrations were used in the configuration illustrated in FIG. 4. A gas barrier film 18 was produced in the same manner except that a hard coat layer (unit) 12 composed of 5 layers having a thickness of 5 was formed.

  In addition, the hard coat layer coating solution for forming each layer is changed to the following addition amount with respect to the coating solution for forming the hard coat layer 7 used for the production of the gas barrier film 9, The amount of the binder resin was adjusted, 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 mass%
<Coating and curing treatment>
After each of the prepared coating liquids for forming a hard coat layer is filtered through a polypropylene filter having a pore size of 0.4 μm, a hard coat layer for forming a first layer is applied from the bottom using a coater capable of simultaneous five-layer coating. After applying the liquid to the fifth layer forming hard coat layer coating solution on the 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, the constant rate drying section temperature 75 After drying at a temperature of 75 ° C. and a reduced rate drying temperature of 75 ° C., the hard coat layer 12 was formed by curing under a condition of 1.0 J / cm ² using a high-pressure mercury lamp in the atmosphere.

  As a result of measuring the silicon content and the silicon dioxide particle content (mass%) by XPS method, the hard coat layer 12 formed here was a surface region T (surface) on the fifth layer on the side in contact with the gas barrier layer. To 400 nm), the silicon dioxide particle content 2 (% by mass) is 49.1% by mass, and the surface region B (from the TAC film surface) in the first layer in contact with the TAC film as the resin substrate In the range of 400 nm, the silicon dioxide particle content 1 (mass%) is 28.4 mass%, and the difference in content 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) was 20.7% by mass.

[Production of gas barrier film 19]
In the production of the gas barrier film 18, the first gas barrier layer is formed by replacing 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 it was formed by the CVD method 2 used for producing the barrier film 4.

[Production of gas barrier films 20 and 21]
In the production of the gas barrier film 3, gas barrier films 20 and 21 were produced in the same manner except that the following PET film and COP film were used instead of the TAC film as the resin base material.

PET film: Biaxially stretched polyethylene terephthalate film, manufactured by Teijin DuPont Films, Inc. KEL86W Film thickness: 125 μm
COP film: cycloolefin polymer film, manufactured by Nippon Zeon Co., Ltd., Zeonea ZF14 film, film thickness: 100 μm
[Preparation of gas barrier film 22]
A gas barrier film 22 was produced in the same manner except that the hard coat layer 3 was not formed in the production of the gas barrier film 3.

[Preparation of gas barrier film 23]
In the preparation of the gas barrier film 3, a gas barrier film 23 was prepared in the same manner as in the preparation of the coating liquid for forming the hard coat layer 3 used for forming the hard coat layer 3, except that the surface-modified silica was removed.

<< Production of organic EL element >>
Next, 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 deposition apparatus, and the following compound No. 10 was put in a resistance heating boat made of tungsten, and the gas barrier film holder and the heating boat were mounted in a first vacuum chamber of a vacuum deposition apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

After depressurizing the first vacuum chamber of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, Compound No. The heating boat containing 10 was energized and 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 / second. The gas barrier film on which the underlayer was formed was transferred to the second vacuum chamber while being vacuumed, and after the pressure in the second vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver was energized and heated. As a result, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 to 0.2 nm / second.

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

  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), a compound A -3 changes the deposition rate so that the content rate is linear with respect to the layer thickness direction and the gradient is 35% to 5%, 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 / second, the compound H-1 has a gradient concentration of 64.6% to 94.6% in the layer thickness direction so that each concentration is constant at 0.2% by mass. The vapor deposition rate was changed so that a co-deposited light emitting layer having a layer thickness of 70 nm was formed.

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

  In addition, the compound No. used for the formation of each organic functional layer was used. 10, Compound HT-1, Compound A-1 to Compound 3, Compound H-1, and Compound ET-1 are compounds shown below.

Next, an aluminum foil with a thickness of 25 μm is used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) is bonded as a sealing resin layer on one surface of the aluminum foil with a thickness of 20 μm. Using the stop member, the resin base material prepared up to the second electrode was superposed. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the ends of the lead wires of the first electrode and the second electrode were exposed.

  Next, the sample including the gas barrier film was placed in a decompression device, and was held for 5 minutes under a reduced pressure condition of 90 ° C. and 0.1 MPa while pressure was applied to the stacked sample and the sealing member. Subsequently, the sample including the gas barrier film was returned to the atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.

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

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

<< Evaluation of gas barrier film and organic EL element >>
[Evaluation of gas barrier film]
(Evaluation of adhesion)
About each produced said gas barrier film, after preserve | saving for 1 week in the environment of 50 degreeC and 80% RH in the state wound by metal roll, the adhesive evaluation was performed according to the following evaluation method of cross-cut adhesion. .

  The cross-cut adhesion is evaluated according to the description of 5.6 (2004 edition) of JIS K 5600. The gas barrier layer and the hard coat layer are formed with a cutter knife on the gas barrier layer forming surface side of each gas barrier film. 100 mm grid cuts of 1 mm square that penetrate and reach the resin substrate are attached using a cutter guide with a 1 mm interval, and cellophane adhesive tape (Nichiban "CT405AP-18"; 18 mm width) is attached to the cut surface. Attaching and rubbing from the top with an eraser to completely adhere the tape, then peeling off in the vertical direction, visually confirming how much the gas barrier layer and hard coat layer remain on the substrate surface, out of 100 The number of peels was examined, and adhesion was evaluated according to the following criteria.

5: The number of peels was 5 or less in the cross cut test 4: The number of peels was 6 or more and 10 or less in the cross cut test 3: The number of peels was 11 in the cross cut test The number of peeling was 16 or more and 20 or less in the cross-cut test, and the number of peel was 21 or more in the cross-cut test. [Organic EL Element evaluation)
About the said organic EL elements 101-123, the electric current of 1 mA / cm < ² > was applied and it was made to light-emit. Next, as for the light emission state immediately after application and after continuous light emission for 300 hours and 500 hours as the light emission time in an environment of 50 ° C. and 80% RH, a 100 × optical microscope (MS-804, manufactured by Moritex Corporation) A part of the organic EL element was magnified and photographed with a lens MP-ZE25-200). Next, the photographed image was cut out in a 2 mm square, and the presence or absence of dark spots was observed for each image. From the observation results, the ratio of the dark spot generation area to the light emission area was determined, and the dark spot resistance was evaluated according to the following criteria.

5: No dark spots are observed even after 500 hours of light emission. 4: Dark spots are not observed even after 300 hours of light emission, but only slightly after 500 hours of light emission. Generation of dark spots is observed (generation area 0.1% or more, less than 3.0%)
3: Slight dark spots are observed in the sample after 300 hours of light emission (generation area 0.1% or more and less than 3.0%)
2: Generation of clear dark spots is observed in the sample after 300 hours of light emission (generation area of 3.0% or more and less than 6.0%)
1: A large number of dark spots are observed in the sample after luminescence for 300 hours (generation area of 6.0% or more).
The results obtained as described above are shown in Table 2.

As is apparent from the results shown in Table 2, the gas barrier film produced by the method defined in the present invention has an adhesion between the layers even when stored for a long period of time in a high temperature and high humidity environment compared to the comparative example. There is no deterioration of sex. Moreover, it turns out that generation | occurrence | production of the dark spot resulting from film | membrane peeling etc. in a high-temperature, high-humidity environment is suppressed by providing an organic EL element with the gas barrier film provided with such a characteristic.

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 Laminated hard coat layer 3T Surface area | region 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 rollers 12A to 12E, 81 preparation kettle 13, 82 coater 14, 83 drying step 15 ultraviolet irradiation device 17 ultraviolet irradiation lamp 18 UV 21, 22, 23, 24 Transport roller 30 Plasma CVD manufacturing apparatus 31, 32 Film forming roller 41 Gas supply pipe 51 Power source for plasma generation 61, 62 Magnetic field generator 71, 93 Winding 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 117a Hole Injection Layer 117b Hole Transport Layer 117c Light Emission Layer 117d Electron Transport Layer 117e Electron Injection Layer 118 Second Electrode 119 Sealing Perching 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 (10)

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, the silicon dioxide particle content 2 (mass%) in the surface region T on the gas barrier layer surface side of the hard coat layer, and the surface region B on the resin substrate surface side. A concentration gradient structure in which the content difference ΔC (silicon dioxide particle content 2−silicon dioxide particle content 1) with respect to the silicon dioxide particle content 1 (mass%) is 10% by mass or more,
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 source gas containing an organic silicon compound and oxygen gas. A method for producing a film.   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 region T on the gas barrier layer side of the hard coat layer, and the silicon dioxide particle content 1 (mass%) in the surface region B on the resin substrate surface side, 3. The method for producing a gas barrier film according to claim 1, wherein a content ratio difference ΔC (silicon dioxide particle content 2 -silicon dioxide particle content 1) is 20% by mass or more.   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 gas barrier layer contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements, and is formed so as 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 continuously changes in the layer thickness direction corresponding to the distance from the surface within a distance range from the surface of the gas barrier layer to 89% of the layer thickness. .
(2) The maximum value of the carbon atom ratio of the gas barrier layer is less than 20 at% within the distance range 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 within the distance range from the surface of the gas barrier layer to 90 to 95% of the layer thickness in the layer thickness direction.
(4) The maximum value of the carbon atom ratio of the gas barrier layer is 20 at% or more within the distance range from the surface of the gas barrier layer to 90 to 95% of the layer thickness in the layer thickness direction.   The method for producing a gas barrier film according to any one of claims 1 to 5, wherein the silicon dioxide particles contained in the hard coat layer are surface-modified silicon dioxide particles.   The gas barrier film according to any one of claims 1 to 6, wherein the hard coat layer contains a polyhydric alcohol-based high boiling point solvent having a boiling point of 150 ° C or higher at normal pressure. Manufacturing method.   The gas barrier film according to any one of claims 1 to 7, wherein the hard coat layer is composed of two or more layers having different silicon dioxide particle content (mass%). Manufacturing method.   A polysilazane-containing liquid is applied and dried on the gas barrier layer, and the formed coating film is irradiated with vacuum ultraviolet light having a wavelength of 200 nm or less to form a second gas barrier layer. The method for producing a gas barrier film according to any one of claims 1 to 8.   An organic electroluminescence device comprising a gas barrier film produced by the method for producing a gas barrier film according to any one of claims 1 to 9.