JP5892030B2 - Method for producing gas barrier film and gas barrier film - Google Patents

Description

  The present invention relates to a method for producing a gas barrier film and a gas barrier film. In more detail, it is related with the manufacturing method and gas barrier film of a gas barrier film mainly used for electronic devices, such as an organic electroluminescent (EL) element.

  Conventionally, a gas barrier film formed by laminating a plurality of layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film is used for various gases such as water vapor and oxygen. It is widely used for packaging of articles that need to be blocked, for example, packaging for preventing deterioration of food, industrial goods, pharmaceuticals, and the like.

  In addition to packaging applications, development to flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, etc. has been demanded, and many studies have been made. However, these flexible electronic devices are required to have a gas barrier property at a glass substrate level, so that a gas barrier film having sufficient performance has not been obtained yet.

  As a method of forming such a gas barrier film, a chemical deposition method (CVD) in which an organic silicon compound typified by tetraethoxysilane (TEOS) is used and a film is formed on a substrate while being oxidized with oxygen plasma under reduced pressure. Gas phase methods such as a chemical vapor deposition (chemical vapor deposition) and a physical deposition method (vacuum evaporation method or sputtering method) in which metal Si is evaporated using a semiconductor laser and a film is formed on a substrate in the presence of oxygen are known.

Patent Document 1 discloses a manufacturing method of forming a 10 -4 ^{g / m} 2 ^{/ 24h} level barrier layer in roll-to-roll method while utilizing the plasma CVD method in the apparatus shown in FIG. 1 . The gas barrier film manufactured above has improved the adhesion and flexibility with the substrate by the CVD method that can arrange many carbon atoms around the substrate. It was found that the gas barrier property and the flexibility of the electronic device including the organic EL element are insufficient under the use environment of high humidity.

  On the other hand, Patent Document 2 discloses a method for producing a gas barrier layer by a coating method that is superior in productivity and cost. In the above production method, polysilazane is used as an inorganic precursor compound, applied and dried, and a gas barrier layer is formed by irradiating the coating film with vacuum ultraviolet light (VUV light). Patent Document 2 discloses a gas barrier film in which an ultraviolet curable resin layer is provided between a substrate and a gas barrier layer for the purpose of preventing bleed out and smoothing. Etc. are not mentioned.

WO2012 / 046767 JP 2011-143577 A

  The present invention has been made in view of the above-mentioned problems and situations, and its solution is to have a gas barrier property necessary for electronic device use even under high-temperature and high-humidity usage environments such as outdoor use, and to be flexible. It is providing the manufacturing method and gas barrier film of a gas barrier film excellent in property (flexibility).

  In order to solve the above-mentioned problems, the present inventor performs transport while bringing the resin base material into contact with each of the pair of film-forming rollers in the process of examining the cause of the above-mentioned problem, and between the pair of film-forming rollers. A method for producing a gas barrier film in which a gas barrier layer is formed on a resin base material by a plasma chemical vapor deposition method (CVD method) in which plasma discharge is performed while supplying a film forming gas. It has been found that a gas barrier film excellent in gas barrier properties and flexibility can be obtained by a production method characterized by having a stress absorbing layer having a specific indentation hardness on both sides, and has led to the present invention.

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

  1. The resin base material is transported while the resin base material is brought into contact with each of the pair of film forming rollers, and plasma discharge is performed while supplying a film forming gas between the pair of film forming rollers. A method for producing a gas barrier film on which a gas barrier layer is formed, wherein the resin substrate has a stress absorption layer having an indentation hardness with respect to a load of 100 μN on both sides within a range of 0.4 to 1.0 GPa. And a method for producing a gas barrier film, comprising forming the gas barrier layer on at least one of the stress absorbing layers.

2. A source gas containing an organosilicon compound and an oxygen gas are used as the deposition gas, the gas barrier layer contains carbon, silicon, and oxygen as constituent elements, and the gas barrier layer in the thickness direction of the gas barrier layer In the carbon distribution curve showing the relationship between the distance from the surface of and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atom ratio),
The carbon atom ratio of the gas barrier layer is in the range of 8 to 20 at% as an average value of the entire layer, and the carbon distribution curve continuously changes in the layer with a concentration gradient. The manufacturing method of the gas barrier film of Claim 1 to do.

  3. The indentation hardness of the surface that contacts the film-forming roller of the stress absorbing layer is smaller in the range of 0.1 to 0.3 GPa than the surface that does not contact, The first or second aspect A method for producing a gas barrier film.

  4). The diameter of the said film-forming roller exists in the range of 300-1000 mmphi, The manufacturing method of the gas barrier film as described in any one of Claim 1 to 3 characterized by the above-mentioned.

  5. A polysilazane-containing liquid is applied onto the gas barrier layer, 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. The method for producing a gas barrier film according to any one of items 1 to 4, wherein:

  6). A resin base material, a gas barrier film in which a stress absorption layer is laminated on both surfaces of the resin base material, and a gas barrier layer is laminated on at least one surface of the stress absorption layer, and the stress absorption layer has a load of 100 μN The indentation hardness of the gas barrier layer is in the range of 0.4 to 1.0 GPa, the gas barrier layer contains carbon, silicon, and oxygen as constituent elements, and the gas barrier layer has a thickness direction of the gas barrier layer. In the carbon distribution curve showing the relationship between the distance from the surface and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atom ratio), the carbon atom ratio of the gas barrier layer is the entire layer A gas barrier characterized in that the carbon distribution curve is continuously changing with a concentration gradient in the layer, and an average value of 8 to 20 at% as an average value of Irumu.

  7). On the gas barrier layer, a polysilazane-containing liquid is applied and dried, and the formed coating film is laminated with a second gas barrier layer that is modified by irradiation with vacuum ultraviolet light having a wavelength of 200 nm or less. 7. The gas barrier film according to item 6, wherein

  By the above means of the present invention, a method for producing a gas barrier film having gas barrier properties necessary for electronic device use and excellent in flexibility (flexibility) even under high-temperature and high-humidity environment such as outdoor use, and A gas barrier film can be provided.

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

  That is, the resin base material having the stress absorption layer adjusted to a specific indentation hardness on both sides is conveyed while being brought into contact with each of the pair of film forming rollers, and the film forming gas is supplied between the pair of film forming rollers. By forming a gas barrier layer by plasma enhanced chemical vapor deposition with plasma discharge, the thermal expansion of the resin base material on the contact surface and non-contact surface of the film formation roller that occurs in a high temperature environment on the film formation roller It is presumed that the residual stress is absorbed by the stress absorbing layer to suppress the generation of minute defects when forming the gas barrier layer. Even under severe conditions of use, high temperature and high humidity, it is possible to suppress the generation of minute defects in the gas barrier layer due to the release of the residual stress. It is estimated that a gas barrier film that sufficiently satisfies the properties can be obtained.

  Excellent flexibility is achieved by the plasma chemical vapor deposition method in which plasma discharge is performed while supplying a deposition gas between a pair of deposition rollers, and the carbon atom component in the gas barrier layer has a concentration gradient and is continuous. Although it is presumed to be an effect of changing to the above, the combined effect with the hardness of the stress absorption layer of the above resin base material maintains and exhibits excellent flexibility even under severe conditions such as high temperature and high humidity Presumed to be.

  By the way, in the CVD method with flat electrode (horizontal transport) type plasma discharge, there is almost no residual stress on the front and back of the resin base material due to horizontal transport, but there is no continuous change in the concentration gradient of carbon atom components. Therefore, a high degree of compatibility between gas barrier properties and flexibility is insufficient.

  In addition, the plasma chemical vapor deposition method in which plasma discharge is performed between a pair of film forming rollers according to the present invention is preferably performed under vacuum, but since there is no moisture or residual dissolved air, it becomes a condition under high temperature and high humidity. Residual stress is likely to occur suddenly. It also increases productivity by increasing the film formation width, increasing the line speed, increasing the diameter of the film formation roller to increase the discharge space, and reducing the thickness of the resin substrate. The residual stress of the gas barrier layer is considered to increase as the intended condition progresses, and in order to achieve both high gas barrier properties and flexibility, the present invention is adjusted to a specific indentation hardness on both sides of the resin substrate. It is estimated that the arrangement of the stress absorbing layer according to the above exhibits an excellent effect in releasing the residual stress.

The basic structure (a) which shows an example of the gas barrier film of this invention, and the schematic diagram which shows another structure (b) Schematic showing an example of gas barrier film manufacturing equipment Silicon distribution curve, oxygen distribution curve and carbon distribution curve of gas barrier layer of Example Comparative gas barrier layer silicon distribution curve, oxygen distribution curve and carbon distribution curve Schematic diagram of an organic EL panel equipped with a gas barrier film

  The method for producing a gas barrier film of the present invention is a plasma in which a resin base material is conveyed while contacting each of a pair of film forming rollers, and plasma discharge is performed while supplying a film forming gas between the pair of film forming rollers. A manufacturing method for forming a gas barrier layer on the resin substrate by chemical vapor deposition, wherein the resin substrate has a stress absorbing layer having a specific indentation hardness on both sides, and at least one of the The gas barrier layer is formed on the stress absorbing layer. This feature is a technical feature common to the inventions according to claims 1 to 7.

  As an embodiment of the present invention, from the viewpoint of manifesting the effect of the present invention, a raw material gas containing an organosilicon compound and an oxygen gas are used as the film forming gas, and carbon, silicon, and oxygen are used as constituent elements of the gas barrier layer. And a carbon distribution curve showing the relationship between the distance from the surface of the layer in the layer thickness direction of the layer and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atom ratio) , The carbon atom ratio of the gas barrier layer is in the range of 8 to 20 at% as an average value of the whole layer, and the carbon distribution curve continuously changes with a concentration gradient in the layer. It is preferable from the viewpoint of improving and achieving both gas barrier properties and flexibility at the time of production and under high temperature and high humidity. In addition, the indentation hardness of the surface that contacts the film forming roller of the stress absorbing layer is smaller in a specific range than the non-contacting surface, so that the effect of absorbing residual stress at the time of manufacturing and under high temperature and high humidity is exhibited. From the viewpoint of

  Furthermore, in the present invention, the film forming roller having a diameter of 300 mmφ or more controls the concentration distribution in the layer having the carbon atom ratio and the distance between extreme values, thereby further improving flexibility. It is preferable because an effect is obtained.

  Further, a polysilazane-containing liquid is applied onto the gas barrier layer, 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. It is also a preferred embodiment because it further improves the gas barrier properties.

  The gas barrier film of the present invention has a stress absorption layer having a specific indentation hardness on both surfaces of a resin substrate, and contains carbon, silicon, and oxygen as constituent elements on at least one of the stress absorption layers. And a gas barrier layer in which the carbon atom ratio of the gas barrier layer is in the range of 8 to 20 at% as an average value of the whole layer and has a concentration gradient and is continuously changed in the layer. Therefore, the gas barrier property and the flexibility under high temperature and high humidity can be improved and compatible.

  Furthermore, a gas barrier layer provided by a CVD method by laminating a second gas barrier layer containing polysilazane and modified by irradiation with vacuum ultraviolet light having a wavelength of 200 nm or less on the gas barrier layer. Since the minute defects remaining on the surface can be filled with the gas barrier component of polysilazane from above, the gas barrier property and flexibility required for the electronic device can be sufficiently exhibited even under high temperature and high humidity, which is preferable.

The “gas barrier property” as used in the present invention is a water vapor permeability (temperature: 60 ± 0.5 ° C., relative humidity (RH): 90 ± 2%) measured by a method according to JIS K 7129-1992. ) Is 3 × 10 ⁻³ g / m ² · 24 h or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less. Means that.

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

<Outline of production method of gas barrier film of the present invention>
The method for producing a gas barrier film of the present invention is a plasma in which a resin base material is conveyed while contacting each of a pair of film forming rollers, and plasma discharge is performed while supplying a film forming gas between the pair of film forming rollers. A method for producing a gas barrier film in which a gas barrier layer is formed on a resin substrate by chemical vapor deposition, wherein the resin substrate has an indentation hardness of 0.4 to 1 against a load of 100 μN on both surfaces. It has a stress absorption layer within a range of 0.0 GPa, and the gas barrier layer is formed on at least one of the stress absorption layers.

<Configuration of gas barrier film>
The gas barrier film 1a of the present invention includes, for example, a stress absorbing layer 2 on both surfaces of a resin base material 1 and a gas barrier layer 3 is laminated on the stress absorbing layer 2 as shown in FIG. This is a four-layer barrier film.

  Moreover, the gas barrier film 1b of the present invention which is another aspect includes, for example, a stress absorbing layer 2 on both surfaces of a resin base material 1 as shown in FIG. A barrier layer 3 is laminated, and a second gas barrier layer 4 containing polysilazane is further laminated on the gas barrier layer 3. It is also a preferred embodiment that an overcoat layer 5 is laminated on the second gas barrier layer 4.

<Resin substrate>
The resin base material of the gas barrier film of the present invention is not particularly limited as long as it is formed of an organic material capable of holding a gas barrier layer having a barrier property described later.

  For example, methacrylic acid ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, and Examples include resin films such as polyetherimide, and resin films formed by laminating two or more layers of the above resins. In terms of cost and availability, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), and the like are preferably used.

  The thickness of the resin base material is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

  Moreover, it is preferable that the resin base material which concerns on this invention is transparent. Since the resin base material is transparent and the layer formed on the resin base material is also transparent, it becomes possible to make a transparent gas barrier film, so that it can be made a transparent substrate such as an organic EL element. Because it becomes.

  Moreover, the unstretched film may be sufficient as the resin base material using the resin etc. which were mentioned above, and a stretched film may be sufficient as it. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression. Moreover, retardation etc. can also be adjusted by extending | stretching.

  The resin base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched resin substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Moreover, an unstretched resin base material that is substantially amorphous and not oriented is obtained by dissolving a resin as a material in a solvent, casting (casting) on an endless metal support, drying, and peeling. It can also be manufactured.

  The unstretched resin base material is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, and other known methods, such as the resin base material flow (vertical axis) direction, or A stretched resin substrate can be produced by stretching in the direction perpendicular to the flow direction of the resin substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin used as the raw material for the resin base material, but is preferably in the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Moreover, the resin base material used for this invention may perform a relaxation | loosening process and off-line heat processing at the point of dimensional stability. The relaxation treatment is preferably carried out in the process from the heat setting in the stretching process of the polyester film to the winding in the transversely stretched tenter or after exiting the tenter. The relaxation treatment is preferably performed at a treatment temperature in the range of 80 to 200 ° C, more preferably in the range of 100 to 180 ° C. Although it does not specifically limit as a method of off-line heat processing, For example, the method of conveying by the roller conveyance method by a several roller group, the air conveyance which blows and blows air to a film, etc. (one side of a film surface heated air from several slits) Or, a method of spraying on both surfaces), a method of using radiant heat from an infrared heater, a method of hanging the film under its own weight, and a method of conveying such as winding below. The conveyance tension of the heat treatment is made as low as possible to promote thermal shrinkage, thereby providing a resin substrate with good dimensional stability. The treatment temperature is preferably in the temperature range of Tg + 50 to Tg + 150 ° C. Tg refers to the glass transition temperature (° C.) of the resin.

In the resin base material according to the present invention, the undercoat layer coating solution can be applied inline on one side or both sides in the film forming process. In the present invention, undercoating during the film forming process is referred to as in-line undercoating. Examples of resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like, and any of them can be preferably used. A conventionally well-known additive can also be added to these undercoat layers. The undercoat layer can be coated by a known method such as roll coating, gravure coating, knife coating, dip coating or spray coating. The coating amount of the undercoat layer is preferably about 0.01 to ² g / m ² (dry state).

<Stress absorbing layer>
The stress-absorbing layer according to the present invention may have any configuration as long as the indentation hardness with respect to the load of 100 μN is in the range of 0.4 to 1.0 GPa. It is preferable to be composed of a curable resin. This is preferable because it can be easily adjusted to the above-mentioned hardness by adjusting the type of curable resin, the type of initiator, the curing conditions, and the like, and productivity, smoothness, and transparency can be compatible.

<Curable resin>
Examples of the curable resin used in the present invention include epoxy resins, acrylic resins, urethane resins, polyester resins, silicone resins, and ethylene vinyl acetate (EVA) resins. The ultraviolet curable resin can be used without particular limitation as long as it forms a transparent resin composition by curing, and particularly preferably acrylic, urethane, and polyester resins from the viewpoint of hardness, smoothness, and transparency. Can be used.

  Examples of the acrylic resin composition include acrylate compounds having a radical reactive unsaturated compound, mercapto compounds having an acrylate compound and a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, glycerol methacrylate and the like. What dissolved the polyfunctional acrylate monomer etc. are mentioned. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  As a photoinitiator, a well-known thing can be used and it can be used by 1 type, or 2 or more types of combination.

  In the stress absorbing layer of the present invention, the indentation hardness with respect to the load of 100 μN is in the range of 0.4 to 1.0 GPa.

  Indentation hardness means that an indenter (triangular pan indenter) is pressed against a sample by an electromagnet and increased at a constant rate, and the depth of penetration of the indenter into the sample is automatically measured as the indenter enters the sample. In this method, the size of the indentation generated at that time is measured with a microscope, and the hardness value is obtained from the plastic deformation.

  The specific indentation hardness was measured under the following conditions.

  Using a microscopic indentation hardness tester TriboScope manufactured by HYSITRON, a load of 100 μN was applied to the sample in an atmosphere of 23 ° C. and 55% RH, and the indentation load P (mgf) was applied throughout the entire process from the start of loading to unloading. The corresponding indentation depth h (nm) was measured continuously to create a Ph curve. The indentation hardness H was determined from the created Ph curve by the following formula (1).

H (GPa) = Pmax / A (1)
[Pmax: maximum load (μN), A: indenter projected area (μm ² )]
The indentation hardness of the stress absorbing layer is in the range of 0.4 to 1.0 GPa, but is particularly preferably in the range of 0.45 to 0.65. If it is less than 0.4 GPa, the residual stress of the gas barrier layer cannot be eliminated, and the barrier properties and adhesion are inferior. On the other hand, if it exceeds 1.0 GPa, the rigidity of the resin substrate is stronger, so the adhesion with the film forming roller becomes insufficient, and the plasma discharge is less likely to occur uniformly, so the concentration gradient of the carbon atom component in the gas barrier layer is It becomes non-uniform and hinders improvement of gas barrier properties and flexibility.

  Adjustment to the indentation hardness range can be performed by selecting a curable resin, adjusting the film thickness, adding a matting agent described later, and the like.

  The indentation hardness on both sides of the stress absorbing layer needs to be in the range of 0.4 to 1.0 GPa, but the indentation hardness of the surface in contact with the film forming roller is 0.1 to 0 than the surface that does not contact. More preferably, it is small within the range of 3 GPa. If the indentation hardness of the surface in contact with the film formation roller is smaller than the indentation hardness of the non-contact surface within the above range, the film curl and rigidity are not affected, the adhesion to the film formation roller is improved, and plasma discharge is prevented. Since it occurs uniformly, the concentration gradient of the carbon atom component in the gas barrier layer becomes uniform, and the gas barrier property and the flexibility tend to be further improved.

  As a solvent used when forming a stress absorption layer using a resin composition in which a curable resin is dissolved or dispersed in a solvent, known alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ketone solvents A solvent, an ester solvent, or the like can be used.

  The stress-absorbing layer of the present invention comprises the resin composition described above, for example, doctor blade method, spin coating method, dipping method, table coating method, spray method, applicator method, curtain coating method, die coating method, ink jet method, dispenser method, etc. It can be formed by applying (adding a curing agent if necessary) and curing the resin composition by heating or ultraviolet irradiation.

  As a method of irradiating ultraviolet rays, ultraviolet rays having a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, etc., or The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

  The thickness of the stress absorbing layer of the present invention is not particularly limited, but is preferably in the range of 0.1 to 10 μm, particularly preferably in the range of 0.5 to 5 μm. The stress absorbing layer may be composed of two or more layers. The thicknesses of the stress absorbing layers on both sides of the resin substrate may be the same or different, and it is preferable to change the thickness as appropriate depending on the design of the indentation hardness on both sides.

  If necessary, additives such as an antioxidant, a plasticizer, a matting agent, and a thermoplastic resin can be added to the stress absorbing layer.

  In particular, it is preferable to add a matting agent to the stress absorbing layer. The matting agent to be used preferably contains inorganic fine particles or organic fine particles. The inorganic fine particles or the organic fine particles can suppress the curing shrinkage of the coating film and improve the adhesion of the stress absorbing layer to the substrate.

  In order not to lower the transparency of the stress absorption layer, the primary particle diameter of the inorganic fine particles is preferably less than 100 nm, and particularly preferably less than 50 nm. When the particle diameter exceeds 100 nm, light scattering occurs, and transparency is lowered due to a decrease in transmittance, which is not preferable.

  Inorganic fine particles include silica fine particles such as dry silica and wet silica, metal oxide fine particles such as titanium oxide, zirconium oxide, zinc oxide, tin oxide, cerium oxide, antimony oxide, indium tin mixed oxide and antimony tin mixed oxide. In particular, organic fine particles such as acrylic and styrene are preferable. From the viewpoints of transparency and hardness, nano-dispersed silica fine particles in which silica fine particles in the range of 10 to 50 nm are dispersed in an organic solvent are preferable.

  In addition, the inorganic fine particles are preferably blended in the range of 5 to 50 parts by weight, particularly preferably in the range of 10 to 40 parts by weight, with respect to 100 parts by weight of the curable resin constituting the stress absorbing layer. The addition amount is also appropriately determined according to the arithmetic average roughness described later.

  The stress absorbing layer according to the present invention preferably has an arithmetic average roughness Ra value in the range of 0.3 to 5 nm. Preferably it is the range of 0.5-3 nm. When the thickness is larger than 0.3 nm, the surface is not too smooth and deterioration of the film forming roller conveyance is not observed, so that the gas barrier layer can be satisfactorily formed by the CVD method. On the other hand, if it is smaller than 5 nm, the adhesion with the film-forming roller is good and does not affect the discharge, so the concentration gradient of the carbon atom component in the gas barrier layer becomes uniform, and the gas barrier properties and flexibility are improved. preferable.

  The arithmetic average roughness (Ra) of the stress absorbing layer of the present invention can be measured by the following method.

Arithmetic mean roughness measurement method; AFM measurement:
Arithmetic mean roughness is calculated from an uneven sectional curve continuously measured by an AFM (Atomic Force Microscope), for example, DI3100 manufactured by Digital Instruments, with a detector having a stylus having a minimum tip radius. This is a roughness related to the amplitude of fine irregularities, measured in a section having a measurement direction of several tens of μm many times with a stylus.

<Gas barrier layer>
The gas barrier layer according to the present invention conveys a resin base material having a stress absorbing layer on both surfaces while contacting each of a pair of film forming rollers, and supplies a film forming gas between the pair of film forming rollers. It is a thin film layer formed on the stress absorbing layer by plasma enhanced chemical vapor deposition with plasma discharge.

  The gas barrier layer uses a source gas containing an organosilicon compound and oxygen gas as a film forming gas, contains carbon, silicon, and oxygen as constituent elements of the gas barrier layer, and the layer in the layer thickness direction of the layer In the carbon distribution curve showing the relationship between the distance from the surface of the metal and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atom ratio), the carbon atom ratio of the gas barrier layer is the layer It is in the range of 8 to 20 at% as a whole average value, and the carbon distribution curve is continuously changing with a concentration gradient in the layer, so that the gas barrier property and flexibility are highly enhanced. It is preferable from the viewpoint of achieving both. The average value of the entire carbon atom ratio layer can be obtained from data obtained by measurement of an XPS depth profile described later.

  In the carbon distribution curve, “total amount of silicon atoms, oxygen atoms and carbon atoms” means the total number of silicon atoms, oxygen atoms and carbon atoms, and “amount of carbon atoms” means the number of carbon atoms. Means. Similarly, the amount of silicon atoms in the silicon distribution curve and the amount of oxygen atoms in the oxygen distribution curve are also synonymous, and the unit is “at% (atomic%)”.

  In addition, the gas barrier layer according to the present invention preferably satisfies the following condition (A).

The layer contains carbon, silicon, and oxygen, and the distance from the surface of the layer in the layer thickness direction of the layer and the amount of silicon atoms relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms. In the silicon distribution curve, oxygen distribution curve and carbon distribution curve showing the relationship between the ratio (silicon atom ratio), the ratio of the amount of oxygen atoms (oxygen atom ratio) and the ratio of the amount of carbon atoms (carbon atom ratio), respectively.
[Condition (A)]
(I) In the distance region where the silicon atomic ratio, oxygen atomic ratio, and carbon atomic ratio are 90% or more of the layer thickness, the following formula (1):
(Oxygen atom ratio)> (silicon atom ratio)> (carbon atom ratio) (1)
Or the following expression (2):
(Carbon atom ratio)> (silicon atom ratio)> (oxygen atom ratio) (2)
Satisfying the condition represented by
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) 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,
Is preferable from the viewpoint of achieving both high gas barrier properties and flexibility.

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

<Gas barrier layer-element extreme value>
The gas barrier layer according to the present invention contains carbon, silicon, and oxygen as constituent elements of the gas barrier layer, and the distance from the surface of the layer in the layer thickness direction of the layer, silicon atoms, oxygen atoms, and carbon atoms In the carbon distribution curve showing the relationship with the ratio of the amount of carbon atoms to the total amount (carbon atom ratio), the carbon atom ratio of the gas barrier layer is in the range of 8 to 20 at% as the average value of the entire layer. More preferably, it is the range of 10-20 at%.

  By setting it within this range, it is possible to form a gas barrier layer that sufficiently satisfies gas barrier properties and flexibility.

  In addition, it is preferable that the carbon atom ratio continuously changes with a concentration gradient from the viewpoint of achieving both gas barrier properties and flexibility. In such a gas barrier layer, 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 gas in the thickness direction of the gas barrier layer at one extreme value and an 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 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.

<Definition of 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 is changed, and from the value of the atomic ratio of the element at that point. This also means that the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer is further changed by 20 nm from that 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 decrease to increase when the distance from the surface of the gas barrier layer is changed, and the value of the atomic ratio of the element at that point Rather, 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 from this point is further changed by 20 nm increases by 3 at% or more.

<Definition of real continuity>
In the present invention, the carbon distribution curve is preferably substantially continuous.

In this specification, that the carbon distribution curve is substantially continuous means that it does not include a portion where the carbon atom ratio in the carbon distribution curve changes discontinuously. Specifically, from the etching rate and the etching time, In the relationship between the distance (x, unit: nm) from the surface of the layer in the layer thickness direction of at least one of the gas barrier layers calculated and the carbon atom ratio (C, unit: at%), Formula (F1) below:
(DC / dx) ≦ 0.5 (F1)
This means that the condition represented by

<Relationship between maximum and minimum carbon atom ratio>
Further, such a gas barrier layer preferably further has (iii) 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. 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 oxygen atom ratio>
In the present invention, the absolute value of the difference between the maximum value and the minimum value in the oxygen distribution curve of the gas barrier layer is preferably 5 at% or more, more preferably 6 at% or more, and 7 at% or more. Is particularly preferred. When the absolute value is 5 at% or more, the gas barrier property when the obtained gas barrier film is bent is sufficient.

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

<About XPS depth profile>
The silicon distribution curve, oxygen distribution curve, and carbon distribution curve in the layer thickness direction of the gas barrier layer, and the distribution curve of the oxygen-carbon total are measured by X-ray photoelectron spectroscopy (XPS), argon, and the like. By using together with rare gas ion sputtering, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time in this way, the etching time generally correlates with the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer in the layer thickness direction. , “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 having a uniform and excellent gas barrier property over the entire film surface, the gas barrier layer is in the film surface direction (direction parallel to the surface of the gas barrier layer). Is substantially uniform. In this specification, 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 number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the atomic ratio of carbon in each carbon distribution curve The absolute value of the difference between the maximum value and the minimum value is the same as each other 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 conditions (i) to (iii), but may include two or more layers that satisfy such conditions. 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.

  In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atom ratio, the oxygen atom ratio, and the carbon atom ratio are expressed by the formula (1) in a distance region that is 90% or more of the layer thickness of the layer. When the conditions to be expressed are satisfied, the silicon atom ratio in the gas barrier layer is preferably in the range of 25 to 45 at%, and more preferably in the range of 30 to 40 at%. The oxygen atom ratio in the gas barrier layer is preferably in the range of 33 to 67 at%, and more preferably in the range of 45 to 67 at%. Furthermore, the carbon atom ratio in the gas barrier layer is preferably in the range of 3 to 33 at%, and more preferably in the range of 3 to 25 at%.

  Further, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atom ratio, the oxygen atom ratio, and the carbon atom ratio are expressed by the formula (2) in a distance region that is 90% or more of the layer thickness of the layer. When the conditions to be expressed are satisfied, the silicon atom ratio in the gas barrier layer is preferably in the range of 25 to 45 at%, and more preferably in the range of 30 to 40 at%. The oxygen atomic ratio in the gas barrier layer is preferably in the range of 1 to 33 at%, and more preferably in the range of 10 to 27 at%. Furthermore, the carbon atom ratio in the gas barrier layer is preferably in the range of 33 to 66 at%, and more preferably in the range of 40 to 57 at%.

<Barrier layer thickness>
The thickness of the gas barrier layer 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 producing gas barrier layer>
The gas barrier layer according to the present invention is a layer formed by a plasma chemical vapor deposition method. More specifically, as the gas barrier layer formed by the plasma chemical vapor deposition method, the resin substrate is transported while being in contact with each of the pair of film forming rollers, and the film forming gas is supplied 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 between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma chemical vapor deposition method preferably contains an organosilicon compound and oxygen, and the content of oxygen in the film forming gas is the same as that in the film forming gas. It is preferable that the amount is less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound. In the gas barrier film of the present invention, the gas barrier layer is preferably a layer formed by a continuous film forming process.

  Next, a method for producing the gas barrier film of the present invention will be described. The gas barrier film of this invention can be manufactured by forming the said gas barrier layer on the stress absorption layer surface of the said resin base material. As a method for forming such a gas barrier layer according to the present invention on the surface of the resin substrate, a plasma chemical vapor deposition method (plasma CVD method) is employed from the viewpoint of gas barrier properties. The plasma enhanced chemical vapor deposition method may be a Penning discharge plasma type chemical vapor deposition method.

  In order to form a layer having a concentration gradient of carbon atoms and continuously changing in the layer, such as the gas barrier layer according to the present invention, plasma is generated in the plasma chemical vapor deposition method. In addition, it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers. In the present invention, a pair of film forming rollers is used, and the resin base material is conveyed while contacting each of the pair of film forming rollers. It is preferable to generate plasma by discharging between the pair of film forming rollers. In this way, by using a pair of film forming rollers, conveying the resin base material on the pair of film forming rollers, and carrying out plasma discharge between the pair of film forming rollers, By changing the distance between the film discharge rollers and the plasma discharge position, it becomes possible to form a gas barrier layer in which the carbon atom ratio has a concentration gradient and continuously changes in the layer. .

  It is also possible to form a film on the surface part of the resin substrate that exists on the other film forming roller while forming a film on the surface part of the resin substrate that exists on one film formation roller. In addition to efficiently producing a thin film, the film formation rate can be doubled, and a film having the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled. It is possible to form a layer that satisfies all of the conditions (i) to (iii).

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

  An apparatus that can be used when producing a gas barrier film by such a plasma chemical vapor deposition method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair It is preferable that the apparatus has a configuration capable of discharging between the film forming rollers. For example, when the manufacturing apparatus shown in FIG. 2 is used, a roll is used while utilizing plasma chemical vapor deposition. It is also possible to manufacture by a to-roll method.

  Hereinafter, the method for producing the gas barrier film of the present invention will be described in more detail with reference to FIG. FIG. 2 is a schematic view showing an example of a production apparatus that can be suitably used for producing the gas barrier film of the present invention. The resin base material 1 in the following description refers to a resin base material having the stress absorption layer according to the present invention on both surfaces.

  The manufacturing apparatus shown in FIG. 2 includes a delivery roller 11, transport rollers 21, 22, 23, 24, film formation rollers 31, 32, a gas supply pipe 41, a plasma generation power source 51, a film formation roller 31, and 32, magnetic field generators 61 and 62 installed inside 32, and a winding roller 71 are provided. In such a manufacturing apparatus, at least the film forming rollers 31, 32, the gas supply pipe 41, the plasma generation power source 51, and the magnetic field generators 61, 62 made of permanent magnets are not shown in the vacuum chamber. Is placed inside. Further, in such a manufacturing apparatus, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 31 and the film-forming roller 32) can function as a pair of counter electrodes. 51 is connected. Therefore, in such a manufacturing apparatus, it is possible to discharge into the space between the film forming roller 31 and the film forming roller 32 by supplying electric power from the plasma generating power source 51, thereby forming the film. Plasma can be generated in the space between the roller 31 and the film forming roller 32. In addition, when using the film-forming roller 31 and the film-forming roller 32 as electrodes as described above, the material and design may be appropriately changed so that the film-forming roller 31 and the film-forming roller 32 can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 31 and 32) so that the central axis may become substantially parallel on the same plane. By arranging a pair of film forming rollers (film forming rollers 31 and 32) in this way, the film forming rate can be doubled, and a film having the same structure can be formed. Can be at least doubled.

  Further, inside the film forming roller 31 and the film forming roller 32, magnetic field generators 61 and 62 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  Furthermore, as the film forming roller 31 and the film forming roller 32, known rollers can be used as appropriate. As such film forming rollers 31 and 32, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rollers 31 and 32 is preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. When the diameter is larger than 300 mmφ, the plasma discharge space is not reduced, productivity is not deteriorated, and the total amount of heat of the plasma discharge can be prevented from being applied to the film in a short time. On the other hand, it is preferable that the diameter is smaller than 1000 mmφ because practicality can be maintained in terms of device design including uniformity of plasma discharge space.

  Moreover, a well-known roller can be used suitably as the sending-out roller 11 and the conveyance rollers 21, 22, 23, and 24 which are used for such a manufacturing apparatus. The winding roller 71 is not particularly limited as long as it can wind the resin base material 1 on which the gas barrier layer is formed, and a known roller can be used as appropriate.

  As the gas supply pipe 41, a pipe capable of supplying or discharging a source gas or the like at a predetermined speed can be used as appropriate. Furthermore, as the plasma generating power source 51, a known power source for a plasma generating apparatus can be used as appropriate. Such a power source 51 for generating plasma supplies power to the film forming roller 31 and the film forming roller 32 connected thereto, and makes it possible to use these as counter electrodes for discharge. As such a plasma generation power source 51, it is possible to more efficiently carry out the plasma CVD method, so that the polarity of the pair of film forming rollers can be alternately reversed (AC power source or the like) ) Is preferably used. Moreover, as such a plasma generating power source 51, it is possible to more efficiently perform the plasma CVD method, so that the applied power can be in the range of 100 W to 10 kW and the AC frequency is 50 Hz to It is more preferable that the frequency range is 500 kHz. As the magnetic field generators 61 and 62, known magnetic field generators can be used as appropriate.

  Using such a manufacturing apparatus shown in FIG. 2, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport speed of the resin substrate By appropriately adjusting, the gas barrier film of the present invention can be produced. That is, using the manufacturing apparatus shown in FIG. 2, a plasma discharge is generated between a pair of film forming rollers (film forming rollers 31 and 32) while supplying a film forming gas (such as a raw material gas) into the vacuum chamber. The film deposition gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer is formed on the surface of the resin base material 1 on the film formation roller 31 and on the surface of the resin base material 1 on the film formation roller 32. Is formed by plasma CVD. In such film formation, the resin base material 1 is conveyed by the delivery roller 11 and the film formation roller 31, respectively, so that the resin base material 1 is formed by a roll-to-roll continuous film formation process. The gas barrier layer is formed on the surface.

<Raw gas>
The source gas in the film forming gas used for forming the gas barrier layer according to the present invention can be appropriately selected and used depending on the material of the gas barrier layer to be formed. As such a source gas, for example, an organosilicon compound containing silicon is preferably used. Examples of such organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Examples thereof include silane, 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 characteristics such as gas barrier properties of the obtained gas barrier layer and handling in film formation. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

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

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

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. If the ratio of the reaction gas is excessive, it is difficult to obtain the gas barrier layer of the present invention. Therefore, in order to obtain the desired performance as a barrier film, when the film-forming gas contains the organosilicon compound and oxygen, the total amount of the organosilicon compound in the film-forming gas is completely reduced. It is preferable that the amount of oxygen be less than or equal to the theoretical oxygen amount necessary for oxidation.

Hereinafter, hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O :) as a source gas and oxygen (O ₂ ) as a reaction gas will be described as representative examples.

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 a silicon-oxygen system In the case of producing a thin film of the following reaction formula (1):
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂ (1)
The reaction shown by follows occurs to produce silicon dioxide. 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, the amount of oxygen must be less than the stoichiometric ratio of 12 moles per mole of hexamethyldisiloxane.

  Note that in the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas ( Even if the flow rate is 12 times the molar amount (flow rate) of hexamethyldisiloxane as the raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when a large excess is supplied as compared with the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by the CVD method, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material. (It may be about 20 times or more the molar amount (flow rate) of siloxane.) Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer to form a desired gas barrier layer. This makes it possible to exhibit excellent barrier properties and flex resistance in the resulting gas barrier film. If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, unoxidized carbon atoms and hydrogen atoms are excessively taken into the gas barrier layer. In this case, the transparency of the barrier film is lowered, and the barrier film cannot be used for a flexible substrate for a device requiring transparency, such as an organic EL device or an organic thin film solar cell. 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 Pa-100 Pa.

<Roller film formation>
In such a plasma CVD method, in order to discharge between the film forming rollers 31 and 32, an electrode drum connected to the plasma generating power source 51 (in this embodiment, the electrode drums are installed on the film forming rollers 31 and 32). The electric power to be applied can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., and cannot be generally stated, but may be in the range of 0.1 to 10 kW. preferable. If the applied power is in this range, no particles are generated and the amount of heat generated during film formation is within the control. Therefore, heat loss or formation of the resin base material due to temperature rise on the surface of the base material during film formation occurs. There is no generation of wrinkles during filming. In addition, the possibility that the resin base material is melted by heat and a large current discharge is generated between the bare film forming rollers to damage the film forming roller itself.

  Although the conveyance speed (line speed) of the resin base material 1 can be suitably adjusted according to the kind of raw material gas, the pressure in a vacuum chamber, etc., it is preferable to set it as the range of 0.25-100 m / min, A range of 0.5 to 20 m / min is more preferable. When the line speed is within the above range, wrinkles due to the heat of the resin base material are hardly generated, and the thickness of the formed gas barrier layer can be sufficiently controlled.

  FIG. 3 shows an example of each element profile in the layer thickness direction based on the XPS depth profile of the gas barrier layer of the present invention formed as described above.

  In FIG. 3, symbols A to D represent A: carbon distribution curve, B: silicon distribution curve, C: oxygen distribution curve, and D: oxygen carbon distribution curve, respectively. FIG. 3 shows that the gas barrier layer of the present invention has a carbon atom ratio in the gas barrier layer in the range of 8 to 20 at% as an average value of the entire gas barrier layer, and has a concentration gradient in the layer. It turns out that it changes continuously and satisfies [condition (A)].

  FIG. 4 is an example of each element profile in the layer thickness direction according to the XPS depth profile of the comparative gas barrier layer. The gas barrier layer is formed by a CVD method using a flat electrode (horizontal transport) type plasma discharge, and it can be seen that a continuous change in the concentration gradient of the carbon atom component does not occur.

<Second gas barrier layer>
In the present invention, a coating film of a coating-type polysilazane-containing liquid is provided on the gas barrier layer according to the present invention, and it is formed by irradiating with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less. It is preferable to provide a second gas barrier layer. By providing the second gas barrier layer on the gas barrier layer provided by the CVD method, minute defects remaining in the gas barrier layer can be filled with the gas barrier component of polysilazane from above, and further gas Since the barrier property and the flexibility can be improved, it is preferable.

  The thickness of the second gas barrier layer is preferably in the range of 1 nm to 500 nm, more preferably in the range of 10 nm to 300 nm. When the thickness is within the above range, gas barrier performance can be exhibited, and cracks are unlikely to occur in the dense silicon oxynitride film.

<Polysilazane>
The “polysilazane” according to the present invention is a polymer having a silicon-nitrogen bond in the structure and is a polymer that is a precursor of silicon oxynitride, and those having the following structure are preferably used.

式中、Ｒ_１、Ｒ_２、Ｒ_３は、各々水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アルキルシリル基、アルキルアミノ基、又はアルコキシ基を表す。

In the formula, each of R ₁ , R ₂ , and R ₃ represents 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 in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is particularly preferable from the viewpoint of the denseness as a film of the obtained 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 a coating liquid containing polysilazane on the gas barrier layer formed by the CVD method and drying it, followed by irradiation with vacuum ultraviolet rays.

  As the organic solvent for preparing the coating solution, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. For example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, ethers such as alicyclic ethers can be used, specifically, There are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, 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 solvent, and a plurality of organic solvents may be mixed.

  The concentration of polysilazane in the coating liquid containing polysilazane varies depending on the thickness of the second gas barrier layer and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.

  In order to promote the modification to silicon oxynitride, the coating solution is coated with a metal catalyst such as an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, or an Rh compound such as Rh acetylacetonate. It 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, more preferably in the range of 0.2 to 5% by mass, and 0.5 to More preferably, it is in the range of 2% by mass. By setting the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.

  Any appropriate method can be adopted as a method of applying the coating liquid containing polysilazane. Specific examples include a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a cast film forming method, a bar coating method, and a gravure printing method.

  The thickness of the coating film can be appropriately set according to the purpose. For example, the thickness of the coating film 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 further preferably in the range of 100 nm to 1 μm. .

<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.

Here, 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 will be described by taking perhydropolysilazane as an example.

Perhydropolysilazane can be represented by a composition of “— (SiH ₂ —NH) _n —”. In the case of SiO _x N _y , x = 0 and y = 1. An external oxygen source is required to achieve x> 0. This is because (i) oxygen and moisture contained in the polysilazane coating solution, and (ii) oxygen taken into the coating film from the atmosphere during the coating and drying process. As an outgas from the substrate side by (iii) oxygen, moisture, ozone, singlet oxygen taken into the coating film from the atmosphere in the vacuum ultraviolet irradiation process, (iv) heat applied in the vacuum ultraviolet irradiation process, etc. Oxygen and moisture moving into the coating film, (v) When the vacuum ultraviolet irradiation process is performed in a non-oxidizing atmosphere, when moving from the non-oxidizing atmosphere to the oxidizing atmosphere, Oxygen, moisture, etc. taken into the coating film 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 Bonds by Hydrolysis / Dehydration Condensation Si—N bonds in perhydropolysilazane are 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 in the air, but during vacuum ultraviolet irradiation in an inert atmosphere, water vapor generated as outgas from the base material by the heat of irradiation is considered to be the main moisture source. When the moisture is 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 SiO2.1 to 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 the perhydropolysilazane is replaced with O to form a Si—O—Si bond and harden. It is thought 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 / excitation Since the energy of vacuum ultraviolet light is higher than the bond energy of Si-N in perhydropolysilazane, the Si-N bond is cleaved, and oxygen, It is considered that when an oxygen source such as ozone or water is present, it is oxidized to form a Si—O—Si bond or a Si—O—N bond. It is thought that recombination of the bond may occur due to 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 irradiation step in the present invention, it is preferable that the illuminance of the vacuum ultraviolet rays in the coating 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. When it is 30 mW / cm ² or more, there is no concern that the reforming efficiency is lowered, and when it is 200 mW / cm ² or less, the coating film is not ablated and the substrate 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 the range of 500~5000mJ / cm ^2. 200 mJ / cm ² or more, the performed modification sufficiently, cracking and not excessive modification is 10000 mJ / cm ² or less, there is no thermal deformation of the substrate.

  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, excimer light of 172 nm is emitted.

  A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, 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), electric charges accumulate on the dielectric surface, and the micro discharge disappears.

  This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and extinguished. 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, since micro discharge occurs only between the electrodes, the outer electrode covers the entire outer surface and transmits light to extract light to the outside in order to cause discharge in the entire 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 outer surface of the lamp. 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 nm 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 such as PET 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 during vacuum ultraviolet irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm, and still more preferably in the range of 1000 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 rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

<Overcoat layer>
An overcoat layer may be formed on the second gas barrier layer according to the present invention in order to further improve the flexibility. As the organic substance used for the overcoat layer, an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used. Can do. These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed by coating from the organic resin composition coating solution to be cured.

<Electronic device>
One feature of the gas barrier film of the present invention is that it is used as a film for an organic element device. Examples of the organic element device of the present invention include an organic electroluminescence element (hereinafter abbreviated as an organic EL element), an organic photoelectric conversion element, and a liquid crystal element.

<Organic EL panel as an electronic device>
The gas barrier film 1a (1b) of the present invention can be used as a sealing film for sealing solar cells, liquid crystal display elements, organic EL elements and the like.

  An example of the organic EL panel P which is an electronic device using the gas barrier film 1a as a sealing film is shown in FIG.

  As shown in FIG. 5, the organic EL panel P is formed on the gas barrier film 1 a through the gas barrier film 1 a, the transparent electrode 6 such as ITO formed on the gas barrier film 1 a, and the transparent electrode 6. And an organic EL element 7 that is a main body of the electronic device, and a counter film 9 disposed via an adhesive layer 8 so as to cover the organic EL element 7. The transparent electrode 6 may form part of the organic EL element 7.

  A transparent electrode 6 and an organic EL element 7 are formed on the surface of the gas barrier film 1a on the gas barrier layer 3 side.

  In the organic EL panel P, the organic EL element 7 is suitably sealed so as not to be exposed to water vapor, and the organic EL element 7 is not easily deteriorated. Therefore, the organic EL panel P can be used for a long time. It becomes possible, and the lifetime of the organic EL panel P is extended.

  The counter film 9 may be a gas barrier film according to the present invention in addition to a metal film such as an aluminum foil. When a gas barrier film is used as the counter film 9, the surface on which the gas barrier layer 3 is formed may be attached to the organic EL element 7 with the adhesive layer 8.

<Organic EL device>
The organic EL element 7 sealed with the gas barrier film 1a in the organic EL panel P will be described.

  Although the preferable specific example of the layer structure of the organic EL element 7 is shown below, this invention is not limited to these.

(1) Anode / light emitting layer / cathode (2) Anode / hole transport layer / light emitting layer / cathode (3) Anode / light emitting layer / electron transport layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) Anode / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode (anode)
As the anode (transparent electrode 6) in the organic EL element 7, an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.

  The anode may be formed by depositing these electrode materials as a thin film by a method such as vapor deposition or sputtering, and the thin film may be formed into a pattern having a desired shape by a photolithography method. The pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.

  When light emission is taken out from the anode, it is desirable that the transmittance be larger than 10%. The sheet resistance as the anode is preferably several hundred Ω / □ or less. Moreover, although the film thickness of an anode is based also on material, it is normally selected in the range of 10-1000 nm, Preferably it is the range of 10-200 nm.

(cathode)
As the cathode in the organic EL element 7, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are suitable as the cathode.

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less. The thickness of the cathode is usually selected in the range of 10 nm to 5 μm, preferably in the range of 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element 7 is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after producing the metal mentioned in the description of the cathode with a film thickness in the range of 1 to 20 nm, a transparent transparent or semi-transparent cathode is produced by producing the conductive transparent material mentioned in the explanation of the anode on the metal. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

(Injection layer: electron injection layer, hole injection layer)
The injection layer includes an electron injection layer and a hole injection layer, and an electron injection layer and a hole injection layer are provided as necessary, between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport. Exist between the layers.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Examples thereof include a phthalocyanine buffer layer typified by phthalocyanine, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  Details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium Metal buffer layer typified by aluminum and aluminum, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. Is mentioned. The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm, although depending on the material.

(Light emitting layer)
The light-emitting layer in the organic EL element 7 is a layer that emits light by recombination of electrons and holes injected from the electrode (cathode, anode) or electron transport layer or hole transport layer, and the light-emitting portion is the light-emitting layer. The interface between the light emitting layer and the adjacent layer may be used.

  The light emitting layer of the organic EL element 7 preferably contains the following dopant compound (light emitting dopant) and host compound (light emitting host). Thereby, the luminous efficiency can be further increased.

(Luminescent dopant)
There are two types of luminescent dopants: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.

  Representative examples of fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.

  Typical examples of the phosphorescent dopant are preferably complex compounds containing metals of Group 8, Group 9, and Group 10 in the periodic table of elements, more preferably iridium compounds and osmium compounds, and most preferable among them. Is an iridium compound.

  The light emitting dopant may be used by mixing a plurality of kinds of compounds.

(Light emitting host)
A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more compounds. For other compounds, “dopant compound ( Simply referred to as a dopant). " For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Further, if the light emitting layer is composed of three types of compound A, compound B and compound C and the mixing ratio is A: B: C = 5: 10: 85, compound A and compound B are dopant compounds, and compound C is a host compound.

  The light emitting host is not particularly limited in terms of structure, but is typically a basic skeleton such as a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, or an oligoarylene compound. Or a carboline derivative or a diazacarbazole derivative (herein, a diazacarbazole derivative is one in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom) And the like). Of these, carboline derivatives, diazacarbazole derivatives and the like are preferably used.

  The light emitting layer can be formed by depositing the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, the range of 5 nm-5 micrometers, Preferably it is chosen in the range of 5-200 nm. This light emitting layer may have a single layer structure composed of one or more dopant compounds and host compounds, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

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

  The hole transport material has any of hole injection or transport and electron barrier properties, 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. The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. 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.

  The hole transport layer can be 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. it can. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, about 5 nm-5 micrometers, Preferably it is the range of 5-200 nm. This hole transport layer may have a single layer structure composed of one or more of the above materials.

(Electron transport layer)
The electron transport layer is made of an electron transport material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

  The electron transport material only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and the material can be selected and used from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, 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 can also be used as an electron transport material. 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, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), 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 (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. Similarly to the hole injection layer and the hole transport layer, an inorganic semiconductor such as n-type-Si or n-type-SiC can also be used as the electron transport material.

  The electron transport layer can be formed by thinning the electron 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. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, about 5 nm-5 micrometers, Preferably it is the range of 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  A method for producing the organic EL element 7 will be described.

  Here, as an example of the organic EL element 7, a method for manufacturing an organic EL element composed of an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on the barrier film 10 so as to have a thickness of 1 μm or less, preferably in the range of 10 to 200 nm. The anode is prepared by the method.

Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which are organic EL element materials, is formed thereon. As a method for forming this organic compound thin film, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method), etc., but a homogeneous film is easily obtained and pinholes are not easily generated. From the point of view, the vacuum deposition method, the spin coating method, the ink jet method and the printing method are particularly preferable. Further, different film forming methods may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature range of 50 to 450 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻² Pa, a vapor deposition rate. It is desirable to select appropriately in the range of 0.01 to 50 nm / second, the substrate temperature in the range of −50 to 300 ° C., the film thickness in the range of 0.1 nm to 5 μm, and preferably in the range of 5 to 200 nm.

  After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained.

  The organic EL element 7 is preferably manufactured from the anode and the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere. In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.

  When a DC voltage is applied to the multicolor display device (organic EL panel 20) including the organic EL element 7 obtained in this manner, the voltage is about 2 to 40 V with the anode being positive and the cathode being negative. Luminescence can be observed by applying. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  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 "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

≪Evaluation conditions≫
<Water vapor transmission coefficient (WVTR)>
The water vapor permeability of the gas barrier film was measured by the following method.
(1) Measurement of water vapor transmission rate (Evaluation A, Evaluation B)
Under conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side, gas was measured using a water vapor transmission meter (GTR Tech, model name “GTR Tech-30XASC”). The water vapor permeability (Evaluation A) of the barrier film was measured. In addition, using a water vapor permeability measuring machine (manufactured by Lyssy, model name “Lyssy-L80-5000”) under conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. The water vapor permeability (evaluation B) of the gas barrier film was measured.
(2) When the evaluation method (1) was below the detection limit, the measurement was performed by the following method.

<< Evaluation of water vapor barrier property (Ca evaluation method) >>
(Water vapor barrier property evaluation sample preparation device)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.), metallic calcium was vapor-deposited with a size of 12 mm × 12 mm through the mask on the surface of the gas barrier layer of the produced gas barrier film. At this time, the deposited film thickness was set to 80 nm.

  Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, the vacuum state is released, quickly transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum deposition surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX). A water vapor barrier property evaluation sample was prepared by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.

  The obtained sample was stored at a high temperature and high humidity of 60 ° C. and 90% RH, and the state in which metallic calcium was corroded with respect to the storage time was observed. Observation is performed every hour for up to 6 hours, every 3 hours for up to 24 hours, every 6 hours for up to 48 hours thereafter, and every 12 hours thereafter, 12 mm x 12 mm metal The area where metallic calcium corroded relative to the calcium deposition area was calculated in%. The time when the area where the metal calcium corrodes becomes 1% is obtained by interpolating from the observation result by a straight line. From the relationship, the water vapor permeability of each gas barrier film was calculated.

<Element profile (XPS data) measurement>
XPS depth profile measurement was performed under the following conditions to obtain a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen-carbon total distribution curve.

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.

  Based on the data evaluated in this way, a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve were prepared with the distance from the surface of the barrier as the horizontal axis. As a representative sample No. Twenty distribution curves are shown in FIG.

  In FIG. 3, symbols A to D represent A: carbon distribution curve, B: silicon distribution curve, C: oxygen distribution curve, and D: oxygen carbon distribution curve, respectively.

<Flexibility evaluation>
Each gas barrier film was subjected to a bending test in which the gas barrier film was wound around a metal rod and allowed to stand for 1 minute, and then the gas barrier film was returned to a flat state to evaluate a water vapor transmission coefficient. The radius of curvature R in the bending test corresponds to ½ of the diameter of the rod, but when the number of turns of the gas barrier film increases, ½ of the diameter when the film is wound is defined as the radius of curvature R. . R was subjected to a flexibility test at 8 mm.

  The ratio between the water vapor transmission coefficient before the flexibility test and the numerical value after the flexibility test was examined and evaluated according to the following criteria.

○: Ratio is 0.95 or more ○ △: Ratio is 0.90 or more and less than 0.95 △: Ratio is 0.80 or more and less than 0.90 △: Ratio is 0.50 or more and less than 0.80 × : Ratio is 0.30 or more and less than 0.50 XX: Ratio is less than 0.30 <High temperature and high humidity treatment + flexibility evaluation>
Each gas barrier film was stored for 3000 hours under high temperature and high humidity conditions in an environment of a temperature of 85 ° C. and a humidity of 85% RH, and subjected to forced deterioration treatment.

  Furthermore, after winding a gas barrier film around a metal rod, a bending test is performed by allowing it to stand for 1 minute, and then the gas barrier film is returned to a flat state to obtain a high-temperature high-humidity treatment + flexibility evaluation sample. Adhesion evaluation was performed.

  The radius of curvature R in the bending test corresponds to ½ of the diameter of the rod, but when the number of turns of the gas barrier film increases, ½ of the diameter when the film is wound is defined as the radius of curvature R. . R was subjected to a flexibility test at 8 mm.

<Indentation hardness evaluation>
Using a microscopic indentation hardness tester TriboScope manufactured by HYSITRON, a load of 100 μN was applied to the sample in an atmosphere of 23 ° C. and 55% RH, and the indentation load P (μN) was applied throughout the entire process from the start of loading to unloading. The corresponding indentation depth h (nm) was measured continuously to create a Ph curve. The indentation hardness H was determined from the created Ph curve by the following equation (1).

H (GPa) = Pmax / A (1)
[Pmax: maximum load (μN), A: indenter projected area (μm ² )]
Example 1
<Preparation of resin base material>
As a thermoplastic resin substrate (support), a 125 μm-thick polyester film (KDL86WA, manufactured by Teijin DuPont Films Ltd.) that was easily bonded on both surfaces was used as the substrate as it was. The surface roughness (based on JIS B 0601) measured only for the substrate was 4 nm for Ra and 320 nm for Rz.

<Formation of stress absorbing layer 2>
Photopolymerization initiator Irgacure 184 (manufactured by BASF Japan) was adjusted to a solid content ratio (mass%) of resin / initiator: 95/5 to Toagosei Co., Ltd. UV curable resin Aronix M-8100. Thus, a stress absorbing layer coating solution 2 was obtained.

The above coating solution 2 is coated on one side of the support, dried at 80 ° C. for 3 minutes, coated with a wire bar so that the dry film thickness is 4 μm, and then curing conditions: 0.5 J / cm ² under high pressure mercury. Curing was performed using a lamp to form the stress absorbing layer 2. The indentation hardness values at this time are shown in Table 1.

<Formation of stress absorbing layer 3>
Photopolymerization initiator Irgacure 184 (manufactured by BASF Japan) is adjusted to DIC Corporation UV curable resin Unidic V-4025 so that the solid content ratio (mass%) is resin / initiator: 95/5. Thus, a stress absorbing layer coating solution 3 was obtained. The coating solution 3 is coated on one side of the support, dried at 80 ° C. for 3 minutes, coated with a wire bar so that the dry film thickness is 4 μm, and then curing conditions: 0.5 J / cm ² under high pressure mercury. Curing was performed using a lamp, and the stress absorbing layer 3 was formed.

<Formation of stress absorbing layers 9 to 11>
The stress-absorbing layer coating solution 3 is applied on both sides of the support, dried at 80 ° C. for 3 minutes, applied with a wire bar so that the dry film thickness is 4 μm, and then cured on each surface; 0.5 J / cm Curing was performed using a high-pressure mercury lamp under ² air, and stress absorbing layers 9 to 11 were formed.

<Formation of stress absorbing layer 4>
The stress-absorbing layer coating solution 2 is coated on both sides of the support, dried at 80 ° C. for 3 minutes, coated with a wire bar so that the dry film thickness is 4 μm, and then cured on each surface; 0.5 J / cm Curing was performed using a high-pressure mercury lamp under ² air, and the stress absorbing layer 4 was formed.

<Formation of stress absorbing layer 5>
The stress absorbing layer coating liquid 2 is applied to one side of the support (gas barrier layer installation side: CVD roll non-contact side), and the stress absorbing layer coating liquid 3 is applied to one side of the support (CVD roll contact side), After drying at 80 ° C. for 3 minutes and applying with a wire bar so that the dry film thickness is 4 μm, curing is performed on each surface using 0.5 J / cm ² air under high pressure mercury lamp to absorb stress Layer 5 was formed.

<Formation of stress absorbing layer 6>
The stress-absorbing layer coating solution 3 was applied on both sides of the support, dried at 80 ° C. for 3 minutes, and applied with a wire bar so that the dry film thickness was 4 μm, and then the curing conditions on each surface: 0.12 J / cm Curing was performed using a high-pressure mercury lamp under ² air, and the stress absorbing layer 6 was formed.

<Formation of Stress Absorbing Layer 12>
The stress absorbing layer coating solution 3 is applied to both sides of the support, dried at 80 ° C. for 3 minutes, and applied with a wire bar so that the dry film thickness becomes 4 μm, and then one side (gas barrier layer installation side: CVD roll non-contact Curing condition on the surface side): 0.5 J / cm ² under air, using a high-pressure mercury lamp. Curing condition on one side (CVD roll contact surface side): 1.0 J / cm ² under air, high-pressure mercury Curing was performed using a lamp, and the stress absorbing layer 12 was formed.

<Formation of stress absorbing layers 13, 20, 21>
UV curable resin JSR Co., Ltd. OPSTAR Z7501 was applied on both sides of the support, dried at 80 ° C. for 3 minutes, and applied with a wire bar so that the dry film thickness was 4 μm, followed by curing conditions: 0.5 J / Curing was performed using a high-pressure mercury lamp under cm ² air to form stress absorbing layers 13, 20, and 21.

<Formation of Stress Absorbing Layer 14>
UV curable resin JSR Co., Ltd. OPSTAR Z7501 was applied on both sides of the support, dried at 80 ° C. for 3 minutes, and applied with a wire bar so that the dry film thickness was 4 μm, and then curing conditions: 1.0 J / Curing was performed using a high-pressure mercury lamp under cm ² air to form the stress absorbing layer 14.

<Formation of stress absorbing layer 15>
UV curable resin JSR Co., Ltd. OPSTAR Z7527 was applied on both sides of the support, dried at 80 ° C. for 3 minutes, and applied with a wire bar so that the dry film thickness was 4 μm, followed by curing conditions: 0.5 J / Curing was performed using a high-pressure mercury lamp under cm ² air to form the stress absorbing layer 15.

<Formation of Stress Absorbing Layer 16>
UV curable resin Arakawa Chemical Industries Co., Ltd. beam set 907 was applied to both sides of the support, dried at 80 ° C. for 3 minutes, and applied with a wire bar so that the dry film thickness was 4 μm, and then the curing conditions: 0 Curing was performed using a high-pressure mercury lamp under 0.5 J / cm ² air to form the stress absorbing layer 16.

<Formation of stress absorbing layer 17>
UV curable resin Toyo Ink Co., Ltd. Ryodurasu LCH1559 was applied to both sides of the support, dried at 80 ° C. for 3 minutes, and applied with a wire bar to a dry film thickness of 4 μm, followed by curing conditions: 0.5 J Curing was performed using a high-pressure mercury lamp under / cm ² air to form the stress absorbing layer 17.

<Formation of Stress Absorbing Layer 18>
UV curable resin Toyo Ink Co., Ltd. Ryoduras LCH1559 on one side (gas barrier layer installation side: CVD roll non-contact surface side), UV curable resin JSR Co., Ltd. OPSTAR Z7501 on one side (CVD roll) Each contact surface side), dried at 80 ° C. for 3 minutes, coated with a wire bar to a dry film thickness of 4 μm, and then cured under curing conditions: 0.5 J / cm ^{2 in} air using a high-pressure mercury lamp. The stress absorbing layer 18 was formed.

<Formation of Stress Absorbing Layer 19>
UV curable resin Arakawa Chemical Industries Co., Ltd. beam set 907 on one side (gas barrier layer installation side: CVD roll non-contact surface side), UV curable resin JSR Co., Ltd. OPSTAR Z7501 on one side of the support ( (Applicable to CVD roll contact surface side), dried at 80 ° C for 3 minutes, coated with a wire bar so that the dry film thickness is 4 µm, and then curing conditions: 0.5 J / cm ² under air, using a high-pressure mercury lamp Curing was performed to form a stress absorbing layer 19.

<Formation of Stress Absorbing Layers 22, 24 to 29>
The resin base material is changed from PET to PEN (polyester film with a thickness of 125 μm that is easily bonded to both surfaces (Q65FWA, manufactured by Teijin DuPont Films Ltd.), , Dried at 80 ° C. for 3 minutes, coated with a wire bar so that the dry film thickness is 4 μm, and then cured under a condition of 0.5 J / cm ² air using a high-pressure mercury lamp, and a stress absorbing layer 22, 24-29 were formed.

<Formation of Stress Absorbing Layer 23>
The resin base material was changed from PET to PC (polycarbonate film having a thickness of 50 μm (manufactured by Teijin Chemicals Ltd., WR-S148)), and UV curable resin JSR Co., Ltd. OPSTAR Z7501 was applied to both sides at 80 ° C. 3 After being partially dried and coated with a wire bar so as to have a dry film thickness of 4 μm, curing was performed using a high-pressure mercury lamp under 0.5 J / cm ² air to form a stress absorbing layer 23.

<Formation of stress absorbing layer 7>
The stress-absorbing layer coating solution 3 is applied to the roll contact surface of the support, dried at 80 ° C. for 3 minutes, applied with a wire bar so that the dry film thickness is 4 μm, and then curing conditions: 0.5 J / cm ² air Below, curing was performed using a high-pressure mercury lamp. Thereafter, seven stress absorbing layers were formed on the non-contact surface of the roll as follows.

(Silicon oxide film formation from polysilazane)
A 10 mass% dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as a coating solution.

<Formation of polysilazane layer>
The polysilazane layer coating solution is applied with a wireless bar so that the (average) film thickness after drying is 300 nm, dried by treatment for 1 minute in an atmosphere at a temperature of 85 ° C. and a humidity of 55% RH, A polysilazane layer was formed by holding for 10 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.) 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 the values shown in Table 1 to perform 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 base material on which the polysilazane layer fixed on the operation stage was formed was modified under the following conditions to form a gas barrier layer.

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 <Formation of stress absorbing layer 8>
A stress-absorbing layer 8 was formed by forming a polysilazane cured layer of the stress-absorbing layer 32 on both sides.

<Formation of gas barrier films 1 to 19, 22, 23, 26>
The stress absorbing layer of the resin substrate with the stress absorbing layer is mounted on the apparatus shown in FIG. 2 so that each of the stress absorbing layers becomes a roll contact surface or a roll non-contact surface, and is based on the following film formation conditions (plasma CVD conditions). A gas barrier layer was formed on the material so as to have a thickness of 500 nm, and gas barrier films 1 to 19, 22, 23, and 26 were produced. The gas barrier film 26 was formed twice.

<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 conveyance speed: 0.8 m / min
Deposition roller diameter: 300mmφ
<Formation of gas barrier film 20>
A gas barrier film 20 having a gas barrier layer having a layer thickness of 300 nm was formed in the same manner as the gas barrier film 1 except that the supply amount of oxygen gas was changed to 750 sccm and the film conveyance speed was changed to 2.5 m / min.

<Formation of gas barrier film 21>
A gas barrier film 21 having a layer thickness of 1000 nm was formed in the same manner as the gas barrier film 1 except that the supply amount of the source gas was changed to 75 sccm and the film conveyance speed was changed to 0.4 m / min.

<Formation of the second gas barrier layers 25 and 27 to 29>
A second gas barrier layer was formed on the gas barrier film as described below, and second gas barrier layer-attached films 25 and 27 to 29 were produced.

(Silicon oxide film formation from polysilazane)
A 10 mass% dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as a coating solution.

<Formation of polysilazane layer>
The polysilazane layer coating solution is applied with a wireless bar so that the (average) film thickness after drying is 300 nm, dried by treatment for 1 minute in an atmosphere at a temperature of 85 ° C. and a humidity of 55% RH, A polysilazane layer was formed by holding for 10 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.) 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 the values shown in Table 1 to perform 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 base material on which the polysilazane layer fixed on the operation stage was formed was modified under the following conditions to form a gas barrier layer.

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 <Formation of overcoat layers 24 and 27 to 29>
In the configuration described in Table 1, an overcoat layer was formed as follows on the gas barrier layer or the second gas barrier layer of the gas barrier film.

  Wasshin Coat MP6103 manufactured by Washin Chemical Industry Co., Ltd. was applied, dried at 120 ° C. for 3 minutes, and overcoat layers 24 and 27 to 29 were formed so that the dry film thickness was 500 nm.

  Further, Glasca HPC7003 manufactured by JSR Co., Ltd. was applied, dried at 120 ° C. for 3 minutes, and the overcoat layer 28 was formed so that the dry film thickness was 500 nm.

  Using the gas barrier film thus prepared and the gas barrier film, evaluation of indentation hardness of the stress absorption layer, measurement of XPS depth profile of the gas barrier film, evaluation of water vapor barrier property, evaluation of flexibility, high temperature and high humidity treatment + Flexibility evaluation was performed and listed in Tables 1 and 2.

表１及び表２記載したように、本発明によれば、十分なガスバリアー性を有しており、しかも高温高湿処理＋フィルムを屈曲させた場合においても、ガスバリアー性の低下を十分に抑制することが可能な耐久性が良好なガスバリアーフィルムを提供することが可能となる。

As described in Tables 1 and 2, according to the present invention, the gas barrier property is sufficient, and even when the high temperature and high humidity treatment + film is bent, the gas barrier property is sufficiently lowered. It becomes possible to provide a gas barrier film with good durability that can be suppressed.

Example 2
<Production of organic EL element>
(Formation of first electrode layer)
A 150 nm-thick ITO (indium tin oxide) film was formed by sputtering on the gas barrier layer, the second gas barrier layer, or the overcoat layer of the gas barrier films 1 to 29 produced in Example 1. Then, patterning was performed by a photolithography method to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.

(Formation of hole transport layer)
On the first electrode layer of each gas barrier film on which the first electrode layer is formed, the following hole transport layer forming coating solution is applied by an extrusion coater in an environment of 25 ° C. and 50% relative humidity. After that, drying and heat treatment were performed under the following conditions to form a hole transport layer. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Before coating the hole transport layer forming coating solution, the cleaning surface modification treatment of the barrier film was performed using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. The charge removal treatment was performed using a static eliminator with weak X-rays.

<Preparation of hole transport layer forming coating solution>
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.

<Drying and heat treatment conditions>
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.

(Formation of light emitting layer)
On the hole transport layer formed above, the following coating solution for forming a white light emitting layer is applied by an extrusion coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. did. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

<White luminescent layer forming coating solution>
As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.

〈塗布条件〉
塗布工程を窒素ガス濃度９９％以上の雰囲気で、塗布温度を２５℃とし、塗布速度１ｍ／ｍｉｎで行った。

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.

<Drying and heat treatment conditions>
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and then a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.

(Formation of the electron transport layer 25)
On the light emitting layer formed above, the following coating liquid for forming an electron transport layer was applied by an extrusion coater under the following conditions, and then dried and heated under the following conditions to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

<Coating liquid for electron transport layer formation>
The electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating liquid for forming an electron transport layer.

〈乾燥及び加熱処理条件〉
電子輸送層形成用塗布液を塗布した後、成膜面に向け高さ１００ｍｍ、吐出風速１ｍ／ｓ、幅手の風速分布５％、温度６０℃で溶媒を除去した後、引き続き、加熱処理部で、温度２００℃で加熱処理を行い、電子輸送層を形成した。

<Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
An electron injection layer 26 was formed on the electron transport layer formed above. First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode)
Aluminum is used as the second electrode forming material on the electron injection layer 26 formed as described above, except for the portion that becomes the extraction electrode of the first electrode 22 under a vacuum of 5 × 10 ⁻⁴ Pa. Then, a mask pattern was formed by vapor deposition so as to have an extraction electrode so that the light emission area was 50 mm square, and a second electrode 27 having a thickness of 100 nm was laminated.

(Cutting)
As described above, each laminate including the second electrode was moved again to a nitrogen atmosphere, and cut to a specified size using an ultraviolet laser to produce an organic EL element.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element, and a flexible printed circuit board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm). , Surface-treated NiAu plating).

  Pressure bonding conditions: Pressure bonding was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.

(Sealing)
As a sealing member, a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) is laminated with a polyethylene terephthalate (PET) film (12 μm thickness) using a dry lamination adhesive (two-component reaction type urethane adhesive). (Adhesive layer thickness 1.5 μm) was prepared.

  A thermosetting adhesive was uniformly applied to the aluminum surface of the prepared sealing member at a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil using a dispenser to form an adhesive layer.

  At this time, an epoxy adhesive containing the following components was used as the thermosetting adhesive.

  Bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY), and epoxy adduct curing accelerator.

  The sealing member is closely attached and arranged so as to cover the joint between the take-out electrode and the electrode lead, and using a pressure roll, pressure bonding conditions, a pressure roll temperature of 120 ° C., a pressure of 0.5 MPa, and an apparatus speed of 0.3 m / min. And sealed tightly.

<< Evaluation of organic EL elements >>
About the produced said organic EL elements 1-29, durability evaluation was performed according to the following method.

[Evaluation of durability]
(Accelerated deterioration processing)
Each of the produced organic EL elements was subjected to an accelerated deterioration treatment for 400 hours in an environment of 60 ° C. and 90% RH, and then evaluated for the following black spots together with the organic EL elements not subjected to the accelerated deterioration treatment. .

(Evaluation of sunspots)
A current of 1 mA / cm ² was applied to the organic EL element subjected to the accelerated deterioration treatment and the organic EL element not subjected to the accelerated deterioration treatment to emit light continuously for 24 hours. A part of the panel was magnified with a Moritex MS-804 and a lens MP-ZE25-200) and photographed. The photographed image was cut out in a 2 mm square, the black spot generation area ratio was determined, the element deterioration resistance rate was calculated according to the following formula, and the durability was evaluated according to the following criteria. If the evaluation rank was ◎ or ◯, it was determined that the characteristic was practically preferable.

Element deterioration tolerance rate = (area of black spots generated in elements not subjected to accelerated deterioration processing / area of black spots generated in elements subjected to accelerated deterioration processing) × 100 (%)
A: The element deterioration resistance rate is 90% or more. B: The element deterioration resistance ratio is 60% or more and less than 90%. Δ: The element deterioration resistance ratio is 20% or more and less than 60%. The deterioration resistance ratio is less than 20%. Table 3 shows the results obtained as described above.

表３に記載の結果より明らかなように、本発明のガスバリアーフィルムを備えた素子は、素子劣化耐性率が９０％以上であり、良好な耐久性を備えている。一方、比較例のガスバリアーフィルムを備えた素子は、素子劣化耐性率が６０％未満であった。

As is apparent from the results shown in Table 3, the element provided with the gas barrier film of the present invention has an element deterioration resistance ratio of 90% or more and has good durability. On the other hand, the element provided with the gas barrier film of the comparative example had an element deterioration resistance rate of less than 60%.

  Therefore, it turns out that the gas barrier film of the Example of this invention has very high gas barrier property of the grade which can be used as a sealing film of an organic EL element.

DESCRIPTION OF SYMBOLS 1a Gas barrier film 1b Gas barrier film 1 Resin base material 2 Stress absorption layer 3 Gas barrier layer 4 2nd gas barrier layer 5 Overcoat layer 6 Transparent electrode 7 Organic EL element (electronic device main body)
8 Adhesive layer 9 Opposite film P Organic EL panel (electronic device)
DESCRIPTION OF SYMBOLS 11 Sending roller 21, 22, 23, 24 Conveyance roller 31, 32 Film-forming roller 41 Gas supply pipe 51 Power supply 61 for plasma generation 61, 62 Magnetic field generator 71 Winding roller A Carbon distribution curve B Silicon distribution curve C Oxygen distribution curve D Oxygen carbon distribution curve

Claims (7)

  The resin base material is transported while the resin base material is brought into contact with each of the pair of film forming rollers, and plasma discharge is performed while supplying a film forming gas between the pair of film forming rollers. A method for producing a gas barrier film on which a gas barrier layer is formed, wherein the resin substrate has a stress absorption layer having an indentation hardness with respect to a load of 100 μN on both sides within a range of 0.4 to 1.0 GPa. And a method for producing a gas barrier film, comprising forming the gas barrier layer on at least one of the stress absorbing layers. A source gas containing an organosilicon compound and an oxygen gas are used as the deposition gas, the gas barrier layer contains carbon, silicon, and oxygen as constituent elements, and the gas barrier layer in the thickness direction of the gas barrier layer In the carbon distribution curve showing the relationship between the distance from the surface of and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atom ratio),
The carbon atom ratio of the gas barrier layer is in the range of 8 to 20 at% as an average value of the entire layer, and the carbon distribution curve continuously changes in the layer with a concentration gradient. The method for producing a gas barrier film according to claim 1.   The indentation hardness of the surface which contacts the said film-forming roller of the said stress absorption layer is smaller in the range of 0.1-0.3 GPa than the surface which does not contact, The Claim 1 or Claim 2 characterized by the above-mentioned. A method for producing a gas barrier film.   The diameter of the said film-forming roller exists in the range of 300-1000 mmphi, The manufacturing method of the gas barrier film as described in any one of Claim 1- Claim 3 characterized by the above-mentioned.   A polysilazane-containing liquid is applied onto the gas barrier layer, 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. The method for producing a gas barrier film according to any one of claims 1 to 4, wherein:   A resin base material, a gas barrier film in which a stress absorption layer is laminated on both surfaces of the resin base material, and a gas barrier layer is laminated on at least one surface of the stress absorption layer, and the stress absorption layer has a load of 100 μN The indentation hardness of the gas barrier layer is in the range of 0.4 to 1.0 GPa, the gas barrier layer contains carbon, silicon, and oxygen as constituent elements, and the gas barrier layer has a thickness direction of the gas barrier layer. In the carbon distribution curve showing the relationship between the distance from the surface and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atom ratio), the carbon atom ratio of the gas barrier layer is the entire layer A gas barrier characterized in that the carbon distribution curve is continuously changing with a concentration gradient in the layer, and an average value of 8 to 20 at% as an average value of Irumu.   On the gas barrier layer, a polysilazane-containing liquid is applied and dried, and the formed coating film is laminated with a second gas barrier layer that is modified by irradiation with vacuum ultraviolet light having a wavelength of 200 nm or less. The gas barrier film according to claim 6.

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