WO2010026852A1 - Film de résine, procédé pour produire le film de résine et élément électroluminescent organique - Google Patents

Film de résine, procédé pour produire le film de résine et élément électroluminescent organique Download PDF

Info

Publication number
WO2010026852A1
WO2010026852A1 PCT/JP2009/064171 JP2009064171W WO2010026852A1 WO 2010026852 A1 WO2010026852 A1 WO 2010026852A1 JP 2009064171 W JP2009064171 W JP 2009064171W WO 2010026852 A1 WO2010026852 A1 WO 2010026852A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
film
resin film
gas
resin
Prior art date
Application number
PCT/JP2009/064171
Other languages
English (en)
Japanese (ja)
Inventor
朋紀 河村
Original Assignee
コニカミノルタホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタホールディングス株式会社 filed Critical コニカミノルタホールディングス株式会社
Priority to JP2010527741A priority Critical patent/JPWO2010026852A1/ja
Publication of WO2010026852A1 publication Critical patent/WO2010026852A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Definitions

  • the present invention is mainly for packaging materials such as food and pharmaceuticals, packages such as electronic devices, or transparent gas barrier films used for display materials such as plastic substrates such as organic EL elements and liquid crystals, and organic electroluminescence using gas barrier films.
  • the present invention relates to a resin film and an organic electroluminescence element.
  • a gas barrier film in which a thin film of metal oxide such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging goods and foods that require blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent the alteration of industrial products and pharmaceuticals. In addition to packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (EL) substrates, and the like.
  • EL organic electroluminescence
  • Aluminum foil, etc. is widely used as packaging material in such fields, but disposal after use is a problem, and it is basically opaque and the contents can be confirmed from the outside.
  • the display material is required to be transparent and cannot be applied at all.
  • transparent films which are being applied to liquid crystal display elements, organic EL elements, etc., in recent years, can be produced in roll-to-roll, in addition to the demands for light weight and large size, long-term reliability, High demands such as a high degree of freedom in shape and the ability to display a curved surface have been added, and films such as transparent plastics have begun to be used instead of glass substrates that are heavy and easily broken.
  • a polymer film as a substrate of an organic electroluminescence element is disclosed (for example, refer to Patent Documents 1 and 2).
  • a film such as transparent plastic has a problem that the gas barrier property is inferior to glass.
  • a film having poor gas barrier properties is used when used as a substrate of an organic electroluminescence element, water vapor or air penetrates and the organic film is deteriorated, which is a factor that impairs light emission characteristics or durability.
  • a polymer substrate is used as a substrate for an electronic device, oxygen permeates the polymer substrate and permeates and diffuses into the electronic device, which deteriorates the device or is required in the electronic device. This causes a problem that the degree of vacuum cannot be maintained.
  • Gas barrier films used for packaging materials and liquid crystal display elements include those obtained by vapor-depositing silicon oxide on a plastic film (for example, see Patent Document 1) and those obtained by vapor-depositing aluminum oxide (for example, see Patent Document 2). It has been.
  • a protective layer and a stress relaxation layer are provided on the barrier layer side (see, for example, Patent Document 3), but the back side is hard, and on the barrier layer or protective layer during roll winding Can not be completely prevented.
  • a technology has been disclosed in which an easy-slip layer is provided on the back surface, and the roll is rolled up smoothly (see, for example, Patent Document 4). The occurrence of scratches on the surface is reduced, but when fine particles with high hardness are mixed, the front and back surfaces may slip, and the scratches may be promoted when the roll is wound.
  • an object of the present invention is to be able to produce a resin film capable of achieving high barrier performance in a roll form, and to use the resin film as a resin film for organic electroluminescence.
  • An organic electroluminescence element is obtained using a resin film for organic electroluminescence.
  • An organic electroluminescence element wherein an organic light emitting medium layer, a cathode layer, and a sealing layer are laminated on the transparent conductive layer.
  • a method for producing a resin film having a gas barrier layer wherein the gas barrier layer is laminated while the resin film is rolled out after the 1 resin film is rolled up.
  • a resin film capable of achieving high barrier performance can be obtained, and a resin film useful as a resin film for organic electroluminescence excellent in high gas barrier properties, a production method thereof, and organic electroluminescence using the film An element can be obtained.
  • the support for the film having a smooth layer 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.
  • the thickness of the support is preferably about 5 to 500 ⁇ m, more preferably 25 to 250 ⁇ m.
  • the resin film support according to the present invention is preferably transparent. Since the support is transparent and the layer formed on the support is also transparent, it becomes possible to make a transparent gas barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. is there.
  • the resin film support using the above-described resins or the like may be an unstretched film or a stretched film.
  • the resin film support used in the present invention can be produced by a conventionally known general method.
  • an unstretched support 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.
  • the unstretched support is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, and other known methods, such as the flow (vertical axis) direction of the support, or
  • a stretched support can be produced by stretching in the direction perpendicular to the flow direction of the support (horizontal axis).
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the support, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.
  • the corona treatment may be performed before forming the vapor deposition film.
  • an anchor coat agent layer may be formed on the surface of the support according to the present invention for the purpose of improving the adhesion to the vapor deposition film.
  • the anchor coating agent used in this anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicone resins, and alkyl titanates. Can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents.
  • the above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to.
  • the application amount of the anchor coating agent is preferably about 0.1 to 5 g / m 2 (dry state).
  • the smooth layer of the present invention flattens the rough surface of the transparent resin film support with protrusions or the like, or fills the irregularities and pinholes generated in the transparent inorganic compound layer with the protrusions present on the transparent resin film support.
  • a smooth layer is basically formed by curing a photosensitive resin.
  • the photosensitive resin of the smooth layer for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate,
  • a resin composition containing an acrylate compound having a radical reactive unsaturated compound for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate
  • examples thereof include resin compositions in which polyfunctional acrylate monomers such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved. It is also possible to use any mixture of the resin compositions as described above, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds
  • Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl.
  • the composition of the photosensitive resin contains a photopolymerization initiator.
  • Photopolymerization initiators include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, ⁇ -amino acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxy
  • the method for forming the smooth layer is not particularly limited, but is preferably formed by a spin coating method, a spray method, a blade coating method, a wet coating method such as a dip method, or a dry coating method such as a vapor deposition method.
  • additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary.
  • an appropriate resin or additive may be used in order to improve the film formability and prevent the generation of pinholes in the film.
  • a resin such as a thermoplastic resin or a thermosetting resin is preferably used as a main component.
  • a resin such as a thermoplastic resin or a thermosetting resin is preferably used as a main component.
  • those having excellent surface smoothness after coating film formation, low gas permeability to oxygen and water vapor, and excellent adhesion to the base resin and the inorganic barrier layer are desirable.
  • the resin for forming the smooth layer include, for example, epoxy resins, phenoxy resins, phenoxy ether resins, phenoxy ester resins, acrylic resins, melamine resins, phenol resins, urethane resins, alkyd resins, silicone resins and mixtures thereof, polyesters.
  • These resins can be used alone or in combination of two or more.
  • a smooth layer is formed by applying a monomer, solution, emulsion or the like of these resins by an existing coating film forming method alone, followed by drying or curing.
  • a polymer that forms a smooth layer with a base film or an inorganic thin film layer by containing a hydrolyzed / condensed product of alkoxysilane such as tetramethoxysilane or tetraethysilane or a silane coupling material in the smooth layer Can improve the adhesion.
  • a smooth layer is formed by applying a solution-like or suspension-like mixture of these resins by an existing coating film forming method, followed by drying and / or curing.
  • a leveling agent may be added to the resin material for forming the smooth layer.
  • the leveling agent that can be used is not particularly limited.
  • a coating leveling agent such as a fluorine nonionic surfactant, a special acrylic resin leveling agent, or a silicone leveling agent can be used.
  • the addition amount of the leveling agent is usually 5 to 50,000 ppm, preferably 10 to 20,000 ppm.
  • the thickness of the smooth layer is not particularly limited, but is 0.02 to 50 ⁇ m, more preferably about 0.1 to 10 ⁇ m.
  • the transparency it is preferable that the light transmittance at 550 nm is 80% or more as in the case of the substrate.
  • Solvents used when forming a smooth layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, ⁇ -Or terpenes such as ⁇ -terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Group hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl
  • the coating solution solid content concentration so that the viscosity of the coating solution is lowered.
  • the coating solution viscosity at 25 ° C. is 1 to 100 cP (1 to 100 mPa ⁇ s), and more preferably 2 to 30 cP (2 to 30 mPa ⁇ s).
  • the drying temperature is also high, convection occurs in the film in the middle of drying, making it difficult to obtain sufficient smoothness.
  • the drying temperature for obtaining high smoothness is usually 20 to 120 ° C, preferably 30 to 100 ° C.
  • smoothness can be obtained by keeping the deposition rate of the smooth layer composition on the support low.
  • a preferable deposition rate is usually 5 to 200 nm / second, preferably 10 to 100 nm / second. When the deposition rate is lower than this, since it takes time to manufacture, the production efficiency is lowered.
  • the resin film of the present invention has a smooth layer on both sides and a gas barrier layer is laminated on at least one side.
  • a gas barrier layer is laminated on at least one side.
  • the smooth layer on both sides of the resin film of the present invention is characterized in that the difference in pencil hardness between the surfaces is two or more and the pencil hardness of the high hardness surface is H or more and 5H or less. If it is lower than this, it will be difficult to suppress surface scratches caused by the entrapment of minute foreign matter during winding of the roll, and conversely, if the hardness is higher than this, bending during roll winding will be difficult. There are concerns about cracks and the like.
  • the difference in pencil hardness between the smooth layer surfaces on both sides of the resin film is two steps or more. It is not possible to sufficiently suppress surface scratches.
  • Pencil hardness is a standard that indicates the hardness of a pencil when it is scratched in 17 levels from 6B to 9H defined by JIS K5600-5-4 scratch hardness (pencil method). As a specific measurement method, measurement is performed under the conditions of 21 to 25 degrees Celsius as the measurement environment and 45 to 55% humidity.
  • the pencil to be used is not sharpened, the tip is flat and the tip is projected 5 to 6 mm, and the pencil is 7 mm at a speed of 0.5 to 1 mm per second with a load of 750 grams at an angle of 45 degrees. Move more. The measurement is performed twice, and if a scratch of 3 mm or more remains in both cases, the measurement is not allowed.
  • Examples of the measuring instrument include a pencil scratch tester manufactured by Cortec.
  • the smoothness of the smooth layer is a value expressed by surface roughness, and the average roughness Ra is usually preferably 20 nm or less, and Ra on the higher hardness side is particularly preferably 5 nm or less.
  • the surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times within a section of ⁇ m.
  • AFM Anatomic Force Microscope
  • One preferred embodiment includes reactive silica particles (hereinafter also simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin.
  • the photopolymerizable photosensitive group include polymerizable unsaturated groups represented by (meth) acryloyloxy groups.
  • the photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be.
  • a photosensitive resin what adjusted solid content by mixing a general-purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.
  • the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 ⁇ m.
  • the average particle size in such a range, the antiglare property and the resolution, which are the effects of the present invention, can be obtained by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 ⁇ m described later. It becomes easy to form a smooth layer having both optical properties satisfying a good balance and hard coat properties. From the viewpoint of making it easier to obtain such effects, it is more preferable to use an average particle size of 0.001 to 0.01 ⁇ m.
  • a polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to a silica particle by generating a silyloxy group by a hydrolysis reaction of a hydrolyzable silyl group.
  • hydrolyzable silyl group examples include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oximesilyl group, and a hydridosilyl group.
  • Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.
  • Matting agents may be added as other additives.
  • the matting agent inorganic particles having an average particle diameter of about 0.1 to 5 ⁇ m are preferable.
  • inorganic particles one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .
  • the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.
  • the smooth layer of the present invention may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the matting agent.
  • thermoplastic resins examples include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof.
  • Vinyl resins such as polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.
  • thermosetting resin examples include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like.
  • an ionizing radiation curable resin it hardens
  • ionizing radiation an ultraviolet ray or an electron beam
  • the photopolymerizable prepolymer an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used.
  • acrylic prepolymer urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.
  • photopolymerization initiators acetophenone, benzophenone, Michler ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propane, ⁇ -acyloxime ester, thioxanthone and the like.
  • the thickness of the smooth layer in the present invention is 1 to 10 ⁇ m, preferably 2 to 7 ⁇ m.
  • the thickness of the smooth layer in the present invention is 1 to 10 ⁇ m, preferably 2 to 7 ⁇ m.
  • the smooth layer as described above is prepared as a coating solution by mixing a hard coating agent, a matting agent, and other components as necessary, and appropriately using a diluent solvent as necessary, and the coating solution is used as a support film.
  • a coating solution After coating on the surface by a conventionally known coating method, it can be formed by irradiating with ionizing radiation and curing.
  • ionizing radiation 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, or the like are irradiated or scanned.
  • the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.
  • FIG. 1 An example of a method for winding a resin film related to the production method of the present invention will be described with reference to the drawings.
  • a coating film containing an ultraviolet curable resin for a smooth layer is applied with a coater 2 while feeding and transporting a resin film (PET film) 5 subjected to easy adhesion treatment on both sides from the original winding roller 1.
  • PET film resin film
  • the same step is similarly performed on the opposite surface of the resin film 5.
  • the resin film 5 having a smooth layer formed on both sides is wound up in a roll shape on a winding roller 6.
  • the smooth layer on the upper surface and the smooth layer on the lower surface are wound to face each other, but depending on the winding tension and the cleanness depending on the production environment, the smooth layer Irregular pressure may be partially applied to the surface.
  • Step A is a step of forming a smooth layer on the upper surface
  • step B is a step of forming a smooth layer on the lower surface. Further, the intermediate transport roller and guide roller are not shown.
  • the tension at the time of winding the roll in the production method of the present invention varies depending on the thickness and material of the resin film support, but is usually 0.01 N / cm or more and 10 N / cm or less. If it is lower than this, winding disturbance will occur, and if it is higher, the roll itself may be deformed, or the smooth layer surfaces may stick to each other, so-called blocking may occur.
  • the gas barrier layer in the present invention has at least one ceramic film on a resin film, and the residual (internal) stress of this ceramic film is 0.01 MPa or more and 20 MPa or less in terms of compressive stress. By forming such a dense film, a gas barrier film having high durability and excellent gas barrier properties can be obtained.
  • the water vapor transmission rate measured according to the method described in JP-A-2005-283561 is 10 ⁇ 5 g / Gas barrier property with m 2 / day or less, preferably 10 ⁇ 6 g / m 2 / day or less and oxygen permeability of 0.01 ml / m 2 / day or less, preferably 0.001 ml / m 2 / day or less
  • a film having a resin film having excellent support as a support is obtained.
  • the gas barrier film of the present invention when used for an application requiring a high water vapor barrier property such as an organic EL display or a high-definition color liquid crystal display, it is extremely small particularly for an organic EL display application. Even so, growing dark spots may occur and the display life of the display may become extremely short, so that the water vapor permeability measured according to the method described in JP-A-2005-283561 is below the above value. Is preferred.
  • the ceramic film in the present invention is not particularly limited as long as it has the above-mentioned residual stress and prevents the permeation of oxygen and water vapor, but the ceramic film (layer) of the present invention is not particularly limited.
  • the constituent material is preferably an inorganic oxide, and examples thereof include ceramic films such as silicon oxide, aluminum oxide, silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, and tin oxide.
  • the method for producing a ceramic film to be a gas barrier layer is not particularly limited.
  • a method for forming a ceramic film using a wet method such as a spray method using a sol-gel method or a spin coating method is described above. It is difficult to obtain such residual stress adjustment and smoothness at the molecular level (nm level), and since a support described later is an organic material because a solvent is used, a usable support or solvent is not available. There is a disadvantage that it is limited. Therefore, in the present invention, it is preferably formed by applying a sputtering method, an ion assist method, a plasma CVD method described later, a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure described later, and the like.
  • the method using atmospheric pressure plasma CVD is preferable because it does not require a decompression chamber or the like and can form a film at a high speed and has high productivity.
  • the gas barrier layer By forming the gas barrier layer by plasma CVD, it is possible to relatively easily form a film having uniform and surface smoothness and very low internal stress (0.01 to 20 MPa). Because.
  • the thickness of these ceramic films in the present invention varies depending on the type and configuration of the material used and is selected as appropriate, but is preferably in the range of 1 to 2000 nm. This is because when the thickness of the gas barrier film is smaller than the above range, a uniform film cannot be obtained, and it is difficult to obtain a barrier property against gas. Further, when the thickness of the gas barrier film is larger than the above range, it is difficult to maintain flexibility in the gas barrier film, and the gas barrier film is cracked due to external factors such as bending and pulling after the film formation. This is because there is a fear of.
  • the thickness is less than this, there are many film defects and sufficient moisture resistance cannot be obtained.
  • the larger the thickness the higher the moisture resistance theoretically.
  • the internal stress becomes unnecessarily large, and it is easy to break, and a preferable moisture resistance cannot be obtained.
  • the ceramic film serving as the gas barrier layer is transparent. This is because when the gas barrier layer is transparent, the gas barrier film can be made transparent, and can be used for applications such as a transparent substrate of an EL element.
  • the light transmittance of the gas barrier film for example, when the wavelength of the test light is 550 nm, the transmittance is preferably 80% or more, and more preferably 90% or more.
  • the gas barrier layer obtained by the plasma CVD method, or the plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure selects conditions such as organometallic compound, decomposition gas, decomposition temperature, and input power as raw materials (also referred to as raw materials) Therefore, ceramic films such as metal carbides, metal nitrides, metal oxides, metal sulfides, etc., and mixtures thereof (metal oxynitrides, metal nitride carbides, etc.) can be formed separately, which is preferable.
  • silicon oxide is generated.
  • zinc compound is used as a raw material compound and carbon disulfide is used as a cracked gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.
  • an inorganic material as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure.
  • gas it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation.
  • a solvent an organic solvent such as methanol, ethanol, n-hexane or a mixed solvent thereof can be used. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.
  • a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide
  • examples thereof include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.
  • metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.
  • These discharge gases are mixed with a discharge gas that tends to be in a plasma state, and the gas is sent to a plasma discharge generator.
  • nitrogen gas and / or an 18th group atom of the periodic table specifically helium, neon, argon, krypton, xenon, radon, etc. are used.
  • nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
  • the film is formed by mixing the discharge gas and the reactive gas and supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator).
  • a plasma discharge generator plasma generator
  • the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% by volume or more with respect to the entire mixed gas.
  • the inorganic compound contained in the ceramic film according to the present invention is, for example, a film containing at least one of O atoms and N atoms and Si atoms by further combining oxygen gas and nitrogen gas in a predetermined ratio with the organic silicon compound. Can be obtained.
  • various inorganic thin films can be formed by using the source gas as described above together with the discharge gas.
  • an adhesion layer and a protective layer are preferably used.
  • the gas barrier film of the present invention preferably has a structure in which an adhesion layer, a ceramic film and a protective layer are sequentially formed on a smooth layer.
  • the adhesion layer and the protective layer are preferably composed of the same composition.
  • the adhesion layer has a role of stress relaxation and improves adhesion and adhesion to the substrate, and the adhesion layer preferably has a thickness of 1 to 500 nm, more preferably 20 to 200 nm.
  • the protective layer preferably has a thickness of 1 to 1000 nm, more preferably 100 to 800 nm, for protecting the ceramic film.
  • the adhesion layer and the protective layer contain the same composition as the ceramic film, and each film contains the same composition.
  • the phrase “containing the same composition” as used in the present invention means that 50% by mass or more of the substances constituting each film is composed of the same compound, and preferably 70% by mass or more.
  • a spray method using a sol-gel method, a spin coating method, a sputtering method using a metal compound, a vacuum deposition method, a plasma CVD method examples thereof include a plasma CVD method at or near atmospheric pressure described later, and are not particularly limited.
  • an inorganic thin film is formed.
  • a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions or radicals, the organometallic compound that is the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of the support on which the inorganic material is formed and can sufficiently form the film on the resin film support.
  • a thin film having a dense performance and a stable performance can be obtained when the ceramic film is formed on the resin film.
  • the residual stress is a compressive stress, and a ceramic film having a range of 0.01 MPa or more and 20 MPa or less is stably obtained.
  • the source gas containing metal and the decomposition gas are appropriately selected from the gas supply means, and a discharge gas that tends to be in a plasma state is mainly mixed with these reactive gases.
  • the ceramic film can be obtained by feeding a gas into the plasma discharge generator.
  • nitrogen gas and / or 18th group atom of the periodic table specifically helium, neon, argon, krypton, xenon, radon, etc. are used as described above.
  • nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
  • atmospheric pressure plasma discharge treatment apparatus for example, atmospheric pressure plasma discharge treatment described in JP-A-2004-68143, 2003-49272, International Patent No. 02/48428, etc. An apparatus can be mentioned.
  • the gas barrier film has a ceramic film on a resin film support, for example, polyethylene terephthalate. Further, the gas barrier film of the present invention may be formed by laminating two or more ceramic layers, and the gas barrier film comprises a resin film support, at least two ceramic films and a ceramic film positioned between the two ceramic films. It has a stress relaxation layer containing a polymer having a low elastic modulus. Since the ceramic film according to the present invention has a dense structure and high hardness, it is preferable to divide such a stress relaxation layer into a plurality of layers when laminated. The stress relaxation layer has a function of relaxing stress generated in the ceramic layer and preventing generation of cracks and defects in the inorganic ceramic film.
  • the polymer layer according to the present invention is a thin film mainly composed of an inorganic polymer, an organic polymer, an organic-inorganic hybrid polymer, etc., and has a film thickness of about 5 to 500 nm and a hardness relative to the gas barrier layer.
  • a low layer with an average carbon content of 5% or more in the layer also called a stress relaxation layer.
  • the inorganic polymer applicable in the present invention is a film having an inorganic skeleton as a main structure and containing an organic component, and includes a polymer obtained by polymerizing an organometallic compound.
  • silicon compounds such as silicone and polysilazane, titanium compounds, aluminum compounds, boron compounds, phosphorus compounds, and tin compounds can be used.
  • the silicon compound that can be used in the present invention is not particularly limited, but is preferably tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltrimethyl.
  • organic polymer known polymerizable organic compounds can be used, and among them, a polymerizable ethylenically unsaturated bond-containing compound having an ethylenically unsaturated bond in the molecule is preferable.
  • polymerizable ethylenic double bond-containing compounds are not particularly limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxy.
  • Monofunctional acrylic acid esters such as ethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, ⁇ -caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane acrylate, or Methacrylic acid, itaconic acid, crotonic acid, malein in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Esters, such as ethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate neo Diacrylate of pentyl glycol, diacrylate of n
  • prepolymers can be used in the same manner as described above.
  • the prepolymers may be used alone or in combination of two or more, and may be used in admixture with the monomers and / or oligomers described above.
  • prepolymers examples include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester in which (meth) acrylic acid is introduced into polyester obtained by the combination of polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Acrylates such as bisphenol A, epichlorohydrin, (meth
  • an organic polymer applicable to the polymer layer according to the present invention it can be easily formed by using an organic substance capable of plasma polymerization as a thin film forming gas.
  • the plasma-polymerizable organic substance include hydrocarbons, vinyl compounds, halogen-containing compounds, and nitrogen-containing compounds.
  • hydrocarbon examples include ethane, ethylene, methane, acetylene, cyclohexane, benzene, xylene, phenylacetylene, naphthalene, propylene, camphor, menthol, toluene, isobutylene, and the like.
  • vinyl compound examples include acrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, allyl methacrylate, acrylamide, styrene, ⁇ -methyl styrene, vinyl pyridine, vinyl acetate, vinyl methyl ether, and the like.
  • halogen-containing compound examples include tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, fluoroalkyl methacrylate and the like.
  • nitrogen-containing compounds examples include pyridine, allylamine, butylamine, acrylonitrile, acetonitrile, benzonitrile, methacrylonitrile, aminobenzene and the like.
  • Examples of the organic-inorganic hybrid polymer according to the present invention include a film in which an inorganic (organic) substance is dispersed in an organic (inorganic) polymer, and a film having both an inorganic skeleton and an organic skeleton as a main structure.
  • the organic-inorganic hybrid polymer that can be applied to the present invention is not particularly limited, but preferably a combination of the above-described inorganic polymer and organic polymer as appropriate can be used.
  • gas barrier films of the present invention can be used as various sealing materials and films.
  • gas barrier films of the present invention can also be used for display elements such as organic EL elements.
  • the gas barrier film of the present invention is transparent, so that the gas barrier film can be used as a support to extract light from this side. That is, on this gas barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin support for an organic electroluminescence element. Then, using the ITO transparent conductive film provided on the support as an anode, an organic EL material layer including a light emitting layer is provided thereon, and further, a cathode made of a metal film is formed to form an organic EL element.
  • the organic EL element layer can be sealed by stacking another sealing material (although it may be the same) and adhering the gas barrier film support to the surroundings and encapsulating the element. The influence on the element by gas can be sealed.
  • the resin support for organic electroluminescence can be obtained by forming a transparent conductive film on the ceramic film of the gas barrier film thus formed.
  • the transparent conductive film is a conductive film that becomes an anode when an organic EL element is formed.
  • the transparent conductive film can be formed by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin.
  • the film thickness of the transparent conductive film is preferably a transparent conductive film in the range of 0.1 nm to 1000 nm.
  • the present invention is characterized in that a gas barrier film having the ceramic film is used as a substrate.
  • a transparent conductive film is further formed on the ceramic film, and this is used as an anode, and an organic EL material layer for calibrating the organic EL element and a metal layer serving as a cathode are laminated thereon. Further, another gas barrier film is sealed as a sealing film by overlapping and bonding.
  • a gas barrier film having a ceramic film having the dense structure according to the present invention can be used as another sealing material (sealing film) used.
  • known gas barrier films used for packaging materials such as silicon oxide or aluminum oxide deposited on plastic films, dense ceramic layers, and flexible impact relaxation polymer layers are laminated alternately
  • a gas barrier film having the structure described above can be used as the sealing film.
  • a resin-laminated (polymer film) metal foil cannot be used as a gas barrier film on the light extraction side, but is a low-cost and low moisture-permeable sealing material and does not intend to extract light (with transparency). When not required), it is preferable as a sealing film.
  • the metal foil refers to a metal foil or film formed by rolling or the like, unlike a metal thin film formed by sputtering or vapor deposition, or a conductive film formed from a fluid electrode material such as a conductive paste. .
  • metal foil there is no limitation in particular in the kind of metal, for example, copper (Cu) foil, aluminum (Al) foil, gold (Au) foil, brass foil, nickel (Ni) foil, titanium (Ti) foil, copper alloy Examples thereof include foil, stainless steel foil, tin (Sn) foil, and high nickel alloy foil.
  • a particularly preferred metal foil is an Al foil.
  • the thickness of the metal foil is preferably 6 to 50 ⁇ m. If it is less than 6 ⁇ m, depending on the material used for the metal foil, pinholes may be vacant during use, and required barrier properties (moisture permeability, oxygen permeability) may not be obtained. If it exceeds 50 ⁇ m, the cost may increase depending on the material used for the metal foil, and the merit of the film may be reduced because the organic EL element becomes thick.
  • polyethylene resin Polypropylene resin, polyethylene terephthalate resin, polyamide resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, acrylonitrile-butadiene copolymer resin, cellophane resin, vinylon resin, vinylidene chloride Based resins and the like.
  • Resins such as polypropylene resins and nylon resins may be stretched and further coated with a vinylidene chloride resin.
  • a low density or a high density thing can also be used for a polyethylene-type resin.
  • a method of sealing the two films for example, a method of laminating a commonly used impulse sealer heat-fusible resin layer, fusing with an impulse sealer, and sealing is preferable.
  • the film thickness exceeds 300 ⁇ m, the handling of the film at the time of sealing work deteriorates and it becomes difficult to heat-seal with an impulse sealer or the like, so the film thickness is 300 ⁇ m or less. desirable.
  • the organic electroluminescence element can be sealed by covering the cathode surface with the sealing film in an environment purged with an inert gas.
  • the inert gas a rare gas such as He and Ar is preferably used in addition to N 2 , but a rare gas in which He and Ar are mixed is also preferable, and the ratio of the inert gas in the gas is 90 to 99.99. It is preferably 9% by volume. Preservability is improved by sealing in an environment purged with an inert gas.
  • a ceramic film is formed on the metal foil instead of the laminated resin film surface.
  • the ceramic film surface is preferably bonded to the cathode of the organic EL element.
  • a resin film that can be fused with a commonly used impulse sealer for example, ethylene vinyl acetate copolymer (EVA), polypropylene (PP) film, polyethylene (PE )
  • EVA ethylene vinyl acetate copolymer
  • PP polypropylene
  • PE polyethylene
  • the dry laminating method is excellent in terms of workability.
  • This method generally uses a curable adhesive layer of about 1.0 to 2.5 ⁇ m.
  • the amount of the adhesive is preferably adjusted to 3 to 5 ⁇ m in dry film thickness. It is preferable.
  • Hot melt lamination is a method in which a hot melt adhesive is melted and an adhesive layer is applied to a support, and the thickness of the adhesive layer can be generally set in a wide range of 1 to 50 ⁇ m.
  • Commonly used base resins for hot melt adhesives include EVA, EEA, polyethylene, butyl rubber, etc., rosin, xylene resin, terpene resin, styrene resin, etc. as tackifiers, and wax etc. as plastics. It is added as an agent.
  • the extrusion laminating method is a method in which a resin melted at a high temperature is coated on a support with a die, and the thickness of the resin layer can generally be set in a wide range of 10 to 50 ⁇ m.
  • LDPE low density polyethylene
  • EVA EVA
  • PP polypropylene
  • each layer (component layer) of the organic EL material constituting the organic EL element will be described.
  • an element having a phosphorescent type light emitting layer containing a phosphorescent dopant in the light emitting layer is preferable because of high luminous efficiency.
  • anode / light emitting layer / electron transport layer / cathode (2) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (4) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (5) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (anode)
  • 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.
  • an electrode substance examples include conductive transparent materials such as metals such as Au, CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as metals such as Au, CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 ⁇ m or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.
  • the transmittance be greater than 10%
  • the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode 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.
  • 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.
  • 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 preferred.
  • 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 the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a film thickness of 1 to 20 nm. 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 is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists 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 layer. May be.
  • 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).
  • anode buffer layer hole injection layer
  • copper phthalocyanine is used.
  • examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • cathode buffer layer (electron injection layer) The 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, aluminum, etc.
  • Metal buffer layer typified by lithium, 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.
  • 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 ⁇ m, although it depends on the material.
  • the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film.
  • the basic constituent layer of the organic compound thin film For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237.
  • the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.
  • the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.
  • the light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.
  • the light emitting layer of the organic EL device of the present invention preferably contains the following host compound and dopant compound. Thereby, the luminous efficiency can be further increased.
  • the light-emitting dopant is roughly classified into two types: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.
  • fluorescent dopant examples include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, Examples include perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
  • Typical examples of the latter are preferably complex compounds containing metals of Groups 8, 9, and 10 in the periodic table of elements, more preferably iridium compounds and osmium compounds. Of these, iridium compounds are most preferred.
  • the light emitting dopant may be used by mixing a plurality of kinds of compounds.
  • 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.
  • dopant compound simply referred to as a dopant.
  • the light-emitting host used in the present invention is not particularly limited in terms of structure, but is typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, an oligo Those having a basic skeleton such as an arylene compound, or a carboline derivative or diazacarbazole derivative (here, a diazacarbazole derivative is a nitrogen atom in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is a nitrogen atom) And the like.) And the like.
  • 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.
  • the thickness of the light emitting layer is not particularly limited, but is usually selected in the range of 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • This light emitting layer may have a single layer structure in which these phosphorescent compounds and host compounds are composed of one or more kinds, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.
  • 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 either hole injection or transport or electron barrier properties, and may be either organic or inorganic.
  • 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.
  • 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.
  • 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.
  • the thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • the electron transport layer is made of a 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 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.
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, Cellulose esters such as cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetate phthalate (TAC), cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotact Tick polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimi , Polyethersulfone (PES), polysulfones, polyetherketoneimide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylates, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured
  • organic EL element As an example of the organic EL element, a method for producing 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.
  • a desired electrode material for example, a thin film made of an anode material is deposited on the substrate (the gas barrier film of the present invention) so as to have a thickness of 1 ⁇ m or less, preferably 10 to 200 nm.
  • an anode is produced.
  • a method for thinning the organic compound thin film there are a vapor deposition method and a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a uniform film and a pinhole. From the point of being difficult to form, a vacuum deposition method, a spin coating method, an ink jet method, and a printing method are particularly preferable. Further, different film forming methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁇ 6 to 10 ⁇ 2 Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within a range of 50 nm / second, a substrate temperature of ⁇ 50 to 300 ° C., and a film thickness of 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • 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 film thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm, and a cathode is provided.
  • a desired organic EL element can be obtained.
  • the organic EL element is preferably produced from 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.
  • a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode.
  • An alternating voltage may be applied.
  • the alternating current waveform to be applied may be arbitrary.
  • Example 1 As a thermoplastic resin support, a 125 ⁇ m-thick polyester-based substrate (Tetron O3, Tetron O3), which was easily bonded on both sides, was annealed at 170 ° C. for 30 minutes and used.
  • the production of the resin film is carried out by rolling the roll after forming the smooth layer by applying the smooth layer coating liquid having a different composition on both sides by the following forming method while transporting the support at a speed of 10 m / min. A resin film was obtained.
  • the resin film having a smooth layer formed on both sides was continuously wound around a 6-inch inner diameter core in a roll shape.
  • the winding tension at this time was 1.5 N / cm.
  • the resin film sample No. 1 provided with a smooth layer on both surfaces was used. 1 to 10 were formed on the smooth layer 2 in the order of adhesion layer / ceramic layer / protective layer in the order shown below while being pulled out horizontally from the roll.
  • the adhesion layer is 50 nm
  • the ceramic layer is 30 nm
  • the protection layer is 400 nm.
  • the support holding temperature during film formation was 120 ° C.
  • Processing is performed using a roll electrode type discharge treatment device.
  • a plurality of rod-shaped electrodes facing the roll electrode were installed in parallel to the film transport direction, and raw materials and electric power were supplied to each electrode portion to form a thin film as follows.
  • the dielectric was coated with 1 mm of single-sided ceramic sprayed material, with both electrodes facing each other.
  • the electrode gap after coating was set to 1 mm.
  • the metal base material coated with the dielectric has a stainless steel jacket specification having a cooling function with cooling water, and was performed while controlling the electrode temperature with cooling water during discharge.
  • a high frequency power source 80 kHz
  • a high frequency power source 13.56 MHz
  • N 2 gas reaction gas 1 5% by volume of oxygen gas with respect to the total gas
  • Reaction gas 2 0.1% by volume of TEOS with respect to the total gas
  • Low frequency side power supply 80 kHz
  • High frequency side power supply 13.56 MHz is changed from 0.8 to 10 W / cm 2 .
  • N 2 gas Reaction gas 1 1% by volume of hydrogen gas with respect to the total gas Reaction gas 2: 0.5% by volume of TEOS (tetraethoxysilane) with respect to the total gas
  • Low frequency side power supply 80 kHz, 10 W / cm 2
  • High frequency side power supply power 13.56 MHz at 5 W / cm 2 .
  • N 2 gas Reaction gas 1 1% by volume of hydrogen gas with respect to the total gas Reaction gas 2: 0.5% by volume of TEOS with respect to the total gas
  • Low frequency side power supply 80 kHz, 10 W / cm 2
  • High frequency side power supply power 13.56 MHz at 5 W / cm 2 .
  • ⁇ Formation of transparent conductive film> As the plasma discharge device, a parallel plate type electrode was used, the transparent film was placed between the electrodes, and a mixed gas was introduced to form a thin film.
  • a ground (ground) electrode a 200 mm ⁇ 200 mm ⁇ 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed film, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried.
  • the electrode was cured by ultraviolet irradiation and sealed, and the dielectric surface thus coated was polished, smoothed, and processed to have an Rmax of 5 ⁇ m.
  • an electrode obtained by coating a dielectric on a hollow square pure titanium pipe under the same conditions as the ground electrode was used. A plurality of application electrodes were prepared and provided to face the ground electrode to form a discharge space.
  • a power source used for plasma generation a high frequency power source CF-5000-13M manufactured by Pearl Industry Co., Ltd. was used, and power of 5 W / cm 2 was supplied at a frequency of 13.56 MHz.
  • a mixed gas having the following composition is allowed to flow between the electrodes to form a plasma state, the gas barrier film is subjected to atmospheric pressure plasma treatment, and a tin-doped indium oxide (ITO) film having a thickness of 100 nm is formed on the gas barrier layer (ceramic film).
  • ITO indium oxide
  • a film was formed and the resin film sample No. 1-10 were obtained.
  • Discharge gas Helium 98.5% by volume
  • Reactive gas 1 0.25% by volume of oxygen
  • Reactive gas 2 Indium acetylacetonate 1.2% by volume
  • Reactive gas 3 Dibutyltin diacetate 0.05% by volume (Production of organic EL element)
  • the gas barrier film substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol and dried with dry nitrogen gas.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of ⁇ -NPD is put into a molybdenum resistance heating boat, and 200 mg of CBP as a host compound is put into another molybdenum resistance heating boat.
  • bathocuproin BCP
  • Ir-1 Ir-1
  • Alq 3 200 mg of bathocuproin
  • the pressure in the vacuum chamber is reduced to 4 ⁇ 10 ⁇ 4 Pa, and then the heating boat containing ⁇ -NPD is energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second.
  • the heating boat containing CBP and Ir-1 was energized and heated, and a light emitting layer was provided by co-evaporation on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing BCP was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer. Furthermore, the heating boat containing Alq 3 is further energized and heated, deposited on the hole blocking layer at a deposition rate of 0.1 nm / second, and further provided with an electron transport layer having a thickness of 40 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.
  • Organic EL element sample Nos. 1 to 10 using 1 to 10 were produced.
  • N 2 gas reaction gas 1 5% by volume of oxygen gas with respect to the total gas
  • Reaction gas 2 0.1% by volume of tetraethoxysilane (TEOS) with respect to the total gas
  • Low frequency side power supply 80 kHz, 10 W / cm 2
  • High frequency side power supply power 13.56 MHz at 10 W / cm 2
  • nitrogen gas in an environment purged with nitrogen gas (inert gas), using an epoxy adhesive, the organic EL element sample No. obtained with the surface of the sealing film provided with the SiO 2 film on the inside was used.
  • Organic electroluminescence element sample No. 1 having both surfaces 1 to 10 sealed. 1 to 10 were produced.
  • vapor deposition device JEE-400, a vacuum vapor deposition device manufactured by JEOL Ltd.
  • Constant temperature and humidity oven Yamato Humidic Chamber IG47M Metal that corrodes by reacting with raw material moisture: Calcium (granular)
  • Water vapor impermeable metal Aluminum ( ⁇ 3-5mm, granular)
  • a vacuum deposition apparatus (JEOL Ltd.) was formed on the layer surface of the barrier films 1 to 10 which had been bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm.
  • the obtained sample with both sides sealed is stored under high temperature and high humidity of 60 ° C. and 90% RH, and based on the method described in JP-A-2005-283561, the amount of moisture permeated into the cell from the corrosion amount of metallic calcium Was calculated.
  • 1 ⁇ 10 ⁇ 6 g / m 2 / day 4 1 ⁇ 10 ⁇ 6 g / m 2 / day or more, less than 1 ⁇ 10 ⁇ 5 g / m 2 / day 3: 1 ⁇ 10 ⁇ 5 g / m 2 / day or more, less than 1 ⁇ 10 ⁇ 4 g / m 2 / day 2: 1 ⁇ 10 ⁇ 4 g / m 2 / day or more, less than 1 ⁇ 10 ⁇ 3 g / m 2 / day 1: 1 ⁇ 10 ⁇ 3 g / m 2 / day or more.
  • Table 2 shows the results of the above evaluations.
  • the composite film of the present invention has a low water vapor transmission rate, and the organic EL device produced using the composite film of the present invention hardly generates dark spots.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention porte sur un film de résine qui peut produire un niveau élevé de propriétés de barrière. Le film de résine, qui est produit en rouleau, est utilisé comme film de résine pour une électroluminescence organique. L'invention porte également sur un élément électroluminescent organique utilisant le film de résine pour une électroluminescence organique. Le film de résine est caractérisé par le fait que ledit film  comporte une couche lisse sur ses deux surfaces, la différence de dureté au crayon de la surface des couches lisses des deux côtés du film de résine, définie par une résistance à la rayure (procédé au crayon) selon la norme JIS K 5600-5-4, étant de deux à quatre degrés, et la dureté au crayon de la surface ayant une dureté plus élevée étant de H à 5H.
PCT/JP2009/064171 2008-09-02 2009-08-11 Film de résine, procédé pour produire le film de résine et élément électroluminescent organique WO2010026852A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010527741A JPWO2010026852A1 (ja) 2008-09-02 2009-08-11 樹脂フィルム及びその製造方法並びに有機エレクトロルミネッセンス素子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008224533 2008-09-02
JP2008-224533 2008-09-02

Publications (1)

Publication Number Publication Date
WO2010026852A1 true WO2010026852A1 (fr) 2010-03-11

Family

ID=41797024

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/064171 WO2010026852A1 (fr) 2008-09-02 2009-08-11 Film de résine, procédé pour produire le film de résine et élément électroluminescent organique

Country Status (2)

Country Link
JP (1) JPWO2010026852A1 (fr)
WO (1) WO2010026852A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1144249A (ja) * 1997-07-28 1999-02-16 Denso Corp エンジン制御装置
WO2014133141A1 (fr) * 2013-02-28 2014-09-04 日本放送協会 Elément à électroluminescence organique
JP2015157411A (ja) * 2014-02-24 2015-09-03 大日本印刷株式会社 ガスバリアフィルム及びその製造方法
JP2015200898A (ja) * 2015-05-19 2015-11-12 大日本印刷株式会社 光学シート、面光源装置及び液晶表示装置
KR20160138447A (ko) * 2014-03-31 2016-12-05 린텍 가부시키가이샤 장척의 가스 배리어성 적층체 및 그 제조 방법
JP2017511759A (ja) * 2014-02-19 2017-04-27 サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ 多層シート、該多層シートの製造方法および使用方法、ならびに該多層シートを含む物品

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60222241A (ja) * 1984-04-19 1985-11-06 住友ベークライト株式会社 透明導電性フィルム
JP2005289041A (ja) * 2004-03-09 2005-10-20 Dainippon Printing Co Ltd 湾曲を防止したガスバリアフィルム
JP2007030307A (ja) * 2005-07-26 2007-02-08 Crd:Kk 透明性シート
JP2008094063A (ja) * 2006-10-16 2008-04-24 Asahi Kasei Chemicals Corp 金属酸化物積層体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60222241A (ja) * 1984-04-19 1985-11-06 住友ベークライト株式会社 透明導電性フィルム
JP2005289041A (ja) * 2004-03-09 2005-10-20 Dainippon Printing Co Ltd 湾曲を防止したガスバリアフィルム
JP2007030307A (ja) * 2005-07-26 2007-02-08 Crd:Kk 透明性シート
JP2008094063A (ja) * 2006-10-16 2008-04-24 Asahi Kasei Chemicals Corp 金属酸化物積層体

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1144249A (ja) * 1997-07-28 1999-02-16 Denso Corp エンジン制御装置
WO2014133141A1 (fr) * 2013-02-28 2014-09-04 日本放送協会 Elément à électroluminescence organique
JP2017143072A (ja) * 2013-02-28 2017-08-17 日本放送協会 有機電界発光素子
JPWO2014133141A1 (ja) * 2013-02-28 2017-02-02 日本放送協会 有機電界発光素子
JP2017511759A (ja) * 2014-02-19 2017-04-27 サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ 多層シート、該多層シートの製造方法および使用方法、ならびに該多層シートを含む物品
US10913247B2 (en) 2014-02-19 2021-02-09 Sabic Global Technologies B.V. Multilayer sheet, methods for making and using the same, and articles comprising the multilayer sheet
JP2015157411A (ja) * 2014-02-24 2015-09-03 大日本印刷株式会社 ガスバリアフィルム及びその製造方法
EP3127696A1 (fr) 2014-03-31 2017-02-08 LINTEC Corporation Stratifié allongé faisant barrière au gaz et son procédé de production
US20170107344A1 (en) 2014-03-31 2017-04-20 Lintec Corporation Elongated gas barrier laminate and method for producing same
KR20160138447A (ko) * 2014-03-31 2016-12-05 린텍 가부시키가이샤 장척의 가스 배리어성 적층체 및 그 제조 방법
TWI664084B (zh) * 2014-03-31 2019-07-01 日商琳得科股份有限公司 長條形氣體阻障性積層體及其製造方法
US10377870B2 (en) 2014-03-31 2019-08-13 Lintec Corporation Elongated gas barrier laminate and method for producing same
KR102352337B1 (ko) * 2014-03-31 2022-01-17 린텍 가부시키가이샤 장척의 가스 배리어성 적층체 및 그 제조 방법
EP3127696B1 (fr) * 2014-03-31 2024-05-01 LINTEC Corporation Stratifié allongé faisant barrière au gaz et son procédé de production
JP2015200898A (ja) * 2015-05-19 2015-11-12 大日本印刷株式会社 光学シート、面光源装置及び液晶表示装置

Also Published As

Publication number Publication date
JPWO2010026852A1 (ja) 2012-02-02

Similar Documents

Publication Publication Date Title
JP5857452B2 (ja) バリアーフィルムの製造方法
WO2010026869A1 (fr) Film composite, film barrière aux gaz et son procédé de production, et élément d’électroluminescence organique
JP6504284B2 (ja) ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス
JP5929775B2 (ja) ガスバリア性フィルムおよびその製造方法、ならびに前記ガスバリア性フィルムを含む電子デバイス
JP5533585B2 (ja) ガスバリアフィルムの製造方法、ガスバリアフィルム及び電子機器
JP5402818B2 (ja) ガスバリア性フィルム、及びガスバリア性フィルムの製造方法
JP5565454B2 (ja) ガスバリアフィルムの製造方法、有機エレクトロルミネッセンス用樹脂基材、それを用いた有機エレクトロルミネッセンス素子
WO2010024149A1 (fr) Film composite, film barrière de gaz et procédé de production de ceux-ci, et élément à électroluminescence organique
JP5716752B2 (ja) ガスバリアフィルムの製造方法、ガスバリアフィルムおよび電子デバイス
JP5895687B2 (ja) ガスバリア性フィルム
JP5445179B2 (ja) ガスバリア性フィルム、ガスバリア性フィルムの製造方法、有機電子デバイス
JP5540949B2 (ja) ガスバリア性フィルム、及び有機光電変換素子、有機エレクトロルミネッセンス素子
JP2015003464A (ja) ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス
JP2007277631A (ja) ガスバリア性薄膜積層体の製造方法、ガスバリア性薄膜積層体、ガスバリア性樹脂基材及び有機エレクトロルミネッセンスデバイス
JP5884531B2 (ja) 水蒸気バリアーフィルムの製造方法、水蒸気バリアーフィルム及び電子機器
WO2010026852A1 (fr) Film de résine, procédé pour produire le film de résine et élément électroluminescent organique
JP6485455B2 (ja) ガスバリアーフィルム及びガスバリアーフィルムの製造方法
JP2006299145A (ja) ガスバリア性フィルム、ガスバリア性フィルムを用いた有機エレクトロルミネッセンス用樹脂基材および有機エレクトロルミネッセンス素子
JP2015103389A (ja) 有機ｅｌ素子
JP2012067193A (ja) ガスバリア性フィルムの洗浄方法、ガスバリア性包装体及び有機電子デバイス
WO2016043141A1 (fr) Film barrière contre les gaz
JP5581834B2 (ja) ガスバリア性フィルムの製造方法、有機電子デバイス
JP6070411B2 (ja) ガスバリアー性フィルム、ガスバリアー性フィルムの製造方法及び有機エレクトロルミネッセンス素子
JP2015131473A (ja) ガスバリア性フィルム、およびこれを用いた電子デバイス
JP5849790B2 (ja) 水蒸気バリアーフィルムの製造方法、水蒸気バリアーフィルム及び電子機器

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09811381

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010527741

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09811381

Country of ref document: EP

Kind code of ref document: A1