JP2006219721A - Method for producing functional film, functional film, display element and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent gas barrier film having barrier properties satisfying a water vapor transmittance of a 10<SP>-5</SP>g/m<SP>2</SP>/day order or an oxygen transmittance of a 10<SP>-4</SP>ml/m<SP>2</SP>/day order. <P>SOLUTION: In the method for producing the functional film having at least two ceramics layers on the surface of a substrate and at least one polymer layer between ceramics layers, at least one layer of the ceramic layers and the polymer layer is formed by feeding a gas containing a thin film deposition gas into a discharge space, applying a high frequency electric field obtaine by superimposing high frequency electric fields different in frequency to the discharge space under the atmospheric pressure or near the atmospheric pressure to excite the gas, and exposing the substrate to the excited gas. In this case, the surface temperature of the substrate during the formation of the ceramic layers and the polymer layer (s) is controlled to 150°C to less than the melting temperature of the substrate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a functional film, a functional film (barrier film) produced by the production method, a display element having display means formed on the functional film (barrier film), and the display The present invention relates to a display device having an element.

  Conventionally, a gas barrier film in which a thin film of a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is a packaging of articles that require blocking of various gases such as water vapor and oxygen, Widely used in packaging applications to prevent the deterioration of food, industrial products and pharmaceuticals. Moreover, it is used as base materials, such as a liquid crystal display element, a solar cell, and organic electroluminescence (EL) besides the packaging use.

  On the other hand, a base material made of polyvinylidene chloride resin or a copolymer resin of vinylidene chloride and other polymers, or a material provided with gas barrier properties by coating these vinylidene chloride resins on polypropylene resin, polyester resin, or polyamide resin However, it is widely used as a packaging material. However, since chlorine gas is generated during the incineration process, it is a problem from the viewpoint of environmental protection. Can not be applied to the field where is required.

  In particular, transparent substrates, which are being applied to liquid crystal display elements, organic EL elements, etc., have recently been required to be lighter and larger, have long-term reliability and a high degree of freedom in shape, and have curved surface display. High demands such as being possible have been added, and substrates such as transparent plastics have begun to be used instead of glass substrates that are heavy and easily broken. For example, JP-A-2-251429 and JP-A-6-124785 disclose an example in which a polymer film is used as a base material of an organic electroluminescence element.

  However, a substrate such as transparent plastic has a problem that the gas barrier property is inferior to glass. For example, when used as a base material for an organic electroluminescence element, if a base material with inferior gas barrier properties is used, water vapor or oxygen will permeate and the electrodes and organic film will deteriorate, leading to factors that impair the light emission characteristics or durability. . In addition, when a polymer substrate is used as the substrate for an electronic device, oxygen permeates the polymer substrate and penetrates and diffuses into the electronic device, degrading the device, Cause the problem that the degree of vacuum required in can not be maintained.

In order to solve such a problem, a manufacturing method of a laminate in which a carbon-containing metal oxide thin film is formed on a substrate by a CVD method using plasma generated under a pressure near atmospheric pressure is known ( (For example, see Patent Document 1.)
JP 2004-10992 A

  With the recent increase in the size of organic EL displays and liquid crystal displays and the development of high-definition displays, higher gas barrier properties have been demanded.

For example, in the case of an organic EL display application, even if it is very small, a growing dark spot may be generated, and the display life of the display may be extremely shortened. Therefore, the water vapor transmission rate measured according to the JIS K7129 B method for gas barrier performance, for example. The demand has increased to about 1 × 10 ⁻³ g / m ² / day, and with the configuration described in Patent Document 1, there is a possibility that sufficient gas barrier properties may not be ensured due to limitations on usable substrates. There was a problem that there was.

The present invention has been made in view of the above problems, and its purpose is to provide a barrier property of the order of 10 ⁻⁶ g / m ² / day for water vapor permeability and the order of 10 ⁻⁴ ml / m ² / day for oxygen permeability. It is providing the transparent gas barrier film which has this.

  The above object can be achieved by the invention described in the following section.

(1) In a method for producing a functional film having at least two ceramic layers on a substrate and at least one polymer layer positioned therebetween,
At least one of the ceramic layer and the polymer layer supplies a gas containing a thin film forming gas to the discharge space, and excites the gas by applying a high-frequency electric field to the discharge space under atmospheric pressure or a pressure in the vicinity thereof. Formed by exposing the substrate to the excited gas,
The high-frequency electric field is a superposition of the first high-frequency electric field and the second high-frequency electric field, and the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, and the first high-frequency electric field is The relationship between the electric field strength V ₁ , the second high frequency electric field strength V ₂ and the discharge starting electric field strength IV satisfies V ₁ ≧ IV> V ₂ or V ₁ > IV ≧ V ₂ . The output density of the second high-frequency electric field is 1 W / cm ² or more, and the substrate surface temperature during the formation of the ceramic layer and the polymer layer is 150 ° C. to less than the melting temperature of the substrate. A method for producing a functional film.

  (2) When forming the polymer layer and the ceramic layer, the base material is in close contact with the base material holding member for positioning the base material and adjusting the temperature of the base material on the surface opposite to the layer forming surface. The method for producing a functional film according to item (1), wherein the functional film is conveyed.

  (3) The ceramic layer is formed of silicon oxide, silicon oxynitride, aluminum oxide, or a mixture thereof, and the polymer layer contains a polymer, described in (1) or (2) A method for producing a functional film.

  (4) The method for producing a functional film according to any one of (1) to (3), wherein the substrate has a glass transition temperature of 120 ° C. or higher.

  (5) A temperature adjusting member for the substrate that heats or cools the substrate, temperature adjusting medium supply means for supplying a temperature adjusting medium to the temperature adjusting member for the substrate, and a medium temperature for heating and cooling the temperature adjusting medium. The surface temperature of the substrate during the formation of the ceramic layer and the polymer layer is set to 150 ° C. to less than the melting temperature of the substrate by temperature adjusting means for adjusting the temperature of the substrate having adjusting means. The method for producing a functional film according to any one of (1) to (4).

  (6) Based on the temperature detection member for measuring the temperature of the temperature adjustment member of the substrate or the temperature of the substrate, and the measured value detected by the temperature detection member, the substrate surface temperature is set to 150 ° C. by the temperature adjustment means. The method for producing a functional film as described in the item (5), wherein the temperature is adjusted to less than the melting temperature of the substrate.

  (7) A functional film produced by the method for producing a functional film according to any one of (1) to (6).

  (8) The functional film according to item (7), wherein the functional film is a gas barrier film.

  (9) A display element, wherein a display means is formed on a gas barrier film which is the functional film according to item (8).

  (10) A display device comprising the display element according to item (9).

According to the invention described in (1) to (6), the water vapor permeability has a barrier property of the order of 10 ⁻⁶ g / m ² / day and the oxygen permeability of the order of 10 ⁻⁴ ml / m ² / day. A method for producing a functional film can be provided.
According to the invention described in (7) or (8), the water vapor permeability has a barrier property of the order of 10 ⁻⁶ g / m ² / day and the oxygen permeability of the order of 10 ⁻⁴ ml / m ² / day. A functional film can be provided.
According to the invention described in (9), it is possible to provide a display element in which display means such as an organic electroluminescence (EL) element is formed on the functional film having the above-described effects.
According to the invention described in (10), it is possible to provide a display device with a long display life in which the occurrence of dark spots or the like is reduced.

  As a result of intensive studies in view of the above problems, the present inventor has at least two ceramic layers on a substrate having a glass transition temperature of 120 ° C. or higher, and at least one polymer layer between the ceramic films. It is possible to realize a gas barrier film having a desired gas barrier property by forming each layer of a gas barrier film having at least one layer by plasma in the vicinity of atmospheric pressure or under atmospheric pressure with the substrate temperature adjusted to a predetermined temperature. It is up to the headline and the present invention.

  First, each layer which comprises the functional film which has the functionality called gas barrier property which reduces permeation | transmission of water vapor | steam and gas is demonstrated.

  In addition, the same number is attached | subjected about the member etc. which have the same structure and function in each drawing.

  Hereinafter, the functional film having gas barrier properties is also referred to as a gas barrier film.

  FIG. 1 is a schematic diagram showing the concept of the layer structure of the gas barrier film of the present invention.

  The gas barrier film 1 has a substrate 2, at least two ceramic layers 3, and a layer 4 containing a polymer located between the ceramic layers 3.

  The figure shows the case where the ceramic layers 3 and the layers 4 containing the polymer are alternately arranged one by one. However, the arrangement may be as long as the layers containing the polymer are sandwiched between the ceramic layers. It doesn't matter.

  Moreover, you may provide the contact bonding layer 5 for raising adhesiveness between each layer.

  As long as each layer constituting the gas barrier film is a layer that blocks permeation of oxygen and water vapor, its composition, configuration, etc. are not particularly limited. In the present invention, at least one polymer layer is formed on the substrate. And two ceramic layers so as to sandwich the polymer layer.

  First, the ceramic layer formed by the method for producing a functional film of the present invention will be described.

  Specifically, an inorganic oxide is preferable as a thin film material constituting the ceramic layer, and silicon oxide, aluminum oxide, silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, tin oxide, or a mixture thereof. Can be mentioned.

  Further, the thickness of the ceramic layer is appropriately selected depending on the type and configuration of the material used, and is suitably selected, but is preferably in the range of 5 to 2000 nm. If the thickness of the ceramic layer is thinner than the above range, it will not be possible to obtain a uniform film, making it difficult to obtain gas barrier properties, and if it is thick, the functional film will retain flexibility. This is because it is difficult to cause a crack in the functional film layer due to external factors such as bending and pulling after film formation.

  In wet methods such as spraying and spin coating, it is difficult to obtain smoothness at the molecular level (nm level). Since a solvent is used, the base material described later is an organic material. There is a disadvantage that the material or solvent is limited.

  Therefore, in the present invention, the formation of the ceramic layer is a method of forming a high-productivity film that does not require a decompression chamber or the like, and forms a uniform and smooth surface film relatively easily. An atmospheric pressure plasma CVD method under atmospheric pressure or a pressure in the vicinity of atmospheric pressure that can be performed is preferable.

  By selecting the organic metal compound as a raw material (also referred to as a raw material), decomposition gas, decomposition temperature, input power, and the like as the formation conditions of the ceramic layer using the plasma CVD method, metal carbide, metal nitride, Metal oxides, metal sulfides, metal halides, and mixtures thereof (metal oxynitrides, metal oxyhalides, metal nitride carbides, etc.) can be formed.

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Further, if a 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.

  As such 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. In the case of 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. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

As such an organometallic compound,
As silicon compounds, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, Diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane, bis (dimethyl Amino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, diethylaminoto Methylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane, tris ( Dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3 -Disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, propargyltri Tylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane , Hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Examples of the titanium compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisoporooxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium. Examples thereof include diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.

  Zirconium compounds include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, Zirconium hexafluoropentanedioate and the like can be mentioned.

  Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyldialuminum tri-s-butoxide. Can be mentioned.

  The boron compounds include diborane, tetraborane, boron fluoride, boron chloride, boron bromide, borane-diethyl ether complex, borane-THF complex, borane-dimethyl sulfide complex, boron trifluoride diethyl ether complex, triethylborane, trimethoxy. Examples include borane, triethoxyborane, tri (isopropoxy) borane, borazole, trimethylborazole, triethylborazole, triisopropylborazole, and the like.

  Examples of tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, Dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate Examples of tin halides such as tin hydrogen compounds include tin dichloride and tin tetrachloride.

  Other organometallic compounds include, for example, antimony ethoxide, arsenic triethoxide, barium 2,2,6,6-tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoropentanedionate, dimethylcadmium, calcium 2,2,6,6-tetramethylheptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, gallium ethoxide, tetraethoxygermane , Tetramethoxygermane, hafnium t-butoxide, hafnium ethoxide, indium acetylacetonate, indium 2,6-dimethylaminoheptanedionate Ferrocene, lanthanum isopropoxide, lead acetate, tetraethyl lead, neodymium acetylacetonate, platinum hexafluoropentanedionate, trimethylcyclopentadienylplatinum, rhodium dicarbonylacetylacetonate, strontium 2,2,6,6-tetramethyl Examples include heptanedionate, tantalum methoxide, tantalum trifluoroethoxide, tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide, magnesium hexafluoroacetylacetonate, zinc acetylacetonate, and diethylzinc.

  In addition, as 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 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.

  Various 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.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator.

  As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). Although 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% or more with respect to the entire mixed gas.

  The ceramic layer according to the present invention is preferably transparent, and the above-mentioned ceramic layer is transparent, so that the gas barrier film can be made transparent and used for a transparent substrate of an organic EL element. Can also be used.

  In general, when an impurity such as a carbon atom is mixed in the gas barrier film, the formed gas barrier film becomes rough and the gas permeability increases. From this, since the ceramic layer is composed of the above-mentioned compound, the carbon content in the ceramic layer is low, so that the bond between oxygen and silicon is not hindered and a high barrier property against gas can be imparted. It becomes possible.

  In general, the ceramic layer is formed by a dry process such as vapor deposition, sputtering, CVD method (chemical vapor deposition), plasma CVD method, plasma CVD method performed under atmospheric pressure or near atmospheric pressure. However, in the method for producing a gas barrier film of the present invention, the formation of the ceramic layer is particularly preferably performed by an atmospheric pressure plasma CVD method using the raw material gas and the discharge gas as described above.

  The atmospheric pressure plasma CVD method will be described in detail later.

  Next, the polymer layer which is located between the ceramic layers described above and is formed by the method for producing a functional film of the present invention will be described.

  The polymer layer (hereinafter, the polymer layer is also referred to as a polymer layer) according to the present invention is a thin film containing a polymer, for example, an inorganic polymer, an organic polymer, an organic-inorganic hybrid polymer, and the like. A layer having a low hardness of 2000 nm and a relative hardness with respect to the ceramic layer, and having an average carbon content of 5% or more in the layer, is also referred to as a stress relaxation layer.

  The range of the thickness of the polymer layer is preferably equal to or less than 10 times the thickness of the ceramic layer. If it is lower than this range, the flexibility is lowered, and when the substrate is bent, micro-cracks enter the barrier layer and the barrier property deteriorates.

  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.

  These inorganic polymers are not particularly limited, and for example, 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. Ethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldi Vinylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoro Propyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane , Aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, diaryldimethoxysilane, butyldimethoxyvinylsilane , Trimethyl-3-vinylthiopropylsilane, phenyltrimethylsilane Dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycidoxypropyl Trimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryl Loxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, dibu Toxidimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, di Acetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropylmethylsilane , Octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenylmethyl Nylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,3,3- Tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) tetramethyldi Siloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotri Siloxane, octamethylcyclotetrasiloxane, 1, 3, 5 7-tetraethoxy-1,3,5,7-tetramethyl cyclotetrasiloxane, may this include decamethylcyclopentasiloxane, and the like.

  As the 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. Radically polymerizable monomers, polyfunctional monomers and polyfunctional oligomers having a plurality of addition-polymerizable ethylenic double bonds in a molecule generally used for resins curable by light, heat, ultraviolet rays, etc. be able to.

  These 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, ε-caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane acrylate, or Methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc. in which these acrylates are replaced with methacrylate, itaconate, crotonate, and maleate. Tel, for example, 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 neopentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl- 5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylo Difunctional acrylic acid esters such as ε-caprolactone adduct of diacrylate, diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itacon in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Acids, crotonic acid, maleic esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, ε-cap of dipentaerythritol hexaacrylate Lactone adducts, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate and other polyfunctional acrylic acid esters, or these acrylates Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of methacrylate, itaconate, crotonate, and maleate.

  Prepolymers can also be used as described above. A prepolymer may use together 1 type, or 2 or more types, and may mix and use the above-mentioned monomer and / or oligomer.

  Examples of prepolymers 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 obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  In addition, the organic polymer applicable to the polymer layer according to the present invention can be easily formed by using an organic substance capable of plasma polymerization as the thin film forming gas. Examples of the plasma-polymerizable organic substance include hydrocarbons, vinyl compounds, halogen-containing compounds, and nitrogen-containing compounds.

  Examples of the hydrocarbon include ethane, ethylene, methane, acetylene, cyclohexane, benzene, xylene, phenylacetylene, naphthalene, propylene, camphor, menthol, toluene, isobutylene, and the like.

  Examples of the vinyl compound include acrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, allyl methacrylate, acrylamide, styrene, α-methyl styrene, vinyl pyridine, vinyl acetate, vinyl methyl ether, and the like.

  Examples of halogen-containing compounds include tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl methacrylate.

  Examples of the nitrogen-containing compound include pyridine, allylamine, butylamine, acrylonitrile, acetonitrile, benzonitrile, methacrylonitrile, aminobenzene and the like.

  In general, the polymer layer is formed by a dry process such as vapor deposition, sputtering, CVD (chemical vapor deposition), plasma CVD, or plasma CVD performed under atmospheric pressure or near atmospheric pressure. However, as with the formation of the ceramic layer, in the gas barrier film manufacturing method of the present invention, the formation of the polymer layer is particularly performed by the atmospheric pressure plasma CVD method using the source gas and the discharge gas as described above. Is preferred.

  Here, the surface temperature of the base material at the time of forming the ceramic layer and the surface temperature of the base material during the formation of the polymer layer are preferably close, and the difference is preferably 50 ° C. or less.

  The atmospheric pressure plasma CVD method will be described in detail later.

  Next, the base material used in the gas barrier film of the present invention will be described.

  Although a base material will not be specifically limited if it is a film | membrane formed with the organic material which can hold | maintain the ceramic layer and polymer layer mentioned above, It is preferable that a glass transition temperature is 120 degreeC or more.

  Specifically, polyolefin (PO) resin such as copolymer, amorphous polyolefin resin (APO) such as cyclic polyolefin, polyester resin such as polyethylene 2,6-naphthalate (PEN), polyamide such as copolymer nylon (PA) resin, polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin, Polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), vinylidene fluoride (PVDF) ), Vinyl fluoride (PVF), perfluoroethylene Down - perfluoro propylene - perfluoro ether - it can be used a fluorine-based resin such as copolymer (EPA).

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, as a base film.

  These materials can be used alone or in combination as appropriate. Among these, commercially available products such as ZEONEX and ZEONOR (manufactured by ZEON CORPORATION), ARTON of amorphous cyclopolyolefin resin film (manufactured by JSR), and pure ace of polycarbonate film (manufactured by Teijin Limited) are preferred Can be used.

  The base material is preferably transparent, and the base material is transparent, and the layer formed on the base material is also transparent, so that it is a transparent gas barrier film, thereby forming a transparent base material such as an organic EL element. Is also possible.

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

  The base material according to the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  The base material may be in the form of a sheet or a web, but in the present invention, since the ceramic layer and the polymer layer are formed by the atmospheric pressure plasma CVD method described later, production on RolltoRoll becomes possible. A long product rolled up into a roll is preferably used.

  Moreover, since the thickness of a base material changes with use of the gas barrier film obtained, and cannot unconditionally define it, as a film thickness of a film-shaped thing, 10-200 micrometers is preferable, More preferably, it is 50-100 micrometers.

  FIG. 2 is a schematic view showing an example of the first embodiment of the method for producing a gas barrier film of the present invention.

  In FIG. 2, a jet-type atmospheric pressure plasma discharge processing apparatus 10 that forms a thin film outside a discharge space according to the first embodiment includes a transport unit 101 that transports a base material F to a processing space 14 that forms a thin film, Plasma discharge treatment means 102 for exciting gas by plasma, electric field application means 103 having two high frequency power supplies, gas supply means 104 for supplying a mixed gas of at least a thin film forming gas and a discharge gas, and the surface temperature of the substrate And substrate temperature adjusting means 105 for adjusting to a predetermined temperature.

  Depending on the temperature of the substrate during the plasma discharge treatment, the properties and composition of the resulting thin film may change, and it is desirable to make the temperature of the substrate uniform over the entire surface of the processing space 14 at a predetermined temperature. For this reason, it is preferable that the substrate is conveyed while being in close contact with the temperature adjusting means of the substrate whose temperature has been adjusted so as not to cause temperature unevenness in the width direction and the longitudinal direction of the substrate as much as possible.

  The transport unit 101 includes a transport roller 1011, and the base material F is transported in close contact with the base material holding member 1051 that performs positioning and temperature adjustment in the width direction and thickness direction of the base material F by the transport roller 1011. Is done.

  Here, when the base material F is in the form of a sheet of each leaf, the conveying means may be a temperature-adjusted horizontally moving stand (not shown), and the first electrode of the plasma discharge processing means 102 may be used. The substrate is placed in close contact with the electrode 11 and the second electrode 12 with a predetermined gap, and moved horizontally. In this case, the opposed surfaces of the first electrode 11 and the second electrode 12 to the gantry are flat surfaces.

  When the base material F has a continuous web shape, the surface of the base material holding member 1051 facing the base material F may have a predetermined curvature in order to maintain close contact with the base material. preferable.

  In the case of sheet conveyance, the surfaces of the first electrode 11 and the second electrode 12 facing the holding member 1051 of the substrate are flat as described above, but in the case of web conveyance, the discharge is made uniform. Therefore, it is preferable that the opposing surfaces of the first electrode 11 and the second electrode 12 to the base material holding member 1051 also have a curvature corresponding to the curvature of the base material holding member 1051.

  Here, the curvature has an arc having a radius of 50 to 2000 mm, preferably a radius of 100 to 1000 mm.

  The adjustment of the surface temperature of the substrate will be described with reference to FIG.

  The temperature control means 105 of the substrate is set so that the substrate surface temperature during the formation of the thin film is 150 ° C. or higher and lower than the melting temperature of the substrate (in practice, selected from this range depending on the melting temperature of the substrate used) The temperature control member 1052 for heating or cooling the base material holding member 1051 that is internally mounted and fixed to the base material holding member 1051, and the temperature of the insulating liquid such as distilled water or silicon oil on the base temperature control member 1052 Plasma discharge processing means comprising a liquid feed pump P and a pipe as temperature adjusting medium supply means 1054 for supplying the adjusting medium 1053, medium temperature adjusting means 1055 for heating / cooling the temperature adjusting medium 1053, a non-contact infrared sensor and the like. And a temperature detection member 1057 that is disposed downstream of 102 and measures the surface temperature of the substrate F.

  The method for adjusting the surface temperature of the base material having the above-described configuration will be described. First, the temperature detection member 1057 measures the base material surface temperature while the layer is being formed by a control means (not shown).

  The measured substrate surface temperature is input to the control means, and the measured substrate surface temperature is compared with a reference temperature set in advance so that the substrate surface temperature is 150 ° C. to less than the melting temperature of the substrate. Depending on the value, the heating means or cooling member (not shown) of the medium temperature adjusting means 1055 is turned ON / OFF by the control means, and the temperature adjusting medium 1053 has a substrate surface temperature of 150 ° C. to less than the melting temperature of the substrate. The temperature is adjusted to

  Here, if the temperature is too low, the denseness of the layer is insufficient, and if it is too high, the substrate is deformed, melted or deteriorated.

  Accordingly, in setting the actual temperature, the temperature is adjusted to a high temperature within a range where the substrate does not deform, melt or deteriorate.

  The surface temperature of the base material F may be measured by a temperature detection member 1056 such as a thermocouple that detects the temperature of the base material holding member 1051 instead of the surface temperature of the base material.

  Specifically, the temperature adjusting medium 1053 temperature-adjusted by the medium temperature adjusting means 1055 flows into the substrate temperature adjusting member 1052 through the liquid feed pump P and the piping, and thereby via the substrate temperature adjusting member 1052. The temperature of the temperature holding member 1051 is changed, and the surface temperature of the base material F conveyed in close contact with the temperature holding member 1051 is to be heated or cooled so that it becomes 150 ° C. to less than the melting temperature of the base material. .

  The temperature adjusting means 105 of the base material connects the first electrode 11 by diverting the temperature adjusting medium 1053 by connecting a part of the piping which is the temperature adjusting medium supply means 1054 to the first electrode 11 and the second electrode 12. It is also possible to adjust the temperature of the second electrode 12.

  The internal temperature of the substrate is set to be lower than the surface temperature.

The plasma discharge processing apparatus 10 has a counter electrode composed of a first electrode 11 and a second electrode 12, and the frequency ω ₁ from the first power supply 21 is output from the first electrode 11 between the counter electrodes. A first high frequency electric field having electric field strength V ₁ and current I ₁ is applied, and a second high frequency electric field having frequency ω ₂ , electric field strength V ₂ and current I ₂ from second power source 22 is applied from second electrode 12. Is applied.

Here, the first high-frequency electric field higher frequency ω2 of the second high-frequency electric field than the frequency ω1 of the strength V ₂ and the discharge start of the first high frequency electric field intensity V ₁ and the second high-frequency electric field The relationship with the electric field strength IV satisfies V ₁ ≧ IV> V ₂ or V ₁ > IV ≧ V _2, and the output density of the second high-frequency electric field is 1 W / cm ² or more.

In addition, as a first power source (high frequency power source) that can be used in the above-described atmospheric pressure plasma CVD discharge processing apparatus of the present invention,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the electric power applied between the electrodes facing each other supplies power (power density) of 1 W / cm ² or more to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. A thin film is formed. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  In addition, a first filter 23 is installed between the first electrode 11 and the first power source 21 to facilitate passage of current from the first power source 21 to the first electrode 11, and from the second power source 22. The second filter 24 is designed between the second electrode 12 and the second power source 22 so that the current from the second power source 22 to the first power source 21 is hardly passed. Is installed, makes it easy to pass the current from the second power source 22 to the second electrode, grounds the current from the first power source 21, and hardly passes the current from the first power source 21 to the second power source. Designed to be.

  The mixed gas G of the ceramic layer or polymer layer thin film forming gas and the discharge gas described above is introduced from the gas supply means 104 between the counter electrodes (discharge space) 13 between the first electrode 11 and the second electrode 12, A high-frequency electric field is applied from the electrode 11 and the second electrode 12 to generate a discharge, and the mixed gas G is blown out in a jet shape to the lower side (the lower side of the paper) of the counter electrode while being in a plasma state. The processing space 14 formed by the lower surface of the counter electrode and the base material F is filled with a plasma gas G °, and is unwound from the base material (unwinder) (not shown) and conveyed, or is a pre-process A thin film is formed in the processing space 14 on the base material F that is conveyed from.

  In order to withstand the above-described discharge, at least one electrode surface is coated with a dielectric described later.

  FIG. 3 is an explanatory diagram when a plurality of jet-type atmospheric pressure plasma discharge treatment apparatuses 10 are arranged in the substrate conveyance direction.

  Each atmospheric pressure plasma discharge treatment apparatus A1, A2, A3 includes a plasma discharge treatment means 102, an electric field application means 103, a gas supply means 104, and a substrate temperature adjustment means 105 similar to those described in FIG. Have.

  With such a configuration, for example, the same gas is supplied to a plurality of atmospheric pressure plasma discharge treatment apparatuses to discharge the gas in the same plasma state at the same time, or different gases are supplied to discharge the gas in different plasma states at the same time. In the former case, a thin film having a predetermined thickness can be formed with high productivity. In the latter case, thin films having different functions can be formed with high productivity.

  In addition, by combining the two, it is possible to form thin films having arbitrary different functions at a predetermined thickness with high productivity.

  For example, as an example in which a plurality of ceramic layers and a polymer layer are continuously formed, a first jet type atmospheric pressure plasma discharge treatment apparatus A1 that forms a ceramic layer on a substrate F, a ceramic layer, and the like. A second jet type atmospheric pressure plasma discharge treatment apparatus A2 that forms a polymer layer thereon; and a third jet type atmospheric pressure plasma discharge treatment apparatus A3 that forms a ceramic layer on the polymer layer. .

  Here, the first jet type atmospheric pressure plasma discharge treatment apparatus A1 and the third jet type atmospheric pressure plasma discharge treatment apparatus A3 are silicon oxides of inorganic oxide as a material constituting the ceramic layer described above. Aluminum oxide, silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, tin oxide, and the like are supplied.

  In addition, the second jet type atmospheric pressure plasma discharge treatment apparatus A2 includes a silicon compound such as silicone or polysilazane, a titanium compound, an aluminum compound, a boron compound, a phosphorus compound as a material constituting the inorganic polymer layer described above. Supply tin compounds.

    In the figure, each of the jet-type atmospheric pressure plasma discharge processing apparatuses A1 to A3 includes one set of plasma discharge processing apparatuses, but a plurality of types may be provided depending on the required layer thickness.

  Further, a large number of jet-type atmospheric pressure plasma discharge treatment apparatuses 10 may be provided so that a gas barrier film having a multilayer structure can be manufactured, and an oxidizing gas is added to some of the jet-type atmospheric pressure plasma discharge treatment apparatuses 10. The surface of the formed thin film may be oxidized.

  By such a gas barrier film manufacturing method, it becomes possible to stably manufacture a ceramic layer and a polymer layer having a predetermined film thickness with the required number of layers with high quality and high productivity.

  FIG. 4 is an explanatory diagram of an example of another embodiment using a jet type atmospheric pressure plasma discharge treatment apparatus.

  In the case of using hydrogen gas or the like whose discharge start electric field intensity is low as the discharge gas, the atmospheric pressure plasma discharge processing apparatus grounds, for example, the first electrode 11 of the two electrodes, and the second power source 22 is connected to the second electrode 12. You may make it connect.

  FIG. 5 is a schematic view showing an example of the second embodiment of the method for producing a gas barrier film of the present invention.

The atmospheric pressure plasma discharge treatment apparatus 20 that forms a thin film in the discharge space according to the second form is the function of the second electrode 12 (discharge electrode function) and the base member holding member 1051 in FIG. A roll-shaped roll rotating electrode 35 having a temperature adjusting function of the base material) and an outer peripheral surface of the roll rotating electrode 35 corresponding to the first electrode 11 in FIG. And atmospheric pressure plasma discharge treatment means 30 having a rectangular tube-shaped fixed electrode group 36 arranged in
The substrate F is conveyed in close contact with the outer periphery of the roll rotating electrode 35 to the discharge space 32 in the opposite area between the roll rotating electrode 35 and the rectangular tube-shaped fixed electrode group 36, and the same ceramic as described in FIG. The mixed gas G is supplied to the discharge space 32 by the gas supply means 104 for supplying the mixed gas G of the thin film forming gas and the discharge gas forming the layer or the polymer layer, and has two high-frequency power sources similar to those described in FIG. A high-frequency electric field is applied between the electrodes by the electric field applying means 10 (the first power source 21 connected to the square tube type fixed electrode group 36 and the second power source 22 connected to the roll rotating electrode 35) to generate plasma. Exciting the mixed gas G, exposing the substrate F to the excited mixed gas to form a thin film on the substrate,
A substrate temperature adjusting means 105 for adjusting the surface temperature of the substrate to a predetermined temperature is provided, and the substrate temperature adjusting means 105 has a substrate surface temperature of 150 ° C. during the formation of a thin film in the same manner as described in FIG. ~ Below the melting temperature of the substrate.

  The substrate F is conveyed in close contact with the roll rotating electrode 35 by guide rollers 64 and 67 corresponding to the conveying roller 1011 in FIG.

  Here, the gap between the roll rotating electrode 35 and the rectangular tube type fixed electrode group 36 is 0.2 to 2 mm, preferably 0.5 to 1.5 mm, as described in FIG.

  Discharged treated exhaust gas G ′ is discharged from the exhaust port 53.

  As described with reference to FIG. 2, electric fields having different frequencies are applied from both the roll rotating electrode 35 and the rectangular tube-shaped fixed electrode group 36, and discharge plasma is generated by the high-frequency electric field in which different frequencies are superimposed in the discharge space 32. .

  Specifically, the second power source 22 is connected to the rectangular tube-shaped fixed electrode group (second electrode) 36, and the first power source 21 is connected to the roll rotating electrode 35. The roll rotating electrode 35 and the rectangular tube-shaped fixed electrode group are connected to each other. A high frequency electric field on which two different frequencies are superimposed is applied to the discharge space 32 between the two.

The roll rotation electrode 35 is rotated by a driving means (not shown) at the same peripheral speed as the conveying speed of the base material, and a first high-frequency electric field having a frequency ω ₁ , an electric field strength V ₁ , and a current I ₁ is It is supposed to be applied.

Further, a second high frequency electric field having a frequency ω ₂ , an electric field strength V ₂ , and a current I ₂ is applied to the square tube type fixed electrode group 36 from the second power source 22.

The relationship between the outputs of the power sources is ω1 <ω2, so that the discharge starts stably at a low voltage with respect to the discharge gas such as nitrogen, and the thin film forming gas can be stably excited even after the discharge starts. And V1 ≧ VI> V2 or V1> VI ≧ V2, and the current I ₁ of the first high-frequency electric field is preferably 0.3 mA / cm ^{2 to} 20 mA / cm ² , more preferably 1.0 mA. / Cm ^{2 to 20} mA / cm ² . The current I ₂ of the second high-frequency electric field is preferably 10 mA / cm ^{2 to} 100 mA / cm ² , more preferably 20 mA / cm ^{2 to} 100 mA / cm ² , and the output density of the second high-frequency electric field is 1 W. / Cm ² or more.

  The base material temperature control means 105 will be described. A base material temperature control member 1052 that is internally mounted and fixed to the roll rotation electrode 35 to heat or cool the roll rotation electrode 35, and a base material temperature control member 1052 with distilled water or Liquid feed pump P and pipes, which are temperature adjustment medium supply means 1054 for supplying temperature adjustment medium 1053 of an insulating liquid such as silicon oil, medium temperature adjustment means 1055 for heating / cooling temperature adjustment medium 1053, and non-contact A temperature detection member 1057 that is made of an infrared sensor or the like and is disposed downstream of the downstream guide roll 67 and measures the surface temperature of the substrate F is provided.

  2 are the same as the configuration and operation described in FIG. 2 except for those described above, and thus the description thereof is omitted.

  FIG. 6 is an explanatory diagram when a plurality of atmospheric pressure plasma discharge treatment apparatuses 20 are arranged in the substrate transport direction.

  Each atmospheric pressure plasma discharge treatment apparatus B1, B2, B3 has a discharge treatment means 30, an electric field application means 10, a gas supply means 104, and a substrate temperature adjustment means 105 similar to those explained in FIG. is doing.

  With such a configuration, for example, the same gas is supplied to a plurality of atmospheric pressure plasma discharge treatment apparatuses to discharge the gas in the same plasma state at the same time, or different gases are supplied to discharge the gas in different plasma states at the same time. In the former case, a thin film having a predetermined thickness can be formed with high productivity. In the latter case, thin films having different functions can be formed with high productivity.

  In addition, by combining the two, it is possible to form thin films having arbitrary different functions at a predetermined thickness with high productivity.

  For example, as an example in which a plurality of ceramic layers and a polymer layer are continuously formed, a first atmospheric pressure plasma discharge treatment apparatus B1 that forms a ceramic layer on the substrate F and a polymer on the ceramic layer are used. A second atmospheric pressure plasma discharge treatment apparatus B2 that forms a layer; and a third atmospheric pressure plasma discharge treatment apparatus B3 that forms a ceramic layer on the polymer layer.

  Here, the first atmospheric pressure plasma discharge treatment apparatus B1 and the third atmospheric pressure plasma discharge treatment apparatus B3 are silicon oxide, aluminum oxide, oxynitridation of inorganic oxide as a material constituting the ceramic layer described above. Silicon, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, tin oxide, and the like are supplied.

  The second atmospheric pressure plasma discharge treatment apparatus B2 uses a silicon compound such as silicone or polysilazane, a titanium compound, an aluminum compound, a boron compound, a phosphorus compound, or a tin compound as a material constituting the inorganic polymer layer. Supply.

    In the figure, each of the atmospheric pressure plasma discharge processing apparatuses B1 to B3 includes one set of plasma discharge processing means and the like, but a plurality of sets may be provided depending on the required layer thickness.

  In addition, a large number of atmospheric pressure plasma discharge treatment apparatuses 20 may be provided so that a gas barrier film having a multilayer structure can be manufactured. An oxidizing gas is supplied to some of the jet type atmospheric pressure plasma discharge treatment apparatuses 10. Thus, the surface of the formed thin film may be oxidized.

  By such a gas barrier film manufacturing method, it becomes possible to stably manufacture a ceramic layer and a polymer layer having a predetermined film thickness with the required number of layers with high quality and high productivity.

  FIG. 7 is an explanatory view of another embodiment of an atmospheric pressure plasma discharge processing apparatus for forming a thin film in the discharge space.

  When a rare gas or the like having a low discharge start electric field strength is used as the discharge gas, the atmospheric pressure plasma discharge processing means 30 grounds, for example, the roll rotating electrode 35 among the two electrodes, and the above-described square tube type fixed electrode group 36 Two power sources 22 may be connected.

  FIG. 8 is a perspective view showing an example of the structure of the metal base material of the electrode and the dielectric material coated thereon.

  FIG. 8 shows the concept of the first electrode 11 and the second electrode 12 shown in FIG. 2, the rectangular tube-shaped fixed electrode group 36 shown in FIG. 5, and the like described above. The electrode 35a shown in FIG. The electrode 11, the second electrode 12, the rectangular tube-type fixed electrode group 36, or the like) is obtained by covering a conductive metal base material 35 </ b> A with a dielectric 35 </ b> B.

  A cable (not shown) connected to the metallic base material 35A is connected to a high frequency power source (not shown).

  2, at least one of the first electrode 11 and the second electrode 12 is covered with a dielectric 35B. In FIG. 3, at least one of the square tube fixed electrode group 36 and the roll rotating electrode 35 is covered. At least the opposite surface is covered with a dielectric 35B.

In order to adjust the surface temperature of the substrate during plasma discharge treatment (during thin film formation), the inside of the electrode 35a serves as a jacket, and a temperature adjusting medium (distilled water or silicon oil) is circulated to reach the predetermined temperature. The temperature is adjusted.
FIG. 8B shows the concept of the above-described roll rotating electrode 35 and the like. The electrode 36a (e.g., corresponding to the roll rotating electrode 35 and the like) is electrically connected to the conductive metallic base material 36A as necessary. The body 36B is covered.

  An armature as energizing means 36D for supplying high-frequency power to the rotating electrode 36a is provided with a shaft portion 36C of the electrode 36a, and a brush 36E connected to a high-frequency power source (not shown) is in sliding contact with the armature. Power supply is possible.

  Further, the shaft portion 36C is provided with a joint (not shown) for supplying a temperature adjusting medium from the temperature adjusting medium supply means 1054 of FIG. 5 to the temperature adjusting member 1052 of the base material.

  In FIG. 8, as the conductive metallic base materials 35A and 36A, titanium metal or titanium alloy, silver, platinum, stainless steel, aluminum, iron, or other metals, composite materials of iron and ceramics, or aluminum and ceramics are used. In particular, titanium metal or titanium alloy is preferable.

  Further, the dielectrics 35B and 36B coated on the surfaces of the metallic base materials 35A and 36A are subjected to sealing treatment using a sealing material made of an inorganic compound after thermal spraying ceramics as a dielectric.

  The dielectrics 35B and 36B only have to be covered with about 1 mm in a single wall, and as a ceramic material used for thermal spraying, alumina, silicon nitride or the like is preferably used. . The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

In more detail,
In the electrode covering the dielectric, it is preferable that the characteristics match between the various metallic base materials and the dielectric. One of the characteristics is a difference in linear thermal expansion coefficient between the metallic base material and the dielectric. Is a combination of 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and further preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

As a combination of a conductive metallic base material and a dielectric having a difference in linear thermal expansion coefficient within this range, the metallic base material is pure titanium or a titanium alloy, and the dielectric is particularly preferably a ceramic sprayed coating, In addition, the metallic base material is pure titanium or a titanium alloy, the dielectric is glass lining, the metallic base material is a composite material of ceramics and iron, the dielectric is a ceramic spray coating, and the metallic base material is ceramics and iron. Composite material, dielectric is glass lining, metallic matrix is ceramic and aluminum composite, dielectric is ceramic sprayed coating, metallic matrix is ceramic and aluminum composite, dielectric is glass lining, etc. There is
There is no deterioration of the electrode during use, especially cracking, peeling, dropping off, etc., and it can withstand long-term use under severe conditions.

  The distance between the opposing electrodes related to the discharge refers to the shortest distance between the surface of the dielectric and the surface of the conductive metallic base material of the other electrode when a dielectric is provided on one of the electrodes, When a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces.

  The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. The gap between the first electrode 11 and the second electrode 12 is 0.2 to 2 mm, preferably 0.5 to 1.5 mm from the viewpoint of carrying out the process, and the rectangular tube-shaped fixed electrode group 36 and the substrate holding member 1051 The gap between the opposing surfaces is 0.2 to 2 mm, preferably 0.5 to 1.5 mm.

  FIG. 9 is a cross-sectional view showing an example of an organic EL display device in which an organic EL display element is formed on a gas barrier film.

  As an example of a display device (display panel) using the gas barrier film of the present invention, an organic EL display device 300 in which an organic EL display element 320 as a display means is formed on the gas barrier film 1 will be described below.

  The organic EL display device 300 includes a gas barrier film 330 (gas barrier film 1) facing the gas barrier film 1 and the organic EL display element 320, and a sealing material 310.

A plurality of anodes (anodes) 321 are provided in parallel to each other on the barrier film 1 described in FIG. A thin film made of a desired electrode material, for example, an anode material is formed by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 10 nm to 200 nm, and an anode (anode) 321 is manufactured. . As an anode in an organic EL display element, a metal, an alloy, an electrically conductive compound and a mixture thereof having a large work function (4 eV or more), such as a metal such as Au, CuI, indium tin oxide (ITO), indium zinc A conductive transparent material such as oxide (IZO), SnO ₂ , or ZnO is used.

  Next, the organic EL layer 322 is formed thereon. That is, although not shown here, an organic EL layer thin film made of each of the above materials such as a hole injection layer, a light emitting layer, and an electron injection layer is formed.

  Next, a cathode (cathode) 333 is formed on the organic EL layer 322 by forming a thin film by a method such as vapor deposition or sputtering. In order to transmit light, if either one of the anode or the cathode of the organic EL display element is transparent or translucent, the light emission efficiency is improved, which is convenient.

As a method for manufacturing each layer of the organic EL layer 322, there are a spin coating method, a casting method, a vapor deposition method, etc., but a vacuum vapor deposition method is preferable because a homogeneous film is easily obtained and pinholes are not easily generated. preferable. When a vacuum deposition method is employed for thinning, the deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposition film, the association structure, etc., but generally a boat heating temperature of 50 to 450 ° C., vacuum It is desirable to select appropriately within the range of a degree of 10 ⁻⁶ to 10 ⁻³ Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a film thickness of 5 nm to 5 μm.

  After forming these layers, 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 μm or less, preferably in the range of 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL display element 320 is obtained.

  The organic EL display element 320 is preferably produced from the hole injection layer to the cathode consistently by a single vacuum, but the production order is reversed, and the cathode, electron injection layer, and light emission are produced. It is also possible to produce a layer, a hole injection layer, and an anode in this order. When a direct current voltage is applied to the organic EL display element 320 thus obtained, light emission can be observed by applying a voltage of about 5 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

  On the upper surface of the cathode (cathode) 333, an opposing gas barrier film 330 (or the gas barrier film 1 may be stacked) is overlaid, whereby the organic EL display element 320 is shut off and sealed from the outside.

  For the blocking / sealing from the outside, the gas barrier film 330 facing the gas barrier film 1 is mutually connected through a substantially frame-shaped sealing material 310 provided by a coating method, a transfer method, or the like in the periphery of the organic EL display element 320. It is done by pasting together.

The sealing material 2 is made of a thermosetting epoxy resin, an ultraviolet curable epoxy resin, a room temperature curable epoxy resin whose reaction starts by microencapsulating and pressurizing a reaction initiator. In this case, an air escape opening or the like is provided at a predetermined location of the sealing material 2 (not shown) to complete the sealing. The air escape opening is either one of the above curable epoxy resins in a reduced pressure atmosphere (preferably with a degree of vacuum of 1.33 × 10 ⁻² MPa or less) in a vacuum apparatus, or in a nitrogen gas or inert gas atmosphere, or Sealed with an ultraviolet curable resin or the like.

  The sealing material 310 needs to have a structure in which a part of the transparent electrode and the aluminum cathode can be taken out as a terminal and a lead wire. Also in FIG. 9, the anode (anode) 321 provided on the base material, and the cathode 323 comprising a thin film pattern of a cathode material formed on the anode and the organic EL layer 322 are sealed. Terminals and lead wires are formed from the closed sealed container through the sealing material to the outside and can be taken out (not shown).

  As described above, the case where the organic EL display element is used as the display unit has been described. However, the display unit sealed with the gas barrier film may be, for example, a known photoexcitation device, or a white light emitting panel using the photoexcitation device.

  An atmospheric pressure plasma discharge treatment was performed under the following conditions using the roll rotating electrode type discharge treatment apparatus described with reference to FIG. 5 to prepare a sample, and the water vapor permeability and oxygen permeability were measured to evaluate the gas barrier property. It was.

  The dielectric was subjected to ceramic spraying of 1 mm with a single wall for both the counter electrodes, and the electrode gap after processing was set to 1 mm.

  In addition, the roll rotating electrode was a titanium jacket specification, and during discharge, the temperature of the substrate was adjusted as shown in the following table by adjusting the electrode temperature by flowing a heat retaining liquid through the jacket.

Base material: PES (polyether sulfone), thickness 100 μm
Ceramic layer Discharge gas: N ₂ gas Reaction gas: Oxygen gas (5% of the total gas)
Thin film forming gas: HMDSO (0.1% of total gas)
First power supply: 80 kHz, 7 kV, 10 W / cm ²
Second power supply: 13.56 MHz, 2 kV, 10 W / cm ²
Polymer layer Discharge gas: N ₂ gas Reaction gas: Methane gas (1% of total gas)
Thin film forming gas: Methyl methacrylate (0.6% of total gas)
First power supply: 80 kHz, 7 kV, 10 W / cm ²
Second power supply: 13.56 MHz, 2 kV, 10 W / cm ²
Under the above conditions, a polymer layer of about 100 nm is formed as the first layer, a ceramic layer of 50 nm is formed in the second layer, and then a polymer layer and a ceramic layer are alternately formed up to the fifth layer. Evaluation was performed.

Each unit is as follows: Roll rotating electrode and substrate surface temperature: ° C., water vapor permeability: g / m ² / day, oxygen permeability: ml / m ² / day
As a result, the substrate surface temperature is between 140 ° C. and 160 ° C., that is, about 150 ° C., the water vapor transmission rate and oxygen transmission rate are greatly reduced, and the target water vapor transmission rate is 10 ⁻⁵ g / m ^2. It has been confirmed that it is possible to provide a transparent gas barrier film having a barrier property of the order of / day or oxygen permeability of 10 ⁻⁴ ml / m ² / day.

It is a schematic diagram which shows the concept of the layer structure of the gas barrier film of this invention. It is the schematic which shows one example of the 1st form of the manufacturing method of the gas barrier film of this invention. It is explanatory drawing at the time of arrange | positioning multiple jet type atmospheric pressure plasma discharge processing apparatuses 10 in a base-material conveyance direction. It is explanatory drawing of the example of the other form using the atmospheric pressure plasma discharge processing apparatus of a jet system. It is the schematic which shows one example of the 2nd form of the manufacturing method of the gas barrier film of this invention. It is explanatory drawing at the time of arrange | positioning multiple atmospheric pressure plasma discharge processing apparatuses 20 in a base-material conveyance direction. It is explanatory drawing of the other form of the atmospheric pressure plasma discharge processing apparatus which forms a thin film in discharge space. It is a perspective view which shows an example of the structure of the metal base material of an electrode, and the dielectric material coat | covered on it. It is sectional drawing which shows an example of the organic electroluminescence display with which the organic electroluminescence display element was formed on the gas barrier film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2, F base material 3 Ceramic layer 4 Layer containing polymer 10 Jet type atmospheric pressure plasma discharge processing apparatus 11 1st electrode 12 2nd electrode 13, 32 Discharge space 14 Processing space 21 1st power supply 22 2nd power supply 30, 102 Plasma discharge treatment means 35 Roll rotating electrodes 35a, 36a Electrodes 35A, 36A Metallic base materials 35B, 36B Dielectric 36 Square tube type fixed electrode group 103 Electric field applying means 104 Gas supply means 105 Base material temperature adjusting means 1051 Holding member for base material 1052 Temperature adjusting member 1053 Temperature adjusting medium 1054 Temperature adjusting medium supply means 1055 Medium temperature adjusting means 1057 Temperature detecting member G Mixed gas G ° plasma state gas

Claims (10)

In a method for producing a functional film having at least two ceramic layers and at least one polymer layer located therebetween on a substrate,
At least one of the ceramic layer and the polymer layer supplies a gas containing a thin film forming gas to the discharge space, and excites the gas by applying a high-frequency electric field to the discharge space under atmospheric pressure or a pressure in the vicinity thereof. Formed by exposing the substrate to the excited gas,
The high-frequency electric field is a superposition of the first high-frequency electric field and the second high-frequency electric field, and the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, and the first high-frequency electric field is The relationship between the electric field strength V ₁ , the second high frequency electric field strength V ₂ and the discharge starting electric field strength IV satisfies V ₁ ≧ IV> V ₂ or V ₁ > IV ≧ V ₂ . The output density of the second high-frequency electric field is 1 W / cm ² or more, and the substrate surface temperature during the formation of the ceramic layer and the polymer layer is 150 ° C. to less than the melting temperature of the substrate. A method for producing a functional film. When forming the polymer layer and the ceramic layer, the base material is in close contact with the base material holding member for positioning the base material and adjusting the temperature of the base material on the surface opposite to the layer forming surface. The method for producing a functional film according to claim 1, wherein: The method for producing a functional film according to claim 1 or 2, wherein the ceramic layer is formed of silicon oxide, silicon oxynitride, aluminum oxide, or a mixture thereof, and the polymer layer includes a polymer. . The method for producing a functional film according to claim 1, wherein the substrate has a glass transition temperature of 120 ° C. or higher. A substrate temperature adjusting member for heating or cooling the substrate; a temperature adjusting medium supplying unit for supplying a temperature adjusting medium to the temperature adjusting member of the substrate; and a medium temperature adjusting unit for heating and cooling the temperature adjusting medium. The surface temperature of the base material during the formation of the ceramic layer and the polymer layer is set to 150 ° C. to less than the melting temperature of the base material by temperature adjusting means for adjusting the temperature of the base material. Item 5. The method for producing a functional film according to any one of Items 1 to 4. Based on the temperature detection member for measuring the temperature of the temperature adjusting member of the base material or the temperature of the base material, and the measured value detected by the temperature detecting member, the temperature of the base material is changed from 150 ° C. to the base material The method for producing a functional film according to claim 5, wherein the temperature is adjusted to be lower than the melting temperature of the functional film. The functional film manufactured by the manufacturing method of the functional film of any one of Claims 1-6. The functional film according to claim 7, wherein the functional film is a gas barrier film. A display element, wherein a display means is formed on the gas barrier film which is the functional film according to claim 8. A display device comprising the display element according to claim 9.

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