JP2007038445A - Gas barrier thin film laminate, gas barrier resin substrate, and organic electroluminescence device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier thin film laminate having high gas barrier ability and excellent curl resistance with good productivity, and to provide adhesion and gas barrier resistance using the gas barrier thin film laminate. The object is to provide an excellent organic electroluminescence device.
SOLUTION: In a gas barrier thin film laminate having at least one ceramic film and a polymer film, at least one layer of the polymer film is photocurable having an ethylenic double bond at the end or side chain of the molecule. It is formed by curing a photo-curable resin composition which is mainly composed of a resin and a photopolymerization initiator and exhibits non-flowability at 25 ° C. and fluidity at a temperature range of 50 ° C. to 100 ° C. A gas barrier thin film laminate having a certain characteristic.
[Selection figure] None

Description

  The present invention relates to a gas barrier thin film laminate having a polymer film formed by curing a photocurable resin having fluidity at high temperature, a gas barrier resin substrate having the gas barrier thin film laminate, and a gas barrier resin substrate. The present invention relates to an organic electroluminescence device having the following.

  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 used to wrap articles that require blocking of various gases such as water vapor and oxygen. It is widely used for packaging, etc. to prevent the deterioration of food, industrial products and pharmaceuticals. In addition to packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (EL) devices, and the like. In particular, transparent substrates, which are being applied to liquid crystal display elements, organic EL devices, 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 display. In addition to high demand factors such as being possible, film base materials such as transparent plastics have begun to be used instead of glass substrates that are heavy and easily broken.

  In addition, the plastic film not only meets the above requirements, but also enables a roll-to-roll method, so that it is superior in productivity to a glass substrate and is advantageous from the viewpoint of economy.

  However, film substrates such as transparent plastics have a problem that gas barrier properties are inferior to substrates such as glass. When a base material with inferior gas barrier properties is used, water vapor or air permeates, for example, the liquid crystal in the liquid crystal cell is deteriorated, resulting in display defects and deterioration of display quality.

  As one method for solving such a problem, there is known a method in which a metal oxide thin film is formed on a film substrate to form a film base material having a gas barrier property.

Examples of gas barrier films used for packaging materials and liquid crystal display elements include, for example, a film obtained by vapor-depositing silicon oxide on a plastic film (for example, see Patent Document 1) or a film obtained by vapor-depositing aluminum oxide (for example, Patent Document 2). All of which have a water vapor barrier property with a water vapor transmission rate of about 1 g / m ² / day.

However, in recent years, due to the development of large-sized organic EL displays and liquid crystal displays that require higher gas barrier properties, high-definition displays, etc., the gas barrier performance required for film substrates is also 0.1 g / The demand has increased to about m ² / day.

  In order to meet the market demands as described above, as a means of expecting higher barrier ability, film formation is being studied by sputtering method or CVD method in which a thin film is formed using plasma generated by glow discharge under low pressure conditions. . A barrier film having a structure in which organic films and inorganic films are alternately laminated. A technique for manufacturing by a vacuum deposition method has been proposed (see, for example, Patent Document 3).

  However, many of these thin film formation methods require thin film formation processing under low pressure conditions, and an expensive vacuum chamber is required as a container for obtaining low pressure, and a vacuum evacuation device is required to be installed. There is. In addition, when processing a substrate with a large area when processing in a vacuum, a large vacuum container must be used, and a vacuum exhaust apparatus with a large output is required. As a result, the required equipment becomes extremely expensive. At the same time, when the surface treatment of a plastic substrate having a high water absorption rate is performed, the absorbed water vaporizes, so that it takes a long time to obtain a predetermined degree of vacuum. And the processing cost is high. Furthermore, in the above method, each time one treatment is performed, it is necessary to perform the next step such as breaking the vacuum state of the vacuum vessel and forming an organic film under atmospheric pressure. In order to obtain the above, the more the organic film and the inorganic film are multi-layered, the more the productivity is impaired.

In order to solve the above problems, a barrier film having a structure in which an organic film and an inorganic film are alternately laminated is disclosed using a discharge plasma treatment under the vicinity of atmospheric pressure to form an inorganic film. As a method for forming the organic film, a coating method or a vacuum film forming method is described (for example, see Patent Document 4). However, in the method described in Patent Document 4, although the inorganic film is formed by the atmospheric pressure plasma method, the organic film is formed by a coating process that requires a drying process or a vacuum film forming method that requires a vacuum chamber. That is not appropriate from a productivity standpoint. Further, in the disclosed method for forming an inorganic film, expensive argon is used as a discharge gas, which is an economic burden factor. Furthermore, since the processing conditions using a known single-frequency pulse electric field described in Patent Document 5 are used as the discharge plasma processing conditions, the plasma density is low and not only a high-quality film can be obtained. The membrane speed is also slow and the productivity is very low.
Japanese Patent Publication No.53-12953 JP 58-217344 A World Publication No. 00/026973 Pamphlet JP 2003-191370 A JP 2001-49443 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a gas barrier thin film laminate having high gas barrier ability and excellent curl resistance with high productivity, and to provide the gas barrier thin film laminate. An object of the present invention is to provide an organic electroluminescence device (hereinafter referred to as organic EL or OLED) excellent in adhesion and gas barrier resistance using a body.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
In the gas barrier thin film laminate each having at least one ceramic film and polymer film, at least one layer of the polymer film is photopolymerized with a photocurable resin having an ethylenic double bond at the terminal or side chain of the molecule. It is formed by curing a photo-curable resin composition having an initiator as a main component and exhibiting non-fluidity at 25 ° C. and exhibiting fluidity in a temperature range of 50 ° C. to 100 ° C. A gas barrier thin film laminate.

(Claim 2)
The gas barrier thin film laminate according to claim 1, wherein the photocurable resin contains epoxy (meth) acrylate as a main component.

(Claim 3)
The epoxy (meth) acrylate is obtained by (meth) acrylicizing both ends or side chains of an epoxy having a bisphenol structure with (meth) acrylic acid, having an average molecular weight of 1,000 to 10,000, and a weight average molecular weight. The gas barrier thin film laminate according to claim 2, wherein when Mw and the number average molecular weight are Mn, the dispersity Mw / Mn is 1.5 to 3.0.

(Claim 4)
The gas barrier thin film laminate according to any one of claims 1 to 3, wherein at least one layer of the ceramic film is mainly composed of metal oxide, metal nitride oxide, or metal nitride.

(Claim 5)
The gas barrier thin film laminate according to any one of claims 1 to 4, wherein the ceramic film has a compressive stress of more than 0 MPa and not more than 20 MPa.

(Claim 6)
The gas barrier thin film laminate according to any one of claims 1 to 5, wherein the ceramic film is formed by an atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied.

(Claim 7)
A gas barrier resin base material comprising the gas barrier thin film laminate according to any one of claims 1 to 6 on at least one surface of the resin base material.

(Claim 8)
An organic electroluminescence device having a sealing film disposed on a substrate so as to cover at least an electrode and an organic compound layer, and covering the electrode and the organic compound layer. 7. An organic electroluminescence device, which is the gas barrier thin film laminate according to any one of 6 above.

(Claim 9)
The substrate has at least an electrode and an organic compound layer, a sealing film is disposed so as to cover the electrode and the organic compound layer, and the sealing film and the substrate are bonded together and sealed. The stopped organic electroluminescent device, wherein the sealing film is the gas barrier resin substrate according to claim 7.

(Claim 10)
The organic electroluminescence device according to claim 8 or 9, wherein the base material is the gas barrier resin base material according to claim 7.

  According to the present invention, a gas barrier thin film laminate having high gas barrier ability and excellent curl resistance is provided with high productivity, and the gas barrier thin film laminate is excellent in adhesion and gas barrier resistance. An organic electroluminescent device can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventor has found that at least one layer of the polymer film in each of the gas barrier thin film laminates having at least one ceramic film and a polymer film is a molecular end or side. Photo-curability comprising a photocurable resin having an ethylenic double bond in the chain and a photopolymerization initiator as main components, non-flowability at 25 ° C., and fluidity at a temperature range of 50 ° C. to 100 ° C. A gas barrier thin film laminate having a high gas barrier ability and excellent curl resistance can be obtained with high productivity by a gas barrier thin film laminate characterized by being formed by curing a resin composition. And an organic electroluminescence having a sealing film disposed on the substrate so as to cover at least the electrode and the organic compound layer and to cover the electrode and the organic compound layer In the vice, it has been found that an organic electroluminescence device excellent in adhesion and gas barrier resistance can be realized by the organic electroluminescence device to which the gas barrier thin film laminate of the present invention is applied as the sealing film. It is.

  Details of the present invention will be described below.

<Gas barrier thin film laminate>
In the gas barrier thin film laminate of the present invention, each has at least one ceramic film and a polymer film, and at least one layer of the polymer film is a light having an ethylenic double bond at the terminal or side chain of the molecule. It is characterized by being formed by curing a photocurable resin composition mainly comprising a curable resin and a photopolymerization initiator.

[Photocurable resin and photocurable resin composition]
The polymer film according to the present invention is characterized in that a photocurable resin having an ethylenic double bond at the end or side chain of the molecule is applied. The compound having an ethylenic double bond at the terminal or side chain of this molecule is non-flowable at room temperature, exhibits fluidity in a temperature range of 50 ° C. to 100 ° C., and uses a photocurable resin as a desired base material. Alternatively, after being laminated on a ceramic film, it is cured by irradiation with ultraviolet rays or the like. Therefore, a large coating line, a drying zone, and a large vacuum chamber for vapor deposition are not required as compared with a wet coating method, a vapor deposition method, or a plasma processing method that has been conventionally applied as a polymer film forming method. In addition, since the molecular weight of the resin is large, there is little cure shrinkage and damage to the barrier film can be reduced.

  As the compound having an ethylenic double bond at the terminal or side chain of the molecule according to the present invention, an acrylic curable resin having a (meth) acryloyl group at the terminal or side chain of the molecule can be preferably used. It is preferably a photocurable resin mainly composed of epoxy (meth) acrylate, and the epoxy (meth) acrylate has both ends of an epoxy having a bisphenol structure such as bisphenol A or bisphenol F skeleton in the main chain or When the side chain is (meth) acrylated with (meth) acrylic acid, the average molecular weight is 1000 to 10,000, the weight average molecular weight is Mw, and the number average molecular weight is Mn, the dispersity Mw / Mn is 1. It is preferable that it is 5-3.0. In this way, by controlling the average molecular weight and degree of dispersion, the coating film accuracy and tackiness of the formed polymer layer are improved, the fluidity during thermocompression bonding is excellent, and the thin film has excellent smoothness without bubbles. Can be obtained.

  The photo-curable resin composition according to the present invention is non-flowable at a normal temperature of 25 ° C. and is a solid or soft solid, and exhibits fluidity at 50 ° C. to 100 ° C., preferably 60 ° C. to 80 ° C. It is characterized by. That is, the photocurable resin composition according to the present invention is excellent in storage stability because it is a solid or soft solid at room temperature (25 ° C), and is heated to 50 ° C to 100 ° C, preferably 60 ° C to 80 ° C. By doing so, it melts and exhibits fluidity.

  Therefore, the photocurable resin such as epoxy (meth) acrylate according to the present invention exhibits fluidity in a temperature range of 50 ° C. to 100 ° C., and is solid or soft solid at room temperature (25 ° C.). It is necessary to use a compound (oligomer or prepolymer) that exhibits non-fluidity.

  As the photocurable oligomer or prepolymer having such behavior due to temperature, for example, a compound represented by the following general formula (1) or (2) is preferable.

In the general formula (1), n1 represents an integer of 1 to 3, and R ₁ represents a hydrogen atom or a lower alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, etc.) which may be the same or different. .

In the general formula (2), n2 represents an integer of 1 to 3, R ₂ represents the same or different and which may hydrogen atom or a lower alkyl group (e.g., methyl group, ethyl group, n- propyl group) .

  These photocurable oligomers and prepolymers can also be obtained as commercial products, and examples thereof include EP-0021 (Exemplary Compound 1 below) manufactured by Kyoeisha Chemical Industry Co., Ltd.

  In exemplary compound 1, n3 represents an integer of 1 to 3.

  As a method for forming a polymer film according to the present invention, the following method can be used.

  1) The photocurable resin according to the present invention is dissolved in an organic solvent, and then a photopolymerization initiator is added and stirred to obtain a uniform liquid photocurable resin composition. The resin composition is spread on the ceramic film to a predetermined thickness, and then the organic solvent is volatilized to form a non-flowable polymer film. This is a method for obtaining a laminated gas barrier thin film laminate, and if necessary, the formation of a ceramic film and a polymer film may be repeated.

  2) The photocurable resin according to the present invention is melted by heating to 50 ° C. or higher, and a photopolymerization initiator is added thereto and stirred to obtain a uniform liquid photocurable resin composition. The photo-curable resin composition is spread to a predetermined thickness on the ceramic film, and this is cooled to form a non-flowable polymer film, which is then cured by irradiation with light, and the ceramic film and the polymer film Is a method for obtaining a laminated gas barrier thin film, and if necessary, the formation of a ceramic film and a polymer film may be repeated.

  The photocurable resin composition according to the present invention contains a photopolymerization initiator for photocuring a compound having an ethylenic double bond.

  Examples of the photopolymerization initiator include photopolymerization initiators that generate active radicals by irradiation with conventionally known active energy rays, for example, ultraviolet rays or visible rays. Specifically, photopolymerization initiators are generally used. Examples thereof include, but are not limited to, benzophenone and acetophenone.

  Among these, polymer type photopolymerization initiators KIP150 and KIP-KK (both manufactured by Lamberti) and the like are preferably used because they have less outgas components after curing. In addition, when cured by visible light irradiation using a photopolymerization initiator having an absorption wavelength in the visible light region, it prevents performance deterioration due to ultraviolet irradiation of an organic EL element or the like to which a polymer layer or a gas barrier thin film laminate is applied. Can do. In this case, it is preferable to use, for example, an acylphosphine oxide-based photopolymerization initiator that can be cured in the visible light region.

  Various additives can be added to the polymer film according to the present invention as necessary.For example, in order to reduce the influence of moisture on the organic EL element, a hygroscopic agent such as barium oxide can be added, A filler can be added to such an extent that the transparency of the polymer film is not impaired.

<Ceramic membrane>
The ceramic film used in the present invention is a film mainly having an effect of blocking gas such as water vapor and oxygen, and at least one layer of the ceramic film is made of metal oxide, metal nitride oxide, or metal nitride. The main component is preferably a metal atom (Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni in the film. Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, Ce , Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc.) is a layer in which the atomic concentration exceeds 5%, preferably 10% or more, More preferably, the film is 20% or more. The metal atom concentration of the ceramic film can be measured by an XPS surface analyzer. The ceramic film according to the present invention preferably contains a ceramic component such as a metal oxide, metal nitride oxide, or metal nitride composed of the above metal element as a main component, and the carbon content is 1% or less. preferable. The film thickness is not particularly limited, but is generally 1 to 10000 nm, and particularly preferably 5 to 1000 nm. Methods for forming the ceramic film according to the present invention include wet processes such as coating, dry processes such as vacuum film forming methods (evaporation, sputtering, plasma CVD, ion plating, etc.), and atmospheric pressure plasma methods. Can be mentioned. The formation method is not particularly limited, but a dry process is preferable for forming a dense ceramic film having a high gas barrier property, and an atmospheric pressure plasma method is more preferable.

  The atmospheric pressure plasma method for forming the ceramic film according to the present invention uses a thin film forming method described in JP-A-10-154598, JP-A-2003-49272, WO02 / 048428, or the like. However, the atmospheric pressure plasma method similar to the method for forming the plasma polymerized film and the thin film forming method described in Japanese Patent Application Laid-Open No. 2004-68143 form a dense ceramic film having high gas barrier properties. Preferably, the atmospheric pressure plasma method is particularly preferable for continuously forming a ceramic film by rolling a web-shaped substrate from a roll-shaped original winding and winding it into a roll.

  Examples of the raw material (thin film forming component) of the ceramic film according to the present invention include organometallic compounds, halogen metal compounds, metal hydride compounds, and the like.

  The organometallic compounds useful in the present invention are preferably those represented by the following general formula (I).

Formula (I)
R ¹ _x MR ² _y R ³ _z
In the formula, M is a metal (Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb. , Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, Lu, etc.), R ¹ is an alkyl group, R ² is an alkoxy group, R ³ is a β-diketone coordination group, β-ketocarboxylate ester coordination group, β- It is a group selected from a ketocarboxylic acid coordinating group and a ketooxy group (ketooxy coordinating group). When the valence of the metal M is m, x + y + z = m, and x = 0 to m, or x = 0 to m. −1, y = 0 to m, z = 0 to m, and each is 0 or a positive integer. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group for R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 3,3,3-trifluoropropoxy group. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. As a group selected from a β-diketone coordination group, a β-ketocarboxylic acid ester coordination group, a β-ketocarboxylic acid coordination group and a ketooxy group (ketooxy coordination group) of R ³ , as a β-diketone coordination group, For example, 2,4-pentanedione (also referred to as acetylacetone or acetoacetone), 1,1,1,5,5,5-hexamethyl-2,4-pentanedione, 2,2,6,6-tetramethyl-3 , 5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione, etc., and β-ketocarboxylic acid ester coordination groups include, for example, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, Acetoacetic acid propyl ester, trimethylacetoacetic acid ethyl, trifluoroacetoacetic acid methyl and the like, and β-ketocarboxylic acid coordinating group Examples thereof include acetoacetic acid and trimethylacetoacetic acid, and examples of ketooxy include acetooxy group (or acetoxy group), propionyloxy group, butyryloxy group, acryloyloxy group, and methacryloyloxy group. it can. The number of carbon atoms of these groups is preferably 18 or less, including the above-mentioned organometallic compounds. Further, as illustrated, it may be linear or branched, or a hydrogen atom substituted with a fluorine atom.

In the present invention, an organometallic compound having a low risk of explosion is preferred from the viewpoint of handling, and an organometallic compound having at least one oxygen in the molecule is preferred. As such, an organometallic compound containing at least one alkoxy group of R ² , a β-diketone coordination group, a β-ketocarboxylic acid ester coordination group, a β-ketocarboxylic acid coordination group and a ketooxy group of R ³ A metal compound having at least one group selected from a group (ketooxy coordination group) is preferred.

  Specific organometallic compounds are shown below.

  Examples of the organosilicon compound include tetraethylsilane, tetramethylsilane, tetraisopropylsilane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethylsilanedi (2 , 4-pentanedionate), methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, etc., as silicon hydrogen compounds, tetrahydrogen silane, hexahydrogen disilane, etc., as halogenated silicon compounds, tetrachlorosilane , Methyltrichlorosilane, diethyldichlorosilane and the like, and any of them can be preferably used in the present invention. Two or more of these may be mixed and used at the same time.

  Examples of titanium compounds include organic titanium compounds, titanium hydrogen compounds, and titanium halides. Examples of organic titanium compounds include triethoxy titanium, trimethoxy titanium, triisopropoxy titanium, tributoxy titanium, tetraethoxy titanium, Tetraisopropoxy titanium, methyldimethoxy titanium, ethyl triethoxy titanium, methyl triisopropoxy titanium, triethyl titanium, triisopropyl titanium, tributyl titanium, tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, tetradimethylamino titanium, dimethyl titanium di ( 2,4-pentanedionate), ethyltitanium tri (2,4-pentanedionate), titanium tris (2,4-pentanedionate), titanium tris (acetomethylaceta) G), triacetoxy titanium, dipropoxypropionyloxy titanium, etc., dibutylyloxy titanium, titanium hydrogen compound as monotitanium hydrogen compound, dititanium hydrogen compound, etc., and halogenated titanium as trichlorotitanium, tetrachlorotitanium, etc. Any of these can be preferably used in the present invention. Two or more of these may be mixed and used at the same time.

Examples of the tin compound include organic tin compounds, tin hydrogen compounds, and tin halides. Examples of the organic tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, and tetraoctyl. Tin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, Tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate, etc., tin hydride compounds, etc. Examples of tin halides include tin dichloride and tin tetrachloride. Any of these can be preferably used in the present invention. Two or more of these may be mixed and used at the same time. In addition, since the tin oxide film formed using these can reduce the surface specific resistance value to 1 × 10 ¹² Ω / □ or less, it is also useful as an antistatic layer.

  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.

<Atmospheric pressure plasma method>
The formation of the ceramic film according to the present invention comprises a raw material gas containing the organometallic compound in the discharge space and a decomposition gas for obtaining an inorganic compound by decomposing the raw material gas at atmospheric pressure or a pressure in the vicinity thereof. A reactive gas and a discharge gas excited to a plasma state, and a high frequency electric field is applied to the discharge space to excite the mixed gas, and a substrate or the like is added to the excited mixed gas. It is preferable to apply an atmospheric pressure plasma method in which a thin film (ceramic film) is formed by exposure, and at this time, it is more preferable to form by an atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied.

  Decomposition gas for decomposing the raw material gas containing these organometallic compounds to obtain an inorganic compound includes 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 nitride oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas. In the invention, at least one layer of the ceramic film is preferably composed mainly of a metal oxide, a metal nitride oxide or a metal nitride.

  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.

  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). The ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, but the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

  In the ceramic film according to the present invention, the inorganic compound contained in the ceramic is preferably at least one selected from silicon oxide, silicon oxynitride, silicon nitride, alumina oxide, and mixtures thereof, particularly water vapor and oxygen. From the viewpoint of gas barrier properties, light transmittance, and suitability for an atmospheric pressure plasma processing method described later, silicon oxide is preferable.

  The inorganic compound according to the present invention, for example, obtains a film containing at least one of O atoms and N atoms, and Si atoms by further combining nitrogen gas, oxygen gas, and ammonia gas with the above organic silicon compound at a predetermined ratio. be able to.

  In order to obtain a stable gas barrier resin base material in which the gas barrier performance does not change even under severe conditions, the ceramic film according to the present invention preferably has a compressive stress of more than 0 MPa and not more than 20 MPa.

  Compared to the sol-gel method, the vacuum deposition method, the sputtering method, etc., the ceramic film formed by the plasma CVD method, particularly the atmospheric pressure plasma method, is characterized in that it can form a film with low internal stress and less distortion.

  The ceramic films formed by these methods are therefore dense and dense, and at the same time, low internal stress means that the film is less distorted, and is smooth and average for deformation due to bending, etc. In order to mean strong, it is preferable that the ceramic film of the present invention is a film having a low compressive stress of more than 0 MPa and 20 MPa or less.

  When the stress is too small, there may be a partial tensile stress, and the film is easily cracked or cracked, resulting in a non-durable film. When the stress is too large, the film is easily cracked.

<Method of measuring internal stress>
The internal stress in the ceramic film is measured by the following method.

  That is, a ceramic film having the same composition and thickness as the measurement film is formed on a quartz substrate having a width of 10 mm, a length of 50 mm, and a thickness of 0.1 mm so as to have a thickness of 1 μm by the same method. , With the concave portion facing up, and measured with a thin film property evaluation apparatus MH4000 manufactured by NEC Saneisha. In general, in the case of a plus curl in which the film side contracts against the substrate due to compressive stress, it is expressed as a positive internal stress (compressive stress), and conversely, when a negative curl is generated by tensile stress, it is expressed as a negative internal stress (tensile stress).

  As described above, when the gas barrier resin base material is configured using the laminated film composed of the ceramic film according to the present invention and the polymer film described above, the ceramic film having a low internal stress according to the present invention is particularly bent. A laminated film resistant to stress such as resistance can be provided, which is preferable.

  Next, details of the above-described atmospheric pressure plasma method and the atmospheric pressure plasma processing apparatus used therefor that can be preferably applied to the present invention will be described.

  As an atmospheric pressure plasma method for forming a ceramic film according to the present invention by plasma polymerization, thin film formation described in JP-A-10-154598, JP-A-2003-49272, WO02 / 048428, etc. Although the method can be used, the thin film forming method described in Japanese Patent Application Laid-Open No. 2004-68143 is preferable because a dense ceramic film having a high gas barrier property and a small compressive stress can be formed.

  The above atmospheric pressure plasma method according to the present invention is performed under atmospheric pressure or a pressure in the vicinity thereof. The atmospheric pressure or the pressure in the vicinity thereof is about 20 kPa to 110 kPa, and the good effects described in the present invention are obtained. In order to obtain, 93 kPa-104 kPa are preferable.

  In the present invention, the discharge condition is that two or more electric fields having different frequencies are applied to the discharge space, and a method of applying an electric field in which the first high-frequency electric field and the second high-frequency electric field are superimposed is preferable.

When two or more electric fields having different frequencies are applied to the discharge space, the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, The relationship between the high-frequency electric field strength V2 of FIG.
V1 ≧ IV> V2
Or V1> IV ≧ V2 is satisfied,
The output density of the second high frequency electric field is preferably 1 W / cm ² or more.

  A high frequency means what has a frequency of at least 0.5 kHz.

  When the superposed high-frequency electric field is both a sine wave, the frequency ω1 of the first high-frequency electric field and the frequency ω2 of the second high-frequency electric field higher than the frequency ω1 are superimposed, and the waveform is a sine of the frequency ω1. A sawtooth waveform in which a sine wave having a higher frequency ω2 is superimposed on the wave is obtained.

  In the present invention, the strength of the electric field at which discharge starts is the lowest electric field intensity that can cause discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) used in the actual thin film formation method. Point to. The discharge start electric field strength varies somewhat depending on the type of gas supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes, but is controlled by the discharge start electric field strength of the discharge gas in the same discharge space.

  By applying a high-frequency electric field as described above to the discharge space, it is presumed that a discharge capable of forming a thin film is caused and high-density plasma necessary for forming a high-quality thin film can be generated.

  What is important here is that such a high-frequency electric field is applied between the opposing electrodes, that is, applied to the same discharge space. As disclosed in JP-A-11-16696, a method in which two application electrodes are juxtaposed and different high-frequency electric fields are applied to different discharge spaces is not preferable.

  Although the superposition of continuous waves such as sine waves has been described above, the present invention is not limited to this, and both pulse waves may be used, one of them may be a continuous wave and the other may be a pulse wave. Further, a third electric field having a different frequency may be included.

  As a specific method for applying the above-described high-frequency electric field to the same discharge space, for example, a first high-frequency electric field having a frequency ω1 and an electric field strength V1 is applied to the first electrode constituting the counter electrode. An atmospheric pressure plasma discharge processing apparatus is used in which a power source is connected and a second power source for applying a second high-frequency electric field having a frequency ω2 and an electric field strength V2 is connected to the second electrode.

  The atmospheric pressure plasma discharge treatment apparatus having the above conditions includes a gas supply means for supplying a discharge gas and a thin film forming gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.

  Further, it is preferable to connect the first filter to the first electrode, the first power source or any of them, and connect the second filter to the second electrode, the second power source or any of them, The first filter facilitates the passage of the first high-frequency electric field current from the first power source to the first electrode, grounds the second high-frequency electric field current, and the second filter from the second power source to the first power source. It makes it difficult to pass the current of the high frequency electric field. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source. A power supply having a function of making it difficult to pass the current of the first high-frequency electric field to the power supply is used. Here, being difficult to pass means that it preferably passes only 20% or less of the current, more preferably 10% or less. On the contrary, being easy to pass means preferably passing 80% or more of the current, more preferably 90% or more.

  For example, as the first filter, a capacitor of several tens of pF to several tens of thousands of pF or a coil of about several μH can be used depending on the frequency of the second power source. As the second filter, a coil of 10 μH or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or capacitors.

  Furthermore, it is preferable that the first power source of the atmospheric pressure plasma discharge processing apparatus of the present invention has a capability of applying a higher electric field strength than the second power source.

  Here, the applied electric field strength and the discharge starting electric field strength referred to in the present invention are those measured by the following method.

Measuring method of applied electric field strengths V1 and V2 (unit: kV / mm):
A high-frequency voltage probe (P6015A) is installed in each electrode portion, and an output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength at a predetermined time is measured.

Measuring method of electric discharge starting electric field intensity IV (unit: kV / mm):
A discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the electric field strength at which discharge starts is defined as a discharge starting electric field strength IV. The measuring instrument is the same as the applied electric field strength measurement.

  In addition, the measurement position of the electric field intensity by the high frequency voltage probe and oscilloscope used for the measurement is shown in FIG.

  By adopting the discharge conditions specified in the present invention, even a discharge gas having a high discharge start electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. It can be carried out.

  According to the above measurement, when the discharge gas is nitrogen gas, the discharge start electric field intensity IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field intensity is Is applied as V1 ≧ 3.7 kV / mm, whereby the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power supply is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. In addition, it is an important point of the present invention to form a dense and high-quality thin film by increasing the plasma density with a high power density.

  Also, by increasing the output density of the first high-frequency electric field, the output density of the second high-frequency electric field can be improved while maintaining the uniformity of discharge. 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.

  As described above, the atmospheric pressure plasma discharge treatment apparatus used in the present invention discharges between the counter electrodes, puts the gas introduced between the counter electrodes into a plasma state, and places the gas between the counter electrodes or between the electrodes. By exposing the substrate to be transferred to the plasma state gas, a thin film is formed on the substrate. As another method, the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes or puts it in a plasma state, and excites or jets the gas outside the counter electrode. There is a jet type apparatus that blows out a plasma gas and exposes a substrate (which may be stationary or transferred) in the vicinity of the counter electrode to form a thin film on the substrate. .

  FIG. 1 is a schematic view showing an example of a jet type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.

  In addition to the plasma discharge processing apparatus and the electric field application means having two power sources, the jet type atmospheric pressure plasma discharge processing apparatus is not shown in FIG. And an electrode temperature adjusting means.

  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 <b> 1 from the first power supply 21 is output from the first electrode 11 between the counter electrodes. A first high-frequency electric field of electric field strength V1 and current I1 is applied, and a second high-frequency electric field of frequency ω2, electric field strength V2, and current I2 from the second power source 22 is applied from the second electrode 12. It has become. The first power source 21 applies a higher frequency electric field strength (V1> V2) than the second power source 22, and the first frequency ω1 of the first power source 21 applies a frequency lower than the second frequency ω2 of the second power source 22. To do.

  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 current from the second power source 22. Is designed so that the current from the second power source 22 to the first power source 21 is less likely to pass through.

  In addition, a second filter 24 is installed between the second electrode 12 and the second power source 22 to facilitate passage of current from the second power source 22 to the second electrode, and from the first power source 21. It is designed to ground the current and make it difficult to pass the current from the first power source 21 to the second power source.

  The above-described thin film forming gas G is introduced from the gas supply means as illustrated in FIG. 2 described later into the space (discharge space) 13 between the opposing electrodes of the first electrode 11 and the second electrode 12, and the first power source 21. The second power source 22 applies the above-described high-frequency electric field between the first electrode 11 and the second electrode 12 to generate a discharge, and the thin film forming gas G described above is brought into a plasma state while the lower side of the counter electrode (below the paper surface). The processing space formed by the lower surface of the counter electrode and the base material F is filled with a gas G ° in a plasma state, and is unwound from a base winding (unwinder) (not shown). A thin film is formed in the vicinity of the processing position 14 on the base material F that is transported or transported from the previous process. During the thin film formation, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG. Depending on the temperature of the base material during the plasma discharge treatment, the properties, composition, etc. of the thin film obtained may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that temperature unevenness in the width direction or longitudinal direction of the substrate does not occur as much as possible.

  FIG. 1 shows a measuring instrument used for measuring the applied electric field strength and the discharge starting electric field strength and the measurement position. Reference numerals 25 and 26 are high-frequency voltage probes, and reference numerals 27 and 28 are oscilloscopes.

  By arranging a plurality of jet-type atmospheric pressure plasma discharge treatment apparatuses in parallel with the transport direction of the base material F and simultaneously discharging gas in the same plasma state, it becomes possible to form a plurality of thin films at the same position, and for a short time. Thus, a desired film thickness can be formed. If a plurality of units are arranged in parallel with the transport direction of the base material F, different thin film forming gases are supplied to each apparatus and different plasma states of the gas are jetted, it is possible to form laminated thin films having different layers.

  FIG. 2 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus that treats a substrate between counter electrodes useful for the present invention.

  The atmospheric pressure plasma discharge treatment apparatus of the present invention is an apparatus having at least a plasma discharge treatment apparatus 30, an electric field application means 40 having two power supplies, a gas supply means 50, and an electrode temperature adjustment means 60.

  Between the counter electrodes 32 (hereinafter referred to as discharge between the counter electrodes) between the roll rotating electrode (first electrode) 35 and the square tube type fixed electrode group (second electrode) 36 (hereinafter, the square tube type fixed electrode group is referred to as a fixed electrode group). In this case, the base material F is plasma-discharged to form a thin film.

  In the discharge space 32 formed between the roll rotating electrode 35 and the fixed electrode group 36, the roll rotating electrode 35 receives a first high-frequency electric field of frequency ω1, electric field strength V1, current I1 from the first power source 41, and A second high-frequency electric field having a frequency ω2, an electric field strength V2, and a current I2 is applied to the fixed electrode group 36 from the second power source 42.

  A first filter 43 is installed between the roll rotation electrode 35 and the first power supply 41. The first filter 43 facilitates the passage of current from the first power supply 41 to the first electrode, and the second power supply. It is designed to ground the current from 42 and make it difficult to pass the current from the second power source 42 to the first power source. In addition, a second filter 44 is installed between the fixed electrode group 36 and the second power source 42, and the second filter 44 facilitates passage of current from the second power source 42 to the second electrode, It is designed to ground the current from the first power supply 41 and make it difficult to pass the current from the first power supply 41 to the second power supply.

  In the present invention, the roll rotation electrode 35 may be the second electrode, and the rectangular tube-shaped fixed electrode group 36 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ω1 <ω2.

The current is preferably I1 <I2. Current I1 of the first high-frequency electric field is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . Furthermore, current I2 of the second high-frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  The thin film forming gas G generated by the gas generator 51 of the gas supply means 50 is introduced into the plasma discharge processing vessel 31 from the air supply port 52 while the flow rate is controlled by a gas flow rate adjusting means (not shown).

  The substrate F is unwound from the original winding (not shown) and conveyed, or is conveyed in the direction of the arrow from the previous process and is accompanied by the nip roll 65 through the guide roll 64 and the substrate. And the like, and while being wound while being in contact with the roll rotating electrode 35, it is transferred to and from the rectangular tube fixed electrode group 36.

  An electric field is applied from both the roll rotating electrode 35 and the fixed electrode group 36 during the transfer, and discharge plasma is generated between the counter electrodes (discharge space) 32. The base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 35.

  A plurality of rectangular tube-shaped fixed electrodes are provided along a circumference larger than the circumference of the roll electrode, and the discharge areas of the electrodes are all the corners facing the roll rotating electrode 35. It is represented by the sum of the areas of the surface of the cylindrical fixed electrode facing the roll rotation electrode 35.

  The base material F passes through the nip roll 66 and the guide roll 67 and is wound up by a winder (not shown) or transferred to the next process.

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

  During the thin film formation, in order to heat or cool the roll rotating electrode 35 and the fixed electrode group 36, the medium whose temperature is adjusted by the electrode temperature adjusting means 60 is sent to both electrodes via the pipe 61 by the liquid feed pump P, and inside the electrodes Adjust the temperature from Reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.

  FIG. 3 is a perspective view showing an example of the structure of the conductive metal base material of the roll rotating electrode shown in FIG. 2 and the dielectric material coated thereon.

  In FIG. 3, a roll electrode 35a is formed by covering a conductive metallic base material 35A and a dielectric 35B thereon. In order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the substrate F at a predetermined value, a temperature adjusting medium (such as water or silicon oil) can be circulated.

  FIG. 4 is a perspective view showing an example of the structure of the conductive metallic base material of the rectangular tube electrode and the dielectric material coated thereon.

  In FIG. 4, a rectangular tube electrode 36a has a coating of a dielectric 36B similar to that of FIG. 3 on a conductive metallic base material 36A, and the structure of the electrode is a metallic pipe. , It becomes a jacket so that the temperature can be adjusted during discharge.

  The rectangular tube electrode 36a shown in FIG. 4 may be a cylindrical electrode, but the rectangular tube electrode has an effect of expanding the discharge range (discharge area) as compared with the cylindrical electrode, and thus is preferably used in the present invention. .

  3 and 4, a roll electrode 35a and a rectangular tube electrode 36a are formed by spraying ceramics as dielectrics 35B and 36B on conductive metallic base materials 35A and 36A, respectively, and then sealing the inorganic compound sealing material. Used and sealed. The ceramic dielectric may be covered by about 1 mm with a single wall. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  Examples of the conductive metal base materials 35A and 36A include titanium metal or titanium alloy, metal such as silver, platinum, stainless steel, aluminum, and iron, a composite material of iron and ceramics, or a composite material of aluminum and ceramics. Although titanium metal or a titanium alloy is particularly preferable for the reasons described later.

  When the dielectric is provided on one of the electrodes, the distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metal base material of the other electrode. Say that. 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. From the viewpoint of performing 0.15 mm, 0.1 to 20 mm is preferable, and 0.5 to 2 mm is particularly preferable.

  Details of the conductive metallic base material and dielectric useful in the present invention will be described later.

  The plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but can be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation. In FIG. 1, it is preferable to cover both side surfaces (up to the vicinity of the base material surface) of both parallel electrodes with an object made of the above material.

As the first power source (high frequency power source) installed in the atmospheric pressure plasma 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. The energy is applied to the thin film forming gas to form a thin film. 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 the area in which discharge occurs between the electrodes.

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. be able to. Thereby, the further uniform high-density plasma can be produced | generated, and the improvement of the film forming speed and the improvement of film quality can be made compatible. 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.

  The electrode used in such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance. Such an electrode is preferably a metal base material coated with a dielectric.

In the dielectric-coated electrode used in the present invention, it is preferable that the characteristics match between various metallic base materials and dielectrics. One of the characteristics is linear thermal expansion between the metallic base material and the dielectric. The combination is such that the difference in coefficient is 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 whose difference in linear thermal expansion coefficient is within this range,
1: Metal base material is pure titanium or titanium alloy, dielectric is ceramic spray coating 2: Metal base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic sprayed coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of the difference in linear thermal expansion coefficient, the above 1 or 2 and 5 to 8 are preferable, and 1 is particularly preferable.

  In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or a titanium alloy as the metal base material, the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.

  The metallic base material of the electrode useful in the present invention is a titanium alloy or titanium metal containing 70% by mass or more of titanium. In the present invention, if the titanium content in the titanium alloy or titanium metal is 70% by mass or more, it can be used without any problem, but preferably contains 80% by mass or more of titanium. As the titanium alloy or titanium metal useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain a very small amount of iron atom, carbon atom, nitrogen atom, oxygen atom, hydrogen atom, etc. As content, it has 99 mass% or more. As the corrosion-resistant titanium alloy, T15PB can be preferably used, and it contains lead in addition to the above-mentioned contained atoms, and the titanium content is 98% by mass or more. Further, as the titanium alloy, T64, T325, T525, TA3, etc. containing aluminum and vanadium or tin in addition to the above atoms except lead can be preferably used. As a quantity, it contains 85 mass% or more. These titanium alloys or titanium metals have a thermal expansion coefficient that is about 1/2 smaller than that of stainless steel, such as AISI 316, and are combined with a dielectric material described later applied on the titanium alloy or titanium metal as a metallic base material. It can withstand the use at high temperature for a long time.

  On the other hand, as a required characteristic of the dielectric, specifically, an inorganic compound having a relative dielectric constant of 6 to 45 is preferable, and examples of such a dielectric include ceramics such as alumina and silicon nitride, Alternatively, there are glass lining materials such as silicate glass and borate glass. In this, what sprayed the ceramics mentioned later and the thing provided by glass lining are preferable. In particular, a dielectric provided by spraying alumina is preferable.

  Alternatively, as one of the specifications that can withstand high power as described above, the porosity of the dielectric is 10% by volume or less, preferably 8% by volume or less, preferably more than 0% by volume and 5% by volume or less. It is. The porosity of the dielectric can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured using a dielectric fragment covered with a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation. High durability is achieved because the dielectric has a low porosity. Examples of the dielectric having a low porosity while having such a void include a high-density, high-adhesion ceramic spray coating by an atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform sealing treatment.

  The above-mentioned atmospheric plasma spraying method is a technique in which fine powder such as ceramics, wire, or the like is put into a plasma heat source and sprayed onto a metallic base material to be coated as fine particles in a molten or semi-molten state to form a film. A plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further given energy to release electrons. This plasma gas injection speed is high, and since the sprayed material collides with the metallic base material at a higher speed than conventional arc spraying or flame spraying, it is possible to obtain a coating film with high adhesion strength and high density. For details, a thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A No. 2000-301655 can be referred to. By this method, the porosity of the dielectric (ceramic sprayed film) to be coated can be obtained.

  Another preferable specification that can withstand high power is that the dielectric thickness is 0.5 to 2 mm. The film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

  In order to further reduce the porosity of the dielectric, it is preferable to further perform a sealing treatment with an inorganic compound on the sprayed film such as ceramics as described above. As the inorganic compound, a metal oxide is preferable, and among these, a compound containing silicon oxide (SiOx) as a main component is particularly preferable.

  The inorganic compound for sealing treatment is preferably formed by curing by a sol-gel reaction. In the case where the inorganic compound for sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

  Here, it is preferable to use energy treatment for promoting the sol-gel reaction. Examples of the energy treatment include thermal curing (preferably 200 ° C. or less) and ultraviolet irradiation. Furthermore, as a method of sealing treatment, when the sealing liquid is diluted and coating and curing are repeated several times in succession, the mineralization is further improved and a dense electrode without deterioration can be obtained.

In the case of performing a sealing treatment that cures by a sol-gel reaction after coating a ceramic sprayed film using the metal alkoxide or the like of the dielectric-coated electrode according to the present invention as a sealing liquid, the content of the metal oxide after curing is 60 It is preferably at least mol%. When alkoxysilane is used as the metal alkoxide of the sealing liquid, the content of SiO _x (x is 2 or less) after curing is preferably 60 mol% or more. The cured SiO _x content is measured by analyzing a tomographic layer of the dielectric layer by XPS (X-ray photoelectron spectroscopy).

  In the present invention, the electrode used in the thin film forming method is adjusted so that the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on at least the side of the electrode in contact with the substrate is 10 μm or less. However, from the viewpoint of obtaining the effects described in the present invention, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less. In this way, the dielectric surface of the dielectric-coated electrode can be polished to keep the dielectric thickness and the gap between the electrodes constant, the discharge state can be stabilized, and the heat shrinkage difference and residual Distortion and cracking due to stress can be eliminated, and durability can be greatly improved with high accuracy. The polishing finish of the dielectric surface is preferably performed at least on the dielectric in contact with the substrate. Furthermore, the centerline average surface roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.

  In the dielectric-coated electrode used in the present invention, another preferred specification that can withstand high power is that the heat-resistant temperature is 100 ° C. or higher. More preferably, it is 120 degreeC or more, Most preferably, it is 150 degreeC or more. The upper limit is 500 ° C. The heat-resistant temperature refers to the highest temperature that can withstand normal discharge without causing dielectric breakdown at the voltage used in the atmospheric pressure plasma treatment. Such heat-resistant temperature can be applied within the range of the difference between the linear thermal expansion coefficient of the metallic base material and the dielectric material by applying the dielectric material provided by the above-mentioned ceramic spraying or layered glass lining with different bubble mixing amounts. This can be achieved by appropriately combining means for appropriately selecting the materials.

<Gas barrier resin base material>
The gas barrier resin base material of the present invention is characterized in that it has the gas barrier thin film laminate of the present invention on at least one surface of the resin base material. The gas barrier thin film laminate of the present invention is directly or on a functional film (for example, an adhesive film, a hard coat film, an antireflection film, an antistatic film, a scratch resistant film, a lubricating film, a smooth film, a reflective film) on the material. By forming a body, it can be used as a gas barrier resin base material, and sealing films such as devices that are vulnerable to gas such as water vapor and oxygen such as OLED on a base material that does not pass gas such as water vapor and oxygen such as glass It is also possible to obtain a resin base material that does not deteriorate the gas barrier property against bending or the like. The gas barrier resin substrate of the present invention may have a unit comprising at least one ceramic film and a polymer film on the resin substrate, but may have a multilayer laminated structure in which a plurality of units are further laminated.

  Although there is no restriction | limiting in particular as a base material used by the gas-barrier resin base material of this invention, It is preferable that it is a transparent resin base material, Cellulose triacetate, cellulose diacetate, cellulose acetate propionate, or cellulose acetate butyrate Cellulose esters, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl alcohol copolymers, syndiotactic polystyrene, polycarbonate, norbornene resins , Polymethylpentene, Polyetherketone, Polyimide, Polyethersulfone, Polysulfone, Polyetherimide, Polyamide Fluororesin, polymethyl acrylate, and the like acrylate copolymer and the like can. These materials can be used alone or in combination as appropriate.

  In addition, the resin base material used in the present invention is not limited to the above description, but when used in flat panel display (OLED, liquid crystal, FED, SED, PDP, etc.) applications and electronic material applications, the glass transition temperature. Is preferably 150 ° C. or higher, polyether sulfone, polycarbonate, norbornene resin, transparent polyimide disclosed in JP-A No. 2003-192787, JP-A No. 2001-139676 and JP-A No. 2002-179784. Copolycarbonates disclosed in Japanese Laid-Open Patent Publications, etc., transparent films disclosed in Japanese Patent Application Laid-Open No. 2004-196841, and the like can be preferably used. Among them, ZEONOR (manufactured by ZEON CORPORATION), ZEONOR (manufactured by ZEON CORPORATION) and ARTON (manufactured by JSR Corporation) of norbornene-based resin film, Pureace of polycarbonate film (manufactured by Teijin Chemicals Ltd.), Commercial products such as polyethersulfone film Sumilite (manufactured by Sumitomo Bakelite Co., Ltd.) can be preferably used. The film thickness is preferably 10 to 1000 μm, more preferably 40 to 500 μm.

As the water vapor permeability of the gas barrier resin substrate of the present invention, the water vapor permeability measured in accordance with JIS K7129 B method when used for applications requiring high gas barrier properties such as organic EL displays and high-definition color liquid crystal displays. It is preferable that the oxygen permeability measured in accordance with JIS K7126 B method is less than 0.1 ml / m ² / day / atm and less than 0.1 g / m ² / day.

  Moreover, the gas barrier resin base material of the present invention can also be bonded by sealing the OLED on the base material via an epoxy adhesive or the like. As the epoxy adhesive, those commercially available from ThreeBond Co., Ltd., Nagase ChemteX Co., Ltd., etc. can be used as OLED sealing materials.

<< Organic EL device >>
Next, the form of the organic EL device of the present invention in which the gas barrier property is enhanced by the above-described gas barrier thin film laminate or the gas barrier resin base material will be described with reference to some representative examples. The form of the organic EL device of the present invention is not limited to the form exemplified here.

  In organic EL devices, electrons and holes injected from the anode and cathode are recombined in the light-emitting layer to generate excitons, and light is emitted when the excitons are deactivated (fluorescence / phosphorescence). ) To emit light, and C.I. W. Tang, S.M. A. VanSlyke. , Applied Physics Letters, Vol. 51, page 913 (1987), etc., as well as in Japanese Patent No. 3093796, Japanese Patent Application Laid-Open No. 63-264692, etc., and the phosphorescent dopant. As for organic electroluminescence devices using phosphorescence emission from excited triplets using a host compound and M.P. A. Baldo et al. , Nature, 395, 15 1-154 (1998), etc., and Japanese Patent Application Laid-Open No. 3-255190 describes the configuration and the like.

  In the present invention, in an organic EL device having at least an electrode and an organic compound layer on a substrate, the gas barrier thin film laminate of the present invention is provided as a sealing film so as to cover the electrode and the organic compound layer. With one feature. Further, in an organic EL device having at least an electrode and an organic compound layer on a substrate, a sealing film composed of the gas barrier resin substrate of the present invention is disposed so as to cover the electrode and the organic compound layer. Furthermore, it is preferable to apply the gas barrier resin substrate of the present invention as the substrate.

  The organic EL device has an organic compound layer such as a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer sandwiched between at least an electrode composed of an anode and a cathode. It has a formed configuration. Accordingly, one form of the organic EL device with improved gas barrier properties according to the present invention is formed on the substrate when a substrate with low moisture permeability such as glass is used as the substrate. The organic compound layer including the electrode and the light emitting layer is disposed and configured so as to be covered with the above-described gas barrier thin film laminate of the present invention, whereby the organic EL device can be sealed. FIG. 5 shows a structural cross-sectional view of this example of the sealing form of the organic EL device.

  In FIG. 5, reference numeral 2 denotes a glass substrate, on which an anode 4, an organic compound layer 5, and a cathode 6 are sequentially formed, and the gas barrier property of the present invention is applied so as to cover the organic compound layer and the cathode. The thin film laminate 7 is formed by, for example, an atmospheric pressure plasma method.

  As another form, an organic compound layer including an electrode and a light emitting layer formed on a substrate such as glass with low moisture permeability is disposed so as to cover the gas barrier resin substrate of the present invention. There is a form in which the organic EL device is sealed by bonding to a substrate such as glass on which these organic EL layers are formed. For the bonding, for example, there is an epoxy adhesive, and as the OLED sealing material, for example, those commercially available from Three Bond Co., Ltd. or Nagase ChemteX Co., Ltd. can be used.

  FIG. 6 is a cross-sectional view showing an example of an organic EL device formed on a glass substrate and sealed with the gas barrier resin substrate of the present invention.

  In FIG. 6, reference numeral 2 denotes a glass substrate. An anode 4, an organic compound layer 5 and a cathode 6 are sequentially formed on the glass substrate, and the gas barrier thin film laminate 3 and the resin base material of the present invention are covered so as to cover them. 1 has a structure in which a gas barrier resin base material composed of 1 is disposed and is adhered and sealed to the glass substrate 2 with an adhesive 9 around each organic EL layer.

  Further, as another form, after forming an organic compound layer including at least an electrode composed of an anode and a cathode and a light emitting layer sandwiched between the electrodes on the gas barrier resin substrate of the present invention, This is a method of sealing the organic EL device by disposing the gas barrier thin film laminate so as to cover these electrodes and the organic compound layer, and this embodiment is shown in FIG.

  In FIG. 7, the anode 4, the organic compound layer 5, and the cathode 6 sequentially formed on the gas barrier resin base material of the present invention in which the gas barrier thin film laminate 3 is formed on the resin base material 1 are shown in FIG. The form sealed by the gas barrier thin film laminate 3 is shown.

  In yet another embodiment, in an organic EL device in which an electrode composed of at least an anode and a cathode and an organic compound layer including a light emitting layer sandwiched between the electrodes are formed on the above-described gas barrier resin substrate of the present invention. Further, the gas barrier resin substrate of the present invention is disposed and bonded so as to cover these electrodes and the organic compound layer, and the organic EL device is sealed with two gas barrier resin substrates. This form is shown in FIG. In FIG. 8, the gas barrier thin film laminate 3 of the present invention is formed so as to cover the anode 4, the organic compound layer 5, and the cathode 6 sequentially formed on the resin base material 1 on which the gas barrier thin film laminate 3 is formed. The gas barrier resin base material composed of the resin base material 1 having the same is disposed, and the gas barrier resin base materials of the present invention are bonded and sealed around the organic EL layers by the adhesive 9.

  Alternatively, the electrode and the organic compound layer may be disposed so as to cover the electrode substrate and the organic compound layer with a low moisture-permeable material substrate such as glass, and may be bonded with an adhesive or the like as described above. This form is shown in FIG.

  In FIG. 9, the anode 4, the organic compound layer 5, and the cathode 6 are sequentially formed on the gas barrier resin base material composed of the gas barrier thin film laminate 3 and the resin base material 1, and have low moisture permeability so as to cover them. For example, a can body (lid) 8 made of glass or the like is covered, and an adhesive 9 is adhered around each organic EL layer to seal each organic EL layer. In these schematic views, lead wires and the like taken out from each electrode are omitted.

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

<< Production of gas barrier resin base material >>
[Production of Sample 101: Present Invention]
(Production of photocurable resin sheet)
Each additive shown below was mixed and the photocurable resin composition 1 was prepared.

<Additive 1>
Photocurable oligomer EP-0021 (Exemplary Compound 1 * 1) 100 parts by mass * 1) manufactured by Kyoeisha Chemical Co., Ltd. However, EP-0021 contains 30% by mass of methyl ethyl ketone in the composition. In addition, the average molecular weight of this photocurable oligomer is 2000, and dispersion degree Mw / Mn is 2.0.

<Additive 2>
Photopolymerization initiator (manufactured by KIP-150 Lamberti) 2 parts by mass The above additive 1 (photocurable oligomer) and additive 2 (photopolymerization initiator) are uniformly mixed to obtain photocurable resin composition 1. After preparing and coating this photocurable resin composition 1 on a polyethylene terephthalate film (thickness 0.3 mm) using a screen printer, this film was further dried at 100 ° C. for 30 minutes in a drying oven. Then, the photocurable resin sheet provided with a polymer film having a dry film thickness of 500 nm was prepared by standing at room temperature.

  In addition, although the surface of this photocurable resin sheet was touched with a finger, although the tack appeared on the surface, the fluidity of the polymer film was not recognized at room temperature (25 ° C.). Moreover, it was confirmed that this polymer film exhibits fluidity in a temperature range of 50 ° C to 100 ° C.

(Formation of gas barrier thin film laminate)
On the resin base material (polyester naphthalate film manufactured by Teijin DuPont Co., Ltd., thickness 125 μm), the prepared photocurable resin sheet is pressure-bonded to the resin base material using a pressing roll heated to 80 ° C. The gaps between the top and the bottom were filled with a polymer film that exhibited fluidity by heating. Then, the polymer film was cured by uniformly irradiating ultraviolet rays from the polyethylene terephthalate film side, and the polyethylene terephthalate film was peeled from the cured polymer film to obtain a cured polymer film 1.

  Next, using the atmospheric pressure plasma processing apparatus in which two electric fields having different frequencies shown in FIG. 2 are applied on the polymer film 1 formed as described above, the ceramic film 1 having a thickness of 100 nm ( A silicon oxide film) was formed.

<Mixed gas composition>
Discharge gas: Nitrogen gas 94.99 volume%
Thin film forming gas: tetraethoxysilane 0.01% by volume
Additive gas: Oxygen gas 5.0% by volume
<Film formation conditions>
1st electrode side Power supply type: A5
Frequency: 100kHz
Output density: 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature: 120 ° C
Second electrode side power supply type: B3
Frequency: 13.56MHz
Output density: 10 W / cm ² (the voltage Vp at this time was ² kV)
Electrode temperature: 90 ° C
Next, the polymer film 1 and the ceramic film 1 are alternately laminated on the ceramic film 1 formed as described above, and resin base material / polymer film 1 / ceramic film 1 / polymer film 1 / ceramic film 1 / polymer film 1 / A gas barrier thin film laminated body (each film thickness: polymer film 1 = 500 nm, ceramic film 1 = 100 nm) having a laminated structure of seven layers of ceramic film 1 / polymer film 1 was formed, and sample 101 was obtained.

[Preparation of Sample 102: Present Invention]
A sample 102 was produced in the same manner as in the production of the sample 101 except that the ceramic film 1 was changed to the ceramic film 2 formed by the following formation method.

  A resin base material having the polymer layer 1 is mounted in a chamber of a magnetron sputtering apparatus, silicon nitride is used as a target, and a silicon oxynitride thin film is formed to a thickness of 100 nm under the following film formation conditions. A ceramic film 2 was formed.

(Deposition conditions)
Deposition pressure: 2.5 × 10 ⁻¹ Pa
Argon gas flow rate: 20 sccm
Nitrogen gas flow rate: 9sccm
Frequency: 13.56MHz
Electric power: 1.2kW
Next, the polymer film 1 and the ceramic film 2 are alternately laminated on the formed ceramic film 2, and resin base material / polymer film 1 / ceramic film 2 / polymer film 1 / ceramic film 2 / polymer film 1 are laminated. A sample 101 was obtained by forming a gas barrier thin film laminate (respective film thicknesses: polymer film 1 = 500 nm, ceramic film 2 = 100 nm) having a laminated structure of 7 layers / ceramic film 2 / polymer film 1.

[Production of Sample 103: Comparative Example]
A sample 103 was prepared in the same manner as the sample 101 except that the polymer film 1 was changed to the polymer film 2 formed by the following forming method.

(Formation of polymer film 2)
To a trifunctional isocyanuric acid ethylene oxide modified triacrylate (Aronix M-315: manufactured by Toagosei Co., Ltd.), a radical initiator (Irgacure 651: manufactured by Ciba Geigy) was added in an amount corresponding to 1% by mass of Aronix M-315, and an appropriate amount. The photocurable resin composition 2 for forming the polymer film 2 was prepared by dissolving in the above solvent. This photocurable resin composition 2 was liquid at room temperature (25 ° C.).

  Next, the photocurable resin composition 2 was wet-coated on a resin substrate (polyester naphthalate film manufactured by Teijin DuPont, thickness 125 μm) using a die coater, and then the solvent was removed in the drying step. The polymer film 2 was formed by curing by UV irradiation.

  The ceramic film 1 is formed on the formed polymer film 2 in the same manner as the method for producing the ceramic film 1 of the sample 101, and then the polymer film 2 and the ceramic film 1 are alternately laminated on the ceramic film 1. Gas barrier thin film laminate comprising 7 layers of resin base material / polymer film 2 / ceramic film 1 / polymer film 2 / ceramic film 1 / polymer film 2 / ceramic film 1 / polymer film 2 (each film thickness: Polymer film 1 = 500 nm, ceramic film 2 = 100 nm) were formed, and sample 103 was obtained.

[Production of Sample 104: Comparative Example]
Sample 104 was prepared in the same manner as in the preparation of Sample 103 except that pentaerythritol triacrylate (NK ester A-TMM-3 manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of Aronix M-315 as the photocurable resin. Was made.

[Production of Sample 105: Comparative Example]
In the production of the sample 101, the sample 105 was produced in the same manner as in the production of the sample 101 except that the polymer film 1 was not formed and ten ceramic films (thickness: 100 nm) were stacked to make the total ceramic film thickness 1000 nm. .

<< Evaluation of gas barrier resin base material >>
[Evaluation 1: Visual evaluation of curl resistance]
The gas barrier resin base material having each of the gas barrier thin film laminates prepared above was cut out on a strip of 100 mm × 10 mm and left on a flat table in an environment of 23 ° C. and 50% RH for 100 hours. The raised heights of the four corners were measured several times (4 to 5 times), the average value was calculated, and the curl resistance was evaluated according to the following criteria.

○: 0 mm or more and less than 5 mm Δ: 5 mm or more and less than 10 mm ×: 10 mm or more [Evaluation 2: Evaluation of dark spot resistance by organic EL device production]
The resin base material with each gas barrier thin film laminate produced above is wound 20 times each on a 100 mmφ cylinder on the surface on which the ceramic film and the polymer film are attached, and then the display substrate for organic EL. A transparent electrode constituting the anode electrode, a hole transporting layer having a hole transporting property, a light emitting layer, an electron injection layer, and a back electrode serving as a cathode are respectively laminated according to a known method, and further, Each formed layer was sealed with a glass can bonded with an epoxy-based sealing material to prepare organic EL devices 1 to 5.

  Next, after each organic EL device was stored in an environment of 60 ° C. and 90% RH for 300 hours and 500 hours, 50 times magnified photographs were taken to visually observe the occurrence of dark spots. According to the evaluation of dark spot resistance.

○: No generation of dark spots was observed even after 500 hours Δ: Generation of dark spots was not observed after storage for 300 hours, but slight generation of dark spots was observed after storage for 500 hours ×: 300 hours Table 1 shows the results obtained with the above-mentioned quality that is unpractical for practical use.

  As is apparent from the results shown in Table 1, it can be seen that the gas barrier resin substrate of the present invention has a lower degree of curl and a lower stress of the formed gas barrier thin film laminate than the comparative example.

  Moreover, the organic EL device to which the gas barrier resin substrate of the present invention is applied as a sealing film is stored for a long time under high temperature and high humidity after bending the gas barrier resin substrate and applying external stress to the comparative example. It can be seen that the sealing properties are excellent afterwards and the generation of dark spots due to cracks in the thin film is suppressed. Furthermore, in evaluation 2 (evaluation of dark spot resistance by organic EL device production), instead of the glass can, the gas barrier resin base material having each of the produced gas barrier thin film laminates was used to seal the organic EL device. However, in the organic EL device of the present invention, similar to the above, after the gas barrier resin substrate was bent and subjected to external stress, the same excellent sealing characteristics even after storage for a long time under high temperature and high humidity We were able to confirm that we have.

It is the schematic which showed an example of the atmospheric pressure plasma discharge processing apparatus of the jet system useful for this invention. It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus of the system which processes a base material between counter electrodes useful for this invention. It is a perspective view which shows an example of the structure of the electroconductive metal base material of a roll rotating electrode, and the dielectric material coat | covered on it. It is a perspective view which shows an example of the structure of the electroconductive metal preform | base_material of a rectangular tube type electrode, and the dielectric material coat | covered on it. It is sectional drawing which shows an example of the sealing form of an organic EL device. It is sectional drawing which shows another example of the sealing form of an organic EL device. It is sectional drawing which shows an example of the organic EL device formed on the gas barrier resin base material of this invention, and sealed with the gas barrier thin film laminated body of this invention. It is sectional drawing which shows an example of the organic EL device formed on the gas barrier resin base material of this invention, and sealed with the gas barrier resin base material of this invention. It is sectional drawing which shows an example of the organic EL device formed on the gas-barrier resin base material of this invention, and sealed with the glass can body.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin base material 2 Glass substrate 3, 7 Gas barrier thin film laminated body 4 Anode 5 Organic compound layer 6 Cathode 8 Can body 9 Adhesive 10, 30 Plasma discharge processing apparatus 11 1st electrode 12 2nd electrode 21 1st power supply 32 Discharge Space 35 Roll rotating electrode 35a Roll electrode 35A Metal base material 35B Dielectric 36 Square tube type fixed electrode group 40 Electric field applying means 41 First power supply 42 Second power supply 50 Gas supply means 51 Gas generator 52 Air supply port 53 Exhaust port 60 Electrode temperature adjusting means G Thin film forming gas G ° Plasma state gas G ′ Treatment exhaust gas

Claims (10)

In the gas barrier thin film laminate each having at least one ceramic film and polymer film, at least one layer of the polymer film is photopolymerized with a photocurable resin having an ethylenic double bond at the terminal or side chain of the molecule It is formed by curing a photo-curable resin composition having an initiator as a main component and exhibiting non-fluidity at 25 ° C. and exhibiting fluidity in a temperature range of 50 ° C. to 100 ° C. A gas barrier thin film laminate. The gas barrier thin film laminate according to claim 1, wherein the photocurable resin contains epoxy (meth) acrylate as a main component. The epoxy (meth) acrylate is obtained by (meth) acrylicizing both ends or side chains of an epoxy having a bisphenol structure with (meth) acrylic acid, having an average molecular weight of 1,000 to 10,000, and a weight average molecular weight. The gas barrier thin film laminate according to claim 2, wherein when Mw and the number average molecular weight are Mn, the dispersity Mw / Mn is 1.5 to 3.0. The gas barrier thin film laminate according to any one of claims 1 to 3, wherein at least one layer of the ceramic film is mainly composed of metal oxide, metal nitride oxide, or metal nitride. The gas barrier thin film laminate according to any one of claims 1 to 4, wherein the ceramic film has a compressive stress of more than 0 MPa and not more than 20 MPa. The gas barrier thin film laminate according to any one of claims 1 to 5, wherein the ceramic film is formed by an atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied. A gas barrier resin base material comprising the gas barrier thin film laminate according to any one of claims 1 to 6 on at least one surface of the resin base material. An organic electroluminescence device having a sealing film disposed on a substrate so as to cover at least an electrode and an organic compound layer, and covering the electrode and the organic compound layer. 6. An organic electroluminescence device, which is the gas barrier thin film laminate according to any one of 6 above. The substrate has at least an electrode and an organic compound layer, a sealing film is disposed so as to cover the electrode and the organic compound layer, and the sealing film and the substrate are bonded together and sealed. The stopped organic electroluminescent device, wherein the sealing film is the gas barrier resin substrate according to claim 7. The organic electroluminescence device according to claim 8 or 9, wherein the base material is the gas barrier resin base material according to claim 7.

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