JP4373270B2 - Gas barrier film, and liquid crystal display element and EL display element formed using the same - Google Patents

Description

  The present invention relates to a gas barrier film suitable for various applications that require high gas barrier properties. In particular, the gas barrier film of the present invention is suitable for use as a substrate for a transparent touch panel, a liquid crystal display element, an organic EL display element or an EL display element of an inorganic EL display element, or a sealing substrate.

  For foods and pharmaceuticals that have a risk of deterioration in quality due to the ingress of oxygen or moisture from the outside, packaging using a gas barrier packaging material has been performed for a long time. Recently, in the field of electronic components and various devices, gas barrier properties have been demanded. The demand for gas barrier properties is not limited to simple packaging of products and semi-finished products, but outside the products themselves. The occupying member is also required.

  Conventionally, glass substrates were often used as support substrates for display (display) elements such as liquid crystal display elements and EL display elements, but in order to eliminate the disadvantages of glass substrates that are heavy, hard and easy to break, Plastic substrates have been proposed. However, the plastic substrate solves the disadvantages of the glass substrate, but has a poor gas barrier property as compared with the glass substrate, and it is impossible to maintain the performance of the display element for a long time.

  Taking an organic EL element, which is one of the display elements, as an example, there is a problem that the luminous performance deteriorates when the illuminant comes into contact with moisture or oxygen, but the plastic substrate has insufficient flatness, pinholes or protrusions. Therefore, even if a process for imparting gas barrier properties is performed, the resulting gas barrier properties are insufficient, causing dark spots that do not emit light. Moreover, in order to manufacture an organic EL display element, it is usually necessary to form several layers through a process in which high temperatures cannot be avoided. Therefore, even a plastic substrate requires heat resistance, Even when used, it is affected by potential and temperature rise. Therefore, when a plastic substrate is used, it is difficult to say that the function of light emission and light modulation of the display element is stable.

  Conventionally, for the purpose of imparting gas barrier properties to a plastic substrate, a vapor deposition layer made of an inorganic compound is used as a first layer on a base material made of a polymer resin, and a water-soluble polymer and (a) one or more metal alkoxides are used. And a hydrolyzate thereof or (b) an aqueous solution containing at least one of tin chloride, or a coating agent mainly composed of a water / alcohol mixed solution, and a gas barrier film formed by heating and drying is laminated as a second layer. A gas barrier laminate film has been proposed. (Patent Document 1).

Moreover, on the base material made of the polymer resin composition, the vapor deposition layer made of an inorganic compound is used as the first layer, and one or more kinds of metal alkoxide or a hydrolyzate thereof, and at least two or more isocyanate groups in the molecule. There has also been proposed a gas barrier laminated film obtained by laminating a coating layer obtained by applying a coating agent mainly composed of a mixed solution with an isocyanate compound, and drying by heating as a second layer. (Patent Document 2).
Japanese Patent Laid-Open No. 7-164591 JP 7-268115 A

However, the gas barrier laminated films disclosed in Patent Document 1 and Patent Document 2 described above are only intended for packaging of foods or pharmaceuticals, and the water vapor transmission rate and the oxygen transmission rate are also provided for the gas barrier properties. All of these are the best, about 0.1 cc / m ² / day · atm, and are not sufficient as a gas barrier film for use in a display element. There is no mention of the flatness of the plastic substrate.

  The inventors have examined that the surface of the plastic substrate has an Ra (arithmetic mean roughness) of more than 6 nm and a PV (maximum height difference) of more than 60 nm. An inorganic compound having a film thickness of 1 μm or less on such a plastic substrate because it has projections as high as (0.5 μm) and is very rough when viewed microscopically. It was found that when the thin film was formed as a gas barrier layer, pinholes were generated in the gas barrier layer due to protrusions on the surface of the plastic substrate, which could cause a decrease in gas barrier properties.

  In the present invention, while using a plastic substrate as the support substrate, the gas barrier property with high gas barrier performance is provided, in which the projections on the surface of the plastic substrate eliminate the inconvenience that causes the unevenness of the gas barrier layer and the generation of pinholes. It is an object of the present invention to provide a substrate having a high gas barrier property that is optimal for use in a display element.

  As a result of investigations by the inventors, it has been found that a gas barrier property is markedly improved by laminating a gas barrier thin film on a plastic substrate via a thin film layer made of silicon oxycarbide or silicon oxynitride carbide. The present invention has been achieved based on the above.

1st invention which solves a subject is laminated | stacked the gas barrier layer which has the laminated structure which consists of a several layer on the single side | surface or both surfaces of a base material sheet, Among the several layers which comprise the said gas barrier layer, At least the layer on the side in contact with the substrate sheet, Ri inorganic compound layer der of an oxide of silicon carbide or oxynitride carbide, the gas barrier layer is, from the side in contact with the base sheet, the oxide silicon carbide or A laminated structure in which an inorganic compound layer made of silicon oxynitride carbide, an organic resin layer, and an inorganic compound layer are sequentially laminated, or an inorganic compound layer made of silicon oxycarbide or silicon oxynitride carbide, an inorganic compound layer, or an organic resin layer And having a laminated structure in which inorganic compound layers are laminated in order, and the organic resin layer is made of cardo resin, A cardo resin containing an epoxy resin having two or more epoxy groups in one molecule as an essential component, and containing a resin having a fluorene skeleton derived from a bisphenol compound represented by the general formula (1) The present invention relates to a gas barrier film characterized by being.

According to a second invention, in the first invention, the inorganic compound layer is made of any one of an inorganic oxide, an inorganic oxynitride, an inorganic nitride, an inorganic oxide carbide, an inorganic oxycarbonitride, or a metal. The present invention relates to a gas barrier film characterized by being.

According to a third invention, in any one of the first to second inventions, the surface roughness Ra of the outermost surface of the gas barrier layer is 6 nm or less, and the maximum height difference PV is 60 nm or less. It relates to a gas barrier film.

In the fourth invention , a liquid crystal layer is sandwiched and sealed between both the back substrate and the front substrate in which the electrode layer and the alignment film are sequentially laminated, and the back substrate or / And the front substrate is a gas barrier film according to any one of the first to third inventions.

In the fifth invention, a substrate, an electrode layer, a light emitting layer, a counter electrode layer, and a sealing layer are sequentially laminated, and the substrate and / or the sealing layer is any one of the first to third inventions. The present invention relates to an EL display element which is a gas barrier film.

  According to the first invention, since the inorganic compound layer made of silicon oxide carbide or silicon oxynitride carbide and the gas barrier layer made of other layers are laminated on one side or both sides of the base sheet, the gas barrier property is high. In addition, it is possible to provide a gas barrier film having high adhesion of the gas barrier layer.

The gas barrier layer is, inorganic compound layer formed of an oxide of silicon carbide or oxynitride carbide, if it has the organic resin layer, and a laminated structure comprising an inorganic compound layer, based on the inorganic compound layer on the surface barrier Due to the presence of the organic resin layer, it is possible to provide a gas barrier film having further enhanced properties.
When the gas barrier layer has a laminated structure composed of an inorganic compound layer, an organic resin layer, and an inorganic compound layer on an inorganic compound layer made of silicon oxycarbide or silicon oxynitride carbide , an organic resin The gas barrier property based on the inorganic compound layer on the lower layer side is enhanced by the layer, and the gas barrier property can be further provided by the inorganic compound layer on the organic resin layer.
Since the organic resin layer is made of cardo resin, it is possible to provide a gas barrier film in which the gas barrier property of the inorganic compound layer under the organic resin layer is further enhanced.

According to 2nd invention , in addition to the effect of 1st invention, the gas barrier film comprised with the familiar raw material which can obtain an inorganic compound layer easily can be provided.

According to the third invention , in addition to the effects of any one of the first and second inventions, the surface roughness and the maximum height difference of the outermost surface of the gas barrier layer are defined. Can be provided. High flatness makes it particularly suitable as a substrate for constituting an EL element.

According to the fourth invention , by using the gas barrier film having the effects of any one of the first to third inventions as the back substrate or / and the front substrate, display performance can be maintained for a long time. The liquid crystal display element which can be provided can be provided.

According to the fifth invention , it is possible to maintain the display performance for a long time by using the gas barrier film having the effects of any one of the first to third inventions as the substrate or / and the sealing layer. An EL display element can be provided.

  FIG. 1 is a view showing a basic laminated structure of a gas barrier film of the present invention. 2 and 3 are views showing a preferred laminated structure of the gas barrier film of the present invention.

  As shown in FIG. 1 (a), the gas barrier film 1 of the present invention most basically has an inorganic compound layer 3a composed of a thin film of silicon oxycarbide or silicon oxynitride carbide on one side of a base sheet 2. It has a laminated structure in which the gas barrier layers 3 made of a plurality of layers having the inorganic compound layer 3a are laminated. As shown in FIG. 1 (b), the gas barrier film 1 of the present invention comprises a thin film of silicon oxycarbide or silicon oxynitride carbide on one side of the base sheet 2 (upper side in FIG. 1 (b)). An inorganic compound layer 3a is laminated, a gas barrier layer 3 composed of a plurality of layers having the inorganic compound layer 3a is laminated, and the opposite surface of the substrate sheet 2 (the lower side in FIG. 1B) Also, an inorganic compound layer 3a ′ made of a thin film of silicon oxycarbide or silicon oxynitride carbide is laminated, and a gas barrier layer 3 ′ made of a plurality of layers having the inorganic compound layer 3a ′ is laminated. It may have a structure.

  As shown in FIG. 2 (a), the gas barrier film 1 of the present invention more specifically is an inorganic material made of silicon oxide or silicon oxynitride carbide on one side of the base sheet 2 from the base sheet 2 side. It is preferable to have a laminated structure in which the gas barrier layer 3 composed of three layers in which the compound layer 3a, the organic resin layer 31, and the inorganic compound layer 32 are laminated in order, and such a gas barrier layer. The two layers 3 and 3 ′ may have a laminated structure in which the base sheet 2 is sandwiched. That is, as shown in FIG. 2B, from the lower surface side of the figure, the inorganic compound layer 32 ′, the organic resin layer 31 ′, the inorganic compound layer 3a ′, the base sheet 2, the inorganic compound layer 3a, and the organic resin layer 31. And the inorganic compound layer 32 are laminated in this order.

  Alternatively, as shown in FIG. 3 (a), the gas barrier film 1 of the present invention has an inorganic compound layer 3a made of silicon oxide carbide or silicon oxynitride carbide on one side of the base sheet 2 from the base sheet 2 side, It is also preferable to have a laminated structure in which the gas barrier layer 3 composed of four layers in which the inorganic compound layer 32a, the organic resin layer 31, and the inorganic compound layer 32b are laminated in order, and such a gas barrier. The two layers of the conductive layers 3 and 3 ′ may have a laminated structure in which the base sheet 2 is sandwiched. That is, as shown in FIG. 3B, from the lower surface side of the figure, the inorganic compound layer 32b ′, the organic resin layer 31 ′, the inorganic compound layer 32a ′, the inorganic compound layer 3a ′, the base sheet 2, the inorganic compound layer. 3a, the inorganic compound layer 32a, the organic resin layer 31, and the inorganic compound layer 32b are laminated in this order.

  As the base material sheet 2, what was comprised with various resin can be used. For example, for crystalline resins, thermoplastic resins such as polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, or syndiotactic polystyrene are used. For thermosetting resins, polyphenylene sulfide, polyether ether ketone, Fluorine resin, polyether nitrile, or the like can be cited as a preferred resin constituting the base sheet 2. Alternatively, as the resin constituting the base sheet 2, a thermoplastic resin such as polycarbonate, modified polyphenylene ether, polycyclohexene, or polynorbornene-based resin is used as an amorphous resin, and polysulfone or polysulfone is used as a thermosetting resin. Ethersulfone, polyarylate, polyamideimide, polyetherimide, thermoplastic polyimide, or the like can be cited as a preferred resin. Among them, since polycarbonate has low water absorption, the base sheet 2 formed using this is preferable because it has a low coefficient of humidity expansion, and has a high glass transition point, deflection temperature under load, and maximum continuous use temperature. The thickness of the base sheet 2 made of such a material is not particularly limited, but is preferably about 60 μm to 2 mm.

  When the gas barrier film 1 is used for an application that preferably has transparency, the base sheet 2 is preferably transparent. Here, the “transparent” transparency is used in the meaning including both colorless transparency and colored transparency. In addition, also when each layer demonstrated below uses the gas-barrier film 1 for the use where it is preferable to have transparency, it is preferable that all layers also have transparency. For example, in a transmissive display element, it is preferable to use a transparent substrate as both the front and back substrates. In a reflective display element, at least a transparent substrate is used as a transparent substrate. It is preferable.

  Prior to laminating the gas barrier layer 3 on the base sheet 2, an adhesive layer (adhesion layer or adhesion improving layer) is laminated between the base sheet 2 and the gas barrier layer 3. Or the process for adhesiveness improvement may be given to the surface of the base material sheet 2. FIG.

As the adhesive layer, an anchor coating agent layer can be formed by vapor deposition of an organic compound or wet coating. The anchor coating agent layer is made of, for example, one or a combination of two or more of an organic titanium anchor coating agent such as an alkyl titanate, an isocyanate anchor coating agent, a polyethyleneimine anchor coating agent, or a polybutadiene anchor coating agent. It can be formed by coating with a known coating method such as roll coating, gravure coating, knife coating, dip coating, or spray coating, and after coating, by drying and removing the solvent, diluent, etc., by wet coating In this case, the coating amount is preferably about 0.1 g / m ^{2 to} 5 g / m ² (dry state).

  A more preferable adhesive layer is the inorganic compound layer 3a made of silicon oxide carbide or silicon oxynitride carbide. The inorganic compound layer (hereinafter sometimes simply referred to as an adhesive inorganic compound layer) 3a made of silicon oxycarbide or silicon oxynitride carbide is in addition to improving the adhesion between the base sheet 2 and the gas barrier layer 3. In addition to providing heat resistance, chemical resistance, and weather resistance to the entire gas barrier film 1, even if there is a defect site in another layer laminated on the adhesive inorganic compound layer 3a, it is filled. This improves the gas barrier property.

  The inorganic compound layer 3a made of silicon oxide carbide is made of a material containing silicon oxide and carbon, and the following organic silicon compound is used as a raw material in the presence of nitrogen gas, oxygen gas, argon gas, helium gas, or the like. It can be formed using a plasma chemical vapor deposition method, preferably a low temperature plasma chemical vapor deposition method. Examples of the organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, and phenylsilane. , Vinyltriethoxysilane, tetramethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc., or others can be used, and tetramethoxysilane ( TMOS) or hexamethyldisiloxane (HMDSO) is preferably used.

  The inorganic compound layer 3a made of silicon oxide carbide is formed by chemical vapor deposition using various alkoxysilanes. Examples of the alkoxysilane that can be used include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, Tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetra-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxide Shishiran, dimethyl-butoxy silane, methyl dimethoxy silane, methyl diethoxy silane or hexyl trimethoxysilane, and the like. When the silicon oxide carbide thin film is formed by the CVD method, the carbon derived from the raw material is contained in the thin film, so that it is considered that the adhesion with the base material sheet 2 made of an organic material is good.

The inorganic compound layer 3a made of silicon oxynitride carbide uses a nitrogen-containing organosilicon compound gas such as organosilazane, and plasma chemical vapor deposition in the presence of nitrogen gas, oxygen gas, argon gas, helium gas or the like. Preferably, it can be formed using a low temperature plasma chemical vapor deposition method. Examples of the nitrogen-containing organosilicon compound include hexamethyldisilazane ((CH ₃ Si) ₂ NH), 4-aminobutyltriethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, 2 -Aminoethylaminomethylbenzyloxydimethylsilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, N- (aminohexyl) aminopropyltrimethoxysilane, aminomethyltrimethylsilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 3- (m-aminophenoxy) propyltrimethoxysilane, Nophenyltrimethoxysilane, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropylmethylbis (trimethylsiloxy) silane, 3- Aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylpentamethyldisiloxane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, di-nbutyltetramethyldisilazane, N, N-diethylaminotrimethylsilane, (diethylamino) trimethylsilane, (diisopropylamino) trimethylsilane, (N, N-diethylamino) dimethylsilane, (N, N-dimethylamino) triethylsilane, or (N, N-di-) Chiruamino) trimethylsilane, and the like.

  The thickness of the adhesive inorganic compound layer 3a made of silicon oxycarbide or silicon oxynitride carbide is preferably 1 nm to 1000 nm, more preferably 5 nm to 300 nm. When the thickness of the inorganic compound layer 3a is thinner than the preferable thickness range, the effect of improving the adhesion is poor. In addition, when the thickness is larger than the preferable thickness range, the effect of improving the adhesion cannot be expected. However, since the inorganic compound layer 3a also has the characteristics of a gas barrier layer, when aiming to improve the gas barrier property. The thickness may be increased beyond the preferable thickness range.

  In addition to the inorganic compound layer 3a, the gas barrier layer 3 can be constituted by selecting and using various inorganic compounds or organic compounds, particularly polymers having gas barrier properties. Preferably, the gas barrier layer 3 has a laminated structure in which the adhesive inorganic compound layer 3a, the organic resin layer 31, and the inorganic compound layer 32 are sequentially laminated as described with reference to FIG. Alternatively, the adhesive inorganic compound layer 3a, the inorganic compound layer 32a, the organic resin layer 31, and the inorganic compound layer 32b are preferably configured to have a laminated structure in this order.

  The inorganic compound layer 32 (including 32a and 32b) is composed of any one of an inorganic oxide, an inorganic oxynitride, an inorganic nitride, an inorganic oxycarbide, an inorganic oxycarbonitride thin film, or a very thin metal thin film. Therefore, the gas barrier film 1 has a high function as a gas barrier layer for blocking water vapor permeation or oxygen permeation. The inorganic compound layer 32 is preferably formed by physical vapor deposition (physical vapor deposition) such as vacuum vapor deposition, sputtering, or ion plating, or by chemical vapor deposition (plasma vapor deposition). can do.

  The inorganic compound constituting the inorganic compound layer 32 is preferably one containing at least one selected from silicon, aluminum, magnesium, titanium, tin, indium, or cerium. For example, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, or indium alloy oxide is preferable. As the inorganic oxynitride, silicon oxynitride is preferable, and as inorganic nitride Is preferably silicon nitride, aluminum nitride, or titanium nitride, and the metal of the substrate thin film is preferably aluminum, silver, tin, chromium, nickel, or titanium.

  The thickness of the inorganic compound layer 32 varies depending on the inorganic compound used, but is preferably in the range of 5 nm to 5000 nm, more preferably 5 nm to 500 nm. In the case of a thin film obtained by vapor deposition of aluminum oxide or silicon oxide, the thickness is preferably in the range of 10 nm to 300 nm. If the thickness of the inorganic compound layer 32 is thinner than the preferred thickness range, the gas barrier property against water vapor, oxygen gas, etc. is reduced. If the thickness is larger than the preferred thickness range, the inorganic compound layer 32 is formed. In the subsequent step, a decrease in gas barrier properties against water vapor, oxygen gas, etc. is observed due to cracks in the inorganic compound layer 32, etc., which is not preferable. The inorganic compound layer 32 is not necessarily limited to a single layer, and may be a laminate of two or more layers. In this case, the same materials may be combined or different materials may be combined. Also good. The materials constituting the adhesive inorganic compound layer 3a and the method for forming the layer 3a using these materials can be applied to the inorganic compound layer 32 as they are.

  The inorganic compound layer 32 is formed by using an inorganic oxide, an inorganic nitride, an inorganic oxynitride or a metal as a raw material and heating them to deposit them on a substrate by introducing oxygen gas into them. Oxidation reaction vapor deposition method to oxidize and deposit on substrate, using these as target raw material, sputtering method to deposit on substrate by introducing argon gas and oxygen gas and sputtering, or plasma gun on these It is possible to use an ion plating method in which the generated plasma beam is heated and vapor-deposited on a substrate. In addition, when a silicon oxide vapor deposition film is formed, plasma chemistry using an organosilicon compound as a raw material is possible. Vapor phase epitaxy can be used.

  When the inorganic compound layer 32 is formed of a silicon oxide thin film, it can be formed by using a low temperature plasma chemical vapor deposition method using the following organic silicon compound as a raw material. Examples of the organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, and phenylsilane. , Vinyltriethoxysilane, tetramethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc., or others can be used, and tetramethoxysilane ( TMOS) or hexamethyldisiloxane (HMDSO) is preferably used. In order to form the inorganic compound layer 32 with a silicon oxide carbide thin film, the same material and method as those used when the adhesive inorganic compound layer 3a is formed of silicon oxide carbide may be used. Further, in order to form the inorganic compound layer 32 with a thin film of silicon oxynitride carbide, the same material and method as those used when the adhesive inorganic compound layer 3a made of silicon oxynitride carbide is formed may be used.

  By the way, when using a gas barrier film as a support substrate of a display element, the flatness is required to be very high. This is because, in a display element, a display layer having a shutter function or a light emitting function corresponding to an electric signal is often formed between a pair of electrodes, and these electrodes and the display layer are formed on a supporting substrate. This is because it is usually formed on the basis of the surface, and if the planarity of the support substrate is insufficient, the formation accuracy of the electrodes and the display layer is lowered. In particular, in the case of an organic EL element, the thickness of the fluorescent light-emitting layer sandwiched between a pair of electrodes is about 20 nm to 30 nm.

  Therefore, in the present invention, the gas barrier film 1 in which the adhesive inorganic compound layer 3a made of silicon oxycarbide or silicon oxynitride carbide, the organic resin layer 31, the inorganic compound layer 32, and the like are laminated on the base sheet 2. The surface roughness of the outermost surface on the side where the base sheet 2 is laminated is preferably 6 nm or less, and the maximum height difference PV is preferably 60 nm or less. By ensuring such flatness, the display element It is possible to provide a gas barrier film 1 that is suitable for use as a support substrate, and particularly suitable for use as a substrate for constituting an EL element.

  In order to match the flatness of the gas barrier film 1 of the present invention with the above-mentioned definition, the adhesive inorganic compound layer 3a, the organic resin layer 31 or the inorganic compound layer 32 laminated on the base sheet 2 is very simply described. Any of the above may be increased. Of these layers, the adhesive inorganic compound layer 3a and the inorganic compound layer 32 are preferably formed by a vapor phase method. Therefore, it is not always preferable to increase the thickness, and the thickness of the organic resin layer 31 is taken into consideration. Alternatively, for the formation of the organic resin layer 31, a resin that can be easily planarized is preferably used.

  The organic resin layer 31 can be preferably formed using a resin having a high gas barrier property. For example, polyvinyl alcohol (PVA) or ethylene-vinyl alcohol copolymer (EVOH) known as a gas barrier coating material is used. Or a mixture thereof, or a crosslinking agent such as an aromatic acid ester, aromatic polyamide, or metal salt added thereto, or a crosslinked structure by adding an inorganic filler, polyamide, PVA Alternatively, a dispersion in which a layered silicate (clay mineral such as montmorillonite) as ultrafine particles of about 1 to 100 nm is dispersed in a resin such as EVOH can be used.

  As a more preferable material constituting the organic resin layer 31, (1) an addition product of an epoxy acrylate resin having a fluorene skeleton and a polybasic acid anhydride, (2) a polyfunctional acrylate monomer, (3) a polymerization initiator, and (4) A cardo resin (also called a cardo polymer) containing an epoxy resin having two or more epoxy groups in one molecule as an essential component can be given. When the organic resin layer 31 made of a cardo polymer is laminated on an inorganic compound layer formed by a sputtering method, an ion plating method, or a chemical vapor deposition method, a filling effect for defects such as fine pinholes in the inorganic compound layer is achieved. In addition to the effect that it can be promoted, there is an advantage that flattening is easy.

  The cardo polymer preferably contains a resin having a fluorene skeleton derived from a bisphenol compound represented by the following general formula (1).

(R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and may be the same or different from each other.

  Specific examples of the bisphenol compound represented by the general formula (1) include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl). ) Fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) ) Fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3) , 5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, etc. Bets can be, in addition to it is possible to use only one of these alone, or can be used in combination of two or more.

  The cardo polymer is derived from an epoxy (meth) acrylate resin obtained by reacting an epoxy group having two or more epoxy groups in one molecule with an unsaturated monocarboxylic acid and a polybasic acid anhydride. An epoxy (meth) acrylate acid adduct is preferable. In addition, the description of (meth) acrylate means an acrylate or a methacrylate.

  Specific examples of the epoxy resin used to form such an epoxy (meth) acrylate acid adduct include bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, and 2,2-bis (4 -Hydroxyphenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, bis (4-hydroxyphenyl) dimethylsilane, 4 , 4′-biphenol, bisphenols such as tetramethyl-4,4′-biphenol, polyfunctional phenols such as a condensation compound of phenol novolac, cresol novolac, naphthol or naphthalene diol and 1,4-bisxylenol, Some of these aromatic ring hydrogens All halogen atom include those having two or more epoxy groups in one molecule obtained by polyfunctional phenols substituted on an alkyl group having 1 to 4 carbon atoms is reacted with epichlorohydrin.

  This epoxy group can be made into an epoxy (meth) acrylate resin by reacting an epoxy resin with an equal amount of acrylic acid such as acrylic acid or methacrylic acid by a known method. Furthermore, this epoxy (meth) acrylate resin Can be made an addition product of an epoxy (meth) acrylate resin and a polybasic acid anhydride by reacting with a polybasic acid anhydride.

  Specific examples of polybasic acid anhydrides used in the formation of such addition products include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride. Acid, alicyclic acid anhydrides such as methylcyclohexene dicarboxylic acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bistrimellitic anhydride. Examples thereof include aromatic acid anhydrides such as glycerol tristrimellitic anhydride and biphenyltetracarboxylic dianhydride, and halogen acid anhydrides such as het anhydride and tetrabromophthalic anhydride. Further, the epoxy resin, acrylate, and acid anhydride may be one kind or a mixture of two or more kinds.

  Among the epoxy (meth) acrylate acid adducts thus obtained, in the present invention, as seen in JP-A-60-152091, JP-A-6-1938, JP-A-8-146111. In addition, it is preferable that the organic resin layer 31 contains a resin having a carboxysyl group and a photopolymerizable unsaturated group in the same molecule and having a weight average molecular weight of 1000 or more. Specifically, an acid adduct of epoxy acrylate having a fluorene skeleton, such as V259M or V301M manufactured by Nippon Steel Chemical Co., Ltd., or a cresol novolac type epoxy acrylate manufactured by Nippon Kayaku Co., Ltd. Can be mentioned.

  The epoxy acrylate resin having a fluorene skeleton is preferably one obtained by reacting an epoxy resin obtained from 9,9-bis (4-hydroxyphenyl) fluorene with acrylic acid.

  Further, as the above-mentioned polyfunctional acrylate monomer used in the present invention, specifically, addition polymerization having a boiling point of 100 ° C. or higher at normal pressure and having at least two ethylenically unsaturated groups in one molecule. What is a compound is mentioned. Such materials include those obtained by combining a polyhydric alcohol and an α, β-unsaturated carboxylic acid, such as diethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol diester. (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,3-propanediol (meth) acrylate, 1,3-butanediol (meth) acrylate, pentaerythritol tetra (meta ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and other polyfunctional acrylates and corresponding polyfunctional methacrylates, 2,2-bis (4-acryloxydiethoxyphenyl) ) A mixture of propane, 2,2-bis (4-methacryloxydipentaethoxysiphenyl) propane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane (made by Shin-Nakamura Chemical Co., Ltd., trade name; BEP-500) and the like, and those obtained by adding an α, β-unsaturated carboxylic acid such as acrylic acid or methacrylic acid to a glycidyl group-containing compound, such as trimethylolpropane triglycidyl ether (meth) acrylate, bisphenol A diester Glycidyl ether di (meth) acrylate, acrylic acid adduct of diglycidyl ether having a fluorene ring (manufactured by Nippon Steel Chemical Co., Ltd., trade name: ASF400), and unsaturated amides such as methylenebisacryloamide 1,6-hexamethylenebisacrylamide and the like, vinyl esters, such as Examples include divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate.

  As a polymerization initiator, if it is possible to generate a radical upon heating and polymerize the unsaturated group of the thermosetting resin having a cardo polymer and the polyfunctional acrylate monomer to form a cured film, a known thermal polymerization is possible. Although an initiator can be used, the 10-hour half-life temperature is preferably 80 ° C. or more and the curing temperature or less, and more preferably 100 ° C. or more and the curing temperature. Examples of the thermal polymerization initiator include t-butylcumyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butyldiperoxyphthalate.

  When the above polymerization is carried out by ultraviolet irradiation, instead of the thermal polymerization initiator. A photopolymerization initiator can also be used. As the photopolymerization initiator, known ones may be used alone or in combination of several kinds. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (Ciba Specialty Chemicals Co., Ltd., trade name: “Irgacure 907”), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Ciba Specialty Chemicals Co., Ltd.) Product name: “Irgacure 369”), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd., product name: “CGI819”), 2,4,6-trimethylbenzoyl Diphenylphosphine oxide (manufactured by BASF, trade name: “Lucirin TPO”) or 2,4-tri Roromechiru - (Pipuroroniru) -6-triazine (Japan Siber Hegner Co., Ltd., trade name; "triazine PP") and the like can be used.

  Furthermore, as the epoxy resin having two or more epoxy groups in one molecule, an epoxy compound having a hydrolyzable chlorine content of less than 1000 ppm is preferable. For example, tetramethyldiphenyl type epoxy resin manufactured by Yuka Shell Co., Ltd. YX4000, EOCN series (EOCN1020, 4400, 102S, 103S, 104S, etc.) manufactured by Nippon Kayaku Co., Ltd., cresol novolac type epoxy resin, phenol novolac type epoxy resin, liquid trifunctional epoxy manufactured by Toto Kasei Co., Ltd. Examples thereof include ZX-1542 as a resin and a polyfunctional epoxy compound in which a glycidyl group is introduced into a secondary hydroxyl group in an epoxy compound. In such an epoxy resin, the epoxy group reacts with the carboxyl group in the resin component containing the cardo polymer by heating or the like, and has a crosslinked structure in addition to the unsaturated group of the resin containing the cardo polymer and the polyfunctional acrylate. To form.

  When the organic resin layer 31 is formed using a card having a directional ring having a good affinity with the underlying inorganic compound, such as the cardo polymer, and having a bulky fluorene skeleton. The effect of flattening is particularly high, but even with a photocurable resin, if the curing is accelerated by heating, the effect of flattening is high, and it is used to constitute the organic resin layer 31. Can do.

  In addition, when the inorganic compound layer 32b is newly laminated on the surface flattened by the lamination of the organic resin layer 31, as described with reference to FIG. Therefore, the oxygen permeability and water vapor permeability of the newly formed inorganic compound layer 32b can be lowered. Of course, the newly laminated inorganic compound layer 32 b also serves to prevent volatilization of volatile components that may be inherent in the organic resin layer 31, so-called degassing prevention. The organic resin layer 31 and the lower or / and upper inorganic compound layer are those in which the inorganic compound layer is formed by an ion plating method, and the organic resin layer 31 is made of a material having a hydroxyl group. In the case where the hydrolysis reaction of the material constituting the inorganic compound layer is promoted to form a glass-like highly oxidized film, and the inorganic compound layer is formed by a sputtering method, fine pins of the inorganic compound layer are formed. The effect of filling holes and the like is promoted, and when the inorganic compound layer is formed by plasma chemical vapor deposition, the organic affinity between the inorganic compound layer and the organic resin layer 31 is improved. It is considered a thing.

In particular, as shown in FIG. 2B, the gas barrier film 1 of the present invention has a base sheet 2, an adhesive inorganic compound layer 3a, an inorganic compound layer 32a, an organic resin layer 31, and an inorganic compound layer 32b in this order. In the case of a laminated structure, the organic resin layer 31 flattens the pinholes generated in the lower inorganic compound layer 32a, and the upper inorganic compound layer 32b is a gas barrier for blocking the permeation of vapor and oxygen. The gas barrier film 1 of the present invention has an oxygen permeability of about 0.01 cc / m ² / day · atm or less, and a water vapor permeability of 0.01 g / m ² / day · An extremely high gas barrier property of about atm or less can be realized.

  The method for forming the organic resin layer 31 is not particularly limited, and a wet coating method such as a spin coating method, a spray coating method, a blade coating method, a dip coating method, a roller coating method, or a land coating method, or vapor deposition. Any dry coating method can be used. In the composition for coating used for coating, in the case of a thermosetting resin or a photocurable resin, an additive such as an antioxidant, an ultraviolet absorber, or a plasticizer, if necessary, in addition to the above-described components. In addition, an appropriate resin or additive may be added in order to improve the film formability and prevent the occurrence of pinholes in the resulting film. As the solvent, a suitable solvent such as diethylene glycol dimethyl ether, cyclohexanone, ethanol, chloroform, tetrahydrofuran, or dioxane can be used. The thickness of the organic resin layer 31 is preferably 0.05 μm to 10 μm, and the refractive index of the organic resin layer 31 is preferably 1.3 to 1.6.

  The gas barrier film 1 of the present invention is not limited to the one having the laminated structure already described with reference to each drawing, and the adhesion of the laminate in which the base sheet 2 and the adhesive inorganic compound layer 3a are laminated. The inorganic compound layer and the organic resin layer may be alternately laminated a plurality of times, such as first laminating the inorganic compound layer on the conductive inorganic compound layer 3a and then laminating the organic resin layer. By increasing the number of times, the gas barrier property can be further improved. The plurality of times is preferably 2 times or 3 times. The outermost layer is preferably an inorganic compound layer in order to prevent volatilization of volatile components from the organic resin layer.

  In the above description, the description has been made mainly on the case where each layer is laminated on one side of the base sheet 2 to give gas barrier properties. However, when each layer is formed only on one side, the gas barrier properties obtained due to the stress generated. The warp or curl of the film 1 is likely to occur. Therefore, for the purpose of eliminating the warp or curl of the gas barrier film 1 based on such a cause, the surface of the base sheet 2 opposite to the above-described layers (the lower surface side in each figure). In addition, an inorganic compound layer may be laminated. By doing in this way, the effect of preventing the degassing from the exposed surface of the base material sheet 2 which may occur when not laminating, in addition to eliminating or alleviating warping or curling of the obtained gas barrier film 1 Therefore, the gas barrier film 1 having higher performance and high stability of the performance can be obtained. The material of the inorganic compound layer laminated on the opposite surface is preferably silicon oxide, silicon nitride, or a composite thereof, but is not limited thereto, and may be any inorganic compound such as aluminum oxide or indium oxide. . Moreover, it is good also considering the raw material of the layer laminated | stacked on both surfaces of the base material sheet 2, thickness, a lamination order, etc. as a surface object across the base material sheet 2, ie, the same laminated structure on the front and back. As a practical and preferred laminated structure, for example, an adhesive inorganic compound layer made of silicon oxide carbide / an organic resin layer / an adhesive inorganic compound layer made of silicon oxide carbide / a base sheet / an adhesive inorganic compound made of silicon oxide carbide A laminated structure of an adhesive inorganic compound layer composed of layer / organic resin layer / silicon oxide carbide can be given.

  Since the gas barrier film 1 of the present invention has the laminated structure as described above, the gas barrier film 1 has very high gas barrier properties. Therefore, the gas barrier film 1 is used in packaging fields such as foods and pharmaceuticals, and particularly when high gas barrier properties are required. Of course, it can be applied as a material for use, but it can also be applied to packaging of electronic parts and various elements in addition to food and pharmaceutical applications. Furthermore, it can be applied to touch panels, liquid crystal display elements, organic EL elements, or inorganic EL elements. Suitable for use as a substrate for an element or the like, or a sealing substrate.

  For example, in a normal liquid crystal display element, each of two glass substrates in which a transparent electrode layer and an alignment film are sequentially laminated face each other so that the alignment films face each other, that is, the alignment film side faces inside, After creating a cell having a hollow inside by providing a gap and sealing the periphery, the inside void is filled with liquid crystal.

  The gas barrier film 1 of the present invention can be replaced with the glass substrate of the above liquid crystal display element, and a transparent electrode layer and an alignment film are formed on either side of the laminate (gas barrier film) as described above. Are prepared in order, and thereafter, a liquid crystal display element can be obtained in the same manner as in the normal liquid crystal display element. When importance is attached to the flatness of the surface to be laminated, it is preferable to laminate a transparent electrode layer and an alignment film on the outermost surface of the gas barrier layer 3 of the gas barrier film 1.

  The transparent electrode layer can be formed by forming a transparent conductive layer and then patterning by photoetching as necessary. The transparent conductive layer is preferably composed of indium tin oxide (hereinafter referred to as ITO) or indium zinc oxide (hereinafter referred to as IZO), such as vacuum evaporation, sputtering, or ion plating. It may be formed by a physical vapor deposition method, and the thickness is about 50 nm to 500 nm. If the thickness is smaller than this range, the conductivity is insufficient. If the thickness is larger than this range, the post-processing step proceeds. It is not preferable because a decrease in conductivity is observed due to cracks in the conductive film. Moreover, as an alignment film, what rubbed the polyimide resin thin film in the fixed direction can be illustrated.

  The EL element includes an organic EL element and an inorganic EL element. In principle, both of these elements are obtained by sequentially laminating a transparent electrode layer, a light emitting layer, and a counter electrode layer on a glass substrate. By replacing the gas barrier film 1 with a glass substrate and laminating these layers in order, an EL element can be obtained.

  The transparent electrode layer can be formed in the same manner as when the gas barrier film 1 of the present invention is used to form a liquid crystal display element.

Taking the organic EL element as an example, in the simplest case, the light emitting layer can be composed of only a light emitting layer composed of an organic fluorescent light emitting layer, but various layers may be added to improve the light emission efficiency. Therefore, the following variations can be illustrated by the positional relationship between the anode and the cathode. Note that the symbol “/” indicates that the left and right ones are stacked.
(1) Anode / light emitting layer / cathode (2) Anode / hole injection layer / light emitting layer / cathode (3) Anode / light emitting layer / electron injection layer / cathode (4) Anode / hole injection layer / light emitting layer / electron Injection layer / cathode (5) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode

  A transparent electrode layer serving as an anode or a cathode is formed on the gas barrier film 1 of the present invention, and two transparent electrode layers serving as an anode and a cathode are formed between them on the gas barrier film 1. Any of those are those for which the gas barrier film 1 of the present invention is used for an EL element, but in addition to the two transparent electrode layers to be the anode and the cathode and each layer between them, If one gas barrier film 1 is used for sealing, the penetration of oxygen gas and moisture into the inside can be further prevented, so that the gas barrier film 1 itself of the present invention can also be applied to EL elements. .

  Since the gas barrier film 1 of the present invention has a very high gas barrier property, when applied to various display elements, the deterioration of the light emitting layer caused by the invasion of oxygen gas or moisture into the material inside the element. In addition, when manufacturing an EL element, the durability is high even when the process is performed at a high temperature, and the flatness can be sufficiently increased. It is possible to effectively suppress the occurrence of dark spots, which is a problem peculiar to EL elements, with little reduction in gas barrier properties. Moreover, in the gas barrier film 1 of this invention, since it has the adhesive inorganic compound layer 3a which consists of silicon oxide carbide or silicon oxynitride carbide in the side which contact | connects the base material sheet 2, the gas barrier layer 3 is comprised. Adhesion with other layers can be improved and gas barrier properties can be improved.

(Reference Example 1)
Laminate of polycarbonate resin film / adhesion layer / transparent inorganic compound layer (sputtering method) / organic resin layer / transparent inorganic compound layer (sputtering method) (formation of adhesion layer)
A polycarbonate resin film (manufactured by Bayer, product name: “macro hole”, thickness: 200 μm, 30 cm × 21 cm) is prepared, and this polycarbonate resin film is placed in a chamber of a plasma CVD apparatus. Film formation was performed until the thickness reached 50 nm, and an adhesion layer made of silicon oxide carbide was formed. In the following description, the unit sccm is an abbreviation for standard cubic centimeter minute, and indicates the supply amount (volume) of gas per minute.
Deposition pressure: 30Pa
Hexamethyldisiloxane gas flow rate; 4 sccm
Oxygen gas flow rate: 12 sccm
Helium gas flow rate: 30 sccm
Frequency: 90kHz
Power: 150W

(Formation of transparent inorganic compound layer)
The polycarbonate resin film / adhesion layer film obtained above is placed in a chamber of a magnetron sputtering apparatus, silicon nitride is used as a target, and the film pressure of silicon oxynitride is 100 nm under the following film formation conditions. Film formation was performed until a transparent inorganic compound layer was formed.
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 9 sccm
Frequency: 13.56kHz
Electric power: 1.2kW

(Formation of organic resin layer)
A solvent solution of a resin having a cardo polymer having a fluorene skeleton on the transparent inorganic compound layer of a film having a laminated structure of polycarbonate resin film / adhesion layer / transparent inorganic compound layer obtained above (Nippon Steel Chemical Co., Ltd.) Manufactured and trade name “V259REH”) was applied by spin coating, and heated at 160 ° C. for 1 hour to form an organic resin layer. The film thickness of the organic resin layer was 1 μm. The deformation of the transparent inorganic compound layer due to the formation of the organic resin layer did not occur, the surface roughness of the exposed surface of the organic resin layer was 0.8 nm, and the maximum height difference PV was 8 nm. .

(Formation of transparent inorganic compound layer)
Further, a transparent inorganic compound layer was formed on the organic resin layer to obtain a gas barrier film. Regarding the formation of the transparent inorganic compound layer, the materials used, the formation conditions, and the thickness of the layer are the same as when the transparent inorganic compound layer is formed on the adhesion layer. Moreover, the surface roughness of the surface of the formed transparent inorganic compound layer was 1.5 nm, and the maximum height difference PV was 20 nm.

(Manufacture of organic EL light-emitting elements)
On the transparent inorganic compound layer on the outermost surface of the barrier film having the laminated structure of the polycarbonate resin film / adhesion layer / transparent inorganic compound layer / organic resin layer / transparent inorganic compound layer obtained as described above, it is transparent as described below. A transparent electrode layer patterned with a conductive layer is formed, and a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron injection layer, and a cathode are further formed thereon as shown below. Thus, an organic EL light emitting device having a six-layer structure of transparent electrode layer (anode) / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode is formed.

(Formation of transparent electrode layer)
First, a transparent conductive layer made of an ITO thin film was formed by sputtering on a transparent inorganic compound layer of a film having a laminated structure of polycarbonate resin film / adhesion layer / transparent inorganic compound layer / organic resin layer / transparent inorganic compound layer. Subsequently, a resist agent (trade name: “OFRP-800”, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied on the transparent conductive layer made of an ITO thin film on the surface, and the transparent conductive layer is patterned by a photolithographic method. Then, a transparent electrode layer (anode) on a stripe pattern having a width of 0.094 mm, an interval of 0.016 mm, and a film thickness of 100 nm was obtained.

The film on which the transparent electrode layer is formed as described above is mounted in a resistance heating vapor deposition apparatus, the pressure inside the vacuum chamber is reduced to 1 × 10 ⁻⁴ Pa, and then a hole injection layer is formed on the front surface of the transparent electrode layer. A hole transport layer, an organic light emitting layer, and an electron injection layer were sequentially formed on the entire surface. As the hole injection layer, copper phthalocyanine was laminated so as to have a film thickness of 100 nm, and as the successful transport layer, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α -NPD) is laminated so that the film thickness is 20 nm, and 4,4'-bis (2,2'-diphenylvinyl (DPVBi) is laminated so that the film thickness is 30 nm as the organic light emitting layer, In addition, as the electron injection layer, tris (8-hydroxyquinoline) aluminum complex (Alq) was laminated so as to have a film thickness of 20 nm. It has a stripe pattern perpendicular to the stripe pattern of the transparent electrode layer (anode), which consists of a 200 nm thick Mg / Ag (mass ratio: 10/1) layer, and has a width of 0.30 mm and an interval of 0.03 mm. To obtain an organic EL device that a cathode formed on the electron injection layer.

  Thereafter, in the dry nitrogen atmosphere in the glove box (both oxygen and moisture concentration are 10 ppm or less), the same laminated structure (polycarbonate resin) as obtained first on the cathode of the organic EL light-emitting device manufactured as described above. (Lamination structure of film / adhesion layer / transparent inorganic compound layer / organic resin layer / transparent inorganic compound layer) so that the transparent inorganic compound layer side of the outermost surface of the barrier film is in contact with each other, and the surroundings using an ultraviolet curable adhesive Sealed.

(Reference Example 2)
Laminate of polycarbonate resin film / adhesion layer / transparent inorganic compound layer (ion plating method) / organic resin layer / transparent inorganic compound layer (ion plating method) Formation of the transparent inorganic compound layer in the chamber of the ion plating apparatus Then, a barrier film was produced in the same manner as in Example 1 except that the film thickness was 100 nm under the following film forming conditions. By forming the organic resin layer, the transparent inorganic compound layer is not deformed, and the surface roughness Ra of the exposed surface of the organic resin layer at the time when the organic resin layer is formed is 0.8 nm. The height difference PV was 8 nm, which was the same as that in Example 1.
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 12 sccm
Nitrogen gas flow rate: 20 sccm
Deposition current value: 100A

  Using the barrier film obtained above, an organic EL light-emitting element was formed in the same manner as in Example 1, provided that the organic EL light-emitting element was placed on the side on which the above layers of the polycarbonate resin film were laminated. Was provided on the opposite side. Thereafter, the laminated structure (polycarbonate resin film / adhesion layer / transparent inorganic compound layer (ion plating method) / organic resin layer / transparent inorganic compound layer (ion) produced on the cathode b of the organic EL light emitting device was used. The barrier film of the plating method) was laminated so that the polycarbonate resin film side of the barrier film was in contact, and the periphery was sealed with an ultraviolet curable adhesive.

(First embodiment)
Laminate of polycarbonate resin film / transparent inorganic compound layer also serving as adhesion layer (plasma CVD method) / organic resin layer / transparent inorganic compound layer (plasma CVD method) Plasma polycarbonate resin film similar to that used in Example 1 The film was placed in the chamber of the CVD apparatus, and film formation was performed under the following film formation conditions until the film thickness reached 100 nm to form a transparent inorganic compound layer made of silicon oxide carbide that also served as an adhesion layer.
Deposition pressure: 30Pa
Hexamethyldisiloxane gas flow rate; 4 sccm
Oxygen gas flow rate: 12 sccm
Helium gas flow rate: 30 sccm
Frequency: 90kHz
Power: 150W

  An organic resin layer was formed in the same manner as in Example 1 on the obtained transparent inorganic compound layer also serving as an adhesion layer. By forming the organic resin layer, the transparent inorganic compound layer that also serves as the adhesion layer is not deformed, and the surface roughness Ra of the exposed surface of the organic resin layer is 0.8 nm, and the maximum height difference P− V was 8 nm, which was the same as that in Example 1.

  Further, a transparent inorganic compound layer having the same thickness was formed on the organic resin layer in the same manner as in the case of the transparent inorganic compound layer also serving as the adhesion layer.

   Using the barrier film obtained above, an organic EL light-emitting element was formed in the same manner as in Example 1, provided that the organic EL light-emitting element was placed on the side on which the above layers of the polycarbonate resin film were laminated. Was provided on the opposite side. Thereafter, on the cathode of the organic EL light emitting device, the laminated structure (polycarbonate resin film / adhesion layer / transparent inorganic compound layer (plasma CVD method) / organic resin layer / transparent inorganic compound layer (plasma CVD method) produced in this Example 3 The barrier film of ()) was laminated so that the polycarbonate resin film side of the barrier film was in contact, and the periphery was sealed with an ultraviolet curable adhesive.

(Second embodiment)
A transparent film made of ITOhm having a thickness of 100 nm is formed by sputtering on the surface of the barrier film obtained in the same manner as in the first example, on the side opposite to the side on which the above layers of the polycarbonate resin film are laminated. A conductive layer was formed, a polyimide resin-based resin solution was applied on the transparent conductive layer, dried by heating, and then rubbed to form an alignment film.

  As described above, two films provided with an alignment film are prepared, stacked so that each alignment film side is inside, and the periphery is bonded with a sealing material, and a liquid crystal material is sealed in a space between the liquid crystal display elements It was.

(Comparative Examples 1-4)
Reference Example 1, Reference Example 2, the first embodiment, in the case of the second embodiment the adhesion layer definitive example (adhesion layer serves as a transparent inorganic compound layer, a transparent inorganic compound layer which also serves as the adhesion layer ) Was the same as in the corresponding examples, except that no formation was made.

(Reference Example 3)
Reference Example 1 except that a layer having a thickness of 50 nm made of silicon oxynitride carbide was formed under the following film forming conditions in place of the adhesion layer and the inorganic compound layer made of silicon oxycarbide in Reference Example 1 The same as in.
Deposition pressure: 30Pa
Hexamethyldisilazane gas flow rate: 4 sccm
Oxygen gas flow rate: 12 sccm
Helium gas flow rate: 30 sccm
Frequency: 90kHz
Power: 150W

(Third embodiment)
In the first example, in place of each of the transparent inorganic compound layer and the transparent inorganic compound layer each serving as an adhesion layer made of silicon oxide carbide, the same film formation conditions as in Reference Example 3 , However, this was performed in the same manner as in the first example , except that the film was formed until the thickness reached 100 nm and a layer made of silicon oxynitride carbide having a thickness of 100 nm was formed.

(Evaluation methods)
About the laminated body produced in said reference Examples 1-3, 1st Example-3rd Example, and Comparative Examples 1-4, and each display substrate, as shown below, the test about the following evaluation items Was done.
(1) Measurement of water vapor transmission rate Using a water vapor transmission rate measuring device (trade name: “PERMATRAN-W 3/31” manufactured by MOCON) under the conditions of measurement temperature: 37.8 ° C., humidity: 100% RH. Measured.
(2) Measurement of oxygen permeability Under conditions of measurement temperature: 23 ° C., humidity: 90% RH, an oxygen gas permeability measurement device (manufactured by MOCON, trade name: “OXTRAN-W 2/20”) is used. It was measured.
(3) Measurement of surface roughness (Ra) and maximum height difference (PV) Scanning probe: 100 μm, scan speed: 90 sec / frame, tabletop probe microscope (manufactured by Seiko Instruments Inc., commercial product) Name; Nanopics).
(4) Measurement of total light transmittance Measured using a turbidimeter (JIS K 7361-1) manufactured by Nippon Denshoku Industries Co., Ltd.
(5) Adhesiveness A cellophane tape peel test was performed, and a peel test was performed using cellophane tape (manufactured by Nichiban Co., Ltd.) with 10 × 10 pieces (each 1 mm apart) cross-cut.

It is a figure which shows the basic laminated structure of the gas barrier film of this invention. It is a figure which shows the preferable laminated structure of the gas barrier film of this invention. It is a figure which shows the other preferable laminated structure of the gas barrier film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Gas barrier film 2 ... Base material sheet 3 ... Gas barrier layer 3a ... Adhesive inorganic compound layer 31 ... Organic resin layer 32 ... Inorganic compound layer

Claims (5)

A gas barrier layer having a laminated structure composed of a plurality of layers is laminated on one side or both sides of the base sheet,
Wherein the plurality of layers constituting the gas barrier layer, a layer which is in contact with at least the base sheet is, Ri inorganic compound layer der of an oxide of silicon carbide or oxynitride carbide,
The gas barrier layer is a laminated structure in which the inorganic compound layer composed of the silicon oxide carbide or silicon oxynitride carbide, the organic resin layer, and the inorganic compound layer are sequentially laminated from the side in contact with the base sheet, or It has a laminated structure in which an inorganic compound layer made of silicon oxycarbide or silicon oxynitride carbide, an inorganic compound layer, an organic resin layer, and an inorganic compound layer are sequentially laminated.
The organic resin layer is made of cardo resin,
The cardo resin is a cardo resin having an epoxy resin having two or more epoxy groups in one molecule as an essential component and having a fluorene skeleton derived from a bisphenol compound represented by the general formula (1) gas barrier film which is characterized in that one containing.

2. The gas barrier according to claim 1, wherein the inorganic compound layer is made of any one of an inorganic oxide, an inorganic oxynitride, an inorganic nitride, an inorganic oxide carbide, an inorganic oxycarbonitride, or a metal. Sex film. The gas barrier film according to any one of claims 1 to 2, wherein the surface roughness Ra of the outermost surface of the gas barrier layer is 6 nm or less, and the maximum height difference PV is 60 nm or less. In either case, a liquid crystal layer is sandwiched and sealed between both the back substrate and the front substrate on which the electrode layer and the alignment film are sequentially laminated, and the back substrate and / or the front substrate are A liquid crystal display element comprising the gas barrier film according to any one of claims 1 to 3 . A board | substrate, an electrode layer, a light emitting layer, a counter electrode layer, and a sealing layer are laminated | stacked in order, The said board | substrate or / and the said sealing layer are gas-barrier films in any one of Claims 1-3. An EL display element.

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